Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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MODIFIED FIBER AND PREPARATION METHOD THEREFOR
Technical field
The present disclosure belongs to the field of fiber preparation, and in
particular
relates to a modified fiber and a preparation method thereof The modified
fiber
includes modified hollow cotton or modified polyamide fiber.
Background
Polyester is an important type of synthetic fibers, and it is the trade name
of
polyester fiber in China, and is a fiber made of polyethylene terephthalate
(PET) or
polybutylene terephthalate (PBT) through spinning and post-processing.
Polyethylene terephthalate (PET) is a fiber-forming polymer made by using
poly-terephthalic acid (PTA) or dimethyl terephthalate (DMT) and ethylene
glycol
(EG) as raw materials through esterification or transesterification and
polycondensation. Polybutylene terephthalate (PBT) is a fiber-forming polymer
made by using poly-terephthalic acid (PTA) or dimethyl terephthalate (DMT) and
1,4-butylene glycol as raw materials through esterification or
transesterification and
polycondensation.
Polyester is the one made by the simplest process among the three major
synthetic
fibers, and it is relatively inexpensive, and is well-popularized due to its
characteristics such as durability, good elasticity, non-easy deformability,
corrosion
resistance, insulation, stiff and smooth, and easy rinsibility and quick
drying, etc.
Polyester hollow cotton is made of different specifications of polyester
superfine
fibers through special process. Since its texture resembles down feather,
polyester
hollow cotton is also called as silk wadding or down cotton, and is widely
used in
various warmth retention products such as down coats, down trousers, ski
shirts,
cotton wadded jackets, down quilts, and seat cushions, etc. The disadvantage
of
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existing polyester hollow cotton is that it has less warmth retention
property, is not
water washable, and is not lightweight.
Polyamide, i.e., polyamide fiber, commonly known as Nylon, which has an
English
name of Polyamide (abbreviated as PA), with a density of about 1.15 g/cm3, is
a
generic name of thermoplastic resins containing repeating amide group -NHCO-
in
the main chain of the molecule, including aliphatic PA, aliphatic-aromatic PA
and
aromatic PA. Among them, there are many types of aliphatic PAs, which have
large
yields and are widely used. The nomenclature is determined by the specific
number
of carbon atoms in the monomers for synthesis.
The most outstanding advantage of polyamide is that its abrasion resistance is
higher
than that of all other fibers. Its abrasion resistance is 10 times higher than
that of
cotton and 20 times higher than that of wool. Adding some polyamide to blended
fabrics can greatly increase the abrasion resistance. When stretched up to 3-
6%, the
elastic recovery rate can reach 100%, and the blended fabrics can withstand
tens of
thousands of times of rupture without breaking. The strength of polyamide
fiber is
1-2 times higher than that of cotton, 4-5 times higher than that of wool, and
3 times
of viscose fiber.
However, polyamide has no thermal insulation property. When it is used as
fabrics
such as socks and clothes, the thermal insulation effect thereof is poor,
which is
especially prone to cause problems such as joint pain, etc. For socks or
intimates,
body scurf is easily left thereon, breeding bacteria and causing odors.
Therefore, there is a need to develop a functional modified polyamide fiber.
Graphene is a two-dimensional crystal stripped from graphite material,
consisting of
carbon atoms, and only having one-layer-atom thick, and is a novel nano-
material
that has been found currently to be the thinnest, have maximal strength and
maximal
electrical and thermal conductivities. The addition of graphene to a substrate
such as
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polyester or polyamide is expected to give new properties to polyester or
polyamide,
especially the addition of biomass graphene with bacteria inhibition and
low-temperature far infrared functions, the polyester or polyamide is expected
to
have bacteria inhibition and low-temperature far infrared functions.
However, the solid state of graphene is easy to agglomerate to form larger
particle
agglomerates, and when it is added to a substrate such as polyester or
polyamide, it
is not easily dispersed uniformly, which greatly reduces the processing
fluidity of
substrate masterbatches such as polyester or polyamide, and thus the spinning
process cannot be performed. Therefore, graphene cannot be applied in a
substrate
material such as polyester or polyamide.
In the related technologies, in order to uniformly disperse graphene, a
dispersing
agent is often added, but the dispersing agent has a degrading effect on the
materials.
Therefore, it is an urgent issue needed to be solved in the art that how to
find a
method for uniformly doping graphene into a substrate such as polyester or
polyamide without adding a dispersing agent, so that the properties of
graphene (e.g.,
thermal insulation property, low-temperature far-infrared and bacteria
inhibition
property) can be fully used.
Summary
In view of the technical problem of the related technologies, i.e., graphene
cannot be
doped into fiber materials (including polyester and polyamide materials)
without
using a dispersing agent to obtain a modified hollow cotton or a modified
polyamide
fiber having thermal insulation property, low-temperature far-infrared and
bacteria
inhibition properties, the object of the present disclosure is to provide a
modified
hollow cotton, which is doped with graphene.
The "modified hollow cotton" of the present disclosure is obtained by doping
with
graphene, and it can also be called by a person skilled in the art as hollow
cotton
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blend, hollow cotton composite, hollow cotton modifier, graphene-containing
hollow
cotton or graphene-containing modified hollow cotton.
The term "doping" used in the present disclosure means that graphene is added
to the
hollow cotton in various forms that can be conceived by those skilled in the
art.
Typical but non-limiting examples may be dispersing graphene on the surface of
the
hollow cotton, or in situ compositing graphene with the substrate of the
modified
hollow cotton, or physically blending graphene with the hollow cotton.
"Doping"
can also be replaced with "containing", "comprising", "dispersing" and
"having",
etc., by those skilled in the art.
The so-called "hollow cotton" is a bat wool product with high warmth retention
property with the fiber material being polyester.
Preferably, the graphene is a biomass graphene.
The biomass graphene is prepared from biomass; preferably, the biomass
graphene is
prepared from biomass-derived cellulose.
Carbon six-membered ring honeycomb lamellar structures having more than 10
layers and a thickness of 100 nm or less are called graphene nanosheets;
carbon
six-membered ring honeycomb lamellar structures having more than 10 layers and
a
thickness of 100 nm or less and prepared by using biomass as carbon source are
called biomass graphene nanosheets; carbon six-membered ring honeycomb
lamellar
structures having 1-10 layers are called graphene; and carbon six-membered
ring
honeycomb lamellar structures having 1-10 layers and prepared by using biomass
as
carbon source are called biomass graphene.
The graphene of the present disclosure includes graphene nanosheet layer and
graphene, and further includes biomass graphene nanosheet layer and biomass
graphene.
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The graphene of the present disclosure can be obtained by different
preparation
methods, for example mechanical exfoliation method, epitaxial growth method,
chemical vapor deposition method, and graphite oxidation-reduction method, and
it
can also be graphene prepared through hydrothermal carbonization of biomass
resources, and other methods in the related technologies. However, no matter
which
method is used, it is difficult to achieve large-scale production of graphene
strictly
theoretically. For example, certain impurity elements, and other allotropes of
carbon
element or graphene structures with non-single-layer or even multi-layer
(e.g., 3
layers, 5 layers, 10 layers, and 20 layers, etc.) will present in the graphene
prepared
in the related technologies, and graphene used in the present disclosure also
includes
nonstrictly theoretically graphene described above.
Preferably, the biomass is any one selected from the group consisting of
agricultural
and forestry wastes, plants, and a combination of at least two selected
therefrom.
Preferably, the plants are any one selected from the group consisting of
coniferous
wood, broadleaf wood, and a combination of at least two selected therefrom.
Preferably, the agricultural and forestry wastes are any one selected from the
group
consisting of corn stalks, corn cobs, sorghum stalks, beet residues, bagasse,
furfural
residues, xylose residues, wood chips, cotton stalks, shells, reeds, and a
combination
of at least two selected therefrom.
Preferably, the agricultural and forestry wastes are corn cobs.
In addition to the above list of biomass, the biomass according to the present
disclosure may be any one of biomass resources that can be known by those
skilled
in the art, which will not be repeated herein.
The biomass graphene of the present disclosure refers to graphene prepared by
using
biomass as carbon source. specific processes for preparing graphene using
biomass
as carbon source have been reported in the art. Typical but non-limiting
examples
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include CN104724699A, which will not be repeated herein.
For the biomass graphene, a typical but non-limiting example may be any one
selected from the group consisting of substance 0, substance 0, substance ,
substance having the properties described in Table a, and a combination of
at
least two:
Table a
Performance indicators
Items
Substance Substance 0 Substance Substance
0
Conductivity, S/m 2800-8000 5000-8000 2800-4000 3000-8000
Specific surface area, 15O ?150-300 250
m2/g
Raman spectrum,
>2.0
IG/ID
C/O 35.0 40.0
Ash content, % 1.0-4.0 2.0-4.0 1.0-2.5 1.0-2.0
Fe, % 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5
Si, % 0.05-0.3 0.05-0.3 0.05-0.3 0.05-0.3
Al, % 0.05-0.4 0.05-0.4 0.05-0.4 0.05-0.4
In Table a, IG/ID is the peak height ratio of G peak to D peak in the Raman
spectrum.
The biomass graphene of the present disclosure has a peak height ratio of the
G peak
to D peak of preferably 2.0 or more, further preferably 3.0 or more, and
particularly
preferably 5.0 or more. Optionally, the biomass graphene of the present
disclosure
has a peak height ratio of the G peak to D peak of 30 or less, for example,
27, 25, 20,
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18, 15, 12, 10, 8, and 7, etc.
Those skilled in the art should understand that the performance indicators of
the
biomass graphene listed in Table a all refer to the indicators of the powder
of the
biomass graphene. If the biomass graphene is slurry, the above indicators are
the
indicators of the powder before preparing the slurry.
When the biomass graphene is powder, the biomass graphene has the following
properties in addition to the performance indicators described in Table a:
black powder, uniform fineness, no significant large particles, a water
content of
3.0% or less, a particle size D90 of 10.0 m or less, a pH of 5.0 to 8.0, and
an
apparent density of 0.2 to 0.4 &In'.
When the biomass graphene is a slurry, it is a product obtained by dispersing
biomass graphene in a solvent, and the biomass graphene has the following
properties in addition to the performance indicators described in Table a:
a solid content of 1.0 to 10.0%, a particle size D50 of 0.7 pm or less, a pH
of 8.0 to
10.0, a Zeta potential of -10 mV or less, and a viscosity of 5.0 to 8.0 mpa.s.
The biomass graphene belongs to carbon nanostructure-containing composite, and
the carbon nanostructure-containing composite contains graphene, amorphous
carbon and non-carbon non-oxygen elements; the non-carbon non-oxygen elements
include elements of Fe, Si and Al; and the content of the non-carbon non-
oxygen
elements is 0.5 wt% to 6 wt% of the composite.
