CN106977768A - A kind of method that spitball shape graphene improves the impact strength of nylon 6 - Google Patents
A kind of method that spitball shape graphene improves the impact strength of nylon 6 Download PDFInfo
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Abstract
The invention provides a kind of method that spitball shape graphene improves the impact strength of nylon 6, belong to macromolecular toughening and be modified field.This method is extruded by the use of spitball shape graphene microballoon as toughener and the melt blending of nylon 6, to improve the impact strength of nylon 6；The surface of the spitball shape graphene microballoon is many fold lamellar structures, with good pliability, the micro-sphere structure formed simultaneously can preferably disperse to be in nylon-6 matrix body, similar to elastic particle effect, the impact strength of nylon 6 material can be significantly improved, graphene also imparts the higher heat resistance of nylon 6 material, resistance to ag(e)ing, anti-flammability and antistatic behaviour simultaneously, improves the water imbibition of nylon, extends the application field of nylon 6 material.
Description
Technical field
Field is modified the invention belongs to macromolecular toughening, and in particular to a kind of spitball shape graphene improves nylon 6 and impacted by force
The method of degree.
Background technology
Nylon yield in five large-engineering plastics is maximum, kind at most, purposes it is most wide, with high mechanical strength, fusing point it is high,
The advantages of wear-resisting, oil resistant, fine heat-resisting performance, it is widely used in the field such as automobile, electric, mechanical.Due to much should
With having higher requirement to the toughness of nylon in field, in order to meet these applications, it is necessary to carry out toughening modifying to nylon.
Under normal circumstances, to toughening modifying main flexible body toughness reinforcing, rigid inorganic filler toughening, the organic rigid of nylon
Three kinds of methods of particle toughening, elastic physical efficiency significantly improves the toughness of nylon material, but the rigidity of material can be greatly lowered simultaneously
And intensity；Inorganic rigid particle and organic rigid-particle can strengthen while toughness reinforcing, but its toughness reinforcing limited extent.Meanwhile,
Found by studying, the form of rigid particles can influence the toughening effect of matrix, the rigidity in sheet, spherical, acicular texture
In particle, the rigid particles of chondritic are best to the toughening effect of material.
Graphene is a kind of nano material with two dimensional crystal structure, with many excellent performances.Graphene is both
Most thin material, is also most tough material, while it has good elasticity again, stretch range can reach own dimensions
20%, thus, with reference to macromolecular toughening mechanism, if Sheet Graphite alkene can be built into chondritic, graphene will certainly will turn into
A kind of preferable toughness-increasing modified material.
The content of the invention
For the existing toughening technology of nylon 6, the impact strength of nylon 6 is improved the invention provides a kind of spitball shape graphene
Method.
The purpose of the present invention, is achieved through the following technical solutions：A kind of spitball shape graphene improves nylon 6 and impacted by force
The method of degree, methods described is to utilize spitball shape graphene toughened Nylon 6, and the spitball shape graphene microballoon is by single-layer graphene
Piece gauffer is formed, and microsphere diameter is 500nm~5 μm, and density is 0.2~0.4g/cm3, carbon-to-oxygen ratio is 20~60, and specific surface area is low
In 200m2/g。
Further, the spitball shape graphene microballoon is prepared by following steps：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon；
(2) the graphene oxide microballoon for obtaining step (1), is placed in reducibility gas atmosphere and is reduced, gone back
Former graphene oxide microballoon；
(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, and temperature is higher than 1000 DEG C, obtained
Spitball shape graphene microballoon.
Further, in the single-layer graphene oxide dispersion liquid of the step (1), reducing agent can also be contained.In atomization
During, fold occurs for graphene oxide sheet, meanwhile, reducing agent is attached to sheet surfaces with molecular conformation.The reducing agent is
Hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, sodium borohydride etc..Reducing agent and single-layer graphene oxide mass ratio be 0.1~
10.Atomization drying temperature in the step (1) is 100~200 DEG C so that be wrapped in the reducing agent in pleated structure to oxidation
Graphene is tentatively reduced.
Further, the reducing atmosphere described in step (2) is hydrazine hydrate steam, hydroiodic acid steam, hydrogen, hydrobromic acid
One or more in steam.Reducing condition is：30min~48h or so is reduced at 60~200 DEG C.
Further, the high-temperature process temperature described in step (3) be 2500~3000 DEG C, processing time be 30min~
48h, atmosphere is one kind in nitrogen, helium, hydrogen argon gas gaseous mixture, argon gas.
