CN110257948B - Black polyester industrial yarn and preparation method thereof - Google Patents
Black polyester industrial yarn and preparation method thereof Download PDFInfo
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- CN110257948B CN110257948B CN201910475941.3A CN201910475941A CN110257948B CN 110257948 B CN110257948 B CN 110257948B CN 201910475941 A CN201910475941 A CN 201910475941A CN 110257948 B CN110257948 B CN 110257948B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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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- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention relates to a black polyester industrial yarn and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out melt spinning on a high-viscosity polyester melt containing a carbon material to prepare a black polyester industrial yarn, wherein the intrinsic viscosity of the high-viscosity polyester is more than or equal to 0.85 dL/g; during melt spinning, the shear rate at the spinneret orifice is 1200-1500 s ‑1 The temperature of the post heater is 310-330 ℃, the cooling air temperature is 20-35 ℃, and the cooling air speed is 0.5-0.9 m/s; compared with the carbon material before being added into the high-viscosity polyester melt, the carbon material in the prepared black polyester industrial yarn has the statistical average size difference of less than or equal to 10nm and the maximum size difference of less than 50 nm; the difference between the content of the carbon material on the surface layer of the black polyester industrial yarn and the content of the carbon material in the center of the black polyester industrial yarn is less than 0.5 wt%. The method is simple and easy to popularize, and effectively improves the mechanical property, color fastness and dimensional stability of the black polyester industrial yarn.
Description
Technical Field
The invention belongs to the technical field of industrial yarns, and relates to a black polyester industrial yarn and a preparation method thereof.
Background
The polyester industrial yarn has the advantages of high strength, good dimensional stability and the like, and is widely applied to the industrial fields of tire cords, airbags, safety belts, filter cloth, lamp house cloth, covering cloth, ropes, geogrids and the like. All of the polyester industrial yarns have such excellent properties, mainly due to the high molecular weight of the polyester used and the high-crystalline, high-orientation ordered structure generated under the specific spinning process conditions, however, the high-order structure brings difficulties for dyeing the polyester industrial yarns and products thereof, and shows that the dyeing rate is low, deep color dyeing is difficult, the color fastness is low, even the polyester industrial yarns are easy to cause strong loss in the dyeing process, and in addition, the dyeing needs to be carried out at high temperature and high pressure, and the defects of high energy consumption, high cost, large discharge capacity and the like in the dyeing process greatly limit the development of the polyester industrial yarns colored products.
The method for preparing the polyester industrial yarn by adopting the stock solution coloring method can effectively overcome the problems, the stock solution coloring method is one of methods for coloring the polyester fiber, and means that a melt is fully and uniformly mixed with a coloring substance before entering a spinning manifold, and the colored melt is spun to directly produce the colored polyester fiber; the method is simpler and more uniform by adding coloring substances into the melt before spinning, the obtained product is more uniformly colored, the dyeing processing in an aqueous medium after the traditional grey cloth pretreatment is omitted, no waste water is generated, and the method is an anhydrous dyeing process.
The color master batch addition method is one of the most widely applied technical means of stock solution coloring at present, and is generally applied to conventional polyester fibers, however, the prepared polyester industrial yarn has the problems of poor mechanical property, low color fastness, poor dimensional stability and the like, and the main reasons are as follows: (1) the uniform dispersion and poor distribution of the pigment or dye in the high viscosity polyester; (2) pigments or dyes affect the thermal conductivity of the high viscosity polyester melt.
For this reason, developers have proposed some technical solutions to the above problems: 1) polyester copolymerization modification method: patents CN201610784610.4, CN201711342802.0 and CN201511018195.3 introduce dihydric alcohol containing branched chain into polyester molecular chain by copolymerization method to reduce melt viscosity, and prepare black industrial yarn by changing arrangement of spinneret orifices or using new oil solution or ultraviolet irradiation, but the above patents do not disclose dispersion and distribution of dye or pigment in industrial yarn, nor disclose related color fastness index, and the method is relatively complex, and is not easy to scale production; 2) mechanical mixing method: the patent CN201510297066.6 discloses a production method of colored polyester industrial yarns, which adds color oil and auxiliary agents into PET melt through an injection port on a melt pipeline, then uniformly mixes the color oil and the PET melt through a plurality of novel static mixers in the melt pipeline, and redistributes the mixed PET melt to a spinning manifold and each spinning position, and the method has no essential difference with the production of the conventional colored