CN107418199B - Graphene modified nylon composite resin and preparation method and application of powder thereof - Google Patents
Graphene modified nylon composite resin and preparation method and application of powder thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G69/14—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention relates to the field of high polymer materials, and provides graphene modified nylon composite resin, a preparation method of powder of the graphene modified nylon composite resin and application of the graphene modified nylon composite resin in 3D printing in order to solve the problems that existing nylon 12 powder is not high in strength, too high in cost and non-conductive. Graphene oxide and nylon have good compatibility, the graphene oxide and lactam are mixed and subjected to anionic ring-opening polymerization to obtain lactam/graphene oxide composite resin slices, then the lactam/graphene oxide composite resin slices are dissolved in a high-pressure kettle through a solvent, and precipitation is conducted to obtain the powder. The prepared nylon composite resin has the advantages of being good in mechanical property, low in shrinkage rate, good in size stability, low in cost, good in electric conductivity and thermal conductivity and the like, and popularization and promotion are facilitated.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to a kind of nylon 6 resin modified based on graphene, powder and
Its application in 3D printing.
Background technique
2004, Univ Manchester UK physicist An Deliehaimu (Andre Geim) and Constantine's promise
Wo Xiaoluo (KonstantinNovoselov), successfully isolates graphene from graphite in an experiment, and confirms that it can be with
Individualism, two people also because of " in the initiative experiment of two-dimensional graphene material ", obtain Nobel Prize in physics in 2010 jointly.
Graphene forms the flat film that hexangle type is in honeycomb lattice by carbon atom with sp2 hybridized orbit, only one carbon atom is thick
The two dimensional crystal material of degree, thickness are about 0.335nm, only 20 a ten thousandths of hair, are the other dimension carbonaceous materials of building
The basic unit of (such as zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite) has fabulous crystallinity, mechanical property and electricity
Learn quality.Single-layer graphene is the most thin material being currently known, and possesses characteristic not available for many carbon materials: superpower
Mechanical strength, high heat conductance, high transparency, high-specific surface area and peculiar electric property etc., cause the wide of domestic and foreign scholars
General concern.Relative to common graphite, graphene microchip has nano thickness, easily uniformly compound with other materials such as polymer material
And good compound interface is formed, high-performance composite materials are obtained in composite material so that the characteristic of graphene be brought into.
Macromolecule nylon dusty material is selective laser sintering (Selective Laser Sintering, abbreviation at present
SLS) the most widely used raw material of manufacturing field, product consistency is high, mechanical property is good, can be widely applied to it is civilian,
The fields such as industry and national defence.At present 12 powder of nylon because its water absorption rate is low, good stability of the dimension due to occupy 95% or so share,
But simple 12 dusty material of nylon preparation and performance have certain limitation, and price is more expensive.And nylon and big
The same most high molecular materials are all the materials with good electrical insulation capability, and product easily causes electrostatic accident, while nylon
Dry friction coefficient it is high, limit its application in Tribological Systems.
The reapective features for combining graphene and nylon thus, are gradually risen using the research of graphene modification of nylon, some
Polyamide-graphene high-performance composite materials also when have been reported that.A kind of such as Chinese invention patent " conductive MC nylon/graphene
In composite material and preparation method " (CN105601909A), it is low, multiple that graphene addition content is prepared using situ aggregation method
The composite material that condensation material conducts electricity very well；A kind of Chinese invention patent " preparation of 6/ graphite oxide nanocomposite of nylon
In method " (CN101760011A), in-situ polymerization is carried out with graphite oxide and caprolactam, gained composite material has preferable
Electric conductivity and certain flame retardant effect.But above two dispersibility not be improved significantly, performance has no and obviously mentions
It rises.In addition, introducing of the graphene oxide layer due to oxygen-content active group, makes it have certain new properties, as hydrophily,
Good dispersibility and compatibility are strong, and the reinforcing agent for being often used as high molecular material uses.But also just due to oxygen-containing work
Property group introducing destroy the pi bond in graphene oxide layer, make the ability of its some lost conduction electronics, therefore it is conductive
Property is poor.Therefore the unsuitable preparation of graphene oxide has the electronic device of more highly conductive Capability Requirement.
Summary of the invention
To solve the problems, such as that current 12 powder strength of nylon is not high, cost is too high and nonconducting, the invention proposes one
The preparation method and the application in 3D printing, the composite material of preparation of kind graphene modified nylon compound resin and its powder
Have many advantages, such as that mechanical property is good, shrinking percentage is low, good stability of the dimension, at low cost, electrical and thermal conductivity is good, convenient for popularizing and pushing away
Extensively.
