CN108588883A - graphene fiber and preparation method and product - Google Patents
graphene fiber and preparation method and product Download PDFInfo
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- CN108588883A CN108588883A CN201810411506.XA CN201810411506A CN108588883A CN 108588883 A CN108588883 A CN 108588883A CN 201810411506 A CN201810411506 A CN 201810411506A CN 108588883 A CN108588883 A CN 108588883A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Abstract
The present invention provides a kind of graphene fiber and preparation method and products, are related to chemical fiber field, and the graphene fiber includes modified graphene masterbatch and polypropylene chip, and modified graphene masterbatch includes graphene oxide, Ag TiO2Composite nano-granule and maleic anhydride inoculated polypropylene, wherein Ag TiO2For composite nano-granule uniform load in graphene oxide layer, maleic anhydride inoculated polypropylene has Ag TiO with load2The graphene oxide of composite nano-granule is keyed by chemistry, is alleviated existing graphene fiber mechanical strength and is promoted unobvious, distinct issues, the present invention do not have Ag TiO by that will load for antibacterial and far-infrared functional2The graphene oxide of composite nano-granule is connect with maleic anhydride inoculated polypropylene, after obtaining modified graphene masterbatch graphene fiber is mixed and made into polypropylene chip again, graphene fiber mechanical property and anti-microbial property made of so that are excellent, and far infrared function protrudes.
Description
Technical field
The present invention relates to chemical fiber fields, more particularly, to a kind of graphene fiber and preparation method and product.
Background technology
Graphene is a kind of flat film forming hexagon in honeycomb lattice by carbon atom with SP2 hybridized orbits, only
The new material of the two-dimensional individual layer laminated structure of one carbon atom thickness, with excellent antibacterial, absorption, health care and mechanical property
Can, thus become the ideal functionality filler for preparing functional fibre.
Existing graphene fiber generally by carrying out spinning again after dispersing graphene in fiber carrier, but due to it
Easily reunite, it is difficult to be uniformly dispersed in fiber carrier, the mechanical strength of made graphene fiber caused to promote unobvious,
Antibacterial and far-infrared functional do not protrude.
In view of this, special propose the present invention.
Invention content
One of the objects of the present invention is to provide a kind of graphene fibers, to alleviate since graphene is easily reunited, it is difficult to
It is evenly dispersed in fiber carrier, cause manufactured graphene fiber mechanical strength to promote unobvious, antibacterial and far-infrared functional
Not prominent technical problem.
Graphene fiber provided by the invention, including modified graphene masterbatch and polypropylene chip, the modified graphene
Masterbatch includes graphene oxide, Ag-TiO2Composite nano-granule and maleic anhydride-graft polypropylene, wherein Ag-TiO2Composite Nano
For grain uniform load in graphene oxide layer, maleic anhydride-graft polypropylene has Ag-TiO with load2The oxygen of composite nano-granule
Graphite alkene is keyed by chemistry.
Further, the mass ratio of the modified graphene masterbatch and polypropylene chip is (5-10)：100, preferably (6-
8)：100.
Further, in the modified graphene masterbatch, graphene oxide, Ag-TiO2Composite nano-granule and maleic anhydride-
The mass ratio of graft polypropylene is (5-20)：(0.5-3):100, preferably (10-20)：(1-2):100.
Further, the Ag-TiO2In composite nano-granule, Ag and TiO2Mass ratio be (2-4)：(1-2), preferably
2:1。
Further, the preparation method of the modified graphene masterbatch includes the following steps：
(a) graphene oxide is scattered in aqueous solution, obtains graphene oxide dispersion；
(b) by Ag-TiO2Composite nano-granule disperses in aqueous solution, to obtain Ag-TiO2Composite nano-granule dispersion liquid；
(c) by Ag-TiO2Composite nano-granule dispersion liquid is added in graphene oxide dispersion, ultrasound so that Ag-TiO2It is multiple
It closes nanoparticle to be dispersed in graphene oxide layer, obtaining load has Ag-TiO2The graphene oxide of composite nano-granule point
Dispersion liquid；
(d) there is Ag-TiO in load2Amine alkyltri silicon is added in the graphene oxide dispersion of composite nano-granule
Alkane, reaction, obtains surface modified graphite alkene；
(e) surface modified graphite alkene is reacted with maleic anhydride-graft polypropylene, obtains modified graphene masterbatch.
