CN109402779A - A kind of skin-core structure noctilucence meta-aramid fibers and its preparation method and application - Google Patents
A kind of skin-core structure noctilucence meta-aramid fibers and its preparation method and application Download PDFInfo
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- CN109402779A CN109402779A CN201811637764.6A CN201811637764A CN109402779A CN 109402779 A CN109402779 A CN 109402779A CN 201811637764 A CN201811637764 A CN 201811637764A CN 109402779 A CN109402779 A CN 109402779A
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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
- 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
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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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
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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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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- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Multicomponent Fibers (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
This application discloses a kind of skin-core structure noctilucence meta-aramid fibers and its preparation method and application, this noctilucence meta-aramid fibers can issue twilight sunset in a dark environment after having left luminous environment, preparation method includes the preparation of noctilucence agent dispersing liquid, the preparation of polymer fluid, the preparation of cortex spinning solution and sandwich layer spinning solution, the spinneret of skin-core structure fiber can be made in selection, spinning is carried out using wet spinning, using coagulating bath, washing, drying, heat treatment, curling, the processes such as cutting, light twilight sunset sustainable 10 hours or more of the noctilucence meta-aramid that this method obtains, and have fire-retardant, high breaking strength, high drawing and it is at low cost the features such as, it has very important significance for the life security guarantee of the night work personnel of special dimension.
Description
Technical field
The application belongs to textile fiber technology field, and in particular to a kind of skin-core structure noctilucence meta-aramid fibers and its system
Preparation Method and application.
Background technique
Meta-aramid, that is, poly, it its with the characteristics such as inherent flame retardant, corrosion-resistant, high temperature resistant,
It is widely used in the fields such as high-temperature smoke filtering, individual protection, thus is a kind of very important special high-performance fiber.
Have it relative to other fibers since meta-aramid fibers have inherent flame retardant characteristic in individual protection field
It has a clear superiority, thus is widely used in rescue clothes, forest extinguishing clothes and other anti-using product made of pure meta-aramid
Protector for collar domain, it plays extremely important protective effect for the life security of operating personnel in related fields.But to working at night
Etc. some special occasions, the personnel of special time service, the problem of there is insufficient light and low visibility due to local environment, though
So with products such as reflective tapes on correlation meta-aramid Protection Product, if but at high temperature or the case where no external light irradiates
Under, the reflective tape due to can not high temperature resistant or can not itself shine cause it not play a role normally.
It is looked into investigation, presently relevant document and there is no noctilucence class meta-aramid product and technology of preparing in the market.
Summary of the invention
The purpose of the application is to provide a kind of not only with resistance for the use demand in existing togs or protection
Combustion, breaking strength is high, the features such as having extended, and can play the role of the one of protection, warning and guidance in pitch-dark environment
Kind skin-core structure noctilucence meta-aramid fibers and preparation method thereof.
The another object of the application is to provide a kind of noctilucence protective garment, can play in pitch-dark environment anti-
Shield, warning and the effect guided.
The further object of the application is to provide a kind of skin-core structure noctilucence meta-aramid fibers in preparation night work
Textile garment, aviation and navigation, fire-fighting emergent, the fabric of communications and transportation or the application in rope.
To realize that above-mentioned at least one purpose, the application adopt the following technical scheme that realization:
In a first aspect, a kind of this skin-core structure noctilucence meta-aramid fibers, including cortex, the sandwich layer coated by cortex, cortex
The light-accumulating photo etching particle of unordered dispersion inorganic phase in organic phase, so that the fiber can be in dark after having left luminous environment
Twilight sunset is issued in environment.
Luminous fiber be it is a kind of can in the case where no external light itself luminous fiber, it is mainly prepared in fiber
In the process, luminescent material is made an addition in polymer in advance, luminous fiber is made through spinning.Currently, luminescent material is broadly divided into
Emissive type and light accumulation type, emissive type luminescent material mainly have using radioactive luminescent material (such as zinc sulphide) and make its use
It is restricted, can only be used in certain special dimensions.Accumulating type Noctilucent material refers in the environment for having light after extinction, in dark
Environment is due to releasing energy and luminous luminescent material.Since accumulating type luminescent material is free of radioactive substance, compare peace
Entirely, especially rare earth aluminate and silicates class light-accumulation long-afterglow Noctilucent material, with energy conservation and environmental protection, safety, brightness
High, the advantages that persistence is long, in the present embodiment, selects light-accumulating photo etching particle as Noctilucent material, safer, and twilight sunset
Time is long.
