CN101525781B - Complex fiber modified by keratin whiskers and preparation method thereof - Google Patents
Complex fiber modified by keratin whiskers and preparation method thereof Download PDFInfo
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- CN101525781B CN101525781B CN2009100488404A CN200910048840A CN101525781B CN 101525781 B CN101525781 B CN 101525781B CN 2009100488404 A CN2009100488404 A CN 2009100488404A CN 200910048840 A CN200910048840 A CN 200910048840A CN 101525781 B CN101525781 B CN 101525781B
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Abstract
The invention provides complex fiber modified by keratin whiskers and a preparation method thereof. The complex fiber modified by keratin whiskers consists of a high molecular material and the keratin whiskers extracted from natural keratin fiber and distributed in the high molecular material, wherein, weight ratio of the keratin whiskers to the high molecular material is 5-20:80-95, and the keratin whiskers are oriented along an axial direction of the fiber in the complex fiber. The complex fiber has mechanical properties meeting production and processing needs, and obviously improved hygroscopicity, dyeability, ultraviolet resistance and static resistance properties. Protein whiskers can be prepared from waste wool or other animal fiber materials without spinning value, and has wide sources of raw materials, low cot and simple processing. The production of whiskers modified complex fiber by wet spinning or dry spinning has the same processing course as the traditional process, is easy to be industrialized and has significant economic benefit.
Description
Technical field
The present invention relates to a kind of complex fiber modified by keratin whiskers and preparation method thereof, belong to the composite fibre technology field.
Background technology
Along with continuous progress in science and technology, numerous protein-modified functional textile fibrous materials have appearred in succession.Traditional chemical fibre is handled the shortcoming not only improved itself moisture absorption, ventilative, dyeability difference by modification, and it is functional also to have antistatic, anti-ultraviolet and a health care etc.At present, existing many patent reports this type of technology.
Chinese patent " acrylic fiber surface graft protein modified fiber and manufacture method thereof " (200510044184.2).This invention has prepared a kind of protein modified fiber of skin-core structure, and cortex is a vegetable protein grafting cover layer, and sandwich layer is acrylic fibers.Fiber top layer after the modification is covered by protein fully, has advantages of good skin compatibility, dyeability and antistatic behaviour.
Chinese patent " milk protein and polyvinyl alcohol copolymerized fibre and manufacture method thereof " (01106274.6).This invention is copolymerzation with cross-linking in reactor with milk and polyvinyl alcohol, and deaeration, spinning obtain milk protein and POLYPROPYLENE GLYCOL copolymer fibre.
Chinese patent " pearl protein function synthetic fibre and manufacture method thereof " (02103890.2).This invention mixes granularity mutually less than auxiliary agents such as a kind of and coupling agent in the pearl powder of 2 μ m and polyamide, modified polyamide or the PP resin, dispersants, and mediate at a high speed the heating back, extrudes through the twin-screw blend, makes functional agglomerate.Dried functional agglomerate is mixed mutually with the fibre resin section, prepare function synthetic fibre through melt spinning.
Chinese patent " a kind of chemical fibre and production method thereof " (200410013429.0) with the modification of natural protein fiber superfine powder.Wool fibre after this invention will be prescinded further is ground into the superfine powder of average grain diameter＜5 μ m with super-refinement powder process equipment.Prepare protein-modified chemical fibre by wet spinning or melt spinning.
The above patented technology is mainly by the protein-modified chemical fibre of prepared in one of two ways: one will be spun to fibre after the protein solution that extract and macromolecular material grafting or the blend; Its two, protein particulate is sneaked in the fibre section, prepare protein-modified chemical fibre by spinning technique.The shortcoming of first kind of mode is that the percent grafting of protein and macromolecular material is lower, the formation of corpus fibrosum is still based on macromolecular material, the premium properties of protein is not fully played on the serviceability of fiber, and the shortcoming of the second way is that sneaking into of nutty structure unit caused the fibre machinery performance degradation easily.
Summary of the invention
The purpose of this invention is to provide a kind of employing complex fiber modified by keratin whiskers and preparation method thereof, to improve dyeability, hygroscopicity, uvioresistant performance, antistatic property and the mechanical property of fiber.
