CN108707319A - A kind of graphene-terylene composite master batch and preparation method thereof - Google Patents
A kind of graphene-terylene composite master batch and preparation method thereof Download PDFInfo
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- CN108707319A CN108707319A CN201810565694.1A CN201810565694A CN108707319A CN 108707319 A CN108707319 A CN 108707319A CN 201810565694 A CN201810565694 A CN 201810565694A CN 108707319 A CN108707319 A CN 108707319A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static 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
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D01F6/92—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 polyesters
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/54—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
A kind of graphene-terylene composite master batch of present invention offer and preparation method thereof, in the graphene-terylene composite master batch, graphene is 0.05-2% relative to the content that dacron polyester is sliced, and bioprotein powder is 1.5-4.5% relative to the content that dacron polyester is sliced.The preparation method, including graphene-terylene composite granule preparation process, bioprotein-terylene composite granule preparation process, mixing, extrusion step；The graphene prepared using the present invention-terylene composite master batch carries out graphene-terylene composite fibre of spinning preparation, has more soft feel, better skin-friendly, moisture pick-up properties is good, does not generate electrostatic, while frictional force becomes larger between fiber, cohesive force becomes strong, and polyester fiber spinnability is obviously improved.
Description
Technical field
The present invention provides a kind of dacron master grain and preparation method thereof, especially a kind of graphene-terylene composite master batch and its
Preparation method.
Background technology
Graphene（Graphene）It is a kind of two dimension that hexangle type being formed in honeycomb lattice with sp2 hybridized orbits by carbon atom
Carbon nanomaterial.Graphene has excellent optics, electricity, mechanical characteristic, in materialogy, micro-nano technology, the energy, biomedicine
It is with important application prospects with drug delivery etc., it is considered to be a kind of future revolutionary material.
In recent years, it is quickly grown by the functionality of representative, fibre in differentiation of graphene, it will be by modification, modified stone
Black alkene is added in the production process of fiber, and there is the graphene fiber of preparation good strength, anti-microbial property and far infrared to release
Playing function, therefore, increasingly by the universal concern of industry and society.
In general, the optimal selection of graphene-terylene nanometer composite fibre is the oxidation through halogenated hydrocarbons functional modification
Graphene, graphene oxide improve after modification with the compatibility of dacron polyester, contribute to graphene in dacron polyester matrix
In be uniformly dispersed, to improve the intensity of graphene-terylene nanometer composite fibre.General industry grade dacron polyester slice passes through
Compound being carried out with the graphene of different component after drying and master batch being made, graphene-is then prepared on melt spinning machine
Terylene nanometer composite fibre.
Such as Publication No. CN105200547A, patent name are a kind of " preparation of graphene-terylene nanometer composite fibre
The Chinese invention patent of method ", main technical schemes are：Dacron polyester is sliced first and is mixed with the graphene after modification
It closes, graphene-dacron polyester composite master batch is made, the master batch of preparation is then prepared into graphene-terylene by spinning technique
Composite fibre mainly solves the problems, such as mainly there are following several respects：（1）Improve the graphene-synthetic fibre nano-composite fiber prepared
Physical strength；（2）The graphene of preparation-terylene composite fibre has antistatic, antibacterial, radioresistance, fire-retardant, smooth nice and cool etc.
Advantage.
In actual production it was found that stone is made in the graphene-dacron polyester composite master batch produced using conventional method
Black alkene-terylene composite fibre is as described in the above-mentioned published patent, graphene-terylene composite fiber surface too light of preparation
Sliding, it is that cohesive force is very poor to cause fiber yarn forming, fiber fluffy, it is not easy to which networking polymerize, and at item difficulty, or even causes the strong of yarn
Degree reduces, and has the risk of broken string, generates prodigious adverse effect to spinning, spinnability is very poor.And under normal circumstances, using table
Face activating agent goes the processing of yarn to improve the cohesive force of yarn fibers, and the effect is unsatisfactory；It goes to assist to improve obvolvent with waxing
Power will enable waxing process under room temperature equably cling in yam surface, Bu Huiyin although effective, but there are disadvantage
The too soft too group of bonding of wax and fill in loom pinprick, too hard and viscous not tight and fall, difficulty is very big；The present invention is based on above-mentioned skill
Art problem and generate.
