CN105002595A - Polymer composite function fibers containing partial graphene, and preparation method thereof - Google Patents
Polymer composite function fibers containing partial graphene, and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a polymer composite function fibers containing partial graphene, and a preparation method thereof. The fibers comprise a component A and a component B, wherein the component A and the component B are combined in a partial exposing manner, side-by-side manner or skin-core manner, and 20-100% of the outer area of each fiber is the component B. The method comprises: crystallizing a polyester containing 0.1-1 wt% of partial reducing graphene and a polyester containing 4-20 wt% of a nanometer composite filler containing partial reducing graphene and TiO2, drying, carrying out melt composite spinning, and carrying out drawing and relaxation heat setting at a temperature of 80-160 DEG C, and reducing the partial graphene in the fibers to achieve the carbon/oxygen atom ratio of 9/1-15/1 through the reducing treatment. According to the present invention, the prepared fibers can be produced at the high spinning speed, and the production efficiency is high; and the fibers have characteristics of low single fineness, high strength and lower resistivity, meets the antistatic requirement, and further has characteristics of anti-bacterial property and flame retardant property so as to provide good application prospects.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of macromolecule composite functional fiber containing partial reduction Graphene and preparation method thereof.
Background technology
Functional fibre refers to the tencel with one or more specific function, as conductive fiber, fire resistance fibre, anti-bacterial fibre etc.Functional fibre has the feature of high technology content, high added value, the high market demand.For conductive fiber, owing to having the characteristic such as antistatic, electromagnetic wave absorption, be antistatic explosion-proof clothing, dust-free sterile clothes, high-grade clothing and family the required raw material of high value added product such as to spin, be applied to the various fields such as Aero-Space, defence and military, petrochemical industry, mining, microelectronics, biological medicine, Precision Machining, textile garment, wide market.
The preparation of functional fibre, generally by adding micron or nanoscale functional stuffing in macromolecule matrix, comprises carbon black, metal and metal oxide powder, CNT or carbon nano-fiber etc., then obtains through spinning technique.For realizing required function as conduction, could form conductive network when the content of filler must be over a certain particular value, this value is commonly called " percolation threshold ".The percolation threshold of conventional filler (as carbon black and metal dust) is higher, often beyond 20 ﹪, brings that spinnability is deteriorated, fibre strength declines thus, the problem such as stiff, the fiber number of feel and density increase.
In addition, the function singleness of conventional filler.Such as: carbon black mainly plays electric action; Magnesium hydroxide plays fire retardation; The metals (or its ion) such as silver, copper, zinc mainly play antibacterial action, etc.For realizing complex function, often needing to add multiple filler simultaneously, when its content all reaches enough high, producing conduction, the effect such as fire-retardant, antibacterial respectively.This certainly will increase the content of filler in macromolecule matrix further, makes the problem of above-mentioned spinnability and fibre property aspect more outstanding.Therefore, although the macromolecule composite functional fiber prospect having several functions concurrently is tempting, its research and development difficult point is still very large.
As a class nano material of latest development after CNT, Graphene has more excellent electric conductivity and high radius-thickness ratio and specific area.It is reported, the percolation threshold of Graphene in various macromolecule is low to moderate 0.1 ~ 3.8vol ﹪, can obtain significant electric conductivity and promote under extremely low addition.Publication number is that the Chinese invention patent application of CN103710790A adopts Graphene to be functional stuffing, bi-component composite polyester fiber that is antistatic, antibacterial, Graphene enhancing is prepared by in-situ polymerization and composite spinning technology, wherein component A is the polyester of not graphene-containing, and B component is the polyester of the Graphene containing percentage by weight 0.3 ~ 3.0 ﹪.Publication number is the preparation method that the Chinese invention patent application of CN103215689A discloses a kind of Graphene modification of nylon 6 fiber, after Graphene being carried out carboxylated, chloride and amination process, obtained nylon 6 melt of Graphene modification by home position polymerization reaction, then obtain Graphene reinforced nylon 6 fiber through melt-spinning technology.
Visible, adopt Graphene to be that functional stuffing is prepared macromolecule composite functional fiber and come into one's own.Utilize the percolation threshold that Graphene is lower, characteristics such as likely realizing enhancing under lower filer content, conduct electricity, be antibacterial.But the nano-lamellar structure of Graphene and surface thereof lack active group also causes its sheet inter-layer bonding force high, directly mix with macromolecule and not easily peel off, form the aggregate of micron level on the contrary, seriously undermine the advantages such as its specific area, high conductivity and low percolation threshold.Known technology carries out to Graphene the dispersion that modification can promote it in macromolecule by means such as chemical grafts, but course of reaction is complicated, preparation efficiency is low, is unfavorable for commercial application.Therefore, be necessary to develop new graphene/polymer composite functional fiber and preparation method thereof to meet the needs of emerging market to composite functional fiber.
Summary of the invention
First object of the present invention is for the above-mentioned state of the art, provides a kind of macromolecule composite functional fiber containing partial reduction Graphene.
Macromolecule composite functional fiber of the present invention comprises component A and B component, and the mass ratio of component A and B component is 75/25 ~ 95/5, and the two is combined with part exposed conveying appliance, parallel type or core-skin type, with 20 ~ 100 ﹪ making every root fibrous outer surfaces long-pending for B component;
Described component A is contain the polyester that mass percent is 0.1 ~ 1 ﹪ partial reduction Graphene;
Described B component is contain the polyester that mass percent is 4 ~ 20 ﹪ nanocomposite fillers; Wherein nanocomposite filler comprises partial reduction Graphene and nano titanium oxide (TiO
2), nano titanium oxide (TiO
2) be 1/3 ~ 3/1 with the mass ratio of partial reduction Graphene;
Carbon/oxygen atom the ratio of above-mentioned partial reduction Graphene reaches 9/1 ~ 15/1;
Further, in described B component, nanocomposite filler is except containing partial reduction Graphene and nano titanium oxide (TiO
2) outward, can also comprise in CNT, nano carbon black one or both;
As preferably, in described B component, the mass percent of part reduced graphene is 1 ~ 5 ﹪;
As preferably, in described B component, the mass ratio of CNT and partial reduction Graphene is 1/1 ~ 3/1;
As preferably, in described B component, the mass ratio of nano carbon black and partial reduction Graphene is 1/1 ~ 9/1;
Described polyester is polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) (PBT) or polyethylene naphthalate (PEN).
Second object of the present invention is the preparation method proposing the above-mentioned macromolecule composite functional fiber containing partial reduction Graphene.
