CN105002595B - 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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- CN105002595B CN105002595B CN201510430677.3A CN201510430677A CN105002595B CN 105002595 B CN105002595 B CN 105002595B CN 201510430677 A CN201510430677 A CN 201510430677A CN 105002595 B CN105002595 B CN 105002595B
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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, it is related to a kind of macromolecule complex function containing partial reduction Graphene
Fiber and preparation method thereof.
Background technology
Functional fibre refers to the tencel with one or more specific functions, such as conductive fiber, fire resistance fibre, antibacterial
Fiber etc..Functional fibre has the characteristics that high technology content, high added value, the high market demand., due to tool taking conductive fiber as a example
There are the characteristics such as antistatic, electromagnetic wave absorption, be the high added values such as antistatic explosion-proof clothing, dust-free sterile clothes, high-grade clothing and home textile
The required raw material of product, is applied to Aero-Space, defence and military, petrochemical industry, mining, microelectronics, biological medicine, Precision Machining, spinning
The various fields such as woven garment, wide market.
The preparation of functional fibre is general to be passed through to add micron or nanoscale functional stuffing in macromolecule matrix, including charcoal
Black, metal and metal oxide powder, CNT or carbon nano-fiber etc., are then obtained through spinning technique.Required for realizing
Function as conductive, the content of filler must be over and could form conductive network during a certain particular value, and this value is commonly known as and " exceedes
Ooze threshold value ".The percolation threshold of conventional filler (as white carbon black and metal dust) is higher, often beyond 20, thus brings spinnability
Be deteriorated, the problems such as fibre strength declines, feel is stiff, fiber number and density increase.
Additionally, the single function of conventional filler.For example: white carbon black primarily serves electric action；Magnesium hydroxide plays fire retardation；
The metals such as silver, copper, zinc (or its ion) primarily serve antibacterial action, etc..For realizing complex function, generally require to add simultaneously
Multiple fillers, when its content all reaches sufficiently high, produce conductive, fire-retardant, antibacterial and other effects respectively.This certainly will increase further
Content in macromolecule matrix for the filler, makes the problem of above-mentioned spinnability and fibre property aspect more prominent.Therefore, have concurrently many
Although the macromolecule composite functional fiber prospect of kind of function is tempting, its research and development difficult point is still very big.
As a class nano material of latest development after CNT, Graphene has more excellent electric conductivity and pole
High radius-thickness ratio and specific surface area.It is reported that, the Graphene as little as 0.1～3.8vol of the percolation threshold in various macromolecules,
Significant electric conductivity lifting can be obtained under extremely low addition.The Chinese invention patent Shen of Publication No. cn103710790a
Please be functional stuffing using Graphene, antistatic, antibacterial, Graphene increasing are prepared by in-situ polymerization and composite spinning technology
Strong bi-component composite polyester fiber, wherein component a are the polyester of not graphene-containing, component b be containing percentage by weight 0.3～
The polyester of 3.0 Graphene.The Chinese invention patent application of Publication No. cn103215689a discloses a kind of Graphene and changes
Property nylon 6 fiber preparation method, Graphene is carried out after carboxylated, chloride and amination process, anti-by in-situ polymerization
Graphene modified nylon 6 melt should be obtained, then obtain Graphene reinforced nylon 6 fiber through melt-spinning technology.
It can be seen that, macromolecule composite functional fiber is prepared for functional stuffing using Graphene and is taken seriously.Using Graphene
Relatively low percolation threshold is it is possible to realize enhancing, the characteristic such as conduction, antibacterial under relatively low filer content.But the receiving of Graphene
Rice lamellar structure and its surface lack active group and also lead to its piece inter-layer bonding force high, directly mix not easy-peel with macromolecule
From the aggregate of formation micron level, has seriously undermined the advantages such as its specific area, high conductivity and low percolation threshold on the contrary.
Known technology is modified to Graphene promoting its dispersion in macromolecule by means such as chemical grafts, but course of reaction
Complicated, preparation efficiency is low, is unfavorable for commercial application.Therefore, it is necessary to the new graphene/polymer composite functional fiber of exploitation
And preparation method thereof to meet the needs to composite functional fiber for the emerging market.
Content of the invention
First purpose of the present invention is for the above-mentioned state of the art, provides a kind of macromolecule containing partial reduction Graphene
Composite functional fiber.
The macromolecule composite functional fiber of the present invention includes a component and b component, and a component is 75/ with the mass ratio of b component
25～95/5, and the two is combined with part exposed conveying appliance, parallel type or core-skin type so that every fibrous outer surfaces amass 20～
100 is b component；
The polyester that it is 0.1～1 partial reduction Graphene containing mass percent that described a group is divided into；
The polyester that it is 4～20 nanocomposite fillers containing mass percent that described b group is divided into；Wherein nanocomposite filler
Including partial reduction Graphene and nano titanium oxide (tio2), nano titanium oxide (tio2) with the matter of partial reduction Graphene
Amount ratio is 1/3～3/1；
The carbon of above-mentioned partial reduction Graphene/oxygen atom ratio reaches 9/1～15/1；
Further, in described b component, nanocomposite filler removes containing partial reduction Graphene and nano titanium oxide
(tio2) outward, one of CNT, nano carbon black or two kinds can also be included；
Preferably, the mass percent of part reduced graphene is 1～5 in described b component；
Preferably, CNT and the mass ratio of partial reduction Graphene are 1/1～3/1 in described b component；
Preferably, nano carbon black and the mass ratio of partial reduction Graphene are 1/1～9/1 in described b component；
Described polyester is polyethylene terephthalate (pet), PTT (ptt), poly- right
Benzene dicarboxylic acid butanediol ester (pbt) or polyethylene naphthalate (pen).
Second object of the present invention is the system proposing the above-mentioned macromolecule composite functional fiber containing partial reduction Graphene
Preparation Method.
