CN115928251A - Preparation method of in-situ graphene modified PET (polyethylene terephthalate) fiber - Google Patents
Preparation method of in-situ graphene modified PET (polyethylene terephthalate) fiber Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 144
- 239000000835 fiber Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 20
- -1 polyethylene terephthalate Polymers 0.000 title abstract description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 title description 85
- 239000005020 polyethylene terephthalate Substances 0.000 title description 85
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 229920000728 polyester Polymers 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000002074 melt spinning Methods 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 238000010309 melting process Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 27
- 239000002356 single layer Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 17
- 230000006855 networking Effects 0.000 claims description 14
- 229910052582 BN Inorganic materials 0.000 claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 abstract description 6
- 230000006750 UV protection Effects 0.000 abstract description 5
- 230000003115 biocidal effect Effects 0.000 abstract description 5
- 230000002265 prevention Effects 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 17
- 239000004744 fabric Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000009987 spinning Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 238000012216 screening Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000008041 oiling agent Substances 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
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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
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Abstract
The invention relates to the technical field of graphene fiber preparation, and discloses a preparation method of in-situ graphene modified PET fibers, which comprises the following steps: (1) Adding a graphene material in the polymerization process of PET polyester to obtain a graphene modified PET raw material; (2) Carrying out melt spinning on the graphene modified PET raw material, and adding a PBT high polymer on line in the melting process to obtain the graphene modified PET fiber. In the preparation process of the PET, the graphene material is added in an in-situ polymerization manner, and due to the structural particularity, the PET fibers can be endowed with the functions of antibiosis, mite prevention, warm keeping, ultraviolet resistance and the like; in the fiber preparation process, the polybutylene terephthalate is added in a melting way in a master batch adding way, so that the spinnability of the fiber preparation and the strength of the fiber finished product can be improved.
Description
Technical Field
The invention relates to the technical field of graphene fiber preparation, in particular to a preparation method of in-situ graphene modified PET fibers.
Background
Due to the structural particularity of the single-layer carbon graphene or single-layer annular boron nitride (white graphene) material, the single-layer carbon graphene or single-layer annular boron nitride (white graphene) material has a photoelectric effect, and graphene fibers spun from the material also have the functions of antibiosis, mite prevention, warm keeping, ultraviolet resistance and the like, so that the material attracts high attention of the industry. However, when graphene is mixed into a fiber polymer by an online addition method of master batch, the graphene is easily agglomerated, a layered structure is broken, and the distribution is not uniform, so that the functionality of the prepared fiber is reduced. Meanwhile, the high polymer fiber material added with graphene is easy to embrittle, and is easy to break in the preparation and use processes, or the monofilament breaks to form quality problems such as broken filaments and broken lumps, the production efficiency is low, the use performance is poor, and the problem becomes a bottleneck problem which restricts the application and development of graphene in the fiber field.
The Chinese patent with publication number CN112301454A discloses a preparation method of a PET-based graphene conductive fiber, which comprises the following steps: 1) Providing graphene/PET functional master batches and PET natural color slices, wherein the water content of the graphene/PET functional master batches and the water content of the PET natural color slices are lower than 30ppm; 2) Melting and blending the graphene/PET functional master batches and PET natural color slices through a dynamic mixer, and feeding the mixture into a double-screw extruder to obtain PET-based graphene nascent fibers, wherein the dynamic mixer is a three-dimensional efficient dynamic mixer; 3) And (3) drafting and heat setting the PET-based graphene nascent fiber to obtain the PET-based graphene conductive fiber. However, the graphene fiber obtained by melt blending of the graphene/PET functional master batch and the PET natural color chips does not well solve the problems of easy embrittlement and easy end breakage of graphene in a fiber material, and the service performance of the fiber is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an in-situ graphene modified PET fiber, which is characterized in that a graphene material is added in an in-situ polymerization manner in the preparation process of PET polyester, and polybutylene terephthalate (PBT) is added in a melting manner in a master batch adding manner in the preparation process of the fiber, so that the graphene modified PET fiber has functionality and simultaneously improves the strength and toughness of the fiber.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of in-situ graphene modified PET fibers, which comprises the following steps:
(1) Adding a graphene material in the polymerization process of PET polyester to obtain a graphene modified PET raw material;
(2) Carrying out melt spinning on the graphene modified PET raw material, and adding a PBT high polymer on line in the melting process to obtain the graphene modified PET fiber.