The inventive method comprises the following steps:
Step (1), preparation containing mass percent be the polyester of 0.1 ~ 1 ﹪ partial reduction Graphene as component A polyester:
Graphene oxide powder adds in alcohol A by 1.1 at normal temperatures, first mechanical agitation 10 ~ 30 minutes, then through ultrasonic wave dispersion 30 ~ 60 minutes, forms mixed serum A that is even, stable dispersion;
Carbon/oxygen atom the ratio of described graphene oxide powder is 3/1 ~ 5/1, the lamella number of plies is 2 ~ 8 layers, lamellar spacing is 2 ~ 20 nanometers, two dimensional surface is of a size of 0.2 ~ 2 micron, and its content in mixed serum A is obtained by the cubage of part reduced graphene in polymerisation efficiency and component A polyester by those skilled in the art;
The 1.2 mixed serum A that step (1.1) is obtained and p-phthalic acid or smart 2, 6-naphthalene diformic acid dimethyl ester carries out esterification in a kettle., polymerization, those skilled in the art can regulate the temperature and time of esterification and polymerisation according to actual conditions such as reaction units, graphene oxide generating portion reduction in the process, thus obtained be the polyethylene terephthalate (PET) of the partial reduction Graphene of 0.1 ~ 1 ﹪ containing mass percent, polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) (PBT) or polyethylene naphthalate (PEN) are as component A polyester,
Step (2), preparation containing mass percent be 4 ~ 20 ﹪ containing partial reduction Graphene and nano titanium oxide (TiO
2) the polyester of nanocomposite filler as B component polyester:
2.1 at normal temperatures by graphene oxide powder and nano titanium oxide (TiO
2) add in homogenizer, stir 5 ~ 25s with the speed of 10000 ~ 30000r/min, repeat this dry state mixed process 2 ~ 6 times; Or first adopt graphene oxide powder and nano titanium oxide (TiO with said method
2) carry out dry state mixing, ensure that it fully contacts, then add CNT or nano carbon black or CNT and nano carbon black two kinds, repeat this dry state mixed process 2 ~ 6 times, obtain nanocomposite filler;
Carbon/oxygen atom the ratio of described graphene oxide powder is 3/1 ~ 5/1, and the lamella number of plies is 2 ~ 8 layers, and lamellar spacing is 2 ~ 20 nanometers, and two dimensional surface is of a size of 0.2 ~ 2 micron;
Nano titanium oxide (TiO in described nanocomposite filler
2) and the mass ratio of graphene oxide be 1/3 ~ 3/1;
As preferably, described nano titanium oxide (TiO
2) diameter be less than or equal to the lamellar spacing of graphene oxide;
CNT in described nanocomposite filler and the mass ratio of graphene oxide are 1/1 ~ 3/1;
As preferably, the external diameter of described CNT is less than or equal to the lamellar spacing of graphene oxide;
Nano carbon black in described nanocomposite filler and the mass ratio of graphene oxide are 1/1 ~ 9/1;
As preferably, the diameter of described nano carbon black is less than or equal to the lamellar spacing of graphene oxide;
The nanocomposite filler powder that step (2.1) obtains to add in alcohol B and carries out hygrometric state mixing, first mechanical agitation 10 ~ 30 minutes by 2.2, then through ultrasonic wave dispersion 30 ~ 90 minutes, formed evenly, the mixed serum B of stable dispersion;
The content of described nanocomposite filler in mixed serum B is obtained by the cubage of nanocomposite filler in polymerisation efficiency and B component polyester by those skilled in the art;
Described alcohol A, alcohol B are independently ethylene glycol, 1,3-PD or BDO separately;
The 2.3 mixed serum B that step (2.2) is obtained and p-phthalic acid or smart 2, 6-naphthalene diformic acid dimethyl ester carries out esterification in a kettle., polymerization, for reducing polymerizate viscosity and improving reaction efficiency, alcohol B and p-phthalic acid or smart 2, the mol ratio of 6-naphthalene diformic acid dimethyl ester is 1.2/1 ~ 2.4/1, those skilled in the art can regulate other conditions of esterification and polymerisation as temperature and time according to actual conditions such as reaction units, graphene oxide generating portion reduction in the process, thus obtain containing mass percent the polyethylene terephthalate (PET) of the nanocomposite filler containing partial reduction Graphene being 4 ~ 20 ﹪, polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) (PBT) or polyethylene naphthalate (PEN) are as B component polyester,
Step (3), preparation comprise the macromolecule composite functional fiber of component A and B component:
Feed respectively after the B component crystallizing polyester that 3.1 component A polyester steps A obtained and step B obtain, drying in single screw extrusion machine in parallel and carry out melt composite spinning, extrude through melt pipeline, measuring pump and composite spinneret, regulate metering revolution speed to make the mass ratio of extruding of component A polyester and B component polyester be 75/25 ~ 95/5, then spinning under the spinning speed of 500 ~ 1500 ms/min, winding obtain the macromolecule compound protofibre comprising component A and B component;
The type of described composite spinneret is part exposed conveying appliance, parallel type or core-skin type, and outlet aperture is 0.3 ~ 0.7mm, and draw ratio is 2 ~ 4;
As preferably, the longitudinal section of described composite spinneret at least has one section of edge and extrudes the shape of shrinking gradually in direction, makes melt being subject to stretching action by during mouth mould; In order to fully realize this stretching action and avoid spinnerets to block, the shape of shrinking gradually in spinnerets longitudinal section is half hyperbola.
Those skilled in the art can choose melt temperature, screw speed etc. according to melt pressure, die swell ratio, spinline tension etc. makes spinnability meet production requirement, and 20 ~ 100 ﹪ that preferably measuring pump rotating speed and spinnerets combination make every root fibrous outer surfaces long-pending are simultaneously B component polyester;
3.2 macromolecule compound protofibres step (3.1) obtained carry out drawing-off and relaxation heat setting at 80 ~ 160 DEG C, draw ratio is 1.5 ~ 2.5 times, lax percentage is 10 ~ 20 ﹪ of draw ratio, and make the partial reduction Graphene in fiber be reduced to carbon/oxygen atom ratio further by reduction treatment to reach 9/1 ~ 15/1, thus obtain the macromolecule composite functional fiber comprising component A and B component;
Described reduction treatment is ultraviolet light irradiation or Cement Composite Treated by Plasma;
Wherein said ultraviolet light irradiation reduction treatment condition is ultraviolet wavelength is 500 ~ 900nm, and exposure time is 30 ~ 90 minutes, and fiber treatment temperature is 20 ~ 160 DEG C;
As preferably, described ultraviolet light irradiation process is carried out in an oxygen-free atmosphere;
Wherein said Cement Composite Treated by Plasma reduction treatment condition is atmosphere be hydrogen or hydrogen/argon gas ratio is the mist of 2/1, and operating air pressure is 10 ~ 100Pa, and power is 50 ~ 100W, and the processing time is 10 ~ 90 minutes, and treatment temperature is 20 ~ 60 DEG C.