Meanwhile it being made in graphene-terylene composite fibre production in graphene-dacron polyester composite master batch, it has been found that
Due to adding other functional components, these functional components produce the strength of manufactured graphene-terylene composite fibre
Influence is given birth to.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of graphene-terylene composite master batch, to solve in the prior art
Existing graphene-terylene composite fibre strength is low, obvolvent force difference, functional difference problem, and it is multiple to reach raising graphene-terylene
The strength of condensating fiber, cohesive force improve fiber spinnability, functional goal of the invention, for this purpose, the particular technique that the present invention uses
Scheme is：
A kind of preparation of graphene-terylene composite master batch specifically includes following steps：
（1）It is prepared by graphene-terylene composite granule
Dacron polyester is sliced and is mixed by mechanical ball mill breakdown mill with graphene, graphene-terylene composite granule is made.
Preferably, the graphene is graphene oxide；It is oxygen-containing that surface of graphene oxide contains abundant hydroxyl, carboxyl etc.
Group can be more easy to disperse in mixed process with the clustering phenomena of the reduction graphene of bottom line, mixed with dacron polyester slice
It closes evenly.
Further, the raw material for preparing of the graphene oxide is expansible graphite, natural flake graphite and ball-type graphite
One or more；The graphene oxide preferably prepared after expansible graphite oxidation；It is prepared after being aoxidized using expansible graphite
Graphene oxide layer surface structure level it is complicated, fold is more, specific surface bigger, therefore is easier to be sliced with dacron polyester
Generate more firm binding force.
Further, prepare raw material expansible graphite, natural flake graphite, the ball-type graphite of the graphene oxide are
80-150 mesh, such as 80,90,95,100,120,150 mesh can be selected etc., but it is total after inventor largely researches and develops, tests
Knot, wherein being preferably 90-120 mesh.Its surface texture gap of the graphene oxide of graphite preparation of different-grain diameter is huge, layer
The quantity of number, surface functional group, thus its to the physical property of graphene-terylene composite master batch of preparation and it is functional have compared with
Big influence, inventor have found by a large number of experiments, when the mesh number that selection is graphite is 90-120 mesh, the graphene-of preparation
Terylene composite master batch has physically better index and functionality.
Preferred, the dacron polyester slicing characteristics viscosity 0.55-0.60dl/g, content of carboxyl end group 16-16.5mol/
T, diethylene glycol content 8.3-85%, 245 DEG C of fusing point；Fusing point, viscosity, content of carboxyl end group and the polyester fiber of polyester resin slice
The size of crystallinity, and the size of crystallinity is the embodiment of fibrous inside fibrillar crystallization, directly influences the graphene of preparation
The quality of master batch and the intensity of fiber, the selection of above-mentioned dacron polyester slice are also the result that inventor studies for a long period of time, summarizes.
（2）It is prepared by bioprotein-terylene composite granule
By bioprotein powder and dacron polyester slice by mechanical ball mill ground and mixed, bioprotein-terylene composite powder is made
Body.
Preferably, step（2）In, the bioprotein powder be wool protein powder, natural silk protein powder body one
Kind is several；Preferably natural silk protein powder body, wool protein powder due to the cortex on surface influence, the short time it is molten
Solution performance ratio natural silk protein powder body is poor, and compound by the way that graphene-terylene prepared by natural silk protein powder body is added
Master batch, skin-friendly are more preferable.Based on this, natural silk protein powder body is selected to be conducive to improve the production effect of production following process
Rate, while the polyester fiber prepared has better skin-friendly, flexibility.
Preferably, the addition of bioprotein powder is the 1.5-4.5% of dacron polyester chipping qualities；
Further, in the bioprotein-terylene composite granule, functional additive is added；The group of the functional additive
Divide and includes：Polyacrylamide, sorbitan monostearate, pentaerythrite；The additive amount of the functional additive is the life
The 10-30% of object protein powder；The group of polyacrylamide, sorbitan monostearate, pentaerythrite in the functional additive
Part mass ratio is：10-20%：35-45%：3-6%.The addition of functional additive can be greatly reduced due to last handling process
Middle protein powder swelling, influence of the denaturation to fibre strength.
