CN109440212A - The preparation method of the highly oriented tough regenerated celulose fibre of height and the highly oriented tough regenerated celulose fibre of height - Google Patents
The preparation method of the highly oriented tough regenerated celulose fibre of height and the highly oriented tough regenerated celulose fibre of height Download PDFInfo
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- CN109440212A CN109440212A CN201811436865.7A CN201811436865A CN109440212A CN 109440212 A CN109440212 A CN 109440212A CN 201811436865 A CN201811436865 A CN 201811436865A CN 109440212 A CN109440212 A CN 109440212A
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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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
The present invention provides a kind of preparation method of highly oriented tough regenerated celulose fibre of height and the highly oriented tough regenerated celulose fibres of height, it is related to fibre technology field, the preparation method includes the following steps: that (a) regenerated cellulose solution is mixed with crosslinking agent, obtains the mixed solution of regenerated cellulose and crosslinking agent；(b) mixed solution is subjected to spinning, and is solidified by coagulating bath, obtain hygrometric state regenerated celulose fibre；(c) confinement of hygrometric state regenerated celulose fibre is dry, obtains the highly oriented tough regenerated celulose fibre of height；It is harsh to improve current regenerated celulose fibre preparation condition, solvent is expensive, and the technical issues of be easy to causeing environmental pollution, preparation method provided by the invention not only simple process, raw material is cheap, and environmentally protective, and manufactured regenerated celulose fibre has high-orientation, high intensity and high tenacity when different, and the apparent optics opposite sex is shown under polarisation, it is a kind of potential functional fibre material.
Description
Technical field
The present invention relates to fibre technology fields, more particularly, to a kind of preparation of highly oriented tough regenerated celulose fibre of height
Method and the highly oriented tough regenerated celulose fibre of height.
Background technique
The consumption of non-renewable resources caused by petroleum base polymeric material and problem of environmental pollution, so that utilizing biology
Based polyalcohol manufacture new material becomes more and more urgent.Currently, being produced using renewable resource substitution petroleum base polymeric material
Plastics and fiber are the trend of prospective material development.Cellulose has low as the most abundant renewable resource in source on the earth
Cost, superior heat-stability and it is degradable the advantages that, the extensive concern by researchers.
Regenerated celulose fibre is widely used to daily life, is related to surgical articles, weaving, at water
The industries such as reason, auto industry.But regenerated celulose fibre preparation condition is harsh at present, solvent is expensive, and be easy to cause environment
Pollution.
Therefore, those skilled in the art need to develop a kind of environmentally protective, low-cost regenerated celulose fibre preparation
Method.
Summary of the invention
One of the objects of the present invention is to provide a kind of preparation methods of highly oriented tough regenerated celulose fibre of height, to change
The technical issues of being apt to current regenerated celulose fibre preparation condition harshness, solvent valuableness, and be easy to causeing environmental pollution.
The preparation method of the highly oriented tough regenerated celulose fibre of height provided by the invention, includes the following steps:
(a) regenerated cellulose solution is mixed with crosslinking agent, obtains the mixed solution of regenerated cellulose and crosslinking agent；
(b) mixed solution of regenerated cellulose and crosslinking agent is subjected to spinning, and is solidified by coagulating bath, obtain hygrometric state again
Raw cellulose fibre；
(c) confinement of hygrometric state regenerated celulose fibre is dry, obtains the highly oriented tough regenerated celulose fibre of height.
Further, in step (a), the mass ratio of crosslinking agent and regenerated cellulose is (0.5-6): (3-7)；
Preferably, the concentration of regenerated cellulose solution is 3-7wt%.
Further, the polymer degree of regenerated cellulose is 200-2000；
Preferably, the recycled fiber sources are in cotton linter pulp, degreasing cotton pulp, straw pulp, wood pulp, bagasse pulp, seaweed
One or more of cellulose and tunicin.