The inventive method, by the kind of preferred nano functional filler, specification and proportioning, produces the macromolecule composite functional fiber of excellent performance under suitable in-situ polymerization and composite spinning condition.First, the carbon of preferential oxidation Graphene/oxygen atom ratio, the lamella number of plies, thickness and two dimensional surface size, realizes its even, stable dispersion in polymerization reaction system and end product; As graphene oxide content higher (>=1 ﹪), for the problem that its dispersion difficulty increases, further adding proportion is suitable, other Nano fillings of size coupling, by specifically dry-wet two-step method mixing, form specific combinations of nanoparticles, produce Coulomb repulsion and space steric effect, realize even, the stable dispersion of the nano combined infill system of high level; By the kind of preferred spinnerets, specification and cross sectional shape in spinning process, not only obtain specific fiber compound structure, and make melt by being subject to intensity and time all sufficiently high elongation flow field effect during spinnerets, promote nano particle preferentially arrangement in the fibre, give play to its effect to fibre property and function to greatest extent; Further by drawing-off, sizing and reduction treatment, improve the carbon/oxygen atom ratio of partial reduction Graphene, play its conduction, antibacterial and fire-retardant multiple action.In a word, the present invention by the formula of preferred nanocomposite filler and addition manner, and uses composite molten spinning to optimize fibre structure, and when overall filler content is lower, (≤20 ﹪) obtains good melting spinnability and fibre property and function.
The macromolecule composite functional fiber containing partial reduction Graphene that the inventive method obtains can be produced under comparatively high spinning speed (500 ~ 1500 ms/min), and production efficiency is higher; There is lower filament number (3 ~ 7dtex), higher intensity (>=2.0cN/dtex) and lower resistivity (≤10
9s/cm), antistatic demand is met; There is antibacterial and fire resistance simultaneously, thus have a good application prospect.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme of the present invention and effect are further described.
Comparative example 1:
Getting two dimensional surface size (particle diameter) is that the graphene powder 10 kilograms of 0.5 ~ 2 micron adds in 90 kg ethylene glycol and mixes, and add 3 kilograms of short agent of dispersion (one or its mixture as silicon ester class or amino silane ester class dispersant), 3 kilograms of coupling agents, grind 3 hours after stirring, 3 hours are disperseed again with ultrasonic wave, make the uniform Graphene/ethylene glycol solution of graphene dispersion, again p-phthalic acid is added Graphene/ethylene glycol solution according to the ratio of the mol ratio (1/1.15) of (p-phthalic acid/ethylene glycol), stir 0.5 hour, form uniform sizing material, then according to polyester production process, heat and carry out esterification and polymerisation, produce polyester fondant, and cooling granulation, the intrinsic viscosity of this polyester granules is 0.658dl/g, the effective mass content of Graphene in this polyester granules is 3.0 ﹪,
Using conventional polyester particle as component A, the polyester granules of above-mentioned graphene-containing 3.0 ﹪ is as B component, after A, B component crystallization respectively, drying, composite spinning technology casing is separately injected respectively by respective screw rod and measurement equipment, A, B component in mass ratio 60/40 ~ 90/10 ratio carry out composite spinning, produce have side by side, the composite fibre of core-skin or core shift structure.The resistivity of this composite fibre reaches 10
5~ 10
9Ω cm, has antistatic and antibacterial action, but does not have fire resistance.Visible, when component a certain in composite fibre not graphene-containing time, this fiber cannot have antistatic, antibacterial and fire resistance concurrently.
Comparative example 2:
Getting carbon/oxygen atom adds in double centner ethylene glycol than 10 kilograms, the graphene oxide powder lower than 5/1, grind 3 hours after stirring, 3 hours are disperseed again with ultrasonic wave, make the finely dispersed graphene oxide/ethylene glycol solution of graphene oxide, again p-phthalic acid is added graphene oxide/ethylene glycol solution according to the ratio of the mol ratio (1/1.15) of (p-phthalic acid/ethylene glycol), stir 0.5 hour, form uniform sizing material, then according to polyester production process, heat and carry out esterification and polymerisation, produce polyester fondant, and cooling granulation, the intrinsic viscosity of this polyester granules is 0.658dl/g, graphene oxide is generating portion reduction in course of reaction, its carbon/oxygen atom ratio is increased to 6/1 ~ 8/1, and the effective mass content in polyester granules is 3.0 ﹪,
Using conventional polyester particle as component A, the above-mentioned polyester granules containing partial reduction Graphene (carbon/oxygen atom ratio is 6/1 ~ 8/1) 3.0 ﹪ is as B component, after A, B component crystallization respectively, drying, composite spinning technology casing is separately injected respectively by respective screw rod and measurement equipment, A, B component in mass ratio 60/40 ~ 90/10 ratio carry out composite spinning, produce have side by side, the composite fibre of core-skin or core shift structure.The resistivity of this composite fibre is higher than 10
13Ω cm, does not have antistatic property, does not also have fire resistance.Visible, when the reducing degree of the graphene oxide in composite fibre or partial reduction Graphene is not enough, when namely carbon/oxygen atom compares lower (<9/1), this fiber does not have the performances such as antistatic.
Embodiment 1:
2.8 kilograms, the graphene oxide powder getting specification shown in table 1 adds in double centner ethylene glycol, at normal temperatures first mechanical agitation 30 minutes, then disperses 30 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; Mixed serum A and p-phthalic acid are added in reactor according to the mol ratio that ethylene glycol/p-phthalic acid is 1.2/1, and add antimony system or Titanium series catalyst, esterification is carried out at 215 ~ 235 DEG C, then be polymerized at 260 ~ 280 DEG C, thus obtained be that the polyethylene terephthalate (PET) of the partial reduction Graphene of 1 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.67dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 3.5/1;
5.7 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 2 nanometers
2) 1.9 kilograms add in homogenizer, stir 5s with the speed of 30000r/min, repeat this dry state mixed process 2 times, obtain containing graphene oxide and nano titanium oxide (TiO
2) nanocomposite filler; Nanocomposite filler obtained above is added in double centner ethylene glycol, at normal temperatures first mechanical agitation 10 minutes, then disperse 60 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; Mixed serum B and p-phthalic acid are added in reactor according to the mol ratio that ethylene glycol/p-phthalic acid is 1.8/1, and add antimony system or Titanium series catalyst, esterification is carried out at 215 ~ 235 DEG C, then be polymerized at 260 ~ 280 DEG C, thus obtained be that the polyethylene terephthalate (PET) of the nanocomposite filler of 4 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.65dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 6/1;
Get component A polyester obtained above and B component crystallizing polyester, feed respectively after drying in single screw extrusion machine in parallel and carry out melt composite spinning, through melt pipeline, measuring pump and entrance hole diameter are 0.9mm, outlet aperture is 0.3mm, draw ratio is 2, longitudinal section is that half hyp 5 exposed conveying appliance composite spinnerets are extruded, metering revolution speed is regulated to make the mass ratio of extruding of component A polyester and B component polyester be 75/25, then spinning under the spinning speed of 1500 ms/min, winding obtains the macromolecule compound protofibre that 20 ﹪ that every root fibrous outer surfaces amasss are B component polyester, and then carry out drawing-off and relaxation heat setting at 160 DEG C, draw ratio is 2.5 times, and lax percentage is 20 ﹪ of draw ratio, and 90 DEG C, carry out ultraviolet light irradiation 90 minutes under oxygen free condition, ultraviolet wavelength is 500nm, finally obtain the macromolecule composite functional fiber that filament number is 3.0dtex, fibrous outer surfaces amasss 20 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 9/1.