In the present embodiment, a kind of low cost is developed, the noctilucence meta-aramid fibers that can shine are worked at night to meet
Relevant staff demand, even if when without external light, such meta-aramid Protection Product also can in pitch-dark environment
Play the role of protection, warning and guidance, it can be extensive using the products such as fabric or rope made of the noctilucence meta-aramid fibers
For fields such as the textile garment of night work, aviation and navigation, fire-fighting emergent, communications and transportation.
Further, light-accumulating photo etching particle is rare earth aluminate or silicates luminous agent particle, and partial size is that 2-6 is micro-
Rice.
Further, rare earth aluminate luminous agent particle is SrAl2O4: Eu2+Or SrAl2O4:Dy 3+, silicates noctilucence
Agent particle is specially SrMgSi2O6:Eu2+Or SrMgSi2O6:Dy3+。
Second aspect, the preparation method of this skin-core structure noctilucence meta-aramid fibers, includes the following steps:
1) preparation of noctilucence agent dispersing liquid: under stiring, dispersing agent is added into solvent, then ground luminous agent particle is divided
It dissipates in solvent；Solvent is one of n,N-Dimethylformamide or n,N-dimethylacetamide, and dispersing agent is polyethylene glycol
The mass ratio of one or both of octyl phenyl ether, polyvinylpyrrolidone, dispersing agent and solvent be 0.008:1 ~
0.015:1, mass percent of the luminous agent particle in entire dispersion liquid are 12% ~ 19%；
2) preparation of two kinds of polymer fluids: by m-phthaloyl chloride and m-phenylene diamine (MPD) be with step 1) in solvent with solvent into
Row polymerization reaction, filters out the hydrogen chloride for being then added in calcium oxide, calcium hydroxide or ammonia neutralizer and dissolving in polymer fluid excessively
Go to neutralize the salt generated, be made respectively a kind of polymer quality percentage concentration be 18% ~ 23%, another polymer quality percentage
The polymer fluid for two kinds of concentration that concentration is 25% ~ 29%；
3) preparation of spinning solution: the polymer fluid for the higher concentration that noctilucence agent dispersing liquid prepared by step 1) is prepared with step 2 is stirred
Mix formation cortex spinning solution after mixing；2) polymer fluid of low concentration is directly as sandwich layer spinning solution in；
4) spinneret of skin-core structure fiber can be made in selection, respectively by cortex spinning solution made from step 3) and sandwich layer spinning
Liquid carries out spinning as raw material, using wet spinning, using the mistake of coagulating bath, washing, drying, heat treatment, curling, cutting
Noctilucence meta-aramid fibers are made in journey.
Further, in the other embodiments of the application, the mass percentage concentration of polymer in above-mentioned cortex spinning solution
It is 18% ~ 23%.
Further, in the other embodiments of the application, the quality percentage of luminous agent particle in above-mentioned cortex spinning solution
Than being 3% ~ 13%.
In the present embodiment, by preparing the polymer fluid of two kinds of various concentrations, and noctilucence agent dispersing liquid is added to highly concentrated
In the polymer fluid of degree, so that the polymer fluid of high concentration is diluted to the polymer in the polymer fluid with low concentration by noctilucence agent dispersing liquid
Concentration it is suitable, conducive to the homogeneity for keeping sandwich layer and outer layer, while can guarantee the dispersing uniformity of luminous agent particle.
Further, in the other embodiments of the application, above-mentioned m-phthaloyl chloride and m-phenylene diamine (MPD) in a solvent into
Row polymerization reaction includes: that first m-phenylene diamine (MPD) is dissolved in solvent, and m-phthaloyl chloride is then added in two portions again, is added for the first time
It after first time polymerization occurs for m-phthaloyl chloride, is neutralized, then second of addition m-phthaloyl chloride occurs to gather for the second time
After conjunction, neutralized again.