polyester, and does not provide a new method for adding high-viscosity polyester, and does not disclose the dispersion and distribution condition of dye or pigment in the industrial yarns, nor disclose related color fastness indexes; patent CN200710067735.6 discloses a production process of colored and functional polyester industrial yarns, which comprises directly injecting a master batch melt into a spinning metering pump in a spinning box through a melt pump, uniformly mixing the master batch melt with a conventional high-viscosity slice melt prepared in a main screw in a static mixer in front of the spinning metering pump, and then conveying the mixed melt to a spinning assembly for spinning, wherein the method reduces the high-temperature retention time of the master batch melt and reduces the degradation of the master batch melt, but the patent does not provide a solution for realizing the dispersion uniformity of pigment or dye in high-viscosity polyester in a short time, does not disclose the dispersion and distribution conditions of the dye or pigment in the industrial yarns, and does not disclose related color fastness indexes; 3) a composite spinning method: the patent CN201810505626.6 discloses a sheath-core colored industrial yarn and a preparation method thereof, wherein a polymer dispersed with pigment or dye is used as a core layer material, a polymer of the same kind as the core layer material is used as a sheath layer material, and melt spinning is carried out through a sheath-core composite component, which has the disadvantages of needing special composite spinning equipment, high investment cost, difficult process control and difficult large-scale popularization; 4) in-situ compounding: patent 201410709477.7 discloses a method for preparing black polyester fiber by adding carbon material in the in-situ polymerization process, which can enhance the dispersion effect to a certain extent, but the pigment or dye will pollute the whole process equipment of polymerization and spinning, and is not easy to be produced in large scale; 5) the low-viscosity master batch method comprises the following steps: at present, the commonly adopted color master batch matrix is low-viscosity polyester (PET with the viscosity of 0.40 dL/g-0.65 dL/g), even some low-melting-point components (such as butylene terephthalate and PBT) or dispersing agents are often added to improve the dispersibility of the color master batch matrix, the introduction of the low-viscosity polyester increases the polydispersity of the melt molecular weight and reduces the uniformity of the melt molecular weight, so that the mechanical property of a final product is reduced, the low-melting-point components can cause asynchronous melting, the uniform melt is influenced, and meanwhile, screw rod ring knot can be caused by advanced melting, and the stability of spinning is influenced.
However, in the production of black polyester industrial yarns, under the conditions of high spinneret orifice shearing rate and high condensing draft ratio, the phenomenon of migration of carbon particles to a surface layer is serious, a skin-core-like distribution structure with less carbon powder inside and more outside is generated, the mechanical property and the product color fastness index are directly influenced, a spinning system of the carbon particles is introduced, the spinning process is certainly different from the conventional spinning technology, the influence of the introduction of the carbon particles on the heat conductivity coefficient of a melt is most direct, the neglect of the carbon particles in the spinning forming process can aggravate the radial temperature difference of a fiber melt, a series of differences such as stress and orientation are widened, the radial crystallization difference of the fiber is finally increased, the mechanical property and the size stability are poor, and no scheme for solving the problems by adopting effective process adjustment in the spinning forming process is reported at present.
Therefore, the research on a method for solving the problems of poor mechanical property, low color fastness, poor dimensional stability and the like of the black polyester industrial yarn has very important significance.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical property, low color fastness and poor dimensional stability of the black polyester industrial yarn in the prior art, and provides the black polyester industrial yarn and the preparation method thereof. According to the invention, the black polyester industrial yarn is prepared by adopting the processes of low shearing, heating after relaxation and low wind speed and high wind temperature cooling, and the processes are mutually matched to effectively improve the dispersion uniformity of the coloring agent in the black polyester industrial yarn and reduce the influence of the coloring agent on the heat conductivity coefficient of the polyester melt, so that the black polyester industrial yarn with excellent mechanical property, high color fastness and good dimensional stability is prepared.
In order to achieve the purpose, the invention adopts the following scheme:
a preparation method of black polyester industrial yarn comprises the steps of carrying out melt spinning on high-viscosity polyester melt containing carbon materials to prepare the black polyester industrial yarn, wherein the intrinsic viscosity of the high-viscosity polyester is more than or equal to 0.85 dL/g; during melt spinning, the shear rate at the spinneret orifice is 1200-1500 s -1 The temperature of the post heater is 310-330 ℃, the cooling air temperature is 20-35 ℃, and the cooling air speed is 0.5-0.9 m/s.
