CN108085766A - A kind of cellulose nanometer fibril enhancing acrylic fiber and preparation method and application - Google Patents
A kind of cellulose nanometer fibril enhancing acrylic fiber and preparation method and application Download PDFInfo
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- CN108085766A CN108085766A CN201711327096.2A CN201711327096A CN108085766A CN 108085766 A CN108085766 A CN 108085766A CN 201711327096 A CN201711327096 A CN 201711327096A CN 108085766 A CN108085766 A CN 108085766A
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- nanometer fibril
- cellulose nanometer
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
Abstract
The invention belongs to polymer shaping technical fields, disclose a kind of cellulose nanometer fibril enhancing acrylic fiber and preparation method and application.The preparation method of the cellulose nanometer fibril enhancing acrylic fiber is divided into two steps：The first step is dissolved in solvent as acrylic fibers stoste after polyacrylonitrile is pre-processed, then adds in cellulose nanometer fibril in acrylic fibers stoste, spinning solution is obtained after being uniformly dispersed.Spinning solution is carried out spinning by second step on spinning-drawing machine, and drawing-off is carried out in certain drawing-off ratio after coagulating bath, and finally curling is packaged.A kind of cellulose nanometer fibril enhancing acrylic fiber not only has good tensile strength, and dyeability is greatly improved compared to traditional acrylic fiber, the fabrics such as woollen blanket and carpet can be made, are alternatively arranged as outdoor fabrics, such as skiing coat, sail, military duck, tent.
Description
Technical field
The invention belongs to polymer shaping technical fields, and in particular to a kind of cellulose nanometer fibril enhancing acrylic fiber and
Its preparation method and application.
Background technology
Nanofiber has become widely studied and application a wiener due to its unique physicochemical properties and characteristic
Rice material.Nanofiber can be divided into Cellulose nanocrystal palpus and cellulose nanometer fibril again.Cellulose nanocrystal must generally pass through
Prepared by acid-hydrolyzed method, have a height-oriented structure, but size it is smaller (a diameter of 2-20nm, length 100-600nm,
Draw ratio 10-100), preparation process needs to use strong acid treatment, and preparation process is complicated, and cost is higher.Cellulose nanometer fibril is fine
The plain raw material of dimension is handled by enzymatic isolation method or Mechanical Method, by the product of cellulose fibril, has higher draw ratio (diameter
10-40nm, length are more than 1 μm, and draw ratio is more than 100) (Siro, I. , ＆Plackett, D. (2010)
.Microfibrillated cellulose and new nanocomposite materials:a
review.Cellulose,17(3),459-494.).Compared to Cellulose nanocrystal palpus, cellulose nanometer fibril preparation method
Simple and cost is lower, it is easier to realize the application in industrialization.
Acrylic fiber is also known as polyacrylonitrile fibre, is known as the laudatory title of " synthetic wool ", although compared with wool hygroscopicity,
Feel, fulling milling type and elasticity etc. also have a certain distance, but acrylic fiber also has the advantages that numerous such as warmth retention properties, prevents
The good characteristics such as mould, mothproof, bulkiness, it is extensive on its application study, at the same time, with sun-resistant, chemical-resistant resistance
Distinguishing feature, with terylene, polyamide fibre and referred to as three it is big close it is fine.But dyeability, the hygroscopicity of acrylic fibers are bad, cause its taking
Can be poor, it is not easy to make high-end acrylic fiber, the overwhelming majority is low value-added product.The intensity of conventional polypropylene nitrile fiber is not
Height, wearability and fatigue resistance are also poor, have researcher by acrylic fiber and cellulosic fibre blend yarn, but single dye face occur
The fiber incomplete mixing of material, acrylic fiber scraping damage cause the crosspieces problems such as filoplume deterioration, further constrain acrylic fibers quality
Raising.