The present invention is achieved by the following technical solutions: a kind of modified nylon compound resin of graphene and its powder
Preparation method is following steps:
(1) graphene oxide is dissolved in the mixed liquor of deionized water and dehydrated alcohol, 1~3h of stirring forms uniform point
Dispersion liquid, then by coupling agent under stiring slowly instill after at 70~100 DEG C reaction 8~for 24 hours, product is obtained by filtration, then distinguish
It is washed several times with dehydrated alcohol and deionized water, paste is placed in 60~110 DEG C of drying box and is dried；
The mass ratio of coupling agent and graphene oxide is 1: 1~1: 4.Preferably, coupling agent selects vinyl oxethyl
Silane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, gamma-aminopropyl-triethoxy-silane,
One or more of γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, isobutyl triethoxy silane.
The mass percent of dehydrated alcohol is 20~80% in the mixed liquor of deionized water and dehydrated alcohol, and usage amount is to make
The amount of solute dissolution.
Preferably, drying box selects vacuum oven.
(2) modified graphene oxide that step (1) obtains is mixed with lactam monomers, in the case where temperature is 121~135 DEG C
Stir 1~3h；Above-mentioned mix monomer is placed in reaction kettle later, and is warming up to 120~140 DEG C of addition catalyst, is vacuumized
After removing water 10~30min, activator is added and stirs, polymerize at 170~185 DEG C, obtains graphene after keeping the temperature 20~60min
Modified nylon compound resin；
The mass ratio of modified graphene oxide and lactam monomers is 1: 50~1: 2000.Preferably, lactam monomers
Selected from one or more of caprolactam, caprinolactam, lauric lactam.
Catalyst amount be lactam monomers mole 0.2~1.0%, preferably, catalyst be selected from KOH, NaOH,
One or more of sodium caprolactam, caprolactam potassium, sodium methoxide etc..
Activator level is the 0.05~0.8% of lactam monomers mole, preferably, activating agent is selected from isocyanic acid
Ester.The isocyanates is selected to toluene 2,4- diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanates
One or more of ester.
Preferably, conventional ultrasonic agitation method is selected in stirring described above；
Water removal is vacuumized, vacuum degree is -100KPa or less.
(3) it is passed through high pure nitrogen in the reaction kettle in step (2), and is warming up to 230~260 DEG C and is allowed to melt, gone out
Cooling and dicing after material mouth discharging obtains the modified nylon compound resin slice of graphene oxide；
The purity of high pure nitrogen described above is 99% or more, and some foreign gases in common nitrogen will affect polymerization effect
Fruit.
(4) slice for obtaining step (3), is placed in autoclave, and solvent and reducing agent is added, is heated to after sealing
60~180 DEG C of temperature, and be gradually cooled to room temperature after being stirred continuously 2-6h, mixed solution is poured out, is filtered, is washed, it is dry, point
Grade is to get the nylon compound resin powder modified to graphene.
Solvent for use be selected from one of ethyl alcohol, methanol, tetrahydrofuran, dimethylformamide, first ethyl-formamide etc. or
It is several, wherein the mass ratio of the modified nylon compound resin slice of graphene and solvent is 1: 5~1: 100, and solvent is as few as possible
With the preparation efficiency of such powder is higher, therefore high molecular solubility is the bigger the better.
The mass ratio of the reducing agent and step (3) product is 1: 100~1: 10000, and wherein reducing agent is selected from hydrazine
One or more of reducing agent, sodium citrate, hydroiodic acid.Preferably, hydrazine reducing agent is selected from hydrazine, hydrazine hydrate, dimethyl
Hydrazine, phenylhydrazine, to one or more of sulfonyloxy methyl hydrazine.
The modified nylon compound resin powder diameter of the graphene is at 5~80 μm, batten made of nylon powder material
Tensile strength be 80~150MPa, impact strength be 100~180J/m, conductivity 10-6To 10-1S/cm, it is average thermally conductive
Coefficient 0.01-1.0W/mK.
The pressure of autoclave is in 0.2-1.0MPa, because it is insoluble for being sliced resin under normal pressure.
