CN108164694A - A kind of graphene oxide, sepiolite, polyamide 6 composite material and preparation method thereof - Google Patents
A kind of graphene oxide, sepiolite, polyamide 6 composite material and preparation method thereof Download PDFInfo
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- CN108164694A CN108164694A CN201711489615.5A CN201711489615A CN108164694A CN 108164694 A CN108164694 A CN 108164694A CN 201711489615 A CN201711489615 A CN 201711489615A CN 108164694 A CN108164694 A CN 108164694A
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- 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
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/02—Ingredients treated with inorganic substances
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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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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Abstract
The invention discloses a kind of graphene oxides, sepiolite, polyamide 6 composite material and preparation method thereof, belong to polymeric material field.For daiamid-6 fiber it is inflammable the problem of, 6 composite material of spinning Flameproof polyamide is prepared the invention discloses a kind of, by the way that graphene oxide liquid mixture and modified meerschaum are carried out graft modification, obtain graft modification product, graphene oxide and sepiolite graft modification product and monomer caprolactam are subjected to polymerisation again and realize that graphene oxide and sepiolite are modified polyamide 6 purpose, polyamide 6 composite material of the invention not only there is anti-flammability to be also equipped with multifunctionality simultaneously.
Description
Technical field
The invention belongs to polymeric material field, more specifically to a kind of graphene oxide, sepiolite, polyamide 6
Composite material and preparation method thereof.
Background technology
- 6 fiber of polyamide is as the capron(e) obtained by the ring-opening polymerisation of monomer caprolactam, spinning, You Mingni
Dragon 6 or polyamide fibre 6, have many advantages, such as high mechanical strength, good toughness, wear-resisting, weak acid and alkali resistance, are now widely used for spinning and engineering
Plastic applications.However, with the quickening of modernization of industry process, traditional polyamide -6 cannot meet the need of people again
It asks, multi-functional -6 fiber of polyamide has become development trend.
Main modified method is that the matrix resin containing polyamide -6 is modified at present, be typically led to glass fibre,
Nano silicon dioxide, carbon nanotube, montmorillonite, mica, nano silver, copper, zinc etc. obtain -6 product of high-performance polyamide.It is above-mentioned
Modification mode can improve the particular characteristic of -6 material of polyamide to a certain extent, and the modification however, as the overwhelming majority is all logical
It crosses what the mode of physical blending carried out, leads to poor dispersion of the modified material in base polyamide -6, easily reunite when modified,
Modified effect is unsatisfactory.
Graphene is the Two-dimensional Carbon atomic piece being made of the carbon atom of hydridization, and carbon atom is cellular in six sides；It is by one layer
The characteristics of carbon atom is formed has been assigned multiple performance；Graphene oxide (GO) be introduced on the basis of graphene it is functional
Group, makes it have a kind of graphene of functionalization of certain new features, and functional group is included positioned at graphene oxide
The carboxyl and hydroxyl of hydroxyl and epoxy group and edge on basal plane can carry out original position using surface of graphene oxide group
Polymeric modification improves dispersibility of the graphene in basis material, reduces the modification dosage of graphene.
Sepiolite is a kind of silicate mineral with chain structure, and crystal structure has continuous oxygen-octahedron
Layer, each oxygen-octahedron layer share three apex angles and are connected with three adjacent tetrahedrons.Oxygen-octahedron unit is with oxygen atom
It is connected on magnesium octahedron and in continuous arrangement.Sepiolite has higher draw ratio, and specific surface area theoretical value is up to 900m2/
G, thermal stability is good, and heat-resisting quantity is up to 1500-1700 DEG C.
Invention content
It is bad and the problem of polyamide 6 is inflammable for bad dispersibility, modified effect existing for modified polyamide 6 fibre,
The present invention provides a kind of graphene oxide, sepiolite, polyamide 6 composite material and preparation method thereof, and the present invention is by by oxygen
Graphite alkene mixed liquor and modified meerschaum carry out graft modification, obtain graft modification product, then by graphene oxide and Hai Pao
Stone graft modification product and monomer caprolactam carry out polymerisation and realize that graphene oxide and sepiolite carry out polyamide -6
Modified purpose.
