CN107460559A - A kind of preparation method of graphene polyester fiber - Google Patents

A kind of preparation method of graphene polyester fiber Download PDF

Info

Publication number
CN107460559A
CN107460559A CN201710791387.0A CN201710791387A CN107460559A CN 107460559 A CN107460559 A CN 107460559A CN 201710791387 A CN201710791387 A CN 201710791387A CN 107460559 A CN107460559 A CN 107460559A
Authority
CN
China
Prior art keywords
graphene
preparation
polyester fiber
esterification
terylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710791387.0A
Other languages
Chinese (zh)
Inventor
郑小华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuzhou Jinan District Chi Technology Enterprise Management Consulting Co Ltd
Original Assignee
Fuzhou Jinan District Chi Technology Enterprise Management Consulting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuzhou Jinan District Chi Technology Enterprise Management Consulting Co Ltd filed Critical Fuzhou Jinan District Chi Technology Enterprise Management Consulting Co Ltd
Priority to CN201710791387.0A priority Critical patent/CN107460559A/en
Publication of CN107460559A publication Critical patent/CN107460559A/en
Pending legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent 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
    • D01F6/92Monocomponent 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/18Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181Acids containing aromatic rings
    • C08G63/183Terephthalic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/82Preparation processes characterised by the catalyst used
    • C08G63/85Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86Germanium, antimony, or compounds thereof
    • C08G63/866Antimony or compounds thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention discloses a kind of preparation method of graphene polyester fiber, belong to textile fabric field, including charging technology, esterification technique, polycondensating process and melt-spinning technology, in the charging technology, terephthalic acid (TPA), ethylene glycol are pressed 1:The weight ratio of (1~2) is put into reactor, while adds catalyst and graphene.The beneficial effects of the invention are as follows:During the mixing of graphene and terylene is advanceed into terylene chips preparation, graphene is added when terephthalic acid (TPA) and ethylene glycol mix, not only terylene can be caused to be sufficiently mixed under molecular cell state with graphene, improve the mixed effect of terylene and graphene, so as to improve graphene polyester fiber character uniformity and fracture strength, and terylene chips realize the mixing of terylene and graphene when preparing and completing, and shorten production technology, reduce production cost.