Embodiment 2:
0.24 kilogram, the graphene oxide powder getting specification shown in table 1 adds in double centner 1,3-PD, at normal temperatures first mechanical agitation 10 minutes, then disperses 60 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; By mixed serum A and p-phthalic acid according to 1, ammediol/p-phthalic acid be 1.2/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 205 ~ 225 DEG C, then be polymerized at 230 ~ 260 DEG C, thus obtained be that the polytrimethylene terephthalate (PTT) of the partial reduction Graphene of 0.1 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.92dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 5.3/1;
5.8 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 10 nanometers
2) 17.4 kilograms add in homogenizer, stir 25s with the speed of 20000r/min, repeat this dry state mixed process 4 times, obtain containing graphene oxide and nano titanium oxide (TiO
2) nanocomposite filler; Nanocomposite filler obtained above is added in double centner BDO, at normal temperatures first mechanical agitation 30 minutes, then disperse 90 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; By mixed serum B and p-phthalic acid according to 1,4-butanediol/p-phthalic acid be 2.4/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 215 ~ 235 DEG C, then be polymerized at 220 ~ 250 DEG C, thus obtained be that the polybutylene terephthalate (PBT) (PBT) of the nanocomposite filler of 20 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.90dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 5/1;
Feed respectively in single screw extrusion machine in parallel after getting component A polyester obtained above and B component crystallizing polyester, drying and carry out melt composite spinning, be 1.5mm through melt pipeline, measuring pump and entrance hole diameter, outlet aperture is 0.5mm, draw ratio is 3, parallel type composite spinneret that longitudinal section is taper extrudes, regulate metering revolution speed to make the mass ratio of extruding of component A polyester and B component polyester be 85/15, then spinning under the spinning speed of 500 ms/min, winding obtain the macromolecule compound protofibre that 60 ﹪ that every root fibrous outer surfaces amasss are B component polyester; And then carry out drawing-off and relaxation heat setting at 80 DEG C, draw ratio is 1.5 times, and lax percentage is 10 ﹪ of draw ratio; And carry out ultraviolet light irradiation 60 minutes at 20 DEG C, ultraviolet wavelength is 700nm, finally obtain the macromolecule composite functional fiber that filament number is 5.0dtex, fibrous outer surfaces amasss 60 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 15/1.
Embodiment 3:
1.2 kilograms, the graphene oxide powder getting specification shown in table 1 adds in double centner BDO, at normal temperatures first mechanical agitation 20 minutes, then disperses 45 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; By mixed serum A and p-phthalic acid according to 1,4-butanediol/p-phthalic acid be 1.2/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 215 ~ 235 DEG C, then be polymerized at 220 ~ 250 DEG C, thus obtained be that the polybutylene terephthalate (PBT) (PBT) of the partial reduction Graphene of 0.55 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.90dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 4.2/1;
7.8 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 18 nanometers
2) 7.8 kilograms add in homogenizer, stir 15s with the speed of 10000r/min, repeat this dry state mixed process 6 times, obtain containing graphene oxide and nano titanium oxide (TiO
2) nanocomposite filler; Nanocomposite filler obtained above is added in double centner 1,3-PD, at normal temperatures first mechanical agitation 20 minutes, then disperse 30 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; By mixed serum B and p-phthalic acid according to 1, ammediol/p-phthalic acid be 2.4/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 205 ~ 225 DEG C, then be polymerized at 230 ~ 260 DEG C, thus obtained be that the polytrimethylene terephthalate (PTT) of the nanocomposite filler of 12 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.89dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 3.4/1;
Feed respectively in single screw extrusion machine in parallel after getting component A polyester obtained above and B component crystallizing polyester, drying and carry out melt composite spinning, be 2.8mm through melt pipeline, measuring pump and entrance hole diameter, outlet aperture is 0.7mm, draw ratio is 4, core-skin type composite spinneret that longitudinal section is taper extrudes, regulate metering revolution speed to make the mass ratio of extruding of component A polyester and B component polyester be 95/5, then spinning under the spinning speed of 1000 ms/min, winding obtain the macromolecule compound protofibre that 100 ﹪ that every root fibrous outer surfaces amasss are B component polyester; And then carry out drawing-off and relaxation heat setting at 120 DEG C, draw ratio is 2.0 times, and lax percentage is 15 ﹪ of draw ratio; And 40 DEG C, Cement Composite Treated by Plasma 90 minutes in hydrogen atmosphere, operating air pressure is 100Pa, power is 50W, finally obtain the macromolecule composite functional fiber that filament number is 7.0dtex, fibrous outer surfaces amasss 100 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 12/1.