In order to achieve the above object, technical scheme of the present invention provides a kind of complex fiber modified by keratin whiskers, it is characterized in that, form by macromolecular material and the keratin crystal whisker that from natural keratin fiber, extracts that is dispersed in the macromolecular material, wherein, the weight ratio of described keratin crystal whisker and macromolecular material is 5-20: 80-95, described keratin crystal whisker in composite fibre along fiber axis to distribution of orientations.
Described natural keratin fiber is preferably wool, ox hair, pig hair, the rabbit hair, the people sends out or camel hair.
The diameter of described keratin crystal whisker is preferably 0.2-3 μ m and length is preferably 20-120 μ m.
Described macromolecular material is preferably polyvinyl alcohol or polyacrylonitrile.
The present invention also provides the preparation method of above-mentioned complex fiber modified by keratin whiskers, it is characterized in that, concrete steps are: macromolecular material is dissolved in is made into macromolecule material solution in the solvent, keratin crystal whisker is scattered in is made into the keratin crystal whisker dispersion liquid identical in the homogeneous solvent with above-mentioned macromolecule material solution concentration, macromolecule material solution and keratin crystal whisker dispersion liquid are mixed, stir 3-8min or obtain spinning solution with speed 8000-12000r/min with power 50-100W and frequency 20-40kHz supersonic oscillations 2-5min, deaeration, wet spinning or dry spinning.
Described macromolecule material solution is preferably the polyacrylonitrile dimethyl formamide solution that polyvinyl alcohol water solution that weight percent concentration is 20%-30%, polyvinyl alcohol water solution that weight percent concentration is 36%-45%, the polyacrylonitrile aqueous solution that weight percent concentration is 20%-30% or weight percent concentration are 25%-30%, wherein, the described polyacrylonitrile aqueous solution is to make by polyacrylonitrile being dissolved in the sodium thiocyanate water solution that weight percent concentration is 45%-60%.
Described macromolecule material solution is weight percentage concentration when being the polyvinyl alcohol water solution of 20%-30%, adopt wet spinning, concrete steps are preferably: spinning solution is pressed into the vinal that is frozen into modified by keratin whiskers in the ammonium sulfate solution coagulating bath that weight percent concentration is 20%-45% from spinneret orifice, wherein, coagulation bath temperature is 30 ℃, the temperature of spinning solution is 50-60 ℃, and spinning speed is 50-100m/min.
Described macromolecule material solution is weight percentage concentration when being the polyvinyl alcohol water solution of 36%-45%, adopt dry spinning, concrete steps are preferably: spinning solution is pressed into from spinneret orifice makes moisture evaporation in the hot-air, obtain the vinal of modified by keratin whiskers, wherein, the temperature of hot-air is 130 ℃, and the temperature of spinning solution is 120-125 ℃, and spinning speed is 100-350m/min.
When described macromolecule material solution is the polyacrylonitrile aqueous solution, the concrete steps of described wet spinning are preferably: spinning solution is pressed into the polyacrylonitrile fibre that is frozen into modified by keratin whiskers in the sodium thiocyanate water solution coagulating bath that weight concentration is 6%-12% from spinneret orifice, wherein, coagulation bath temperature is 30 ℃, the temperature of spinning solution is 50-60 ℃, and spinning speed is 50-100m/min.
When described macromolecule material solution is the polyacrylonitrile dimethyl formamide solution, the concrete steps of described dry spinning are preferably: spinning solution is pressed into from spinneret orifice makes solvent evaporates in the hot-air, obtain the polyacrylonitrile fibre of modified by keratin whiskers, wherein, the temperature of hot-air is 100 ℃, the temperature of spinning solution is a room temperature, and spinning speed is 200-500m/min.
What the present invention sneaked into is whisker shape material, on the yardstick for sub-micron to micro-meter scale, and be anisotropy and obform body, completely different on strengthening the property with the graininess hybrid mode of second method.The nutty structure unit sneak into the intensity decreases that makes composite fibre, structure deterioration; And whisker strengthens the intensity enhancing of composite fibre, structure optimization.Though comparing with the second way all is that solid matter is sneaked into, the present invention adopts the keratin crystal whisker packing material to have following characteristics: 1. by the whisker structure body that extracts in the natural keratin fiber kept natural keratin animal fiber self intrinsic structure; 2. keratin crystal whisker is fibril shape, elongated anisotropic body, but not by cutting, grind or isotropic spherical particle powder of dissolving back spray drying gained fully.Whisker of the present invention in form with different fully with the spherical particle powder in nature.Because whisker has certain draw ratio, spinning solution flow and the process of orientation drawing-off in can form along fiber axis to distribution of orientations.Compare with the isotropism granular materials that disintegrating process forms, whisker packing material of the present invention can play humidification to fiber when giving the good dyeability of modified fibre, hygroscopicity, uvioresistant performance and antistatic property.