According to the invention, a graphene material is added in the preparation process of PET polyester through in-situ polymerization, and due to the structural particularity of graphene or single-layer boron nitride (white graphene), the PET fiber can be endowed with the functions of antibiosis, mite prevention, warm keeping, ultraviolet resistance and the like. In addition, in order to improve the quality problems of easy embrittlement, easy end breakage and the like in the spinning or using process of the graphene fiber, polybutylene terephthalate (PBT) is melt-added in the preparation process of the fiber in a master batch adding mode, the high polymer is close to PET in performance, the high polymer and the PET are good in compatibility, the rheological property is very good, the toughness is good, and the spinnability and the finished product strength of the fiber are improved by adding a proper amount of PBT. If flexible macromolecule (PBT) is added for copolymerization in the polymerization process, the polymerization degree of PET macromolecule is reduced, and the overall strength of the fiber is reduced.
The graphene modified PET fiber can obtain higher strength and quality uniformity of a fiber finished product, and particularly improves production efficiency and reduces end breakage rate, and meanwhile, the production efficiency of the fiber in downstream weaving is improved, and the machine halt rate and the cloth cover defect rate are reduced.
Preferably, the addition amount of the graphene material is 1-1.5 per mill of the mass of the PET polyester.
Preferably, the addition amount of the PBT high polymer is 2-4% of the mass of the graphene modified PET raw material.
Preferably, the graphene material is graphene or a single layer of boron nitride.
Preferably, the graphene material is added in the middle-later stage of the polycondensation reaction in the polymerization process.
In the preparation process of the PET macromolecular material, the graphene and the glycol are firstly blended into a solution with the mass concentration of 50%, and in order to avoid influencing the polymerization degree of two monomers of terephthalic acid (PTA) and glycol, thereby reducing the strength of PET fibers, therefore, after the first pre-polycondensation of polymerization is carried out, and the polycondensation reaction is basically completed, a certain proportion of single-layer carbon graphene or boron nitride lamellar ring functional modified material with special photoelectric effect is added in the second pre-polycondensation link before the final polycondensation, so as to ensure that the single-layer carbon graphene or boron nitride lamellar ring of the graphene is distributed on the surface of a macromolecular chain in an inlaying mode, thereby maintaining the lamellar ring structure of the modified material and enabling the distribution to be uniform, thereby enabling multiple functions of antibacterial, anti-mite, ultraviolet-resistant, far infrared heat preservation, antistatic performance and the like of the prepared macromolecular material to be more prominent, and the functional uniformity and durability of fabrics to be good.
Preferably, the tows obtained by melt spinning are sequentially subjected to first oiling, pre-networking, hot roller stretching, second oiling, networking and winding forming to obtain the graphene modified PET fibers.
The oiling is performed twice in the fiber preparation process, the oiling rate and the oiling uniformity are improved, the toughness and the strength of the fiber are improved from the fiber macromolecular microstructure, the production process is optimized from the fiber preparation process, the damage to the fiber is reduced, and the service performance of the prepared fiber is improved.
Preferably, the mass concentration of the oil agent used by the oil nozzle during the first oiling is 13-15%; and the mass concentration of the oil agent used by the oil nozzle during the second oiling process is 8-10%.
Preferably, the total oiling rate of the first oiling and the second oiling is 0.7-1.1%, wherein the oiling rate of the first oiling is 70-80% of the total oiling rate.
The primary oiling has the main function of improving the convergence among single fibers, further improving the running stability of tows, and ensuring the emulsibility and permeability of an oiling agent, so that a lower oiling agent concentration and a higher oiling amount are adopted. In addition, the graphene fiber prepared by adding graphene into a polymer material has poor dispersibility of an inorganic additive in a polymer, and particularly, in the fiber spinning process, the compatibility of the graphene in the polymer is influenced by the unique sheet structure of the graphene, so that broken ends, broken filaments and the like are easily generated in the preparation or use of tows, and the spinning difficulty of the fiber is improved. And set up first oiling device before the hot roller device, and after melt spinning obtains the silk bundle, carry out oiling processing for the first time immediately, the compatibility and the stability of graphite alkene in the fibre can be promoted in the effect simultaneously of surface oil phase and hot roller draft, and then the quality of graphite alkene fibre can be optimized.