Further, the method that described spitball shape graphene improves the impact strength of nylon 6, passes through following steps：
(1) it is 100 by nylon 6 and graphene microspheres weight proportioning:0.05~1, premixed, mixed in mixer
The uniform graphene premix of nylon 6/ is closed, first by nylon 6 and graphene microballoon in vacuum drying oven in 80~105 DEG C before premix
Drying 8~12 hours；
(2) the premix double screw extruder for obtaining step (1) is in 230~250 DEG C of processing temperature, and rotating speed 150~
Melt blending is extruded under conditions of 250rpm, is cooled down, and the graphene composite material of nylon 6/ is made in granulation.
The beneficial effects of the invention are as follows：
1st, the present invention prepares graphene oxide microballoon by atomization drying method first, by reducing agent before atomization drying
Add in graphene oxide dispersion, be well mixed, reducing agent is supported on graphene oxide sheet surface with molecular forms.Afterwards
During atomization drying, the oxygen-containing functional group of partial reduction agent and surface of graphene oxide reacts, and product is with solvent
Volatilization and deviate from, remaining reducing agent is then attached to graphene oxide sheet surface with molecular forms, and is wrapped with its gauffer
Come.Second step uses electronation, under reducing atmosphere, and the oxygen-containing functional group on inside graphene oxide microballoon and surface is with going back
Former agent is fully reacted, relatively low temperature make it that the generation and release of gas are slow, it is to avoid group quickly takes off in direct thermal reduction
Except produce gas, the phenomenon for causing volume drastically to expand, thus maintain graphene still combined closely in the form of fold piece and
Do not separate.On the one hand 3rd step high temperature thermal reduction makes remaining a small amount of oxygen-containing functional group removing, and repairs in graphene oxide sheet
Defect sturcture, on the other hand, make the moisture of residual in microballoon, reduzate and the removing of unreacted reducing agent.In addition, we
Have been surprisingly found that in an experiment, at extreme temperatures under (2500~3000 DEG C), the diameter of graphene microballoon is gradually reduced, density increases
Greatly, specific surface area is reduced.This is probably the perfect structure of graphene film so that graphene fold due under graphitization temperature
Adhesion strengthens, and graphene film intermolecular forces increase, Distance Shortened each other progressively makes the compact structure of graphene ball
Change.
2nd, spitball shape graphene microballoon is used for the plasticized modifier of nylon 6 material, and the graphene particle of chondritic is more held
Easily it is dispersed in nylon-6 matrix body, it is more preferable that the micro- fold morphology and structure of graphene microsphere surface impart graphene particle again
Flexibility, relatively common lamella filler can be buffered further to stress, be acted on similar to elastic particle, improve the material of nylon 6
The impact strength of material.
3rd, spitball shape graphene toughened Nylon 6 composite is processed by way of melt blending is extruded, this method operation
Technique is simple, solvent-free pollution, and production efficiency is high, is adapted to large-scale production.
4th, nylon 6 material is modified using graphene, graphene not only increases the impact strength of nylon 6 material,
Also there is facilitation to 6 crystallizations of nylon simultaneously, and then further improve the rigidity and heat resistance of material, separately due to graphite
It is comprehensive that the combination property of alkene can also assign the more excellent antistatic behaviour of material, anti-ultraviolet ageing, anti-flammability and water resistance etc.
Energy.
Brief description of the drawings
Fig. 1 is the microscopic appearance of the spitball shape graphene microballoon prepared through the embodiment of the present invention.
Fig. 2 is the microscopic appearance of the expanded graphite alkene microballoon prepared through comparative example 2 of the present invention.
Embodiment
A kind of method that spitball shape graphene improves the impact strength of nylon 6, step is as follows：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon.The list
Reducing agent can also be contained in layer graphene oxide dispersion, in atomization process, fold occurs for graphene oxide sheet, meanwhile,
Reducing agent is attached to sheet surfaces with molecular conformation.Reducing agent is hydrogen iodide, hydrogen bromide, hydrazine hydrate, vitamin C, sodium borohydride
Deng.Reducing agent is 0.1~10 with single-layer graphene oxide mass ratio.Atomization drying temperature is 100~200 DEG C so that be wrapped in
Reducing agent in pleated structure is tentatively reduced to graphene oxide；
(2) the graphene oxide microballoon for obtaining step (1), is placed in reducibility gas atmosphere, at 60~200 DEG C also
Former 30min~48h obtains redox graphene microballoon；Described reducing atmosphere is hydrazine hydrate steam, hydroiodic acid steam, hydrogen
One or more in bromic acid steam；
(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, and temperature is higher than 1000 DEG C, obtained
Spitball shape graphene microballoon；Atmosphere is one kind in nitrogen, helium, hydrogen argon gas gaseous mixture, argon gas, and processing time is 30min
~48h.Further, the temperature treatment temperature is 2500~3000 DEG C.