The black polyester industrial yarn is prepared by adopting the processes of low shearing, heating after relaxation and low wind speed and high wind temperature cooling;
firstly, the problem of dispersion and uneven distribution of carbon materials in fibers is effectively solved by reducing the shearing rate, the low molecular weight or blended powder added in a polymer can migrate to the surface layer of the melt under the shearing action of a high molecular melt, and particularly, the phenomenon is serious under the high shearing rate of spinning, and for the condition of adding the carbon materials, the carbon materials are enriched to the surface of the fibers under the high shearing rate, so that the mechanical property of the fibers is directly influenced on one hand, and on the other hand, the carbon materials enriched on the surface can influence the fastness of the fibers, particularly the rubbing fastness;
wherein the content of the first and second substances,
is the shear rate(s) -1 ) R is the radius of the micropores (mm), n is the number of micropores, and Q is the pump supply (mm) 3 /s)；
Wherein, P 1 Indicating the pressure drop of the spinning liquid through the distributor plate(Pa)，L 1 Denotes the hole length (mm), d 1 Denotes the pore diameter (mm), η 1 Is melt viscosity (Pa · s), q 1 Represents the flow rate in mm of a single pore volume through the distributor plate 3 /s)；
From the above formula, increasing the spinneret aperture is the most reasonable method for reducing the shear rate, and the spinning pressure drop is not expected to change in the actual production, and the parameters determining the pressure drop are the melt viscosity, the aperture and the aperture length, the melt viscosity after adding the carbon material is obviously increased, the influence caused by the viscosity increase can be eliminated by reducing the spinneret aperture length and increasing the spinneret aperture, the shear rate is reduced, the uniformity of the dispersion and distribution of the carbon material in the fiber is improved, and the mechanical property and the color fastness of the fiber are further improved;
secondly, the heating process after the relaxation can ensure the viscosity and the strength of the melt after the melt exits from the spinneret plate, maintain stable nozzle drawing, in the production of industrial yarns, the post-heating aims at compensating the heat loss of the melt after the melt is discharged from the spinneret plate, preventing the sudden increase of viscosity and difficult stretching caused by the sudden drop of the temperature of the melt from influencing the production stability and the fiber quality, in the production of general industrial yarn, the post-heating temperature is 330-350 ℃, and in the production of industrial yarn added with carbon material, because the carbon material has excellent heat conductivity coefficient, after the carbon material is introduced into a melt system, the rate of heat absorption of the melt under strong heat radiation is obviously improved, in the post-heating step, the temperature of the fiber is properly reduced to relieve strong heat absorption caused by the change of the heat conductivity coefficient, and the fiber mechanical property reduction and the deteriorated spinning conditions such as broken ends, broken filaments, even plates and the like caused by the low melt viscosity and the reduced melt strength are avoided;
finally, the low-wind-speed high-wind-temperature cooling process can moderate the cooling environment, reduce the unevenness of the radial structure of the fiber, and improve the mechanical property and the dimensional stability of the fiber, and the specific mechanism is as follows:
in the process of melt spinning, polymer melt trickle flows from a spinneret plate to a condensation solidification process, and due to the difference of heat dissipation inside and outside the fiber, a temperature gradient difference exists in the radial direction of the fiber, and the formula is as follows:
wherein the content of the first and second substances,
is the radial temperature gradient, xi represents a dimensionless axial coordinate, theta represents a dimensionless temperature, h is the average surface heat transfer coefficient of the fiber, k is the melt heat conductivity coefficient, R is the distance from the center of the fiber, R is the fiber radius, T r Is the temperature at radius r, T u Is the ambient temperature, T s Is the spinning temperature;
according to the formula, the temperature gradient exists from outside to inside in the fiber during spinning, and the surface temperature is lower than the internal temperature;
when T is>T m When the temperature of the water is higher than the set temperature,
η (r) ＝(AM W ) 3.35 exp[B/(T (r) +273)]；
when T is<T m When the temperature of the water is higher than the set temperature,
η (r) ＝(AM W ) 3.35 exp[B/(T (r) +273)][a(c/c ∞ ) b ]；
wherein, T m Is the polymer melting point; eta (r) Is the melt viscosity at radius r; A. b, a and b are specific constant parameters; m W Represents a weight average molecular weight; c is the degree of crystallinity;
represents the degree of crystallinity at infinity;
from the above formula, it can be seen that for a homogeneous polymer, the melt viscosity and the temperature are in inverse proportion, and when the temperature is high, the melt viscosity is low, that is, the melt viscosity of the fiber is gradually reduced from the outside to the inside, and the surface viscosity is greater than the internal viscosity;
wherein the content of the first and second substances,
representing a spinning speed gradient;
the formula shows that the spinning speed gradient is constant, the stress and the melt viscosity are in a direct proportion relation, and the stress is gradually reduced from the surface layer to the inner layer;
wherein f is (r) For orientation, Δ n denotes the birefringence, Δ 0 Represents a characteristic birefringence, and is constant; c represents a stress optical coefficient and is a constant;
the formula shows that the orientation is in direct proportion to the stress, the orientation of the outer layer of the fiber is larger than that of the inner layer, the orientation induces crystallization, and further the inner and outer crystallization are different, so that the structural difference is caused;
the analysis shows that the radial temperature difference is closely related to the heat conductivity coefficient of the melt, when other conditions are not changed, the radial temperature gradient difference is more serious when the heat conductivity coefficient of the melt is increased, and in the production of the carbon-containing industrial yarn, because the heat conductivity coefficient of the carbon material is excellent, after the carbon material is introduced into a melt system, the heat absorption rate of the melt is obviously improved under strong heat radiation, so the radial temperature difference is increased, and the difference of the radial structure of the fiber is larger;
the cooling wind speed of the prior art is generally more than 0.9m/s, the wind temperature is generally 20 ℃, the wind speed is lower, the wind temperature is higher, the cooling environment is effectively eased, the heat conductivity coefficient of a spinning melt system added with carbon materials is increased, the cooling rate is inevitably much faster than that of a conventional melt without adding during blowing cooling, the conventional cooling process is adopted, the wind temperature is lower, the wind speed is faster, namely the blowing process aggravates the heat dissipation cooling rate of the functional melt system, the fiber has a temperature gradient along the radial direction, the surface layer is cooled too fast, the temperature difference between the inside and the outside of the fiber is increased, the stress, the orientation and the crystallization are more obviously different along the radial direction of the fiber, the wind speed of the blowing wind is reduced, the cooling wind temperature is increased, the cooling environment of the fiber is milder, the negative influence caused by the increase of the heat conductivity coefficient and the increase of the heat dissipation rate caused by the carbon materials is compensated, the unevenness of the radial structure of the fiber is reduced, and the mechanical property and the dimensional stability of the fiber are further improved.