Further, in the other embodiments of the application, the m-phthaloyl chloride being added for the first time accounts for a phenyl-diformyl
The 80-95% of chlorine total amount, second of m-phthaloyl chloride being added account for the 5-20% of m-phthaloyl chloride total amount.
By the way that m-phthaloyl chloride is added portionwise in the present embodiment, and the amount being added for the first time accounts for the 80-95% of total amount,
Polymerization reaction can occur with most m-phenylene diamine (MPD), at this point, carrying out neutralizing to remove in polymerization process for the first time generating
Hydrochloric acid, the viscosity of liquid becomes larger at this time, further be added m-phthaloyl chloride polymerize, can further promote fiber
Intensity, polymerization effect is more preferably.
Further, in the other embodiments of the application, using wet spinning to cortex spinning solution and sandwich layer spinning solution
Carrying out spinning includes: to be passed through cortex spinning solution in the entrance of the outer ring of spinneret, and sandwich layer spinning solution is passed through to the entrance of core bore
It is interior, carry out wet spinning.
In the present embodiment, by the way that cortex spinning solution and sandwich layer spinning solution are each led into the entrance of outer ring and core bore
In entrance, realization disposably prepares cortex and sandwich layer, and cortex is wrapped in the surface of sandwich layer.
Further, the inlet diameter of the core bore of spinneret and outer ring is greater than outlet diameter, and the presentation of its section is trapezoidal,
The ratio that the outlet diameter and outer ring of middle core bore go out mouth width is 4.5:1 ~ 8:1.
In the present embodiment, by being greater than the setting of outlet using entrance, so that spinneret in spinning process, has centainly
Pressure, can be improved the density and intensity of fiber.
Further, in the other embodiments of the application, core bore include the first pressurized segment being sequentially communicated, constant pressure section with
And second pressurized segment, the section of the first pressurized segment and the second pressurized segment is trapezoidal, the rectangular in cross-section of constant pressure section, the first pressurized segment
It is gradually reduced with the diameter of the second pressurized segment, the minimum diameter of the first pressurized segment is equal to the diameter of constant pressure section and is equal to second and adds
Press the maximum gauge of section.
By the change in size of the diameter of control core bore in the present embodiment, by pressurizeing twice, and material was pressurizeing
The direction of motion constantly changes in journey, the structure helping to obtain is more preferably close, and intensity more preferably sandwich layer, pressure effect is more
It is good.
Further, it is characterised in that coagulating bath is that the aluminate containing 5% ~ 13% mass percent or silicate are water-soluble
Liquid, salt used are sodium salt or sylvite, and the temperature of coagulating bath is 25 DEG C ~ 45 DEG C.
Further, the number of washing is 3 ~ 8 times, and the temperature of drying is 136 DEG C ~ 168 DEG C, and the temperature of heat treatment is
176℃~ 205℃。
The third aspect, a kind of noctilucence protective garment are using above-mentioned skin-core structure noctilucence meta-aramid fibers or above-mentioned skin
The skin-core structure noctilucence meta-aramid fibers that the preparation method of cored structure noctilucence meta-aramid fibers is prepared are as raw material system
It is standby to form.
The preparation of fourth aspect, a kind of skin-core structure noctilucence meta-aramid fibers or skin-core structure noctilucence meta-aramid fibers
The skin-core structure noctilucence meta-aramid fibers that method is prepared are preparing the textile garment of night work, aviation and navigation, fire-fighting
Emergency, the fabric of communications and transportation or the application in rope.
The beneficial effect of the present embodiment includes for example: relative to the common meta-aramid fibers of no noctilucence, the night of the application
Although the more common meta-aramid fibers performance of the main performance of light meta-aramid is declined slightly, it is able to satisfy clothes or other completely
The requirement to high breaking strength, high drawing meta-aramid fibers performance is protected, and duration can be generated up to 10 hours or more
Twilight sunset.Simultaneously as only cortex contains luminous agent, come relative to all fibers containing luminous agent in production all fibres
It says, this method about 12%-17% at low cost.
Specific embodiment
Below with reference to embodiment, present context is further illustrated.It should be appreciated that the implementation of the application is not limited to
In the following examples, the accommodation in any form and/or change made to the application fall within the application protection scope.