Description

A kind of preparation method of graphene polyester fiber
Technical field
The present invention relates to fiber art, more particularly to a kind of preparation method of graphene polyester fiber.
Background technology
Graphene is the two-dimensional sheet nano material being made up of single layer of carbon atom, is carbon atom with sp2Hydridization bonds together to form , the flat film with hexagonal honeycomb lattice structure.With superior light, electrical, thermal and mechanical properties, numerous grind is caused The interest for the person of studying carefully, shoot up as the study hotspot of material and theoretical research field, only just achieve between several years and much rouse oneself The progress of the popular feeling.Graphene is another star's carbon nanomaterial being born after CNT.It possesses the theory of superelevation Specific surface area (2630m2/ g), high intrinsic mobility (200000cm2/ V/s), high Young's modulus (~1.0T Pa) and theoretical conductance Rate, and the features such as high transmission rate (~5000W/m/K) and electrical conductivity, in energy stores, transparency electrode etc. has greatly Application potential.So far, graphene oneself through as two-dimension nano materials representative promote nano composite material, sensor, The progress and innovation in the fields such as the energy, catalysis, electronics and optics.
Terylene is an important kind in synthetic fibers, is the trade name of China's polyester fiber.It is to benzene two with essence Formic acid or dimethyl terephthalate (DMT) and ethylene glycol be raw material through esterification or ester exchange with it is into fine high poly- prepared by polycondensation reaction Thing --- polyethylene terephthalate (PET), through fiber made of spinning and post processing.Terylene has many uses, largely For manufacturing clothing fabric and industrial product.Terylene has extremely excellent setting performance.Spun polyester thread or fabric are after setting Generation it is flat very, fluffy form or rivel etc., in use through repeatedly washing, remain to prolonged constant.
The production of traditional high tenacity polyester filament needs to first pass through polyester slice thickening and then carries out PET production, needed for this method The equipment wanted is numerous and diverse, expensive, complex manufacturing, considerably increases production cost.At present, arrived by adding Nano filling It is a kind of simple and easy, cost-effective preparation method that high performance PET fiber is prepared in dacron polyester matrix.Publication No. CN103756265A application for a patent for invention discloses a kind of PET composite material containing attapulgite, recessed by adding modification Convex rod soil so that obtained PET composite material good mechanical property, easily processed into type, compatibility is good.But the deficiency of this method It is difficult that attapulgite is peeled off completely and evenly spread in PET matrix that part, which is, and the performance of PET composite material uses with follow-up It is very restricted.
Publication No. CN104278350A application for a patent for invention discloses that a kind of anti-electrostatic nano titanium dioxide is compound to be washed For synthetic fibre monofilament using PET sections as base material, the nanoscale antistatic additive titanium dioxide for then adding configuration in the substrate prepares Masterbatch, Extrude from spin duct spout with polyester slice mixed melting, then solidified by coagulator again, drawing rollers carry out drawing-off, winding Anti-electrostatic nano titanium dioxide composite terylene monofilament product is obtained, this method efficiency is low, is not suitable for mass producing, and prepare Polyester monofilament low intensity, practicality is restricted.
The above-mentioned method for preparing terylene nanometer composite fibre focuses mostly in basic research and lab scale exploratory stage, nano combined The overall performance of fiber is not high, does not possess the prospect and actual application value of industrialized production.
The content of the invention
For overcome in the prior art product graphene polyester fiber production existing for equipment it is numerous and diverse, it is expensive, production work The problems such as skill is complicated, cost is high, the invention provides a kind of preparation method of graphene polyester fiber, including charging technology, ester Chemical industry skill, polycondensating process and melt-spinning technology, in the charging technology, terephthalic acid (TPA), ethylene glycol are pressed 1:(1~2) Weight ratio is put into reactor, while adds catalyst and graphene.
During the mixing of graphene and terylene is advanceed into terylene chips preparation, mixed in terephthalic acid (TPA) and ethylene glycol Graphene is added during conjunction, not only terylene can be caused to be sufficiently mixed under molecular cell state with graphene, improve terylene With the mixed effect of graphene, so as to improve graphene polyester fiber character uniformity and fracture strength, and terylene chips The mixing of terylene and graphene is realized when preparing and completing, production technology is shortened, reduces production cost.
Further, in the charging technology, the percentage by weight for adding the catalyst is 0.01~0.05wt%.
Further, in the charging technology, the percentage by weight for adding the graphene is 0.001~0.5wt%.
Using the graphene of optimization design and the content of catalyst so that graphene is distributed in polyester fiber inner homogeneous, So that graphene polyester fiber can not only fully demonstrate the characteristics such as antistatic grapheme material, antibacterial, radioresistance, but also can be with The influence to polyester fiber mechanical property itself is reduced, has widened the use range of product significantly.
Further, the charging technology whole process is carried out under nitrogen protection, set nitrogen pressure as 0.1~ 0.5MPa, mixing speed are 50~100r/min.
Further, in the esterification technique, esterification temperature is 200~300 DEG C, after esterification starts, treats that the amount of steaming of water reaches To the 85~95% of theoretical value, pressure release to normal pressure, esterification is completed.
Further, in the polycondensating process, condensation temperature is 250~300 DEG C, and the polycondensation time is 100~300min, polycondensation After end, discharge simultaneously pelletizing.
Further, the catalyst uses antimony-based catalyst.
Further, the catalyst is that three oxidations two are terraced, antimony acetate, the one or more in antimony glycol.
Catalyst is adopted using antimony, specially treated is carried out to graphene particles surface so that graphene particles and terylene particle The combination on surface is even closer, and the distribution inside polyester fiber is more uniform, or even has one to the intensity of polyester fiber in itself Fixed booster action.
Further, the graphene can be graphene oxide, modified graphene, the reduction-oxidation graphite of high-temperature heat expansion Redox graphene, electrochemical stripping graphene, electrochemical stripping graphene, the machine of modification obtained by alkene, low temperature thermal expansion Tool ball milling peels off graphene, three-roll grinder tool peels off graphene, CVD growth graphene, CO 2 supercritical expand and peeled off It is prepared by graphene, the graphene oxide of chemical oxidation stripping, the graphene of Hummers methods preparation, Modified Hummers methods Graphene in one or more.
Further, in the polycondensating process, after fire retardant and terminal hydroxy group siloxanes are mixed evenly, it is added drop-wise to anti- Answer in kettle, the mixed proportion of the fire retardant and terminal hydroxy group siloxanes is 1:(0.1~0.5).
Further, the fire retardant is 2- carboxyethyl phenyl hypophosphorous acid.
Further, temperature is 120 DEG C when the fire retardant mixes with the terminal hydroxy group siloxanes, mixing time 1h.
Further, the fire retardant is blended in N with the terminal hydroxy group siloxanes2Carried out under environmental protection.
Further, in the melt-spinning technology, it is added in high speed mixer, is mixed as raw material using above-mentioned master batch Spinning manifold is squeezed into through extruder after uniformly, then graphene polyester fiber is made by drawing process.
Further, the spinning speed control of the spinning manifold is controlled 250 in 1100~1200m/min, spinning temperature ~260 DEG C.