The inventive method comprises the following steps:
Step (1), preparation containing mass percent be 0.1～1 partial reduction Graphene polyester as a component polyester:
Graphene oxide powder is added in alcohol a by 1.1 at normal temperatures, first mechanical agitation 10～30 minutes, then through ultrasound wave
Dispersion 30～60 minutes, forms uniform, the mixed serum a of stable dispersion；
For 3/1～5/1, the lamella number of plies is 2～8 layers to the carbon/oxygen atom of described graphene oxide powder ratio, lamellar spacing
For 2～20 nanometers, a size of 0.2～2 micron of two dimensional surface, its content in mixed serum a is led to by those skilled in the art
The cubage crossing part reduced graphene in polyreaction efficiency and a component polyester obtains；
The 1.2 mixed serum a obtaining step (1.1) and p-phthalic acid or smart 2,6- naphthalene diformic acid dimethyl ester are anti-
Answer and carry out in kettle being esterified, be polymerized, those skilled in the art can adjust esterification and polyreaction according to practical situations such as reaction units
Temperature and time, in the process graphene oxide occur partial reduction, thus be obtained containing mass percent be 0.1～1
The polyethylene terephthalate (pet) of partial reduction Graphene, PTT (ptt), poly- to benzene
Dioctyl phthalate butanediol ester (pbt) or polyethylene naphthalate (pen) are as a component polyester；
Step (2), preparation containing mass percent be 4～20 Graphene containing partial reduction and nano titanium oxide
(tio2) nanocomposite filler polyester as b component polyester:
2.1 at normal temperatures by graphene oxide powder and nano titanium oxide (tio2) add in homogenizer, with
The speed of 10000～30000r/min stirs 5～25s, repeats this dry state mixed process 2～6 times；Or first adopt in aforementioned manners
By graphene oxide powder and nano titanium oxide (tio2) carry out dry state mixing it is ensured that it is fully contacted, add carbon nanometer
Pipe or nano carbon black or CNT and two kinds of nano carbon black, repeat this dry state mixed process 2～6 times, obtain nano combined filling out
Material；
For 3/1～5/1, the lamella number of plies is 2～8 layers to the carbon/oxygen atom of described graphene oxide powder ratio, lamellar spacing
For 2～20 nanometers, a size of 0.2～2 micron of two dimensional surface；
Nano titanium oxide (tio in described nanocomposite filler2) and graphene oxide mass ratio be 1/3～3/
1；
Preferably, described nano titanium oxide (tio2) diameter be less than or equal to graphene oxide piece thickness
Degree；
The mass ratio of the CNT in described nanocomposite filler and graphene oxide is 1/1～3/1；
Preferably, the external diameter of described CNT is less than or equal to the lamellar spacing of graphene oxide；
The mass ratio of the nano carbon black in described nanocomposite filler and graphene oxide is 1/1～9/1；
Preferably, the diameter of described nano carbon black is less than or equal to the lamellar spacing of graphene oxide；
Carry out hygrometric state mixing, first mechanical agitation in the 2.2 nanocomposite filler powder addition alcohol b that step (2.1) is obtained
10～30 minutes, then disperse 30～90 minutes through ultrasound wave, form uniform, the mixed serum b of stable dispersion；
Content in mixed serum b for the described nanocomposite filler passes through polyreaction efficiency by those skilled in the art
Cubage with nanocomposite filler in b component polyester obtains；
Described alcohol a, alcohol b each stand alone as ethylene glycol, 1,3-PD or BDO；
The 2.3 mixed serum b obtaining step (2.2) and p-phthalic acid or smart 2,6- naphthalene diformic acid dimethyl ester are anti-
Answer and carry out in kettle being esterified, be polymerized, for reducing polymerizate viscosity and raising reaction efficiency, alcohol b and p-phthalic acid or essence 2,
The mol ratio of 6- naphthalene diformic acid dimethyl ester is 1.2/1～2.4/1, and those skilled in the art can be according to practical situations such as reaction units
Adjust the other conditions such as temperature and time of esterification and polyreaction, graphene oxide occurs partial reduction in the process, from
And the poly terephthalic acid second two of the nanocomposite filler containing partial reduction Graphene that containing mass percent be 4～20 is obtained
Alcohol ester (pet), PTT (ptt), polybutylene terephthalate (PBT) (pbt) or poly- to naphthalenedicarboxylic acid second
Diol ester (pen) is as b component polyester；
Step (3), preparation include the macromolecule composite functional fiber of a component and b component:
B component crystallizing polyester that the 3.1 a component polyester obtaining step a and step b obtain, be dried after feed respectively simultaneously
Carry out melt composite spinning in the single screw extrusion machine of connection, through melt pipeline, dosing pump and composite spinneret extrusion, adjust metering
It is 75/25～95/5 that revolution speed makes the extrusion mass ratio of a component polyester and b component polyester, then at 500～1500 ms/min
Under spinning speed, spinning, winding obtain being combined protofibre including the macromolecule of a component and b component；
The type of described composite spinneret is part exposed conveying appliance, parallel type or core-skin type, outlet aperture is 0.3～
0.7mm, draw ratio is 2～4；
Preferably, the longitudinal section of described composite spinneret at least has one section of shape gradually tapering up along extrusion direction
Shape, makes melt be stretched effect when by mouth mould；In order to fully realize this stretching action and avoid spinneret to block, spray
Gradually taper up in filament plate longitudinal section is shaped as half hyperbola.
Those skilled in the art can choose melt temperature according to melt pressure, die swell ratio, spinline tension etc., screw rod turns
Speed etc. makes spinnability meet production requirement, and preferably metering revolution speed and spinneret combination make long-pending 20 of every fibrous outer surfaces simultaneously
～100 is b component polyester；
The 3.2 compound protofibres of macromolecules obtaining step (3.1) carry out drawing-off at 80～160 DEG C and lax heat is fixed
Type, draw ratio is 1.5～2.5 times, and lax percentage ratio is the 10～20 of draw ratio, and makes the portion in fiber by reduction treatment
Divide reduced graphene to be reduced to carbon/oxygen atom ratio further and reach 9/1～15/1, thus obtaining the height including a component and b component
Molecule composite functional fiber；
Described reduction treatment is ultraviolet light irradiation or corona treatment；
Wherein said ultraviolet light irradiation reduction treatment condition is a length of 500～900nm of ultraviolet light wave, and exposure time is 30
～90 minutes, fiber treatment temperature was 20～160 DEG C；
Preferably, described ultraviolet light irradiation is processed carrying out in an oxygen-free atmosphere；
Wherein said corona treatment reduction treatment condition is that atmosphere is hydrogen or hydrogen/argon ratio is 2/1
Mixed gas, operating air pressure is 10～100pa, and power is 50～100w, and process time is 10～90 minutes, and treatment temperature is 20
～60 DEG C.
The inventive method by the species of preferred nano functional filler, specification and proportioning, in suitable in-situ polymerization and multiple
Close the macromolecule composite functional fiber producing excellent performance under spinning condition.First, the carbon/oxygen atom of preferred graphene oxide
Than, the lamella number of plies, thickness and two dimensional surface size, realize its uniform, stable point in polymerization reaction system and final product
Dissipate；When graphene oxide content higher (>=1), disperse the problem that difficulty increases for it, further adding proportion suitably,
Other Nano fillings of size coupling, by specifically doing-wet two-step method mixing, form specific combinations of nanoparticles, produce quiet
Electricity repels and space steric effect, realizes uniform, the stable dispersion of high level nano combined filling system；Logical in spinning process
Cross species, specification and the cross sectional shape of preferred spinneret, not only obtain specific fiber compound structure, and so that melt is being passed through
It is subject to intensity and time all sufficiently high elongation flow field to act on during spinneret, promote nanoparticle preferentially arrangement in the fibre,
Give play to its effect to fibre property and function to greatest extent；Pass through drawing-off, sizing and reduction treatment, raising portion further
Divide the carbon/oxygen atom ratio of reduced graphene, play its conductive, antibacterial and fire-retardant multiple action.In a word, the present invention passes through preferably
The formula of nanocomposite filler and addition manner, and optimize fibre structure with composite molten spinning, relatively low in overall filler content
When (≤20) obtain good melting spinnability and fibre property and function.
The macromolecule composite functional fiber containing partial reduction Graphene that the inventive method is obtained can be compared with high spinning speed
Produce under (500～1500 ms/min), production efficiency is higher；There is relatively low filament number (3～7dtex), higher intensity
(>=2.0cn/dtex) and relatively low resistivity (≤109S/cm), meet antistatic demand；There is antibacterial and anti-flammability simultaneously
Can, thus have a good application prospect.
Specific embodiment
With reference to embodiment, technical scheme and effect are further described.