The second oiling has the main functions of improving the strength and the uniformity of an oil film on the surface of the fiber, enhancing the protection property on the surface of the fiber, further improving the protection performance of the fiber in subsequent network adding and winding processes, reducing the end breakage rate, and improving the tensile property, the wear resistance and other properties in the weaving and using process.
Preferably, the filament bundles are all rotary filament guides in the melt spinning process by using the filament guides.
The yarn guide in the fiber manufacturing process adopts the rotary yarn guide, and especially the yarn guide below the first oil nozzle and the yarn guide above and below the second oil nozzle adopt the rotary yarn guide, so that the friction between the fiber strand silk and the yarn guide is changed from sliding friction into static friction, and the fluctuation of the running of the strand silk and the damage to the strand silk are reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the preparation process of PET polyester, graphene materials are added in an in-situ polymerization manner, and due to the structural particularity of graphene or single-layer boron nitride (white graphene), PET fibers can be endowed with functions of antibiosis, mite prevention, warm keeping, ultraviolet resistance and the like;
(2) In the fiber preparation process, polybutylene terephthalate (PBT) is melt-added in a master batch adding mode, the high polymer is close to the PET in performance, the PET and the high polymer have good compatibility, very good rheological property and good toughness, and the spinnability and the finished fiber strength of the fiber preparation are improved by adding a proper amount of PBT;
(3) The oiling is carried out twice, the oiling rate and the oiling uniformity are improved, the toughness and the strength of the fiber are improved from the fiber macromolecule microstructure, the production process is optimized from the fiber preparation process, the damage to the fiber is reduced, and the service performance of the prepared fiber is improved.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
The preparation method comprises the following steps:
(1) Adding 1 per mill of single-layer carbon graphene with mass fraction in the preparation process of PET high polymer, and firstly, preparing the single-layer carbon graphene and ethylene glycol into a solution with mass concentration of 50%; the temperature of the polycondensation reaction of the PET high polymer is 280 ℃, the reaction time is 6 hours, the vacuum degree is-0.15 Mp, and the solution is added in the middle and later stages of the polycondensation reaction (after 4 hours of polycondensation reaction) to prepare the graphene modified PET slice;
(2) Carrying out melt spinning on the graphene modified PET slices, blending PBT high polymer in an online adding mode in the melting process, wherein the adding amount of the PBT high polymer accounts for 2.0% of the mass of the graphene modified PET slices; and then obtaining tows through melt spinning, and sequentially carrying out first oiling, pre-screening, hot roller stretching, second oiling, screening and winding forming to obtain the graphene modified PET fibers (125 dtex/72f graphene modified polyester fibers POY). Wherein the spinning speed is 3000m/min; the mass concentration of the oil used by the first oiling nozzle is 13%, the oiling rate is 0.64%, the mass concentration of the oil used by the second oiling nozzle is 8%, the oiling rate is 0.16%, and the total oiling rate is 0.8%; and the yarn guides below the first oiling nozzle and the yarn guides above and below the second oiling nozzle are all rotary yarn guides.
And (3) elasticizing the 125dtex/72F graphene modified polyester fiber POY to obtain 75D/72F graphene modified polyester fiber DTY, and then preparing a finished knitted fabric product.
Example 2
The preparation method comprises the following steps:
(1) Adding 1.5 per mill of single-layer annular boron nitride in the preparation process of the PET high polymer, and firstly preparing single-layer carbon graphene and ethylene glycol into a solution with the mass concentration of 50%; the temperature of the polycondensation reaction of the PET high polymer is 280 ℃, the reaction time is 6 hours, the vacuum degree is-0.15 Mp, and the solution is added in the middle and later stages of the polycondensation reaction (after 4 hours of polycondensation reaction) to prepare the graphene modified PET slice;
(2) Carrying out melt spinning on the graphene modified PET slices, blending PBT high polymer in an online adding mode in the melting process, wherein the adding amount of the PBT high polymer accounts for 3.0% of the mass of the graphene modified PET slices; and then carrying out melt spinning to obtain tows, and sequentially carrying out first oiling, pre-networking, hot roller stretching, second oiling, networking and winding forming to obtain the graphene modified PET fibers (75D/48 f graphene modified polyester fibers FDY). Wherein the spinning speed is 4000m/min; the mass concentration of the oil used by the first oiling nozzle is 14%, the oiling rate is 0.70%, the mass concentration of the oil used by the second oiling nozzle is 9%, the oiling rate is 0.30%, and the total oiling rate is 1.0%; and the yarn guide below the first oiling nozzle and the yarn guide above and below the second oiling nozzle both use rotary yarn guides.