Further, the drawing process includes drawing-off and batched, and drawing-off uses oil bath drawing-off and steam drafting twice drawing-off Technique, at 1.5~2 times, drawing temperature is controlled at 70~80 DEG C for drafting multiple control, and the oil bath that oil bath drawing-off uses is formulated as 20 ~30 parts by weight tow smooth agents, 30~40 parts by weight softening agents, 10~18 parts by weight antistatic additive, 5~8 part by weight of hydrophilic Agent, the crosslinking agent of 3~5 parts by weight, the water of 1300 parts by weight;The drafting multiple of steam drafting is 1.05~1.15, temperature 130 ~150 DEG C.
Further, the extruder is provided with six temperature provinces, and the temperature of each temperature province is different, is respectively set to 265 DEG C, 286 DEG C, 274 DEG C, 268 DEG C, 280 DEG C, 269 DEG C, drop temperature is arranged to 275 DEG C;The spinning manifold unloading position Place is provided with measuring pump, and the rotating speed of measuring pump is 35r/min.
Compared with prior art, the beneficial effects of the invention are as follows:
(1) during the mixing of graphene and terylene being advanceed into terylene chips preparation, in terephthalic acid (TPA) and second two Graphene is added when alcohol mixes, not only terylene can be caused to be sufficiently mixed under molecular cell state with graphene, improved The mixed effect of terylene and graphene, so as to improve graphene polyester fiber character uniformity and fracture strength, and terylene Cut into slices and the mixing of terylene and graphene is realized when preparing and completing, shorten production technology, reduce production cost;
(2) using the graphene of optimization design and the content of catalyst so that graphene is in polyester fiber inner homogeneous point Cloth so that graphene polyester fiber can not only fully demonstrate the characteristics such as antistatic grapheme material, antibacterial, radioresistance, but also The influence to polyester fiber mechanical property itself can be reduced, has widened the use range of product significantly;
(3) antimony-based catalyst is used, specially treated is carried out to graphene particles surface so that graphene particles and terylene The combination on grain surface is even closer, and the distribution inside polyester fiber is more uniform, or even has to the intensity of polyester fiber in itself Certain booster action.
Embodiment
With reference to embodiments, the present invention will be described in further detail.It is it should be appreciated that described herein specific real Example is applied only to explain the present invention, is not intended to limit the present invention.
Embodiment one:
A kind of preparation method of graphene polyester fiber is present embodiments provided, its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1 weight ratio is put into reactor, while adds 0.03wt% catalysis The graphene of agent antimony glycol and 0.001wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.3MPa, Mixing speed is 70r/min, and esterification temperature is 240 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 85% of theoretical value, lets out Normal pressure is depressed into, esterification terminates;Condensation temperature is set as 250 DEG C, the polycondensation time is 150min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Embodiment two:
A kind of preparation method of graphene polyester fiber is present embodiments provided, its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.2 weight ratios are put into reactor, while add urging for 0.04wt% The graphene of agent antimony glycol and 0.01wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.4MPa, Mixing speed is 80r/min, and esterification temperature is 260 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 90% of theoretical value, lets out Normal pressure is depressed into, esterification terminates;Condensation temperature is set as 260 DEG C, the polycondensation time is 180min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Embodiment three:
A kind of preparation method of graphene polyester fiber is present embodiments provided, its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.5 weight ratios are put into reactor, while add urging for 0.03wt% The graphene of agent second antimony acetate and 0.1wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.2MPa, Mixing speed is 60r/min, and esterification temperature is 280 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 90% of theoretical value, lets out Normal pressure is depressed into, esterification terminates;Condensation temperature is set as 270 DEG C, the polycondensation time is 200min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk;Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min;A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Example IV:
A kind of preparation method of graphene polyester fiber is present embodiments provided, its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.8 weight ratios are put into reactor, while add urging for 0.05wt% The graphene of agent antimony glycol and 0.3wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.3MPa, Mixing speed is 90r/min, and esterification temperature is 270 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 95% of theoretical value, lets out Normal pressure is depressed into, esterification terminates;Condensation temperature is set as 280 DEG C, the polycondensation time is 250min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Embodiment five:
A kind of preparation method of graphene polyester fiber is present embodiments provided, its preparation process is as follows:
(1) preparation of graphene-dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:2 weight ratios are put into reactor, while add 0.03wt% catalysis The graphene of the ladder of the oxidation of agent three two and 0.5wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.4MPa, Mixing speed is 70r/min, and esterification temperature is 250 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 90% of theoretical value, lets out Normal pressure is depressed into, esterification terminates;Condensation temperature is set as 260 DEG C, the polycondensation time is 300min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min;A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example one:
This comparative example provides a kind of preparation method of polyester fiber, and its preparation process is as follows:
(1) preparation of dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.2 weight ratios are put into reactor, and whole process is under nitrogen protection Carry out, set nitrogen pressure as 0.4MPa, mixing speed 80r/min, esterification temperature is 260 DEG C, after esterification starts, treats water The amount of steaming reaches the 90% of theoretical value, pressure release to normal pressure, and esterification terminates.Condensation temperature is set as 260 DEG C, the polycondensation time is 180min, after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example two:
This comparative example provides a kind of preparation method of graphene polyester fiber, and its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:0.8 weight ratio is put into reactor, while adds urging for 0.03wt% The graphene of agent antimony glycol and 0.001wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.3MPa, mixing speed 70r/min, esterification temperature are 240 DEG C, after esterification starts, treat that the amount of steaming of water reaches theoretical value 85%, pressure release to normal pressure, esterification terminates.Condensation temperature is set as 250 DEG C, the polycondensation time is 150min, after polycondensation terminates, discharging And pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example three:
This comparative example provides a kind of preparation method of graphene polyester fiber, and its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:2.5 weight ratios are put into reactor, while add urging for 0.03wt% The ladder of the oxidation of agent three two and 0.5wt% graphenes, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.4MPa, mixing speed 70r/min, esterification temperature are 250 DEG C, after esterification starts, treat that the amount of steaming of water reaches theoretical value 90%, pressure release to normal pressure, esterification terminates.Condensation temperature is set as 260 DEG C, the polycondensation time is 300min, after polycondensation terminates, discharging And pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example four:
This comparative example provides a kind of preparation method of graphene polyester fiber, and its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.2 weight ratios are put into reactor, while add 0.01wt% stone Black alkene, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.4MPa, mixing speed 80r/min, esterification temperature For 260 DEG C, after esterification starts, treat that the amount of steaming of water reaches the 90% of theoretical value, pressure release to normal pressure, esterification terminates.Set polycondensation Temperature is 260 DEG C, and the polycondensation time is 180min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example five:
This comparative example provides a kind of preparation method of graphene polyester fiber, and its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.2 weight ratios are put into reactor, while add urging for 0.005wt% The graphene of agent antimony glycol and 0.01wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.4MPa, Mixing speed is 80r/min, and esterification temperature is 260 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 90% of theoretical value, lets out Normal pressure is depressed into, esterification terminates.Condensation temperature is set as 260 DEG C, the polycondensation time is 180min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example six:
This comparative example provides a kind of preparation method of graphene polyester fiber, and its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.2 weight ratios are put into reactor, while add urging for 0.06wt% The graphene of agent antimony glycol and 0.01wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.4MPa, Mixing speed is 80r/min, and esterification temperature is 260 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 90% of theoretical value, lets out Normal pressure is depressed into, esterification terminates.Condensation temperature is set as 260 DEG C, the polycondensation time is 180min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example seven:
This comparative example provides a kind of preparation method of graphene polyester fiber, and its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.5 weight ratios are put into reactor, while add urging for 0.03wt% The graphene of agent second antimony acetate and 0.0005wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.2MPa, mixing speed 60r/min, esterification temperature are 280 DEG C, after esterification starts, treat that the amount of steaming of water reaches theoretical value 90%, pressure release to normal pressure, esterification terminates.Condensation temperature is set as 270 DEG C, the polycondensation time is 200min, after polycondensation terminates, discharging And pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example eight:
This comparative example provides a kind of preparation method of graphene polyester fiber, and its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.5 weight ratios are put into reactor, while add urging for 0.03wt% The graphene of agent second antimony acetate and 0.6wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.2MPa, Mixing speed is 60r/min, and esterification temperature is 280 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 90% of theoretical value, lets out Normal pressure is depressed into, esterification terminates.Condensation temperature is set as 270 DEG C, the polycondensation time is 200min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
Comparative example nine:
This comparative example provides a kind of preparation method of graphene polyester fiber, and its preparation process is as follows:
(1) preparation of graphene dacron master grain
Terephthalic acid (TPA) and ethylene glycol are pressed 1:1.5 weight ratios are put into reactor, while add urging for 0.03wt% The graphene of agent second antimony acetate and 0.2wt%, whole process are carried out under nitrogen protection, set nitrogen pressure as 0.2MPa, Mixing speed is 60r/min, and esterification temperature is 280 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 80% of theoretical value, lets out Normal pressure is depressed into, esterification terminates.Condensation temperature is set as 270 DEG C, the polycondensation time is 200min, and after polycondensation terminates, discharge simultaneously pelletizing.
(2) melt spinning
1g polymer beads are weighed every time, are added in spinning equipment, 270 DEG C, after being completely melt are warming up to, by applying Plus-pressure is extruded, and under outside pulled out condition, melt stream thins down to silk.Then filament is allowed to add by hot-stretch device The temperature of hot cylinder is set as 110 DEG C, and in the presence of draw roll, fiber is stretched 4 times, is finally wound in take-up roll, winding Speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, spinning equipment will be cleaned up, prevent dirt Dye.
The graphene that specification is 0.17tex × 51mm is made in the fiber that above-mentioned five groups of embodiments, nine groups of comparative examples obtain Polyester staple fiber, and fracture strength, fault number and conducting performance test are carried out to it, it is as a result as follows:
The graphene polyester fiber embodiment comparative example general performance test data of table 1
The fiber that above-mentioned five groups of embodiments, nine groups of comparative examples obtain is made the graphene that specification is 0.17tex × 51mm and washed Synthetic fibre chopped fiber, and bacteriostasis property (staphylococcus aureus, Escherichia coli and Candida albicans) test is carried out to it, as a result such as Under:
The graphene polyester fiber embodiment comparative example anti-microbial property test data (%) of table 2
As can be seen that the graphene polyester fiber that embodiment one to five obtains has good fracture strong from table 1 and 2 Power, electric conductivity and bacteriostasis property, and the fault situation of fiber in itself is also less, high yield rate, its electric conductivity and biocidal property Conventional polyester fiber can be substantially better than.
Comparative example one is conventional polyester fiber, although performance is excellent in terms of its mechanical property, electric conductivity and antibacterial Obvious deficiency in terms of the features such as performance be present;The mixing ratio of terephthalic acid (TPA) and ethylene glycol in comparative example two and comparative example three Example is unreasonable to cause its ultimate strength and fault number is intended to the fiber that is obtained in significantly more than embodiment, and wastage of material be present The problem of;It is no in comparative example four to use catalyst so that graphenic surface is untreated to be combined with terylene, is caused The combination defective tightness of graphene and terylene and uniformly, influence the electric conductivity and ultimate strength of fiber, and graphene is using During can come off or offset in fibrous inside;The catalyst content added in comparative example five is very few, and its principle is the same as contrast Example four;Excessive catalyst is added in comparative example six, is destroyed graphenic surface characteristic, obtained fiber has intensity Difference, not the problems such as wash resistant, the feature such as conductive, antibacterial of graphene in itself can not also play one's part to the full;In comparative example seven The graphene amount of addition is very few, and its electric conductivity and bacteriostasis property are compared with being poor in embodiment;The graphite added in comparative example eight Alkene amount is excessive, and its ultimate strength performance is substantially deteriorated, and fibre defect number also increases;The amount of the steaming mistake of the reclaimed water of comparative example nine Few, reactor esterification technique does not complete fully also, and it is poor compared with the fiber in embodiment to show as ultimate strength performance.
The preferred embodiments of the present invention have shown and described in described above, as previously described, it should be understood that the present invention is not office Be limited to form disclosed herein, be not to be taken as the exclusion to other embodiment, and available for various other combinations, modification and Environment, and can be changed in the scope of the invention is set forth herein by the technology or knowledge of above-mentioned teaching or association area It is dynamic., then all should be appended by the present invention and the change and change that those skilled in the art are carried out do not depart from the spirit and scope of the present invention In scope of the claims.