Comparative example 1:
10 kilograms of the graphene powder that two dimensional surface size (particle diameter) is 0.5～2 micron is taken to add in 90 kilograms of ethylene glycol
Mixing, and add 3 kilograms of dispersions rush agent (as one kind or its mixture of silane esters or amino silane esters dispersant), 3,000
Gram coupling agent, grinds 3 hours after stirring, then is disperseed 3 hours with ultrasound wave, make the uniform Graphene of graphene dispersion/
Ethylene glycol solution, then p-phthalic acid is added according to the ratio of the mol ratio (1/1.15) of (p-phthalic acid/ethylene glycol)
Enter Graphene/ethylene glycol solution, stir 0.5 hour, form uniform sizing material, then according to polyester production process, heat and carry out
Esterification and polyreaction, produce polyester fondant, and cooling granulation, and the intrinsic viscosity of this polyester granules is 0.658dl/g, Graphene
Effective mass content in this polyester granules is 3.0；
Using conventional polyester particle as a component, the polyester granules of above-mentioned graphene-containing 3.0 as b component, by a, b group
Point respectively crystallization, be dried after, be injected separately in the respective casing of composite spinning technology by respective screw rod and measurement equipment, a,
The ratio of b component in mass ratio 60/40～90/10 carries out composite spinning, produce have side by side, core-skin or core shift structure compound
Fiber.The resistivity of this composite fibre reaches 105～109ω cm, has antistatic and antibacterial action, but does not have anti-flammability
Energy.It can be seen that, when a certain component not graphene-containing in composite fibre, this fiber cannot have antistatic, antibacterial and fire resistance concurrently.
Comparative example 2:
Carbon/oxygen atom is taken to add in double centner ethylene glycol for 10 kilograms than the graphene oxide powder less than 5/1, stirring is all
Grind 3 hours after even, then disperseed 3 hours with ultrasound wave, make the finely dispersed graphene oxide/ethylene glycol of graphene oxide molten
Liquid, then p-phthalic acid is added oxidation stone according to the ratio of the mol ratio (1/1.15) of (p-phthalic acid/ethylene glycol)
Black alkene/ethylene glycol solution, stirs 0.5 hour, forms uniform sizing material, then according to polyester production process, heats and be esterified
And polyreaction, produce polyester fondant, and cooling granulation, the intrinsic viscosity of this polyester granules is 0.658dl/g, graphene oxide
There is partial reduction during the course of the reaction, its carbon/oxygen atom ratio is increased to 6/1～8/1, and the effective mass in polyester granules
Content is 3.0；
Using conventional polyester particle as a component, above-mentioned Graphene containing partial reduction (carbon/oxygen atom than for 6/1～8/1)
3.0 polyester granules as b component, a, b component is crystallized respectively, be dried after, divided by respective screw rod and measurement equipment
Zhu Ru not be in the respective casing of composite spinning technology, the ratio of a, b component in mass ratio 60/40～90/10 carries out composite spinning,
Produce the composite fibre with arranged side by side, core-skin or core shift structure.The resistivity of this composite fibre is higher than 1013ω cm, does not have
Antistatic property, does not have fire resistance yet.It can be seen that, when the graphene oxide in composite fibre or partial reduction Graphene also
Former degree is not enough, and that is, during carbon/oxygen atom relatively low frequently (< 9/1), this fiber does not have the performances such as antistatic.
Embodiment 1:
2.8 kilograms of graphene oxide powder taking specification shown in table 1 adds in double centner ethylene glycol, first chance at normal temperatures
Tool stirs 30 minutes, then disperses 30 minutes through ultrasound wave, forms uniform, the mixed serum a of stable dispersion；By mixed serum a and
P-phthalic acid adds in reactor according to the mol ratio that ethylene glycol/p-phthalic acid is 1.2/1, and adds antimony system or titanium
Series catalysts, are esterified at 215～235 DEG C, are then polymerized at 260～280 DEG C, thus be obtained containing mass percent being
The polyethylene terephthalate (pet) of 1 partial reduction Graphene is as a component polyester, after testing, polyester therein
Intrinsic viscosity be 0.67dl/g, the carbon/oxygen atom of partial reduction Graphene ratio is for 3.5/1；
Take the nano titanium oxide that 5.7 kilograms of the graphene oxide powder of specification shown in table 1 is 2 nanometers with average diameter
(tio2) in 1.9 kilograms of addition homogenizers, 5s is stirred with the speed of 30000r/min, repeats this dry state mixed process 2 times,
Obtain containing graphene oxide and nano titanium oxide (tio2) nanocomposite filler；Nanocomposite filler obtained above is added
Enter in double centner ethylene glycol, at normal temperatures first mechanical agitation 10 minutes, then disperse 60 minutes through ultrasound wave, formed uniform, stable
Scattered mixed serum b；By mixed serum b and p-phthalic acid according to ethylene glycol/p-phthalic acid be 1.8/1 mole
Ratio adds in reactor, and adds antimony system or Titanium series catalyst, is esterified at 215～235 DEG C, then enters at 260～280 DEG C
Row polymerization, thus be obtained polyethylene terephthalate (pet) conduct of the nanocomposite filler being 4 containing mass percent
B component polyester, after testing, the intrinsic viscosity of polyester therein is 0.65dl/g, and the carbon/oxygen atom ratio of partial reduction Graphene is
6/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 0.9mm, outlet aperture be 0.3mm, draw ratio
It is half hyp 5 points of exposed conveying appliance composite spinnerets extrusion for 2, longitudinal section, adjusting metering revolution speed makes a component polyester and b group
The extrusion mass ratio of segregation ester is 75/25, and then under 1500 ms/min of spinning speed, spinning, winding obtain outside every fiber
The 20 of surface area are that the macromolecule of b component polyester is combined protofibre；And then carry out drawing-off and relaxation heat setting at 160 DEG C,
Draw ratio is 2.5 times, and lax percentage ratio is the 20 of draw ratio；And carry out 90 points of ultraviolet light irradiation under 90 DEG C, oxygen free condition
Clock, a length of 500nm of ultraviolet light wave, finally give filament number be 3.0dtex, fibrous outer surfaces amass 20 be b component polyester
Macromolecule composite functional fiber, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, partial reduction therein
The carbon of Graphene/oxygen atom ratio reaches 9/1.