As a preferable scheme:
the preparation method of the black polyester industrial yarn has the advantages that the first-roller speed is 600-650 m/min, the hot-roller drawing rate is 5.4-5.7 times, and the temperatures of the first roller to the fifth roller are 65-70 ℃, 95-100 ℃, 125-130 ℃, 225-235 ℃ and 135-150 ℃ respectively;
the invention adopts the low-heat roller back drawing process, after the carbon material is introduced into a polymer system, the carbon material can play a role of a crystallization nucleating agent to accelerate the crystallization rate, the crystal grain size is increased, the crystallization is too fast, the crystallinity is too high, the fiber rigidity is enhanced, the stability of the back drawing is not facilitated, the fiber strength is influenced, and the crystallization rate and the temperature of the polymer are important influence factors.
According to the preparation method of the black polyester industrial yarn, the mass fraction of the carbon material in the high-viscosity polyester melt containing the carbon material is 0.5-0.8%, wherein the lower limit of the mass fraction of the carbon material in the melt is the lower limit meeting the functional requirements, namely the mass fraction of the carbon material is only more than 0.5%, the black polyester industrial yarn can be obtained, and the upper limit is the upper limit of the strength guarantee, namely the mass fraction of the carbon material is only less than 0.8%, so that the strength of the obtained black polyester industrial yarn can meet the use requirements.
According to the preparation method of the black polyester industrial yarn, the high-viscosity polyester melt containing the carbon material is prepared by blending and melting the carbon material master batch and the polyester I, wherein the intrinsic viscosity of the polyester I is 0.85-1.05 dL/g, and the carbon material master batch mainly comprises the carbon material and the polyester II with the intrinsic viscosity of 0.50-0.85 dL/g.
According to the preparation method of the black polyester industrial yarn, the mass fraction of the carbon material in the carbon material master batch is 20-40%, and the polyester I and the polyester II are both PET.
According to the preparation method of the black polyester industrial yarn, the carbon material is more than one of carbon black, carbon nano tubes and graphene, the particle size of the carbon black is less than 20nm, the length of the carbon nano tubes is less than 3 mu m, the diameter of the carbon nano tubes is less than 50nm, the diameter of the graphene is less than 3 mu m, and the thickness of the graphene is less than 10 nm.
The invention also provides the black polyester industrial yarn prepared by the preparation method of the black polyester industrial yarn, compared with the carbon material before being added into the high-viscosity polyester melt, the difference of the statistical average size of the carbon material in the black polyester industrial yarn is less than or equal to 10m, and the difference of the maximum size is less than 50 nm; the difference between the content of the carbon material on the surface layer of the black polyester industrial yarn and the content of the carbon material in the center of the black polyester industrial yarn is less than 0.5 wt%.
As a preferable scheme:
according to the black polyester industrial yarn, the filament number of the black polyester industrial yarn is 3-10 dtex, the breaking strength is greater than 7.8cN/dtex, and the elongation at break is 12.5-15%.
According to the black polyester industrial yarn, the color fastness to washing of the black polyester industrial yarn is more than grade 4, and the color fastness to rubbing is more than grade 4.
The black polyester industrial yarn is used in the fields of automobiles, aviation safety belts, marine cables, hoisting belts or tarpaulins.
Has the advantages that:
(1) the preparation method of the black polyester industrial yarn effectively solves the problem of poor dispersion and distribution uniformity of carbon materials in polyester, and improves the mechanical property and color fastness of the black polyester industrial yarn;
(2) according to the preparation method of the black polyester industrial yarn, the influence of the addition of carbon materials on the heat conductivity coefficient of the polyester melt is effectively avoided, and the mechanical property and the dimensional stability of the black polyester industrial yarn are improved;
(3) the preparation method of the black polyester industrial yarn is simple and easy to implement and has great popularization value;
(4) the black polyester industrial yarn prepared by the invention has the advantages of excellent comprehensive performance, good mechanical property and dimensional stability and high color fastness.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of black polyester industrial yarn mainly comprises the following steps:
(1) preparation of a high-viscosity polyester melt containing carbon black: blending and melting carbon black master batches and PET with the intrinsic viscosity of 1.05dL/g to prepare a high-viscosity polyester melt containing the carbon black, wherein the carbon black master batches comprise 20% of carbon black with the average particle size of 10nm and the PET with the intrinsic viscosity of 0.50 dL/g;
(2) carrying out melt spinning on a high-viscosity polyester melt containing 0.5wt% of carbon black to prepare a black polyester industrial yarn;
the main process parameters of melt spinning are as follows: shear rate at the orifice of the spinneret was 1500s -1 The temperature of the post heater is 330 ℃, the cooling air temperature is 20 ℃, the cooling air speed is 0.9m/s, the speed of one roller is 650m/min, the drawing ratio after hot rolling is 5.7 times, and the temperatures of the one roller to the five rollers are 70 ℃, 100 ℃, 130 ℃ and 235℃ respectivelyAnd 150 ℃.