（3）Mixing squeezes out
By step（1）The graphene of preparation-terylene composite granule, step（2）The bioprotein of preparation-terylene composite granule gathers
Ester slice after drying, is uniformly mixed, finally by the feeding for being added to double screw extruder respectively into high-speed kneading machine
Tape after mixing squeezes in a certain temperature conditions, is sent into pelleter and carries out pelletizing, the graphite that as prepared by the present invention by storehouse
Alkene-terylene composite master batch.
Preferably, the drying temperature is 100-120 DEG C, and dry moisture is in 40ppm hereinafter, preferably smaller than 20ppm.
Dacron polyester slice in moisture seriously affect preparation graphene-terylene composite master batch performance, undried polyester slice,
Moisture content is usually about 0.4%, removes the moisture in polyester slice to avoid violent water is generated in follow-up spinning process
Solution.
The present invention is prepared by graphene-terylene composite granule respectively, prepared by bioprotein-terylene composite granule, high speed
Kneader mixes, and graphene, protein powder are evenly distributed in graphene-terylene composite master batch of preparation, and clustering phenomena does not occur,
It avoids generating broken end risk in the follow-up spinning process of graphene dacron master grain.
The present invention in preparing graphene-terylene composite master batch by being added protein powder, using the stone of the invention prepared
Black alkene-terylene composite master batch carries out the graphene polyester fiber of spinning preparation, has a more soft feel, better skin-friendly,
Moisture pick-up properties is good, does not generate electrostatic, while frictional force becomes larger between fiber, and cohesive force becomes strong, and fiber spinnability is obviously improved.
Further, in the graphene-terylene composite master batch, addition that wherein graphene is sliced relative to dacron polyester
Amount is 0.05-2%, and bioprotein powder is 1.5-4.5% relative to the addition that dacron polyester is sliced；The wherein addition of graphene
Amount is preferably 0.05-0.5%；When the graphene oxide especially prepared after using above-mentioned expansible graphite oxidation, stone is aoxidized
The addition of black alkene is preferably 0.05-0.1%, can significantly reduce production cost.
The addition of bioprotein powder is for for the present invention, being important.Inventor is in R&D process
Middle discovery, when the addition of bioprotein powder is less than 1.5%, although the strength of fiber becomes strong, due to bioprotein powder
The reduction of addition, manufactured graphene polyester fiber side-friction variation is little, and spinnability is not significantly improved.Work as life
When the addition of object protein powder is more than 4.5%, the strength of fiber decrease beyond 20%, it is clear that does not have actual production substantially
Meaning.
Further, the double screw extruder draw ratio is 40：1, engine speed 120-150Hz, water cooling pelletizing；Its
Middle each area's extrusion temperature of double screw extruder is to be respectively：268 DEG C, 278 DEG C, 282 DEG C, 285 DEG C, 278 DEG C.Patent of the present invention exists
The temperature in each area of double screw extruder, can make graphene be uniformly dispersed in dacron polyester, steadily prepare composite master batch.
In addition, the present invention also provides a kind of preparation method of graphene-terylene composite fibre, mainly include the following steps that：
Graphene prepared by the present invention-terylene composite master batch is sent into feeding chamber, and entering manifold by screw extruder carries out
Then annealing device is passed through in spinning, cross air blasting is cooled and shaped, oils, and stretches through two pairs of rollers one, two pairs of rollers two, two pairs of rollers three and finally rolls up
Turn to graphene-terylene composite fibre.
Wherein, the temperature of the manifold is 260-270 DEG C；The temperature of the annealing device is 245-255 DEG C；The side
The temperature of blowing device is 35-40 DEG C, humidity 55-60%, wind speed 0.1-0.3m/s；Described oil be with the rotating speed of oil tanker
25-30r/min；The two pairs of rollers one, two pairs of rollers two, the temperature of two pairs of rollers three are respectively 70-85 DEG C, 95-100 DEG C, 125-135 DEG C.