Further, the Ag-TiO2Composite nano-granule is prepared in accordance with the following steps：
(m) in aqueous solution by nano-titanium dioxide dispersion, nano-titanium dioxide aqueous solution is obtained；
(n) by silver salt be added titanium dioxide aqueous solution in, stir evenly, be added reducing agent, be filtered successively, dry and
Ball milling obtains Ag-TiO2Composite nano-granule.
Further, in step (n), silver salt is silver nitrate；
Preferably, in step (n), reducing agent is at least one in sodium borohydride, ethylene glycol, glucose or citric acid
Kind；
Preferably, the molar ratio of reducing agent and silver salt is (2-7)：1, preferably (2-4):1.
The second object of the present invention provides the preparation method of above-mentioned graphene fiber, includes the following steps：
Modified graphene masterbatch is uniformly mixed with polypropylene chip, melt spinning is carried out, obtains graphene fiber.
Further, polypropylene chip is divided into the first polypropylene chip and the second polypropylene chip, it then will modified stone
Black alkene masterbatch is mixed with the first polypropylene chip, functional agglomerate is made, then functional agglomerate is mixed with the second polypropylene chip, into
Row melt spinning；
Preferably, the mass ratio of the first polypropylene chip and the second polypropylene chip is 1：(3-6), preferably 1:4.
The present invention provides product made of above-mentioned graphene fiber, including facial mask, washcloth or underwear.
Graphene fiber provided by the invention, by by Ag-TiO2Composite nano-granule is dispersed in graphene oxide sheet
In layer, and load is set to have Ag-TiO by chemical bond2The graphene oxide of composite nano-granule and maleic anhydride-graft polypropylene
Connection, obtains modified graphene masterbatch so that and modified graphene masterbatch stable and uniform can disperse in polypropylene chip, to
Graphene fiber made of so that not only has good mechanical property, but also has excellent antibacterial bacteriostatic performance, simultaneously also
A large amount of far infrareds can be discharged, body microcirculation is improved, promote health.
The preparation method of graphene fiber provided by the invention is simple for process, easy to operate, and it is big can be suitable for industrialization
Production improves production efficiency.
Graphene product graphene fiber provided by the present invention provided by the invention is prepared, and not only has good
Mechanical property, and there is excellent antibacterial bacteriostatic performance, while a large amount of far infrareds can also be discharged, improve body microcirculation,
Promote health.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to an aspect of the present invention, the present invention provides a kind of graphene fiber, including modified graphene masterbatch and
Polypropylene chip, the modified graphene masterbatch include graphene oxide, Ag-TiO2Composite nano-granule and maleic anhydride-grafting
Polypropylene, wherein Ag-TiO2Composite nano-granule uniform load in graphene oxide layer, maleic anhydride-graft polypropylene with
Load has Ag-TiO2The graphene oxide of composite nano-granule is keyed by chemistry.
In the present invention, it be the number of plies is 2-10 layers of multilayer graphene oxide that graphene oxide, which is made,.
In the present invention, silver-series antibacterial agent is contacted by slow release silver ion with microorganism, is destroyed microorganism group and is made into
Point, body function failure is generated, causes metabolic disorder, to kill bacterium, to Escherichia coli, gonococcus, chlamydia trachomatis
Etc. tens of kinds pathogenic microorganisms have strong inhibition and killing effect, and not will produce drug resistance.
Nano-titanium dioxide is a kind of fluffy white powder, has uvioresistant, antibacterial, self-cleaning and anti-aging work(
Energy.
Graphene oxide is product of the graphene powder after chemical oxidation and stripping, because of increasing for oxygen-containing functional group thereon
And make property more active compared with graphene.
Graphene fiber provided by the invention, by by Ag-TiO2Composite nano-granule is dispersed in graphene oxide sheet
In layer, and load is set to have Ag-TiO by chemical bond2The graphene oxide of composite nano-granule and maleic anhydride-graft polypropylene
Connection, obtains modified graphene masterbatch so that and modified graphene masterbatch stable and uniform can disperse in polypropylene chip, to
Graphene fiber made of so that not only has good mechanical property, but also has excellent antibacterial bacteriostatic performance, simultaneously also
A large amount of far infrareds can be discharged, body microcirculation is improved, promote health.