Embodiment 2:
0.24 kilogram of graphene oxide powder taking specification shown in table 1 adds in double centner 1,3-PD, at normal temperatures
First mechanical agitation 10 minutes, then disperse 60 minutes through ultrasound wave, form uniform, the mixed serum a of stable dispersion；By mixed serum
A and p-phthalic acid add in reactor according to the mol ratio that 1,3-PD/p-phthalic acid is 1.2/1, and add
Titanium series catalyst, is esterified at 205～225 DEG C, is then polymerized at 230～260 DEG C, thus be obtained containing mass percent
The PTT (ptt) of the partial reduction Graphene for 0.1 is as a component polyester, after testing, therein
The intrinsic viscosity of polyester is 0.92dl/g, and the carbon/oxygen atom of partial reduction Graphene ratio is for 5.3/1；
Take the nano titanium oxide that 5.8 kilograms of the graphene oxide powder of specification shown in table 1 is 10 nanometers with average diameter
(tio2) in 17.4 kilograms of addition homogenizers, 25s is stirred with the speed of 20000r/min, repeats this dry state mixed process 4
Secondary, obtain containing graphene oxide and nano titanium oxide (tio2) nanocomposite filler；Nano combined fill out obtained above
Material adds in double centner BDO, at normal temperatures first mechanical agitation 30 minutes, then disperses 90 minutes through ultrasound wave, is formed
Uniformly, the mixed serum b of stable dispersion；By mixed serum b and p-phthalic acid according to BDO/p-phthalic acid
Mol ratio for 2.4/1 adds in reactor, and adds Titanium series catalyst, is esterified at 215～235 DEG C, then 220～
250 DEG C are polymerized, thus the polybutylene terephthalate (PBT) of the nanocomposite filler that containing mass percent be 20 is obtained
(pbt) as b component polyester, after testing, the intrinsic viscosity of polyester therein is 0.90dl/g, the carbon of partial reduction Graphene/
Oxygen atom is than for 5/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 1.5mm, outlet aperture be 0.5mm, draw ratio
The parallel type composite spinneret extrusion being taper for 3, longitudinal section, adjusting metering revolution speed makes a component polyester and b component polyester
Extrusion mass ratio is 85/15, and then under 500 ms/min of spinning speed, spinning, winding obtain what every fibrous outer surfaces amassed
60 is the compound protofibre of macromolecule of b component polyester；And then carrying out drawing-off and relaxation heat setting at 80 DEG C, draw ratio is
1.5 times, lax percentage ratio is the 10 of draw ratio；And carrying out ultraviolet light irradiation 60 minutes at 20 DEG C, ultraviolet light wave is a length of
700nm, finally give filament number be 5.0dtex, fibrous outer surfaces amass 60 be b component polyester macromolecule complex function
Fiber, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, the carbon/oxygen of partial reduction Graphene therein is former
Sub- ratio reaches 15/1.
Embodiment 3:
1.2 kilograms of graphene oxide powder taking specification shown in table 1 adds in double centner BDO, at normal temperatures
First mechanical agitation 20 minutes, then disperse 45 minutes through ultrasound wave, form uniform, the mixed serum a of stable dispersion；By mixed serum
A and p-phthalic acid add in reactor according to the mol ratio that BDO/p-phthalic acid is 1.2/1, and add
Titanium series catalyst, is esterified at 215～235 DEG C, is then polymerized at 220～250 DEG C, thus be obtained containing mass percent
The polybutylene terephthalate (PBT) (pbt) of the partial reduction Graphene for 0.55 as a component polyester, after testing, wherein
The intrinsic viscosity of polyester be 0.90dl/g, the carbon/oxygen atom of partial reduction Graphene ratio is for 4.2/1；
Take the nano titanium oxide that 7.8 kilograms of the graphene oxide powder of specification shown in table 1 is 18 nanometers with average diameter
(tio2) in 7.8 kilograms of addition homogenizers, 15s is stirred with the speed of 10000r/min, repeats this dry state mixed process 6
Secondary, obtain containing graphene oxide and nano titanium oxide (tio2) nanocomposite filler；Nano combined fill out obtained above
Material adds in double centner 1,3-PD, at normal temperatures first mechanical agitation 20 minutes, then disperses 30 minutes through ultrasound wave, is formed
Uniformly, the mixed serum b of stable dispersion；By mixed serum b and p-phthalic acid according to 1,3-PD/p-phthalic acid
Mol ratio for 2.4/1 adds in reactor, and adds Titanium series catalyst, is esterified at 205～225 DEG C, then 230～
260 DEG C are polymerized, thus the PTT of the nanocomposite filler that containing mass percent be 12 is obtained
(ptt) as b component polyester, after testing, the intrinsic viscosity of polyester therein is 0.89dl/g, the carbon of partial reduction Graphene/
Oxygen atom is than for 3.4/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 2.8mm, outlet aperture be 0.7mm, draw ratio
The core-skin type composite spinneret extrusion being taper for 4, longitudinal section, adjusting metering revolution speed makes a component polyester and b component polyester
Extrusion mass ratio is 95/5, and then under 1000 ms/min of spinning speed, spinning, winding obtain what every fibrous outer surfaces amassed
100 is the compound protofibre of macromolecule of b component polyester；And then carrying out drawing-off and relaxation heat setting at 120 DEG C, draw ratio is
2.0 times, lax percentage ratio is the 15 of draw ratio；And 40 DEG C, hydrogen atmosphere plasma process 90 minutes, operating air pressure
For 100pa, power is 50w, finally gives that filament number is 7.0dtex, fibrous outer surfaces amass 100 is b component polyester
Macromolecule composite functional fiber, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, partial reduction stone therein
The carbon of black alkene/oxygen atom ratio reaches 12/1.
Embodiment 4:
3.8 kilograms of graphene oxide powder taking specification shown in table 1 adds in double centner ethylene glycol, first chance at normal temperatures
Tool stirs 20 minutes, then disperses 60 minutes through ultrasound wave, forms uniform, the mixed serum a of stable dispersion；By mixed serum a and
Smart 2,6- naphthalene diformic acid dimethyl ester adds reactor according to the mol ratio that ethylene glycol/essence 2,6- naphthalene diformic acid dimethyl ester is 1.15/1
In, and add Titanium series catalyst, it is esterified at 230～250 DEG C, is then polymerized at 270～290 DEG C, thus be obtained containing
Mass percent be the polyethylene naphthalate (pen) of 1 partial reduction Graphene as a component polyester, through inspection
Survey, the intrinsic viscosity of polyester therein is 0.86dl/g, the carbon/oxygen atom of partial reduction Graphene ratio is for 4.5/1；
Take the nano titanium oxide that 3.7 kilograms of the graphene oxide powder of specification shown in table 1 is 5 nanometers with average diameter
(tio2) in 3.7 kilograms of addition homogenizers, 5s is stirred with the speed of 30000r/min, repeats this dry state mixed process 6 times,
Add 7.4 kilograms of the SWCN that average diameter is 2 nanometers, 5s is stirred with the speed of 30000r/min, repeat this and do
State mixed process 6 times, obtains containing graphene oxide, nano titanium oxide (tio2) and CNT nanocomposite filler；Will
Nanocomposite filler obtained above adds in double centner ethylene glycol, at normal temperatures first mechanical agitation 10 minutes, then through ultrasound wave
Dispersion 60 minutes, forms uniform, the mixed serum b of stable dispersion；By mixed serum b and smart 2,6- naphthalene diformic acid dimethyl ester according to
Ethylene glycol/essence NDA dimethyl ester is in 1.2/1 mol ratio addition reactor, and adds Titanium series catalyst, 230
～250 DEG C are esterified, and are then polymerized at 260～290 DEG C, thus be obtained containing mass percent be 4 nano combined
As b component polyester, after testing, the intrinsic viscosity of polyester therein is the polyethylene naphthalate (pen) of filler
0.89dl/g, the carbon/oxygen atom of partial reduction Graphene is than for 5/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 1.0mm, outlet aperture be 0.3mm, draw ratio
It is half hyp 3 points of exposed conveying appliance composite spinnerets extrusion for 3, longitudinal section, adjusting metering revolution speed makes a component polyester and b group
The extrusion mass ratio of segregation ester is 75/25, and then under 1000 ms/min of spinning speed, spinning, winding obtain outside every fiber
The 60 of surface area are that the macromolecule of b component polyester is combined protofibre；And then carry out drawing-off and relaxation heat setting at 160 DEG C,
Draw ratio is 2.5 times, and lax percentage ratio is the 20 of draw ratio；And carry out 30 points of ultraviolet light irradiation under 160 DEG C, oxygen free condition
Clock, a length of 900nm of ultraviolet light wave, finally give filament number be 7.0dtex, fibrous outer surfaces amass 60 be b component polyester
Macromolecule composite functional fiber, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, partial reduction therein
The carbon of Graphene/oxygen atom ratio reaches 12/1.
