CN108085766B - Cellulose nano fibril reinforced acrylic fiber and preparation method and application thereof - Google Patents

Cellulose nano fibril reinforced acrylic fiber and preparation method and application thereof Download PDF

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CN108085766B
CN108085766B CN201711327096.2A CN201711327096A CN108085766B CN 108085766 B CN108085766 B CN 108085766B CN 201711327096 A CN201711327096 A CN 201711327096A CN 108085766 B CN108085766 B CN 108085766B
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acrylic fiber
cellulose
solution
spinning
polyacrylonitrile
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CN108085766A (en
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李金鹏
陈克复
王斌
***
曾劲松
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South China University of Technology SCUT
Wuhan Textile University
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Wuhan Textile University
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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 the technical field of polymer forming, and discloses a cellulose nanofibril reinforced acrylic fiber, and a preparation method and application thereof. The preparation method of the cellulose nanofibril reinforced acrylic fiber comprises the following two steps: firstly, pretreating polyacrylonitrile, dissolving the pretreated polyacrylonitrile in a solvent to obtain an acrylic fiber stock solution, adding cellulose nanofibrils into the acrylic fiber stock solution, and dispersing uniformly to obtain a spinning solution. And secondly, spinning the spinning solution on a spinning machine, drawing the spinning solution according to a certain drawing ratio after coagulating bath, and finally curling and packaging. The cellulose nano fibril reinforced acrylic fiber not only has good tensile strength, but also has greatly improved dyeing property compared with the traditional acrylic fiber, can be used for manufacturing fabrics such as blankets, carpets and the like, and can also be used as outdoor fabrics such as ski coats, sails, military canvases, tents and the like.

Description

Cellulose nano fibril reinforced acrylic fiber and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer forming, and particularly relates to cellulose nanofibril reinforced acrylic fibers and a preparation method and application thereof.
Background
Nanofibers have become one-dimensional nanomaterials for extensive research and application due to their unique physicochemical properties and characteristics. Nanofibers can be further divided into cellulose nanowhiskers and cellulose nanofibrils. The cellulose nanowhiskers are generally prepared by an acid hydrolysis method, have a highly oriented structure, but have small size (the diameter is 2-20nm, the length is 100-600nm, and the length-diameter ratio is 10-100), and the preparation process needs to be treated by strong acid, so that the preparation process is complex and the cost is high. The cellulose nano-fibrils are products obtained by processing cellulose raw materials through an enzymatic hydrolysis method or a mechanical method to filamentize cellulose fibers, and have high length-diameter ratio (the diameter is 10-40nm, the length is more than 1 mu m, and the length-diameter ratio is more than 100) (Siro, I., & Plackett, D. (2010), micro-fibrous cellulose and new nanocomposite materials: areview. cellulose,17(3), 459-. Compared with the cellulose nano whisker, the preparation method of the cellulose nano fibril is simple and has lower cost, and the application in industrialization is easier to realize.
Although the synthetic wool has a certain distance in the aspects of hygroscopicity, hand feeling, down shrinkage, elasticity and the like compared with the wool, the acrylic fiber also has various advantages such as good heat retention, mildew resistance, moth resistance, fluffiness and the like, has wide application research, has the remarkable characteristics of sun resistance and chemical resistance, and is called three synthetic fibers together with the terylene and the chinlon. However, the acrylic fibers have poor dyeability and hygroscopicity, so that the wearability of the acrylic fibers is poor, the acrylic fibers are not easy to be made into high-end acrylic fibers, and most of the acrylic fibers are products with low added value. The traditional polyacrylonitrile fiber is not high in strength, poor in wear resistance and fatigue resistance, and researchers can blend acrylic fiber and cellulose fiber, but the problems that the fiber of single-dyed fabric is not uniformly mixed, hairiness is deteriorated due to scraping damage of the acrylic fiber and the like are solved, and the improvement of the acrylic quality is further restricted.