The present invention has preferable compatibility using graphene oxide and nylon, first mixes graphene oxide with lactams
Lactams/graphene oxide compound resin slice is obtained through anionic ring-opening polymerization, dissolves, sinks through solvent in autoclave later
Forming sediment becomes powder.Because graphene oxide layer due to the introducing of oxygen-content active group, destroys the π in graphene oxide layer
Key, the ability for making it lose conduction electronics, therefore its electric conductivity and the capacity of heat transmission are poor.For this purpose, addition is also while dissolution
Graphene oxide reduction is become graphene by former agent, and the nylon compound resin and its powder for keeping graphene modified have good lead
Electricity and heat-transfer capability.Such technology compensates for the graphene of conventional blend method preparation, and bad dispersibility is not in matrix resin
Foot, increases the adhesion strength between polyamide substrate and graphene, meanwhile, it also gives the good conduction of particulate composite and leads
Hot property enables the characteristic property of graphene to fully demonstrate, therefore nylon compound resin, powder that graphene is modified are useful in
In 3D printing field, so that product dimensional stability, electric conductivity, thermal conductivity are improved significantly.
Compared with prior art, the beneficial effects of the present invention are:
(1) electrical and thermal conductivity performance of the modified nylon compound resin of graphene is improved significantly；
(2) compatibility of the modified nylon compound resin of graphene is good, and impact strength significantly improves；
(3) the modified nylon compound resin powder of graphene of the invention, powder particle is uniform, and 3D printing product size is steady
Qualitative, toughness, electric conductivity and thermal conductivity significantly improve, and compared with existing 12 powder of nylon, cost is greatly reduced.
Specific embodiment
Below by embodiment to the present invention make further, it is raw materials used commercially available in embodiment or use conventional method
Preparation.
Embodiment 1
12g graphene oxide is dissolved in the mixed liquor of deionized water and dehydrated alcohol that dehydrated alcohol mass concentration is 50%
In, ultrasonic 1h forms uniform dispersion liquid, then by 3g vinylethoxysilane coupling agent under stiring slowly instill after, 70
Reacted at DEG C for 24 hours, product be obtained by filtration, after washed three times with dehydrated alcohol and deionized water respectively again, paste is placed in 70
DEG C vacuum oven in dry, obtain modified graphene oxide 1.
0.02g modified graphene oxide is mixed with 40g caprolactam monomer, in the case where temperature is 125 DEG C of constant temperature
It is ultrasonically treated 1h；Above-mentioned mix monomer is placed in reaction kettle later, and is warming up to 130 DEG C of addition catalyst KOH1.2mmol,
After vacuumizing water removal 30min, toluene 2 is rapidly joined, 4- diisocyanate activator 0.3mmol is stirred evenly, at 172 DEG C
Polymerization, heat preservation 60min obtain the in-situ modified nylon compound resin of graphene oxide.It is passed through High Purity Nitrogen in a kettle later,
And be warming up to 235 DEG C and be allowed to melt, the cooling and dicing after discharge hole for discharge obtains the modified nylon compound resin of graphene oxide
Slice 1.
Slice 40g is placed in 0.5MPa autoclave, ethyl alcohol 240ml and 0.01g hydrazine reducing agent is added, is added after sealing
Heat is stirred continuously to 80 DEG C, is allowed to sufficiently dissolve.It is gradually cooled to room temperature afterwards, mixed solution is poured out, filter, wash, do
It is dry, it is classified to get the nylon compound resin powder 1 modified to graphene.
Powder diameter is 50~80 μm, and the tensile strength of product 1 is 80MPa, impact strength 100J/m, and conductivity is
10-6S/cm, mean coefficient of heat conductivity 0.01W/mK.
Embodiment 2
12g graphene oxide is dissolved in the mixed liquor of deionized water and dehydrated alcohol that dehydrated alcohol mass concentration is 80%
In, ultrasonic 2h forms uniform dispersion liquid, then by 6g vinyltrimethoxysilane under stiring slowly instill after, at 80 DEG C
React 16h, product is obtained by filtration, after washed three times with dehydrated alcohol and deionized water respectively again, paste is placed in 70 DEG C
It is dried in vacuum oven, obtains modified graphene oxide 2.