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows：
A kind of graphene oxide, sepiolite, polyamide 6 composite material preparation method, include the following steps：
Step 1, graphene oxide powder is dispersed in open loop solution, obtains dispersion liquid；
Step 2, modified meerschaum is scattered in the dispersion liquid that step 1 obtains, graft modification is carried out to sepiolite, it is described
Modified meerschaum and the mass ratio of graphene oxide powder are (1~20):1, the reaction condition of the graft modification be 70~
120 DEG C, under normal pressure, it is stirred to react 2~6h；
Step 3, the compounding dispersion liquid and caprolactam liquid step 2 obtained is according to graphene oxide, caprolactam
Mass ratio is 1:(10~200) are mixed, are disperseed, mixed liquor after being disperseed,
Step 4, mixed liquor step 3 obtained carries out ring-opening reaction, polymerisation, slice, extraction, drying successively, obtains
To graphene oxide, sepiolite, polyamide 6 composite material.
Further, the dispersing mode in the step 1 and step 3 be ultrasound, shearing, emulsification be carried out at the same time answer
Close mixing dispersing mode.
Further, the piece diameter of the graphene oxide powder in the step 1 is 100~500nm, and lamellar spacing is
1.0~3.5nm.
Further, the open loop solution in the step 1 is deionized water, aminocaproic acid aqueous solution, aminocaproic acid have
One or more in machine solution, hexamethylene diamine aqueous solution.
Further, the modified meerschaum in the step 2 silane coupler modified is obtained by amino-containing
Modified meerschaum, the amino-containing silane coupling agent for KH-540, KH-550, KH-551, KH-602, KH-791, KH-792,
The one or more of KH-901, KH-902, the sepiolite in the step 2 are 5000 mesh.
Further, the mixed liquor vacuum distillation that the step 3 obtains is gone after water removal to carry out the step 4 again
Operation.
Further, the ring-opening reaction condition in the step 4 is 255~275 DEG C, 0.15~0.85MPa, during reaction
Between be 1.5~4h；Polymeric reaction condition in the step 4 is 240~255 DEG C, -0.05~-0.20MPa, and the reaction time is
3~10h.
Further, further include pre-treatment step, the pre-treatment step before step 1, by graphene oxide
Disperseed, washed, be dried and obtain graphene oxide powder.
Further, the dispersing mode in the pre-treatment step is carried out at the same time compound mixed for ultrasonic, shearing, emulsification
Dispersing mode is closed, the dispersant in the pre-treatment step is n,N-Dimethylformamide, water, tetrahydrofuran, N- methylpyrroles
One or more in alkanone, ethylene glycol.
A kind of graphene oxide, sepiolite, polyamide 6 composite material, are prepared using preceding method.