Further, further include dissolving step before oiling after the cooling and shaping；The purpose of the dissolving step
It is the process by the graphene after spinning-terylene composite fibre filament by dissolving, the albumen of fiber sheath will be attached to
Powder section dissolves, and so that graphene PET fiber surface is formed certain concave-convex microstructure, fiber is further increased to reach
Between side-friction, to achieve the purpose that improve fibre cohesion, achieve the purpose that improve fiber spinnability.
The concrete technology of the dissolving includes：
By the graphene polyester fiber tow of preparation, it is placed in protein enzyme solution and carries out enzymatic treatment；In the protein enzyme solution, institute
It is 45-65 DEG C to state enzymatic treatment temperature, and enzyme processing time processing is 10-30min；
It further, will be by by the graphene polyester fiber tow after enzymatic treatment, immersing sodium hydrogensulfite, guanidine hydrochloride, TCEP
Mixed liquor in handle 30-50min；The temperature of the mixed liquor is 50-85 DEG C, the concentration of the mixed liquor sulfite hydrogen sodium
For 150-185g/L, a concentration of 160-200g/L of guanidine hydrochloride in the mixed liquor；A concentration of 30-60g/L of the TCEP.
Based on above-mentioned dissolution process, the protein powder for being attached to fiber sheath is partly dissolved, makes graphene polyester fiber
Surface forms concave-convex microstructure, improves the side-friction between fiber, improves fibre cohesion, finally improves
The spinnability of fiber.
By adopting the above-described technical solution, the present invention has following advantageous effect：
1, the present invention makes the compound mother of graphene-terylene of preparation by the way that graphene to be added in the preparation of dacron polyester master batch
There is grain good antibiotic property, antistatic, heat conductivility, conductivity to be up to 3.0 × 104S/cm, perceptual sensitivity are more than 4.1
More than, it is extremely suitable for wearing motion detection, health detection, medical treatment detection textile.
2, the compound fibre of graphene-terylene of spinning preparation is carried out using graphene-terylene composite master batch prepared by the present invention
Dimension has more soft feel, and better skin-friendly, moisture pick-up properties is good, in the normal atmosphere of relative humidity 65%, moisture absorption
Property be up to 9% or more, do not generate electrostatic, while frictional force becomes larger between fiber, cohesive force becomes strong, and polyester fiber spinnability improves
Obviously.
3, the present invention is prepared by graphene-terylene composite granule respectively, prepared by bioprotein-terylene composite granule, high
Fast kneader mixes, and graphene is evenly distributed in graphene-terylene composite master batch of preparation, and clustering phenomena, graphene-does not occur
It avoids generating broken end risk in the follow-up spinning process of terylene composite master batch, end breakage rate reduces 41%-45%.
4, present invention selection is using the graphene oxide prepared using expansible graphite, in the preparation of graphene dacron master grain
In the process, the goal of the invention of the present invention seldom can be realized in addition；The addition of graphene oxide only needs 0.05-0.1%, can
Significantly to reduce production cost.
When 5, producing graphene-terylene composite fibre using graphene-terylene composite master batch prepared by the present invention, in spinning
In last handling process, dissolving step is introduced, at the technique that the graphene after spinning-terylene composite fibre filament is passed through dissolving
Reason, makes the protein powder for being attached to fiber sheath be partly dissolved, graphene-terylene composite fiber surface is made to form certain bumps
Microstructure, to reach the side-friction between further increasing fiber, to achieve the purpose that improve fibre cohesion, into
And improve fiber spinnability.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the common skill of this field
For art personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to this
The protection domain of invention.
A kind of preparation of 1 graphene of embodiment-terylene composite master batch specifically includes following steps：
（1）It is prepared by graphene-terylene composite granule
It is that graphene oxide made of raw material passes through mechanical ball by the natural flake graphite that dacron polyester is sliced with mesh number is 90 mesh
Ground and mixed is ground, graphene-terylene composite granule is made.Wherein dacron polyester slicing characteristics viscosity 0.55-0.60dl/g, end
Carboxyl-content 16-16.5mol/t, diethylene glycol content 8.3-85%, 245 DEG C of fusing point.