Preferably, the content of carbon element in the carbon nanostructure-
containing
composite is 80 wt% or more, for example 82 wt%, 86 wt%, 89 wt%, 91 wt%, 94
wt%, 97 wt%, and 99 wt%, etc., preferably 85 wt% to 97 wt%, more preferably 90
wt% to 95 wt%.
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Preferably, the non-carbon non-oxygen elements account for 0.3 wt% to 5 wt% of
the carbon nanostructure-containing composite, for example 0.7 wt%, 1.1 wt%,
1.3
wt%, 1.6 wt%, 2 wt%, 2.8 wt%, 3.5 wt%, 4.2 wt%, 5.3 wt% or 5.8 wt%, preferably
1.5 wt% to 5 wt%.
In the carbon nanostructure-containing composite of the present disclosure,
the
graphene structure preferably has a carbon six-membered ring honeycomb
lamellar
structure having a thickness of 100 nm or less, preferably a carbon six-
membered
ring honeycomb lamellar structure having a thickness of 20 nm or less, further
preferably any one or a combination of at least two of carbon six-membered
ring
honeycomb lamellar structures having 1-10 layers, preferably any one or a
combination of at least two of single layer, double layers or 3-10 layers
structures;
preferably, the carbon six-membered ring honeycomb lamellar structure in the
composite microscopically shows any one conformation selected from the group
consisting of warping, curling and folding, and a combination of at least two
selected
therefrom.
The carbon nanostructure-containing composite of the present disclosure
preferably
comprises graphene structure and amorphous carbon; non-carbon non-oxygen non
hydrogen elements are adsorbed on the surface or inside of the carbon
nanostructure
in a form of any one or a combination of more of simple substance, oxide, and
carbide. The amorphous carbon also comprises two-dimensional graphite layers
or
three-dimensional graphite crystallites, on the edge of which there are a
large
number of irregular bonds. Besides a large number of sp2 carbons, there are
many
sp3 carbons. In fact, their (amorphous carbon) interior structures are
crystals having
the same structure as graphite, rather than real amorphous solid, besides that
the
layered structure formed by the hexagonal annular plane of carbon atoms is
messy
and irregular. There are defects in the formation of the crystal; the majority
of
amorphous carbon is formed by molecular debris having graphite layer structure
which are roughly parallel to each other, and irregularly stacked together,
referred to
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as chaotic layer structure. The layers or debris is connected by carbon atom
bonds in
the form of the tetrahedral bonding of diamond structure.
By way of example, the biomass graphene can be obtained by the method for
preparing the carbon nanostructure-containing composite, which includes the
following steps (labelled as method 1):
(1) catalyzing a biomass carbon source under the action of a catalyst to
obtain a
precursor;
(2) maintaining the temperature of the precursor at 140 C-180 C for 1.5-2.5h
under
the condition of protective gas to obtain a first intermediate;
(3) heating the first intermediate to 350 C -450 C under the condition of
protective
gas and maintaining the temperature for 3h-4h to obtain a second intermediate;
(4) heating the second intermediate to 1100 C -1300 C under the condition of
protective gas and maintaining the temperature for 2h-4h to obtain a third
intermediate;
(5) alkali washing, acid washing and water washing the third intermediate in
sequence to obtain a composite;
wherein the temperatures in steps (3) and (4) are increased at a rate of 14 C
/min-18 C /min.
Preferably, the biomass carbon source is one or more of lignocellulose,
cellulose and
lignin.
By way of example, the biomass graphene can be obtained by the method for
preparing the carbon nanostructure-containing composite, which includes the
following steps (labelled as method 2):
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(1) mixing a biomass carbon source and a catalyst, stirring and catalyzing,
then
drying to obtain a precursor;
(2) maintaining the temperature of the precursor under protective atmosphere
at 280
to 350 C for 1.5 to 2.5 hours, then heating by temperature programming to 950
to
1200 C at a heating rate of 15 to 20 C/min, maintaining that temperature for 3
to 4
hours to obtain a crude product;
(3) washing the crude product to obtain a carbon nanostructure-containing
composite.
In the second alternative, the biomass carbon source and the catalyst have a
mass
ratio of 1:(0.1-10), preferably 1:(0.5-5), further preferably 1:(1-3);
preferably, the catalyst is anyone selected from the group consisting of
manganese
compounds, iron-containing compound, cobalt-containing compound,
nickel-containing compound, and a combination of at least two selected
therefrom.
Preferably, the iron-containing compound is anyone selected from the group
consisting of halogen compounds of iron, iron cyanides, iron-containing salts
of acid,
and a combination of at least two selected therefrom. Preferably, the
cobalt-containing compound is anyone selected from the group consisting of
halogen
compounds of cobalt, cobalt-containing salts of acid, and a combination of at
least
two selected therefrom. Preferably, the nickel-containing compound is anyone
selected from the group consisting of nickel chlorides, nickel-containing
salts of acid,
and a combination of at least two selected therefrom. Preferably, the catalyst
is
anyone selected from the group consisting of ferric chloride, ferrous
chloride, ferric
nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium
ferricyanide,
potassium ferrocyanide, potassium trioxalatoferrate, cobalt chloride, cobalt
nitrate,
cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel
sulfate, nickel
acetate, and a combination of at least two selected therefrom.
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The stirring and catalyzing treatment is carried out at a temperature of 150
to 200 C
for 4 hours or more, preferably 4 to 14 hours; preferably, the water content
in the
precursor is 10 wt% or lower; preferably, the precursor is heated to 280 to
350 C at a
heating rate of 3 to 5 C/min; preferably, the protective atmosphere is any one
selected from the group consisting of nitrogen, helium, argon, and a
combination of
at least two selected therefrom, preferably nitrogen; preferably, the crude
product is
subjected to acid washing and water washing successively; and the acid washing
is
preferably carried out by using hydrochloric acid with a concentration of 3
wt% to 6
wt%, further preferably hydrochloric acid with a concentration of 5 wt%; the
water
washing is preferably carried out by using deionized water and/or distilled
water;
preferably, the washing is carried out at a temperature of 55 to 65 C,
preferably
60 C.
The biomass carbon source is cellulose and/or lignin, preferably cellulose,
further
preferably porous cellulose;
preferably, the porous cellulose is obtained by the following method of:
acid hydrolyzing a biomass source to obtain lignocellulose, then porous
post-processing to obtain porous cellulose; optionally, the porous cellulose
is used
after bleaching;
Preferably, the biomass carbon source is any one selected from the group
consisting
of plants, agricultural and forestry wastes, and a combination of at least two
selected
therefrom; preferably, any one selected from agricultural and forestry wastes,
and a
combination of at least two selected therefrom; preferably, the agricultural
and
forestry wastes are any one selected from the group consisting of corn stalks,
corn
cobs, sorghum stalks, beet residues, bagasse, furfural residues, xylose
residues, wood
chips, cotton stalks, reeds, and a combination of at least two selected
therefrom,
preferably corn cobs.
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By way of example, the biomass graphene can be obtained by the method for
preparing the carbon nanostructure-containing composite, which includes the
following steps (labelled as method 3):
(1') acid hydrolyzing corn cobs to obtain lignocellulose, and then porous
post-processing to obtain porous cellulose, wherein the porous cellulose is
bleached
for standby;
(1) mixing the porous cellulose in step (1') with a catalyst in a mass ratio
of 1:0.5-1.5,
stirring at 150-200 C, catalyzing for 4h or more, and drying to a water
content of
less than 10 wt% to obtain a precursor;
(2) heating the precursor to 280-350 C at a rate of 3-5 C/mmn under protective
atmosphere, then heating by temperature programming to 950-1200 C at an
increasing rate of 15-20 C/min, maintaining the temperature for 3-4h to obtain
a
crude product;
(3) acid washing the crude product at 55-65 C with hydrochloric acid having a
concentration of 5 wt%, water washing to obtain a composite.
The carbon nanostructure-containing composite prepared by the above methods
also
belongs to the case of biomass containing graphene.
The biomass graphene of the present disclosure can be obtained by the
following
method for preparing the carbon nanostructure-containing composite:
Method 4:
The biomass source is used to obtain active carbon via current processes.
Since the
types and contents of microelements within different plants are greatly
different,
later steps such as acid washing and water washing are used to control the
amount of
the non-carbon non-oxygen elements. Graphene is introduced on such a basis to
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make the amount of the non-carbon non-oxygen element be 0.5wt%-6wt% of the
composite.
Method 5
Commercially available lignose is high-temperature carbonized under inert gas,
or
graphitization reaction was not thoroughly carried out. Then graphene is
added. A
combination of any three or more selected from nano-P, Si, Ca, Al, Na, Fe, Ni,
Mn,
K, Mg, Cr, S or Co is introduced later, and the content thereof is controlled
to be
0.5wt%-6wt%.
Method 6
Some organic wastes such as phenolic resin cystosepiment are carbonized. Then
graphene is added. A combination of any three or more selected from nano-P,
Si, Ca,
Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or Co is introduced later, and the content
thereof is
controlled to be 0.5wt%-6wt%.
Method 7
Active carbon and graphene are added to nano-graphite. A combination of any
three
or more selected from nano-P, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or Co
is
introduced later, and the content thereof is controlled to be 0.5wt%-6wt%.
The preparation of the biomass graphene of the present disclosure is not
limited to
the above preparation methods. The biomass graphenes obtained by the methods 1-
3
are superior to those obtained by the methods 4-7 in terms of the far infrared
and
bacteria resistance properties. However, all the biomass graphenes can be
dispersed
uniformly in the modified fiber without activation or modification treatment
when
the down-stream products are produced, which can play a certain effect,
especially
for methods 1-3.
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Preferably, the content of graphene in the modified hollow cotton is 0.2-10
wt%,
preferably 0.3-8 wt%, further preferably 0.5-5 wt%.
By way of example, the content of graphene in the modified hollow cotton
according
to the present disclosure is 0.3 wt%, 0.6 wt%, 0.9 wt%, 1.1 wt%, 1.4 wt%, 1.6
wt%,
1.8 wt%, 2.1 wt%, 2.4 wt%, 2.5 wt%, 2.8 wt%, 3.0 wt%, 3.4 wt%, 3.6 wt%, 3.9
wt%,
4.2 wt%, 4.5 wt%, 4.9 wt%, 5.2 wt%, 5.8 wt%, 6.3 wt%, 6.5 wt%, 6.6 wt%, 6.9
wt%,
7.3 wt%, 7.5 wt%, 7.9 wt%, 8.2 wt%, 8.8 wt%, 9.3 wt%, and 9.9 wt%, etc.
Preferably, the doping amount of graphene in the modified polyamide fiber is
0.2-10
wt%, preferably 0.3-8 wt%, further preferably 0.5-5 wt%.