In this application, if not refering in particular to, all equipment and raw material etc. are commercially available or industry is common.Under
The method in embodiment is stated, is the conventional method of this field unless otherwise instructed.
Embodiment 1
A kind of preparation method of skin-core structure noctilucence meta-aramid fibers, includes the steps that are as follows:
It takes 460g m-phenylene diamine (MPD) to be dissolved in 4.0L n,N-dimethylacetamide, then total amount about 850g isophthalic is added portionwise thereto
Dimethyl chloride is polymerize, and after the completion of polymerization, the hydrogen chloride for being added in ammonia and dissolving in polymer fluid is filtered to remove neutralization and generates
Ammonium chloride after, obtain polymer concentration be 21% polymer fluid.Separately 460g m-phenylene diamine (MPD) is taken to be dissolved in 2.9L N, N- dimethyl methyl
In amide, then total amount about 850g m-phthaloyl chloride is added portionwise thereto and is polymerize, subsequent processing mode is identical, is made poly-
Close the polymer fluid that object content is 27%.
Under stiring, it is added Triton X-100 into n,N-dimethylacetamide, then by luminous agent
SrMgSi2O6:Eu2+It is ground to after partial size is 2-5 microns and is dispersed therein, the quality point of luminous agent in noctilucence agent composition is made
Number is 12%, and the mass ratio of Triton X-100 used and n,N-dimethylacetamide is 0.009:1.Under stiring, will
In the polymer fluid that it is 27% to polymer quality percentage composition that the noctilucence agent composition, which is added, luminous agent is in meta position after keeping dispersion
Mass fraction in aramid fiber polymer fluid is 3%.
The above-mentioned noctilucence meta-aramid polymer fluid prepared is used for spinning, method used by spinning is wet spinning,
Wherein polymer fluid used in core fiber layer is the polymer fluid that the polymer quality percentage composition without luminous agent is 21%, used in cortex
Polymer fluid is the polymer fluid containing luminous agent.The outlet diameter of spinneret core bore and the ratio of ring width (outlet) are 6:1.Cortex is spun
In the entrance for the outer ring that silk liquid is passed through spinneret, sandwich layer spinning solution is passed through in the entrance of core bore, carries out wet spinning.Polymer fluid
It by spinneret Cheng Sihou, is solidified into coagulation bath, coagulation bath is water-soluble containing 8% sodium metasilicate of mass percentage
Liquid, the temperature of coagulating bath used are 26 DEG C.After coagulating bath, fiber is at by 3 washings, 138 DEG C of drying and 177 DEG C of warm
After reason, the noctilucence meta-aramid fibers of final obtained 1D.
Embodiment 2
A kind of preparation method of skin-core structure noctilucence meta-aramid fibers, includes the steps that are as follows:
It takes 460g m-phenylene diamine (MPD) to be dissolved in 3.74L n,N-Dimethylformamide, then total amount about 850g isophthalic is added portionwise thereto
Dimethyl chloride is polymerize, and after the completion of polymerization, the hydrogen chloride for being added in calcium oxide and dissolving in polymer fluid is filtered to remove neutralization life
At calcium chloride after, obtain polymer concentration be 22% polymer fluid.Separately 460g m-phenylene diamine (MPD) is taken to be dissolved in 3.2L N, N- dimethyl
In acetamide, then total amount about 850g m-phthaloyl chloride is added portionwise thereto and is polymerize, subsequent processing mode is identical, is made
The polymer fluid that polymer content is 25%.
Under stiring, it is added polyvinylpyrrolidone into n,N-Dimethylformamide, then by luminous agent SrAl2O4:
Dy 3+It being ground to after partial size is 2-5 microns and is dispersed therein, the mass fraction that luminous agent in noctilucence agent composition is made is 16%,
The mass ratio of polyvinylpyrrolidone used and N,N-dimethylformamide is 0.012:1.Under stiring, which is mixed
It closes object to be added in the polymer fluid for being 25% to polymer quality percentage composition, luminous agent is in meta-aramid polymer fluid after keeping dispersion
In mass fraction be 8%.