Compared with the prior art, beneficial effects of the present invention are：
(1) present invention is mainly changed by carrying out in-situ polymerization again after graphene oxide and modified meerschaum progress graft modification
Property polyamide -6, the method for the graft modification of graphene oxide and modified meerschaum allow graphene oxide and sepiolite in polyamide
Good dispersion has been obtained in 6 matrixes；Multi-functional nylon 6 fiber is obtained, the prior art can only be reached by certain modification
Simple function fiber, the present invention provides a kind of by nano-material modified while obtain the fibre modification side of multiple functions
Method, and modified cost is relatively low；
(2) preparation method of composite material of the invention by graphene oxide using open loop solution is dispersed to first, then
Modified meerschaum and graphene oxide dispersion are subjected to graft modification, then mixed liquor is mixed with liquid caprolactam
The mode of dispersion reaction is closed, direct addition graphene oxide powder, liquid caprolactam, ring opening agent in the prior art is overcome and mixes
The solid, liquid generated during conjunction mixes non-uniform defect, preparation condition using the present invention, graphene oxide, passing through of sepiolite
It learns bond to close, dispersion in the base is more uniform, and modified polyamide 6 has preferable spinnability；
(3) ring opening agent is configured to open loop solution as graphene oxide by the preparation method of composite material of the invention first
Dispersion liquid, then gained mixed liquor and modified meerschaum are subjected to graft modification, ring opening agent can be made more fully to dissolve, disperse,
Superior effect is played, the dispersion compared with conventional mineral is powder-modified in the base is more uniform, gives full play to modified effect
Fruit；
(4) preparation method of composite material of the invention, the dispersing mode condition that the ultrasound of use, shearing, emulsification combine
More mild, the deionized water of dispersant selectable environments friendly, ethylene glycol reagent, method of the prior art is improves oxygen
Dispersibility usually requires to carry out graphene oxide covalent modification graphite alkene in the solution, needs to make during modification
With the organic reagent that a large amount of toxicity are larger, larger load is caused to environment；The method of this patent can substantially reduce environmental pollution；
(5) the preparation method step of composite material of the invention is simple, the material product comprehensive performance obtained by this method
It is good, carbon, element silicon ratio in composite material are adjusted by the mass ratio for adjusting graphene oxide and modified meerschaum and reach coordination resistance
Fuel efficiency should；
(6) in the preparation method of composite material of the invention, when mixed liquor is reacted, ring-opening reaction is carried out first, is opened
Heating ensures the molten condition of entire reaction system during ring, and reaction is enable to carry out, then carries out polymerisation, since polycondensation is put down
There is water generation in the weighing apparatus stage, and negative pressure plays the role of dehydration, the positive of polycondensation reaction is contributed to carry out, the entire stage of reaction expends the time
Shorter, reaction efficiency is high.
Specific embodiment
The present invention is further described below with reference to specific embodiment.Following embodiment is only used for clearly saying
Bright technical scheme of the present invention, and be not intended to limit the protection scope of the present invention and limit the scope of the invention.
Embodiment 1
Step 1,100kg graphene oxide slurries are spray-dried to obtain graphene oxide powder, the oxidation
Graphene slurry solid content is 3%, purchased from Changzhou No.6 Element Material Technology Co., Ltd.；Then with deionized water by oxygen
Graphite alkene powder repeatedly wash, is filtered, and obtains graphene oxide filter cake, and carrying out microwave to graphene oxide filter cake does
It is dry, obtain pure graphene oxide powder.Washing, the purpose filtered are to remove remaining in graphene oxide preparation process
The metal ions such as Ka, Na, Mn, Ca, Mg, Al.
Step 2, the graphene oxide powder that step 1 obtains in 100kgDMF solution is disperseed, is by dispersing mode
The compound mixing dispersing mode that ultrasound, shearing, emulsification are carried out at the same time handles to obtain graphene oxide DMF dispersion liquids, by dispersion liquid
It is spray-dried to obtain the high graphene oxide powder of nanoscale, individual layer rate, obtained graphene oxide powder piece diameter is
250nm, lamellar spacing 1.8nm.
Step 3, graphene oxide powder step 2 obtained is according to graphene oxide：Hexamethylene diamine mass ratio is 1:5 ratio
Example is dispersed in hexamethylene diamine aqueous solution, obtains graphene oxide dispersion liquid again.Hexamethylene diamine aqueous solution as graphene oxide again
Dispersant during secondary dispersion, while open loop and initiator when polymerizeing can be hydrolyzed in hexamethylene diamine as caprolactam.
Step 4, by KH540, ethyl alcohol, water according to 20：72：8 wiring solution-formings, mixed liquor are according to mass ratio with sepiolite powder
1：1.6 are warming up to 70 DEG C of reaction 2h under stiring, filtered, wash, be dried to obtain modified meerschaum powder, sepiolite powder 5000
Mesh.