Keratin crystal whisker of the present invention is extracted from the natural keratin animal fiber, can adopt discarded animal fiber as raw material, and is cheap, wide material sources; Production method is simple, the productive rate height; The keratin fiber waste recycle can reduce environmental pollution, is beneficial to sustainable development.The process of wet spinning or dry spinning is identical with traditional handicraft, is easy to industrialization production, remarkable in economical benefits.
Modified by keratin whiskers composite fibre of the present invention, whisker anisotropic structures wherein and fiber axis are to being distribution of orientations, fiber is played humidification, the composite fibre mechanical performance can satisfy the needs of production and processing, and hygroscopicity, dyeability, uvioresistant performance and antistatic property are significantly improved, and can be used for developing grade textiles and regrown material.
The specific embodiment
Specify the present invention below by embodiment.
Embodiment 1
The waste wool of cleaning is cut into the long segment of fiber of 3-5mm, is that 1g/100ml is immersed in the pure formic acid in 20 ℃ of waters bath with thermostatic control with frequency 20kHz and power 200W supersonic oscillations 5h with the solid-to-liquid ratio; Remove by filter unreacted natural keratin fiber with 80 eye mesh screens, filtrate is filtered with 350 eye mesh screens obtain the micron order keratin crystal whisker, it is dry to clean the back with distilled water; With the keratin crystal whisker that obtains is that 1g/100ml is immersed in the pure formic acid in 20 ℃ of waters bath with thermostatic control with frequency 20kHz and power 50W supersonic oscillations 5h with the solid-to-liquid ratio; After the mixture that obtains filtered with 350 eye mesh screens, filtrate is obtained the submicron order keratin crystal whisker at 15 ℃ with rotating speed 3000rpm centrifugation 2h, it is dry to clean the back with distilled water.
With 95 weight account polyethylene alcohol (degree of polymerization 4000-6000) weight percent concentration that is made into soluble in water under 100 ℃ temperature is 20% polyvinyl alcohol water solution, (diameter is 0.2-3 μ m with 5 weight portion keratin crystal whiskers, length is 20-120 μ m) be scattered in the keratin crystal whisker dispersion soln that is made into same concentrations in the water, polyvinyl alcohol water solution and keratin crystal whisker solution are mixed, stir 3min with speed 12000r/min and obtain spinning solution, deaeration, 50 ℃ of spinning solutions are pressed into weight concentration from spinneret orifice be the vinal that is frozen into modified by keratin whiskers in 20% the ammonium sulfate solution coagulating bath, keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, coagulation bath temperature is 30 ℃, and spinning speed is 50m/min.
Embodiment 2
The discarded yak hair of cleaning is cut into the long segment of fiber of 3-5mm, is that 4g/100ml is immersed in the pure dichloroacetic acid in 100 ℃ of waters bath with thermostatic control with frequency 40kHz and power 600W supersonic oscillations 2h with the solid-to-liquid ratio; Remove by filter unreacted natural keratin fiber with 120 eye mesh screens, filtrate is filtered with 450 eye mesh screens obtain the micron order keratin crystal whisker, it is dry to clean the back with distilled water; With the keratin crystal whisker that obtains is that 4g/100ml is immersed in the pure dichloroacetic acid in 100 ℃ of waters bath with thermostatic control with frequency 40kHz and power 200W supersonic oscillations 2h with the solid-to-liquid ratio; After the mixture that obtains filtered with 450 eye mesh screens, filtrate is obtained the submicron order keratin crystal whisker at 25 ℃ with rotating speed 7000rpm centrifugation 1h, it is dry that distilled water cleans the back.
With 90 weight account polyethylene alcohol (degree of polymerization 4000-6000) weight percent concentration that is made into soluble in water under 90 ℃ temperature is 30% polyvinyl alcohol water solution, (diameter is 0.2-3 μ m with 10 weight portion keratin crystal whiskers, length is 20-120 μ m) be scattered in the keratin crystal whisker dispersion soln that is made into same concentrations in the water, polyvinyl alcohol water solution and keratin crystal whisker solution are mixed, stir 8min with speed 8000r/min and obtain spinning solution, deaeration, 60 ℃ of spinning solutions are pressed into weight concentration from spinneret orifice be the vinal that is frozen into modified by keratin whiskers in 45% the ammonium sulfate solution coagulating bath, keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, wherein, coagulation bath temperature is 30 ℃, and spinning speed is 100m/min.