(4) it is 100 by weight ratio by the graphene microballoon obtained by nylon 6 and step (3):0.05~1, in mixer
Premixed, obtain first drying nylon 6 and graphene microballoon in vacuum before the well mixed graphene premix of nylon 6/, premix
Dried 8~12 hours in 80~105 DEG C in case；
(5) by the premix double screw extruder obtained by step (4) in 230~250 DEG C of processing temperature, rotating speed 150
Melt blending is extruded under conditions of~250rpm, is cooled down, and the enhanced graphene composite wood of nylon 6/ of impact strength is made in granulation
Material.
The composite of the preparation of the present invention is molded using ASTM standard, and injection machine is molded under the conditions of 230~260 DEG C
Type, sample shaping after temperature be 23 ± 2 DEG C, humidity for 50 ± 5% standard environment in place 88h after test, test environment
It it is 23 ± 2 DEG C for temperature, humidity is 50 ± 5%.
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
Bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment belong to protection scope of the present invention.
Embodiment 1：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and 1h is reduced at 60 DEG C and is obtained
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, as shown in figure 1, its density is 0.2g/cm3, carbon-to-oxygen ratio is 22.8, and specific surface area is
190m2/g.Composite is molded into standard testing batten with injection machine and carries out Mechanics Performance Testing, the graphene increases after tested
The normal temperature Izod notched impact strength of tough nylon 6 composite material is 25.44KJ/m2。
Embodiment 2：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and 1h is reduced at 90 DEG C and is obtained
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, its density is 0.23g/cm3, carbon-to-oxygen ratio is 23.1, and specific surface area is 181m2/g.Will be multiple
Condensation material is molded into standard testing batten with injection machine and carries out Mechanics Performance Testing, and the nylon 6 of the graphene toughness reinforcing is answered after tested
The normal temperature Izod notched impact strength of condensation material is 26.56KJ/m2。
Embodiment 3：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, its density is 0.25g/cm3, carbon-to-oxygen ratio is 23.2, and specific surface area is 166m2/g.Will be multiple
Condensation material be molded into injection machine standard testing batten carry out Mechanics Performance Testing after tested the graphene toughness reinforcing nylon 6 be combined
The normal temperature Izod notched impact strength of material is 27.15KJ/m2。
By comparative example 1~3, final stone can be significantly reduced by improving second step reduction temperature and time
The specific surface area of black alkene microballoon, improves density, but influence little to carbon-to-oxygen ratio.This is due to that second step reduction mainly makes oxidation
The group of graphenic surface is slowly removed, reduction temperature is low or the time it is short can cause that reduction is insufficient, the group of residual exists
Removing is may proceed to during the 3rd high-temperature heat treatment, gas is produced and graphene film is outwards expanded.And spitball shape graphene is micro-
When the specific surface area of ball is big, graphene powder less efficient dispersal, toughening effect is impacted.Therefore, to sum up consider, second step is also
Old terms is preferably high reduction temperature and long recovery time.
Embodiment 4：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 0.1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, is molded into standard testing batten with injection machine by composite and carries out mechanical property survey
Examination, specific nature is as shown in table 1.
Embodiment 5：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, is molded into standard testing batten with injection machine by composite and carries out mechanical property survey
Examination, specific nature is as shown in table 1.
Embodiment 6：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 5, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 1000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, is molded into standard testing batten with injection machine by composite and carries out mechanical property survey
Examination, specific nature is as shown in table 1.
Embodiment 7：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 2000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, is molded into standard testing batten with injection machine by composite and carries out mechanical property survey
Examination, specific nature is as shown in table 1.
Embodiment 8：
(1) it will be dried by atomization drying method containing ascorbic single-layer graphene oxide dispersion liquid, and obtain graphite oxide
The mass ratio of alkene microballoon, vitamin C and graphene oxide is 1, and atomization temperature is 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 3000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, is molded into standard testing batten with injection machine by composite and carries out mechanical property survey
Examination, specific nature is as shown in table 1.