The filament number of the finally prepared black polyester industrial yarn is 3dtex, the breaking strength is 7.80cN/dtex, the elongation at break is 12.5%, the color fastness to washing is 4 grade, the color fastness to rubbing is 4 grade, the difference of the statistical average size of the carbon black in the black polyester industrial yarn is 10nm compared with the carbon black before being added into the high-viscosity polyester melt, and the difference of the maximum size is 40 nm; the difference between the content of the carbon black on the surface layer of the black polyester industrial yarn and the content of the carbon black in the center of the black polyester industrial yarn is 0.45 wt%; the prepared black polyester industrial yarn is used in the field of tarpaulin.
Comparative example 1
A process for preparing a black polyester industrial yarn, substantially as in example 1, except that the shear rate at the spinneret during spinning is 1800s -1 The filament number of the finally prepared black polyester industrial yarn is 3dtex, the breaking strength is 7.6cN/dtex, the elongation at break is 12.1%, the color fastness to washing is 4 grade, the color fastness to rubbing is 3-4 grade, the difference of the statistical average size of the carbon black in the black polyester industrial yarn is 20nm compared with the carbon black before being added into the high-viscosity polyester melt, and the difference of the maximum size is 60 nm; the difference between the content of carbon black in the surface layer of the black polyester industrial yarn and the content of carbon black in the center of the black polyester industrial yarn was 5 wt%.
Comparing example 1 with comparative example 1, it can be seen that the industrial yarn prepared in example 1 has excellent performance index and the carbon black is uniformly dispersed and distributed, because the shear rate of example 1 is low, the migration of the carbon black to the surface due to shear is reduced, and the carbon black concentration gradient of the fiber along the diameter direction is small and the distribution is uniform.
Comparative example 2
A preparation method of black polyester industrial yarn is basically the same as that in the embodiment 1, except that the post-heating temperature is 350 ℃ during spinning, the filament number of the finally prepared black polyester industrial yarn is 3dtex, the breaking strength is 6.8cN/dtex, the elongation at break is 12.6%, the color fastness to washing is 4 grade, the color fastness to rubbing is 4 grade, the difference of the statistical average size of the carbon black in the black polyester industrial yarn is 25nm compared with the carbon black before being added into a high-viscosity polyester melt, and the difference of the maximum size is 70 nm; the difference between the content of the carbon material in the surface layer of the black polyester industrial yarn and the content of the carbon material in the center of the black polyester industrial yarn is 0.76 wt%.
Comparing example 1 with comparative example 2, it can be seen that the strength index of the industrial yarn prepared in example 1 is excellent, because the post-heating temperature of example 1 is low, the strong heat absorption caused by the change of the thermal conductivity coefficient can be alleviated, and the instability of the melt and the low strength of the spinning finished product caused by the low melt viscosity can be avoided.
Comparative example 3
A preparation method of black polyester industrial yarn is basically the same as that in example 1, except that the cooling air speed is 1.0m/s, the air temperature is 18 ℃, the filament number of the finally prepared black polyester industrial yarn is 3dtex, the breaking strength is 7.1cN/dtex, the elongation at break is 11.8%, the color fastness to washing is 4 grade, the color fastness to rubbing is 3-4 grade, the difference of the statistical average size of carbon materials in the black polyester industrial yarn is 20nm compared with that of carbon black before being added into a high-viscosity polyester melt, and the difference of the maximum size is 60 nm; the difference between the content of carbon black in the surface layer of the black polyester industrial yarn and the content of carbon black in the center of the black polyester industrial yarn was 0.5 wt%.
Comparing example 1 with comparative example 3, it can be seen that example 1 is significantly superior in strength and more uniform in carbon black distribution because example 1 has a lower wind speed and a higher wind temperature, effectively moderates the cooling environment and makes the radial structure of the fibers more uniform.
Example 2
A preparation method of black polyester industrial yarn mainly comprises the following steps:
(1) preparation of a high-viscosity polyester melt containing carbon black: blending and melting carbon black master batches and PET with the intrinsic viscosity of 0.85dL/g to prepare a high-viscosity polyester melt containing the carbon black, wherein the carbon black master batches consist of the carbon black with the mass fraction of 30% and the average particle size of 15nm and the PET with the intrinsic viscosity of 0.85 dL/g;
(2) carrying out melt spinning on a high-viscosity polyester melt containing 0.6 wt% of carbon black to prepare a black polyester industrial yarn;
the main technological parameters of melt spinning are as follows: shear rate at spinneret orifice 1200s -1 Rear heaterThe temperature of (A) was 310 ℃, the cooling air temperature was 35 ℃, the cooling air speed was 0.5m/s, the one-roll speed was 600m/min, the draw ratio after the hot-rolling was 5.4 times, and the temperatures of the one-roll to the five-roll were 65 ℃, 95 ℃, 125 ℃, 225 ℃ and 135 ℃ respectively.