And preparing the 75D/48f graphene modified polyester fiber FDY into a finished knitted fabric product.
Example 3
The preparation method comprises the following steps:
(1) Adding single-layer carbon graphene with the mass fraction of 1.2 per mill in the preparation process of the PET high polymer, and firstly, preparing the single-layer carbon graphene and ethylene glycol into a solution with the mass concentration of 50%; the temperature of the polycondensation reaction of the PET high polymer is 280 ℃, the reaction time is 6h, the vacuum degree is-0.15 Mp, and the solution is added in the middle and later stages of the polycondensation reaction (after 4h of polycondensation reaction) to prepare the graphene modified PET slice;
(2) Carrying out melt spinning on the graphene modified PET slices, and blending PBT high polymer in an online adding manner in the melting process, wherein the adding amount of the PBT high polymer accounts for 4.0% of the mass of the graphene modified PET slices; and then carrying out melt spinning to obtain tows, and sequentially carrying out first oiling, pre-networking, hot roller stretching, second oiling, networking and winding forming to obtain the graphene modified PET fiber (175 dtex/72f graphene modified polyester fiber POY). Wherein the spinning speed is 3100m/min; the mass concentration of the oil used by the first oiling nozzle is 15%, the oiling rate is 0.60%, the mass concentration of the oil used by the second oiling nozzle is 10%, the oiling rate is 0.20%, and the total oiling rate is 0.8%; and the yarn guide below the first oiling nozzle and the yarn guide above and below the second oiling nozzle both use rotary yarn guides.
And (3) elasticizing the 175dtex/72F graphene modified polyester fiber POY to obtain 100D/72F graphene modified polyester fiber DTY, and then preparing a finished knitted fabric product.
Comparative example 1
The difference from example 3 is that: only one application of oil was performed.
The preparation method comprises the following steps:
(1) Adding 1.2 per mill of single-layer carbon graphene in the preparation process of PET high polymer, and firstly preparing the single-layer carbon graphene and ethylene glycol into a solution with the mass concentration of 50%; the temperature of the polycondensation reaction of the PET high polymer is 280 ℃, the reaction time is 6 hours, the vacuum degree is-0.15 Mp, and the solution is added in the middle and later stages of the polycondensation reaction (after 4 hours of polycondensation reaction) to prepare the graphene modified PET slice;
(2) Carrying out melt spinning on the graphene modified PET slices, and blending PBT high polymer in an online adding manner in the melting process, wherein the adding amount of the PBT high polymer accounts for 4.0% of the mass of the graphene modified PET slices; and then carrying out melt spinning to obtain tows, and sequentially carrying out first oiling, pre-networking, hot roller stretching, networking and winding forming to obtain the graphene modified PET fiber (175 dtex/72f graphene modified polyester fiber POY). Wherein the spinning speed is 3100m/min; the mass concentration of the oil used by the first oiling nozzle is 15%, and the oiling rate is 0.80%; the thread guide below the first oil applying nozzle is a rotary thread guide.
And (3) elasticizing the 175dtex/72F graphene modified polyester fiber POY to obtain 100D/72F graphene modified polyester fiber DTY, and then preparing a finished knitted fabric product.
Comparative example 2
The difference from example 3 is that: the oiling rate of the first oiling is too low.