0.2g modified graphene oxide is mixed with 40g caprinolactam monomer, is surpassed in the case where temperature is 132 DEG C of constant temperature
Sonication 2h；Above-mentioned mix monomer is placed in reaction kettle later, and is warming up to 133 DEG C of addition catalyst n aOH1.6mmol, is taken out
After vaccum dewatering 30min, '-diphenylmethane diisocyanate activator 0.6mmol is rapidly joined, is stirred evenly, gathered at 175 DEG C
It closes, heat preservation 30min obtains the in-situ modified nylon compound resin of graphene oxide.It is passed through High Purity Nitrogen in a kettle later, and
It is warming up to 242 DEG C to be allowed to melt, the cooling and dicing after discharge hole for discharge, obtains the modified nylon compound resin of graphene oxide and cut
Piece 2.
Slice 40g is placed in 0.8MPa autoclave, methanol 500ml and 0.1g reducing agent hydrazine hydrate, sealing is added
After be heated to 80 DEG C, and be stirred continuously, be allowed to sufficiently dissolve.It is gradually cooled to room temperature afterwards, mixed solution is poured out, filter, wash
It washs, it is dry, it is classified to get the nylon compound resin powder 2 modified to graphene.
Powder diameter is 30~60 μm, and the tensile strength of product 2 is 110MPa, impact strength 125J/m, conductivity
It is 10-4S/cm, mean coefficient of heat conductivity 0.08W/mK.
Embodiment 3
12g graphene oxide is dissolved in the mixed liquor of deionized water and dehydrated alcohol that dehydrated alcohol mass concentration is 20%
In, ultrasonic 3h forms uniform dispersion liquid, then by 12g7- aminopropyl triethoxysilane under stiring slowly instill after, 100
React 8h at DEG C, product be obtained by filtration, after washed three times with dehydrated alcohol and deionized water respectively again, paste is placed in 70 DEG C
Vacuum oven in dry, obtain modified graphene oxide 3.
0.8g modified graphene oxide is mixed with 40g lauric lactam monomer, in the case where temperature is 135 DEG C of constant temperature
It is ultrasonically treated 3h；Above-mentioned mix monomer is placed in reaction kettle later, and is warming up to 135 DEG C of addition catalyst sodium caprolactams
1.8mmol rapidly joins hexamethylene diisocyanate activator 0.6mmol and stirs evenly after vacuumizing water removal 30min,
It polymerize at 180 DEG C, heat preservation 20min obtains the in-situ modified nylon compound resin of graphene oxide.It is passed through in a kettle later
High Purity Nitrogen, and be warming up to 255 DEG C and be allowed to melt, the cooling and dicing after discharge hole for discharge obtains the modified nylon of graphene oxide
Compound resin slice 3.
Slice 40g is placed in 0.3MPa autoclave, dimethylformamide 1000ml and 0.4g reducing agent lemon is added
Lemon acid sodium, is heated to 155 DEG C, and be stirred continuously after sealing, be allowed to sufficiently dissolve.It is gradually cooled to room temperature afterwards, by mixed solution
It pours out, filters, wash, it is dry, it is classified to get the nylon compound resin powder 3 modified to graphene.
Powder diameter is 15~40 μm, and the tensile strength of product 3 is 148MPa, impact strength 175J/m, conductivity
For 5*10-2S/cm, mean coefficient of heat conductivity 0.8W/mK.
Comparative example uses not mixed with the poly-lactam material of graphene as prior art comparative example
Comparative example 1:
At reduced pressure, 40g caprolactam monomer is placed in reaction kettle, and is warming up to 130 DEG C of addition catalyst
KOH1.0mmol rapidly joins isocyanates (TDI) activator 0.3mmol, stirs evenly after vacuumizing water removal 30min,
It polymerize at 172 DEG C, heat preservation 20min obtains nylon material.It is passed through High Purity Nitrogen in a kettle later, and is warming up to 235 DEG C and is allowed to
Melting, the cooling and dicing after discharge hole for discharge obtain nylon material slice 1.
Nylon material slice 40g is placed in autoclave, ethyl alcohol 240ml is added, 80 DEG C are heated to after sealing, not
Disconnected stirring, is allowed to sufficiently dissolve.Gradually be cooled to room temperature afterwards, mixed solution poured out, filter, wash, it is dry, classification to get
To nylon powder.Powder diameter is 50~80 μm, and the tensile strength of nylon material 1 is 60MPa, and impact strength 60J/m is led
Electric rate is 10-8S/cm, mean coefficient of heat conductivity 10-4W/mK。
Comparative example 2
At reduced pressure, 40g caprinolactam monomer is placed in reaction kettle, and is warming up to 132 DEG C of addition catalyst
NaOH1.6mmol rapidly joins Isocyanate activator 0.6mmol, stirs evenly, at 175 DEG C after vacuumizing water removal 30min
Lower polymerization, heat preservation 30min obtain nylon material.It is passed through High Purity Nitrogen in a kettle later, and is warming up to 242 DEG C and is allowed to melt,
The cooling and dicing after discharge hole for discharge obtains nylon material slice 2.