Most of the prior published acrylic fiber related patent reports focus on the functionalization of acrylic fiber, such as flame resistance (chinese patent application No. 2015101883251), pilling resistance (chinese patent application No. 2012103590942), antibacterial property (chinese patent application No. 2016104843744), ultraviolet resistance (chinese patent application No. 2015104585036), and conductivity (chinese patent application No. 2008100742254); however, there are only few patent reports on the direct reinforcement of acrylic fibers by cellulose nanofibrils. The Chinese patent application with the application number of 201610425121X discloses calcium titanate nano-fiber and acrylic pulp enhanced thermal insulation mortar and a preparation method thereof, the method adopts a calcium titanate nano-material to enhance and improve the thermal insulation and corrosion resistance of acrylic pulp to be used as a building thermal insulation material, and the application in the aspect of acrylic fiber is not disclosed. Chinese patent application No. 2013101658127 discloses a method for preparing high-strength viscose fibers, which achieves the purpose of reinforcing viscose fibers by adding nanowhiskers into viscose liquid, but the nanowhiskers used are small in size and high in industrial preparation cost, and are not beneficial to large-scale industrial application.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art and obtain acrylic fibers with high tensile strength, good moisture absorption performance, good dyeing performance and good wearability, the invention mainly aims at providing a preparation method of cellulose nanofibril reinforced acrylic fibers. The invention improves the traditional preparation process of the acrylic fiber, introduces the cellulose nano-fibril as a reinforcing phase, obtains the acrylic fiber with good tensile strength, moisture absorption performance, dyeing performance and wearability, and enlarges the application range of the cellulose nano-fibril. The cellulose nanofibril surface contains abundant hydroxyl groups, has high Young modulus and extremely high specific surface area, and makes the cellulose nanofibril surface the choice of materials for many advanced applications. On the other hand, the cellulose nano-fibrils have the characteristic that natural fibers are easy to absorb moisture and regain moisture, and can also be used for the improvement of material functionalization.
The invention also aims to provide the cellulose nano-fibril reinforced acrylic fiber.
The invention further aims to provide application of the cellulose nano-fibril reinforced acrylic fiber.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of cellulose nano fibril reinforced acrylic fiber comprises the following steps:
(1) pretreating Polyacrylonitrile (PAN) and dissolving the pretreated PAN in a dissolving solution to prepare an acrylic fiber stock solution with a certain mass fraction;
(2) adding Cellulose Nanofibrils (CNF) into the acrylic fiber stock solution to enable the CNF/PAN to reach a proper proportion, and preparing acrylic fiber spinning solution; defoaming the acrylic fiber spinning solution in vacuum;
(3) spinning the defoamed acrylic spinning solution on a spinning machine, adjusting the draft multiple after coagulating bath, washing and drying, and collecting the cellulose nanofibril reinforced acrylic fibers.
Preferably, the pretreatment in step (1) is an alkaline pretreatment, and the specific conditions are as follows: treating the mixture for 30-150 min at 60-100 ℃ in an aqueous solution with 1-20% by mass of sodium hydroxide and 75-95% by mass of ethanol.
Preferably, the dissolving solution in the step (1) can be one of dimethylformamide, dimethyl sulfoxide, sodium thiocyanate, zinc chloride and the like, and is preferably dimethylformamide;
preferably, in the step (1), the mass fraction of the PAN in the dissolved solution is 1 to 50% (i.e. the mass fraction of the acrylic fiber stock solution is 1 to 50%).
Preferably, the CNF/PAN in the step (2) is in a mass ratio of 1 (1-100);
preferably, the cellulose nanofibrils in the step (2) have a diameter of 10-100 nm, a length of more than 1 μm and an aspect ratio of more than 100. The chemical groups, specific surfaces and reactivity of the surface of the cellulose nanofibrils with different length-diameter ratios are different, so that the length and diameter of the cellulose nanofibrils influence the performances such as tensile strength, elongation at break, elastic modulus and the like.
More preferably, the cellulose nanofibrils in the step (2) have a diameter of 10 to 100nm and a length of 2 to 10 μm.
Preferably, the vacuum defoaming condition in the step (2) is that the vacuum degree is-0.1 MPa, and the defoaming time is 1-10 h.