The above-mentioned noctilucence meta-aramid polymer fluid prepared is used for spinning, method used by spinning is wet spinning,
Wherein polymer fluid used in core fiber layer is the polymer fluid that the polymer quality percentage composition without luminous agent is 22%, used in cortex
Polymer fluid is the polymer fluid containing luminous agent.The outlet diameter of spinneret core bore and the ratio of ring width (outlet) are 4.5:1.By cortex
Spinning solution is passed through in the entrance of the outer ring of spinneret, and sandwich layer spinning solution is passed through in the entrance of core bore, carries out wet spinning.Polymerization
Liquid passes through spinneret Cheng Sihou, is solidified into coagulation bath, and coagulation bath is to contain 9% potassium aluminate water of mass percentage
Solution, the temperature of coagulating bath used are 35 DEG C.After coagulating bath, fiber is by 5 washings, 151 DEG C of drying and 183 DEG C of warm
After processing, the noctilucence meta-aramid fibers of final obtained 5D.
Embodiment 3
A kind of preparation method of skin-core structure noctilucence meta-aramid fibers, includes the steps that are as follows:
It takes 460g m-phenylene diamine (MPD) to be dissolved in 3.6L n,N-dimethylacetamide, then total amount about 850g isophthalic is added portionwise thereto
Dimethyl chloride is polymerize, and after the completion of polymerization, is added in the neutralizers such as calcium oxide, calcium hydroxide or ammonia and is dissolved in polymer fluid
Hydrogen chloride, be filtered to remove neutralize generate salt after, obtain polymer concentration be 23% polymer fluid.Separately take 460g m-phenylene diamine (MPD)
It is dissolved in 2.6L n,N-dimethylacetamide, then total amount about 850g m-phthaloyl chloride is added portionwise thereto and is polymerize, after
Continuous processing mode is identical, and the polymer fluid that polymer content is 29% is made.
Under stiring, the Triton X-100 that mass percent is 1:1 is added into n,N-dimethylacetamide
And polyvinylpyrrolidone, then by luminous agent SrAl2O4: Eu2+It is ground to after partial size is 2-5 microns and is dispersed therein, be made
The mass fraction of luminous agent is 19% in noctilucence agent composition, Triton X-100 used and n,N-dimethylacetamide
Mass ratio be 0.015:1.Under stiring, by the noctilucence agent composition be added to polymer quality percentage composition be 29% it is poly-
It closes in liquid, keeping mass fraction of the luminous agent in meta-aramid polymer fluid after dispersion is 13%.
The above-mentioned noctilucence meta-aramid polymer fluid prepared is used for spinning, method used by spinning is wet spinning,
Wherein polymer fluid used in core fiber layer is the polymer fluid that the polymer quality percentage composition without luminous agent is 23%, used in cortex
Polymer fluid is the polymer fluid containing luminous agent.The outlet diameter of spinneret core bore and the ratio of ring width (outlet) are 8:1.Cortex is spun
In the entrance for the outer ring that silk liquid is passed through spinneret, sandwich layer spinning solution is passed through in the entrance of core bore, carries out wet spinning.Polymer fluid
It by spinneret Cheng Sihou, is solidified into coagulation bath, coagulation bath is water-soluble containing 12% potassium aluminate of mass percentage
Liquid, the temperature of coagulating bath used are 44 DEG C.After coagulating bath, fiber is at by 8 washings, 165 DEG C of drying and 204 DEG C of warm
After reason, the noctilucence meta-aramid fibers of final obtained 13D.
Embodiment 4
A kind of preparation method of skin-core structure noctilucence meta-aramid fibers, includes the steps that are as follows:
It takes 460g m-phenylene diamine (MPD) to be dissolved in 4.8L n,N-dimethylacetamide, then total amount about 850g isophthalic is added portionwise thereto
Dimethyl chloride is polymerize, and after the completion of polymerization, is added in the neutralizers such as calcium oxide, calcium hydroxide or ammonia and is dissolved in polymer fluid
Hydrogen chloride, be filtered to remove neutralize generate salt after, obtain polymer concentration be 18% polymer fluid.Separately take 460g m-phenylene diamine (MPD)
It is dissolved in 3.2L n,N-dimethylacetamide, then total amount about 850g m-phthaloyl chloride is added portionwise thereto and is polymerize, after
Continuous processing mode is identical, and the polymer fluid that polymer content is 25% is made.