The preparation method comprises the following steps:
(1) Adding single-layer carbon graphene with the mass fraction of 1.2 per mill in the preparation process of the PET high polymer, and firstly, preparing the single-layer carbon graphene and ethylene glycol into a solution with the mass concentration of 50%; the temperature of the polycondensation reaction of the PET high polymer is 280 ℃, the reaction time is 6h, the vacuum degree is-0.15 Mp, and the solution is added in the middle and later stages of the polycondensation reaction (after 4h of polycondensation reaction) to prepare the graphene modified PET slice;
(2) Carrying out melt spinning on the graphene modified PET slices, and blending PBT high polymer in an online adding manner in the melting process, wherein the adding amount of the PBT high polymer accounts for 4.0% of the mass of the graphene modified PET slices; and then carrying out melt spinning to obtain tows, and sequentially carrying out first oiling, pre-screening, hot roller stretching, second oiling, screening and winding forming to obtain the graphene modified PET fiber (175 dtex/72f graphene modified polyester fiber POY). Wherein the spinning speed is 3100m/min; the mass concentration of the oil used by the first oiling nozzle is 15%, the oiling rate is 0.50%, the mass concentration of the oil used by the second oiling nozzle is 10%, the oiling rate is 0.30%, and the total oiling rate is 0.80%; and the yarn guide below the first oiling nozzle and the yarn guide above and below the second oiling nozzle both use rotary yarn guides.
And (3) elasticizing the 175dtex/72F graphene modified polyester fiber POY to obtain 100D/72F graphene modified polyester fiber DTY, and then preparing a finished knitted fabric product.
Comparative example 3
The difference from example 3 is that: the addition ratio of graphene is too high.
The preparation method comprises the following steps:
(1) Adding 2.0 per mill of single-layer carbon graphene in mass fraction in the preparation process of the PET high polymer, and firstly preparing the single-layer carbon graphene and ethylene glycol into a solution with the mass concentration of 50%; the temperature of the polycondensation reaction of the PET high polymer is 280 ℃, the reaction time is 6 hours, the vacuum degree is-0.15 Mp, and the solution is added in the middle and later stages of the polycondensation reaction (after 4 hours of polycondensation reaction) to prepare the graphene modified PET slice;
(2) Carrying out melt spinning on the graphene modified PET slices, blending PBT high polymer in an online adding mode in the melting process, wherein the adding amount of the PBT high polymer accounts for 4.0% of the mass of the graphene modified PET slices; and then carrying out melt spinning to obtain tows, and sequentially carrying out first oiling, pre-networking, hot roller stretching, second oiling, networking and winding forming to obtain the graphene modified PET fiber (175 dtex/72f graphene modified polyester fiber POY). Wherein the spinning speed is 3100m/min; the mass concentration of the oil used by the first oiling nozzle is 15%, the oiling rate is 0.60%, the mass concentration of the oil used by the second oiling nozzle is 10%, the oiling rate is 0.20%, and the total oiling rate is 0.8%; and the yarn guide below the first oiling nozzle and the yarn guide above and below the second oiling nozzle both use rotary yarn guides.
And (3) elasticizing the 175dtex/72F graphene modified polyester fiber POY to obtain 100D/72F graphene modified polyester fiber DTY, and then preparing a finished knitted fabric product.
Comparative example 4
The difference from example 3 is that: the addition proportion of PBT is too low.
The preparation method comprises the following steps:
(1) Adding single-layer carbon graphene with the mass fraction of 1.2 per mill in the preparation process of the PET high polymer, and firstly, preparing the single-layer carbon graphene and ethylene glycol into a solution with the mass concentration of 50%; the temperature of the polycondensation reaction of the PET high polymer is 280 ℃, the reaction time is 6 hours, the vacuum degree is-0.15 Mp, and the solution is added in the middle and later stages of the polycondensation reaction (after 4 hours of polycondensation reaction) to prepare the graphene modified PET slice;
(2) Carrying out melt spinning on the graphene modified PET slice, blending PBT high polymer in an online adding mode in the melting process, wherein the adding amount of the PBT high polymer accounts for 1.0% of the mass of the graphene modified PET slice; and then carrying out melt spinning to obtain tows, and sequentially carrying out first oiling, pre-networking, hot roller stretching, second oiling, networking and winding forming to obtain the graphene modified PET fiber (175 dtex/72f graphene modified polyester fiber POY). Wherein the spinning speed is 3100m/min; the mass concentration of the oil used by the first oiling nozzle is 15%, the oiling rate is 0.60%, the mass concentration of the oil used by the second oiling nozzle is 10%, the oiling rate is 0.20%, and the total oiling rate is 0.8%; and the yarn guides below the first oiling nozzle and the yarn guides above and below the second oiling nozzle are all rotary yarn guides.
And (3) elasticizing the 175dtex/72F graphene modified polyester fiber POY to obtain 100D/72F graphene modified polyester fiber DTY, and then preparing a finished knitted fabric product.