In terms of published acrylic fibers related patents report has focused largely on the functionalization of acrylic fiber at present, such as anti-flammability
(Chinese Patent Application No. 2015101883251), anti-pilling (Chinese Patent Application No. 2012103590942), antibiotic property
(Chinese Patent Application No. 2016104843744), ultraviolet-resistent property (Chinese Patent Application No. 2015104585036) and electric conductivity
(Chinese Patent Application No. 2008100742254) etc.；But rarely have directly enhances acrylic fibers fibre on cellulose nanometer fibril at present
The patent report of dimension.The Chinese patent application of Application No. 201610425121X discloses a kind of calcium titanate nanofiber and nitrile
Thermal insulation mortar of synthetic fibre pulp enhancing and preparation method thereof, this method are enhanced and are improved acrylic fibers pulp using calcium titanate nano material
Heat preservation and corrosion resistance are used as building thermal insulation material, are not disclosed in the application in terms of acrylic fiber.Application No.
2013101658127 Chinese patent application discloses a kind of preparation method of polynosic fibre, by viscose
The purpose that nano whisker realizes enhancing viscose rayon is added, but nano whisker size used is smaller, preparation of industrialization cost
It is larger, it is unfavorable for heavy industrialization application.
The content of the invention
To solve the disadvantage that the prior art and shortcoming, high tensile is obtained, moisture pick-up properties, dyeability and take
The good acrylic fiber of performance, primary and foremost purpose of the invention are to provide a kind of preparation of cellulose nanometer fibril enhancing acrylic fiber
Method.Present invention improves over the traditional preparation processes of acrylic fiber, introduce cellulose nanometer fibril as enhancing phase, are stretched
Intensity, the good acrylic fiber of moisture pick-up properties, dyeability and wearability expand the application range of cellulose nanometer fibril.It is fine
Abundant hydroxyl is contained on the plain nanofibrils surface of dimension, high Young's modulus and with high specific surface area, becomes many elder generations
Into the selection of application material.On the other hand, cellulose nanometer fibril has the characteristic of natural fiber moisture regain easy to moisture absorption again, can also
In terms of material functional improvement.
Another object of the present invention is to provide a kind of cellulose nanometer fibril enhancing acrylic fiber.
It is still another object of the present invention to provide the applications of above-mentioned cellulose nanometer fibril enhancing acrylic fiber.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber, includes the following steps：
(1) polyacrylonitrile (PAN) is dissolved in lysate after pretreatment, the acrylic fibers for being made into certain mass fraction are former
Liquid；
(2) cellulose nanometer fibril (CNF) is added into acrylic fibers stoste so that CNF/PAN reaches suitable ratio, matches somebody with somebody
Acrylic spinning liquid is made；By the deaeration under vacuo of acrylic spinning liquid；
(3) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, after coagulating bath, adjusts drafting multiple, washing
The acrylic fiber of cellulose nanometer fibril enhancing is collected after drying.
Preferably, pretreatment is alkalescence pretreatment described in step (1), and actual conditions is：In sodium hydroxide mass fraction
In the aqueous solution for being 75~95% for 1~20%, ethyl alcohol mass fraction, 60~100 DEG C of 30~150min of processing.
Preferably, lysate described in step (1) can be dimethylformamide, dimethyl sulfoxide (DMSO), sodium sulfocyanate and chlorine
Change one kind in zinc etc., be preferably dimethylformamide；
Preferably, mass fractions of the PAN in lysate described in step (1) is 1~50% (the i.e. quality of acrylic fibers stoste
Fraction is 1~50%).
Preferably, the CNF/PAN described in step (2) is mass ratio 1:(1~100)；
Preferably, a diameter of 10~100nm of the cellulose nanometer fibril described in step (2), length are more than 1 μm, major diameter
Than being more than 100.Cellulose nanometer fibril surface chemistry group, specific surface area and the reactivity of different draw ratios are different from,
So the length of cellulose nanometer fibril, diameter influence the performances such as tensile strength, elongation at break and elasticity modulus.
It is furthermore preferred that a diameter of 10~100nm of the cellulose nanometer fibril described in step (2), length is 2~10 μm.