Embodiment 3
The discarded pig hair of cleaning is cut into the long segment of fiber of 3-5mm, with the solid-to-liquid ratio be 1g/100ml immerse pure trifluoroacetic acid in adopt the broken 3h of probe type ultrasonic crumbling method, ice-water bath cooling at 20 ℃ with frequency 20kHz and power 200W; Remove by filter unreacted natural keratin fiber with 80 eye mesh screens, filtrate is filtered with 350 eye mesh screens obtain the micron order keratin crystal whisker, it is dry to clean the back with distilled water; With the keratin crystal whisker that obtains is that 1g/100ml is immersed in the pure trifluoroacetic acid at 20 ℃ and adopts the broken 3h of probe type ultrasonic crumbling method with frequency 20kHz and power 50W with the solid-to-liquid ratio; After the mixture that obtains filtered with 350 eye mesh screens, filtrate is obtained the submicron order keratin crystal whisker at 15 ℃ with rotating speed 3000rpm centrifugation 2h, it is dry to clean the back with distilled water.
With 85 weight account polyethylene alcohol (degree of polymerization 4000-6000) weight percent concentration that is made into soluble in water under 110 ℃ temperature is 36% polyvinyl alcohol water solution, (diameter is 0.2-3 μ m with 15 weight portion keratin crystal whiskers, length is 20-120 μ m) be scattered in that to be made into weight percent concentration in the water be 36% keratin crystal whisker dispersion soln, polyvinyl alcohol water solution and keratin crystal whisker solution are mixed, obtain spinning solution with power 50W and frequency 20kHz supersonic oscillations 5min, deaeration, spinning solution is pressed into from spinneret orifice makes moisture evaporation in the hot-air, obtain the vinal of modified by keratin whiskers, keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, wherein, the temperature of hot-air is 130 ℃, the temperature of spinning solution is 120 ℃, and spinning speed is 100m/min.
Embodiment 4
The discarded people who cleans is sent out the segment of fiber that cuts into 3-5mm length, with the solid-to-liquid ratio be 1g/100ml to immerse mass percent concentration be 80% aqueous formic acid in adopt the broken 1h of probe type ultrasonic crumbling method, ice-water bath cooling at 40 ℃ with frequency 40kHz and power 600W; Remove by filter unreacted natural keratin fiber with 80 eye mesh screens, filtrate is filtered with 350 eye mesh screens obtain the micron order keratin crystal whisker, it is dry to clean the back with distilled water; With the keratin crystal whisker that obtains is that to be immersed in mass percent concentration be to adopt the broken 1h of probe type ultrasonic crumbling method at 40 ℃ with frequency 40kHz and power 200W in 80% the aqueous formic acid to 1g/100ml with the solid-to-liquid ratio; After the mixture that obtains filtered with 350 eye mesh screens, filtrate is obtained the submicron order keratin crystal whisker at 15 ℃ with rotating speed 3000rpm centrifugation 2h, it is dry to clean the back with distilled water.
With 80 weight account polyethylene alcohol (degree of polymerization 4000-6000) weight percent concentration that is made into soluble in water under 120 ℃ temperature is 45% polyvinyl alcohol water solution, (diameter is 0.2-3 μ m with 20 weight portion keratin crystal whiskers, length is 20-120 μ m) be scattered in that to be made into weight percent concentration in the water be 45% keratin crystal whisker dispersion soln, polyvinyl alcohol water solution and keratin crystal whisker solution are mixed, obtain spinning solution with power 100W and frequency 40kHz supersonic oscillations 3min, deaeration, spinning solution is pressed into from spinneret orifice makes moisture evaporation in the hot-air, obtain the vinal of modified by keratin whiskers, keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, wherein, the temperature of hot-air is 130 ℃, the temperature of spinning solution is 125 ℃, and spinning speed is 350m/min.