Further, the crosslinking agent is selected from epoxide and/or aldehyde compound；
Preferably, the epoxide includes epoxychloropropane and epoxy chlorobutane；
Preferably, the aldehyde compound includes glutaraldehyde and butanedial.
Further, in step (b), cross-linked regenerated cellulose solution is squeezed into coagulating bath by spinning nozzle；
Preferably, the diameter of hygrometric state regenerated celulose fibre is 50-200 μm.
Further, the coagulating bath is acidic aqueous solution or ethyl alcohol；
Preferably, the solute of acidic aqueous solution in hydrochloric acid, sulfuric acid, acetic acid, phytic acid, nitric acid and benzoic acid at least one
Kind；
Preferably, the concentration of solute is 0.1-2mol/L in acidic aqueous solution.
It further, is 0.2-1MPa to the pressure that cross-linked regenerated cellulose solution applies when spinning in step (b).
Further, in step (c), dry confinement is dry under 2D tension environment.
The second object of the present invention is to provide a kind of highly oriented tough regenerated celulose fibre of height, provide according to the present invention
The preparation method of the highly oriented tough regenerated celulose fibre of height obtain.
The third object of the present invention is to provide the highly oriented tough regenerated celulose fibre of height in functional fibre material
Using.
The preparation method of the highly oriented tough regenerated celulose fibre of height provided by the invention first passes through molten to regenerated cellulose
Liquid is crosslinked, dry using spinning solidification and confinement, not only simple process, and raw material is cheap, and environmentally protective, will not be right
Environment pollutes, while manufactured regenerated celulose fibre has covalent bond and non-covalent bond crosslinking points simultaneously, to have
High-orientation, high intensity and high tenacity, and the apparent optics opposite sex is shown under polarisation, it is a kind of potential functional fibre material
Material.
The highly oriented tough regenerated celulose fibre of height provided by the invention has covalent bond and non-covalent bond crosslinking points simultaneously,
Not only there is high-orientation, high intensity and high tenacity, but also show the apparent optics opposite sex under polarisation, be a kind of potential
Functional fibre material has broad application prospects.
Detailed description of the invention
Fig. 1 is the petrographic microscope photo for the regenerated celulose fibre that embodiment 6 provides；
Fig. 2 (a) is the low range scanning electron microscope (SEM) photograph for the regenerated celulose fibre that embodiment 3 provides；
Fig. 2 (b) is the enlarged drawing of curved portion in Fig. 2 (a)；
Fig. 3 is the atomic force microscopy for the regenerated celulose fibre that embodiment 5 provides；
Fig. 4 is the regenerated celulose fibre and comparative example 2 that the regenerated celulose fibre that provides of embodiment 6, comparative example 1 provide
The XRD diagram of the regenerated celulose fibre of offer.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
It should be understood that
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation method
It can be combined with each other to form new technical solution.
In the present invention, if percentage (%) or part refer to the weight relative to composition without particularly illustrating
Percentage or parts by weight.
In the present invention, if related each component or its preferred ingredient can be combined with each other shape without particularly illustrating
The technical solution of Cheng Xin.
In the present invention, unless otherwise indicated, numberical range " a~b " indicates the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as numberical range " 6~22 " indicate herein all listed " 6~22 " it
Between whole real numbers, " 6~22 " be these combinations of values breviary indicate.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, it is each reaction or operating procedure can sequentially carry out, can also in sequence into
Row.Preferably, reaction method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
According to an aspect of the present invention, the present invention provides a kind of preparations of highly oriented tough regenerated celulose fibre of height
Method includes the following steps:
(a) regenerated cellulose solution is mixed with crosslinking agent, obtains the mixed solution of regenerated cellulose and crosslinking agent；
(b) mixed solution of regenerated cellulose and crosslinking agent is subjected to spinning, and is solidified by coagulating bath, obtain hygrometric state again
Raw cellulose fibre；
(c) confinement of hygrometric state regenerated celulose fibre is dry, obtains the highly oriented tough regenerated celulose fibre of height.