（2）It is prepared by bioprotein-terylene composite granule
By wool protein powder, functional additive, dacron polyester slice by mechanical ball mill ground and mixed, wool protein-is made
Terylene composite granule；Wherein the addition of wool protein powder is the 1.5% of dacron polyester chipping qualities, the group of functional additive
Divide and includes：Polyacrylamide, sorbitan monostearate, pentaerythrite；The additive amount of functional additive is the biological egg
The 15% of white powder body；Polyacrylamide in functional additive, sorbitan monostearate, pentaerythrite component mass ratio be：
10：32：5.
（3）Mixing squeezes out
By step（1）The graphene of preparation-terylene composite granule, step（2）The wool protein of preparation-terylene composite granule gathers
Ester slice is 100 DEG C of dryings in temperature, and dry moisture is in 40ppm hereinafter, being then uniformly mixed in high-speed kneading machine, finally
It is added to the feeding bin of double screw extruder, after mixing squeezes in a certain temperature conditions, tape is sent into pelleter and is carried out
Pelletizing, graphene-terylene composite master batch that as prepared by the present invention.
In the graphene of preparation-terylene composite master batch, wherein graphene is 1% relative to the addition that dacron polyester is sliced,
Wool protein powder is 1.5% relative to the addition that dacron polyester is sliced；
Double screw extruder draw ratio is 40：1, engine speed 120Hz, water cooling pelletizing；Wherein each area of double screw extruder is squeezed
It is to be respectively to go out temperature：268 DEG C, 278 DEG C, 282 DEG C, 285 DEG C, 278 DEG C.
The graphene of preparation-terylene composite master batch is sent into feeding chamber, manifold is entered by screw extruder and is spun
Then silk passes through annealing device, cross air blasting is cooled and shaped, oils, through two pairs of rollers one, two pairs of rollers two, the stretching of two pairs of rollers three and last winding
Graphene-terylene composite fibre is made.
Wherein, in spinning process, the temperature of manifold is 270 DEG C；The temperature of annealing device is 255 DEG C；Cross air blowing device
Temperature be 40 DEG C, humidity 55%, wind speed 0.1m/s；The rotating speed of oil tanker is 25r/min；It is the two pairs of rollers one, two pairs of rollers two, right
The temperature of roller three is respectively 70 DEG C, 95 DEG C, 125 DEG C.
Further include dissolving step before oiling after cooling and shaping；The concrete technology of dissolving includes：
By the graphene polyester fiber tow of preparation, it is initially positioned in protein enzyme solution and carries out enzymatic treatment；In protein enzyme solution, enzyme
Treatment temperature is 45 DEG C, and enzyme processing time processing is 30min；Then it by the graphene polyester fiber tow after enzymatic treatment, immerses
Sodium hydrogensulfite, guanidine hydrochloride, TCEP mixed liquor in handle 30min；The temperature of mixed liquor is 50 DEG C, mixed liquor sulfite hydrogen
A concentration of 150g/L of sodium, a concentration of 160g/L of guanidine hydrochloride in mixed liquor；A concentration of 30g/L of TCEP.
Based on this, graphene-terylene composite fibre made of the graphene-terylene composite master batch prepared using invention, tool
There is good spinnability, while there is soft feel, excellent antistatic property and anti-microbial property.
A kind of preparation of 2 graphene of embodiment-terylene composite master batch specifically includes following steps：
（1）It is prepared by graphene-terylene composite granule
It is that graphene oxide made of raw material passes through mechanical ball mill by the expansible graphite that dacron polyester is sliced with mesh number is 100 mesh
Breakdown mill mixes, and graphene-terylene composite granule is made.Wherein dacron polyester slicing characteristics viscosity 0.55-0.60dl/g, end,
Carboxyl-content 16-16.5mol/t, diethylene glycol content 8.3-85%, 245 DEG C of fusing point.
（2）It is prepared by bioprotein-terylene composite granule
By natural silk protein powder body and dacron polyester slice by mechanical ball mill ground and mixed, silk fibroin-is made and washs
Synthetic fibre composite granule.