Preferably, the coagulating bath in the step (3) is an aqueous solution of sodium sulfate, zinc sulfate and sulfuric acid; the mass concentrations of the sodium sulfate, the zinc sulfate and the sulfuric acid are respectively 1-20%, 1-20% and 1-20%.
Preferably, the drafting multiple in the step (3) is 1-20 times;
preferably, the drying condition in the step (3) is drying for 1-24 hours at 40-150 ℃.
The cellulose nano fibril reinforced acrylic fiber can be widely applied to the textile field, can be used for manufacturing fabrics such as blankets and carpets, and can also be used as outdoor fabrics such as ski coats, sails, military canvases, tents and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the preparation method of the cellulose nano-fibril reinforced acrylic fiber comprises the steps of firstly, partially hydrolyzing polyacrylonitrile under alkaline condition to ensure that cyano (-C ≡ N) and OH are reacted-Nucleophilic addition reaction occurs to finally generate carboxyl and amido. On one hand, CNF contains a large amount of-OH, and generates strong hydrogen bond effect with N atoms, carboxyl and amide groups in the modified polyacrylonitrile structure in the drying process, thereby increasing the strength of the acrylic fiber. On the other hand, by utilizing the characteristics of high crystallinity and small size of the CNF, the CNF and the PAN spinning solution are mixed and then spun, and the yarn is drafted by means of external acting force, so that the CNF is tightly arranged along the radial direction, and the aim of reinforcing the acrylic fiber is fulfilled. On the other hand, the cellulose nano-fibril keeps the characteristic that natural fiber is easy to absorb moisture and regain moisture, and can improve the moisture absorption performance of acrylic fiber to a certain extent.
Drawings
FIG. 1 is a schematic view of the preparation process of cellulose nanofibril reinforced acrylic fiber of the invention.
FIG. 2 is a figure of the cellulose nanofibril reinforced acrylic fiber prepared by the invention.
FIG. 3 is a drawing diagram of the tensile strength of acrylic fibers.
FIG. 4 is a graph showing the elongation of acrylic fibers.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The starting materials in the preparation method of the invention are all available from the market.
The preparation methods of cellulose nanofibrils used in the examples refer to the related reports (chenkun, shangsong, shanghun, li jinpeng) before we]2016. CN106367455A), cellulose nanofibrils (i.e. the micro nanofibrils described in patent CN106367455A)Vitamin) diameter and length can be controlled according to different homogenization treatment conditions. The specific method comprises the following steps: mixing a plant fiber raw material with a citric acid-sodium citrate buffer solution with a pH value of (5-8) according to a liquid ratio of 1: (25-35) g/ml, adding cellulase (model number of Novozymes company is 20-40 IU/g) in the ratio of the cellulase to the plant fiber raw material
Figure BDA0001505879610000051
D) and shaking for 18-24 hours at 40-50 ℃ to obtain a cellulose suspension, filtering and washing, and inactivating the filtrate at a high temperature of 80-90 ℃. Microfibrillating and grinding the treated cellulose under the pressure of 1000-1500 Bar to obtain micro-nano cellulose pulp with the pulp concentration of 15 wt%, and then treating for 3-10 times under the pressure of 20000-30000 Bar by using a high-pressure microjet homogenizer to obtain the cellulose nanofibril with the diameter of 10-100 nm and the length of 2-10 microns.
Comparative example
The cellulose nanofibrils of this comparative example were prepared as follows:
mixing plant fiber raw materials with a citric acid-sodium citrate buffer solution with the pH value of 6 according to the liquid ratio of 1:20 g/ml of cellulase (model number of Novozymes corporation) at a ratio of 30IU/g to the plant fiber material was added
Figure BDA0001505879610000052
D) at 40 ℃ for 24h to obtain a cellulose suspension, filtering and washing, and inactivating the filtrate at 85 ℃. Microfibrillating and grinding the treated cellulose under the pressure of 1000Bar to obtain micro-nano cellulose pulp with the pulp concentration of 5 wt%, and then treating for 10 times by using a high-pressure microjet homogenizer under the pressure of 20000Bar to obtain cellulose nanofibrils with the diameter of 5nm and the length of 1.5 mu m.