In step (a), cross-linking reaction carries out under the conditions of regenerated fiber glue temperature.
The preparation method of the highly oriented tough regenerated celulose fibre of height provided by the invention first passes through molten to regenerated cellulose
Liquid is crosslinked, dry using spinning solidification and confinement, not only simple process, and raw material is cheap, and environmentally protective, will not be right
Environment pollutes, while manufactured regenerated celulose fibre has covalent bond and non-covalent bond crosslinking points simultaneously, to have
High-orientation, high intensity and high tenacity, and the apparent optics opposite sex is shown under polarisation, it is a kind of potential functional fibre material
Material.
In the preferred embodiment of the present invention, in step (a), the mass ratio of crosslinking agent and regenerated cellulose is
(0.5-6): (3-7).By controlling the mass ratio of crosslinking agent and regenerated cellulose, to guarantee that regenerated cellulose can be crosslinked more
It adds complete.
It is typical but non-limiting, the mass ratio of crosslinking agent and regenerated cellulose for example 0.5:6,0.5:1,0.5:7,1:
4,1:5,1:6,1:7,1:8,1:3,4:3,2:1,3:7,2:7 or 4:7.
In the preferred embodiment of the present invention, the concentration of regenerated cellulose solution is 3-7wt%.Pass through control
The concentration of regenerated cellulose solution, to guarantee that regenerated cellulose cross-linking reaction carries out more complete.
It is typical but non-limiting, the concentration of regenerated cellulose solution for example 3wt%, 3.5wt%, 4wt%,
4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt% or 7wt%.
In the preferred embodiment of the present invention, the degree of polymerization of regenerated cellulose is 200-2000.It is poly- by selecting
The degree of polymerization is the regenerated cellulose of 200-2000 as raw material, and raw material is cheaper, is also easier to carry out being crosslinked with crosslinking agent anti-
It answers.It is typical but non-limiting, the degree of polymerization of regenerated cellulose for example 200,300,400,5000,800,1000,1200,
1500,1800 or 2000.
In the preferred embodiment of the present invention, regenerated cellulose derives from cotton linter pulp, degreasing cotton pulp, stalk
Slurry, one or more of wood pulp, bagasse pulp, alginate fibre element and tunicin.Select above-mentioned raw materials preparation regeneration fine
Dimension element is turned waste into wealth, and further reduced the cost of raw material.
In the preferred embodiment of the present invention, crosslinking agent is selected from epoxide and/or aldehyde compound.
Epoxide and aldehyde compound are more easier to crosslink with regenerated cellulose to react, to improve the friendship generated
Join the intensity and toughness of regenerated fiber.
In present invention further optimization embodiment, epoxide is selected from epoxychloropropane and/or epoxy neoprene
It when alkane, especially selection epoxychloropropane, is easier to crosslink with regenerated cellulose and react, be more advantageous to raising crosslinking again
The intensity and toughness of raw fibrousness.
In present invention further optimization embodiment, aldehyde compound is selected from glutaraldehyde and/or butanedial, especially
It is when selecting glutaraldehyde, to be easier to crosslink with regenerated cellulose and react, is more advantageous to and improves cross-linked regenerated cellulose
Intensity and toughness.
In the preferred embodiment of the present invention, in step (b), cross-linked regenerated cellulose solution is sprayed by spinning
Head is squeezed into coagulating bath.Cross-linked regenerated cellulose solution is solidified by squeezing into coagulating bath after spinning nozzle progress spinning
Type obtains hygrometric state regenerated celulose fibre.
In the preferred embodiment of the present invention, the diameter of hygrometric state regenerated celulose fibre is 50-200 μm.It is typical
But it is unrestricted, the diameter of hygrometric state regenerated celulose fibre for example 50,60,70,80,90,100,110,120,130,140,
150,160,170,180,190 or 200 μm.