Embodiment 4:
3.8 kilograms, the graphene oxide powder getting specification shown in table 1 adds in double centner ethylene glycol, at normal temperatures first mechanical agitation 20 minutes, then disperses 60 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; By mixed serum A and essence 2,6-naphthalene diformic acid dimethyl ester is according to ethylene glycol/essence 2,6-naphthalene diformic acid dimethyl ester be 1.15/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 230 ~ 250 DEG C, then be polymerized at 270 ~ 290 DEG C, thus obtained be that the polyethylene naphthalate (PEN) of the partial reduction Graphene of 1 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.86dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 4.5/1;
3.7 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 5 nanometers
2) 3.7 kilograms add in homogenizer, 5s is stirred with the speed of 30000r/min, repeat this dry state mixed process 6 times, add the Single Walled Carbon Nanotube 7.4 kilograms that average diameter is 2 nanometers again, 5s is stirred with the speed of 30000r/min, repeat this dry state mixed process 6 times, obtain containing graphene oxide, nano titanium oxide (TiO
2) and the nanocomposite filler of CNT; Nanocomposite filler obtained above is added in double centner ethylene glycol, at normal temperatures first mechanical agitation 10 minutes, then disperse 60 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; By mixed serum B and essence 2,6-naphthalene diformic acid dimethyl ester is according to ethylene glycol/essence 2,6-naphthalene diformic acid dimethyl ester be 1.2/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 230 ~ 250 DEG C, then be polymerized at 260 ~ 290 DEG C, thus obtained be that the polyethylene naphthalate (PEN) of the nanocomposite filler of 4 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.89dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 5/1;
Get component A polyester obtained above and B component crystallizing polyester, feed respectively after drying in single screw extrusion machine in parallel and carry out melt composite spinning, through melt pipeline, measuring pump and entrance hole diameter are 1.0mm, outlet aperture is 0.3mm, draw ratio is 3, longitudinal section is that half hyp 3 exposed conveying appliance composite spinnerets are extruded, metering revolution speed is regulated to make the mass ratio of extruding of component A polyester and B component polyester be 75/25, then spinning under the spinning speed of 1000 ms/min, winding obtains the macromolecule compound protofibre that 60 ﹪ that every root fibrous outer surfaces amasss are B component polyester, and then carry out drawing-off and relaxation heat setting at 160 DEG C, draw ratio is 2.5 times, and lax percentage is 20 ﹪ of draw ratio, and 160 DEG C, carry out ultraviolet light irradiation 30 minutes under oxygen free condition, ultraviolet wavelength is 900nm, finally obtain the macromolecule composite functional fiber that filament number is 7.0dtex, fibrous outer surfaces amasss 60 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 12/1.
Embodiment 5:
2.1 kilograms, the graphene oxide powder getting specification shown in table 1 adds in double centner ethylene glycol, at normal temperatures first mechanical agitation 30 minutes, then disperses 60 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; By mixed serum A and essence 2,6-naphthalene diformic acid dimethyl ester is according to ethylene glycol/essence 2,6-naphthalene diformic acid dimethyl ester be 1.15/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 230 ~ 250 DEG C, then be polymerized at 270 ~ 290 DEG C, thus obtained be that the polyethylene naphthalate (PEN) of the partial reduction Graphene of 0.55 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.88dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 5.6/1;
4.3 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 10 nanometers
2) 4.3 kilograms add in homogenizer, 15s is stirred with the speed of 20000r/min, repeat this dry state mixed process 4 times, to add average diameter be again the multi-walled carbon nano-tubes 4.3 kilograms of 10 nanometers and average diameter is the nano carbon black 4.3 kilograms of 10 nanometers, 15s is stirred with the speed of 20000r/min, repeat this dry state mixed process 4 times, obtain containing graphene oxide, nano titanium oxide (TiO
2), the nanocomposite filler of CNT and nano carbon black; Nanocomposite filler obtained above is added in double centner ethylene glycol, at normal temperatures first mechanical agitation 10 minutes, then disperse 60 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; Mixed serum B and p-phthalic acid are added in reactor according to the mol ratio that ethylene glycol/p-phthalic acid is 2.4/1, and add zinc system or Titanium series catalyst, esterification is carried out at 215 ~ 240 DEG C, then be polymerized at 260 ~ 280 DEG C, thus obtained be that the polyethylene terephthalate (PET) of the nanocomposite filler of 12 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.58dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 3.9/1;
Get component A polyester obtained above and B component crystallizing polyester, feed respectively after drying in single screw extrusion machine in parallel and carry out melt composite spinning, through melt pipeline, measuring pump and entrance hole diameter are 2.4mm, outlet aperture is 0.5mm, draw ratio is 4, longitudinal section is that half hyp 3 exposed conveying appliance composite spinnerets are extruded, metering revolution speed is regulated to make the mass ratio of extruding of component A polyester and B component polyester be 85/15, then spinning under the spinning speed of 1500 ms/min, winding obtains the macromolecule compound protofibre that 20 ﹪ that every root fibrous outer surfaces amasss are B component polyester, and then carry out drawing-off and relaxation heat setting at 160 DEG C, draw ratio is 2.0 times, and lax percentage is 15 ﹪ of draw ratio, and 160 DEG C, carry out ultraviolet light irradiation 60 minutes under oxygen free condition, ultraviolet wavelength is 500nm, finally obtain the macromolecule composite functional fiber that filament number is 5.0dtex, fibrous outer surfaces amasss 20 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 9/1.
Embodiment 6:
1.6 kilograms, the graphene oxide powder getting specification shown in table 1 adds in double centner 1,3-PD, at normal temperatures first mechanical agitation 10 minutes, then disperses 45 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; By mixed serum A and p-phthalic acid according to 1, ammediol/p-phthalic acid be 1.8/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 205 ~ 225 DEG C, then be polymerized at 230 ~ 260 DEG C, thus obtained be that the polytrimethylene terephthalate (PTT) of the partial reduction Graphene of 1 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.92dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 3.3/1;
6.4 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 12 nanometers
2) 6.4 kilograms add in homogenizer, 25s is stirred with the speed of 10000r/min, repeat this dry state mixed process 2 times, add the nano carbon black 12.8 kilograms that average diameter is 12 nanometers again, 25s is stirred with the speed of 10000r/min, repeat this dry state mixed process 2 times, obtain containing graphene oxide, nano titanium oxide (TiO
2) and the nanocomposite filler of nano carbon black; Nanocomposite filler obtained above is added in double centner 1,3-PD, at normal temperatures first mechanical agitation 30 minutes, then disperse 90 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; By mixed serum B and p-phthalic acid according to 1, ammediol/p-phthalic acid be 2.4/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 205 ~ 230 DEG C, then be polymerized at 230 ~ 260 DEG C, thus obtained be that the polytrimethylene terephthalate (PTT) of the nanocomposite filler of 20 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.86dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 5.5/1;
Feed respectively in single screw extrusion machine in parallel after getting component A polyester obtained above and B component crystallizing polyester, drying and carry out melt composite spinning, be 1.4mm through melt pipeline, measuring pump and entrance hole diameter, outlet aperture is 0.7mm, draw ratio is 2,3 exposed conveying appliance composite spinnerets that longitudinal section is taper extrude, regulate metering revolution speed to make the mass ratio of extruding of component A polyester and B component polyester be 95/5, then spinning under the spinning speed of 500 ms/min, winding obtain the macromolecule compound protofibre that 20 ﹪ that every root fibrous outer surfaces amasss are B component polyester; And then carry out drawing-off and relaxation heat setting at 80 DEG C, draw ratio is 1.5 times, and lax percentage is 10 ﹪ of draw ratio; And 60 DEG C, Cement Composite Treated by Plasma 10 minutes in hydrogen atmosphere, operating air pressure is 10Pa, power is 100W, finally obtain the macromolecule composite functional fiber that filament number is 7.0dtex, fibrous outer surfaces amasss 20 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 9/1.