Preferably, the vacuum defoamation condition described in step (2) is that vacuum degree is -0.1MPa, and inclined heated plate is 1~10h.
Preferably, the coagulating bath described in step (3) is the aqueous solution of sodium sulphate, zinc sulfate and sulfuric acid；Sodium sulphate, zinc sulfate
It is respectively 1~20%, 1~20% and 1~20% with h 2 so 4 concentration.
Preferably, the drafting multiple described in step (3) is 1~20 times；
Preferably, the drying condition described in step (3) at 40~150 DEG C dry 1~for 24 hours.
A kind of above-mentioned cellulose nanometer fibril enhancing acrylic fiber can be widely applied to field of textiles, can make woollen blanket and
The fabrics such as carpet are alternatively arranged as outdoor fabrics, such as skiing coat, sail, military duck, tent.
Compared with prior art, the present invention has the following advantages and beneficial effects：
A kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber of the present invention, first exists polyacrylonitrile
Partial hydrolysis is carried out under alkaline condition, makes cyano (- C ≡ N) and OH-Generation nucleophilic addition, ultimately generates carboxyl and amide
Base.On the one hand, in CNF containing substantial amounts of-OH, in the drying process with the N atoms in modified polyacrylonitrile structure and carboxyl,
Amide group generates the effect of strong hydrogen bond, increases the intensity of acrylic fiber.On the other hand, CNF high-crystallinities and small are utilized
The characteristics of size, by spinning after being mixed to CNF and PAN spinning solutions, by external forces drawing-off yarn, realizes CNF along footpath
To close-packed arrays, achieve the purpose that enhance acrylic fiber.It is another in another aspect, cellulose nanometer fibril remains natural fiber easily inhales
The characteristic of wet moisture regain can improve acrylic fiber moisture pick-up properties to a certain extent.
Description of the drawings
Fig. 1 is the preparation process schematic diagram that a kind of cellulose nanometer fibril of the present invention enhances acrylic fiber.
Fig. 2 is the shape appearance figure that cellulose nanometer fibril prepared by the present invention enhances acrylic fiber.
Fig. 3 is the tensile strength figure of acrylic fiber.
Fig. 4 is the elongation figure of acrylic fiber.
Specific embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Each starting material is commercially available in preparation method of the present invention.
The preparation method of the cellulose nanometer fibril used in embodiment with reference to before us relevant report (Chen Kefu,
A kind of preparation method of micro-nano cellulose [P] .2016. CN106367455A of Zeng Jingsong, Wang Bin, Li Jinpeng), cellulose is received
The diameter of rice fibril (micro-nano cellulose i.e. described in patent CN106367455A) can be according to Bu Tong equal with the control of length
Matter treatment conditions are realized.Specific method is as follows：The citric acid-sodium citrate buffering of plant fiber material and pH=(5~8) is molten
Liquid presses liquor ratio 1：(25~35) g/ml is mixed, and adds in the cellulase for 20~40IU/g with plant fiber material ratio
(Novozymes company models areThe cellulase of D), at 40~50 DEG C shake 18~for 24 hours, obtain fiber
Plain suspension, after filtration washing, filtrate is in 80~90 DEG C of high-temperature inactivations.By treated cellulose pressure for 1000~
Fibrillation defibrination under 1500 Bar obtains the micro-nano cellulose slurries that concentration of slurry is 15wt%, then with high pressure microjet
Homogenizer is handled 3~10 times under 20000~30000Bar pressure, you can a diameter of 10~100nm is made, length is 2~10 μ
The cellulose nanometer fibril of m.
Comparative example
The preparation method of the cellulose nanometer fibril of this comparative example is as follows：
The citric acid-sodium citrate buffer of plant fiber material and pH=6 are pressed into liquor ratio 1：20g/ml is mixed, and is added in
(Novozymes company models are with cellulase that plant fiber material ratio is 30IU/gThe cellulose of D
Enzyme), it is shaken at 40 DEG C for 24 hours, obtains cellulose suspension, after filtration washing, filtrate is in 85 DEG C of high-temperature inactivations.By above-mentioned processing
Cellulose afterwards is fibrillation defibrination under 1000Bar in pressure, obtains the micro-nano cellulose slurries that concentration of slurry is 5wt%,
Then handled 10 times under 20000Bar pressure with high pressure Microfluidizer, obtain a diameter of 5nm, the fibre that length is 1.5 μm
The plain nanofibrils of dimension.