In the preferred embodiment of the present invention, the diameter of spinning nozzle is 90-200 μm, to control the wet of generation
The diameter of state regenerated celulose fibre is 50-200 μm.It is typical but non-limiting, the diameter of spinning nozzle for example 90,100,
110,120,130,140,150,160,170,180,190 or 200 μm.
In the preferred embodiment of the present invention, coagulating bath is acidic aqueous solution or ethyl alcohol.Select acidic aqueous solution
Or ethyl alcohol, as coagulating bath, not only cost is less expensive, is also easier to hygrometric state regenerated celulose fibre forming solidification.
In the further preferred embodiment of invention, the solute of acidic aqueous solution be selected from hydrochloric acid, sulfuric acid, acetic acid, phytic acid,
One or more of nitric acid and benzoic acid.
In the preferred embodiment of the present invention, the concentration of solute is 0.1-2mol/L in acidic aqueous solution.Pass through
The concentration of solute in acidic aqueous solution is controlled, to improve the solidification rate of hygrometric state regenerated celulose fibre, improves preparation efficiency.Allusion quotation
Type but unrestricted, the typical but non-limiting concentration for example 0.1 of solute in acidic aqueous solution, 0.2,0.5,0.8,1,
1.2,1.5,1.8 or 2mol/L.
In the preferred embodiment of the present invention, in step (b), when spinning, cross-linked regenerated cellulose solution is applied
The pressure added is 0.2-1.2MPa.Preferably, regenerated fiber solution will be crosslinked using metering pump and applies pressure, so that crosslinking is bred
Fiber solution is squeezed out by spinning nozzle, is formed into solidifying in coagulating bath.It is typical but non-limiting, metering pump to crosslinking again
For example 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1, the 1.1 or 1.2MPa of pressure that raw cellulose applies.
In the preferred embodiment of the present invention, in step (c), dry confinement is dry under 2D tension environment.It is logical
It crosses after silk cylinder winding on hygrometric state regenerated celulose fibre, fixed both ends, confinement is dry, to improve the degree of orientation of fiber, thus
Obtain the highly oriented tough regenerated celulose fibre of height.
According to the second aspect of the invention, the present invention provides a kind of highly oriented tough regenerated celulose fibre of height,
It is obtained according to the preparation method of the highly oriented tough regenerated celulose fibre of height provided by the invention.
The highly oriented tough regenerated celulose fibre of height provided by the invention has covalent bond and non-covalent bond crosslinking points simultaneously,
Not only there is high-orientation, high intensity and high tenacity, but also show the apparent optics opposite sex under polarisation, be a kind of potential
Functional fibre material has broad application prospects.
According to the third aspect of the present invention, the present invention provides the above-mentioned highly oriented tough regenerated celulose fibres of height in function
Application in energy fibrous material.
Technical solution provided by the invention is further described below with reference to embodiment and comparative example.
Embodiment 1
The present embodiment provides a kind of regenerated celulose fibres, are prepared in accordance with the following steps:
(1) 1000mL concentration is added as 5wt% regeneration in 30mL epoxychloropropane (mass concentration 99%) at 0 DEG C
In cellulose (number-average molecular weight 100000) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；
(2) mixed solution is placed in wet-spinning frame barrel, applies the pressure of 0.8MPa to barrel, makes mixed solution
The spinning nozzle for being 120 μm by diameter is that the chemical crosslinking of 0.2 mol/L sulfuric acid solution coagulating bath Quick stop is anti-into concentration
It should and solidify, obtain hygrometric state regenerated celulose fibre；
(3) by after the washing of hygrometric state regenerated celulose fibre, to the fixed both ends of the hygrometric state fiber after upper silk cylinder winding, confinement is dry
It is dry to get arrive the highly oriented tough regenerated celulose fibre of height.