In the preferred embodiment of the present invention, the mass ratio of modified graphene masterbatch and polypropylene chip is (5-
10):100。
In the typical but non-limiting embodiment of the present invention, the quality of modified graphene masterbatch and polypropylene chip
For example it is 5:100、5.2:100、5.5:100、5.8:100、6:100、6.2:100、6.5:100、6.8:100、7:100、7.2:
100、7.5:100、7.8:100、8:100、8.2:100、8.5:100、9:100、9.2:100、9.5:100、9.8:100、10:
100。
By the way that the mass ratio of modified graphene masterbatch and polypropylene chip is limited to (5-10):100, to ensure modified stone
Black alkene masterbatch uniform and stable dispersion in polypropylene chip, so that manufactured graphene fiber has excellent mechanical property
And anti-microbial property.
In the preferred embodiment of the present invention, in modified graphene masterbatch, graphene oxide, Ag-TiO2It is compound
The mass ratio of nanoparticle and maleic anhydride-graft polypropylene is (5-20)：(0.5-3):100, preferably (10-20)：(1-2):
100。
In the typical but non-limiting embodiment of the present invention, in modified graphene masterbatch, with maleic anhydride-grafting
Polypropylene is 100 mass parts meters, the mass fraction of graphene oxide as 5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,10,
10.5、11、11.5、12、12.5、13、13.5、14、14.5、15、15.5、16、16.5、17、17.5、18、18.5、19、19.5
Or 20 parts；Ag-TiO2The mass fraction of composite nano-granule as 0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,
1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9 or 3 parts.
In the preferred embodiment of the present invention, Ag-TiO2In composite nano-granule, Ag and TiO2Mass ratio be (2-
4)：(1-2), preferably 2:1.
In the typical but non-limiting embodiment of the present invention, Ag and TiO2Quality be such as：2:1、2.2:1、
2.5:1、2.8:1、3:1、3.2:1、3.5:1、3.8:1、4:1、2:1.5、2.2:1.5、2.5:1.5、2.8:1.5、3:1.5、
3.2:1.5、3.5:1.5、3.8:1.5、4:1.5、2:2、2.2:2、2.5:2、2.8:2、3:2、3.2:2、3.5:2、3.8:2、4:
2。
By controlling Ag-TiO2In composite nano-granule, Ag and TiO2Mass ratio be (2-4)：(1-2) so that Ag with receive
Rice TiO2It acts synergistically so that Ag-TiO2Have the function of superior antibacterial and self-cleaning in composite nano-granule.
In the preferred embodiment of the present invention, the preparation method of modified graphene masterbatch includes the following steps：
(a) graphene oxide is scattered in aqueous solution, obtains graphene oxide dispersion；
(b) by Ag-TiO2Composite nano-granule disperses in aqueous solution, to obtain Ag-TiO2Composite nano-granule dispersion liquid；
(c) by Ag-TiO2Composite nano-granule dispersion liquid is added in graphene oxide dispersion, ultrasound so that Ag-TiO2It is multiple
It closes nanoparticle to be intercalation into graphene oxide layer, obtaining load has Ag-TiO2The graphene oxide dispersion of composite nano-granule；
(d) there is Ag-TiO in load2Amine alkyltri silicon is added in the graphene oxide dispersion of composite nano-granule
Alkane obtains surface modified graphite alkene；
(e) surface modified graphite alkene is reacted with maleic anhydride-graft polypropylene, obtains modified graphene masterbatch.
In the preferred embodiment of the present invention, it in step (a), adds graphene oxide into aqueous solution, surpasses
Sound 30-60min so that graphene oxide is evenly dispersed in aqueous solution, to obtain oxidation evenly dispersed in aqueous solution
Graphene dispersing solution.
In the preferred embodiment of the present invention, in step (b), by Ag-TiO2Composite nano-granule is added water-soluble
In liquid, ultrasonic 45-90min, so that Ag-TiO2Composite nano-granule uniform and stable dispersion in aqueous solution, obtains Ag-TiO2It is multiple
Close nanoparticle dispersion liquid；
In the preferred embodiment of the present invention, in step (c), by Ag-TiO2Composite nano-granule dispersion liquid adds
Enter in graphene oxide dispersion, ultrasonic 2-3h, so that Ag-TiO2Composite nano-granule evenly spreads to graphene oxide layer
In, obtaining load has Ag-TiO2The graphene oxide dispersion of composite nano-granule, while during ultrasound so that oxidation
The surface of graphene further activates, convenient for being subsequently chemically bonded with other materials.