Embodiment 7:
1.2 kilograms, the graphene oxide powder getting specification shown in table 1 adds in double centner BDO, at normal temperatures first mechanical agitation 20 minutes, then disperses 45 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; By mixed serum A and p-phthalic acid according to 1,4-butanediol/p-phthalic acid be 1.2/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 215 ~ 235 DEG C, then be polymerized at 220 ~ 250 DEG C, thus obtained be that the polybutylene terephthalate (PBT) (PBT) of the partial reduction Graphene of 0.55 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.90dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 3.3/1;
2.2 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 18 nanometers
2) 4.4 kilograms add in homogenizer, 15s is stirred with the speed of 30000r/min, repeat this dry state mixed process 2 times, add the nano carbon black 19.8 kilograms that average diameter is 18 nanometers again, 15s is stirred with the speed of 30000r/min, repeat this dry state mixed process 2 times, obtain containing graphene oxide, nano titanium oxide (TiO
2) and the nanocomposite filler of nano carbon black; Nanocomposite filler obtained above is added in double centner BDO, at normal temperatures first mechanical agitation 20 minutes, then disperse 30 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; By mixed serum B and p-phthalic acid according to 1,4-butanediol/p-phthalic acid be 1.2/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 225 ~ 245 DEG C, then be polymerized at 240 ~ 260 DEG C, thus obtained be that the polybutylene terephthalate (PBT) (PBT) of the nanocomposite filler of 12 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.84dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 4/1;
Get component A polyester obtained above and B component crystallizing polyester, feed respectively after drying in single screw extrusion machine in parallel and carry out melt composite spinning, through melt pipeline, measuring pump and entrance hole diameter are 1.4mm, outlet aperture is 0.3mm, draw ratio is 3, longitudinal section is that half hyp 5 exposed conveying appliance composite spinnerets are extruded, metering revolution speed is regulated to make the mass ratio of extruding of component A polyester and B component polyester be 75/25, then spinning under the spinning speed of 1000 ms/min, winding obtains the macromolecule compound protofibre that 60 ﹪ that every root fibrous outer surfaces amasss are B component polyester, and then carry out drawing-off and relaxation heat setting at 80 DEG C, draw ratio is 2.0 times, and lax percentage is 20 ﹪ of draw ratio, and carry out ultraviolet light irradiation 20 minutes at 90 DEG C, ultraviolet wavelength is 900nm, finally obtain the macromolecule composite functional fiber that filament number is 3.0dtex, fibrous outer surfaces amasss 60 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 9/1.
Embodiment 8:
2.9 kilograms, the graphene oxide powder getting specification shown in table 1 adds in double centner ethylene glycol, at normal temperatures first mechanical agitation 30 minutes, then disperses 45 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; Mixed serum A and p-phthalic acid are added in reactor according to the mol ratio that ethylene glycol/p-phthalic acid is 1.15/1, and add antimony system or Titanium series catalyst, esterification is carried out at 215 ~ 235 DEG C, then be polymerized at 260 ~ 280 DEG C, thus obtained be that the polyethylene terephthalate (PET) of the partial reduction Graphene of 1 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.63dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 4.4/1;
1.8 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 2 nanometers
2) 5.4 kilograms add in homogenizer, 5s is stirred with the speed of 30000r/min, repeat this dry state mixed process 6 times, to add average diameter be again the Single Walled Carbon Nanotube 5.4 kilograms of 2 nanometers and average diameter is the nano carbon black 9 kilograms of 2 nanometers, 25s is stirred with the speed of 10000r/min, repeat this dry state mixed process 6 times, obtain containing graphene oxide, nano titanium oxide (TiO
2), the nanocomposite filler of CNT and nano carbon black; Nanocomposite filler obtained above is added in double centner ethylene glycol, at normal temperatures first mechanical agitation 10 minutes, then disperse 60 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; By mixed serum B and essence 2,6-naphthalene diformic acid dimethyl ester is according to ethylene glycol/essence 2,6-naphthalene diformic acid dimethyl ester be 2.4/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 230 ~ 250 DEG C, then be polymerized at 260 ~ 290 DEG C, thus obtained be that the polyethylene naphthalate (PEN) of the nanocomposite filler of 12 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.78dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 4.9/1;
Feed respectively in single screw extrusion machine in parallel after getting component A polyester obtained above and B component crystallizing polyester, drying and carry out melt composite spinning, be 2.8mm through melt pipeline, measuring pump and entrance hole diameter, outlet aperture is 0.5mm, draw ratio is 4, longitudinal section is that half hyp parallel type composite spinneret is extruded, regulate metering revolution speed to make the mass ratio of extruding of component A polyester and B component polyester be 75/25, then spinning under the spinning speed of 1500 ms/min, winding obtain the macromolecule compound protofibre that 60 ﹪ that every root fibrous outer surfaces amasss are B component polyester; And then carry out drawing-off and relaxation heat setting at 160 DEG C, draw ratio is 2.0 times, and lax percentage is 15 ﹪ of draw ratio; And 60 DEG C, hydrogen/argon gas ratio is Cement Composite Treated by Plasma 50 minutes in the mixed-gas atmosphere of 2/1, operating air pressure is 55Pa, power is 75W, finally obtain the macromolecule composite functional fiber that filament number is 7.0dtex, fibrous outer surfaces amasss 60 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 12/1.
Embodiment 9:
0.29 kilogram, the graphene oxide powder getting specification shown in table 1 adds in double centner ethylene glycol, at normal temperatures first mechanical agitation 20 minutes, then disperses 30 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; Mixed serum A and p-phthalic acid are added in reactor according to the mol ratio that ethylene glycol/p-phthalic acid is 1.15/1, and add antimony system or Titanium series catalyst, esterification is carried out at 215 ~ 235 DEG C, then be polymerized at 260 ~ 280 DEG C, thus obtained be that the polyethylene terephthalate (PET) of the partial reduction Graphene of 0.1 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.65dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 5.3/1;
2.2 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 10 nanometers
2) 6.6 kilograms add in homogenizer, 25s is stirred with the speed of 20000r/min, repeat this dry state mixed process 6 times, to add average diameter be again the multi-walled carbon nano-tubes 6.6 kilograms of 10 nanometers and average diameter is the nano carbon black 6.6 kilograms of 10 nanometers, 15s is stirred with the speed of 10000r/min, repeat this dry state mixed process 6 times, obtain containing graphene oxide, nano titanium oxide (TiO
2), the nanocomposite filler of CNT and nano carbon black; Nanocomposite filler obtained above is added in double centner BDO, at normal temperatures first mechanical agitation 10 minutes, then disperse 60 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; By mixed serum B and p-phthalic acid according to 1,4-butanediol/p-phthalic acid be 2.4/1 mol ratio add in reactor, and add antimony system or Titanium series catalyst, esterification is carried out at 225 ~ 235 DEG C, then be polymerized at 230 ~ 260 DEG C, thus obtained be that the polybutylene terephthalate (PBT) (PBT) of the nanocomposite filler of 20 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.81dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 5.5/1;
Feed respectively in single screw extrusion machine in parallel after getting component A polyester obtained above and B component crystallizing polyester, drying and carry out melt composite spinning, be 1.8mm through melt pipeline, measuring pump and entrance hole diameter, outlet aperture is 0.3mm, draw ratio is 4, longitudinal section is that half hyp core-skin type composite spinneret is extruded, regulate metering revolution speed to make the mass ratio of extruding of component A polyester and B component polyester be 95/5, then spinning under the spinning speed of 500 ms/min, winding obtain the macromolecule compound protofibre that 100 ﹪ that every root fibrous outer surfaces amasss are B component polyester; And then carry out drawing-off and relaxation heat setting at 120 DEG C, draw ratio is 1.5 times, and lax percentage is 10 ﹪ of draw ratio; And 60 DEG C, Cement Composite Treated by Plasma 90 minutes in hydrogen atmosphere, operating air pressure is 10Pa, power is 100W, finally obtain the macromolecule composite functional fiber that filament number is 3.0dtex, fibrous outer surfaces amasss 100 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 15/1.