Embodiment 2
The present embodiment provides a kind of regenerated celulose fibres, are prepared in accordance with the following steps:
(1) 1000mL concentration is added as 6wt% regeneration in 10mL epoxychloropropane (mass concentration 99%) at 5 DEG C
In cellulose (number-average molecular weight 100000) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；
(2) mixed solution is placed in wet-spinning frame barrel, applies the pressure of 0.4MPa to barrel, makes mixed solution
The spinning nozzle for being 160 μm by diameter is that the chemical crosslinking of 0.5 mol/L plant acid solution coagulating bath Quick stop is anti-into concentration
It should and solidify, obtain hygrometric state regenerated celulose fibre；
(3) by after the washing of hygrometric state regenerated celulose fibre, to the fixed both ends of the hygrometric state fiber after upper silk cylinder winding, confinement is dry
It is dry to get arrive the highly oriented tough regenerated celulose fibre of height.
Embodiment 3
The present embodiment provides a kind of regenerated celulose fibres, are prepared in accordance with the following steps:
(1) at 5 DEG C by 20mL epoxychloropropane (mass concentration 99%) be added 1000mL concentration be 4.5wt% again
In raw cellulose (number-average molecular weight 10000) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；
(2) mixed solution is placed in wet-spinning frame barrel, applies the pressure of 0.6MPa to barrel, makes mixed solution
The spinning nozzle for being 200 μm by diameter is that the chemical crosslinking of 0.5 mol/L hydrochloric acid solution coagulating bath Quick stop is anti-into concentration
It should and solidify, obtain hygrometric state regenerated celulose fibre；
(3) by after the washing of hygrometric state regenerated celulose fibre, to the fixed both ends of the hygrometric state fiber after upper silk cylinder winding, confinement is dry
It is dry to get arrive the highly oriented tough regenerated celulose fibre of height.
Embodiment 4
The present embodiment provides a kind of regenerated celulose fibres, are prepared in accordance with the following steps:
(1) 1000mL concentration is added as 5wt% regeneration in 60mL epoxychloropropane (mass concentration 99%) at 0 DEG C
In cellulose (number-average molecular weight 100000) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；
(2) mixed solution is placed in wet-spinning frame barrel, applies the pressure of 1MPa to barrel, passes through mixed solution
Diameter is 90 μm of spinning nozzle, into concentration be 0.1mol/L nitric acid solution coagulating bath Quick stop chemical crosslink reaction simultaneously
Solidification, obtains hygrometric state regenerated celulose fibre；
(3) by after the washing of hygrometric state regenerated celulose fibre, to the fixed both ends of the hygrometric state fiber after upper silk cylinder winding, confinement is dry
It is dry to get arrive the highly oriented tough regenerated celulose fibre of height.
Embodiment 5
The present embodiment provides a kind of regenerated celulose fibres, are prepared in accordance with the following steps:
(1) 1000mL concentration is added as 6wt% regeneration in 0.5mL epoxychloropropane (mass concentration 99%) at 0 DEG C
In cellulose (number-average molecular weight is) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；
(2) mixed solution is placed in wet-spinning frame barrel, applies the pressure of 0.2MPa to barrel, makes mixed solution
The spinning nozzle for being 180 μm by diameter is 1mol/L acetum coagulating bath Quick stop chemical crosslink reaction into concentration
And solidify, obtain hygrometric state regenerated celulose fibre；
(3) by after the washing of hygrometric state regenerated celulose fibre, to the fixed both ends of the hygrometric state fiber after upper silk cylinder winding, confinement is dry
It is dry to get arrive the highly oriented tough regenerated celulose fibre of height.
Embodiment 6
The present embodiment provides a kind of regenerated celulose fibres, are prepared in accordance with the following steps:
(1) 1000mL concentration is added in 5mL epoxychloropropane (mass concentration 99%) at 0 DEG C is that 7wt% regeneration is fine
It ties up in plain (number-average molecular weight 100000) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；
(2) mixed solution is placed in wet-spinning frame barrel, applies the pressure of 1MPa to barrel, passes through mixed solution
The spinning nozzle that diameter is 120 μm is 1mol/L acetum coagulating bath Quick stop chemical crosslink reaction into concentration and consolidates
Change, obtains hygrometric state regenerated celulose fibre；
(3) by after the washing of hygrometric state regenerated celulose fibre, to the fixed both ends of the hygrometric state fiber after upper silk cylinder winding, confinement is dry
It is dry to get arrive the highly oriented tough regenerated celulose fibre of height.