In the preferred embodiment of the present invention, in step (d), there is Ag-TiO in load2Composite nano-granule
Amine alkyltrialkoxysilaneand is added in graphene oxide dispersion so that exist and the oxygen anion in surface of graphene oxide
(O-) with the oxyalkylation reaction of amine alkyltrialkoxysilaneand so that graphene oxide passes through chemical bond and three alkane of amine alkyl
Oxysilane connects, and obtains surface modified graphite alkene；
In present invention further optimization embodiment, amine alkyltrialkoxysilaneand is selected from 3- aminopropyl trimethoxies
One kind in base silane, 3-aminopropyltriethoxysilane, 5- Aminopentyl dimethoxyethoxy silane.
Wherein, the mass ratio of amine alkyltrialkoxysilaneand and graphene oxide is (10-20):100, to ensure that surface changes
Property graphene surface is bonded with a large amount of amidos.
In the typical but non-limiting embodiment of the present invention, amine alkyltrialkoxysilaneand and graphene oxide
Quality is such as 10:100、10.5；100、11；100、11.5:100、12：100、12.5:100、13:100、13.5:100、14:
100、14.5:100、15:100、15.5:100、16:100、16.5:100、17:100、17.5:100、18:100、18.5:100、
19:100、19.5:100 or 20:100.
In one embodiment of the invention, in step (d), load has Ag-TiO2The oxidation stone of composite nano-granule
Amine alkyltrialkoxysilaneand is added in black alkene dispersion liquid, stirs 10-15h, to ensure that the reaction was complete so that modified graphene table
Face chemical bonding has a large amount of amidos.
In the preferred embodiment of the present invention, in step (e), by surface modified graphite alkene and maleic anhydride-
Graft polypropylene reacts so that a large amount of amine agent on surface modified graphite alkene surface and the Malaysia in maleic anhydride-graft polypropylene
Acid anhydrides is reacted, to obtain modified graphene masterbatch.
Since the modified graphene masterbatch surface chemistry is bonded with a large amount of polypropylene so that the modified graphene masterbatch can
The uniform and stable dispersion in polypropylene chip, to which the graphene fiber of excellent in mechanical performance be made.
In present invention further optimization embodiment, the grafting rate of maleic anhydride-graft polypropylene is 10-15%,
To ensure the reactivity of itself and surface modified graphite alkene.
In the typical but non-limiting embodiment of the present invention, the grafting rate of maleic anhydride-graft polypropylene is such as
10%, 10.2%, 10.5%, 10.8%, 11%, 11.2%, 11.5%, 11.8%, 12%, 12.2%, 12.5%,
12.8%, 13%, 13.2%, 13.5%, 13.8%, 14%, 14.2%, 14.5%, 14.8% or 15%.
In the preferred embodiment of the present invention, Ag-TiO2Composite nano-granule is prepared in accordance with the following steps：
(m) in aqueous solution by nano-titanium dioxide dispersion, nano-titanium dioxide aqueous solution is obtained；
(n) by silver salt be added titanium dioxide aqueous solution in, stir evenly, be added reducing agent, be filtered successively, dry and
Ball milling obtains Ag-TiO2Composite nano-granule.
In present invention further optimization embodiment, in step (m), aqueous solution is added in nano-titanium dioxide
In, ultrasonic 1-2h, to obtain the nano-titanium dioxide aqueous solution of nano-titanium dioxide uniform and stable dispersion in aqueous solution.
In present invention further optimization embodiment, in step (n), titanium dioxide aqueous solution is added in silver salt
In, after stirring evenly, add reducing agent, you can so that the Ag restored is wrapped in nano-titanium dioxide surface, obtain Ag-
TiO2Composite nano-granule.
In further preferably embodiment of the invention, reducing agent is in sodium borohydride, ethylene glycol, glucose or citric acid
At least one.
In the preferred embodiment of the present invention, reducing agent, mole of reducing agent and silver salt are added under agitation
Than for (2-7)：1, preferably (2-4):1.Amount of substance by controlling reducing agent is in excess in the amount of substance of silver salt, so that silver salt
It is completely reduced.The time that reduction reaction carries out is 60-90min, so that reduction reaction carries out completely.