The filament number of the finally prepared black polyester industrial yarn is 5dtex, the breaking strength is 9.8cN/dtex, the elongation at break is 15%, the color fastness to washing is 5 grade, the color fastness to rubbing is 5 grade, the difference of the statistical average size of the carbon black in the black polyester industrial yarn is 5nm compared with the carbon black before being added into the high-viscosity polyester melt, and the difference of the maximum size is 10 nm; the difference between the content of carbon black on the surface layer of the black polyester industrial yarn and the content of carbon black in the center of the black polyester industrial yarn is 0.35 wt%; the prepared black polyester industrial yarn is used in the field of aviation safety belts.
Example 3
A preparation method of black polyester industrial yarn mainly comprises the following steps:
(1) preparing a high-viscosity polyester melt containing carbon nano tubes: blending and melting carbon nanotube master batches and PET with the intrinsic viscosity of 1.02dL/g to prepare a high-viscosity polyester melt containing carbon nanotubes, wherein the carbon nanotube master batches comprise the carbon nanotubes with the mass fraction of 40%, the average length of 2 mu m and the average diameter of 30nm and the PET with the intrinsic viscosity of 0.65 dL/g;
(2) carrying out melt spinning on the high-viscosity polyester melt containing 0.8 wt% of carbon nano tubes to prepare black polyester industrial yarns;
the main process parameters of melt spinning are as follows: shear rate at the orifice of the spinneret was 1500s -1 The temperature of the post-heater was 315 ℃, the cooling air temperature was 25 ℃, the cooling air speed was 0.7m/s, the one-roll speed was 650m/min, the hot-roll post-draw ratio was 5.7 times, and the temperatures of the one-roll to the five-roll were 67 ℃, 96 ℃, 127 ℃, 228 ℃ and 139 ℃, respectively.
The filament number of the finally prepared black polyester industrial yarn is 8dtex, the breaking strength is 8.2cN/dtex, the elongation at break is 14.0%, the color fastness to washing is 5 grade, the color fastness to rubbing is 5 grade, the difference of the statistical average size of the carbon nano tubes in the black polyester industrial yarn is 8nm compared with the carbon nano tubes before being added into the high-viscosity polyester melt, and the difference of the maximum size is 30 nm; the difference between the content of the carbon nano tube on the surface layer of the black polyester industrial yarn and the content of the carbon nano tube in the center of the black polyester industrial yarn is 0.4 wt%; the prepared black polyester industrial yarn is used in the field of automobiles.
Example 4
A preparation method of black polyester industrial yarn mainly comprises the following steps:
(1) preparing a graphene-containing high-viscosity polyester melt: blending and melting graphene master batches and PET (polyethylene terephthalate) with the intrinsic viscosity of 0.95dL/g to prepare a high-viscosity polyester melt containing graphene, wherein the graphene master batches comprise 35% of graphene with the mass fraction, the average diameter of 2 mu m and the average thickness of 8nm and the PET with the intrinsic viscosity of 0.75 dL/g;
(2) carrying out melt spinning on a high-viscosity polyester melt containing 0.7 wt% of graphene to prepare a black polyester industrial yarn;
the main process parameters of melt spinning are as follows: shear rate at the orifice was 1300s -1 The temperature of the post-heater was 320 ℃, the cooling air temperature was 20 ℃, the cooling air speed was 0.5m/s, the one-roll speed was 620m/min, the hot-roll post-draw ratio was 5.5 times, and the temperatures of the one-roll to the five-roll were 70 ℃, 100 ℃, 130 ℃, 235 ℃ and 150 ℃, respectively.
The filament number of the finally prepared black polyester industrial yarn is 10dtex, the breaking strength is 8.7cN/dtex, the elongation at break is 14.5%, the color fastness to washing is 4-5 grade, the color fastness to rubbing is 4-5 grade, the difference of the statistical average size of graphene in the black polyester industrial yarn is 9nm compared with the graphene before being added into the high-viscosity polyester melt, and the difference of the maximum size is 40 nm; the difference between the content of the graphene on the surface layer of the black polyester industrial yarn and the content of the graphene in the center of the black polyester industrial yarn is 0.45 wt%; the prepared black polyester industrial yarn is used in the field of marine cables.