Embodiment 10:
1.4 kilograms, the graphene oxide powder getting specification shown in table 1 adds in double centner 1,3-PD, at normal temperatures first mechanical agitation 10 minutes, then disperses 30 minutes through ultrasonic wave, forms mixed serum A that is even, stable dispersion; By mixed serum A and p-phthalic acid according to 1, ammediol/p-phthalic acid be 1.15/1 mol ratio add in reactor, and add Titanium series catalyst, esterification is carried out at 205 ~ 225 DEG C, then be polymerized at 230 ~ 260 DEG C, thus obtained be that the polytrimethylene terephthalate (PTT) of the partial reduction Graphene of 0.55 ﹪ is as component A polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.92dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 3.2/1;
7 kilograms, the graphene oxide powder getting specification shown in table 1 and average diameter are the nano titanium oxide (TiO of 18 nanometers
2) 3.5 kilograms add in homogenizer, 15s is stirred with the speed of 10000r/min, repeat this dry state mixed process 6 times, to add average diameter be again the multi-walled carbon nano-tubes 7 kilograms of 10 nanometers and average diameter is the nano carbon black 7 kilograms of 10 nanometers, 25s is stirred with the speed of 20000r/min, repeat this dry state mixed process 4 times, obtain containing graphene oxide, nano titanium oxide (TiO
2), the nanocomposite filler of CNT and nano carbon black; Nanocomposite filler obtained above is added in double centner ethylene glycol, at normal temperatures first mechanical agitation 30 minutes, then disperse 90 minutes through ultrasonic wave, form mixed serum B that is even, stable dispersion; Mixed serum B and p-phthalic acid are added in reactor according to the mol ratio that ethylene glycol/p-phthalic acid is 2/1, and add Titanium series catalyst, esterification is carried out at 215 ~ 235 DEG C, then be polymerized at 260 ~ 280 DEG C, thus obtained be that the polyethylene terephthalate (PET) of the nanocomposite filler of 14 ﹪ is as B component polyester containing mass percent, after testing, the intrinsic viscosity of polyester is wherein 0.62dL/g, and the carbon/oxygen atom ratio of partial reduction Graphene is 5.6/1;
Feed respectively in single screw extrusion machine in parallel after getting component A polyester obtained above and B component crystallizing polyester, drying and carry out melt composite spinning, be 1.4mm through melt pipeline, measuring pump and entrance hole diameter, outlet aperture is 0.7mm, draw ratio is 2, parallel type composite spinneret that longitudinal section is taper extrudes, regulate metering revolution speed to make the mass ratio of extruding of component A polyester and B component polyester be 85/15, then spinning under the spinning speed of 1000 ms/min, winding obtain the macromolecule compound protofibre that 20 ﹪ that every root fibrous outer surfaces amasss are B component polyester; And then carry out drawing-off and relaxation heat setting at 120 DEG C, draw ratio is 2.0 times, and lax percentage is 15 ﹪ of draw ratio; And 90 DEG C, carry out ultraviolet light irradiation 30 minutes under oxygen free condition, ultraviolet wavelength is 700nm, finally obtain the macromolecule composite functional fiber that filament number is 5.0dtex, fibrous outer surfaces amasss 20 ﹪ are B component polyester, its performance is as shown in table 1, have antistatic, antibacterial and flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene wherein reaches 9/1.
Table 1 embodiment 1 ~ 10 graphene oxide raw material specification and meet fibre property data
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet application claims, all belongs to protection scope of the present invention.
Claims (10)
1. the macromolecule composite functional fiber containing partial reduction Graphene, it is characterized in that comprising component A and B component, the mass ratio of component A and B component is 75/25 ~ 95/5, and the two is combined with part exposed conveying appliance, parallel type or core-skin type, with 20 ~ 100 ﹪ making every root fibrous outer surfaces long-pending for B component;
Described component A is contain the polyester that mass percent is 0.1 ~ 1 ﹪ partial reduction Graphene;
Described B component is contain the polyester that mass percent is 4 ~ 20 ﹪ nanocomposite fillers; Wherein nanocomposite filler comprises partial reduction Graphene and nano titanium oxide (TiO
2), nano titanium oxide (TiO
2) be 1/3 ~ 3/1 with the mass ratio of partial reduction Graphene;
Carbon/oxygen atom the ratio of described partial reduction Graphene reaches 9/1 ~ 15/1;
Described polyester is polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) (PBT) or polyethylene naphthalate (PEN).
2. a kind of macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 1, to is characterized in that in described B component that nanocomposite filler is except containing partial reduction Graphene and nano titanium oxide (TiO
2) outward, can also comprise in CNT, nano carbon black one or both.
3. a kind of macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 1, is characterized in that the mass percent of part reduced graphene in described B component is 1 ~ 5 ﹪.
4. a kind of macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 2, is characterized in that the mass ratio of CNT and partial reduction Graphene in described B component is 1/1 ~ 3/1; In described B component, the mass ratio of nano carbon black and partial reduction Graphene is 1/1 ~ 9/1.