In the preferred embodiment of the present invention, by controlling silver salt in nano-TiO2Mass ratio be (3-6)：
(1-2), so that the Ag-TiO generated2In composite nano-granule, Ag and TiO2Mass ratio be (2-4)：(1-2).
In the typical but non-limiting embodiment of the present invention, time that reduction reaction carries out as 60,62,65,
68,70,72,75,78,80,82,85,88 or 90min；Typical but non-limiting mole of reducing agent and silver salt is such as 2:
1、2.5:1、3:1、3.5:1、4:1、4.5:1、5:1、5.5:1、6:1、6.5:1 or 7:1.
According to the second aspect of the invention, the present invention provides a kind of preparation method of graphene fiber, including it is as follows
Step：
Modified graphene masterbatch is uniformly mixed with polypropylene chip, melt spinning is carried out, obtains graphene fiber.
The preparation method of graphene fiber provided by the invention is simple for process, easy to operate, and it is big can be suitable for industrialization
Production improves production efficiency.
In present invention further optimization embodiment, the preparation method of graphene fiber specifically comprises the following steps：
Polypropylene chip is divided into the first polypropylene chip and the second polypropylene chip, then by modified graphene masterbatch with
First polypropylene chip mixes, and functional agglomerate is made, then functional agglomerate is mixed with the second polypropylene chip, carries out melting spinning
Silk.
In the preferred embodiment of the present invention, first modified graphene masterbatch is mixed with the first polypropylene chip, with
It after being uniformly dispersed in the first polypropylene chip convenient for modified graphene masterbatch, is granulated by twin-screw, functional agglomerate is made, then
Functional agglomerate is mixed with the second polypropylene chip and carries out melt spinning, in order to which functional agglomerate mixes in the second polypropylene chip
It closes uniformly, so that load has Ag-TiO2The graphene oxide of composite nano-granule disperses in manufactured graphene fiber
It is even.
In present invention further optimization embodiment, the mass ratio of the first polypropylene chip and the second polypropylene chip
It is 1：(3-6), preferably 1:4.
In the typical but non-limiting embodiment of the present invention, the first polypropylene chip and the second polypropylene chip
Quality is such as 1:3、1:3.5、1:4、1:4.5、1:5、1:5.5 or 1:6.
According to the third aspect of the present invention, the present invention provides a kind of graphene product, graphite provided by the present invention
Alkene fiber is prepared, including but not limited to washcloth, facial mask or underwear etc..
Graphene product graphene fiber provided by the present invention provided by the invention is prepared, and not only has good
Mechanical property, and there is excellent antibacterial bacteriostatic performance, while a large amount of far infrareds can also be discharged, improve body microcirculation,
Promote health.
Technical solution provided by the invention is further described with reference to embodiment and comparative example.
Embodiment 1
Present embodiments provide a kind of graphene fiber, including the following raw material according to the mass fraction：Polypropylene chip 100
Part, 5 parts of modified graphene masterbatch, wherein modified graphene masterbatch includes graphene oxide, Ag-TiO2Composite nano-granule and horse
Carry out acid anhydrides-graft polypropylene, the mass ratio of three is 5:3:100；Wherein, modified graphene masterbatch prepare in accordance with the following steps and
At：(a) graphene oxide is scattered in aqueous solution, ultrasonic 45min obtains graphene oxide dispersion；
(b) by Ag-TiO2Composite nano-granule disperses in aqueous solution, and ultrasonic 60min obtains Ag-TiO2Composite nano-granule point
Dispersion liquid；
(c) by Ag-TiO2Composite nano-granule dispersion liquid is added in graphene oxide dispersion, ultrasonic 2h so that Ag-TiO2
Composite nano-granule is evenly spread in graphene oxide layer, and obtaining load has Ag-TiO2The graphene oxide of composite nano-granule
Dispersion liquid；
(d) there is Ag-TiO in load2Three ethoxy of 3- aminopropyls is added in the graphene oxide dispersion of composite nano-granule
Base silane, and the mass ratio of 3-aminopropyltriethoxysilane and graphene oxide is 1:10,12h is reacted, obtains to surface and changes