By way of example, the doping amount of graphene in the modified polyamide
fiber
according to the present disclosure is 0.3 wt%, 0.6 wt%, 0.9 wt%, 1.1 wt%, 1.4
wt%,
1.6 wt%, 1.8 wt%, 2.1 wt%, 2.4 wt%, 2.5 wt%, 2.8 wt%, 3.0 wt%, 3.4 wt%, 3.6
wt%,
3.9 wt%, 4.2 wt%, 4.5 wt%, 4.9 wt%, 5.2 wt%, 5.8 wt%, 6.3 wt%, 6.5 wt%, 6.6
wt%,
6.9 wt%, 7.3 wt%, 7.5 wt%, 7.9 wt%, 8.2 wt%, 8.8 wt%, 9.3 wt%, and 9.9 wt%,
etc.
Preferably, the far infrared detection normal emissivity of the modified
hollow
cotton according to the present disclosure is greater than 0.85, for example
0.87, 0.89,
0.91, 0.92, and 0.93, etc., preferably greater than 0.88.
The thermal insulation effect of the modified hollow cotton provided by the
present
disclosure is 1 kg of the modified hollow cotton of the present disclosure has
the
same thermal insulation effect as that of 2.5-3 kg of ordinary hollow cotton,
and the
air permeability is good while ensuring the thermal insulation effect.
Preferably, the far infrared detection normal emissivity of the modified
polyamide
fiber according to the present disclosure is greater than 0.85, for example
0.87, 0.89,
0.91, 0.92, and 0.93, etc., preferably greater than 0.88.
The modified polyamide fiber provided by the present disclosure has far-
infrared
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function, and the socks or clothes made therefrom have far-infrared emission,
which
can protect human joints from catching cold; in addition, the modified
polyamide
fiber with addition of graphene has bacteria resistance and inhibition
effects, and the
fabrics, etc., made therefrom will not produce odors during long-term use.
The second object of the present disclosure is to provide another method for
preparing the modified hollow cotton as described in the first object, which
includes
the following steps:
(A'- l) mixing graphene with blank polyester chips, screw extruding, and
drying to
obtain graphene-containing polyester masterbatches;
(A'-2) uniformly mixing the graphene-containing polyester masterbatches with a
portion of blank polyester chips, and then mixing with the remaining blank
polyester
chips b;
(A'-3) melt spinning the resulting materials, and then opening to obtain the
modified
hollow cotton;
The present disclosure adopts a physical method to disperse solid graphene
into the
polyester substrate, thereby obtaining a modified hollow cotton containing
uniformly
dispersed graphene. Specifically, according to the present disclosure, the
hollow
cotton containing uniformly dispersed graphene is obtained by firstly mixing
the
blank polyester chips with solid graphene, screw extruding the mixture to
obtain
graphene composite polyester masterbatches, in which polyester masterbatches
serve
as carrier of graphene for primary dispersion of graphene; then, physically
mixing
the graphene-loaded polyester masterbatches with the blank polyester chips in
two
steps according to the formulation amount to obtain the materials to be spun,
in
which the graphene is uniformly dispersed; finally, spinning according to the
conventional preparation process of hollow cotton to obtain the hollow cotton
containing uniformly dispersed graphene. The method of the present disclosure
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solves the technical problem of uneven dispersion of graphene in the related
technologies, and obtains a modified hollow cotton showing excellent thermal
insulation property, air permeability, low-temperature far-infrared and
bacteria
resistance properties.
In the present disclosure, primary dispersion is achieved by firstly
dispersing the
graphene particles which are easy to agglomerate in the blank polyester chips,
and
then physically mixing the obtained masterbatches with the blank polyester
chips in
two steps to achieve uniform dispersion of the graphene, thereby obtaining the
uniformly dispersed materials to be spun.
preferably, the blank polyester chips of step (A'-1) and step (A'-2) are each
independently PET and/or PBT.
Preferably, the blank polyester chips of step (A'-1) are PET.
The selection of the blank polyester chips according to step (A'-1) and step
(A'-2) of
the present disclosure is not specifically limited, and they can be selected
by a person
skilled in the art according to actual situations. However, the melting point
of PET is
about 220 C, and the melting point of PBT is about 270 C. From the view of
energy
saving of the process temperature, the blank polyester chips of the present
disclosure
are preferably PET.
Preferably, the graphene content in the graphene-containing polyester
masterbatches
is 1-20wt%, for example 2 wt%, 4 wt%, 6 wt%, 8 wt%, 12 wt%, 15 wt%, 17 wt%,
19wt%, etc., preferably 5-15 wt%, further preferably 6-10 wt%.
Preferably, the melting temperature of the screw extrusion of step (A'-1) is
230-270 C, for example 235 C, 240 C, 244 C, 249 C, 253 C, 258 C, 262 C, 267 C,
etc., preferably 240-260 C.
Preferably, the moisture content of the graphene-containing polyester
masterbatches
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is 600 ppm or less, for example 50 ppm, 80 ppm, 130 ppm, 180 ppm, 230 ppm, 280
ppm, 350 ppm, 390 ppm, 420 ppm, 450 ppm, 480 ppm, etc., preferably 300 ppm or
less.
Preferably, the mass ratio of the graphene-containing polyester masterbatches
to the
blank polyester chips in step (A'-2) is 1:(5-30), for example 1:6, 1:7, 1:9,
1:13, 1:16,
1:22, 1:26, 1:29, etc., preferably 1:(15-20).
Preferably, in step (A'-2), the ratio of the part of the blank polyester chips
to the
integral blank polyester chips added in step (b) is 1:(2-10), for example 1:3,
1:4, 1:5,
1:6, 1:7, 1:8, 1:9, etc., preferably 1:(4-8).
The integral blank polyester chip b refers to the sum of the masses of the
part of the
blank polyester chips b and the remaining blank polyester chips b.
Preferably, the intrinsic viscosity of the raw materials for melt spinning in
step (A'-3)
is 0.60 dL/g or more, for example 0.62 dL/g, 0.66 dL/g, 0.69 dL/g, 0.72 dL/g,
0.75
dL/g, 0.78 dL/g, 0.80d L/g, and 0.85 dL/g, etc., preferably 0.65 dL/g or more.
The addition of graphene of the present disclosure will reduce the viscosity
of the
chips, however the spinning step cannot be performed if the viscosity is too
low.
Preferably, step (A'-1') is performed before step (A'-1): smashing the blank
polyester
chips into blank polyester chip particles for mixing with the graphene of step
(A'-1);
preferably, the particle size of the blank polyester chip particles is 3 mm or
less, for
example 0.1 mm, 0.5 mm, 0.9 mm, 1.3 mm, 1.8 mm, 2.2 mm, 2.5 mm, 2.8 mm, etc.
In step (a'), blank polyester chips are chopped to increase the rough surface,
which
increases the specific surface area and frictional force of the graphene
attached
thereto, and further improving the dispersibility of the graphene.
Further preferably, step (A'-2') is set between step (A'-2) and step (A'-3):
screw
17
CA 03005917 2018-05-22
extruding the materials uniformly mixed in step (A'-2) again;
preferably, the melting temperature of the screw extrusion of the modified
hollow
cotton is 230-270 C, for example 235 C, 240 C, 244 C, 249 C, 253 C, 258 C,
262 C, 267 C, etc., preferably 240-260 C.
After the conventional polyester is subjected to the screw extrusion twice,
the
cleavage of the polyester polymer molecules will be caused, which reduces the
length of its molecular chain and the strength of the polyester, eventually
resulting in
insufficient wiredrawing length during the process of preparing the hollow
cotton; by
means of adding graphene particles to the polyester substrate in the present
disclosure, the melting temperature of the screw extrusion can be improved,
even if
the screw extrusion is performed twice, the length of the molecular chain of
the
obtained polyester fiber has less change, enabling the preparation of the
hollow
cotton fiber.
As an optional technical solution, a method for preparing the hollow cotton
according to the present disclosure includes the following steps:
(A'-l') smashing PET blank chips to obtain PET blank chip particles;
(A'-l) mixing graphene with PET blank chip particles, then screw extruding at
a
melting temperature of 230-270 C, drying the extruded product to a moisture
content
of 600 ppm or less to obtain graphene-containing PET polyester masterbatches;
(A'-2) mixing the graphene-containing PET polyester masterbatches with PET
polyester chips to obtain materials with intrinsic viscosity of 0.60 dL/g or
more;
(A'-3) melt spinning the resulting materials, and then opening to obtain the
hollow
cotton.
The third object of the present disclosure is to provide another method for
preparing
18
CA 03005917 2018-05-22
a modified polyamide fiber as described in the first object, which includes
the
following steps:
(B'-1) mixing graphene with blank polyamide chips, screw extruding, and drying
to
obtain graphene-containing polyamide masterbatches;
(B'-2) uniformly mixing the graphene-containing polyamide masterbatches with a
portion of blank polyamide chips, and then mixing with the remaining blank
polyamide chips b;
(B'-3) melt spinning the resulting materials to obtain the modified polyamide
fiber.
The present disclosure adopts a physical method to disperse solid graphene
into the
polyamide substrate, thereby obtaining a modified polyamide fiber containing
uniformly dispersed graphene. Specifically, according to the present
disclosure, the
modified polyamide fiber containing uniformly dispersed graphene is obtained
by
firstly mixing the blank fiber chips with solid graphene, screw extruding the
mixture
to obtain graphene composite fiber masterbatches, in which fiber masterbatches
serve as carrier of graphene for primary dispersion of graphene; then,
physically
mixing the graphene-loaded fiber masterbatches with the blank fiber chips in
two
steps according to the formulation amount to obtain the materials to be spun,
in
which the graphene is uniformly dispersed; finally, spinning according to the
conventional preparation process of polyamide spinning to obtain the modified
polyamide fiber containing uniformly dispersed graphene. The method of the
present
disclosure solves the technical problem of uneven dispersion of graphene in
the
related technologies, and obtains a modified polyamide fiber showing excellent
low-temperature far-infrared and bacteria resistance properties.
In the present disclosure, primary dispersion is achieved by firstly
dispersing the
graphene particles which are easy to agglomerate in the blank polyamide chips,
and
then physically mixing the obtained masterbatches with the blank polyamide
chips in
19
k
. . CA 03005917 2018-05-22
A
two steps to achieve uniform dispersion of the graphene, thereby obtaining the
uniformly dispersed materials to be spun.
Preferably, the blank polyamide chips of step (B'-1) and step (B'-2) are each
independently any one of PA-6, PA-66, PA-610, PA-1010, and MCPA.
The selection of the blank polyamide chips according to step (B'-1) and step
(B'-2)
of the present disclosure is not specifically limited, and they can be
selected by a
person skilled in the art according to actual situations.
Preferably, the graphene content in the graphene-containing polyamide
masterbatches is 3-10 wt%, for example 4 wt%, 6 wt%, 8 wt%, 9 wt%, etc.,
preferably 5-8 wt%.
Preferably, the melting temperature of the screw extrusion of step (B'-1) is
210-240 C, for example 215 C, 217 C, 221 C, 225 C, 228 C, 231 C, 234 C, 238 C,
etc., preferably 240-260 C.