Embodiment 7
The present embodiment provides a kind of regenerated celulose fibres, are prepared in accordance with the following steps:
(1) 1000mL concentration is added in 3mL epoxychloropropane (mass concentration 99%) at 0 DEG C is that 3wt% regeneration is fine
It ties up in plain (number-average molecular weight 100000) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；
(2) mixed solution is placed in wet-spinning frame barrel, applies the pressure of 0.3MPa to barrel, makes mixed solution
The spinning nozzle for being 150 μm by diameter is the chemical crosslinking of 0.2mol/L benzoic acid solution coagulating bath Quick stop into concentration
It reacts and solidifies, obtain hygrometric state regenerated celulose fibre；
(3) by after the washing of hygrometric state regenerated celulose fibre, to the fixed both ends of the hygrometric state fiber after upper silk cylinder winding, confinement is dry
It is dry to get arrive the highly oriented tough regenerated celulose fibre of height.
Embodiment 8
Present embodiments provide a kind of regenerated celulose fibre, the present embodiment and embodiment 6 the difference is that: in step
Suddenly in (1), it is 7wt% regenerated fiber that 1000mL concentration, which is added, in 0.3mL epoxychloropropane (mass concentration 99%) at 0 DEG C
In plain (number-average molecular weight 100000) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；Remaining step (2) and
(3) same as Example 6, details are not described herein.
Embodiment 9
Present embodiments provide a kind of regenerated celulose fibre, the present embodiment and embodiment 6 the difference is that: in step
Suddenly in (1), it is that 1.5wt% regeneration is fine that 1000mL concentration, which is added, in 0.1mL epoxychloropropane (mass concentration 99%) at 0 DEG C
It ties up in plain (number-average molecular weight 100000) solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；Remaining step (2) and
(3) same as Example 6, details are not described herein.
Comparative example 1
This comparative example provides a kind of regenerated celulose fibre, with the regenerated cellulose model phase used in embodiment 6
Together, preparation method includes the following steps:
It (1) is that 7wt% regenerated cellulose (number-average molecular weight 100000) solution is placed in wet spinning by 1000mL concentration
In machine barrel, apply the pressure of 1MPa to barrel, so that mixed solution is passed through 120 μm of diameter of spinning nozzle, be into concentration
1mol/L acetum coagulating bath Quick stop chemical crosslink reaction simultaneously solidifies, and obtains hygrometric state regenerated celulose fibre；
(2) by after the washing of hygrometric state regenerated celulose fibre, to the fixed both ends of the hygrometric state fiber after upper silk cylinder winding, confinement is dry
It is dry to get arrive regenerated celulose fibre.
Comparative example 2
This comparative example 2 provides a kind of regenerated celulose fibre, is prepared in accordance with the following steps: by 5mL at 0 DEG C
It is that (number-average molecular weight is 7wt% regenerated cellulose that 1000mL concentration, which is added, in epoxychloropropane (mass concentration 99%)
100000) in solution, evacuation and centrifugal degassing, obtains mixed solution after mixing evenly；
(2) mixed solution is placed in wet-spinning frame barrel, applies the pressure of 1MPa to barrel, passes through mixed solution
The spinning nozzle that diameter is 120 μm obtains hygrometric state regenerated celulose fibre after dry into solidification is regenerated in water-bath.
Test example 1
The regenerated celulose fibre that embodiment 1-9 and comparative example 1-2 are provided carries out polarized light microscope observing, as a result shows
Show, the regenerated celulose fibre that embodiment 1-9 is provided all has iris anisotropy behavior, and comparative example 1-2 is provided again
Raw cellulose fibre does not have iris anisotropy behavior, and the rainbow of the regenerated celulose fibre of embodiment 1-7 offer then
Color anisotropy behavior is substantially better than embodiment 8-9.