Embodiment 5
The discarded camel hair of cleaning is cut into the long segment of fiber of 3-5mm, with the solid-to-liquid ratio be 1g/100ml to immerse mass percent concentration be 70% the dichloroacetic acid aqueous solution in adopt the broken 1h of probe type ultrasonic crumbling method, ice-water bath cooling at 40 ℃ with frequency 40kHz and power 600W; Remove by filter unreacted natural keratin fiber with 80 eye mesh screens, filtrate is filtered with 350 eye mesh screens obtain the micron order keratin crystal whisker, it is dry to clean the back with distilled water; With the keratin crystal whisker that obtains is that to be immersed in mass percent concentration be to adopt the broken 1h of probe type ultrasonic crumbling method at 40 ℃ with frequency 40kHz and power 200W in 70% the dichloroacetic acid aqueous solution to 1g/100ml with the solid-to-liquid ratio; After the mixture that obtains filtered with 350 eye mesh screens, filtrate is obtained the submicron order keratin crystal whisker at 15 ℃ with rotating speed 3000rpm centrifugation 2h, it is dry that distilled water cleans the back.
95 weight portion polyacrylonitrile (degree of polymerization 60000-70000) are made into weight percent concentration 50 ℃ of following stirring and dissolving in weight concentration is 45% sodium thiocyanate water solution be the 20% polyacrylonitrile aqueous solution, (diameter is 0.2-3 μ m with 5 weight portion keratin crystal whiskers, length is 20-120 μ m) to be scattered in weight concentration be that to be made into weight percent concentration in 45% the sodium thiocyanate water solution be 20% keratin crystal whisker dispersion soln, macromolecule material solution and keratin crystal whisker solution are mixed, stir 3min with speed 12000r/min and obtain spinning solution, deaeration, spinning solution is pressed into weight concentration from spinneret orifice be the polyacrylonitrile fibre that is frozen into modified by keratin whiskers in 6% the sodium thiocyanate water solution coagulating bath, keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, wherein, coagulation bath temperature is 30 ℃, the temperature of spinning solution is 50 ℃, and spinning speed is 50m/min.
Embodiment 6
The discarded rabbit hair of cleaning is cut into the long segment of fiber of 3-5mm, with the solid-to-liquid ratio be 1g/100ml to immerse mass percent concentration be 70% trifluoroacetic acid aqueous solution in adopt the broken 1h of probe type ultrasonic crumbling method, ice-water bath cooling at 40 ℃ with frequency 40kHz and power 600W; Remove by filter unreacted natural keratin fiber with 80 eye mesh screens, filtrate is filtered with 350 eye mesh screens obtain the micron order keratin crystal whisker, it is dry to clean the back with distilled water; With the keratin crystal whisker that obtains is that to be immersed in mass percent concentration be to adopt the broken 1h of probe type ultrasonic crumbling method at 40 ℃ with frequency 40kHz and power 200W in 70% the trifluoroacetic acid aqueous solution to 1g/100ml with the solid-to-liquid ratio; After the mixture that obtains filtered with 350 eye mesh screens, filtrate is obtained the submicron order keratin crystal whisker at 15 ℃ with rotating speed 3000rpm centrifugation 2h, it is dry that distilled water cleans the back.
90 weight portion polyacrylonitrile (degree of polymerization 60000-70000) are made into weight percent concentration 60 ℃ of following stirring and dissolving in weight concentration is 60% sodium thiocyanate water solution be 30% the polyacrylonitrile aqueous solution, (diameter is 0.2-3 μ m with 10 weight portion keratin crystal whiskers, length is 20-120 μ m) to be scattered in weight concentration be that to be made into weight percent concentration in 60% the sodium thiocyanate water solution be 30% keratin crystal whisker dispersion soln, macromolecule material solution and keratin crystal whisker solution are mixed, stir 8min with speed 8000r/min and obtain spinning solution, deaeration, spinning solution is pressed into weight concentration from spinneret orifice be the polyacrylonitrile fibre that is frozen into modified by keratin whiskers in 12% the sodium thiocyanate water solution coagulating bath, keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, wherein, coagulation bath temperature is 30 ℃, the temperature of spinning solution is 60 ℃, and spinning speed is 100m/min.