Cellulose nanometer fibril enhances the comparative example of acrylic fiber, and specific preparation method is as follows：
(1) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after 100 DEG C of processing 90min with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in sulphur
In Zassol, the acrylic fibers stoste that polyacrylonitrile mass fraction is 20% is made into.
(2) by a diameter of 5nm, length is that 1.5 μm of cellulose nanometer fibril (CNF) is added into acrylic fibers stoste so that
The mass ratio of CNF and PAN reaches 1.5:1, acrylic spinning liquid is configured to after stirring evenly.Acrylic spinning liquid is true under -0.1MPa
Empty deaeration 36h.
(3) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 8%, 12% and 20% coagulating bath after coagulation forming, it is 1 times to adjust drafting multiple, is received after washing is dry
Collect the acrylic fiber of cellulose nanometer fibril enhancing.
Carry out measuring mechanical property to the fiber of preparation by monfil tensiometer, test method for GB T 14337~
2008, experimental result show in the comparative example tensile strength of fiber and elongation at break be respectively 1.93 cN/Tex and
7.56%.
Embodiment 1
The preparation method of no added acrylic fiber is as follows：
(1) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after handling 30min at 85 DEG C with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in
In dimethylformamide, the acrylic fibers stoste that polyacrylonitrile mass fraction is 10% is made into.Acrylic spinning liquid is true under -0.1MPa
Empty deaeration 10h.
(2) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 20%, 5% and 10% coagulating bath after coagulation forming, it is 5 times to adjust drafting multiple, is received after washing is dry
Collect acrylic fiber.
Embodiment 2
The acrylic fiber of inorganic nano silicon carbide whisker enhancing, its preparation method are as follows：
(1) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after handling 30min at 85 DEG C with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in
In dimethylformamide, the acrylic fibers stoste that polyacrylonitrile mass fraction is 10% is made into.
(2) a diameter of 20nm, the inorganic nano carborundum that length is 800nm are added into acrylic fibers stoste so that inorganic
The mass ratio of nanometer silicon carbide and PAN reach 1:100, acrylic spinning liquid is configured to after stirring evenly.By acrylic spinning liquid-
Vacuum defoamation 10h under 0.1MPa.
(3) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 10%, 20% and 1% coagulating bath after coagulation forming, it is 2 times to adjust drafting multiple, is received after washing is dry
Collect the acrylic fiber of inorganic nano silicon carbide whisker enhancing.
Embodiment 3
Nano-cellulose whisker reinforcement acrylic fiber, its preparation method are as follows：
(1) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after handling 30min at 85 DEG C with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in
In dimethylformamide, the acrylic fibers stoste that polyacrylonitrile mass fraction is 15% is made into.
(2) a diameter of 5nm, the nano-cellulose whisker (NCC) that length is 200nm are added into acrylic fibers stoste so that
The mass ratio of NCC and PAN reaches 1:100, acrylic spinning liquid is configured to after stirring evenly.Acrylic spinning liquid is true under -0.1MPa
Empty deaeration 10h.
(3) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 10%, 20% and 1% coagulating bath after coagulation forming, it is 20 times to adjust drafting multiple, is received after washing is dry
Collect the acrylic fiber of nanometer cellulose whiskers enhancing.