The specific preparation method of the cellulose nanofibril reinforced acrylic fiber comprises the following steps:
(1) treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 100 ℃ for 90min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in sodium thiocyanate to prepare an acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 20%.
(2) Adding Cellulose Nanofibrils (CNF) with the diameter of 5nm and the length of 1.5 mu m into the acrylic fiber stock solution to ensure that the mass ratio of the CNF to the PAN reaches 1.5:1, and stirring uniformly to prepare the acrylic fiber spinning solution. And (3) defoaming the acrylic spinning solution in vacuum under-0.1 MPa for 36 hours.
(3) Spinning the defoamed acrylic spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively consisting of 8%, 12% and 20% of sodium sulfate, zinc sulfate and sulfuric acid in mass fraction, adjusting the draft multiple to be 1 time, washing and drying, and collecting the cellulose nanofibril reinforced acrylic fibers.
The mechanical property of the prepared fiber is tested by a monofilament fiber tensile tester, the testing method is GB T14337-2008, and the experimental result shows that the tensile strength and the elongation at break of the fiber in the comparative example are 1.93 cN/Tex and 7.56% respectively.
Example 1
The preparation method of the acrylic fiber without the additive comprises the following steps:
(1) treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 85 ℃ for 30min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in dimethylformamide to prepare acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 10%. And (3) defoaming the acrylic spinning solution in vacuum for 10 hours under the pressure of-0.1 MPa.
(2) Spinning the defoamed acrylic fiber spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively consisting of 20%, 5% and 10% of sodium sulfate, zinc sulfate and sulfuric acid in mass fraction, adjusting the draft multiple to be 5 times, washing and drying, and collecting acrylic fibers.
Example 2
The preparation method of the inorganic nanometer silicon carbide whisker reinforced acrylic fiber comprises the following steps:
(1) treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 85 ℃ for 30min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in dimethylformamide to prepare acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 10%.
(2) Adding inorganic nano silicon carbide with the diameter of 20nm and the length of 800nm into the acrylic fiber stock solution to ensure that the mass ratio of the inorganic nano silicon carbide to the PAN reaches 1:100, and stirring uniformly to prepare the acrylic fiber spinning solution. And (3) defoaming the acrylic spinning solution in vacuum for 10 hours under the pressure of-0.1 MPa.
(3) Spinning the defoamed acrylic spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively comprising 10%, 20% and 1% of sodium sulfate, zinc sulfate and sulfuric acid in mass fraction, adjusting the draft multiple to be 2 times, washing and drying, and collecting the inorganic nano silicon carbide whisker reinforced acrylic fibers.
Example 3
The preparation method of the nano cellulose whisker reinforced acrylic fiber comprises the following steps:
(1) treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 85 ℃ for 30min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in dimethylformamide to prepare acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 15%.
(2) Adding nano cellulose whisker (NCC) with the diameter of 5nm and the length of 200nm into the acrylic fiber stock solution to ensure that the mass ratio of the NCC to the PAN reaches 1:100, and stirring uniformly to prepare the acrylic fiber spinning solution. And (3) defoaming the acrylic spinning solution in vacuum for 10 hours under the pressure of-0.1 MPa.
(3) Spinning the defoamed acrylic spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively comprising 10%, 20% and 1% of sodium sulfate, zinc sulfate and sulfuric acid, adjusting the draft multiple to be 20 times, washing and drying, and collecting the nano-cellulose whisker reinforced acrylic fibers.
Example 4
A preparation method of cellulose nano fibril reinforced acrylic fiber comprises the following steps:
(1) preparation of cellulose nanofibrils: mixing plant fiber raw material with citric acid-sodium citrate buffer solution with pH of 8 at a liquid ratio of 1: 40g/ml of cellulase (model number of Novozymes corporation: 35 IU/g) is added
Figure BDA0001505879610000071
D) at 40 ℃ for 18h to obtain a cellulose suspension, filtering and washing, and inactivating the filtrate at a high temperature of 80 ℃. Microfibrillating and pulping the treated cellulose under the pressure of 1000Bar to obtain micro-nano cellulose pulp with the pulp concentration of 8 wt%, and then treating for 4 times under the pressure of 25000Bar by using a high-pressure microfluidizer to obtain cellulose nanofibrils with the diameter of 10nm and the length of 5 microns.