The addition of bioprotein powder is the 3% of dacron polyester chipping qualities；
In bioprotein-terylene composite granule, functional additive is added；The component of functional additive includes：Polyacrylamide,
Sorbitan monostearate, pentaerythrite；The additive amount of functional additive is the 20% of biological protein powder；Functional additive
Middle polyacrylamide, sorbitan monostearate, pentaerythrite component mass ratio be： 20：35：1.
（3）Mixing squeezes out
By step（1）The graphene of preparation-terylene composite granule, step（2）The silk fibroin of preparation-terylene composite powder
Body, polyester slice are after temperature is 120 DEG C dry, and dry moisture is in 20ppm or less.
It is uniformly mixed subsequently into high-speed kneading machine, finally by the feeding bin for being added to double screw extruder, certain
Temperature condition under after mixing squeezes, tape is sent into pelleter and carries out pelletizing, as graphene-terylene for preparing of the present invention is multiple
Close master batch.
In graphene-terylene composite master batch, wherein graphene is 0.05% relative to the addition that dacron polyester is sliced,
Bioprotein powder is 2.5% relative to the addition that dacron polyester is sliced.
Double screw extruder draw ratio is 40：1, engine speed 150Hz, water cooling pelletizing；Wherein double screw extruder is each
Area's extrusion temperature is to be respectively：268 DEG C, 278 DEG C, 282 DEG C, 285 DEG C, 278 DEG C.
The graphene of preparation-terylene composite master batch is sent into feeding chamber, manifold is entered by screw extruder and is spun
Then silk passes through annealing device, cross air blasting is cooled and shaped, dissolves, oils, and is stretched through two pairs of rollers one, two pairs of rollers two, two pairs of rollers three and last
Graphene-terylene composite fibre is made in winding.
Wherein, the temperature of manifold is 270 DEG C；The temperature of annealing device is 245 DEG C；The temperature of cross air blowing device is 35
DEG C, humidity 60%, wind speed 0.3m/s；It is 25r/min to oil with the rotating speed of oil tanker；The temperature of two pairs of rollers one, two pairs of rollers two, two pairs of rollers three
Degree is respectively 75 DEG C, 100 DEG C, 130 DEG C.
The concrete technology wherein dissolved includes：
By the graphene polyester fiber tow of preparation, it is initially positioned in protein enzyme solution and carries out enzymatic treatment；In protein enzyme solution, enzyme
Treatment temperature is 55 DEG C, and enzyme processing time processing is 30min；Then it by the graphene polyester fiber tow after enzymatic treatment, immerses
Sodium hydrogensulfite, guanidine hydrochloride, TCEP mixed liquor in handle 30min；The temperature of mixed liquor is 85 DEG C, mixed liquor sulfite hydrogen
A concentration of 185g/L of sodium, a concentration of 160g/L of guanidine hydrochloride in mixed liquor；A concentration of 40g/L of TCEP.
Based on this, graphene-terylene composite fibre made of the graphene-terylene composite master batch prepared using invention, tool
There is good spinnability, while there is soft feel, excellent antistatic property and anti-microbial property.
A kind of preparation of 3 graphene of embodiment-terylene composite master batch specifically includes following steps：
（1）It is prepared by graphene-terylene composite granule
It is that graphene oxide made of raw material is ground by mechanical ball by the ball-type graphite that dacron polyester is sliced with mesh number is 120 mesh
Graphene-terylene composite granule is made in ground and mixed.Wherein dacron polyester slicing characteristics viscosity 0.55-0.60dl/g, end, carboxylic
Base content 16-16.5mol/t, diethylene glycol content 8.3-85%, 245 DEG C of fusing point.
（2）It is prepared by bioprotein-terylene composite granule
By wool protein powder and dacron polyester slice by mechanical ball mill ground and mixed, wool protein-terylene composite powder is made
Body.
The addition of bioprotein powder is the 4.5% of dacron polyester chipping qualities；
In bioprotein-terylene composite granule, functional additive is added；The component of functional additive includes：Polyacrylamide,
Sorbitan monostearate, pentaerythrite；The additive amount of functional additive is the 10% of biological protein powder；Functional additive
Middle polyacrylamide, sorbitan monostearate, pentaerythrite component mass ratio be：5：20：2.