Under stiring, the Triton X-100 that mass percent is 1:1 is added into n,N-dimethylacetamide
And polyvinylpyrrolidone, then by luminous agent SrAl2O4: Eu2+It is ground to after partial size is 2-5 microns and is dispersed therein, be made
The mass fraction of luminous agent is 19% in noctilucence agent composition, Triton X-100 used and n,N-dimethylacetamide
Mass ratio be 0.013:1.Under stiring, by the noctilucence agent composition be added to polymer quality percentage composition be 29% it is poly-
It closes in liquid, keeping mass fraction of the luminous agent in meta-aramid polymer fluid after dispersion is 15%.
The above-mentioned noctilucence meta-aramid polymer fluid prepared is used for spinning, method used by spinning is wet spinning,
Wherein polymer fluid used in core fiber layer is the polymer fluid that the polymer quality percentage composition without luminous agent is 18%, used in cortex
Polymer fluid is the polymer fluid containing luminous agent.The outlet diameter of spinneret core bore and the ratio of ring width (outlet) are 6:1.Core bore includes
The section of the first pressurized segment, constant pressure section and the second pressurized segment being sequentially communicated, the first pressurized segment and the second pressurized segment is trapezoidal,
The diameter of the rectangular in cross-section of constant pressure section, the first pressurized segment and the second pressurized segment is gradually reduced, and the minimum of the first pressurized segment is straight
Diameter is equal to the diameter of constant pressure section and is equal to the maximum gauge of the second pressurized segment.Outer ring is equal with the holding of the spacing of core bore.
Cortex spinning solution is passed through in the entrance of the outer ring of spinneret, sandwich layer spinning solution is passed through in the entrance of core bore, into
Row wet spinning.Polymer fluid passes through spinneret Cheng Sihou, is solidified into coagulation bath, and coagulation bath is to contain quality percentage
12% aluminic acid aqueous solutions of potassium of content, the temperature of coagulating bath used are 43 DEG C.After coagulating bath, fiber is by 5 washings, 168
After DEG C drying and 205 DEG C of heat treatments, the noctilucence meta-aramid fibers of final obtained 15D.
Embodiment 5
A kind of noctilucence protective garment is present embodiments provided, the skin-core structure noctilucence for using above-described embodiment one to four to prepare
Meta-aramid fibers are prepared as a raw material.Its textile garment that can be applied to night work, aviation and navigation, fire-fighting emergent,
In communications and transportation.
Comparative experiments
One, influence of the parameter to properties of product
Comparative example 1: general fibre (5D)
Comparative example 2: the mass ratio of Triton X-100 and DMAC N,N' dimethyl acetamide in embodiment one is replaced with
0.005:1；
Comparative example 3: the mass ratio of Triton X-100 and DMAC N,N' dimethyl acetamide in embodiment one is replaced with
0.02:1；
Comparative example 4: the mass percent of luminous agent particle in the cortex spinning solution in embodiment one is replaced with 1%；
Comparative example 5: the mass percent of luminous agent particle in the cortex spinning solution in embodiment one is replaced with 20%；
Comparative example 6: the spinneret of the trapezoidal spout in embodiment one is replaced with into the identical straight-tube shape of entrance and exit diameter
Spinneret；
Comparative example 7: it m-phthaloyl chloride will be added portionwise in embodiment one changes into and be added at one time the isophthalic two of required total amount
Formyl chloride.
The meta-aramid fibers that above-described embodiment 1-4 and comparative example 1-7 is obtained carry out performance detection, and testing result is such as
Under:
As can be seen from the above table, embodiment 1-4 provided by the present application can reach and the approximate properties of product of general fibre and tool
Have a longer twilight sunset duration, and comparative example 2-3 by changing Triton X-100 and n,N-dimethylacetamide
Mass ratio will lead to elongation at break and become larger, be easy to produce deformation, and comparative example 4-5, change noctilucence in cortex spinning solution
The mass percent of agent particle will lead to twilight sunset duration and change, while the breaking strength of comparative example 5 reduces, extension at break
Rate reduces.And comparative example 6 will lead to breaking strength reduction, elongation at break increases, and fibre density reduces, and comparative example 7 will lead to
Breaking strength is substantially reduced.Therefore, the comprehensive performance of embodiment 1-4 provided by the present application is substantially better than comparative example 1-7.