Embodiment 7
The discarded cashmere of cleaning is cut into the long segment of fiber of 3-5mm, with the solid-to-liquid ratio be 1g/100ml to immerse mass percent concentration be 70% trifluoroacetic acid aqueous solution in adopt the broken 1h of probe type ultrasonic crumbling method, ice-water bath cooling at 40 ℃ with frequency 40kHz and power 600W; Remove by filter unreacted natural keratin fiber with 80 eye mesh screens, filtrate is filtered with 350 eye mesh screens obtain the micron order keratin crystal whisker, it is dry to clean the back with distilled water; With the keratin crystal whisker that obtains is that to be immersed in mass percent concentration be to adopt the broken 1h of probe type ultrasonic crumbling method at 40 ℃ with frequency 40kHz and power 200W in 70% the trifluoroacetic acid aqueous solution to 1g/100ml with the solid-to-liquid ratio; After the mixture that obtains filtered with 350 eye mesh screens, filtrate is obtained the submicron order keratin crystal whisker at 15 ℃ with rotating speed 3000rpm centrifugation 2h, it is dry that distilled water cleans the back.
With 85 weight portion polyacrylonitrile (degree of polymerization 60000-70000) at room temperature stirring and dissolving to be made into weight percent concentration in dimethyl formamide be 45% the polyacrylonitrile aqueous solution, (diameter is 0.2-3 μ m with 15 weight portion keratin crystal whiskers, length is 20-120 μ m) be scattered in that to be made into weight percent concentration in the dimethyl formamide be 45% keratin crystal whisker dispersion soln, the polyacrylonitrile aqueous solution and keratin crystal whisker solution are mixed, obtain spinning solution with power 50W and frequency 20kHz supersonic oscillations 5min, deaeration, spinning solution is pressed into from spinneret orifice makes solvent evaporates in the hot-air, obtain the polyacrylonitrile fibre of modified by keratin whiskers, keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, wherein, the temperature of hot-air is 100 ℃, the temperature of spinning solution is a room temperature, and spinning speed is 200m/min.
Embodiment 8
The discarded yak hair of cleaning is cut into the long segment of fiber of 3-5mm, with the solid-to-liquid ratio be 1g/100ml to immerse mass percent concentration be 70% trifluoroacetic acid aqueous solution in adopt the broken 1h of probe type ultrasonic crumbling method, ice-water bath cooling at 40 ℃ with frequency 40kHz and power 600W; Remove by filter unreacted natural keratin fiber with 80 eye mesh screens, filtrate is filtered with 350 eye mesh screens obtain the micron order keratin crystal whisker, it is dry to clean the back with distilled water; With the keratin crystal whisker that obtains is that to be immersed in mass percent concentration be to adopt the broken 1h of probe type ultrasonic crumbling method at 40 ℃ with frequency 40kHz and power 200W in 70% the trifluoroacetic acid aqueous solution to 1g/100ml with the solid-to-liquid ratio; After the mixture that obtains filtered with 350 eye mesh screens, filtrate is obtained the submicron order keratin crystal whisker at 15 ℃ with rotating speed 3000rpm centrifugation 2h, it is dry that distilled water cleans the back.
With 80 weight portion polyacrylonitrile (degree of polymerization 60000-70000) at room temperature stirring and dissolving to be made into weight percent concentration in dimethyl formamide be the 30% polyacrylonitrile aqueous solution, (diameter is 0.2-3 μ m with 20 weight portion keratin crystal whiskers, length is 20-120 μ m) be scattered in that to be made into weight percent concentration in the dimethyl formamide be 30% keratin crystal whisker dispersion soln, the polyacrylonitrile aqueous solution and keratin crystal whisker solution are mixed, obtain spinning solution with power 100W and frequency 40kHz supersonic oscillations 2min, deaeration, spinning solution is pressed into from spinneret orifice makes solvent evaporates in the hot-air, obtain the polyacrylonitrile fibre of modified by keratin whiskers, keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, wherein, the temperature of hot-air is 100 ℃, the temperature of spinning solution is a room temperature, and spinning speed is 500m/min.
The performance of table 1 protein particulate and whisker modified polyvinyl alcohol composite fiber
The performance of table 2 protein particulate and whisker modified polyacrylonitrile composite fiber
From table 1 and table 2 as can be seen, whisker modified polyvinyl alcohol composite fiber and polyacrylonitrile composite fiber are less with the increase of increase ultimate strength and the extension at break decline of whisker content, and protein particulate modified polyethylene alcohol composite fibre and polyacrylonitrile composite fiber are very obvious with the increase ultimate strength and the extension at break decline of whisker content.Especially the protein particulate addition is greater than after 10%, and composite fibre is powerful obviously to descend.