5. preparation a kind of method containing the macromolecule composite functional fiber of partial reduction Graphene as claimed in claim 1, is characterized in that the method comprises the following steps:
Step (1), preparation containing mass percent be the polyester of 0.1 ~ 1 ﹪ partial reduction Graphene as component A polyester:
1.1 at normal temperatures by carbon/oxygen atom than be 3/1 ~ 5/1, the lamella number of plies is 2 ~ 8 layers, lamellar spacing is 2 ~ 20 nanometers, two dimensional surface is of a size of 0.2 ~ 2 micron graphene oxide powder adds in alcohol A, first mechanical agitation 10 ~ 30 minutes, again through ultrasonic wave dispersion 30 ~ 60 minutes, form mixed serum A that is even, stable dispersion;
The 1.2 mixed serum A that step (1.1) is obtained and p-phthalic acid or smart 2,6-naphthalene diformic acid dimethyl ester carries out esterification, polymerization in a kettle., obtain and contain polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) (PBT) or the polyethylene naphthalate (PEN) that mass percent is the partial reduction Graphene of 0.1 ~ 1 ﹪, as component A polyester;
Step (2), preparation containing mass percent be 4 ~ 20 ﹪ containing partial reduction Graphene and nano titanium oxide (TiO
2) the polyester of nanocomposite filler as B component polyester:
2.1 at normal temperatures by carbon/oxygen atom than be 3/1 ~ 5/1, the lamella number of plies is 2 ~ 8 layers, lamellar spacing is 2 ~ 20 nanometers, two dimensional surface is of a size of graphene oxide powder and the nano titanium oxide (TiO of 0.2 ~ 2 micron
2) add in homogenizer, stir 5 ~ 25s with the speed of 10000 ~ 30000r/min, repeat this dry state mixed process 2 ~ 6 times; Or first adopt graphene oxide powder and nano titanium oxide (TiO with said method
2) carry out dry state mixing, ensure that it fully contacts, then add CNT or nano carbon black or CNT and nano carbon black two kinds, repeat this dry state mixed process 2 ~ 6 times, obtain nanocomposite filler;
Nano titanium oxide (TiO in described nanocomposite filler
2) and the mass ratio of graphene oxide be 1/3 ~ 3/1;
CNT in described nanocomposite filler and the mass ratio of graphene oxide are 1/1 ~ 3/1;
Nano carbon black in described nanocomposite filler and the mass ratio of graphene oxide are 1/1 ~ 9/1;
The nanocomposite filler powder that step (2.1) obtains to add in alcohol B and carries out hygrometric state mixing, first mechanical agitation 10 ~ 30 minutes by 2.2, then through ultrasonic wave dispersion 30 ~ 90 minutes, formed evenly, the mixed serum B of stable dispersion;
Described alcohol A, B are independently ethylene glycol, 1,3-PD or BDO separately;
The 2.3 mixed serum B that step (2.2) is obtained and p-phthalic acid or smart 2,6-naphthalene diformic acid dimethyl ester carries out esterification, polymerization in a kettle., and obtained is that the polyethylene terephthalate (PET) of the nanocomposite filler containing partial reduction Graphene of 4 ~ 20 ﹪, polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) (PBT) or polyethylene naphthalate (PEN) are as B component polyester containing mass percent;
The mol ratio of described alcohol B and p-phthalic acid or smart NDA dimethyl ester is 1.2/1 ~ 2.4/1;
Step (3), preparation comprise the macromolecule composite functional fiber of component A and B component:
Feed respectively after the B component crystallizing polyester that 3.1 component A polyester steps A obtained and step B obtain, drying in single screw extrusion machine in parallel and carry out melt composite spinning, extrude through melt pipeline, measuring pump and composite spinneret, metering revolution speed is regulated to make the mass ratio of extruding of component A polyester and B component polyester be 75/25 ~ 95/5, then spinning under the spinning speed of 500 ~ 1500 ms/min, winding obtain the macromolecule compound protofibre comprising component A and B component, and 20 ~ 100 ﹪ making every root fibrous outer surfaces long-pending are B component polyester;
3.2 macromolecule compound protofibres step (3.1) obtained carry out drawing-off and relaxation heat setting at 80 ~ 160 DEG C, draw ratio is 1.5 ~ 2.5 times, lax percentage is 10 ~ 20 ﹪ of draw ratio, and make the partial reduction Graphene in fiber be reduced to carbon/oxygen atom ratio further by reduction treatment to reach 9/1 ~ 15/1, thus obtain the macromolecule composite functional fiber comprising component A and B component.
6. the preparation method of a kind of macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 5, is characterized in that the nano titanium oxide (TiO described in step (2)
2) diameter be less than or equal to the lamellar spacing of graphene oxide; The external diameter of described CNT is less than or equal to the lamellar spacing of graphene oxide; The diameter of described nano carbon black is less than or equal to the lamellar spacing of graphene oxide.
7. the preparation method of a kind of macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 5, it is characterized in that the type of the composite spinneret described in step (3.1) is part exposed conveying appliance, parallel type or core-skin type, outlet aperture is 0.3 ~ 0.7mm, and draw ratio is 2 ~ 4.
8. the preparation method of a kind of macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 7, it is characterized in that the longitudinal section of described composite spinneret at least has one section of edge and extrudes the shape of shrinking gradually in direction, make melt being subject to stretching action by during mouth mould; In order to fully realize this stretching action and avoid spinnerets to block, the shape of shrinking gradually in spinnerets longitudinal section is half hyperbola.
9. the preparation method of a kind of macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 5, is characterized in that the reduction treatment described in step (3.1) is ultraviolet light irradiation or Cement Composite Treated by Plasma;
Wherein said ultraviolet light irradiation reduction treatment condition is ultraviolet wavelength is 500 ~ 900nm, and exposure time is 30 ~ 90 minutes, and fiber treatment temperature is 20 ~ 160 DEG C;
Wherein said Cement Composite Treated by Plasma reduction treatment condition is atmosphere be hydrogen or hydrogen/argon gas ratio is the mist of 2/1, and operating air pressure is 10 ~ 100Pa, and power is 50 ~ 100W, and the processing time is 10 ~ 90 minutes, and treatment temperature is 20 ~ 60 DEG C.
10. the preparation method of a kind of macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 9, is characterized in that ultraviolet light irradiation process is carried out in an oxygen-free atmosphere.
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| CN110230110A (en) * | 2019-07-09 | 2019-09-13 | 杭州高烯科技有限公司 | A kind of low cost, the terylene of antistatic and preparation method thereof |
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| CN112981608B (en) * | 2019-12-02 | 2023-02-17 | 江苏鑫博高分子材料有限公司 | Low-elasticity linen-like two-component polyester fiber |
| CN111171296A (en) * | 2020-02-12 | 2020-05-19 | 东华大学 | Preparation method and application of antibacterial antistatic flame-retardant polyester resin |
| CN111138643A (en) * | 2020-02-12 | 2020-05-12 | 东华大学 | Preparation method and application of antistatic flame-retardant polyester resin |
| CN111138643B (en) * | 2020-02-12 | 2021-03-16 | 东华大学 | Preparation method and application of antistatic flame-retardant polyester resin |
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