Claims (9)

1. a kind of preparation method of graphene polyester fiber, it is characterised in that including charging technology, esterification technique, polycondensating process And melt-spinning technology, in the charging technology, terephthalic acid (TPA), ethylene glycol are pressed 1:The weight ratio of (1~2) puts into reaction In kettle, while add catalyst and graphene.
A kind of 2. preparation method of graphene polyester fiber according to claim 1, it is characterised in that the charging technology In, the percentage by weight for adding the catalyst is 0.01~0.05wt%.
A kind of 3. preparation method of graphene polyester fiber according to claim 2, it is characterised in that the charging technology In, the percentage by weight for adding the graphene is 0.001~0.5wt%.
A kind of 4. preparation method of graphene polyester fiber according to claim 1, it is characterised in that the charging technology Whole process is carried out under nitrogen protection, sets nitrogen pressure as 0.1~0.5MPa, and mixing speed is 50~100r/min.
A kind of 5. preparation method of graphene polyester fiber according to claim 1, it is characterised in that the esterification technique In, esterification temperature is 200~300 DEG C, after esterification starts, treats that the amount of steaming of water reaches the 85~95% of theoretical value, and pressure release is to normal Pressure, complete esterification.
A kind of 6. preparation method of graphene polyester fiber according to claim 1, it is characterised in that the polycondensating process In, condensation temperature is 250~300 DEG C, and the polycondensation time is 100~300min, and after polycondensation terminates, discharge simultaneously pelletizing.
7. the preparation method of a kind of graphene polyester fiber according to claim 1, it is characterised in that the catalyst is adopted Use antimony-based catalyst.
8. the preparation method of a kind of graphene polyester fiber according to claim 7, it is characterised in that the catalyst is Three oxidations two are terraced, antimony acetate, the one or more in antimony glycol.
9. the preparation method of a kind of graphene polyester fiber according to claim 1, it is characterised in that the graphene can For the oxygen reduction fossil obtained by graphene oxide, modified graphene, the redox graphene of high-temperature heat expansion, low temperature thermal expansion Black alkene, electrochemical stripping graphene, the electrochemical stripping graphene of modification, mechanical ball mill peel off graphene, three-roll grinder tool Peel off graphene, CVD growth graphene, the graphite oxide that graphene is peeled off in CO 2 supercritical expansion, chemical oxidation is peeled off One or more in graphene prepared by alkene, the graphene of Hummers methods preparation, Modified Hummers methods.
CN201710791387.0A 2017-09-05 2017-09-05 A kind of preparation method of graphene polyester fiber Pending CN107460559A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710791387.0A CN107460559A (en) 2017-09-05 2017-09-05 A kind of preparation method of graphene polyester fiber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710791387.0A CN107460559A (en) 2017-09-05 2017-09-05 A kind of preparation method of graphene polyester fiber