Step 5, the modified meerschaum powder that will be obtained in graphene oxide hexamethylene diamine dispersion liquid and step 4 that step 3 obtains
The mass ratio of progress graft modification, graphene oxide and modified meerschaum is 1：1,6h is reacted under 70 DEG C of stirrings, is mixed
Liquid.
Step 6, compounding mixed liquor and liquid caprolactam mixing step 5 obtained, it is multiple by ultrasound, shearing, emulsification
Technical finesse is closed, into polymerization reaction kettle, stirring, vacuum distillation removal H2O obtains mixed liquor；Stone is aoxidized in the mixed liquor
Black alkene, modified meerschaum powder, hexamethylene diamine, caprolactam mass ratio be 1:1:5:10.
Step 7, the mixed liquor obtained in step 6 is reacted, first at 275 DEG C, open loop is anti-under conditions of 0.85MPa
Answer 1.5 hours, then at 255 DEG C, polyase 13 hour under conditions of -0.15MPa, the fluid after being polymerize, since polycondensation is put down
There is water generation in the weighing apparatus stage, and negative pressure dehydration contributes to the positive of polycondensation reaction to carry out, the fluid after polymerization is passed through in pelleter and is cut
Then slice is placed in extraction tower by piece, extracted with 90 DEG C of deionized waters, the slice after extraction is in the drying for being connected with hot nitrogen
It is dry in tank, obtain graphene oxide the polyamide -6 that is modified of sepiolite powder.
Using the present embodiment graphene oxide -6 spinning of polyamide that is modified of sepiolite prepare FDY filament, specification is：
140d/32f, which is carried out respectively fracture strength, elongation at break, oxygen index (OI), antibacterial bacteriostatic performance, far infrared performance,
Uvioresistant oxidation susceptibility is tested, and oxygen index (OI) represents the flame retardant property of the long filament.
Embodiment 2
Step 1,100kg graphene oxide slurries are spray-dried to obtain graphene oxide powder, then spend from
Graphene oxide powder repeatedly wash, be filtered by sub- water, obtains graphene oxide filter cake, graphene oxide filter cake is carried out
Microwave drying obtains pure graphene oxide powder.
Step 2, graphene oxide powder ultrasonic disperse step 1 obtained passes through in 100kgN- methyl pyrrolidones
High frequency ultrasound, high speed shear, emulsification complex technique processing 2h obtain the N-Methyl pyrrolidone dispersion liquid of graphene oxide, and will
Dispersion liquid is spray-dried to obtain the high graphene oxide powder of nanoscale, individual layer rate, obtained graphene oxide powder
Piece diameter 500nm, lamellar spacing 1.0nm.
Step 3, graphene oxide powder step 2 obtained is according to graphene oxide：Aminocaproic acid mass ratio is 1：10
Ratio be dispersed in aminocaproic acid aqueous solution, obtain graphene oxide dispersion liquid again；Aminocaproic acid aqueous solution is as oxidation
Dispersant when graphene disperses again, while open loop and initiation when polymerizeing can be hydrolyzed in aminocaproic acid as caprolactam
Agent.
Step 4, by KH551, ethyl alcohol, water according to 20：72：8 wiring solution-formings, mixed liquor are according to mass ratio with sepiolite powder
1：1.6 are warming up to 70 DEG C of reaction 2h under stiring, filtered, wash, be dried to obtain modified meerschaum powder.
Step 5, the modified meerschaum powder that will be obtained in graphene oxide hexamethylene diamine dispersion liquid and step 4 that step 3 obtains
The mass ratio of progress graft modification, graphene oxide and modified meerschaum is 1：20,2h is reacted under 120 DEG C of stirrings, is mixed
Close liquid.
Step 6, the graphene oxide graft modification sepiolite mixed liquor and liquid caprolactam that step 5 obtains pass through high frequency
Ultrasound, high speed shear, emulsifying device on-line mixing squeeze into polymerization reaction kettle, stirring, vacuum distillation removal H2O obtains mixed liquor,
Vacuum distillation removal H2The purpose of O is further to promote ring-opening polymerization to carry out, and graphene oxide in the mixed liquor changes
Property sepiolite powder, aminocaproic acid, caprolactam mass ratio be 1:20:10:190.
