CN107460559A - A kind of preparation method of graphene polyester fiber - Google Patents
A kind of preparation method of graphene polyester fiber Download PDFInfo
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- 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
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- 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
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.
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