Preferably, the moisture content of the graphene-containing polyamide
masterbatches is 600 ppm or less, for example 50 ppm, 80 ppm, 130 ppm, 180
ppm,
230 ppm, 280 ppm, 350 ppm, 390 ppm, 420 ppm, 450 ppm, 480 ppm, etc.,
preferably 300 ppm or less.
Preferably, the mass ratio of the graphene-containing polyamide masterbatches
to the
blank polyamide chips in step (B'-2) is 1:(5-30), for example 1:6, 1:7, 1:9,
1:13, 1:16,
1:22, 1:26, 1:29, etc., preferably 1:(15-20).
Preferably, in step (B'-2), the ratio of the part of the blank polyamide chips
to the
integral blank polyamide chips added in step (B'-2) is 1:(2-10), for example
1:3, 1:4,
1:5, 1:6, 1:7, 1:8, 1:9, etc., preferably 1:(4-8).
The integral blank polyamide chip refers to the sum of the masses of the part
of the
. CA 03005917 2018-05-22
,
blank polyamide chips and the remaining blank polyamide chips.
Preferably, the intrinsic viscosity of the raw materials for melt spinning in
step (B'-3)
is 3 dL/g or less, preferably 2.7 dL/g or less.
The addition of graphene of the present disclosure will increase the viscosity
of the
chips, however the spinning step cannot be performed if the viscosity is too
high.
As a preferred technical solution, step (B'-1') is performed before step (B'-
1):
smashing the blank polyamide chips into blank polyamide chip particles for
mixing
with the graphene of step (B'-1);
preferably, the particle size of the blank polyamide chip particles is 3 mm or
less, for
example 0.1 mm, 0.5 mm, 0.9 mm, 1.3 mm, 1.8 mm, 2.2 mm, 2.5 mm, 2.8 mm, etc.
In step (B'-1'), blank polyamide chips are chopped to increase the rough
surface,
which increases the specific surface area and frictional force of the graphene
attached thereto, and further improving the dispersibility of the graphene.
Further preferably, step (B'-2') is set between step (B'-2) and step (B'-3):
screw
extruding the materials uniformly mixed in step (B'-2) again;
preferably, the melting temperature of the screw extrusion in the preparation
method
of the modified polyamide fiber is 210-240 C, for example 215 C, 217 C, 221 C,
225 C, 228 C, 231 C, 234 C, 238 C, etc., preferably 240-260 C.
After the conventional polyamide is subjected to the screw extrusion twice,
the
cleavage of the polyamide polymer molecules will be caused, which reduces the
length of its molecular chain and the strength of the polyamide, eventually
resulting
in insufficient wiredrawing length during the process of preparing the
modified
polyamide fiber; by means of adding graphene particles to the polyamide
substrate in
the present disclosure, the melting temperature of the screw extrusion can be
21
CA 03005917 2018-05-22
improved, even if the screw extrusion is performed twice, the length of the
molecular
chain of the obtained polyamide fiber has less change, enabling the
preparation of
the modified polyamide fiber.
The third object of the present disclosure is to provide one method for
preparing a
modified hollow cotton as described in the first object, which includes the
following
steps:
(A-1) smashing blank polyester chip to obtain blank polyester chip particles;
(A-2) mixing graphene with blank polyester chip particles, screw extruding,
and
drying to obtain graphene-containing polyester masterbatches;
(A-3) uniformly mixing the graphene-containing polyester masterbatches with
the
blank polyester chips;
(A-4) melt spinning the resulting materials, and then opening to obtain the
modified
hollow cotton.
The present disclosure adopts a physical method to disperse solid graphene
into the
polyester substrate, thereby obtaining a modified hollow cotton containing
uniformly
dispersed graphene. Specifically, according to the present disclosure, the
hollow
cotton containing uniformly dispersed graphene is obtained by firstly chopping
the
blank polyester chips to increase the rough surface, so as to increase the
specific
surface area and frictional force of the graphene attached thereto, which will
improve
the dispersibility of the graphene; then dispersing the solid graphene in the
blank
polyester chip particles, screw extruding the mixture to obtain graphene
composite
polyester masterbatches, in which polyester masterbatches serve as carrier of
graphene for primary dispersion of graphene; then, physically mixing the
graphene-loaded polyester masterbatches with the blank polyester chips
according to
the formulation amount to obtain the materials to be spun, in which the
graphene is
uniformly dispersed; finally, melt spinning according to the conventional
preparation
22
A
CA 03005917 2018-05-22
process of hollow cotton to obtain the modified hollow cotton uniformly doped
with
graphene. The method of the present disclosure solves the technical problem of
uneven dispersion of graphene in the related technologies, and obtains a
modified
hollow cotton showing excellent thermal insulation property, air permeability,
low-temperature far-infrared and bacteria resistance properties.
In the present disclosure, primary dispersion is achieved by dispersing the
graphene
particles which are easy to agglomerate in the blank polyester chip particles,
and
then mixing the obtained masterbatches with the blank polyester chips again to
obtain the uniformly dispersed materials to be spun.
The blank polyester chips of the present disclosure refers to the polyester
chips
without adding functional graphene particles.
Uniform distribution refers to: the probabilities of the measured values
appearing in
a certain range are the same. For this application, the uniform dispersion
means that
the content of graphene in the modified hollow cotton is less different for
any cubic
centimeter ranges.
Preferably, the particle size of the blank polyester chip particles is 3 mm or
less, for
example 0.1 mm, 0.5 mm, 0.9 mm, 1.3 mm, 1.8 mm, 2.2 mm, 2.5 mm, 2.8 mm, etc.
Preferably, the blank polyester chips of step (A-1) and step (A-3) are each
independently PET (polyethylene terephthalate) and/or PBT (polybutylene
terephthalate).
Preferably, the blank polyester chips of step (A-1) are PET.
The selection of the blank polyester chips according to step (A-1) and step (A-
3) of
the present disclosure is not specifically limited, and they can be selected
by a person
skilled in the art according to actual situations. However, the melting point
of PET is
about 220 C, and the melting point of PBT is about 270 C. From the view of
energy
23
=
, CA 03005917 2018-05-22
= =
saving of the process temperature, the first blank polyester chips of the
present
disclosure are preferably PET, and the second blank polyester chips are PET.
Preferably, the graphene content in the graphene-containing polyester
masterbatches
is 1-20 wt%, for example 2 wt%, 4 wt%, 6 wt%, 8 wt%, 12 wt%, 15 wt%, 17 wt%,
19 wt%, etc., preferably 5-15 wt%, most preferably 6-10 wt%.
Preferably, the melting temperature of the screw extrusion of step (A-2) is
230-270 C, for example 235 C, 240 C, 244 C, 249 C, 253 C, 258 C, 262 C, 267 C,
etc., preferably 240-260 C.
Preferably, the moisture content of the graphene-containing polyester
masterbatches
is 600 ppm or less, for example 50 ppm, 80 ppm, 130 ppm, 180 ppm, 230 ppm, 280
ppm, 350 ppm, 390 ppm, 420 ppm, 450 ppm, 480 ppm, etc., preferably 300 ppm or
less.
Preferably, the mass ratio of the graphene-containing polyester masterbatches
to the
blank polyester chips in step (A-3) is 1:(5-30), for example 1:6, 1:7, 1:9,
1:13, 1:16,
1:22, 1:26, 1:29, etc., preferably 1:(15-20).
Preferably, the intrinsic viscosity of the raw materials for melt spinning in
step (A-4)
is 0.60 dL/g or more, for example 0.62 dL/g, 0.66 dL/g, 0.69 dL/g, 0.72 dL/g,
0.75
dL/g, 0.78 dL/g, 0.80d L/g, and 0.85 dL/g, etc., preferably 0.65 dL/g or more.
The addition of graphene of the present disclosure will reduce the viscosity
of the
chips, however the spinning step cannot be performed if the viscosity is too
low.
As a preferred technical solution, mixing the graphene-containing polyester
masterbatches with the blank polyester chips in step (A-3) of the present
disclosure
includes the following steps:
(A-3a) uniformly mixing the graphene-containing polyester masterbatches with a
24
,
' ' CA 03005917 2018-05-22
part of the blank polyester chips;
(A-3b) continuously adding the remaining blank polyester chips to the mixture
of
step (A-3a) to mix uniformly.
The graphene-containing polyester masterbatches is diluted and dispersed in
two
steps with polyester chips, so that the concentration of the graphene
particles reaches
a predetermined requirement, and the graphene can be dispersed more uniformly,
the
modified hollow cotton obtained can exhibit more excellent thermal insulation,
low-temperature far-infrared and bacteria resistance properties.
Preferably, in step (A-3a), the mass ratio of the part of the blank polyester
chips to
the integral blank polyester chip added in step (A-3a) is 1:(2-10), for
example 1:3,
1:4, 1:5, 1:6, 1:7, 1:8, 1:9, etc., preferably 1:(4-8).
The integral blank polyester chip added in step (A-3a) refers to the sum of
the
masses of the part of the blank polyester chips and the remaining blank
polyester
chips.
Further preferably, step (A-3') is set between step (A-3) and step (A-4):
screw
extruding the materials uniformly mixed in step (A-3) again;
Preferably, the melting temperature of the screw extrusion is 230-270 C, for
example 235 C, 240 C, 244 C, 249 C, 253 C, 258 C, 262 C, 267 C, etc.,
preferably 240-260 C.
After the conventional polyester is subjected to the screw extrusion twice,
the
cleavage of the polyester polymer molecules will be caused, which reduces the
length of its molecular chain and the strength of the polyester, eventually
resulting in
insufficient wiredrawing length during the process of preparing the hollow
cotton; by
means of adding graphene particles to the polyester substrate in the present
disclosure, the melting temperature of the screw extrusion can be improved,
even if
CA 03005917 2018-05-22
g
the screw extrusion is performed twice, the length of the molecular chain of
the
obtained polyester fiber has less change, enabling the preparation of the
hollow
cotton fiber.
As an optional technical solution, a method for preparing the hollow cotton
according to the present disclosure includes the following steps:
(A-1) smashing PET blank chips to obtain PET blank chip particles;
(A-2) mixing graphene with PET blank chip particles, then screw extruding at a
melting temperature of 230-270 C, drying the extruded product to a moisture
content
of 600 ppm or less to obtain graphene-containing PET polyester masterbatches;
(A-3) mixing the graphene-containing PET polyester masterbatches with PET
polyester chips to obtain materials with intrinsic viscosity of 0.60 dL/g or
more;
(A-4) melt spinning the resulting materials, and then opening to obtain the
modified
hollow cotton.
The second object of the present disclosure is to provide a method for
preparing a
modified polyamide fiber as described in the first object, which includes the
following steps:
(B-1) smashing blank polyamide chips to obtain blank polyamide chip particles;
(B-2) mixing graphene with blank polyamide chip particles, screw extruding,
and
drying to obtain graphene-containing polyamide masterbatches;
(B-3) uniformly mixing the graphene-containing polyamide masterbatches with
the
blank polyamide chips;
(B-4) melt spinning the resulting materials to obtain the modified polyamide
fiber.