Embodiment 9：
(1) dried by atomization drying method single-layer graphene oxide dispersion liquid, obtain graphene oxide microballoon, atomization temperature
For 130 DEG C；
(2) the graphene oxide microballoon for obtaining step (1), is placed in hydrazine hydrate steam, and reductase 12 4h is obtained at 90 DEG C
Redox graphene microballoon；
(3) the redox graphene microballoon for obtaining step (2) is put into tube furnace, is continually fed into nitrogen, temperature liter
To 3000 DEG C, 1h is incubated, spitball shape graphene microballoon is obtained；
(4) the spitball shape graphene microballoon for obtaining nylon 6 and step (3) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(5) premix for obtaining step (4) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein spitball shape graphene microballoon is under microcosmic
Fold microballoon for diameter at 3~5 μm, is molded into standard testing batten with injection machine by composite and carries out mechanical property survey
Examination, specific nature is as shown in table 1.
Comparative example 1：It is not added with the nylon 6 material of graphene.
Comparative example 2：Without the direct thermal reduction of electronation
(1) the single-layer graphene oxide dispersion liquid for being prepared Hummers methods by atomization drying method is dried, and obtains oxygen
Graphite alkene microballoon, atomization temperature is 130 DEG C；
(2) the redox graphene microballoon for obtaining step (1) is put into tube furnace, be continually fed into it is hydrogen-argon-mixed,
Temperature rises to 3000 DEG C, and programming rate is 5 DEG C/min, is incubated 1h；
(3) the spitball shape graphene microballoon for obtaining nylon 6 and step (2) is by weight 100:0.2, mixed in mixer
Close uniform, obtain 90 DEG C of vacuum drying in vacuum drying oven by nylon 6 and graphene microballoon before the graphene premix of nylon 6/, premix
12 hours
(4) premix for obtaining step (3) melt blending in double screw extruder is extruded, and melting temperature is 250 DEG C,
Screw speed is 200rpm.
The nylon 6 composite material of graphene toughness reinforcing is obtained through above step, wherein graphene outward appearance is black fluffy powder,
As shown in Fig. 2 microcosmic is hollow ball shell of the diameter at 1~10 μm, composite is molded into standard testing batten with injection machine
Mechanics Performance Testing is carried out, specific nature is as shown in table 1.
The embodiment design parameter of table 1 and property
Comparative example 3~6 is it can be found that the amount of the reducing agent added by improving before atomization drying can be effectively facilitated
Reducing degree of the graphene oxide microballoon before three step process, this is due to that reducing agent is dispersed in oxidation with molecular forms
Graphenic surface, can roll into a ball step-reaction, slow reduced graphene so that carbon-to-oxygen ratio is put forward in the first step and second step with ether ring
Rise, specific surface area reduction.And contrast knowable to before and after the reduction of the 3rd step, high-temperature heat treatment causes inside redox graphene microballoon
The group not removed departs from (carbon-to-oxygen ratio increase), and the swelling graphene interlayer structure of gas of generation causes specific surface area to rise.But
It is to be improved by adding reducing agent after reproducibility, the release gas that graphene microballoon can be less in the 3rd step high-temperature heat treatment,
Reduce volumetric expansion so that structure is more closely knit.Therefore, in order to obtain high density, low specific surface area graphene microballoon, plus
It is significant to enter reducing agent.
Comparative example 5,7 is it can be found that in the case where ensureing that first two steps reducing condition is consistent, improve the reduction of the 3rd step
Temperature causes specific surface area to increase, density reduction, and this is due to that the further release of gas causes lamellar structure further to strut.
However, surprisingly, after temperature rises to 3000 DEG C (embodiment 8), specific surface area is greatly lowered, it may be possible to which temperature is high
In after graphitization temperature, the big π structures of graphene are repaired, and the adhesion between lamella is greatly promoted, interlamellar spacing reduction, because
And cause graphene microballoon to center " aggregation ", more densification.
Comparative example 3,9 is understood, if being added without reducing agent, can significantly reduce graphite by 3000 DEG C of heat treatments merely
The specific surface area of alkene microballoon.But comparative example 8 is understood, add reducing agent and realize that most of functional group's removing can before heat treatment
To obtain the graphene microballoon of more consolidation.
Comparative example 8 and comparative example 1 are understood, graphene oxide microballoon directly is carried out into high-temperature heat treatment in comparative example,
A large amount of gas effusions cause volume rapid expanding during reduction, and specific surface area is high, and density is very low.