Embodiment 4
A kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber, step are as follows：
(1) preparation of cellulose nanometer fibril：The citric acid-sodium citrate of plant fiber material and pH=8 are buffered molten
Liquid presses liquor ratio 1：40g/ml is mixed, and adds in cellulase (the Novozymes companies for 35IU/g with plant fiber material ratio
ModelThe cellulase of D), 18h is shaken at 40 DEG C, obtains cellulose suspension, after filtration washing, filter
Liquid is in 80 DEG C of high-temperature inactivations.In pressure it is fibrillation defibrination under 1000Bar by treated cellulose, obtains concentration of slurry
For the micro-nano cellulose slurries of 8wt%, then handled 4 times, obtained under 25000Bar pressure with high pressure Microfluidizer
A diameter of 10nm, the cellulose nanometer fibril that length is 5 μm.
(2) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after handling 30min at 85 DEG C with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in
In dimethylformamide, the acrylic fibers stoste that polyacrylonitrile mass fraction is 50% is made into.
(3) a diameter of 10nm, the cellulose nanometer fibril (CNF) that length is 5 μm are added into acrylic fibers stoste so that
The mass ratio of CNF and PAN reaches 1:100, acrylic spinning liquid is configured to after stirring evenly.Acrylic spinning liquid is true under -0.1MPa
Empty deaeration 10h.
(4) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 10%, 20% and 1% coagulating bath after coagulation forming, it is 20 times to adjust drafting multiple, is received after washing is dry
Collect the acrylic fiber of cellulose nanometer fibril enhancing.
Embodiment 5
A kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber, step are as follows：
(1) preparation of cellulose nanometer fibril：The citric acid-sodium citrate of plant fiber material and pH=7 are buffered molten
Liquid presses liquor ratio 1：30g/ml is mixed, and adds in cellulase (the Novozymes company types for 20IU/g with plant fiber material ratio
Number it isThe cellulase of D), 20h is shaken at 45 DEG C, obtains cellulose suspension, after filtration washing, filtrate
In 90 DEG C of high-temperature inactivations.In pressure it is fibrillation defibrination under 1300Bar by treated cellulose, obtaining concentration of slurry is
Then the micro-nano cellulose slurries of 1wt% are handled 3 times with high pressure Microfluidizer under 28000Bar pressure, obtain straight
The cellulose nanometer fibril that footpath is 50nm, length is 10 μm.
(2) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after handling 60min at 60 DEG C with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in
In dimethyl sulfoxide, the acrylic fibers stoste that polyacrylonitrile mass fraction is 10% is made into.
(3) a diameter of 50nm, the cellulose nanometer fibril (CNF) that length is 10 μm are added into acrylic fibers stoste so that
The mass ratio of CNF and PAN reaches 1:80, acrylic spinning liquid is configured to after stirring evenly.By acrylic spinning liquid under -0.1MPa vacuum
Deaeration 5h.
(4) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 20%, 1% and 10% coagulating bath after coagulation forming, it is 10 times to adjust drafting multiple, is received after washing is dry
Collect the acrylic fiber of cellulose nanometer fibril enhancing.
Embodiment 6
A kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber, step are as follows：
(1) preparation of cellulose nanometer fibril：
The citric acid-sodium citrate buffer of plant fiber material and pH=7.5 are pressed into liquor ratio 1：25g/ml is mixed, and is added
Enter that (Novozymes company models are with cellulase that plant fiber material ratio is 25IU/gThe fiber of D
Plain enzyme), 20h is shaken at 50 DEG C, obtains cellulose suspension, after filtration washing, filtrate is in 90 DEG C of high-temperature inactivations.By above-mentioned place
Cellulose after reason is fibrillation defibrination under 1000Bar in pressure, obtains the micro-nano cellulose that concentration of slurry is 5wt% and starches
Then liquid is handled 5 times with high pressure Microfluidizer under 30000Bar pressure, obtain a diameter of 50nm, length is 5 μm
Cellulose nanometer fibril.
(2) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after 100 DEG C of processing 90min with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in
In sodium sulfocyanate, the acrylic fibers stoste that polyacrylonitrile mass fraction is 1% is made into.
(3) a diameter of 20nm, the cellulose nanometer fibril (CNF) that length is 2.5 μm are added into acrylic fibers stoste so that
The mass ratio of CNF and PAN reaches 1:50, acrylic spinning liquid is configured to after stirring evenly.By acrylic spinning liquid under -0.1MPa vacuum
Deaeration 1h.