Embodiment 5:
2.1 kilograms of graphene oxide powder taking specification shown in table 1 adds in double centner ethylene glycol, first chance at normal temperatures
Tool stirs 30 minutes, then disperses 60 minutes through ultrasound wave, forms uniform, the mixed serum a of stable dispersion；By mixed serum a and
Smart 2,6- naphthalene diformic acid dimethyl ester adds reactor according to the mol ratio that ethylene glycol/essence 2,6- naphthalene diformic acid dimethyl ester is 1.15/1
In, and add Titanium series catalyst, it is esterified at 230～250 DEG C, is then polymerized at 270～290 DEG C, thus be obtained containing
Mass percent is the polyethylene naphthalate (pen) of 0.55 partial reduction Graphene as a component polyester, warp
Detection, the intrinsic viscosity of polyester therein is 0.88dl/g, and the carbon/oxygen atom of partial reduction Graphene ratio is for 5.6/1；
Take the nano titanium oxide that 4.3 kilograms of the graphene oxide powder of specification shown in table 1 is 10 nanometers with average diameter
(tio2) in 4.3 kilograms of addition homogenizers, 15s is stirred with the speed of 20000r/min, repeats this dry state mixed process 4
Secondary, add the nano carbon black 4.3 of 4.3 kilograms and averagely a diameter of 10 nanometers of the multi-walled carbon nano-tubes that average diameter is 10 nanometers
Kilogram, 15s is stirred with the speed of 20000r/min, repeats this dry state mixed process 4 times, obtain containing graphene oxide, nanometer two
Titanium oxide (tio2), the nanocomposite filler of CNT and nano carbon black；Nanocomposite filler obtained above is added 100
In kilogram ethylene glycol, first mechanical agitation 10 minutes at normal temperatures, then disperse 60 minutes through ultrasound wave, formed uniformly, stable dispersion
Mixed serum b；Mixed serum b and p-phthalic acid are added according to the mol ratio that ethylene glycol/p-phthalic acid is 2.4/1
Enter in reactor, and add zinc system or Titanium series catalyst, be esterified at 215～240 DEG C, then gathered at 260～280 DEG C
Close, thus the polyethylene terephthalate (pet) of the nanocomposite filler that containing mass percent be 12 is obtained as b group
Segregation ester, after testing, the intrinsic viscosity of polyester therein is 0.58dl/g, and the carbon/oxygen atom ratio of partial reduction Graphene is
3.9/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 2.4mm, outlet aperture be 0.5mm, draw ratio
It is half hyp 3 points of exposed conveying appliance composite spinnerets extrusion for 4, longitudinal section, adjusting metering revolution speed makes a component polyester and b group
The extrusion mass ratio of segregation ester is 85/15, and then under 1500 ms/min of spinning speed, spinning, winding obtain outside every fiber
The 20 of surface area are that the macromolecule of b component polyester is combined protofibre；And then carry out drawing-off and relaxation heat setting at 160 DEG C,
Draw ratio is 2.0 times, and lax percentage ratio is the 15 of draw ratio；And carry out 60 points of ultraviolet light irradiation under 160 DEG C, oxygen free condition
Clock, a length of 500nm of ultraviolet light wave, finally give filament number be 5.0dtex, fibrous outer surfaces amass 20 be b component polyester
Macromolecule composite functional fiber, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, partial reduction therein
The carbon of Graphene/oxygen atom ratio reaches 9/1.
Embodiment 6:
1.6 kilograms of graphene oxide powder taking specification shown in table 1 adds in double centner 1,3-PD, at normal temperatures
First mechanical agitation 10 minutes, then disperse 45 minutes through ultrasound wave, form uniform, the mixed serum a of stable dispersion；By mixed serum
A and p-phthalic acid add in reactor according to the mol ratio that 1,3-PD/p-phthalic acid is 1.8/1, and add
Titanium series catalyst, is esterified at 205～225 DEG C, is then polymerized at 230～260 DEG C, thus be obtained containing mass percent
The PTT (ptt) of the partial reduction Graphene for 1 is as a component polyester, after testing, therein poly-
The intrinsic viscosity of ester is 0.92dl/g, and the carbon/oxygen atom of partial reduction Graphene ratio is for 3.3/1；
Take the nano titanium oxide that 6.4 kilograms of the graphene oxide powder of specification shown in table 1 is 12 nanometers with average diameter
(tio2) in 6.4 kilograms of addition homogenizers, 25s is stirred with the speed of 10000r/min, repeats this dry state mixed process 2
Secondary, add 12.8 kilograms of the nano carbon black that average diameter is 12 nanometers, 25s is stirred with the speed of 10000r/min, repeats this
Dry state mixed process 2 times, obtains containing graphene oxide, nano titanium oxide (tio2) and nano carbon black nanocomposite filler；
Nanocomposite filler obtained above is added in double centner 1,3-PD, first mechanical agitation 30 minutes, then warp at normal temperatures
Ultrasound wave disperses 90 minutes, forms uniform, the mixed serum b of stable dispersion；By mixed serum b and p-phthalic acid according to 1,
Ammediol/p-phthalic acid is in 2.4/1 mol ratio addition reactor, and adds Titanium series catalyst, 205～230
DEG C it is esterified, is then polymerized at 230～260 DEG C, thus the nanocomposite filler that containing mass percent be 20 is obtained
PTT (ptt) as b component polyester, after testing, the intrinsic viscosity of polyester therein is 0.86dl/
G, the carbon/oxygen atom of partial reduction Graphene is than for 5.5/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 1.4mm, outlet aperture be 0.7mm, draw ratio
3 points of exposed conveying appliance composite spinneret extrusions being taper for 2, longitudinal section, adjusting metering revolution speed makes a component polyester and b group segregation
The extrusion mass ratio of ester is 95/5, and then under 500 ms/min of spinning speed, spinning, winding obtain every fibrous outer surfaces and amass
20 be b component polyester macromolecule be combined protofibre；And then carrying out drawing-off and relaxation heat setting at 80 DEG C, draw ratio is
1.5 times, lax percentage ratio is the 10 of draw ratio；And 60 DEG C, hydrogen atmosphere plasma process 10 minutes, operating air pressure
For 10pa, power is 100w, finally give filament number be 7.0dtex, fibrous outer surfaces amass 20 be b component polyester height
Molecule composite functional fiber, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, partial reduction graphite therein
The carbon of alkene/oxygen atom ratio reaches 9/1.
