CN106012082A - Polyamide or blend/graphene composite material wire rod and preparation method thereof - Google Patents
Polyamide or blend/graphene composite material wire rod and preparation method thereof Download PDFInfo
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- CN106012082A CN106012082A CN201610211552.6A CN201610211552A CN106012082A CN 106012082 A CN106012082 A CN 106012082A CN 201610211552 A CN201610211552 A CN 201610211552A CN 106012082 A CN106012082 A CN 106012082A
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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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- 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
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyamide or blend/graphene composite material wire rod; the polyamide or blend/graphene composite material wire rod has the tensile strength increased by more than or equal to 50% relative to the tensile strength of a pure matrix wire rod, and has the breaking elongation rate reduced by less than 20%; the polyamide or blend/graphene composite material wire rod is characterized in that the polyamide or blend/graphene composite material wire rod contains 0.08%-0.5% of graphene according to the weight percentage. The polyamide or blend/graphene composite material wire rod has the tensile strength varied along with the graphene content and the diameter of the wire rod; in the graphene content range of 0.1%-0.5% and in the diameter range of 0.1-0.5 mm, the tensile strength is increased by at least 50% than graphene-free wire rods prepared under the same conditions and having same diameter; through adjusting the graphene content, the highest tensile strength can be increased by 100% or more. The adopted method has the advantages of low cost, convenience in implementation and easy large-scale popularization, and can be widely used for improving the quality of traditional nylon wire rod products.
Description
Technical field
The present invention relates to a kind of polyamide or blend/graphene composite material wire rod and preparation method thereof, belong to
In field of polymer composite material.
Background technology
Diameter, at the polyamide of 0.1 to 0.5 millimeter or polyamide blend filament, is mainly used in various day
With fabric and fishery netting gear, rope tool, under the conditions of not reducing disrumpent feelings elongation percentage, improve this kind of material
Tensile strength, can improve the durability of product, is improved particularly a large amount of lossy nets that fish production uses
Tool, the life-span of rope tool, not only reduce production cost, and reduce cost recovery and environmental pollution, have
Overall economic efficiency and social benefit.The tensile strength of existing polyamide and blend material is by matrix material
With the restriction of reinforcement, often while improving tensile strength, have lost elongation percentage, and for Asia
The filament of mm dia, tradition short glass fiber or short carbon fiber reinforcement exist wire-drawing performance reduction
Shortcoming, and nano material reinforcement needs just to improve a lot tensile strength when loading is more, and
Disrumpent feelings elongation percentage is had certain reduction.
Nylon-6 has the advantages such as high intensity, high-wearing feature, high chemical stability, but its poor water resistance exists
To a certain degree reduce its long-term life-span soaked in water environment, in order to improve its resistance to water, by nylon
-6 make intermingling material with modified polypropene, can be under conditions of significantly reducing nylon-6 tensile strength
Significantly improve its resistance to water.
Graphene is a kind of two-dimensional sheet graphite, and its thickness is which floor graphite flake is arrived, and lamella size is divided
Cloth scope is from tens nanometers to tens micron, owing to being covalent structure carbon atom in graphite flake, and tension in sheet
Intensity, elastic modelling quantity are high, and Graphene thickness is minimum, therefore has the highest specific surface area, this
Two dimension graphite-structure can obtain the graphite flake of Surface oxygen-containing groups, referred to as graphite oxide by surface oxidation
Alkene, the surface functional group that graphene oxide enriches is its surface grafting and polymerization macromolecule chain offer link bit
Point, the graphene oxide of surface grafting can be dispersed in aqueous solution and multiple organic solvent simultaneously,
It is made to be suitable for using in-situ polymerization to prepare high-dispersion nano composite.