Fig. 1 is the petrographic microscope photo for the regenerated celulose fibre that embodiment 6 provides, from figure 1 it will be seen that implementing
The regenerated celulose fibre that example 6 provides has colored anisotropy behavior.
Test example 2
Embodiment 1-9 and comparative example the 1-2 regenerated celulose fibre provided are scanned Electronic Speculum observation, the results show that
The regenerated celulose fibre that embodiment 1-9 and comparative example 1 provide all has orientation, and the regenerated cellulose that comparative example 2 provides
Fiber does not have an orientation, and the orientation of regenerated celulose fibre that embodiment 1-7 is provided is significantly higher than embodiment 8-9 and right
Ratio 1.
Fig. 2 (a) is the low range scanning electron microscope (SEM) photograph for the regenerated celulose fibre that embodiment 3 provides；Fig. 2 (b) is Fig. 2 (a)
The enlarged drawing of middle curved portion；From Fig. 2 (a) and Fig. 2 (b) as can be seen that the regenerated celulose fibre surface that embodiment 3 provides
With high orientation.
Test example 3
The regenerated celulose fibre that embodiment 1-9 and comparative example 1-2 are provided carries out atomic force microscope observation, as a result shows
Show that regenerated celulose fibre that embodiment 1-9 and comparative example 1 provide all has orientation, and the regenerated fiber that comparative example 2 provides
Cellulose fiber do not have orientation, and embodiment 1-7 provide regenerated celulose fibre orientation be significantly higher than embodiment 8-9 and
Comparative example 1.
Fig. 3 is the atomic force microscopy for the regenerated celulose fibre that embodiment 5 provides, from figure 3, it can be seen that implementing
The regenerated celulose fibre that example 5 provides has high orientation.
Test example 4
The regenerated celulose fibre that embodiment 1-9 and comparative example 1-2 are provided carries out Mechanics Performance Testing, as a result such as table 1
It is shown, wherein each embodiment measures 4 samples, it is averaged.
1 regenerated celulose fibre mechanical performance data table of table
As can be seen from the table, the elasticity modulus for the regenerated celulose fibre that embodiment 1-9 is provided is all remarkably higher than comparison
Example 1-2, this illustrates that the preparation method of the highly oriented tough regenerated celulose fibre of height of present invention offer is first passed through to regenerated cellulose
Solution is crosslinked, and dry using spinning solidification and confinement, the intensity and toughness of manufactured regenerated celulose fibre significantly mention
It is high.
Can be seen that from the comparison of embodiment 1-7 and embodiment 8-9 by selecting concentration is regenerated cellulose, and is crosslinked
The mass ratio of agent and regenerated cellulose is (0.5-6): when (3-7), the intensity and toughness of manufactured regenerated celulose fibre are higher.
Test example 5
Regenerated celulose fibre and comparative example 2 that regenerated celulose fibre that embodiment 6 provides, comparative example 1 provide are mentioned
The regenerated celulose fibre of confession carries out XRD test, and test results are shown in figure 4.
From fig. 4, it can be seen that the regenerated celulose fibre that comparative example 2 provides has amorphous peak, this illustrates that comparative example 2 mentions
The regenerated celulose fibre of confession has covalently cross-linked point, and the regenerated celulose fibre that comparative example 1 provides has peak crystallization, this
Illustrate that the regenerated celulose fibre that comparative example 1 provides is crosslinked with non-covalent bond, and the regenerated celulose fibre that embodiment 5 provides
Not only have amorphous peak, but also have peak crystallization, this illustrate embodiment 5 provide regenerated celulose fibre simultaneously have covalent bond with
Non-covalent bond crosslinking points.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of the highly oriented tough regenerated celulose fibre of height, which comprises the steps of:
(a) regenerated cellulose solution is mixed with crosslinking agent, obtains the mixed solution of regenerated cellulose and crosslinking agent；
(b) mixed solution of regenerated cellulose and crosslinking agent is subjected to spinning, and is solidified by coagulating bath, it is fine to obtain hygrometric state regeneration
Cellulose fiber；
(c) confinement of hygrometric state regenerated celulose fibre is dry, obtains the highly oriented tough regenerated celulose fibre of height.