Embodiment 7:
1.2 kilograms of graphene oxide powder taking specification shown in table 1 adds in double centner BDO, at normal temperatures
First mechanical agitation 20 minutes, then disperse 45 minutes through ultrasound wave, form uniform, the mixed serum a of stable dispersion；By mixed serum
A and p-phthalic acid add in reactor according to the mol ratio that BDO/p-phthalic acid is 1.2/1, and add
Titanium series catalyst, is esterified at 215～235 DEG C, is then polymerized at 220～250 DEG C, thus be obtained containing mass percent
The polybutylene terephthalate (PBT) (pbt) of the partial reduction Graphene for 0.55 as a component polyester, after testing, wherein
The intrinsic viscosity of polyester be 0.90dl/g, the carbon/oxygen atom of partial reduction Graphene ratio is for 3.3/1；
Take the nano titanium oxide that 2.2 kilograms of the graphene oxide powder of specification shown in table 1 is 18 nanometers with average diameter
(tio2) in 4.4 kilograms of addition homogenizers, 15s is stirred with the speed of 30000r/min, repeats this dry state mixed process 2
Secondary, add 19.8 kilograms of the nano carbon black that average diameter is 18 nanometers, 15s is stirred with the speed of 30000r/min, repeats this
Dry state mixed process 2 times, obtains containing graphene oxide, nano titanium oxide (tio2) and nano carbon black nanocomposite filler；
Nanocomposite filler obtained above is added in double centner BDO, first mechanical agitation 20 minutes, then warp at normal temperatures
Ultrasound wave disperses 30 minutes, forms uniform, the mixed serum b of stable dispersion；By mixed serum b and p-phthalic acid according to 1,
4- butanediol/p-phthalic acid is in 1.2/1 mol ratio addition reactor, and adds Titanium series catalyst, 225～245
DEG C it is esterified, is then polymerized at 240～260 DEG C, thus the nanocomposite filler that containing mass percent be 12 is obtained
Polybutylene terephthalate (PBT) (pbt) as b component polyester, after testing, the intrinsic viscosity of polyester therein is 0.84dl/
G, the carbon/oxygen atom of partial reduction Graphene is than for 4/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 1.4mm, outlet aperture be 0.3mm, draw ratio
It is half hyp 5 points of exposed conveying appliance composite spinnerets extrusion for 3, longitudinal section, adjusting metering revolution speed makes a component polyester and b group
The extrusion mass ratio of segregation ester is 75/25, and then under 1000 ms/min of spinning speed, spinning, winding obtain outside every fiber
The 60 of surface area are that the macromolecule of b component polyester is combined protofibre；And then carry out drawing-off and relaxation heat setting at 80 DEG C, lead
Stretch ratio for 2.0 times, lax percentage ratio is the 20 of draw ratio；And carry out ultraviolet light irradiation 20 minutes at 90 DEG C, ultraviolet wavelength
For 900nm, finally give that filament number is 3.0dtex, fibrous outer surfaces amass 60 is that the macromolecule of b component polyester is combined work(
Energy fiber, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, the carbon/oxygen of partial reduction Graphene therein
Atomic ratio reaches 9/1.
Embodiment 8:
2.9 kilograms of graphene oxide powder taking specification shown in table 1 adds in double centner ethylene glycol, first chance at normal temperatures
Tool stirs 30 minutes, then disperses 45 minutes through ultrasound wave, forms uniform, the mixed serum a of stable dispersion；By mixed serum a and
P-phthalic acid according to ethylene glycol/p-phthalic acid be 1.15/1 mol ratio add reactor in, and add antimony system or
Titanium series catalyst, is esterified at 215～235 DEG C, is then polymerized at 260～280 DEG C, thus be obtained containing mass percent
The polyethylene terephthalate (pet) of the partial reduction Graphene for 1 is as a component polyester, after testing, therein poly-
The intrinsic viscosity of ester is 0.63dl/g, and the carbon/oxygen atom of partial reduction Graphene ratio is for 4.4/1；
Take the nano titanium oxide that 1.8 kilograms of the graphene oxide powder of specification shown in table 1 is 2 nanometers with average diameter
(tio2) in 5.4 kilograms of addition homogenizers, 5s is stirred with the speed of 30000r/min, repeats this dry state mixed process 6 times,
Add 9 kilograms of the nano carbon black of 5.4 kilograms and averagely a diameter of 2 nanometers of the SWCN that average diameter is 2 nanometers, with
The speed stirring 25s of 10000r/min, repeats this dry state mixed process 6 times, obtains containing graphene oxide, nano titanium oxide
(tio2), the nanocomposite filler of CNT and nano carbon black；Nanocomposite filler obtained above is added double centner second
In glycol, first mechanical agitation 10 minutes at normal temperatures, then disperse 60 minutes through ultrasound wave, form the uniform, mixing of stable dispersion
Serosity b；Mixed serum b and smart 2,6- naphthalene diformic acid dimethyl ester are 2.4/1 according to ethylene glycol/essence 2,6- naphthalene diformic acid dimethyl ester
Mol ratio add in reactor, and add Titanium series catalyst, be esterified at 230～250 DEG C, then enter at 260～290 DEG C
Row polymerization, thus the polyethylene naphthalate (pen) that the nanocomposite filler that containing mass percent be 12 is obtained is made
For b component polyester, after testing, the intrinsic viscosity of polyester therein is 0.78dl/g, the carbon/oxygen atom ratio of partial reduction Graphene
For 4.9/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 2.8mm, outlet aperture be 0.5mm, draw ratio
It is half hyp parallel type composite spinneret extrusion for 4, longitudinal section, adjusting metering revolution speed makes a component polyester and b group segregation
The extrusion mass ratio of ester is 75/25, and then under 1500 ms/min of spinning speed, spinning, winding obtain every fibrous outer surfaces
Long-pending 60 are that the macromolecule of b component polyester is combined protofibre；And then carry out drawing-off and relaxation heat setting, drawing-off at 160 DEG C
For 2.0 times, lax percentage ratio is the 15 of draw ratio to ratio；And 60 DEG C, hydrogen/argon ratio be 2/1 mixed-gas atmosphere
Plasma is processed 50 minutes, and operating air pressure is 55pa, and power is 75w, and finally giving filament number is 7.0dtex, fiber
The 60 of external surface area are the macromolecule composite functional fiber of b component polyester, and its performance as shown in table 1, has antistatic, antibacterial
And flame retardant effect, the carbon/oxygen atom ratio of partial reduction Graphene therein reaches 12/1.