Property graphene；
(e) surface modified graphite alkene is dispersed in DMF solution, it is poly- that maleic anhydride-grafting that grafting rate is 15% is added
Propylene, ultrasonic 1.5h, washing obtain modified graphene masterbatch after dry；
Above-mentioned Ag-TiO2In composite nano-granule, Ag and TiO2Mass ratio be 1:1, the Ag-TiO2Composite nano-granule according to
Following steps are prepared：
(m) in aqueous solution by nano-titanium dioxide dispersion, ultrasonic 2h obtains nano-titanium dioxide aqueous solution；
(n) silver nitrate is added in titanium dioxide aqueous solution, is stirred evenly, after sodium borohydride progress reduction reaction is added,
It is filtered, dries and ball milling successively, obtain Ag-TiO2The mass ratio of composite nano-granule, above-mentioned sodium borohydride and silver nitrate is
3:1。
Embodiment 2
Present embodiments provide a kind of graphene fiber, including the following raw material according to the mass fraction：Polypropylene chip 100
Part, 10 parts of modified graphene masterbatch, wherein modified graphene masterbatch includes graphene oxide, Ag-TiO2Composite nano-granule and horse
Carry out acid anhydrides-graft polypropylene, the mass ratio of three is 20:0.5:100, Ag-TiO2In composite nano-granule, Ag and TiO2Quality
Than being 4:1, modified graphene masterbatch and Ag-TiO in the present embodiment2The preparation method is the same as that of Example 1 for composite nano-granule, herein not
It repeats again.
Embodiment 3
Present embodiments provide a kind of graphene fiber, including the following raw material according to the mass fraction：Polypropylene chip 100
Part, 6 parts of modified graphene masterbatch, wherein modified graphene masterbatch includes graphene oxide, Ag-TiO2Composite nano-granule and horse
Carry out acid anhydrides-graft polypropylene, the mass ratio of three is 10:2:100, Ag-TiO2In composite nano-granule, Ag and TiO2Mass ratio
It is 2:1, modified graphene masterbatch and Ag-TiO in the present embodiment2The preparation method is the same as that of Example 1 for composite nano-granule, herein no longer
It repeats.
Embodiment 4
Present embodiments provide a kind of graphene fiber, including the following raw material according to the mass fraction：Polypropylene chip 100
Part, 8 parts of modified graphene masterbatch, wherein modified graphene masterbatch includes graphene oxide, Ag-TiO2Composite nano-granule and horse
Carry out acid anhydrides-graft polypropylene, the mass ratio of three is 20:1:100, Ag-TiO2In composite nano-granule, Ag and TiO2Mass ratio
It is 2:1, modified graphene masterbatch and Ag-TiO in the present embodiment2The preparation method is the same as that of Example 1 for composite nano-granule, herein no longer
It repeats.
Embodiment 5
Present embodiments provide a kind of graphene fiber, including the following raw material according to the mass fraction：Polypropylene chip 100
Part, 7 parts of modified graphene masterbatch, wherein modified graphene masterbatch includes graphene oxide, Ag-TiO2Composite nano-granule and horse
Carry out acid anhydrides-graft polypropylene, the mass ratio of three is 15:2:100, Ag-TiO2In composite nano-granule, Ag and TiO2Mass ratio
It is 2:1, modified graphene masterbatch and Ag-TiO in the present embodiment2The preparation method is the same as that of Example 1 for composite nano-granule, herein no longer
It repeats.
Embodiment 6
A kind of graphene fiber is present embodiments provided, difference lies in modified graphene is female with embodiment 5 for the present embodiment
Material is 2 parts.
Embodiment 7
A kind of graphene fiber is present embodiments provided, difference lies in modified graphene is female with embodiment 5 for the present embodiment
Material is 30 parts.
Embodiment 8
A kind of graphene fiber is present embodiments provided, difference lies in modified graphene is female with embodiment 5 for the present embodiment
In material, graphene oxide, Ag-TiO2The mass ratio of composite nano-granule and maleic anhydride-graft polypropylene is 1:5:100.
Embodiment 9
A kind of graphene fiber is present embodiments provided, difference lies in modified graphene is female with embodiment 5 for the present embodiment
In material, graphene oxide, Ag-TiO2The mass ratio of composite nano-granule and maleic anhydride-graft polypropylene is 50:0.1:100.