(2) Treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 85 ℃ for 30min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in dimethylformamide to prepare acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 50%.
(3) Adding Cellulose Nanofibrils (CNF) with the diameter of 10nm and the length of 5 mu m into the acrylic fiber stock solution to ensure that the mass ratio of the CNF to the PAN reaches 1:100, and stirring uniformly to prepare the acrylic fiber spinning solution. And (3) defoaming the acrylic spinning solution in vacuum for 10 hours under the pressure of-0.1 MPa.
(4) Spinning the defoamed acrylic spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively comprising 10%, 20% and 1% of sodium sulfate, zinc sulfate and sulfuric acid in mass fraction, adjusting the draft multiple to 20 times, washing and drying, and collecting the cellulose nanofibril reinforced acrylic fibers.
Example 5
A preparation method of cellulose nano fibril reinforced acrylic fiber comprises the following steps:
(1) preparation of cellulose nanofibrils: mixing plant fiber raw materials with a citric acid-sodium citrate buffer solution with the pH value of 7 according to the liquid ratio of 1: mixing at 30g/ml, adding cellulase (Novozymes, model number: 20 IU/g) at a ratio to plant fiber materialD cellulase) Shaking at 45 deg.C for 20 hr to obtain cellulose suspension, filtering, washing, and inactivating the filtrate at 90 deg.C. Microfibrillating and grinding the treated cellulose under the pressure of 1300Bar to obtain micro-nano cellulose pulp with the pulp concentration of 1 wt%, and then treating for 3 times under the pressure of 28000Bar by using a high-pressure microfluidizer to obtain cellulose nanofibrils with the diameter of 50nm and the length of 10 microns.
(2) Treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 60 ℃ for 60min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in dimethyl sulfoxide to prepare an acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 10%.
(3) Adding Cellulose Nanofibrils (CNF) with the diameter of 50nm and the length of 10 mu m into the acrylic fiber stock solution to ensure that the mass ratio of the CNF to the PAN reaches 1:80, and stirring uniformly to prepare the acrylic fiber spinning solution. And (3) defoaming the acrylic spinning solution in vacuum for 5 hours under the pressure of-0.1 MPa.
(4) Spinning the defoamed acrylic spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively consisting of 20%, 1% and 10% of sodium sulfate, zinc sulfate and sulfuric acid in mass fraction, adjusting the draft multiple to 10 times, washing and drying, and collecting the cellulose nanofibril reinforced acrylic fibers.
Example 6
A preparation method of cellulose nano fibril reinforced acrylic fiber comprises the following steps:
(1) preparation of cellulose nanofibrils:
mixing plant fiber raw materials with a citric acid-sodium citrate buffer solution with the pH value of 7.5 according to the liquid ratio of 1: mixing at 25g/ml, adding cellulase (Novozymes, model number: 25 IU/g) at a ratio to plant fiber material
Figure BDA0001505879610000091
D) at 50 ℃ for 20h to obtain a cellulose suspension, filtering and washing, and inactivating the filtrate at a high temperature of 90 ℃. Microfibrillating and grinding the treated cellulose under the pressure of 1000Bar to obtain the micro-nano fiber with the slurry concentration of 5 wt%The cellulose slurry was then treated 5 times with a high pressure microfluidizer at a pressure of 30000Bar to give cellulose nanofibrils of 50nm diameter and 5 μm length.
(2) Treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 100 ℃ for 90min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in sodium thiocyanate to prepare acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 1%.
(3) Adding Cellulose Nanofibrils (CNF) with the diameter of 20nm and the length of 2.5 mu m into the acrylic fiber stock solution to ensure that the mass ratio of the CNF to the PAN reaches 1:50, and stirring uniformly to prepare the acrylic fiber spinning solution. And (3) defoaming the acrylic spinning solution under-0.1 MPa in vacuum for 1 h.