Claims (9)
1. complex fiber modified by keratin whiskers, it is characterized in that, form by macromolecular material and the keratin crystal whisker that from natural keratin fiber, extracts that is dispersed in the macromolecular material, wherein, the weight ratio of described keratin crystal whisker and macromolecular material is 5-20: 80-95, described keratin crystal whisker in composite fibre along fiber axis to distribution of orientations, described macromolecular material is polyvinyl alcohol or polyacrylonitrile.
2. a kind of complex fiber modified by keratin whiskers as claimed in claim 1 is characterized in that, described natural keratin fiber is wool, ox hair, pig hair, the rabbit hair, the people sends out or camel hair.
3. a kind of complex fiber modified by keratin whiskers as claimed in claim 1 is characterized in that, the diameter of described keratin crystal whisker is that 0.2-3 μ m and length are 20-120 μ m.
4. the preparation method of the described complex fiber modified by keratin whiskers of claim 1, it is characterized in that, concrete steps are: macromolecular material is dissolved in is made into macromolecule material solution in the solvent, keratin crystal whisker is scattered in is made into the keratin crystal whisker dispersion liquid identical in the homogeneous solvent with above-mentioned macromolecule material solution concentration, macromolecule material solution and keratin crystal whisker dispersion liquid are mixed, stir 3-8min or obtain spinning solution with speed 8000-12000r/min with power 50-100W and frequency 20-40kHz supersonic oscillations 2-5min, deaeration, wet spinning or dry spinning.
5. the preparation method of complex fiber modified by keratin whiskers as claimed in claim 4, it is characterized in that, the described macromolecule material solution concentration that is weight percentage is the polyvinyl alcohol water solution of 20%-30%, weight percent concentration is the polyvinyl alcohol water solution of 36%-45%, weight percent concentration is the polyacrylonitrile aqueous solution of 20%-30% or the polyacrylonitrile dimethyl formamide solution that weight percent concentration is 25%-30%, wherein, the described polyacrylonitrile aqueous solution is to make by polyacrylonitrile being dissolved in the sodium thiocyanate water solution that weight percent concentration is 45%-60%.
6. the preparation method of complex fiber modified by keratin whiskers as claimed in claim 5, it is characterized in that, described macromolecule material solution is weight percentage concentration when being the polyvinyl alcohol water solution of 20%-30%, adopt wet spinning, concrete steps are: spinning solution is pressed into the vinal that is frozen into modified by keratin whiskers in the ammonium sulfate solution coagulating bath that weight percent concentration is 20%-45% from spinneret orifice, wherein, coagulation bath temperature is 30 ℃, the temperature of spinning solution is 50-60 ℃, and spinning speed is 50-100m/min.
7. the preparation method of complex fiber modified by keratin whiskers as claimed in claim 5, it is characterized in that, described macromolecule material solution is weight percentage concentration when being the polyvinyl alcohol water solution of 36%-45%, adopt dry spinning, concrete steps are: spinning solution is pressed into from spinneret orifice makes moisture evaporation in the hot-air, obtain the vinal of modified by keratin whiskers, wherein, the temperature of hot-air is 130 ℃, the temperature of spinning solution is 120-125 ℃, and spinning speed is 100-350m/min.
8. the preparation method of complex fiber modified by keratin whiskers as claimed in claim 5, it is characterized in that, when described macromolecule material solution is the polyacrylonitrile aqueous solution, the concrete steps of described wet spinning are: spinning solution is pressed into the polyacrylonitrile fibre that is frozen into modified by keratin whiskers in the sodium thiocyanate water solution coagulating bath that weight concentration is 6%-12% from spinneret orifice, wherein, coagulation bath temperature is 30 ℃, and the temperature of spinning solution is 50-60 ℃, and spinning speed is 50-100m/min.
9. the preparation method of complex fiber modified by keratin whiskers as claimed in claim 5, it is characterized in that, when described macromolecule material solution is the polyacrylonitrile dimethyl formamide solution, the concrete steps of described dry spinning are: spinning solution is pressed into from spinneret orifice makes solvent evaporates in the hot-air, obtain the polyacrylonitrile fibre of modified by keratin whiskers, wherein, the temperature of hot-air is 100 ℃, the temperature of spinning solution is a room temperature, and spinning speed is 200-500m/min.
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2009
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