CN103215673A - Preparation method of flat fibers - Google Patents
Preparation method of flat fibers Download PDFInfo
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- CN103215673A CN103215673A CN2013101593315A CN201310159331A CN103215673A CN 103215673 A CN103215673 A CN 103215673A CN 2013101593315 A CN2013101593315 A CN 2013101593315A CN 201310159331 A CN201310159331 A CN 201310159331A CN 103215673 A CN103215673 A CN 103215673A
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Abstract
The invention relates to a preparation method of flat fibers. The dry-spraying wet spinning technology is adopted, after squeezed out through round spinneret orifices, spinning solution enters a first coagulating bath, the drawing ratio of a spinneret is 2-10 times, the solvent content in strands out of the coagulating bath is 25-50 wt%, then the spinning solution is drawn in a coagulating mode in a second coagulating bath, the coagulating drawing is that drawing is carried out in the process of continuous coagulating of the spinning solution, through washing, the drying and drawing are carried out on the spinning solution to prepare and obtain the flat fibers. The prepared flat fibers have excellent performance and are characterized in respects such as gloss, elasticity, anti-pilling performance, bulkiness and hand feel, due to good rigidity of the flat fibers, when used as filtering material, the flat fibers can form an airflow channel, wherein the size and the form of the airflow channel can not be achieved through common round-section fibers, and the flat fibers have great development space in the application field of special requirements.
Description
Technical field
The present invention relates to a kind of preparation method of flat fiber.
Background technology
The related invention patent that applicant/patentee applies for for Mitsubishi Rayon Co. Ltd.: JP02-169712 " method of Production of dry spun flat acrylic fiber(dry process flat acrylic fiber) ", this invention relates to a kind of fiber with natural animal hair luster, feel, the cross section is flat, thereby is applicable to by dry method weaving acrylonitrile making clothes.Spinning solution carries out the dry method spinning by the spinnerets with a plurality of rectangular openings, and the long limit of spinnerets is 4: 1 with the ratio of minor face.
The Germany invention DE3040970 of Germany Bayer application " method of Processes for the production of dry-spun polyacrylonitrile profiled fibres and filaments(dry process polyacrylonitrile profiled filament) ", this disclosure of the Invention a kind of method of dry process acrylonitrile profiled filament, the area≤0.2mm of irregularly-shaped hole spinnerets
2, side is wide≤0.17mm.
The patent that relates to other polymer fibers preparation method has been announced a kind of aromatic polysulfonamide fiber preparation method as patent Chinese patent CN102358958A; Chinese patent CN102251302A has announced a kind of method for preparing cellulose fibre; Chinese patent CN102534839A discloses a kind of method for preparing meta-aramid fibers; Chinese patent CN102154725A discloses fire-retardant polyacrylic and polyester fiber of a kind of superelevation and production method thereof; Chinese patent CN1508303 the invention discloses a kind of animal protein fiber and preparation method thereof; Chinese patent CN101748499A disclose a kind of chitin fiber and a kind of be the method that solvent prepares chitin fiber with the ionic liquid.
Chinese patent CN102677208A discloses flat viscose of a kind of sheet and preparation method thereof, this invention prepares the blend spinning viscose by add carbonate in spinning solution, spinning technique under the molding condition that relaxes relatively, through bigger spinning head and the drawing-off between the seal wire spare, fluffy nascent strand is drawn into the flat pattern of sheet then.
There are a series of problems in the existing technology:
The spinning process of above-mentioned polymer fiber, what a part of spinning process obtained is that cross sectional shape is circular or approaching circular general fibre; The spinning process of another part polymer though obtained the flat pattern fiber, can only pass through special-shaped spinneret orifice, and as the preparation of yi word pattern spinneret orifice, and the making of profile spinneret will expend lot of manpower and material resources, does not meet the environmental requirement of energy-saving and emission-reduction.
As seen in the existing polymer spinning technology, all less than extruding behind the spinneret orifice in coagulating bath coagulation grade at spinning solution and the draft speed that goes out the coagulating bath strand being controlled simultaneously, can not reach the fiber flatness and reach controlled technology with the spinning technique adjustment, the coagulation grade of spinning solution strand in coagulating bath influenced the plasticity of fiber, can utilize the moulding adjusting process of fiber to obtain profiled fibre.
As everyone knows, flat acrylic is similar to animal hair, and is all characteristic at aspects such as gloss, elasticity, anti-pilling, bulkiness and feels, can play the effect unique of emulation animal skin.And the flat pattern fiber has favorable rigidity, and the time as filtering material, can form general circular cross-section fiber be beyond one's reach gas channel size and form, so the flat pattern polymer fiber can be applicable to the field of specific (special) requirements, as the high-temperature-resistant filtering material aspect, flat fragrant sulfonamide copolymer fibre also has very big development space, and how to adopt the mode of low energy consumption and environmental protection more to obtain the direction that the polymer flat fiber is called the scientific research concern.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of flat fiber, be intended to reach the purpose of fibre section controllable shapes, and then obtain flat fiber by technology rather than dependence profile spinneret by the coagulation grade of control extrusion solution in coagulating bath and the draft speed that goes out the coagulating bath strand.