(4) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 8%, 12% and 20% coagulating bath after coagulation forming, it is 20 times to adjust drafting multiple, is received after washing is dry
Collect the acrylic fiber of cellulose nanometer fibril enhancing.
Embodiment 7
A kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber, step are as follows：
(1) preparation of cellulose nanometer fibril：The citric acid-sodium citrate of plant fiber material and pH=6 are buffered molten
Liquid presses liquor ratio 1：35g/ml is mixed, and adds in cellulase (the Novozymes company types for 30IU/g with plant fiber material ratio
Number it isThe cellulase of D), 18h is shaken at 50 DEG C, obtains cellulose suspension, after filtration washing, filtrate
In 90 DEG C of high-temperature inactivations.In pressure it is fibrillation defibrination under 1500Bar by treated cellulose, obtaining concentration of slurry is
Then the micro-nano cellulose slurries of 1wt% are handled 6 times with high pressure Microfluidizer under 25000Bar pressure, obtain straight
The cellulose nanometer fibril that footpath is 30nm, length is 5 μm.
(2) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after 85 DEG C of processing 150min with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in
In dimethylformamide, the acrylic fibers stoste that polyacrylonitrile mass fraction is 50% is made into.
(3) a diameter of 30nm, the cellulose nanometer fibril (CNF) that length is 5 μm are added into acrylic fibers stoste so that
The mass ratio of CNF and PAN reaches 1:1, acrylic spinning liquid is configured to after stirring evenly.By acrylic spinning liquid under -0.1MPa vacuum
Deaeration 10h.
(4) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 1%, 12% and 5% coagulating bath after coagulation forming, it is 1 times to adjust drafting multiple, is collected after washing is dry
The acrylic fiber of cellulose nanometer fibril enhancing.
Embodiment 8
A kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber, step are as follows：
(1) preparation of cellulose nanometer fibril：The citric acid-sodium citrate of plant fiber material and pH=8 are buffered molten
Liquid presses liquor ratio 1：35g/ml is mixed, and adds in cellulase (the Novozymes company types for 35IU/g with plant fiber material ratio
Number it isThe cellulase of D), it is shaken at 40 DEG C for 24 hours, obtains cellulose suspension, after filtration washing, filtrate
In 80 DEG C of high-temperature inactivations.In pressure it is fibrillation defibrination under 1000Bar by treated cellulose, obtaining concentration of slurry is
Then the micro-nano cellulose slurries of 0.5wt% are handled 10 times under 30000Bar pressure with high pressure Microfluidizer, obtained
A diameter of 10nm, the cellulose nanometer fibril that length is 2 μm.
(2) by polyacrylonitrile (PAN) in the aqueous solution that sodium hydroxide mass fraction is 1%, ethyl alcohol mass fraction is 95%
In, it is washed after 85 DEG C of processing 30min with clear water to neutrality, 5h is dried at 105 DEG C.Pretreated polyacrylonitrile is dissolved in two
In methylformamide, the acrylic fibers stoste that polyacrylonitrile mass fraction is 15% is made into.
(3) a diameter of 10nm, the cellulose nanometer fibril (CNF) that length is 2 μm are added into acrylic fibers stoste so that
The mass ratio of CNF and PAN reaches 1:20, acrylic spinning liquid is configured to after stirring evenly.By acrylic spinning liquid under -0.1MPa vacuum
Deaeration 8h.
(4) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, the matter formed through sodium sulphate, zinc sulfate and sulfuric acid
Amount fraction be respectively 10%, 12% and 5% coagulating bath after coagulation forming, it is 5 times to adjust drafting multiple, is received after washing is dry
Collect the acrylic fiber of cellulose nanometer fibril enhancing.
The tensile strength and elongation of the acrylic fiber of Examples 1 to 8 preparation are detected, test method is GB T
14337~2008, test result is as shown in Figure 3 and Figure 4.