（3）Mixing squeezes out
By step（1）The graphene of preparation-terylene composite granule, step（2）The wool protein of preparation-terylene composite granule gathers
Ester slice after temperature is 110 DEG C dry, dry moisture in 40ppm hereinafter, be uniformly mixed subsequently into high-speed kneading machine,
Finally by the feeding bin for being added to double screw extruder, after mixing squeezes in a certain temperature conditions, tape feeding is cut
Grain machine carries out pelletizing, graphene-terylene composite master batch that as prepared by the present invention.
Wherein, in graphene-terylene composite master batch, graphene is 2% relative to the addition that dacron polyester is sliced, biology
Protein powder is 2.0% relative to the addition that dacron polyester is sliced.
Double screw extruder draw ratio is 40：1, engine speed 150Hz, water cooling pelletizing；Wherein double screw extruder is each
Area's extrusion temperature is to be respectively：268 DEG C, 278 DEG C, 282 DEG C, 285 DEG C, 278 DEG C.
The graphene of preparation-terylene composite master batch is sent into feeding chamber, manifold is entered by screw extruder and is spun
Then silk passes through annealing device, cross air blasting is cooled and shaped, dissolves, oils, and is stretched through two pairs of rollers one, two pairs of rollers two, two pairs of rollers three and last
Graphene-terylene composite fibre is made in winding.
Wherein, the temperature of manifold is 260 DEG C；The temperature of annealing device is 255 DEG C；The temperature of cross air blowing device is 35
DEG C, humidity 55%, wind speed 0.3m/s；It is 30r/min to oil with the rotating speed of oil tanker；The two pairs of rollers one, two pairs of rollers two, two pairs of rollers three
Temperature be respectively 70 DEG C, 98 DEG C, 128 DEG C.
The concrete technology wherein dissolved includes：
By the graphene polyester fiber tow of preparation, it is initially positioned in protein enzyme solution and carries out enzymatic treatment；In protein enzyme solution, enzyme
Treatment temperature is 55 DEG C, and enzyme processing time handles 30min；Then it by the graphene polyester fiber tow after enzymatic treatment, immerses sub-
Niter cake, guanidine hydrochloride, TCEP mixed liquor in handle 50min；The temperature of mixed liquor is 75 DEG C, mixed liquor sulfite hydrogen sodium
A concentration of 150g/L, a concentration of 180g/L of guanidine hydrochloride in mixed liquor；A concentration of 60g/L of TCEP.
Based on this, graphene-terylene composite fibre made of the graphene-terylene composite master batch prepared using invention, by force
Degree is high, there is good spinnability, end breakage rate to reduce 41%-45%.There is soft feel simultaneously, in the mark of relative humidity 65%
In quasi- air, hygroscopicity is up to 9% or more, and excellent antistatic property and anti-microbial property, specific Testing index are shown in Table 1
Table 1
Comparative example 4
The present embodiment and the method for embodiment 3 are almost the same, the difference is that：In step（2）Bioprotein-terylene is compound
In powder preparation process, it is added without the component of functional additive, the graphene-terylene composite fibre specific targets prepared are shown in Table
2
Table 2
As can be seen from Table 2, graphene-terylene made of graphene-terylene composite master batch using the invention preparation of this comparative example
Composite fibre, after removing the component of functional additive, the fibrous fracture intensity of preparation declines obviously, surprisingly,
Conductivity also significantly decreases.
Unless specifically indicated, ratio of the present invention is mass ratio, and the percentage is mass percent.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of graphene-terylene composite master batch, it is characterised in that：In the graphene-terylene composite master batch, graphene is opposite
It is 0.05-2% in the content of dacron polyester slice, bioprotein powder is 1.5-4.5% relative to the content that dacron polyester is sliced.
2. a kind of preparation method of graphene dacron master grain described in claim 1, it is characterised in that：Including graphene-terylene
Composite granule preparation process, bioprotein-terylene composite granule preparation process, mixing, extrusion step；The extrusion is using double spiral shells
Bar extruder；The double screw extruder draw ratio is 40：1, engine speed 120-150Hz；The double screw extruder is each
Area's extrusion temperature is to be respectively：268 DEG C, 278 DEG C, 282 DEG C, 285 DEG C, 278 DEG C.