26
,
,
. CA 03005917 2018-05-22
,
The present disclosure adopts a physical method to disperse solid graphene
into the
polyamide substrate, thereby obtaining a modified polyamide fiber containing
uniformly dispersed graphene. Specifically, according to the present
disclosure, the
hollow cotton containing uniformly dispersed graphene is obtained by firstly
chopping the blank polyamide chips to increase the rough surface, so as to
increase
the specific surface area and frictional force of the graphene attached
thereto, which
will improve the dispersibility of the graphene; then dispersing the solid
graphene in
the blank polyamide chip particles, screw extruding the mixture to obtain
graphene
composite polyamide masterbatches, in which polyamide masterbatches serve as
carrier of graphene for primary dispersion of graphene; then, physically
mixing the
graphene-loaded polyamide masterbatches with the blank polyamide chips
according
to the formulation amount to obtain the materials to be spun, in which the
graphene
is uniformly dispersed; finally, melt spinning according to the conventional
spinning
preparation process of polyamide fiber to obtain the modified polyamide fiber
uniformly doped with graphene. The method of the present disclosure solves the
technical problem of uneven dispersion of graphene in the related
technologies, and
obtains a modified polyamide fiber showing excellent thermal insulation
property,
air permeability, low-temperature far-infrared and bacteria resistance
properties.
In the present disclosure, primary dispersion is achieved by dispersing the
graphene
particles which are easy to agglomerate in the blank polyamide chip particles,
and
then mixing the obtained masterbatches with the blank polyamide chips again to
obtain the uniformly dispersed materials to be spun.
The blank polyamide chips of the present disclosure refers to the polyamide
chips
without adding functional graphene particles.
Uniform distribution refers to: the probabilities of the measured values
appearing in
a certain range are the same. For this application, the uniform dispersion
means that
the content of graphene in the modified polyamide fiber is less different for
any
cubic centimeter ranges.
27
I
. . 1 CA 03005917 2018-05-22
preferably, the particle size of the blank polyamide chip particles is 3 mm or
less, for
example 0.1 mm, 0.5 mm, 0.9 mm, 1.3 mm, 1.8 mm, 2.2 mm, 2.5 mm, 2.8 mm, etc.
Preferably, the blank polyamide chips of step (1) and step (3) are each
independently
any one of PA-6, PA-66, PA-610, PA-1010, and MCPA.
The selection of the blank polyamide chips according to step (B-1) and step (B-
3) of
the present disclosure is not specifically limited, and they can be selected
by a person
skilled in the art according to the actual situations.
Preferably, the graphene content in the graphene-containing polyamide
masterbatches is 3-10 wt%, for example 4 wt%, 6 wt%, 8 wt%, 9 wt%, preferably
5-8 wt%.
Preferably, the melting temperature of the screw extrusion of step (B-2) is
210-240 C, for example 215 C, 217 C, 221 C, 225 C, 228 C, 233 C, 236 C, 238 C,
etc., preferably 220-230 C.
The addition of graphene will affect the melting temperature of the extruded
plastics
of polyamide. Too high melting temperature will cause the polyamide molecular
chain to break, affecting the strength of polyamide fiber, instead too low
melting
temperature will not achieve the base of polyamide fiber.
Preferably, the moisture content of the graphene-containing polyamide
masterbatches is 600 ppm or less, for example 50 ppm, 80 ppm, 130 ppm, 180
ppm,
230 ppm, 280 ppm, 350 ppm, 390 ppm, 420 ppm, 450 ppm, 480 ppm, etc.,
preferably 300 ppm or less.
Preferably, the mass ratio of the graphene-containing polyamide masterbatches
to the
blank polyamide chips in step (B-3) is 1:(5-30), for example 1:6, 1:7, 1:9,
1:13, 1:16,
1:22, 1:26, 1:29, etc., preferably 1:(15-20).
28
=
= CA 03005917 2018-05-22
Preferably, the intrinsic viscosity of the raw materials for melt spinning in
step (B-4)
is 3 dL/g or less, preferably 2.7 dL/g or less.
The addition of graphene of the present disclosure will increase the viscosity
of the
polyamide chips, however the spinning step will be affected if the viscosity
is too
high.
As a preferred technical solution, mixing the graphene-containing polyamide
masterbatches with the blank polyamide chips in step (B-3) of the present
disclosure
includes the following steps:
(B-3a) uniformly mixing the graphene-containing polyamide masterbatches with a
part of the blank polyamide chips;
(B-3b) continuously adding the remaining blank polyamide chips to the mixture
of
step (B-3a) to mix uniformly.
The graphene-containing polyamide masterbatches is diluted and dispersed in
two
steps with polyamide chips, so that the concentration of the graphene
particles
reaches a predetermined requirement, and the graphene can be dispersed more
uniformly, no harsh process condition for melt spinning is needed, and the
modified
polyamide fiber obtained can maintain good strength while exhibiting excellent
low-temperature far-infrared and bacteria resistance properties.
Preferably, in step (B-3a), the mass ratio of the part of the blank polyamide
chips to
the integral blank polyamide chip added in step (B-3a) is 1:(2-10), for
example 1:3,
1:4, 1:5, 1:6, 1:7, 1:8, 1:9, etc., preferably 1:(4-8).
The integral blank polyamide chip added in step (B-3a) refers to the sum of
the
masses of the part of the blank polyamide chips and the remaining blank
polyamide
chips.
29
=
=
= CA 03005917 2018-05-22
=
Further preferably, step (B-3') is set between step (B-3) and step (B-4):
screw
extruding the materials uniformly mixed in step (B-3) again;
Preferably, the melting temperature of the screw extrusion is 210-240 C, for
example 215 C, 217 C, 219 C, 224 C, 227 C, 228 C, etc., preferably 240-260 C.
After the conventional polyamide is subjected to the screw extrusion twice,
the
cleavage of the polyamide polymer molecules will be caused, which reduces the
length of its molecular chain and the strength of the polyamide, eventually
resulting
in insufficient wiredrawing length during the process of preparing the
modified
polyamide fiber; by means of adding graphene particles to the polyamide
substrate in
the present disclosure, the melting temperature of the screw extrusion can be
improved, even if the screw extrusion is performed twice, the length of the
molecular
chain of the obtained polyamide fiber has less change, enabling the
preparation of
the modified polyamide fiber.
As an optional technical solution, a method for preparing the modified
polyamide
fiber according to the present disclosure includes the following steps:
(B-1) smashing blank polyamide chips to obtain blank polyamide chip particles;
(B-2) mixing graphene with blank polyamide chip particles, then screw
extruding at
a melting temperature of 210-240 C, drying the extruded product to a moisture
content of 600 ppm or less to obtain graphene-containing polyamide
masterbatches;
(B-3) mixing the graphene-containing polyamide masterbatches with blank
polyamide chips to obtain materials with intrinsic viscosity of 3 dL/g or
less;
(B-4) melt spinning the resulting materials, then opening to obtain the
modified
polyamide fiber.
In the method for producing the modified fiber according to the present
disclosure,
= = CA 03005917 2018-05-22
the spinning (step (A-4), step (V-4), step (A'-3) or step (B'-3)) of step (A'-
3), step
(B'-3), step (A-4), and step (B-4) is well known in the art.
Melt spinning method is to obtain hollow fiber through hollow spinneret plate,
which is economical and reasonable, the relevant technologies are mature, and
process conditions can be controlled.
Melt spinning is carried out by inserting a microporous tube into a hollow
spinneret
plate and filling the cavity of the fiber with nitrogen or air to obtain an
inflated
hollow fiber with high hollowness, avoiding the reduction of the hollowness
due to
flattening of the fiber by mechanical actions during the production process.
In
addition, the thermal conductivity of the fiber is worse than that of air,
which greatly
improves the warmth retention property. The control of the gas flow is a well-
known
method in the art. Those skilled in the art can also change the shape of the
spinneret
orifice to produce hollow fibers with various profiled cross-sections such as
triangle
and quincunx, etc., to increase the specific surface area of the fibers, or to
obtain
porous hollow fibers with 3 to 7 holes through special spinneret plates, but
the
hollowness of which may not be high, being only within 30%. Hollow fiber or
three-dimensional crimped hollow fiber can also be obtained by those skilled
in the
art through direct melt spinning with designing the shape of the spinneret
plate and
properly adjusting the spinning process (asymmetric cooling with circular
blowing
and post-spinning stretch controlling technology).
As is well known to those skilled in the art, a desired hollowness can be
achieved by
adjusting the process conditions of melt spinning. Typical but not limiting
process
conditions can be:
(I) design of the spinneret plate for melt spinning of the hollow fiber
The design of the spinneret plate includes both its shape and structural
dimensions.
The former is used for hollow fibers with profiled cross-sections, and the
design of
31
,
= . CA 03005917 2018-05-22
which is related to the production requirements, and the commonly used hole
shapes
include polygonal, c-shaped, circular arc, multi-point shapes, etc. The design
of the
structural dimensions of the spinneret plate can include feature size data
such as the
slit length of the spinneret orifices, the distance between the tips of two
slits, the
equivalent diameters, the cross-sectional area, the aspect ratio, and the
like;
A typical, but non limiting example of preparation of warmth retention
three-dimensional crimped hollow fibers by melt-spinning is the use of a
circular arc
slit spinneret plate, by which fibers with finer outer diameter and suitable
hollowness
can be easily spun. At present, the circular arc slit spinneret plates with
good effect
mainly include C-shaped and triangle-shaped spinneret plates and porous hollow
fiber spinneret plates with circular arc combinations, etc, which are used to
spin
hollow fibers of four-hole, seven-hole and even dozen-hole. After the melt is
extruded out of the circular arc slit of the spinneret plate, the circular arc-
shaped melt
expands and and the ends of which binds to form a hollow cavity, which is
thinned
and solidified to form a hollow fiber.
As is well known in the art, the size of the gap in the circular arc slit of
the spinneret
plate may affect the formation of the hollow cavity: when the gap is too
large, the
hollow of the fibers cannot be closed and only the opening fibers can be spun;
but
when the gap is too small, the melt will quickly expand and bond after extrude
from
the spinneret orifice, so that the hollow cavity cannot be formed. Moreover,
from the
viewpoint of mechanical strength, the smaller the gap of the spinneret plate
is, the
lower the strength is, and the spinneret plate is easily damaged. Therefore,
for
materials with different properties, there are different suitable sizes of
gaps in the
spinneret plates. Typical but non limiting example is the expanding ratio of
the die
orifice for the extrusion of the melt materials can guide the design of the
size of the
gaps in the spinneret plates, and the width ratio at the center of the gaps is
slightly
less than the expansion ratio of the die orifice for the melt materials.