Polyamide uses caprolactam catalyzing and condensing (nylon-6) and hexamethylene diamine adipate condensation polymerization (Buddhist nun
Dragon-66) method synthesis, graphenic surface grafted amino group group, nylon-6 polymer molecule can be coupled to
On chain, thus when Graphene addition is less than 0.5% weight ratio, matrix tensile strength is improved and is not less than
50%, it is suitable for drawing the wire rod of diameter 0.1 to 0.5 millimeter.And due to Graphene during in-situ polymerization
Content can bring up to 15% weight ratio, in-situ polymerized composite can serve as performed polymer and finished-product material
At the mixing of goods process segment, after polymerization, it is configured to the composite of different Graphene content, for material
Material design and processing provide the preparation method of low cost.The present invention obtains by designing suitable prepolymerization conditions
The performed polymer arrived, can be combined with matrix material in the materials processing stage easily, improve nylon significantly
-6 or the tensile strength of nylon-6/polypropylene blend wire rod, there are the biggest secondary development potentiality.
Summary of the invention
An object of the present invention, should for providing a kind of polyamide or blend/graphene composite material wire rod
The tensile strength of composite relatively pure matrix wire rod improves more than 50%, and disrumpent feelings elongation percentage reduces less than 20%.
The two of the purpose of the present invention are that offer utilizes above-mentioned polyamide or blend/graphene composite material
The preparation method of wire rod.
As a kind of polyamide or the blend/graphene composite material wire rod of first aspect present invention, this gathers
The tensile strength of amide or blend/graphene composite material wire rod relatively pure matrix wire rod improve 50% with
On, disrumpent feelings elongation percentage reduces less than 20%, it is characterised in that this polyamide or blend/Graphene are combined
Containing percentage by weight in material wire rod is 0.08%～0.5% Graphene.
In a preferred embodiment of the invention, described polyamide is pure nylon-6.
In a preferred embodiment of the invention, described blend is that nylon-6 is total to polyacrylic binary
Mixed thing, wherein nylon-6 percentage by weight is not less than 50%.
In a preferred embodiment of the invention, described polyamide or blend/graphene composite material line
A diameter of 0.1～0.5 millimeter of material.
In a preferred embodiment of the invention, described Graphene refer to native graphite oxidized,
Peeling off the graphene oxide micron-stage sheet-like material obtained, thickness range is about at 0.55 to 2.2 nanometers, stone
The ink alkene microplate size range oxygen at 0.5 to 50 microns, in described graphene oxide micron-stage sheet-like material
Content is 30% to 50% mol ratio.
A kind of polyamide or the system of blend/graphene composite material wire rod as second aspect present invention
Preparation Method, comprises the steps:
(1) graininess performed polymer preparation process
By blended with nylon-6 fabricated in situ raw material for amination graphene oxide, disperse, be polymerized, pelletize
Step is prepared as graininess performed polymer；
(2) composite wire rod preparation process
Graininess performed polymer prepared by step (1) and nylon-6 or blended with polypropylene binary blend,
Melting, extrusion, drawing step obtain the composite wire rod that diameter is at 0.1～0.5 millimeter.
In a preferred embodiment of the invention, in described performed polymer the dilute percentage by weight of graphite be 5%～
15%.
In a preferred embodiment of the invention, the preparation process of described amination graphene oxide is:
First by natural flake graphite concentrated sulphuric acid and the potassium permanganate oxidation of particle size 10 to 150 microns,
To thickness 0.55 to 2.2 nanometer, the graphene oxide thin slice of size 0.5 to 50 microns；Then should
After graphene oxide thin slice fully washs, process with thionyl chloride, then with reacting ethylenediamine, obtain table
The face graphene oxide thin slice containing amino；Or use graphene oxide 1-(3-dimethylamino-propyl)-3-
Ethyl-carbodiimide hydrochloride (EDC) adds N-hydroxy-succinamide (NHS) and reacting ethylenediamine,
The graphene oxide thin slice of amino is contained to surface；Surface in the graphene oxide thin slice containing amino of the described surface
Amino and surface carbon atomic ratio are not less than 30% mol ratio.