Fig. 2 is the exterior appearance figure of the acrylic fiber prepared in Examples 1 to 5, it can be seen that has added cellulose nanometer
Acrylic fiber exterior appearance has no too big change after fibril.By Fig. 3 and Fig. 4 as it can be seen that compared to check experiment (Examples 1 to 3),
Nano whisker (inorganic carbon nanotubes and nano-cellulose whisker etc.) and cellulose nanometer fibril can play acrylic fiber
Enhancing effect, but cellulose nanometer fibril the mechanical performance of acrylic fiber is enhanced it is better.Work as cellulose nanometer fibril
Addition mass ratio with polyacrylonitrile is 1:When 90, the tensile strength of the acrylic fiber of preparation substantially increases.With cellulose
The increase of nanofibrils concentration in acrylic fiber, tensile strength first increases and then decreases, it may be possible to cellulose nanometer be excessively added
Fibril causes in polyacrylonitrile to disperse uneven and wad a quilt with cotton and gather, and ultimately resulting in strength reduces.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber, which is characterized in that include the following steps：
(1) polyacrylonitrile is dissolved in lysate after pretreatment, is made into the acrylic fibers stoste of certain mass fraction；
(2) cellulose nanometer fibril is added into acrylic fibers stoste so that cellulose nanometer fibril/polyacrylonitrile reaches suitable
Ratio is configured to acrylic spinning liquid；By the deaeration under vacuo of acrylic spinning liquid；
(3) the acrylic spinning liquid after deaeration carries out spinning on spinning-drawing machine, after coagulating bath, adjusts drafting multiple, washs drying
The acrylic fiber of cellulose nanometer fibril enhancing is collected afterwards.
2. a kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber according to claim 1, which is characterized in that
Pretreatment is alkalescence pretreatment described in step (1), and actual conditions is：It is 1~20%, ethyl alcohol matter in sodium hydroxide mass fraction
It measures in the aqueous solution that fraction is 75~95%, 60~100 DEG C of 30~150min of processing；
Lysate described in step (1) can be one in dimethylformamide, dimethyl sulfoxide (DMSO), sodium sulfocyanate and zinc chloride
Kind；Mass fraction of the polyacrylonitrile in lysate described in step (1) is 1~50%.
3. a kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber according to claim 1, which is characterized in that
A diameter of 10~100nm of cellulose nanometer fibril described in step (2), length are more than 1 μm, and draw ratio is more than 100.
4. a kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber according to claim 1, which is characterized in that
Cellulose nanometer fibril/polyacrylonitrile described in step (2) is mass ratio 1:(1~100).
5. a kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber according to claim 1, which is characterized in that
Vacuum defoamation condition described in step (2) is that vacuum degree is -0.1MPa, and inclined heated plate is 1~10h.
6. a kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber according to claim 1, which is characterized in that
Coagulating bath described in step (3) is the aqueous solution of sodium sulphate, zinc sulfate and sulfuric acid；Sodium sulphate, zinc sulfate and h 2 so 4 concentration
Respectively 1~20%, 1~20% and 1~20%.
7. a kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber according to claim 1, which is characterized in that
Drafting multiple described in step (3) is 1~20 times；
Drying condition described in step (3) at 40~150 DEG C dry 1~for 24 hours.
8. a kind of cellulose nanometer fibril enhances acrylic fiber, which is characterized in that it is by claim 1 to 7 any one of them
A kind of preparation method of cellulose nanometer fibril enhancing acrylic fiber is made.
9. the cellulose nanometer fibril described in claim 8 enhances application of the acrylic fiber in field of textiles.
10. application according to claim 9, which is characterized in that the cellulose nanometer fibril enhancing acrylic fiber is used for
Make woollen blanket, carpet, skiing coat, sail, military duck or tent.
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| CN112080816A (en) * | 2020-08-24 | 2020-12-15 | 北京化工大学 | Carbon fiber with cellulose nanocrystal-polyacrylonitrile composite fiber as precursor and preparation method thereof |
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