For the spinneret hole, if the slit width is large, the extrusion volume of a
single hole
32
CA 03005917 2018-05-22
is large, the cross-sectional area of the spun fiber is large, and the
hollowness of the
fiber is small; the slit width is small, the extrusion volume of a single hole
is small,
and the hollowness of the spun fiber is large. However, if the slit is too
small, the
wall of the spun fiber is too thin, the hollow regularity is low, and the
hollow is easy
to deform. For the C-shaped spinneret plate, the width at the center of the
gap is
equal to 1.0-fold of the slit width; for the triangle-shaped spinneret plate,
the width at
the center of the gap is equal to 0.8-fold of the slit width. A person skilled
in the art
has ability to set the specific sizes of the gap and slit of the spinneret
plate according
to the product requirements and the different properties of the spinning
materials.
In addition to the C-shaped and triangle-shaped spinneret plates for melt
spinning of
the hollow fiber films, there may also exist double circular and double
circular
sleeved spinneret plates. The hollow fibers spun by the latter two spinneret
plates
have uniform inner and outer diameters and good concentricity. Due to the
support
of the gap materials in the c-shaped and the triangle-shaped spinneret plates,
they
can be easily used to shape a plurality of single holes simultaneously on one
spinneret plate for spinning filament beam with large production. However,
since the
double circular and double circular sleeved spinneret plates are composed of a
plurality of components, it is difficult to make multi-hole spinneret plates,
and most
of them are used only for spinning single hollow fiber films.
(2) Asymmetric cooling with circular blowing
As well known to those skilled in the art, factors affecting the hollowness of
the
melt-spun hollow fibers include factors such as spinning temperature, and
cooling
and shaping conditions, etc. in addition to size of spinneret plate; if the
spinning
temperature is high, the melt viscosity is small, and the expansion phenomenon
of
melt after exiting the spinneret hole is greatly reduced, the resistance to
melt
deformation decreases, and the surface tension also decreases, which causing
the
melt trickle to produce surface shrink, so that the cavity portion becomes
smaller,
and the spun hollowness decreases.
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Cooling and shaping conditions include conditions such as wind speed, wind
temperature, and blowing distance, etc., which have a great influence on the
physical
parameters such as rheological properties of the melt trickle in the spinning
path, for
example the elongational flow viscosity and tensile stress, etc., and directly
determine the hollowness.
Typically, as the wind speed increases, the cooling conditions intensify, the
solidifying rate of the melt trickle increases, so that the cavities in the
hollow fibers
formed on the spinning path are less likely to shrink and quickly solidify,
which is
favorable to the formation of cavities of hollow fibers, so that the fiber has
a high
hollowness, but if the wind speed is too high, it will cause the silk sliver
to shake and
produce turbulence, thereby decreasing the temperature of the plate surface of
the
spinneret plate, so that the silk yarn cannot be smoothly drawn, the hardhead
filament and doubling will be easily produced, causing broken end. As the wind
temperature decreases, the cooling and shaping conditions are strengthened,
increasing the solidification rate of the melt trickle, and the hollowness of
the spun
fiber is high. However, if the air temperature is too low, the plate surface
of the
spinneret plate is easy to be blown cold, so that the spinning becomes
difficult. For
double circular sleeved spinneret plates, the size of the gas flow passing
through the
sleeve may also affect the hollowness of the fibers. A person skilled in the
art has
ability to prepare a hollow fiber film with suitable hollowness by selecting
the ratio
of the gas supply amount to the pumping amount of the spinning slurry.
A person skilled in the art can reduce the formation of three-dimensional
crimps and
prevent deterioration of the post-spinning tensile properties of the hollow
fibers
obtained by direct melt spinning through controlling the asymmetric cooling
with
circular blowing. The asymmetric cooling with circular blowing process
includes
four aspects of blowing speed, temperature and humidity, as well as
uniformity.
Increasing the wind speed can enhance the asymmetrical structure of the
fiber's
cross-section to obtain as-spun fibers with potentially better crimp. However,
if the
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wind speed is too high, causing the silk sliver to oscillate, so that the silk
yarn cannot
be smoothly drawn, the pre-orientation degree of the precursor fibers may be
large,
and the tensile properties may deteriorate, etc. Therefore, a person skilled
in the art
can select an appropriate wind speed to balance the potential crimp and the
tensile
properties of the precursor fibers; although reducing the circular blowing
wind
temperature makes the cooling conditions intensify, the pre-orientation of the
precursor fibers increases at the same time, and the tensile properties
decrease, thus
it is also necessary for a person skilled in the art to select a suitable wind
temperature;
and the circular blowing wind can also have a certain humidity to reduce the
electrostatic phenomenon and turbulence of silk sliver in the spinning
process, and
control the cooling conditions; at the same time, the uniformity of the
circular
blowing wind is increased to ensure stable spinning and post-spinning tensile
properties.
(3) Post-spinning stretch
The purpose of stretching the three-dimensional crimped hollow fibers is not
to
improve the mechanical properties of the fibers, but to embody the stress
difference
and potential crimp inside the as-spun fibers. It is necessary to not only
pull apart the
stress difference on the cross-section of each single fiber during the
stretching as
much as possible, but also keep such differences between single fibers at the
same
level, therefore one-stretch process is generally used for hollow fibers.
Stretching method, stretching temperature and stretching ratio are technical
parameters in post-spinning stretch, and those skilled in the art can select
according
to their own professional knowledges. Typical, but without limitation, there
are
steam stretching and water bath stretching according to the stretching medium:
the
water bath stretching takes the heated oil and water as medium, and the fibers
produce a secondary orientation during stretching, resulting in a decrease in
the
intrinsic structural difference of the fibers, and reduction in the crimp and
fluffy
properties; whereas the steam stretching uses saturated steam as the medium,
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therefore it is adiabatic stretching, and the orientation is completed at one
time.
Comparatively speaking, the crystal structure of the fibers after steam
stretching is
more pronounced and stable. Both the stretching ratio and the temperature must
be
chosen by taking into consideration of both the tensile properties of the as-
spun
fibers and the release of the crimp.
(4) Control technology of hollowness
The hollow control of the hollowness runs through the entire melt spinning
process.
There is a control of the hollowness from the size of the spinneret orifice to
the
post-spinning stretch process. The typical but non-limiting slit width of the
spinneret
orifice and the distance between the tips of the two slits are suitable
preconditions
for the hollowness of the spun circular hollow fibers; and the spinning
temperature
and the cooling and shaping conditions are the main process factors for
controlling
the hollowness. Low spinning temperature, large melt viscosity, and large melt
deformation resistance and the surface tension are beneficial to the formation
of
hollow, but too low of these will cause hard filaments, etc.; and as the
stretching
ratio increases, the fiber walls become thinner, resulting in the increased
hollowness.
In addition, those skilled in the art can also investigate the process
conditions such as
moisture content of chips (generally dehumidified by the compressed air
through a
molecular sieve drying device), spinning temperature and speed, relaxation
heat
setting process, and oiling agent formulation and oiling mode of the
silicon-containing products, etc. needed to be controlled in the conventional
spinning.
As the melt spinning process is well known in the art, those skilled in the
art can
consult the background technology according to their own professional
knowledges
to obtain specific melt spinning process conditions. Typical but non-limiting
melt
spinning process conditions can be:
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CA 03005917 2018-05-22
Spinning conditions Index parameters
Product specifications 1.2D x 25 mm
Spinning speed 1200 m/min
Melting temperature 260 C
Screw extrusion pressure 7.0MPa
Wind speed 0.3-0.5 m/min
Cooling air Wind temperature 20-30 C
Humidity 70%
The present disclosure also provides a use of the modified hollow cotton as
described in the first object, and the modified hollow cotton is used as a
filler for a
warmth retention product;
preferably, the warmth retention product is selected from the group consisting
of
quilts, pillows, cushions, clothes, sleeping bags and tents;
preferably, the clothes are selected from the group consisting of warmth
retention
shirts, thermal underwear, down jackets, down vests and down pants.
The preparation methods of the quilts, pillows, cushions, clothes, sleeping
bags or
tents, as well as the warmth retention shirts, thermal underwear, down jackets
according to the present disclosure can be made reference to the preparation
methods
of the corresponding products of the related techinologies in the art, and no
specific
limitations are made thereto in the present disclosure, and even the processes
for
preparing the corresponding products through the unmodified hollow cotton in
the
art can be made reference to.
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The present disclosure also provides a use of the modified polyamide fiber as
described in the first object, and the modified polyamide fiber is used as any
one of
knitwears, medical supplies and outdoor products.
Preferably, the modified polyamide fiber is used as a polyamide sock, a
polyamide
gauze kerchief, a mosquito net, a polyamide lace, a stretch polyamide garment,
a
polyamide silk or an interlaced silk fabric.
Preferably, the modified polyamide fiber is used for blending with wool
products of
wool or other chemical fiber to make materials for clothing.
Preferably, the modified polyamide fiber is used as cord thread, industrial
fabrics,
cable, conveyor belt, tent, fishing net or fishing line.
A polyamide fabric is woven or blended from the modified polyamide fiber as
described in the first object.
A polyamide sock is woven or blended from the modified polyamide fiber as
described in the first object.
Compared with the prior art, the present disclosure has the following
beneficial
effects:
(1) by means of a physical method, uniform dispersion of graphene in a hollow
cotton is realized in the present disclosure, the technology is simple, a
dispersing
agent is not needed, and industrial production is easy;
(2) by means of a physical method, uniform dispersion of graphene in a
polyamide
fiber is realized in the present disclosure, the technology is simple, a
dispersing
agent is not needed, and industrial production is easy; and the spinning
process of
the modified polyamide fiber of the present disclosure is the same with that
of the
existing polyamide fiber, without needing any change, and both the spinning
time
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CA 03005917 2018-05-22
and the spinning length can reach the spinning requirements of the existing
unmodified polyamide fiber;
(3) by introducing graphene into hollow cotton, and particularly introducing
biomass
graphene into the hollow cotton, the modified hollow cotton is enabled to have
a
low-temperature far infrared function, the far infrared normal emissivity
thereof is
0.85 or more; the antibacterial performance is 90% or more, and the thermal
insulation performance and the air permeability are both excellent. When the
content
of the biomass graphene is 1.4%, the thermal insulation rate is about 90%
which is
equivalent to that of white duck down with a down content of 90%, but the air
permeability is about 240 minis which is far higher than that of the duck
down.
(4) by introducing graphene into the polyamide fiber, and particularly
introducing
biomass graphene into the polyamide fiber, the modified polyamide fiber is
enabled
to have a low-temperature far infrared function, the far infrared normal
emissivity
thereof is 0.85 or more; the antibacterial performance is 90% or more.
Detail Description
The technical solutions of the present disclosure will be further described
below by
way of specific embodiments.
It will be apparent to those skilled in the art that the examples are merely
illustrations
of the present disclosure and should not be construed as specific limitations
to the
present disclosure.