(4) Spinning the defoamed acrylic spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively consisting of 8%, 12% and 20% of sodium sulfate, zinc sulfate and sulfuric acid in mass fraction, adjusting the draft multiple to be 20 times, washing and drying, and collecting the cellulose nanofibril reinforced acrylic fibers.
Example 7
A preparation method of cellulose nano fibril reinforced acrylic fiber comprises the following steps:
(1) preparation of cellulose nanofibrils: mixing plant fiber raw materials with a citric acid-sodium citrate buffer solution with the pH value of 6 according to the liquid ratio of 1: 35g/ml of cellulase (model number of Novozymes corporation) at a ratio of 30IU/g to the plant fiber material was addedD) at 50 ℃ for 18h to obtain a cellulose suspension, filtering and washing, and inactivating the filtrate at a high temperature of 90 ℃. Microfibrillating and grinding the treated cellulose under the pressure of 1500Bar to obtain micro-nano cellulose pulp with the pulp concentration of 1 wt%, and then treating for 6 times under the pressure of 25000Bar by using a high-pressure microfluidizer to obtain cellulose nanofibrils with the diameter of 30nm and the length of 5 microns.
(2) Treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 85 ℃ for 150min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in dimethylformamide to prepare acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 50%.
(3) Adding Cellulose Nanofibrils (CNF) with the diameter of 30nm and the length of 5 mu m into the acrylic fiber stock solution to ensure that the mass ratio of the CNF to the PAN reaches 1:1, and stirring uniformly to prepare the acrylic fiber spinning solution. And (3) defoaming the acrylic spinning solution in vacuum for 10 hours under the pressure of-0.1 MPa.
(4) Spinning the defoamed acrylic spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively consisting of 1%, 12% and 5% of sodium sulfate, zinc sulfate and sulfuric acid in mass fraction, adjusting the draft multiple to be 1 time, washing and drying, and collecting the cellulose nanofibril reinforced acrylic fibers.
Example 8
A preparation method of cellulose nano fibril reinforced acrylic fiber comprises the following steps:
(1) preparation of cellulose nanofibrils: mixing plant fiber raw materials with a citric acid-sodium citrate buffer solution with the pH value of 8 according to the liquid ratio of 1: 35g/ml of cellulase (model number of Novozymes corporation: 35 IU/g) is added
Figure BDA0001505879610000102
D) at 40 ℃ for 24h to obtain a cellulose suspension, filtering and washing, and inactivating the filtrate at a high temperature of 80 ℃. Microfibrillating and grinding the treated cellulose under the pressure of 1000Bar to obtain micro-nano cellulose pulp with the pulp concentration of 0.5 wt%, and then treating for 10 times under the pressure of 30000Bar by using a high-pressure microjet homogenizer to obtain cellulose nanofibrils with the diameter of 10nm and the length of 2 microns.
(2) Treating Polyacrylonitrile (PAN) in aqueous solution containing 1 mass percent of sodium hydroxide and 95 mass percent of ethanol at 85 ℃ for 30min, washing with clear water to neutrality, and drying at 105 ℃ for 5 h. And dissolving the pretreated polyacrylonitrile in dimethylformamide to prepare acrylic fiber stock solution with the mass fraction of the polyacrylonitrile being 15%.
(3) Adding Cellulose Nanofibrils (CNF) with the diameter of 10nm and the length of 2 mu m into the acrylic fiber stock solution to ensure that the mass ratio of the CNF to the PAN reaches 1:20, and stirring uniformly to prepare the acrylic fiber spinning solution. And (3) defoaming the acrylic spinning solution in vacuum for 8 hours under the pressure of-0.1 MPa.
(4) Spinning the defoamed acrylic spinning solution on a spinning machine, coagulating and forming by coagulating baths respectively comprising 10%, 12% and 5% of sodium sulfate, zinc sulfate and sulfuric acid, adjusting the draft multiple to be 5 times, washing and drying, and collecting the cellulose nanofibril reinforced acrylic fibers.