In a preferred embodiment of the invention, surface is specifically contained ammonia by described performed polymer preparation process
The graphene oxide thin slice of base mixes with epsilon-caprolactams, under strong phosphoric acid or 6-aminocaprolc acid are catalyzed,
With water as initiator, carrying out in-situ polymerization under nitrogen protection, polymerization temperature is 160～260 DEG C, by stone
Ink alkene thin slice, in covalent bond mode, is highly dispersed to be coupled in nylon-6 macromolecule network matrix and makes
Performed polymer, performed polymer obtains performed polymer granule through pelletize after purification.
In a preferred embodiment of the invention, surface is the most specifically contained by described performed polymer preparation process
The graphene oxide thin slice of amino mixes with epsilon-caprolactams, under strong phosphoric acid or 6-aminocaprolc acid are catalyzed,
With water as initiator, 160～200 DEG C, prepolymerization 30 to 60 minutes under nitrogen protection, then exist
240～260 DEG C of lower continuation of nitrogen protection are polymerized 1 to 2 hours, are then evacuated down to 100kPa, keep 1
Hour, pelletize, wash, be dried, obtain graininess performed polymer.
In a preferred embodiment of the invention, described composite wire rod preparation process is by graininess
Performed polymer mixes, under nitrogen protection with polypropylene binary blend granule with nylon-6 granule or nylon-6
Mix and blend melting 0.5 to 2 hours, mix and blend smelting temperature is 240～260 DEG C, the most directly extrudes
Extrude wire drawing after wire drawing or pelletize to obtain.
The polyamide of the present invention or blend/graphene composite material wire rod, its tensile strength contains with Graphene
Amount and gauge or diameter of wire and change, in the range of Graphene content 0.1% to 0.5, diameter 0.1 to 0.5 milli
In the range of meter, not graphene-containing wire rod that tensile strength is all prepared than the same terms, same diameter improves
At least 50%, by regulation Graphene content, tensile strength is the highest can improve more than 100%.The present invention
The method used is with low cost, it is convenient to implement, be prone to large-scale promotion, can be widely used for promoting tradition Buddhist nun
Dragon class wire product quality.
Accompanying drawing explanation
Fig. 1 is the pure nylon-6 of diameter 0.25mm, the tensile load/displacement of Graphene composite nylon-6 wire rod
Curve.
Detailed description of the invention
Embodiment 1
Step 1: graphene oxide uses Hummers method to prepare, natural by granularity 10 to 150 microns
Crystalline flake graphite granule 5 grams, mixes with 2.5 grams of sodium nitrates and 115 milliliters of concentrated sulphuric acids, stirs at 0 DEG C
Uniformly, it is gradually added into 15 grams of potassium permanganate, after reacting 1 hour, keeps 30 minutes 35 DEG C of water-baths,
Add deionized water 250 milliliters, be heated to 98 DEG C, keep 15 minutes, then add deionized water and arrive
2000 milliliters, add 30 milliliters of hydrogen peroxide.Again by above-mentioned solution microporous filter membrane sucking filtration, use dilute hydrochloric acid
Washing, then sucking filtration, deionized water wash repeatedly, until solution is neutrality, be dried much filtrate, obtain
Graphite oxide.