Preparation Example 1 of graphene (redox graphene)
The method of Example 1 in the patent with publication number CN105217621A
was used, which specifically included the following steps:
(A) in a reactor, reacting 2 g of graphite powder with a mixed system of 3 g
of
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potassium dithionate, 3 g of phosphorus pentoxide, and 12 mL of concentrated
sulfuric acid, and stirring at 80 C in a water bath for 4 hours until a dark
blue
solution was formed, the dark blue solution was cooled, suction filtered, and
dried to
obtain pre-oxidized graphite;
(B) weighing 2 g of the graphite oxide obtained in step (A) into a three-
necked flask,
adding 150 g of concentrated sulfuric acid solution under an ice-water bath
condition,
gradually adding 25 g of potassium permanganate, and stirring for 2 hours;
(C) transferring the three-necked flask of the above step (B) to an oil bath,
raising
the temperature to 35 C, and stirring for 2 hours, then adding a mixed
solution of 30
wt % hydrogen peroxide and deionized water in an amount of 1:15 by volume with
continuous stirring; the mixture was suction filtered, and washed with 4 mL of
dilute
hydrochloric acid with 10% mass fraction and deionized water once,
respectively,
then centrifuged, and dried to obtain first oxidized graphene oxide;
(D) mixing 2 g of graphene oxide prepared in step (C) again with 50 mL of
concentrated sulfuric acid solution in a three-necked flask under an ice-water
bath
condition, then gradually adding 8 g of 1(1\4n04 thereto, followed by stirring
for 1
hour;
(E) transferring the three-necked flask of the above step (D) to an oil bath,
raising
the temperature to 40 C and stirring for 1 hour, then continuously raising the
temperature to 90 C and stirring for 1 hour, followed by adding a mixed
solution of
30 wt % hydrogen peroxide and deionized water in an amount of 1:7 by volume
with
continuous stirring, the mixture was cooled after continuous stirring for 6
hours, then
suction filtered, and washed with 4 mL of dilute hydrochloric acid with 10%
mass
fraction and deionized water twice, respectively, then centrifuged, and dried
to
obtain graphene oxide with uniform size.
Preparation Example 2 of graphene (biomass graphene)
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The method of Example 10 in the patent with publication number CN104724696A
was used, which specifically included the following steps:
Collecting straws, cutting them into small pieces after cleaned, which were
then
impregnated in an ethanol solution, the resulting solution was stirred at a
constant
speed of 100 r/min for 5 hours; then transferring the solution to a high-speed
centrifuge with the rotation speed set at 3000 r/min, and centrifuging for 20
minutes,
withdrawing smashed sample in the lower layer at the end. Under normal
pressure
and temperature, charging the smashed sample into a cell culture dish with a
diameter of 15 cm, then placing the culture dish at the air inlet, and
adjusting the
flow parameters, with the wind speed set at 6 m/s and the air volume of 1400
m3/h,
and maintaining the ventilation state for 12 hours; heating a tube furnace to
1300 C,
and introducing inert gas for protection, and maintaining for 30 minutes;
placing the
dried smashed sample into the tube furnace to heate 5 hours, graphene with
distinct
exfoliation was obtained after cooling to room temperature.
Preparation Example 3 of graphene (biomass graphene of a special source)
Preparation method of conventional cellulose, which specifically included the
following steps:
(1) after wheat straws were smashed and pretreated, cooking the treated wheat
straws
by using an organic acid solution of formic acid and acetic acid having a
total acid
concentration of 80 wt%. The mass ratio of acetic acid to formic acid in the
organic
acid solution of this Example is 1:12, and before adding the raw materials,
adding
hydrogen peroxide (H202) in an amount of 1 wt% of the wheat straw raw
materials
as a catalyst, controlling the reaction temperature at 120 C to react for 30
minutes
with a solid-liquid mass ratio of 1:10, and subjecting the resulting reaction
solution
to first solid-liquid separation;
(2) adding the solid obtained by the first solid-liquid separation to an
organic acid
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solution of formic acid and acetic acid having a total acid concentration of
75 wt%
for acid washing, wherein hydrogen peroxide (H202) in an amount of 8 wt% of
the
wheat straw raw material was added to the organic acid solution having a total
acid
concentration of 75 wt% as a catalyst and the mass ratio of acetic acid to
formic acid
was 1:12, the temperature was controlled at 90 C, washed for 1 hour, the solid-
liquid
mass ratio was 1:9, and the reaction solution was subjected to second solid-
liquid
separation;
(3) collecting the liquid obtained by the first and second solid-liquid
separations to
be evaporated at high temperature and high pressure at 120 C and 301 kPa to
dryness, condensing the obtained formic acid and acetic acid vapors back to
the
reaction kettle of step (1) as cooking liquor for the cooking in step (1);
(4) collecting the solid obtained by the second solid-liquid separation, and
washing
with water, wherein the temperature for water washing was controlled at 80 C,
and
the water washed pulp concentration was 6 wt%, then subjecting the water
washed
pulp to third solid-liquid separation;
(5) collecting the liquid obtained by the third solid-liquid separation,
subjecting it to
water and acid distillation, and recycling the resulting mixed acid solution
to the
reaction kettle of step (1) as cooking liquor for the cooking in step (1), and
recycling
the resulting water to step (5) for water washing;
(6) collecting the solid obtained by the third solid-liquid separation, and
screening to
obtain desired screened pulp cellulose.
Preparation of biomass graphene using cellulose as raw material:
(1) mixing cellulose and ferrous chloride in a mass ratio of 1: 1, stirring at
150 C
and catalyzing for 4 hours, drying to the water content of the precursor to be
10 wt%,
to obtain a precursor;
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(2) heating the precursor to 170 C at a heating rate of 3 C/min under N2
atmosphere,
and maintaining the temperature for 2 hours, then heating by temperature
programming to 400 C and maintaining the temperature for 3 hours, and then
heating to 1200 C and maintaining the temperature for 3 hours to obtain a
crude
product; wherein the heating rate of the temperature programming was 15 C/min;
(3) washing the crude product with sodium hydroxide solution having a
concentration of 10% and acid washing with hydrochloric acid having a
concentration of 4 wt% at 55 to 65 C, and then water washing to obtain a
biomass
graphene.
By way of example, specifically, the hollow cotton was prepared by using PET
as a
raw material below:
Example Al
A hollow cotton, which was prepared by the following method:
(1) smashing PET blank polyester chips to an average particle size of 1 mm, so
as to
obtain PET blank polyester chip particles;
(2) mixing 1 kg of graphene powder (graphene powder obtained in Preparation
Example 3 of graphene) and 9 kg of PET blank polyester chip particles, screw
extruding at a melting temperature of 250 C, and drying in a vacuum drying
oven to
a moisture content of less than 300 ppm to obtain graphene-containing
polyester
masterbatches;
(3) uniformly mixing 1 kg of the graphene-containing polyester masterbatches
with
1 kg of PET blank polyester chips, and then continuously adding 5 kg of PET
blank
polyester chips to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, opening
after
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b
completing post spinning to obtain a polyester hollow cotton with a graphene
content
of 1.4 wt%.
Example A2
A hollow cotton, which differed from Example Al in that:
(3) uniformly mixing 1 kg of the graphene-containing polyester masterbatches
with
1 kg of PET blank polyester chips, and then continuously adding 3 kg of PET
blank
polyester chips to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, opening
after
completing post spinning to obtain a polyester hollow cotton with a graphene
content
of 2 wt%.
Example A3
A hollow cotton, which differed from Example Al in that:
(3) uniformly mixing 1 kg of the graphene-containing polyester masterbatches
with
1 kg of PET blank polyester chips, and then continuously adding 8kg of PET
blank
polyester chips to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, opening
after
completing post spinning to obtain a polyester hollow cotton with a graphene
content
of 1 wt%.
Example A4
A hollow cotton, which differed from Example Al in that:
(3) uniformly mixing 1 kg of the graphene-containing polyester masterbatches
with
4.5kg of PET blank polyester chips, and then continuously adding 45kg of PET
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CA 03005917 2018-05-22
blank polyester chips to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, opening
after
completing post spinning to obtain a polyester hollow cotton with a graphene
content
of 0.2 wt%.
Example A5
A hollow cotton, which differed from Example Al in that:
Step (3') was performed after step (3): screw extruding the material obtained
in step
(3) at 250 C.
Example A6
A hollow cotton, which was prepared by the following method:
(1) smashing PET blank polyester chips to an average particle size of 1 mm, so
as to
obtain PET blank polyester chip particles;
(2) mixing 1 kg of graphene powder (graphene powder obtained in Preparation
Example 3 of graphene) and 4kg of PET blank polyester chip particles, screw
extruding at a melting temperature of 250 C, and drying in a vacuum drying
oven to
a moisture content of less than 300 ppm to obtain graphene-containing
polyester
masterbatches;
(3) uniformly mixing 1 kg of the graphene-containing polyester masterbatches
with
1 kg of PET blank polyester chips, and then continuously adding 4.7 kg of PET
blank polyester chips to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, opening
after
completing post spinning to obtain a polyester hollow cotton with a graphene
content
of 3 wt%.
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Example A7
A hollow cotton, which differed from Example A6 in that:
(3) uniformly mixing 1 kg of the graphene-containing polyester masterbatches
with
1 kg of PET blank polyester chips, and then continuously adding 2kg of PET
blank
polyester chips to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, opening
after
completing post spinning to obtain a polyester hollow cotton with a graphene
content
of 5 wt%.
Example A8
A hollow cotton, which differed from Example A6 in that:
(3) uniformly mixing 1 kg of the graphene-containing polyester masterbatches
with
0.5kg of PET blank polyester chips, and then continuously adding 0.5kg of PET
blank polyester chips to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, opening
after
completing post spinning to obtain a polyester hollow cotton with a graphene
content
of 10 wt%.
Example A9
A hollow cotton, which differed from Example Al in that: the smashing step of
step
(1) was not performed, and 1 kg of graphene powder (graphene powder obtained
from Preparation Example 3 of graphene) and 9 kg of PET blank polyester chips
were directly mixed in step (2).
Example Al 0
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CA 03005917 2018-05-22
A hollow cotton, which differed from Example Al in that: 1 kg of the
graphene-containing polyester masterbatches and 6 kg of PET blank polyester
chips
were directly mixed in step (3); and then step (4) was performed.
Example All
A hollow cotton, which differed from Example Al in that: the graphene powder
obtained from Preparation Example 3 of graphene was replaced with the graphene
powder obtained from Preparation Example 1 of graphene in step (2).
Example A 12
A hollow cotton, which differed from Example Al in that: the graphene powder
obtained from Preparation Example 3 of graphene was replaced with the graphene
powder obtained from Preparation Example 2 of graphene in step (2).
Comparative Example Al
Comparative Example Al differed from Example Al in that: the smashing step of
step (1) was not performed, and 1 kg of graphene powder and 9 kg of PET blank
polyester chips were directly mixed in step (2); and 1 kg of the graphene-
containing
polyester masterbatches and 6 kg of PET blank polyester chips were directly
mixed
uniformly in step (3); and then step (4) was performed.
Comparative Example A2
White duck down with a down content of 90% was used as Comparative Example
A2.