Embodiment 9:
0.29 kilogram of graphene oxide powder taking specification shown in table 1 adds in double centner ethylene glycol, first chance at normal temperatures
Tool stirs 20 minutes, then disperses 30 minutes through ultrasound wave, forms uniform, the mixed serum a of stable dispersion；By mixed serum a and
P-phthalic acid according to ethylene glycol/p-phthalic acid be 1.15/1 mol ratio add reactor in, and add antimony system or
Titanium series catalyst, is esterified at 215～235 DEG C, is then polymerized at 260～280 DEG C, thus be obtained containing mass percent
The polyethylene terephthalate (pet) of the partial reduction Graphene for 0.1 is as a component polyester, after testing, therein
The intrinsic viscosity of polyester is 0.65dl/g, and the carbon/oxygen atom of partial reduction Graphene ratio is for 5.3/1；
Take the nano titanium oxide that 2.2 kilograms of the graphene oxide powder of specification shown in table 1 is 10 nanometers with average diameter
(tio2) in 6.6 kilograms of addition homogenizers, 25s is stirred with the speed of 20000r/min, repeats this dry state mixed process 6
Secondary, add the nano carbon black 6.6 of 6.6 kilograms and averagely a diameter of 10 nanometers of the multi-walled carbon nano-tubes that average diameter is 10 nanometers
Kilogram, 15s is stirred with the speed of 10000r/min, repeats this dry state mixed process 6 times, obtain containing graphene oxide, nanometer two
Titanium oxide (tio2), the nanocomposite filler of CNT and nano carbon black；Nanocomposite filler obtained above is added 100
In kilogram BDO, first mechanical agitation 10 minutes at normal temperatures, then disperse 60 minutes through ultrasound wave, formed uniformly, stable
Scattered mixed serum b；Mixed serum b and p-phthalic acid are 2.4/1 according to BDO/p-phthalic acid
Mol ratio adds in reactor, and adds antimony system or Titanium series catalyst, is esterified at 225～235 DEG C, then 230～260
DEG C it is polymerized, thus the polybutylene terephthalate (PBT) of the nanocomposite filler that containing mass percent be 20 is obtained
(pbt) as b component polyester, after testing, the intrinsic viscosity of polyester therein is 0.81dl/g, the carbon of partial reduction Graphene/
Oxygen atom is than for 5.5/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 1.8mm, outlet aperture be 0.3mm, draw ratio
It is half hyp core-skin type composite spinneret extrusion for 4, longitudinal section, adjusting metering revolution speed makes a component polyester and b group segregation
The extrusion mass ratio of ester is 95/5, and then under 500 ms/min of spinning speed, spinning, winding obtain every fibrous outer surfaces and amass
100 be b component polyester macromolecule be combined protofibre；And then carry out drawing-off and relaxation heat setting, draw ratio at 120 DEG C
For 1.5 times, lax percentage ratio is the 10 of draw ratio；And 60 DEG C, hydrogen atmosphere plasma process 90 minutes, work gas
Press as 10pa, power is 100w, finally give that filament number is 3.0dtex, fibrous outer surfaces amass 100 is b component polyester
Macromolecule composite functional fiber, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, partial reduction therein
The carbon of Graphene/oxygen atom ratio reaches 15/1.
Embodiment 10:
1.4 kilograms of graphene oxide powder taking specification shown in table 1 adds in double centner 1,3-PD, at normal temperatures
First mechanical agitation 10 minutes, then disperse 30 minutes through ultrasound wave, form uniform, the mixed serum a of stable dispersion；By mixed serum
A and p-phthalic acid add in reactor according to the mol ratio that 1,3-PD/p-phthalic acid is 1.15/1, and add
Titanium series catalyst, is esterified at 205～225 DEG C, is then polymerized at 230～260 DEG C, thus be obtained containing mass percent
The PTT (ptt) of the partial reduction Graphene for 0.55 as a component polyester, after testing, wherein
The intrinsic viscosity of polyester be 0.92dl/g, the carbon/oxygen atom of partial reduction Graphene ratio is for 3.2/1；
Take the nano titanium oxide that 7 kilograms of the graphene oxide powder of specification shown in table 1 is 18 nanometers with average diameter
(tio2) in 3.5 kilograms of addition homogenizers, 15s is stirred with the speed of 10000r/min, repeats this dry state mixed process 6
Secondary, add the nano carbon black 7,000 of 7 kilograms and averagely a diameter of 10 nanometers of the multi-walled carbon nano-tubes that average diameter is 10 nanometers
Gram, 25s is stirred with the speed of 20000r/min, repeats this dry state mixed process 4 times, obtain containing graphene oxide, nano-silica
Change titanium (tio2), the nanocomposite filler of CNT and nano carbon black；Nanocomposite filler obtained above is added 100,000
In gram ethylene glycol, first mechanical agitation 30 minutes at normal temperatures, then disperse 90 minutes through ultrasound wave, formed uniformly, stable dispersion
Mixed serum b；Mixed serum b and p-phthalic acid are added anti-according to the mol ratio that ethylene glycol/p-phthalic acid is 2/1
Answer in kettle, and add Titanium series catalyst, be esterified at 215～235 DEG C, be then polymerized at 260～280 DEG C, thus making
The polyethylene terephthalate (pet) that the nanocomposite filler that mass percent is 14 must be contained is as b component polyester, warp
Detection, the intrinsic viscosity of polyester therein is 0.62dl/g, and the carbon/oxygen atom of partial reduction Graphene ratio is for 5.6/1；
The single screw extrusion machine of parallel connection is fed respectively after taking a component polyester obtained above and b component crystallizing polyester, drying
In carry out melt composite spinning, through melt pipeline, dosing pump and entrance hole diameter be 1.4mm, outlet aperture be 0.7mm, draw ratio
The parallel type composite spinneret extrusion being taper for 2, longitudinal section, adjusting metering revolution speed makes a component polyester and b component polyester
Extrusion mass ratio is 85/15, and then under 1000 ms/min of spinning speed, spinning, winding obtain what every fibrous outer surfaces amassed
20 is the compound protofibre of macromolecule of b component polyester；And then carrying out drawing-off and relaxation heat setting at 120 DEG C, draw ratio is
2.0 times, lax percentage ratio is the 15 of draw ratio；And carry out ultraviolet light irradiation under 90 DEG C, oxygen free condition 30 minutes, ultraviolet light
Wavelength is 700nm, finally give filament number be 5.0dtex, fibrous outer surfaces amass 20 be b component polyester macromolecule multiple
Close functional fibre, its performance as shown in table 1, has antistatic, antibacterial and flame retardant effect, partial reduction Graphene therein
Carbon/oxygen atom ratio reaches 9/1.
Table 1 embodiment 1～10 graphene oxide raw material specification and meet fibre property data
Above-described embodiment is not the restriction for the present invention, and the present invention is not limited only to above-described embodiment, as long as meeting
Application claims, belong to protection scope of the present invention.
Claims (10)
1. a kind of macromolecule composite functional fiber containing partial reduction Graphene is it is characterised in that include a component and b component, a group
Divide the mass ratio with b component to be 75/25～95/5, and the two is combined with part exposed conveying appliance, parallel type or core-skin type, so that often
Root fibrous outer surfaces amass 20～100 be b component；
The polyester that it is 0.1～1 partial reduction Graphene containing mass percent that described a group is divided into；
The polyester that it is 4～20 nanocomposite fillers containing mass percent that described b group is divided into；Wherein nanocomposite filler includes
Partial reduction Graphene and nano titanium oxide tio2, nano titanium oxide tio2Mass ratio with partial reduction Graphene is 1/3
～3/1；
The carbon of described partial reduction Graphene/oxygen atom ratio reaches 9/1～15/1；
Described polyester is polyethylene terephthalate pet, PTT ptt, poly terephthalic acid
Butanediol ester pbt or polyethylene naphthalate pen.
2. as claimed in claim 1 a kind of macromolecule composite functional fiber containing partial reduction Graphene it is characterised in that institute
In the b component stated, nanocomposite filler removes containing partial reduction Graphene and nano titanium oxide tio2Outward, carbon can also be included
One of nanotube, nano carbon black or two kinds.