Above-mentioned nylon material slice 40g is placed in autoclave, ethyl alcohol 500ml is added, 80 DEG C are heated to after sealing,
And be stirred continuously, it is allowed to sufficiently dissolve.It is gradually cooled to room temperature afterwards, mixed solution is poured out, filter, wash, dry, classification,
Obtain nylon powder.Powder diameter is 40~60 μm, and the tensile strength of nylon material 2 is 63MPa, impact strength 65J/
M, conductivity 10-8S/cm, mean coefficient of heat conductivity 10-4W/mK。
Comparative example 3
At reduced pressure, 40g lauric lactam monomer is placed in reaction kettle, and is warming up to 135 DEG C of addition catalysis
Agent NaOH1.8mmol rapidly joins Isocyanate activator 0.6nnol, stirs evenly, 180 after vacuumizing water removal 30min
It polymerize at DEG C, heat preservation 30min obtains nylon material.It is passed through High Purity Nitrogen in a kettle later, and is warming up to 255 DEG C and is allowed to molten
Melt, the cooling and dicing after discharge hole for discharge, obtains nylon material slice 3.
Above-mentioned nylon material slice 40g is placed in autoclave, 1000ml dimethylformamide is added, adds after sealing
Heat is stirred continuously to 155 DEG C, is allowed to sufficiently dissolve.It is gradually cooled to room temperature afterwards, mixed solution is poured out, filter, washing,
It is dry, it is classified to get nylon powder is arrived.Powder diameter is 30~50 μm, and the tensile strength of nylon material 3 is 67MPa, shock resistance
Intensity is 70J/m, conductivity 10-8S/cm, mean coefficient of heat conductivity 10-4W/mK。
It is as shown in table 1 that embodiment 1-3 and comparative example 1-3 is subjected to impact strength, conductivity, mean coefficient of heat conductivity.
1 performance parameter table of table
The tensile strength and impact strength of the modified poly-lactam composite material of graphene of the invention compare the prior art
Product improves 2 times or more, and conductivity improves several orders of magnitude, and mean coefficient of heat conductivity is also substantially improved.
Claims (10)
1. the preparation method of a kind of modified nylon compound resin of graphene and its powder, which is characterized in that the preparation side
Method is following steps:
(1) graphene oxide is dissolved in the mixed liquor of deionized water and dehydrated alcohol, stirs 1~3h, then coupling agent is being stirred
Reaction 8~for 24 hours is mixed after lower instillation at 70~100 DEG C, product is obtained by filtration, then washed respectively with dehydrated alcohol and deionized water
Several times, paste is placed in 60~110 DEG C of drying box and is dried, obtain modified graphene oxide；
(2) modified graphene oxide that step (1) obtains is mixed with lactam monomers, is stirred at being 121~135 DEG C in temperature
1~3h；Above-mentioned mix monomer is placed in reaction kettle later, and is warming up to 120~140 DEG C of addition catalyst, vacuumizes water removal 10
After~30min, activator is added and stirs, polymerize at 170~185 DEG C, obtains graphene oxide after 20~60min of heat preservation and change
The nylon compound resin of property；
(3) it is passed through high pure nitrogen in the reaction kettle in step (2), and is warming up to 230~260 DEG C and is allowed to melt, in discharge port
Cooling and dicing after discharging obtains the modified nylon compound resin slice of graphene oxide；
(4) slice for obtaining step (3), is placed in autoclave, and solvent and reducing agent is added, is heated to temperature after sealing
60 ~ 180 DEG C, and be gradually cooled to room temperature after being stirred continuously 2-6h, mixed solution is poured out, is filtered, is washed, dry, classification, i.e.,
The modified nylon compound resin powder of graphene is obtained,
Wherein, the mass ratio of the modified nylon compound resin slice of graphene and solvent is 1:5 ~ 1:100, autoclave
Pressure is in 0.2-1.0MPa.