Publications (1)

Publication Number Publication Date
CN107460559A true CN107460559A (en) 2017-12-12

Family

ID=60551080

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710791387.0A Pending CN107460559A (en) 2017-09-05 2017-09-05 A kind of preparation method of graphene polyester fiber

Country Status (1)

Country Link
CN (1) CN107460559A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109620553A (en) * 2018-11-11 2019-04-16 南通强生石墨烯科技有限公司 A kind of preparation method of Graphene antibiosis amenities chip
CN111171297A (en) * 2020-02-12 2020-05-19 东华大学 Antistatic flame-retardant resin and preparation method and application thereof
CN111676541A (en) * 2020-06-10 2020-09-18 浙江恒澜科技有限公司 Preparation method of antistatic low-temperature far infrared polyester fiber
CN113322543A (en) * 2021-06-22 2021-08-31 浙江正凯化纤有限公司 Ice-cool composite polyester fiber and preparation method thereof
CN113774510A (en) * 2021-08-26 2021-12-10 浙江恒澜科技有限公司 Preparation method of expanded graphite polyester flame-retardant fabric
CN114134709A (en) * 2021-12-09 2022-03-04 南通强生新材料科技股份有限公司 Protective gloves for electric welding and preparation method thereof
CN114716732A (en) * 2022-03-31 2022-07-08 浙江氧倍加新材料科技有限公司 Preparation method of graphene surface modified micron-sized tourmaline negative ion release functional powder