Embodiment 10
Present embodiments provide a kind of graphene fiber, the present embodiment with embodiment 5 the difference is that, Ag-TiO2
In composite nano-granule, Ag and TiO2Mass ratio be 1:5.
Embodiment 11
Present embodiments provide a kind of graphene fiber, the present embodiment with embodiment 5 the difference is that, Ag-TiO2
In composite nano-granule, Ag and TiO2Mass ratio be 10:1.
Embodiment 12
Embodiment 12 provides a kind of preparation method of graphene fiber, and the graphene fiber that embodiment 1-11 is provided is pressed
It is prepared according to following steps：
(s) polypropylene chip is divided into the first polypropylene chip and the second polypropylene chip, the first polypropylene chip and
The mass ratio of propylene dimer slice is 1:4；.
(r) modified graphene masterbatch is mixed with the first polypropylene chip, is granulated by twin-screw, obtains functional agglomerate；
(t) functional agglomerate is mixed with the second polypropylene chip, carries out melt spinning, obtains graphene fiber.
Comparative example 1
This comparative example provides a kind of graphene fiber, and difference lies in modified graphene is female with embodiment 5 for this comparative example
It does not include maleic anhydride-graft polypropylene in material.
Comparative example 2
This comparative example provides a kind of graphene fiber, and difference lies in modified graphene is female with embodiment 5 for this comparative example
Do not include Ag-TiO in material2Composite nano-granule.
Comparative example 3
This comparative example provides a kind of graphene fiber, and difference lies in modified graphene is female with embodiment 5 for this comparative example
In material, Ag-TiO is replaced using nano silver2Composite nano-granule.
Comparative example 4
This comparative example provides a kind of graphene fiber, and difference lies in modified graphene is female with embodiment 5 for this comparative example
In material, Ag-TiO is replaced using nano-titanium dioxide2Composite nano-granule.
Comparative example 5
This comparative example provides a kind of graphene fiber, and difference lies in modified graphene is female with embodiment 5 for this comparative example
In material, Ag-TiO is replaced using the mixture of nano-silver powder and nano-titanium dioxide2Composite nano-granule, and nano-silver powder and nanometer
The mass ratio of titanium dioxide is 2:1.
Comparative example 6
This comparative example provides a kind of graphene fiber, and difference lies in modified graphene is female with embodiment 5 for this comparative example
In material, graphene oxide is substituted using biomass graphene.
The preparation method for the fiber that above-mentioned comparative example 1-6 is provided is similar with embodiment 5, the difference is that according to raw material
Difference has adjusted corresponding steps, and details are not described herein.
Test example
The graphene fiber that embodiment 1-11 and comparative example 1-6 are provided is subjected to fracture strength, far infrared warming respectively
Can be with the measurement of antibacterial bacteriostatic performance, mid and far infrared warming can be according to CAS115《Healthcare function textile》Defined experiment
Method measures, and antibacterial bacteriostatic performance is evaluated according to evaluation method as defined in GB/T20944.3, and the results are shown in Table 1.
1 polyester fiber performance data table of table
It is fine to can be seen that graphene provided by the invention for the data comparison of embodiment 1-11 and comparative example 1-6 from table 1
Dimension, by by Ag-TiO2Composite nano-granule is dispersed in graphene oxide layer, and obtaining load has Ag-TiO2Composite Nano
The graphene oxide of grain, and so that load is had Ag-TiO by chemical bond2The graphene oxide of composite nano-granule connects with maleic anhydride-
The polyacrylic connection of branch, obtains modified graphene masterbatch so that modified graphene masterbatch can be stablized in polypropylene chip
Even dispersion so that manufactured graphene fiber not only has good mechanical property, but also has excellent antibacterial bacteriostatic
Performance, while a large amount of far infrareds can also be discharged, improve body microcirculation, promotes health.
From table 1, the comparison of embodiment 1-5 and embodiment 6-11 can be seen that when graphene masterbatch and polypropylene chip
Mass ratio be (5-10)：100, and in modified graphene masterbatch, graphene oxide, Ag-TiO2Composite nano-granule and maleic acid
The mass ratio of acid anhydride-graft polypropylene is (5-20)：(0.5-3):100, and Ag-TiO2In composite nano-granule, Ag and TiO2Quality
Than for (2-4)：When (1-2), the fracture strength bigger of made graphene fiber, the far infrared of release is more, antibacterial work(
Can be better, it can more improve body microcirculation, promote blood flow, ensure health.