Step 7, the mixed liquor that step 6 obtains carries out polymerisation, and first at 255 DEG C, open loop is anti-under conditions of 0.15MPa
It answers 4 hours, then at 245 DEG C, polymerize 8 hours under conditions of -0.05MPa, the fluid is passed through by fluid after being polymerize
It is sliced in pelleter, then slice is placed in extraction tower, extracted with 90 DEG C of deionized waters, the slice after extraction is being connected with heat
It is dry in the drying chamber of nitrogen, obtain graphene oxide the polyamide -6 that is modified of sepiolite.
Using the present embodiment graphene oxide -6 spinning of polyamide that is modified of sepiolite prepare FDY filament, specification is：
140d/32f, which is carried out respectively fracture strength, elongation at break, oxygen index (OI), antibacterial bacteriostatic performance, far infrared performance,
The performance test of uvioresistant oxidation.
Embodiment 3
Step 1,100kg graphene oxide slurries are spray-dried to obtain graphene oxide powder, then spend from
Graphene oxide powder repeatedly wash, be filtered by sub- water, obtains graphene oxide filter cake, graphene oxide filter cake is carried out
Microwave drying obtains pure graphene oxide powder.
Step 2, graphene oxide powder ultrasonic disperse step 1 obtained is surpassed in 100kg tetrahydrofurans by high frequency
Sound, high speed shear, emulsification complex technique processing 3h obtain the tetrahydrofuran dispersion liquid of graphene oxide, and dispersion liquid is sprayed
Mist is dried to obtain the high graphene oxide powder of nanoscale, individual layer rate, and obtained graphene oxide powder piece diameter 350nm is left
The right side, lamellar spacing about 1.5nm.
Step 3, graphene oxide powder step 2 obtained is according to graphene oxide：Aminocaproic acid mass ratio is 1:20
Ratio be dispersed in aminocaproic acid aqueous solution, obtain graphene oxide dispersion liquid again；Aminocaproic acid aqueous solution is as oxidation
Dispersant when graphene disperses again, while open loop and initiation when polymerizeing can be hydrolyzed in aminocaproic acid as caprolactam
Agent.
Step 4, by KH791, ethyl alcohol, water according to 20：72：8 wiring solution-formings, mixed liquor are according to mass ratio with sepiolite powder
1：1.6 are warming up to 70 DEG C of reaction 2h under stiring, filtered, wash, be dried to obtain modified meerschaum.
Step 5, the modified meerschaum that will be obtained in graphene oxide aminocaproic acid dispersion liquid and step 4 that step 3 obtains
The mass ratio of powder progress graft modification, graphene oxide and modified meerschaum is 1：15,4h is reacted under 90 DEG C of stirrings, is mixed
Close liquid.
Step 6, graphene oxide graft modification sepiolite mixed liquor and liquid caprolactam that step 5 obtains are passed through into height
Frequency ultrasound, high speed shear, emulsifying device on-line mixing squeeze into polymerization reaction kettle, stir, vacuum distillation removal H2O is mixed
Liquid, graphene oxide in the mixed liquor, sepiolite powder, aminocaproic acid, caprolactam mass ratio be 1:15:20:180.
Step 7, the mixed liquor that step 6 obtains is made to carry out polymerisation, first at 260 DEG C, open loop under conditions of 0.25MPa
Reaction 2.5 hours, then at 240 DEG C, polymerize 10 hours, fluid after being polymerize leads to the fluid under conditions of -0.2MPa
Enter in pelleter and be sliced, then slice is placed in extraction tower, extracted with 80 DEG C of deionized waters, the slice after extraction is being connected with
It is dry in the drying chamber of hot nitrogen, obtain graphene oxide the polyamide -6 that is modified of sepiolite.