2. preparation method according to claim 1, which is characterized in that in step (a), the matter of crosslinking agent and regenerated cellulose
Amount is than being (0.5-6): (3-7)；
Preferably, the concentration of regenerated cellulose solution is 3-7wt%.
3. preparation method according to claim 1, which is characterized in that the degree of polymerization of regenerated cellulose is 200-2000；
Preferably, the recycled fiber sources are in cotton linter pulp, degreasing cotton pulp, straw pulp, wood pulp, bagasse pulp, alginate fibre
One or more of element and tunicin.
4. preparation method according to claim 1, which is characterized in that the crosslinking agent is selected from epoxide and/or aldehyde
Class compound；
Preferably, the epoxide includes epoxychloropropane and epoxy chlorobutane；
Preferably, the aldehyde compound includes glutaraldehyde and butanedial.
5. preparation method according to claim 1, which is characterized in that in step (b), cross-linked regenerated cellulose solution passes through
Spinning nozzle is squeezed into coagulating bath；
Preferably, the diameter of hygrometric state regenerated celulose fibre is 50-200 μm.
6. preparation method according to claim 1, which is characterized in that the coagulating bath is acidic aqueous solution or ethyl alcohol；
Preferably, the solute of acidic aqueous solution is selected from least one of hydrochloric acid, sulfuric acid, acetic acid, phytic acid, nitric acid and benzoic acid；
Preferably, the concentration of solute is 0.1-2mol/L in acidic aqueous solution.
7. preparation method according to claim 1, which is characterized in that in step (b), when spinning, to crosslinking regenerated fiber
The pressure that plain solution applies is 0.2-1MPa.
8. preparation method according to claim 1-7, which is characterized in that in step (c), confinement is dry in 2D
It is dry under tension environment.
9. a kind of highly oriented tough regenerated celulose fibre of height, which is characterized in that system according to claim 1-8
Preparation Method obtains.
10. application of the highly oriented tough regenerated celulose fibre of height according to claim 9 in functional fibre material.
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| CN110592714A (en) * | 2019-10-09 | 2019-12-20 | 福建工程学院 | Super-tough nano-assembled cellulose filament and preparation method thereof |
| CN112143041A (en) * | 2020-09-04 | 2020-12-29 | 五邑大学 | Elementary sequence structured cellulose-based nano-fluid ionic conductor material, and preparation method and application thereof |
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| CN107417934A (en) * | 2017-08-09 | 2017-12-01 | 武汉大学 | It is a kind of that there is power to cause the high-strength of optics anisotropic approach, high-ductility cellulose aquagel and preparation method thereof |
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| CN106192212A (en) * | 2016-07-03 | 2016-12-07 | 郑州轻工业学院 | A kind of preparation method of nano-cellulose based carbon fiber mesh non-woven fabrics flexible electrode |
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| CN110592714A (en) * | 2019-10-09 | 2019-12-20 | 福建工程学院 | Super-tough nano-assembled cellulose filament and preparation method thereof |
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| CN112143041A (en) * | 2020-09-04 | 2020-12-29 | 五邑大学 | Elementary sequence structured cellulose-based nano-fluid ionic conductor material, and preparation method and application thereof |
| CN112657347A (en) * | 2020-12-16 | 2021-04-16 | 杭州科百特科技有限公司 | Regenerated cellulose ultrafiltration membrane and application and preparation method thereof |
| CN112657347B (en) * | 2020-12-16 | 2022-11-29 | 杭州科百特科技有限公司 | Regenerated cellulose ultrafiltration membrane and application and preparation method thereof |
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