Comparative Example A3
A hollow cotton, which was prepared by the following method:
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,
(1) smashing the PET blank polyester chips to an average particle size of 1
mm, so
as to obtain the PET blank polyester chip particles;
(2) melting the material obtained in step (1), and then spinning, opening
after
completing post spinning to obtain a polyester hollow cotton.
Performance tests
The polyester hollow cottons prepared by the Examples and Comparative Examples
were tested as follows:
(1) Warmth retention rate: Test method GBT11048-2008 Textiles-Physiological
effects-Measurement of thermal and water-vapour resistance under steady-state
conditions;
(2) Air permeability: Test method GBT5453-1997 Textiles--Determination of the
permeability of fabrics to air;
(3) Far infrared normal emissivity: The far infrared normal emissivity is
tested
according to FZ/T64010-2000 Test Method by National Textiles Supervision
Testing
Center;
(4) Bacteria inhibition property: Bacteria inhibition property is tested
according to
GB/T20944.3-2008 Test Method by National Textiles Supervision Testing Center,
exemplified by Staphylococcus aureus;
The test results were shown in Table 1:
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Table 1-1 Performance Test Results of Examples Al-A9
Examples
Test items
Al A2 A3 A4 A5 A6 A7 A8 A9
Warmth retention
90.03 90.73 89.50 85.21 89.83 91.05 89.98 82.10 88.03
rate (%)
Air permeability
232.4 238.2 227.3 210.3 231.4 238.3 238.4 230.12 230.1
(mm/s)
Far infrared
normal emissivity 0.89 0.89 0.88 0.85 0.89 0.90
0.92 0.88 0.87
(%)
Bacteria inhibition
95 95 95 93 95 99 99 90 92
property (%)
Table 1-2 Performance Test Results of Examples 10-12 and Comparative Examples
Examples Comparative Examples
Test items
A10 All Al2 Al A2 A3
Warmth retention rate (%) 88.12 84.12 87.16 80.20 90.67
77.17
Air permeability (mm/s) 229.5 200.3 222.4 236.3
57.6 -- 241.1
Far infrared normal emissivity (%) 0.87 0.80 0.82 0.80 0.72
0.70
Bacteria inhibition property (%) 93 66 80 80 10
10
By way of example, specifically, modified polyamide fiber was prepared by
using
PA-6 and PA-66 as raw materials:
Example B1
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e
A modified polyamide fiber, which was prepared by the following method:
(1) smashing blank PA-6 chips to an average particle size of 1 mm, so as to
obtain
blank PA-6 chip particles;
(2) mixing 1 kg of graphene powder (graphene powder obtained in Preparation
Example 3 of graphene) and 9 kg of blank PA-6 chip particles, screw extruding
at a
melting temperature of 220 C, and drying in a vacuum drying oven to a moisture
content of less than 300 ppm to obtain graphene-containing PA-6 masterbatches;
(3) uniformly mixing 1 kg of the graphene-containing PA-6 masterbatches with 1
kg
of blank PA-6 chips, and then continuously adding 5 kg of blank PA-6 chips to
mix
uniformly;
(4) melting the material obtained in step (3), and then spinning, modified PA-
6 fiber
with a graphene content of 1.4 wt% was obtained after completing post
spinning,
which could be spun normally for 8 hours without yarn breaking.
Example B2
A modified polyamide fiber, which differed from Example B1 in that:
(3) uniformly mixing 1 kg of the graphene-containing PA-6 masterbatches with 1
kg
of blank PA-6 chips, and then continuously adding 3 kg of blank PA-6 chips to
mix
uniformly;
(4) melting the material obtained in step (3), and then spinning, modified PA-
6 fiber
with a graphene content of 2 wt% was obtained after completing post spinning,
which could be spun normally for 8 hours without yarn breaking.
Example B3
A modified polyamide fiber, which differed from Example B1 in that:
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(3) uniformly mixing 1 kg of the graphene-containing PA-6 masterbatches with 1
kg
of blank PA-6 chips, and then continuously adding 8kg of blank PA-6 chips to
mix
uniformly;
(4) melting the material obtained in step (3), and then spinning, modified PA-
6 fiber
with a graphene content of 1 wt% was obtained after completing post spinning,
which could be spun normally for 8 hours without yarn breaking.
Example B4
A modified polyamide fiber, which differed from Example B1 in that:
(3) uniformly mixing 1 kg of the graphene-containing PA-6 masterbatches with
4.5kg of blank PA-6 chips, and then continuously adding 45kg of blank PA-6
chips
to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, modified PA-
6 fiber
with a graphene content of 0.2 wt% was obtained after completing post
spinning,
which could be spun normally for 8 hours without yarn breaking.
Example B5
A modified polyamide fiber, which differed from Example B1 in that:
Step (3') was performed after step (3): screw extruding the material obtained
in step
(3) at 210 C.
Example B6
A modified polyamide fiber, which was prepared by the following method:
(1) smashing blank PA-66 chips to an average particle size of 1 mm, so as to
obtain
blank PA-66 chip particles;
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(2) mixing 1 kg of graphene powder (graphene powder obtained in Preparation
Example 3 of graphene) and 4 kg of blank PA-66 chip particles, screw extruding
at a
melting temperature of 240 C, and drying in a vacuum drying oven to a moisture
content of less than 300 ppm to obtain graphene-containing PA-66
masterbatches;
(3) uniformly mixing 1 kg of the graphene-containing PA-66 masterbatches with
1
kg of blank PA-66 chips, and then continuously adding 4.7 kg of blank PA-66
chips
to mix uniformly;
(4) melting the material obtained in step (3), and then spinning, modified PA-
66 fiber
with a graphene content of 3 wt% was obtained after completing post spinning,
which could be spun normally for 8 hours without yarn breaking.
Example B7
A modified polyamide fiber, which differed from Example B6 in that:
(3) uniformly mixing 1 kg of the graphene-containing PA-66 masterbatches with
1
kg of blank PA-66 chips, and then continuously adding 2 kg of blank PA-66
chips to
mix uniformly;
(4) melting the material obtained in step (3), and then spinning, modified PA-
66 fiber
with a graphene content of 5 wt% was obtained after completing post spinning,
which could be spun normally for 8 hours without yarn breaking.
Example B8
A modified polyamide fiber, which differed from Example B6 in that:
(3) uniformly mixing 1 kg of the graphene-containing PA-66 masterbatches with
0.5kg of blank PA-66 chips, and then continuously adding 0.5kg of blank PA-66
chips to mix uniformly;
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(4) melting the material obtained in step (3), and then spinning, modified PA-
66 fiber
with a graphene content of 10 wt% was obtained after completing post spinning,
which could be spun normally for 8 hours without yarn breaking.
Example B9
A modified polyamide fiber, which differed from Example 81 in that: the
smashing
step of step (1) was not performed, and 1 kg of graphene powder (graphene
powder
obtained from Preparation Example 3 of graphene) and 9 kg of blank PA-66 chips
were directly mixed in step (2), which could be spun normally for 8 hours
without
yarn breaking.
Example B10
A modified polyamide fiber, which differed from Example B1 in that: 1 kg of
the
graphene-containing PA-66 masterbatches and 6 kg of blank PA-66 chips were
directly mixed uniformly in step (3); and then step (4) was performed.
Example B11
A modified polyamide fiber, which differed from Example B1 in that: the
graphene
powder obtained from Preparation Example 3 of graphene was replaced with the
graphene powder obtained from Preparation Example 1 of graphene in step (2).
Example B12
A modified polyamide fiber, which differed from Example B I in that: the
graphene
powder obtained from Preparation Example 3 of graphene was replaced with the
graphene powder obtained from Preparation Example 2 of graphene in step (2).
Comparative Example B1
Comparative Example B1 differed from Example B1 in that: the smashing step of
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step (1) was not performed, and 1 kg of graphene powder and 9 kg of blank PA-6
chips were directly mixed in step (2); and 1 kg of the graphene-containing PA-
6
masterbatches and 6 kg of blank PA-6 chips were directly mixed uniformly in
step
(3); and then step (4) was performed.
Comparative Example B2
A polyamide fiber, which was prepared by the following method:
(1) smashing blank PA-6 chips to an average particle size of 1 mm, so as to
obtain
blank PA-6 chip particles;
(2) melting the material obtained in step (1), and then spinning, PA-6 fiber
was
obtained after completing post spinning.
Performance testS
The modified polyamide fibers and the polyamide fibers prepared by the
Examples
and Comparative Examples were tested as follows:
(1) Breaking strength and elongation at break: Breaking strength and
elongation at
break were tested according to the test method of GB/T 3923.1-1997
Testiles-Determination of breaking force and elongation at breaking force;
(2) Air permeability: Test method GBT5453-1997 Textiles--Determination of the
permeability of fabrics to air;
(3) Far infrared normal emissivity: The far infrared normal emissivity is
tested
according to FZ/T64010-2000 Test Method by National Textiles Supervision
Testing
Center;
(4) Bacteria inhibition property: Bacteria inhibition property is tested
according to
GB/T20944.3-2008 Test Method by National Textiles Supervision Testing Center,
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exemplified by Staphylococcus aureus;
The test results were shown in Table 2:
Table 2-1 Performance Test Results of Examples 1-9
Examples
Test items
B1 B2 B3 B4 B5 B6 B7 B8 B9
Breaking
strength 56 56 55 55 55 56 57 56 56
(N/tex)
Elongation at
60 63 56 55 60 64 65 62 58
break (%)
Air
permeability 232.4 238.2 227.3 210.3 231.4 238.3 238.4 230.12 230.1
(mm/s)
Far infrared
normal
0.89 0.89 0.88 0.85 0.89 0.90 0.92 0.88 0.87
emissivity
(%)
Bacteria
inhibition 95 95 95 93 95 99 99 90 92
property (%)
Spinning time >8h >8h >8h >8h >8h >8h >8h >8h >8h
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Table 2-2 Performance Test Results of Examples 10-12 and Comparative Examples
Comparative
Examples
Examples
Test items
B10 B11 B12 B1 B3
Breaking strength (N/tex) 55 54 55 20 64
Elongation at break (%) 60 56 62 5 65
Air permeability (mm/s) 229.5 200.3 222.4
236.3 241.1
Far infrared normal emissivity (%) 0.87 0.80 0.82
0.80 0.70
Bacteria inhibition property (%) 93 66 80 80 10
Spinning time >8h >8h >8h
Break at>8h
1 hour
Applicant has stated that although the process methods of the present
disclosure have
been described by the above Examples in the present disclosure, the present
disclosure is not limited thereto, that is to say, it is not meant that the
present
disclosure has to be implemented depending on the above process methods. It
will be
apparent to those skilled in the art that any improvements made to the present
disclosure, equivalent replacements and addition of adjuvant ingredients to
the raw
materials selected in the present disclosure, and selections of the specific
implementations, etc., all fall within the protection scope and the disclosure
scope of
the present disclosure.
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