3. a kind of preparation method of graphene-terylene composite master batch according to claim 2, it is characterised in that：Described
In bioprotein-terylene composite granule, contain functional additive；The component of the functional additive includes：Polyacrylamide, mountain
Pears alcohol acid anhydride monostearate, pentaerythrite；The additive amount of the functional additive is the 10-30% of the bioprotein powder；Institute
State polyacrylamide in functional additive, sorbitan monostearate, pentaerythrite component mass ratio be：10-20%：35-
45%：3-6%.
4. a kind of preparation method of graphene-terylene composite master batch according to claim 2, it is characterised in that：The stone
Black alkene is graphene oxide；The raw material for preparing of the graphene oxide is expansible graphite, natural flake graphite and ball-type graphite
One or more.
5. a kind of preparation method of graphene-terylene composite master batch according to claim 4, it is characterised in that：It is described can
The mesh number of expanded graphite, natural flake graphite and ball-type graphite is 90-120 mesh；The dacron polyester slicing characteristics viscosity 0.55-
0.60dl/g, content of carboxyl end group 16-16.5mol/t, diethylene glycol content 8.3-85%, 245 DEG C of fusing point.
6. a kind of preparation method of graphene-terylene composite master batch according to claim 2, it is characterised in that：The life
Object protein powder is the one or more of wool protein powder, natural silk protein powder body.
7. a kind of side preparing graphene-terylene composite fibre using graphene described in claim 1-terylene composite master batch
Method, it is characterised in that：The method includes：The graphene of preparation-terylene composite master batch is sent into feeding chamber, passes through Screw Extrusion
Machine enters manifold and carries out spinning, then passes through annealing device, and cross air blasting is cooled and shaped, oils, through two pairs of rollers one, two pairs of rollers two, right
Roller three stretches and graphene-terylene composite fibre is made in last winding；The temperature of the manifold is 260-270 DEG C；It is described slow
The temperature of device for cooling is 245-255 DEG C；The temperature of the cross air blowing device is 35-40 DEG C, humidity 55-60%, wind speed are
0.1-0.3m/s。
8. the method for graphene according to claim 7-terylene composite fibre, it is characterised in that：Described oil uses oil tanker
Rotating speed be 25-30r/min；The two pairs of rollers one, two pairs of rollers two, the temperature of two pairs of rollers three are respectively 70-85 DEG C, 95-100 DEG C, 125-
135℃。
9. the method for graphene according to claim 7-terylene composite fibre, it is characterised in that：In the cooling and shaping
Later, further include dissolving step before oiling；It is initially positioned in protein enzyme solution and carries out enzymatic treatment；In the protein enzyme solution,
The enzymatic treatment temperature is 45-65 DEG C, and enzyme processing time processing is 10-30min.
10. the method for graphene according to claim 8-terylene composite fibre, it is characterised in that：The dissolving step is also
Including：By the graphene polyester fiber tow after enzymatic treatment, immerses in the mixed liquor of sodium hydrogensulfite, guanidine hydrochloride, TCEP and handle
30-50min；The temperature of the mixed liquor is 50-85 DEG C, a concentration of 150-185g/L of the mixed liquor sulfite hydrogen sodium,
A concentration of 160-200g/L of guanidine hydrochloride in the mixed liquor；A concentration of 30-60g/L of the TCEP.
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| CN109796753A (en) * | 2019-01-24 | 2019-05-24 | 广州大学 | A kind of antistatic antibacterial fabric master batch and preparation method thereof |
| CN110406213A (en) * | 2019-07-18 | 2019-11-05 | 柯林(福建)服饰有限公司 | Antistatic, antibacterial, far infrared, the eiderdown shell fabric production method of absorbing fast-drying |
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| CN111155199A (en) * | 2020-01-10 | 2020-05-15 | 特烯（厦门）科技有限公司 | Preparation method of graphene composite fiber |
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| CN113871084A (en) * | 2021-05-23 | 2021-12-31 | 张志明 | Special woven data line for flame-retardant fibers |
| CN113871084B (en) * | 2021-05-23 | 2024-04-09 | 张志明 | Special braided data line for flame-retardant fiber |
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