In addition, the comparison by embodiment 1-5 and comparative example 3-5 can also be seen that by modified graphene masterbatch
Ag-TiO is added2Composite nano-granule so that Ag-TiO2With graphene synergistic effect occurs for composite nano-granule, and anti-microbial property is long-range
Anti-microbial property when being individually added into nano silver, nano-titanium dioxide or the mixture of nano silver and nano-titanium dioxide is added.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of graphene fiber, which is characterized in that including modified graphene masterbatch and polypropylene chip, the modified graphene
Masterbatch includes graphene oxide, Ag-TiO2Composite nano-granule and maleic anhydride-graft polypropylene, wherein Ag-TiO2Composite Nano
For grain uniform load in graphene oxide layer, maleic anhydride-graft polypropylene has Ag-TiO with load2The oxygen of composite nano-granule
Graphite alkene is keyed by chemistry.
2. graphene fiber according to claim 1, which is characterized in that the modified graphene masterbatch and polypropylene chip
Mass ratio be (5-10)：100, preferably (6-8)：100.
3. graphene fiber according to claim 1, which is characterized in that in the modified graphene masterbatch, graphite oxide
Alkene, Ag-TiO2The mass ratio of composite nano-granule and maleic anhydride-graft polypropylene is (5-20)：(0.5-3):100, preferably
(10-20)：(1-2):100.
4. graphene fiber according to claim 1, which is characterized in that the Ag-TiO2In composite nano-granule, Ag with
TiO2Mass ratio be (2-4)：(1-2), preferably 2:1.
5. according to claim 1-4 any one of them graphene fibers, which is characterized in that the system of the modified graphene masterbatch
Preparation Method includes the following steps：
(a) graphene oxide is scattered in aqueous solution, obtains graphene oxide dispersion；
(b) by Ag-TiO2Composite nano-granule disperses in aqueous solution, to obtain Ag-TiO2Composite nano-granule dispersion liquid；
(c) by Ag-TiO2Composite nano-granule dispersion liquid is added in graphene oxide dispersion, ultrasound so that Ag-TiO2It is compound to receive
The grain of rice is dispersed in graphene oxide layer, and obtaining load has Ag-TiO2The graphene oxide dispersion of composite nano-granule；
(d) there is Ag-TiO in load2Amine alkyltrialkoxysilaneand is added in the graphene oxide dispersion of composite nano-granule, instead
It answers, obtains surface modified graphite alkene；
(e) surface modified graphite alkene is reacted with maleic anhydride-graft polypropylene, obtains modified graphene masterbatch.
6. according to claim 1-4 any one of them graphene fibers, which is characterized in that the Ag-TiO2Composite nano-granule is pressed
It is prepared according to following steps：
(m) in aqueous solution by nano-titanium dioxide dispersion, nano-titanium dioxide aqueous solution is obtained；
(n) silver salt is added in titanium dioxide aqueous solution, is stirred evenly, reducing agent is added, be filtered, dry and ball successively
Mill, obtains Ag-TiO2Composite nano-granule.
7. graphene fiber according to claim 6, which is characterized in that in step (n), silver salt is silver nitrate；
Preferably, in step (n), reducing agent is at least one of sodium borohydride, ethylene glycol, glucose or citric acid；
Preferably, the molar ratio of reducing agent and silver salt is (2-7)：1, preferably (2-4):1.
8. according to the preparation method of claim 1-7 any one of them graphene fibers, which is characterized in that including walking as follows
Suddenly：
Modified graphene masterbatch is uniformly mixed with polypropylene chip, melt spinning is carried out, obtains graphene fiber.
9. the preparation method of graphene fiber according to claim 8, which is characterized in that include the following steps：By poly- third
Alkene slice is divided into the first polypropylene chip and the second polypropylene chip, then by modified graphene masterbatch and the first polypropylene chip
Mixing, is made functional agglomerate, then functional agglomerate is mixed with the second polypropylene chip, carries out melt spinning；
Preferably, the mass ratio of the first polypropylene chip and the second polypropylene chip is 1：(3-6), preferably 1:4.
10. according to product made of claim 1-7 any one of them graphene fibers, which is characterized in that including facial mask, wash
Face towel or underwear.
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