The tensile strength and the elongation of the acrylic fibers prepared in examples 1 to 8 were measured by methods GB T14337 to 2008, and the test results are shown in fig. 3 and 4.
FIG. 2 is an appearance and appearance diagram of the acrylic fibers prepared in examples 1 to 5, which shows that the appearance and appearance of the acrylic fibers are not greatly changed after the cellulose nanofibers are added. As can be seen from fig. 3 and 4, both the nanowhiskers (inorganic carbon nanotubes, nanocellulose whiskers, etc.) and the cellulose nanofibrils can exert a reinforcing effect on the acrylic fibers, compared to the control tests (examples 1 to 3), but the cellulose nanofibrils have a better effect of reinforcing the mechanical properties of the acrylic fibers. When the mass ratio of the cellulose nano-fibrils to the polyacrylonitrile is 1:90, the tensile strength of the prepared acrylic fiber is obviously increased. With the increase of the concentration of the cellulose nanofibrils in the acrylic fiber, the tensile strength is increased first and then decreased, and it is possible that the excessive addition of the cellulose nanofibrils leads to uneven dispersion in the polyacrylonitrile and flocculation, and finally leads to the decrease of the strength.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A preparation method of cellulose nanofibril reinforced acrylic fiber is characterized by comprising the following steps:
(1) pretreating polyacrylonitrile, and dissolving in a dissolving solution to prepare an acrylic fiber stock solution with a certain mass fraction; the dissolving solution can be one of dimethylformamide, dimethyl sulfoxide, sodium thiocyanate and zinc chloride;
(2) adding the cellulose nano-fibrils into the acrylic fiber stock solution to enable the cellulose nano-fibrils/polyacrylonitrile to reach a proper proportion, and preparing acrylic fiber spinning solution; defoaming the acrylic fiber spinning solution in vacuum; the diameter of the cellulose nano-fibril is 10-100 nm, the length is more than 1 mu m, and the length-diameter ratio is more than 100; the mass ratio of the cellulose nano-fibril to the polyacrylonitrile is 1 (1-100);
(3) spinning the defoamed acrylic spinning solution on a spinning machine, adjusting the draft multiple after coagulating bath, washing and drying, and collecting the cellulose nanofibril reinforced acrylic fibers; the drafting multiple is 1-20 times.
2. The method for preparing cellulose nanofibril reinforced acrylic fiber according to claim 1, wherein the pretreatment in the step (1) is alkaline pretreatment, and the specific conditions are as follows: treating the mixture for 30-150 min at 60-100 ℃ in an aqueous solution with 1-20% by mass of sodium hydroxide and 75-95% by mass of ethanol;
the dissolving solution in the step (1) can be one of dimethylformamide, dimethyl sulfoxide, sodium thiocyanate and zinc chloride; in the step (1), the mass fraction of the polyacrylonitrile in the dissolving solution is 1-50%.
3. The method for preparing cellulose nanofibril reinforced acrylic fiber according to claim 1, wherein the vacuum defoaming condition in the step (2) is-0.1 MPa of vacuum degree and 1-10 h of defoaming time.
4. The method for preparing cellulose nanofibril reinforced acrylic fiber according to claim 1, wherein the coagulating bath in step (3) is an aqueous solution of sodium sulfate, zinc sulfate and sulfuric acid; the mass concentrations of the sodium sulfate, the zinc sulfate and the sulfuric acid are respectively 1-20%, 1-20% and 1-20%.
5. The method for preparing cellulose nanofibril reinforced acrylic fiber according to claim 1, wherein the drying condition in the step (3) is 40-150 ℃ for 1-24 hours.
6. A cellulose nanofibril reinforced acrylic fiber characterized in that it is produced by the method for producing a cellulose nanofibril reinforced acrylic fiber according to any one of claims 1 to 5.
7. The use of the cellulose nanofibril reinforced acrylic fiber according to claim 6 in the textile field.
8. The use according to claim 7, wherein the cellulose nanofibril reinforced acrylic fibres are used for making carpets, ski coats, sails, military canvases or tents.
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