Using the present embodiment graphene oxide -6 spinning of polyamide that is modified of sepiolite prepare FDY filament, specification is：
140d/32f, which is carried out respectively fracture strength, elongation at break, oxygen index (OI), antibacterial bacteriostatic performance, far infrared performance,
Uvioresistant oxidation susceptibility is tested.
Embodiment 4
Step 1,100kg graphene oxide slurries are spray-dried to obtain graphene oxide powder, then spend from
Graphene oxide powder repeatedly wash, be filtered by sub- water, obtains graphene oxide filter cake, graphene oxide filter cake is carried out
Microwave drying obtains pure graphene oxide powder.
Step 2, graphene oxide powder ultrasonic disperse step 1 obtained passes through in 100kgN- methyl pyrrolidones
High frequency ultrasound, high speed shear, emulsification complex technique processing 2.5h obtain the N-Methyl pyrrolidone dispersion liquid of graphene oxide, and
Dispersion liquid is spray-dried to obtain the high graphene oxide powder of nanoscale, individual layer rate, obtained graphene oxide powder
Body piece diameter 100nm, lamellar spacing 3.5nm.
Step 3, graphene oxide powder step 2 obtained is according to graphene oxide：Hexamethylene diamine mass ratio is 1:8 ratio
Example is dispersed in hexamethylene diamine aqueous solution, obtains graphene oxide dispersion liquid again；Hexamethylene diamine aqueous solution as graphene oxide again
Dispersant during secondary dispersion, while open loop and initiator when polymerizeing can be hydrolyzed in hexamethylene diamine as caprolactam.
Step 4, by KH902, ethyl alcohol, water according to 20：72：8 wiring solution-formings, mixed liquor are according to mass ratio with sepiolite powder
1：1.6 are warming up to 70 DEG C of reaction 2h under stiring, filtered, wash, be dried to obtain modified meerschaum powder.
Step 5, the modified meerschaum powder that will be obtained in graphene oxide hexamethylene diamine dispersion liquid and step 4 that step 3 obtains
The mass ratio of progress graft modification, graphene oxide and modified meerschaum is 1：10,4.5h is reacted under 80 DEG C of stirrings, is mixed
Close liquid.
Step 6, the graphene oxide graft modification sepiolite mixed liquor and liquid caprolactam that step 5 obtains pass through high frequency
Ultrasound, high speed shear, emulsifying device on-line mixing squeeze into polymerization reaction kettle, stirring, vacuum distillation removal H2O obtains mixed liquor,
Graphene oxide in the mixed liquor, sepiolite, hexamethylene diamine, caprolactam mass ratio be 1:10:8:200.
Step 7, the mixed liquor that step 6 obtains carries out polymerisation, and first at 258 DEG C, open loop is anti-under conditions of 0.2MPa
It answers 2.5 hours, then at 255 DEG C, polymerize 6 hours under conditions of -0.08MPa, the fluid is passed through by fluid after being polymerize
It is sliced in pelleter, then slice is placed in extraction tower, extracted with 85 DEG C of deionized waters, the slice after extraction is being connected with heat
It is dry in the drying chamber of nitrogen, obtain graphene oxide the polyamide -6 that is modified of sepiolite.
Using the present embodiment graphene oxide -6 spinning of polyamide that is modified of sepiolite prepare FDY filament, specification is：
140d/32f, which is carried out respectively fracture strength, elongation at break, oxygen index (OI), antibacterial bacteriostatic performance, far infrared performance,
Uvioresistant oxidation susceptibility is tested.
Comparative example 1
For this comparative example substantially with embodiment 1, the difference lies in be not modified answering for sepiolite and graphene oxide
With graft modification；- 6 spinning of polyamide that this comparative example is modified prepares FDY filament, and specification is：140d/32f, as a comparison case
1, carry out fracture strength, elongation at break, oxygen index (OI), antibacterial bacteriostatic performance, far infrared performance, uvioresistant oxygen respectively to the product
Change performance test.