Example 5
A preparation method of black polyester industrial yarn mainly comprises the following steps:
(1) preparing a high-viscosity polyester melt containing carbon black and carbon nanotubes: blending and melting the mixed master batch and PET with the intrinsic viscosity of 1.05dL/g to prepare a high-viscosity polyester melt containing carbon black and carbon nano tubes, wherein the mixed master batch consists of a mixture with the mass fraction of 25% and the PET with the intrinsic viscosity of 0.85dL/g, the mixture is a mixture of the carbon black and the carbon nano tubes with the mass ratio of 1:1, the average particle size of the carbon black is 10nm, the average length of the carbon nano tubes is 0.5 mu m, and the average diameter of the carbon nano tubes is 10 nm;
(2) carrying out melt spinning on a high-viscosity polyester melt containing carbon black and carbon nano tubes to prepare black polyester industrial yarns;
the main process parameters of melt spinning are as follows: shear rate at the orifice was 1280s -1 The temperature of the post-heater was 310 ℃, the cooling air temperature was 35 ℃, the cooling air speed was 0.5m/s, the one-roll speed was 630m/min, the hot-roll post-draw ratio was 5.4 times, and the temperatures of the one-roll to the five-roll were 65 ℃, 95 ℃, 125 ℃, 225 ℃ and 135 ℃ respectively.
The filament number of the finally prepared black polyester industrial yarn is 8dtex, the breaking strength is 8.8cN/dtex, the elongation at break is 15%, the color fastness to washing is 5 grade, the color fastness to rubbing is 5 grade, the difference of the statistical average size of the carbon black and the carbon nano tube in the black polyester industrial yarn is 6nm compared with the carbon black and the carbon nano tube before being added into the high-viscosity polyester melt, and the difference of the maximum size is 20 nm; the difference between the content of the carbon black and the carbon nano tube on the surface layer of the black polyester industrial yarn and the content of the carbon black and the carbon nano tube in the center of the black polyester industrial yarn is 0.35 wt%; the prepared black polyester industrial yarn is used in the field of hoisting belts.
Example 6
A preparation method of black polyester industrial yarn mainly comprises the following steps:
(1) preparation of a high-viscosity polyester melt containing carbon black: blending and melting carbon black master batches and PET with the intrinsic viscosity of 0.95dL/g to prepare a high-viscosity polyester melt containing the carbon black, wherein the carbon black master batches consist of the carbon black with the mass fraction of 20% and the average particle size of 15nm and the PET with the intrinsic viscosity of 0.85 dL/g;
(2) carrying out melt spinning on a high-viscosity polyester melt containing 0.5wt% of carbon black to prepare black polyester industrial yarns;
the main process parameters of melt spinning are as follows: shear rate at the orifice was 1350s -1 The temperature of the post heater is 330 ℃, the temperature of the cooling air is 30 ℃, and the cooling air speed is 0.7mThe speed of one roll was 600m/min, the draw ratio after hot rolling was 5.7 times, and the temperatures of one roll to five rolls were 65 ℃, 95 ℃, 128 ℃, 230 ℃ and 145 ℃ respectively.
The filament number of the finally prepared black polyester industrial yarn is 5dtex, the breaking strength is 8.4cN/dtex, the elongation at break is 13.5%, the color fastness to washing is 4-5 grade, the color fastness to rubbing is 4-5 grade, the difference of the statistical average size of the carbon black in the black polyester industrial yarn is 8nm compared with the carbon black before being added into the high-viscosity polyester melt, and the difference of the maximum size is 35 nm; the difference between the content of carbon black on the surface layer of the black polyester industrial yarn and the content of carbon black in the center of the black polyester industrial yarn is 0.4 wt%; the prepared black polyester industrial yarn is used in the field of automobiles.
Example 7
A preparation method of black polyester industrial yarn mainly comprises the following steps:
(1) preparation of a high-viscosity polyester melt containing carbon black: blending and melting carbon black master batches and PET with the intrinsic viscosity of 1.05dL/g to prepare a high-viscosity polyester melt containing the carbon black, wherein the carbon black master batches comprise the carbon black with the mass fraction of 30% and the average particle size of 10nm and the PET with the intrinsic viscosity of 0.65 dL/g;
(2) carrying out melt spinning on a high-viscosity polyester melt containing 0.8 wt% of carbon black to prepare black polyester industrial yarns;
the main process parameters of melt spinning are as follows: shear rate at spinneret orifice was 1400s -1 The temperature of the afterheater was 310 ℃, the cooling air temperature was 20 ℃, the cooling air speed was 0.6m/s, the one-roll speed was 650m/min, the hot-roll afterdraft ratio was 5.4 times, and the temperatures of the one-roll to the five-roll were 65 ℃, 97 ℃, 125 ℃, 227 ℃ and 138 ℃, respectively.
The filament number of the finally prepared black polyester industrial yarn is 7dtex, the breaking strength is 8.6cN/dtex, the elongation at break is 12.5%, the color fastness to washing is 4-5 grade, the color fastness to rubbing is 4-5 grade, the difference of the statistical average size of the carbon black in the black polyester industrial yarn is 7nm compared with the carbon black before being added into the high-viscosity polyester melt, and the difference of the maximum size is 30 nm; the difference between the content of carbon black on the surface layer of the black polyester industrial yarn and the content of carbon black in the center of the black polyester industrial yarn is 0.38 wt%; the prepared black polyester industrial yarn is used in the field of hoisting belts.