3. as claimed in claim 1 a kind of macromolecule composite functional fiber containing partial reduction Graphene it is characterised in that institute
In the b component stated, the mass percent of part reduced graphene is 1～5.
4. as claimed in claim 2 a kind of macromolecule composite functional fiber containing partial reduction Graphene it is characterised in that institute
In the b component stated, CNT and the mass ratio of partial reduction Graphene are 1/1～3/1；In described b component nano carbon black with
The mass ratio of partial reduction Graphene is 1/1～9/1.
5. preparation a kind of method of the macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 1, its
It is characterised by that the method comprises the following steps:
Step (1), preparation containing mass percent be 0.1～1 partial reduction Graphene polyester as a component polyester:
1.1 at normal temperatures by carbon/oxygen atom than for 3/1～5/1, the lamella number of plies be 2～8 layers, lamellar spacing be 2～20 nanometers,
The graphene oxide powder that a size of 0.2～2 micron of two dimensional surface adds in alcohol a, first mechanical agitation 10～30 minutes, then through super
Sound wave disperses 30～60 minutes, forms uniform, the mixed serum a of stable dispersion；
The 1.2 mixed serum a obtaining step 1.1 and p-phthalic acid or smart 2,6- naphthalene diformic acid dimethyl ester are in a kettle.
Carry out being esterified, be polymerized, the polyethylene terephthalate of the partial reduction Graphene that containing mass percent be 0.1～1 is obtained
Ester pet, PTT ptt, polybutylene terephthalate (PBT) pbt or polyethylene naphthalate
Pen, as a component polyester；
Step (2), preparation containing mass percent be 4～20 Graphene containing partial reduction and nano titanium oxide tio2Receive
The polyester of rice compounded mix is as b component polyester:
2.1 at normal temperatures by carbon/oxygen atom than for 3/1～5/1, the lamella number of plies be 2～8 layers, lamellar spacing be 2～20 nanometers,
The graphene oxide powder that a size of 0.2～2 micron of two dimensional surface and nano titanium oxide tio2Add in homogenizer, with
The speed of 10000～30000r/min stirs 5～25s, repeats this dry state mixed process 2～6 times；Or first in aforementioned manners will
Graphene oxide powder and nano titanium oxide tio2Carry out dry state mixing it is ensured that it is fully contacted, add CNT or
Nano carbon black or CNT and two kinds of nano carbon black, repeat this dry state mixed process 2～6 times, obtain nanocomposite filler；
Nano titanium oxide tio in described nanocomposite filler2Mass ratio with graphene oxide is 1/3～3/1；
The mass ratio of the CNT in described nanocomposite filler and graphene oxide is 1/1～3/1；
The mass ratio of the nano carbon black in described nanocomposite filler and graphene oxide is 1/1～9/1；
Carry out hygrometric state mixing, first mechanical agitation 10～30 in the 2.2 nanocomposite filler powder addition alcohol b that step 2.1 is obtained
Minute, then disperse 30～90 minutes through ultrasound wave, form uniform, the mixed serum b of stable dispersion；
Described alcohol a, b each stand alone as ethylene glycol, 1,3-PD or BDO；
The 2.3 mixed serum b obtaining step 2.2 and p-phthalic acid or smart 2,6- naphthalene diformic acid dimethyl ester are in a kettle.
Carry out being esterified, be polymerized, the nanocomposite filler containing partial reduction Graphene that containing mass percent be 4～20 poly- right is obtained
PET pet, PTT ptt, polybutylene terephthalate (PBT) pbt or poly- are to naphthalene two
Formic acid glycol ester pen is as b component polyester；
Described alcohol b is 1.2/1～2.4/1 with the mol ratio of p-phthalic acid or smart 2,6- naphthalene diformic acid dimethyl ester；
Step (3), preparation include the macromolecule composite functional fiber of a component and b component:
B component crystallizing polyester that the 3.1 a component polyester obtaining step a and step b obtain, be dried after feed respectively in parallel
Carry out melt composite spinning in single screw extrusion machine, through melt pipeline, dosing pump and composite spinneret extrusion, adjust dosing pump and turn
It is 75/25～95/5 that speed makes the extrusion mass ratio of a component polyester and b component polyester, then in 500～1500 ms/min of spinning
Under speed, spinning, winding obtain being combined protofibre including the macromolecule of a component and b component, and so that every fibrous outer surfaces is amassed
20～100 be b component polyester；
3.2 macromolecules obtaining step 3.1 are combined protofibre and carry out drawing-off and relaxation heat setting, drawing-off at 80～160 DEG C
For 1.5～2.5 times, lax percentage ratio is the 10～20 of draw ratio to ratio, and makes the partial reduction in fiber by reduction treatment
Graphene is reduced to carbon/oxygen atom ratio further and reaches 9/1～15/1, thus the macromolecule obtaining including a component and b component is multiple
Close functional fibre.
6. a kind of preparation method of the macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 5, its
It is characterised by the nano titanium oxide tio described in step (2)2Diameter be less than or equal to graphene oxide lamellar spacing；Institute
The external diameter of the CNT stated is less than or equal to the lamellar spacing of graphene oxide；The diameter of described nano carbon black is less than or waits
Lamellar spacing in graphene oxide.
7. a kind of preparation method of the macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 5, its
The type being characterised by composite spinneret described in step 3.1 is part exposed conveying appliance, parallel type or core-skin type, and outlet aperture is
0.3～0.7mm, draw ratio is 2～4.
8. a kind of preparation method of the macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 7, its
It is characterised by that the longitudinal section of described composite spinneret at least has one section of shape gradually tapering up along extrusion direction, so that melt is existed
It is stretched effect during by mouth mould；In order to fully realize this stretching action and avoid spinneret to block, spinneret longitudinal section
In gradually taper up be shaped as half hyperbola.
9. a kind of preparation method of the macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 5, its
It is characterised by that the reduction treatment described in step 3.2 is ultraviolet light irradiation or corona treatment；
Wherein said ultraviolet light irradiation reduction treatment condition is a length of 500～900nm of ultraviolet light wave, and exposure time is 30～90
Minute, fiber treatment temperature is 20～160 DEG C；
Wherein said corona treatment reduction treatment condition is atmosphere is hydrogen or mixing that hydrogen/argon ratio is 2/1
Gas, operating air pressure is 10～100pa, and power is 50～100w, and process time is 10～90 minutes, and treatment temperature is 20～60
℃.
10. a kind of preparation method of the macromolecule composite functional fiber containing partial reduction Graphene as claimed in claim 9, its
It is characterised by that ultraviolet light irradiation is processed to carry out in an oxygen-free atmosphere.
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| CN106592013A (en) * | 2016-12-05 | 2017-04-26 | 嘉兴博锐新材料有限公司 | Electroconductive carbon fiber production technology |
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| CN103111274B (en) * | 2013-02-28 | 2014-09-17 | 山东大学 | Preparation method of graphene/TiO2 fiber |
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| CN103603088B (en) * | 2013-10-22 | 2015-05-06 | 浙江大学 | Conductive fiber with scabbard type structure and preparation method thereof |
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| CN103710790A (en) * | 2013-12-30 | 2014-04-09 | 厦门翔鹭化纤股份有限公司 | Antistatic, antibacterial and graphene-reinforced composite polyester fiber and preparation method thereof |
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