2. the preparation method of a kind of graphene according to claim 1 modified nylon compound resin and its powder, special
Sign is, the mass ratio of coupling agent and graphene oxide in step (1) is 1:1~1:4, deionized water and dehydrated alcohol it is mixed
The mass percent for closing dehydrated alcohol in liquid is 20 ~ 80%.
3. the preparation method of a kind of graphene according to claim 1 or 2 modified nylon compound resin and its powder,
It is characterized in that, coupling agent selects vinylethoxysilane, vinyltrimethoxysilane, (the 'beta '-methoxy ethoxy of vinyl three
Base) silane, gamma-aminopropyl-triethoxy-silane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, three second of isobutyl group
One or more of oxysilane.
4. the preparation method of a kind of graphene according to claim 1 modified nylon compound resin and its powder, special
Sign is that the mass ratio of modified graphene oxide and lactam monomers is 1:50 ~ 1:2000 in step (2), and catalyst amount is
The 0.2 ~ 1.0% of lactam monomers mole, activator level are the 0.05 ~ 0.8% of lactam monomers mole.
5. the preparation method of a kind of graphene according to claim 1 or 4 modified nylon compound resin and its powder,
It is characterized in that, catalyst is selected from one of KOH, NaOH, sodium caprolactam, caprolactam potassium, sodium methoxide or several in step (2)
Kind, activating agent is selected from isocyanates.
6. the preparation method of a kind of graphene according to claim 1 modified nylon compound resin and its powder, special
Sign is that in step (4), solvent for use is in ethyl alcohol, methanol, tetrahydrofuran, dimethylformamide, diethylformamide
It is one or more of, wherein the mass ratio of the modified nylon compound resin slice of graphene and solvent is 1:5 ~ 1:100.
7. the preparation method of a kind of graphene according to claim 1 modified nylon compound resin and its powder, special
Sign is that the mass ratio of the reducing agent and step (3) product is 1:100 ~ 1:10000, and wherein reducing agent is selected from hydrazine also
One or more of former agent, sodium citrate, hydroiodic acid.
8. the preparation method of a kind of graphene according to claim 7 modified nylon compound resin and its powder, special
Sign is that hydrazine reducing agent is selected from one or more of hydrazine, hydrazine hydrate, dimethylhydrazine, phenylhydrazine.
9. the preparation method of a kind of graphene according to claim 1 modified nylon compound resin and its powder, special
Sign is, the modified nylon compound resin powder diameter of the graphene is at 5 ~ 80 μm, the modified nylon compound resin of graphene
The tensile strength of batten made of powder is 80 ~ 150MPa, and impact strength is 100 ~ 180J/m, conductivity 10-6To 10- 1S/cm, mean coefficient of heat conductivity 0.01-1.0W/mK.
10. a kind of preparation method of the nylon compound resin and its powder modified by a kind of graphene described in claim 1 obtains
To application of the modified nylon compound resin powder of graphene in 3D printing field.
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| CN111040434A (en) * | 2019-12-30 | 2020-04-21 | 湖南华曙高科技有限责任公司 | Graphene reinforced nylon powder for selective laser sintering and preparation method thereof |
| CN111040444A (en) * | 2019-12-31 | 2020-04-21 | 湖南华曙高科技有限责任公司 | Nylon powder for selective laser sintering and preparation method thereof |
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| GB2480914B (en) * | 2010-05-28 | 2013-08-21 | Univ Texas | Carbocatalysts for chemical transformations |
| CN103254400B (en) * | 2013-05-20 | 2015-06-24 | 常州大学 | Preparation method of graphene oxide/waterborne polyurethane nanometer composite material |
| KR101709156B1 (en) * | 2014-03-18 | 2017-02-22 | 서울대학교산학협력단 | Nanocomposite material |
| CN105038212B (en) * | 2015-07-28 | 2017-10-03 | 长沙新材料产业研究院有限公司 | Graphene oxide enhancing nylon material and its preparation method and application |
| CN105295028B (en) * | 2015-08-03 | 2018-02-02 | 杭州师范大学 | A kind of graphene in-situ modified poly-lactam composite and preparation method and application |
| CN105254870B (en) * | 2015-11-04 | 2017-07-11 | 四川大学 | A kind of high-performance monomer moulding casting nylon/graphene nanocomposite material and its in-situ polymerization method for preparing |
| CN105968375B (en) * | 2016-05-27 | 2019-06-14 | 丹阳新华美塑料有限公司 | A kind of reactive extrursion preparation method of polyamide nano master batch |
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