Example 8
A preparation method of black polyester industrial yarn mainly comprises the following steps:
(1) preparing a high-viscosity polyester melt containing carbon nano tubes: blending and melting carbon nanotube master batches and PET with the intrinsic viscosity of 1.05dL/g to prepare a high-viscosity polyester melt containing carbon nanotubes, wherein the carbon nanotube master batches comprise the carbon nanotubes with the mass fraction of 28%, the average length of 1 mu m and the average diameter of 20nm and the PET with the intrinsic viscosity of 0.85 dL/g;
(2) carrying out melt spinning on the high-viscosity polyester melt containing 0.7 wt% of carbon nano tubes to prepare black polyester industrial yarns;
the main process parameters of melt spinning are as follows: shear rate at spinneret orifice 1200s -1 The temperature of the post-heater was 315 ℃, the cooling air temperature was 28 ℃, the cooling air speed was 0.5m/s, the one-roll speed was 600m/min, the hot-roll post-draw ratio was 5.6 times, and the temperatures of the one-roll to the five-roll were 67 ℃, 96 ℃, 127 ℃, 228 ℃ and 137 ℃ respectively.
The monofilament titer of the finally prepared black polyester industrial yarn is 6dtex, the breaking strength is 9.2cN/dtex, the elongation at break is 14.5%, the color fastness to washing is 5 grade, the color fastness to rubbing is 5 grade, the difference of the statistical average size of the carbon nano tubes in the black polyester industrial yarn is 5nm compared with the carbon nano tubes before being added into the high-viscosity polyester melt, and the difference of the maximum size is 15 nm; the difference between the content of the carbon material on the surface layer of the black polyester industrial yarn and the content of the carbon material in the center of the black polyester industrial yarn is 0.35 wt%; the prepared black polyester industrial yarn is used in the field of aviation safety belts.
Claims (8)
1. A preparation method of black polyester industrial yarn is characterized by comprising the following steps: carrying out melt spinning on a high-viscosity polyester melt containing a carbon material to prepare a black polyester industrial yarn, wherein the intrinsic viscosity of the high-viscosity polyester is more than or equal to 0.85 dL/g; during melt spinning, the shearing rate at the spinneret orifice is 1200-1500 s -1 The temperature of the post heater is 310-330 ℃, the cooling air temperature is 20-35 ℃, and the cooling air speed is 0.5-0.9 m/s; high viscosity polyester melt containing carbon materialThe mass fraction of the medium carbon material is 0.5-0.8%; the high-viscosity polyester melt containing the carbon material is prepared by blending and melting carbon material master batches and polyester I, wherein the intrinsic viscosity of the polyester I is 0.85-1.05 dL/g, and the carbon material master batches are composed of the carbon material and polyester II with the intrinsic viscosity of 0.50-0.85 dL/g; the difference between the content of the carbon material on the surface layer of the black polyester industrial yarn and the content of the carbon material in the center of the black polyester industrial yarn is less than 0.5 wt%.
2. The method of claim 1, wherein the melt spinning has a first roll speed of 600 to 650m/min, a draw ratio of 5.4 to 5.7 times after hot rolling, and temperatures of 65 to 70 ℃, 95 to 100 ℃, 125 to 130 ℃, 225 to 235 ℃ and 135 to 150 ℃ for one to five rolls, respectively.
3. The preparation method of the black polyester industrial yarn according to claim 1, wherein the mass fraction of the carbon material in the carbon material master batch is 20-40%, and the polyester I and the polyester II are both PET.
4. The preparation method of the black polyester industrial yarn according to claim 1, wherein the carbon material is more than one of carbon black, carbon nanotubes and graphene, the particle size of the carbon black is less than 20nm, the length of the carbon nanotubes is less than 3 μm, the diameter of the carbon nanotubes is less than 50nm, the diameter of the graphene is less than 3 μm, and the thickness of the graphene is less than 10 nm.
5. The black polyester industrial yarn prepared by the preparation method of the black polyester industrial yarn according to any one of claims 1 to 4 is characterized in that: compared with the carbon material before being added into the high-viscosity polyester melt, the carbon material in the black polyester industrial yarn has the statistical average size difference of less than or equal to 10nm and the maximum size difference of less than 50 nm; the difference between the content of the carbon material on the surface layer of the black polyester industrial yarn and the content of the carbon material in the center of the black polyester industrial yarn is less than 0.5 wt%.
6. The black polyester industrial yarn according to claim 5, wherein the black polyester industrial yarn has a single filament fineness of 3 to 10dtex, a breaking strength of 7.8cN/dtex, and an elongation at break of 12.5 to 15%.
7. The black polyester industrial yarn according to claim 5, wherein the black polyester industrial yarn has a color fastness to washing of 4 or more and a color fastness to rubbing of 4 or more.
8. The black polyester industrial yarn of claim 5, wherein the black polyester industrial yarn is used in the fields of automobiles, aviation safety belts, marine cables, sling belts, or tarpaulins.
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| CN105504243A (en) * | 2015-12-29 | 2016-04-20 | 江苏恒力化纤股份有限公司 | Heat-resistant polyester colored industrial yarn and preparation method thereof |
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