Step 2: 1 gram of graphite oxide is inserted in 1000 ml deionized water, sonic oscillation repeatedly, directly
Time extremely without precipitum, sucking filtration, it is dried, obtains graphene oxide sheet, this graphene oxide sheet footpath is 0.5
To 50 microns, thickness 0.55 to 2.2 nanometer, oxygen content is in 30% to 50% mol ratio；
Step 3: 1 gram of above-mentioned graphene oxide sheet is joined 200 milliliters of thionyl chlorides and 5 milliliters anhydrous
In dimethylformamide (DMF), 70 DEG C are refluxed 24 hours, the decompression unreacted thionyl chloride of volatilization,
Add 200 milliliters of DMF, ultrasonic disperse, dispersion liquid be slowly dropped in 10 grams of ethylenediamines of 0 DEG C,
To keep 72 hours at 120 DEG C after mixed liquor ultrasonic disperse, sucking filtration, washing, dried, obtain table
Face amino and surface carbon atomic ratio are not less than the amination Graphene of 30% mol ratio；
Step 4: 1 gram of above-mentioned amination Graphene and 10 are restrained oneself lactams, 0.5 gram of 6-aminocaprolc acid
Mixing, after ultrasonic disperse, 160～200 DEG C, prepolymerization 30 to 60 minutes under nitrogen protection, then
Under 240～260 DEG C of nitrogen protections, continue polymerization 1 to 2 hours, be then evacuated down to 100kPa, keep
1 hour, pelletize, wash, be dried, obtain the graininess performed polymer of graphene-containing 10%；
Step 5: by the performed polymer granule of above-mentioned graphene-containing 10% with pure nylon-6 granule with 1:100 mass
Than mixing, mixing 0.5 to 2 hours at 240～260 DEG C of stirred under nitrogen atmosphere, then directly extrusion is drawn
Extruding wire drawing after silk or pelletize, drawing condition is identical with pure nylon-6, and obtaining Graphene content is 0.1% matter
Continuous graphite alkene composite nylon-6 wire rod of amount ratio, tensile strength filament cupping machine is measured, and measures
A length of 300 millimeters.
Embodiment 2
The preparation method of graphene oxide with step 1 in embodiment 1,2；
Step 3: 1 gram of graphene oxide is mixed with 2 grams of EDC and 2 grams of NHS, adds under nitrogen protection
Enter 240 milliliters of DMF ultrasonic disperse, after 3 hours, mixed solution adds 3 milliliters of ethylenediamines, at nitrogen
Stir 24 hours under gas shielded, sucking filtration, deionized water cyclic washing, be dried to obtain amino content and be not less than
The amination Graphene of 30%；
Step 4: graininess performed polymer preparation method is with the step 4 in embodiment 1；
Step 5:: by performed polymer granule and nylon-6/poly-third of 50% weight ratio of above-mentioned graphene-containing 10%
Alkene blend mixes with 1:100 mass ratio, and this blended system uses maleic anhydride melt grafting polypropylene method
The blend that the modified polypropene of preparation is prepared with double screw extrusion method with nylon-6, maleic anhydride melt
Graft polypropylene uses and will add 10 parts of maleic anhydrides and 1.5 parts of peroxidating diisopropyls in 90 parts of polypropylene
Benzene, at 210 DEG C, extrudes polypropylene with double screw extruder under 40 turns per minute, then by modified poly-third
Alkene granule mixes with 50% mass ratio with nylon-6 granule, uses double screw extruder extruding pelletization, extrusion temperature
Spend 210 DEG C, obtain nylon-6/polypropene blended granule；
Step 6:10% Graphene performed polymer granule prepare continuous wire drawing method compound with blended nylon is with implementing
Step 5 in example 1.
Table 1 is the pure nylon-6 of different-diameter, the Graphene composite nylon-6 of different Graphene content and not
Measure with Graphene composite nylon-6/ polypropylene blend rupture strength of Graphene content, disrumpent feelings elongation percentage
Result (is measured by GB GB/T21032-2007).
Table 1
Claims (11)
1. polyamide or blend/graphene composite material wire rod, this polyamide or blend/graphite
The tensile strength of alkene composite wire rod relatively pure matrix wire rod improves more than 50%, and disrumpent feelings elongation percentage reduces little
In 20%, it is characterised in that containing weight hundred in this polyamide or blend/graphene composite material wire rod
Proportion by subtraction is 0.08%～0.5% Graphene.
2. a kind of polyamide as claimed in claim 1 or blend/graphene composite material wire rod, it is special
Levying and be, described polyamide is pure nylon-6.
3. a kind of polyamide as claimed in claim 1 or blend/graphene composite material wire rod, it is special
Levying and be, described blend is nylon-6 and polyacrylic binary blend, wherein nylon-6 weight percent
Ratio is not less than 50%.