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109620553A (en) * 2018-11-11 2019-04-16 南通强生石墨烯科技有限公司 A kind of preparation method of Graphene antibiosis amenities chip
CN111171297A (en) * 2020-02-12 2020-05-19 东华大学 Antistatic flame-retardant resin and preparation method and application thereof
CN111171297B (en) * 2020-02-12 2021-09-10 东华大学 Antistatic flame-retardant resin and preparation method and application thereof
CN111676541B (en) * 2020-06-10 2022-10-11 浙江恒逸石化研究院有限公司 Preparation method of antistatic low-temperature far-infrared polyester fiber
CN111676541A (en) * 2020-06-10 2020-09-18 浙江恒澜科技有限公司 Preparation method of antistatic low-temperature far infrared polyester fiber
CN113322543A (en) * 2021-06-22 2021-08-31 浙江正凯化纤有限公司 Ice-cool composite polyester fiber and preparation method thereof
CN113322543B (en) * 2021-06-22 2022-04-15 浙江正凯化纤有限公司 Preparation method of cool composite polyester fiber
CN113774510A (en) * 2021-08-26 2021-12-10 浙江恒澜科技有限公司 Preparation method of expanded graphite polyester flame-retardant fabric
CN113774510B (en) * 2021-08-26 2023-05-12 浙江恒逸石化研究院有限公司 Preparation method of expanded graphite polyester flame-retardant fabric
CN114134709A (en) * 2021-12-09 2022-03-04 南通强生新材料科技股份有限公司 Protective gloves for electric welding and preparation method thereof
WO2023103779A1 (en) * 2021-12-09 2023-06-15 南通强生新材料科技股份有限公司 Protective glove for electric welding, and manufacturing method therefor
CN114716732A (en) * 2022-03-31 2022-07-08 浙江氧倍加新材料科技有限公司 Preparation method of graphene surface modified micron-sized tourmaline negative ion release functional powder
CN114716732B (en) * 2022-03-31 2024-08-16 浙江氧倍加新材料科技有限公司 Preparation method of graphene surface modified micron-sized tourmaline negative ion release functional powder

Similar Documents

Publication Publication Date Title
CN107460559A (en) A kind of preparation method of graphene polyester fiber
CN107366036B (en) Modified spandex fibre of a kind of graphene and preparation method thereof, application
CN105200547B (en) A kind of preparation method of graphene-terylene nanometer composite fibre
CN108193318B (en) Graphene modified polylactic acid fiber and preparation method thereof
EP3626758A1 (en) Graphene composite material and preparation method therefor
CN105002595B (en) Polymer composite function fibers containing partial graphene, and preparation method thereof
CN106012093B (en) A kind of preparation method of composite conducting fiber
CN106367836B (en) A kind of manufacturing method of hollow biomass graphene polyester fiber
CN105525384B (en) A kind of purposes of modified hollow cotton
CN105603568B (en) A kind of modified hollow cotton and preparation method thereof
CN105586658A (en) Modified chinlon fiber, preparation method and application
KR101965990B1 (en) Composite polyester material, composite polyester fiber, processes for preparing the same and uses thereof
CN105063796A (en) High-molecular composite conductive fiber and preparation method thereof
EP3378978A1 (en) Modified fiber and preparation method therefor
CN106995946A (en) The preparation method of graphene spandex composite fibre
KR102596719B1 (en) Composition for carbon nanotube nanocomposite conductive fiber and method for manufacturing the same
CN109537088B (en) Method for manufacturing different-shrinkage polyester low-stretch yarns
CN102251308A (en) Method for preparing colored light-extinction polyester filament
CN107313128A (en) A kind of PBT fiber fabrication process
CN106120013B (en) A kind of static resistant polyamide fiber applied to underwear
CN114351279A (en) Preparation method of aerogel-containing special-shaped polyester staple fibers
CN111560662B (en) Preparation method of modified graphene PTT antistatic composite elastic fiber
CN107523896B (en) Graphene-polyester conductive polyester filament and preparation method and application thereof
CN110195266B (en) Production method of functional fiber
CN107663665B (en) A kind of preparation method of the special bright floss silk polyester drafting silk of high-strength low-shrinkage

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20171212

WD01 Invention patent application deemed withdrawn after publication