When spitball shape graphene microballoon is with nylon-6 matrix bluk recombination, big specific surface area can strengthen the boundary of graphene and matrix
Glue effect in face so that more energy are absorbed when material is by percussion, play more preferable toughening effect, but work as specific surface area
When excessive, graphene powder is easily reunited, in the base less efficient dispersal, and stress concentration point reduction material is more readily formed on the contrary
Expect performance.In addition, because the fold-like structures of spitball shape graphene microballoon make its own have extraordinary pliability, microballoon
Structure is more closely knit, is less susceptible to destroy the toughness of material because of deformation big after microballoon is under pressure.So, in actual applications
Effect can be prepared by the method disclosed in the patent of invention come balance paper nodular graphite alkene microballoon specific surface area and the degree of packing
Optimal graphene toughener, for the impact strength to improving nylon 6 material, meanwhile, it is higher that graphene also imparts material
Heat resistance, resistance to ag(e)ing and the combination property such as antistatic, improve water imbibition, extend the application of nylon 6 material.
Claims (9)
1. a kind of method that spitball shape graphene improves the impact strength of nylon 6, it is characterised in that this method is to utilize spitball shape stone
Black alkene microballoon carries out toughness reinforcing to nylon material, and the spitball shape graphene microballoon is formed by single-layer graphene film gauffer, and microballoon is straight
Footpath is 500nm~5 μm, and density is 0.2~0.4g/cm3, carbon-to-oxygen ratio is 20~60, and specific surface area is less than 200m2/g。
2. in accordance with the method for claim 1, it is characterised in that the spitball shape graphene microballoon is obtained by following steps：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon；
(2) the graphene oxide microballoon for obtaining step (1), is placed in reducibility gas atmosphere and is reduced, obtain oxygen reduction
Graphite alkene microballoon；
(3) the redox graphene microballoon for obtaining step (2) carries out high-temperature process, and temperature is higher than 1000 DEG C, obtains spitball
Shape graphene microballoon.
3. method according to claim 2, it is characterised in that in the single-layer graphene oxide dispersion liquid of the step (1),
Reducing agent can also be contained.
4. method according to claim 3, it is characterised in that the reducing agent is hydrogen iodide, hydrogen bromide, hydrazine hydrate, dimension
Raw element C, sodium borohydride etc..Reducing agent is 0.1~10 with single-layer graphene oxide mass ratio.
5. method according to claim 2, it is characterised in that atomization drying temperature in the step (1) for 100~
200℃。
6. method according to claim 2, it is characterised in that the reducing atmosphere in the step (2) is steamed for hydrazine hydrate
One or more in vapour, hydroiodic acid steam, hydrobromic acid steam.Reducing condition is：30min~48h is reduced at 60~200 DEG C
Left and right.
7. method according to claim 2, it is characterised in that high-temperature process temperature in the step (3) for 2500~
3000℃。
8. method according to claim 2, it is characterised in that the high-temperature process atmosphere in the step (3) is nitrogen, helium
One kind in gas, hydrogen argon gas gaseous mixture, argon gas, processing time is 30min~48h.
9. according to the method described in claim 1, it is characterised in that characterized in that, step is as follows：
(1) it is 100 according to weight proportion by nylon 6 and graphene microballoon:0.05~1, premixed, mixed in mixer
The uniform graphene premix of nylon 6/ is closed, first by nylon 6 and graphene microballoon in vacuum drying oven in 80~105 DEG C before premix
Drying 8~12 hours；
(2) the premix double screw extruder for obtaining step (1) is in 230~250 DEG C of processing temperature, and rotating speed 150~
Melt blending is extruded under conditions of 250rpm, is cooled down, and the graphene composite material of nylon 6/ is made in granulation.
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| CN201710302912.8A CN106977768B (en) | 2017-05-03 | 2017-05-03 | A kind of method that spitball shape graphene improves 6 impact strength of nylon |
| PCT/CN2018/077221 WO2018196474A1 (en) | 2017-04-28 | 2018-02-26 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
| EP18791151.6A EP3617141B1 (en) | 2017-04-28 | 2018-02-26 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
| RU2019138451A RU2734476C1 (en) | 2017-04-28 | 2018-02-26 | Graphene microspheres in form of paper lump, composite material of such microspheres and method of making such microspheres |
| US16/622,953 US11225414B2 (en) | 2017-04-28 | 2018-02-26 | Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor |
| KR1020197034665A KR102307001B1 (en) | 2017-04-28 | 2018-02-26 | Paperball-type graphene microspheres and their composite material and manufacturing method |
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