Far infrared emissivity: according to the standard of GB/T30127-2013 detection and evaluation of far infrared performance of textiles.
Ultraviolet transmittance: according to the standard of AATCC183 test standards for the ultraviolet radiation resistance of textiles.
Antibacterial property: according to the standard of GB/T20944.3-2008 evaluation part 3 oscillation method of antibacterial property of textile.
Emissivity of negative oxygen ions: according to the standard of GB/T30127-2013 detection and evaluation of far infrared performance of textiles.
The finished knitted fabrics in examples and comparative examples were subjected to performance tests, and the results are shown in table 1.
TABLE 1
The fiber quality and the service performance of the graphene modified PET fibers in the examples and the comparative examples during the preparation process and the downstream weaving use process of the prepared fibers were tested, and the results are shown in table 2.
TABLE 2
In table 2, the production efficiency is calculated by the ratio of the actual production to the theoretical production per unit time of one machine.
As shown in Table 1, in the preparation process of PET polyester, the graphene material is added in an in-situ polymerization manner, and due to the structural particularity of the graphene or the single-layer boron nitride (white graphene), the PET fiber can be endowed with functions of antibiosis, mite prevention, warm keeping, ultraviolet resistance and the like.
As shown in Table 2, comparative examples 1 and 2 show that twice oiling is adopted, the oiling rate and the oiling uniformity are improved, the toughness and the strength of the fiber are improved from the aspect of fiber macromolecular microstructure, the production process is optimized from the fiber preparation process, the damage to the fiber is reduced, and the end breakage rate and the fiber use performance can be reduced; the oiling rate of the secondary oiling needs to be controlled, so that the finished product strength of the fiber is better. Comparative examples 3 and 4 show that the addition ratio of the raw materials for preparing the fiber affects the spinnability of the fiber and the use performance of the fiber, and the fiber spun outside the range defined by the present invention is liable to have quality problems.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications of the equivalent structures and equivalent processes of the present invention, which are directly or indirectly applied to other related fields, are included in the scope of the present invention.
Claims (9)
1. A preparation method of in-situ graphene modified PET fibers is characterized by comprising the following steps:
(1) Adding a graphene material in the polymerization process of PET polyester to obtain a graphene modified PET raw material;
(2) Carrying out melt spinning on the graphene modified PET raw material, and adding a PBT high polymer on line in the melting process to obtain the graphene modified PET fiber.
2. The method for preparing the in-situ graphene modified PET fiber according to claim 1, wherein the addition amount of the graphene material is 1 to 1.5 per mill of the mass of the PET polyester.
3. The method for preparing the in-situ graphene modified PET fiber according to claim 1, wherein the PBT high polymer is added in an amount of 2-4% by mass of the graphene modified PET raw material.
4. The method for preparing in-situ graphene-modified PET fibers according to any one of claims 1 to 3, wherein the graphene material is graphene or single-layer boron nitride.
5. The method for preparing in-situ graphene modified PET fiber according to any one of claims 1 to 3, wherein the graphene material is added in the polymerization process of PET polyester through a polycondensation reaction in the polymerization process.
6. The method for preparing the in-situ graphene modified PET fiber according to claim 1, wherein the melt spinning to obtain the filament bundle is sequentially subjected to first oiling, pre-networking, hot roller stretching, second oiling, networking and winding forming to obtain the graphene modified PET fiber.
7. The method for preparing the in-situ graphene modified PET fiber according to claim 6, wherein the mass concentration of an oil agent used for an oil nozzle in the first oiling process is 13-15%; and the mass concentration of the oil agent used by the oil nozzle during the second oiling is 8-10%.
8. The preparation method of the in-situ graphene modified PET fiber according to claim 6 or 7, wherein the total oiling rate of the first oiling and the second oiling is 0.7-1.1%, and the oiling rate of the first oiling is 70-80% of the total oiling rate.
9. The method for preparing the in-situ graphene modified PET fiber according to claim 1 or 6, wherein the filament bundle adopted by filament guides in the melt spinning process are all rotary filament guides.
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| CN202211626920.5A CN115928251A (en) | 2022-12-16 | 2022-12-16 | Preparation method of in-situ graphene modified PET (polyethylene terephthalate) fiber |
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