From the above, light-accumulating photo etching particle is dispersed using during preparing cortex and sandwich layer in the application
In cortex spinning solution, spinning is carried out, light-accumulating photo etching particle is scattered in the organic phase of cortex, is entirely being made
During standby, by controlling mass percent, the concentration of sandwich layer spinning solution and cortex spinning solution of luminous agent particle, it can obtain
The preferable skin-core structure noctilucence meta-aramid fibers of performance, relative to the common meta-aramid fibers of no noctilucence, the night of the application
Although the more common meta-aramid fibers performance of the main performance of light meta-aramid is declined slightly, it is able to satisfy clothes or other completely
The requirement to high breaking strength, high drawing meta-aramid fibers performance is protected, and duration can be generated up to 10 hours or more
Twilight sunset.Simultaneously as only cortex contains luminous agent, come relative to all fibers containing luminous agent in production all fibres
It says, this method about 12%-17% at low cost.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Industrial applicibility
Skin-core structure noctilucence meta-aramid fibers provided by the present application, fracture needed for can satisfy meta-aramid fibers are strong
The performance requirement of degree, extension at break, can generate duration up to 10 hours or more twilight sunset.Simultaneously as only cortex contains
There is luminous agent, relative in production all fibres all for the fiber containing luminous agent, this method about 12%-17% at low cost.Its
Can be applied to the preparation textile garment of night work, aviation and navigation, fire-fighting emergent, communications and transportation fabric or rope in.
Claims (10)
1. a kind of skin-core structure noctilucence meta-aramid fibers, it is characterised in that: the fiber includes cortex, the core coated by cortex
Layer, the light-accumulating photo etching particle of unordered dispersion inorganic phase in the organic phase of the cortex, so that the fiber is leaving the ring of light
Twilight sunset can be issued behind border in a dark environment.
2. a kind of skin-core structure noctilucence meta-aramid fibers according to claim 1, it is characterised in that: the light-accumulating
Photo etching particle is rare earth aluminate or silicates luminous agent particle, and partial size is 2-6 microns.
3. a kind of skin-core structure noctilucence meta-aramid fibers according to claim 2, it is characterised in that: the rare earth aluminic acid
Salt luminous agent particle is SrAl2O4: Eu2+Or SrAl2O4:Dy 3+, the silicates luminous agent particle is SrMgSi2O6:Eu2+
Or SrMgSi2O6:Dy3+。
4. a kind of any preparation method of skin-core structure noctilucence meta-aramid fibers of claim 1-3, which is characterized in that packet
Include following steps:
1) preparation of noctilucence agent dispersing liquid: under stiring, dispersing agent is added into solvent, then ground luminous agent particle is divided
It dissipates in solvent；The solvent is one of n,N-Dimethylformamide or n,N-dimethylacetamide, and the dispersing agent is
One or both of Triton X-100, polyvinylpyrrolidone, the quality of the dispersing agent and the solvent
Than for 0.008:1 ~ 0.015:1, mass percent of the luminous agent particle in entire dispersion liquid is 12% ~ 19%；
2) preparation of two kinds of polymer fluids: by m-phthaloyl chloride and m-phenylene diamine (MPD) be with step 1) in solvent with solvent into
Row polymerization reaction, filters out the hydrogen chloride for being then added in calcium oxide, calcium hydroxide or ammonia neutralizer and dissolving in polymer fluid excessively
Go to neutralize the salt generated, be made respectively a kind of polymer quality percentage concentration be 18% ~ 23%, another polymer quality percentage
The polymer fluid for two kinds of concentration that concentration is 25% ~ 29%；
3) preparation of spinning solution: the polymer fluid for the higher concentration that noctilucence agent dispersing liquid prepared by step 1) is prepared with step 2 is stirred
Mix formation cortex spinning solution after mixing；The polymer fluid of low concentration is directly as sandwich layer spinning solution；
4) spinneret of skin-core structure fiber can be made in selection, respectively by cortex spinning solution made from step 3) and sandwich layer spinning
Liquid carries out spinning as raw material, using wet spinning, using the mistake of coagulating bath, washing, drying, heat treatment, curling, cutting
Noctilucence meta-aramid fibers are made in journey.