Comparative example 2
This comparative example substantially with embodiment 3, the difference lies in, sepiolite powder is carried out it is silicone-modified, directly
The mixed liquor for having carried out sepiolite and graphene oxide is compounded, prepared by -6 spinning of polyamide that this comparative example is modified
FDY filament, specification are：140d/32f, as a comparison case 2, it carries out fracture strength, elongation at break, oxygen respectively to the product and refers to
Number, the test of antibacterial bacteriostatic performance, far infrared performance, uvioresistant oxidation susceptibility.
Comparative example 3
This comparative example carries out under the reaction condition of same embodiment 2, aminocaproic acid:The mass ratio of caprolactam is 1：19,
Graphene oxide and modified meerschaum powder are not added.- 6 spinning of polyamide that this comparative example is modified prepares FDY filament, specification
For：155d/48f, as a comparison case 3, fracture strength, elongation at break, oxygen index (OI), antibacterial bacteriostatic are carried out respectively to the product
Performance, far infrared performance, the test of uvioresistant oxidation susceptibility.
Comparative example 4
This comparative example is substantially with embodiment 1, and the difference lies in dispersion of the graphene oxide powder in open loop agent solution
And single shearing is taken in liquid caprolactam and graphene oxide, the dispersion for being grafted compounding mixed liquor of modified meerschaum powder
Dispersion.- 6 spinning of polyamide that this comparative example is modified prepares FDY filament, and specification is：140d/32f, as a comparison case 4, to this
Product carries out fracture strength, elongation at break, oxygen index (OI), antibacterial bacteriostatic performance, far infrared performance, uvioresistant oxidation susceptibility respectively
Test.
The grafting compounding condition of 1 embodiment of table and graphene oxide and modified meerschaum powder
2 embodiment of table and reference examples spun articles test result
Note：Table 2 the 5th arranges the mass ratio that the mass ratio is graphene oxide, sepiolite powder and caprolactam three.
As shown in Table 2：Whether the modification of sepiolite, intercalation compounding whether there is no shadow to the antibacterial bacteriostatic effect of composite fibre
It rings, as long as graphene oxide is added in all embodiments and is modified all has good antibacterial bacteriostatic effect, so antibacterial bacteriostatic
Effect is mainly that the modification of graphene oxide is brought, and in addition to comparative example 4, antibacterial bacteriostatic effect is both greater than under different additive amounts
99%, this has benefited from, and dispersion effect of the graphene oxide in polyamide 6 matrix is good, and the antibacterial bacteriostatic performance in comparative example 4 is but
It is substantially reduced, this is primarily due to the single dispersion of the lower graphene oxide powder of dispersing mode effect in a polymer matrix not
It is enough uniform, there is agglomeration, cause local graphite alkene content small, even without, so antibacterial bacteriostatic performance reduces, it is of the invention
Ultrasound, shear, to emulsify integrated dispersing method effect more preferable.
3 embodiment of table and reference examples product test result
Note：Mass ratio described in 3 secondary series of table is the mass ratio of graphene oxide, sepiolite powder and caprolactam three.