4. a kind of polyamide as claimed in claim 1 or blend/graphene composite material wire rod, it is special
Levy and be, described polyamide or a diameter of 0.1～0.5 millimeter of blend/graphene composite material wire rod.
5. a kind of polyamide as claimed in claim 1 or blend/graphene composite material wire rod, it is special
Levying and be, described Graphene refers to the graphene oxide micron that, stripping oxidized with native graphite obtains
Level flaky material, thickness range is about in 0.55 to 2.2 nanometers, and graphene microchip size range arrives 0.5
50 microns, the oxygen content in described graphene oxide micron-stage sheet-like material is 30% to 50% mol ratio.
6. polyamide or blend/Graphene described in claim 1 to a 5 any one claim are multiple
The preparation method of condensation material wire rod, it is characterised in that comprise the steps:
(1) graininess performed polymer preparation process
By blended with nylon-6 fabricated in situ raw material for amination graphene oxide, disperse, be polymerized, pelletize
Step is prepared as graininess performed polymer；
(2) composite wire rod preparation process
Graininess performed polymer prepared by step (1) and nylon-6 or blended with polypropylene binary blend,
Melting, extrusion, drawing step obtain the composite wire rod that diameter is at 0.1～0.5 millimeter.
7. preparation method as claimed in claim 6, it is characterised in that in described performed polymer, graphite is dilute heavy
Amount percentage ratio is 5%～15%.
8. preparation method as claimed in claim 6, it is characterised in that described amination graphene oxide
Preparation process be: first by natural flake graphite concentrated sulphuric acid and the height of particle size 10 to 150 microns
Potassium manganate aoxidizes, and obtains thickness 0.55 to 2.2 nanometer, the graphene oxide of size 0.5 to 50 microns
Thin slice；Then, after this graphene oxide thin slice fully being washed, process with thionyl chloride, then with second two
Amine reacts, and obtains the surface graphene oxide thin slice containing amino；Or use graphene oxide 1-(3-
Dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) adds N-hydroxy-succinamide (NHS)
With reacting ethylenediamine, obtain the surface graphene oxide thin slice containing amino；The oxidation containing amino of the described surface
In graphene platelet, surface amino groups and surface carbon atomic ratio are not less than 30% mol ratio.
9. preparation method as claimed in claim 6, it is characterised in that described performed polymer preparation process has
Body is that the graphene oxide thin slice that surface contains amino mixes with epsilon-caprolactams, at strong phosphoric acid or 6-ammonia
Base caproic acid catalysis under, with water as initiator, carry out in-situ polymerization under nitrogen protection, polymerization temperature be 160～
260 DEG C, by graphene platelet in covalent bond mode, it is highly dispersed to be coupled at nylon-6 macromolecule network
The performed polymer made in matrix, performed polymer obtains performed polymer granule through pelletize after purification.
10. preparation method as claimed in claim 9, it is characterised in that described performed polymer preparation process is also
The graphene oxide thin slice that surface specifically contains amino mixes with epsilon-caprolactams, at strong phosphoric acid or 6-
Aminocaproic acid catalysis under, with water as initiator, 160～200 DEG C, nitrogen protection under prepolymerization 30 to 60
Minute, then under 240～260 DEG C of nitrogen protections, continue polymerization 1 to 2 hours, be then evacuated down to
100kPa, keeps 1 hour, pelletize, wash, be dried, obtain graininess performed polymer.
11. preparation methoies as claimed in claim 6, it is characterised in that prepared by described composite wire rod
Step is to be mixed with polypropylene binary blend granule with nylon-6 granule or nylon-6 by graininess performed polymer
Closing, mix and blend melting 0.5 to 2 hours under nitrogen protection, mix and blend smelting temperature is
240～260 DEG C, extrude wire drawing after the most directly extruding wire drawing or pelletize and obtain.
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