5. a kind of preparation method of skin-core structure noctilucence meta-aramid fibers according to claim 4, which is characterized in that institute
The mass percent for stating luminous agent particle described in cortex spinning solution is 3% ~ 13%.
6. a kind of preparation method of skin-core structure noctilucence meta-aramid fibers according to claim 4, which is characterized in that institute
State m-phthaloyl chloride and the m-phenylene diamine (MPD) carry out in a solvent polymerization reaction include: first the m-phenylene diamine (MPD) is dissolved in it is described
In solvent, the m-phthaloyl chloride is then added in two portions again, the m-phthaloyl chloride is added for the first time and occurs for the first time
It after polymerization, is neutralized, the m-phthaloyl chloride is then added for the second time and occurs second after polymerizeing, is neutralized again；
The m-phthaloyl chloride being added for the first time accounts for the 80-95% of the m-phthaloyl chloride total amount, be added for second it is described between
Phthalyl chloride accounts for the 5-20% of the m-phthaloyl chloride total amount.
7. a kind of preparation method of skin-core structure noctilucence meta-aramid fibers according to claim 4, which is characterized in that adopt
Carrying out spinning to the cortex spinning solution and the sandwich layer spinning solution with wet spinning includes: that the cortex spinning solution is passed through institute
In the entrance for stating the outer ring of spinneret, in the entrance for the core bore that the sandwich layer spinning solution is passed through the spinneret, wet process is carried out
Spinning；The inlet diameter of the core bore of the spinneret and outer ring is greater than outlet diameter, and trapezoidal, wherein core bore is presented in its section
The ratio that outlet diameter and outer ring go out mouth width is 4.5:1 ~ 8:1；The core bore includes the first pressurized segment, the constant pressure being sequentially communicated
The section of section and the second pressurized segment, first pressurized segment and second pressurized segment is trapezoidal, the section of the constant pressure section
In rectangle, the diameter of first pressurized segment and second pressurized segment is gradually reduced, and the minimum of first pressurized segment is straight
Diameter is equal to the diameter of the constant pressure section and is equal to the maximum gauge of second pressurized segment.
8. a kind of preparation method of skin-core structure noctilucence meta-aramid fibers according to claim 4, it is characterised in that institute
State coagulating bath be aluminate or aqueous silicate solution containing 5% ~ 13% mass percent, salt used be sodium salt or sylvite, it is described
The temperature of coagulating bath is 25 DEG C ~ 45 DEG C；The number of the washing is 3 ~ 8 times, and the temperature of the drying is 136 DEG C ~ 168
DEG C, the temperature of the heat treatment is 176 DEG C ~ 205 DEG C.
9. a kind of noctilucence protective garment, which is characterized in that it is using skin-core structure noctilucence as described in any one of claims 1-3
It is prepared by the preparation method of meta-aramid fibers or such as described in any item skin-core structure noctilucence meta-aramid fibers of claim 4-9
Made of skin-core structure noctilucence meta-aramid fibers be prepared as a raw material.
10. a kind of skin-core structure noctilucence meta-aramid fibers as described in any one of claims 1-3 or such as claim 4-9
The skin-core structure noctilucence meta-aramid that the preparation method of skin-core structure noctilucence meta-aramid fibers described in one is prepared is fine
Tie up the preparation textile garment of night work, aviation and navigation, fire-fighting emergent, communications and transportation fabric or rope in application.
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| CN201811168698.2A CN109234842A (en) | 2018-10-08 | 2018-10-08 | A kind of skin-core structure noctilucence meta-aramid fibers and preparation method thereof |
| CN2018111686982 | 2018-10-08 |
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| CN201811637764.6A Pending CN109402779A (en) | 2018-10-08 | 2018-12-29 | A kind of skin-core structure noctilucence meta-aramid fibers and its preparation method and application |
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| CN111962180A (en) * | 2020-08-07 | 2020-11-20 | 闽江学院 | Red long afterglow luminous composite fiber filament and preparation method thereof |
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| CN109234842A (en) | 2019-01-18 |
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