As shown in Table 3, as the graft modification mass ratio of graphene oxide and modified meerschaum changes, fibrous fracture
The purer PA6 fibers of intensity increase, and elongation at break reduces and between 18~20, and the elongation at break in the range of this is
What current routine PA6 cannot accomplish, and the industrial yarn current needs amount in this elongation at break ranges is very big.It finds simultaneously
Fracture strength and elongation at break are compared with without graft modification after graphene oxide and the progress graft modification of modified meerschaum powder
There is significant difference, this is because the graphene oxide and modified meerschaum powder that pass through graft modification are by chemical bonds,
Dispersibility in PA matrixes enhances the binding force with matrix again while raising.By comparison find different quality than oxidation
In-situ polymerization modified Pa 6 material oxygen index (OI) is carried out after graphene and the graft modification of modified meerschaum powder to be greatly improved,
This is because sepiolite has heat-resisting quantity in itself, the cooperative flame retardant of graphene oxide and sepiolite is realized after graft modification
Effect.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformation can also be made, these are improved and deformation
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of a kind of graphene oxide, sepiolite, polyamide 6 composite material, which is characterized in that including following step
Suddenly：
Step 1, graphene oxide powder is dispersed in open loop solution, obtains dispersion liquid；
Step 2, modified meerschaum is scattered in the dispersion liquid that step 1 obtains, graft modification, the modification is carried out to sepiolite
Sepiolite and the mass ratio of graphene oxide powder are (1~20):1, the reaction condition of the graft modification is 70~120
DEG C, under normal pressure, it is stirred to react 2~6h；
Step 3, the quality of dispersion liquid and caprolactam liquid according to graphene oxide, caprolactam is compounded by what step 2 obtained
Than being 1:(10~200) are mixed, are disperseed, mixed liquor after being disperseed,
Step 4, mixed liquor step 3 obtained carries out ring-opening reaction, polymerisation, slice, extraction, drying successively, obtains oxygen
Graphite alkene, sepiolite, polyamide 6 composite material.
2. the preparation method of graphene oxide according to claim 1, sepiolite, polyamide 6 composite material, feature exist
In the dispersing mode in the step 1 and step 3 is ultrasound, shearing, emulsifies the compound mixing dispersing mode being carried out at the same time.
3. the preparation method of graphene oxide according to claim 1, sepiolite, polyamide 6 composite material, feature exist
In the piece diameter of the graphene oxide powder in the step 1 is 100~500nm, and lamellar spacing is 1.0~3.5nm.
4. the preparation method of graphene oxide according to claim 1, sepiolite, polyamide 6 composite material, feature exist
In open loop solution in the step 1 is deionized water, aminocaproic acid aqueous solution, aminocaproic acid organic solution, hexamethylene diamine are water-soluble
One or more in liquid.
5. the preparation method of graphene oxide according to claim 1, sepiolite, polyamide 6 composite material, feature exist
In, the modified meerschaum in the step 2 be by amino-containing silane coupler modified obtained modified meerschaum, it is described to contain
The silane coupling agent of amino is the one of KH-540, KH-550, KH-551, KH-602, KH-791, KH-792, KH-901, KH-902
Kind or more than one, sepiolite in the step 2 is 5000 mesh.
6. the preparation method of graphene oxide according to claim 1, sepiolite, polyamide 6 composite material, feature exist
In the vacuum distillation of mixed liquor that the step 3 obtains is gone after water removal to carry out the operation of the step 4 again.
7. the preparation method of graphene oxide according to claim 1, sepiolite, polyamide 6 composite material, feature exist
In the ring-opening reaction condition in the step 4 is 255~275 DEG C, 0.15~0.85MPa, and the reaction time is 1.5~4h；It is described
Polymeric reaction condition in step 4 is 240~255 DEG C, -0.05~-0.20MPa, and the reaction time is 3~10h.
8. the preparation side of graphene oxide according to any one of claims 1 to 7, sepiolite, polyamide 6 composite material
Method, which is characterized in that further include pre-treatment step, before step 1, graphene oxide is divided for the pre-treatment step
It dissipates, wash, drying process obtains graphene oxide powder.
9. the preparation method of graphene oxide according to claim 8, sepiolite, polyamide 6 composite material, feature exist
In the dispersing mode in the pre-treatment step is ultrasound, shearing, emulsifies the compound mixing dispersing mode being carried out at the same time, described
Dispersant in pre-treatment step is N,N-dimethylformamide, in water, tetrahydrofuran, N-Methyl pyrrolidone, ethylene glycol
It is one or more kinds of.
10. a kind of graphene oxide, sepiolite, polyamide 6 composite material, which is characterized in that using as in claim 1~9
Any one the method is prepared.
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