The preparation method of a kind of flat fiber of the present invention, adopt dry-jet wet spinning technology, polymer solution enters first coagulating bath after circular spinneret orifice is extruded, by regulating the concentration of coagulating bath, temperature and the extrusion solution time of staying in coagulating bath, guarantee in coagulating bath, not exclusively to solidify, go out that solvent is 25～50wt% in the coagulating bath strand, make it have plasticity, and the spinneret draft ratio is 2～10 times, after fiber goes out coagulating bath, the high power traction of running roller is subjected to coming from the normal pressure of running roller down on the vertical distraction direction, make the fibre section shape change, solidify stretching in second coagulating bath then, solvent in the minimizing fiber also carries out drawing-off to fiber and reduces fibre fineness, improves fiber orientation, afterwards through washing, and carry out the fiber of the dry flat cross section for preparing of stretching, and for certain polymer fiber, also will carry out elevated temperature heat to stretch, just can obtain flat fiber.Cross sectional shape is a pancake, and can regulate the control that spinneret draft recently realizes the fibre section shape.
As optimized technical scheme:
The preparation method of aforesaid a kind of flat fiber, the concentration of described polymer solution are 5～30wt%; Described first and second coagulation bath compositions are solvent and the excess water consistent with polymer solution; Described first coagulation bath temperature is 0～30 ℃, the described first coagulating bath concentration is 40～70wt%, under the condition of described coagulating bath, make polymer solution in coagulating bath, not exclusively solidify, and the solvent that goes out the coagulating bath strand reaches the requirement of 25～50wt%, makes it have enough deformation plasticity.
The preparation method of aforesaid a kind of flat fiber, the setting time of described extrusion solution in coagulating bath is 20～80s, echo mutually with the condition of above-mentioned coagulating bath, in order to make polymer solution in coagulating bath, not exclusively solidify, and the solvent that goes out the coagulating bath strand reaches the requirement of 25～50wt%, makes it have enough deformation plasticity.
The preparation method of aforesaid a kind of flat fiber, described second coagulation bath temperature is 40～70 ℃, the described second coagulating bath concentration is 20～40wt%, and effect is the solvent in the minimizing fiber and fiber is carried out drawing-off reduce fibre fineness, improves fiber orientation.
The preparation method of aforesaid a kind of flat fiber, described polymer is one or more the combination in polyacrylonitrile, fragrant sulfonamide homopolymers or copolymer, poly, cellulose, protein or the chitin; Described polyacrylonitrile is polyacrylonitrile homopolymers and the acrylonitrile copolymer that contains first monomer, second monomer and the 3rd monomer, wherein, first monomer is an acrylonitrile, second monomer is taken from a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate or the acrylamide, and the 3rd monomer is taken from a kind of in itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine or the 2-methyl-5-vinylpyridine; Described fragrant sulfonamide copolymer is the homopolymers be made up of a kind of construction unit in structural formula (1)～(4) or the random copolymer be made up of any two kinds or above construction unit in structural formula (1)～(4);
Structural formula (1)
Structural formula (2)
Structural formula (3)
Structural formula (4)
When described polymer is fragrant sulfonamide homopolymers or copolymer (or poly), after described dry the stretching, also needs to carry out elevated temperature heat and stretch.
The preparation method of aforesaid a kind of flat fiber, the solvent of described polymer is following one or more: dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylacetylamide, 4-methyl morpholine-N-oxide, 1-butyl-3-methylimidazole chlorate, 1-butyl-3-methyl-imidazoles Bromide or 1-allyl-3-methyl-imidazoles chlorate.
The preparation method of aforesaid a kind of flat fiber also contains inorganic salts in the solvent of described polymer solution, described inorganic salts are calcium chloride or lithium chloride, and content is smaller or equal to 6wt%.
The preparation method of aforesaid a kind of flat fiber, described spinneret orifice is shaped as circle, and diameter is 0.1～0.8mm.
The preparation method of aforesaid a kind of flat fiber, 80～160 ℃ of described dry draft temperatures, draw ratio is 1.01～1.5 times.
The preparation method of aforesaid a kind of flat fiber, described elevated temperature heat stretches, and temperature is 300～400 ℃, and draw ratio is 1.03～3 times.
The preparation method of aforesaid a kind of flat fiber, described flat fiber flatness is 4～15, the fiber number of flat fiber is 1～10dtex.
The preparation method of aforesaid a kind of flat fiber, described flat fiber flatness improves with the increase of spinneret draft ratio, this is owing to increase spinneret draft than being increased in the normal pressure that comes from running roller on the vertical distraction direction, makes fiber produce bigger deformation; The raising that goes out the solvent of coagulating bath strand simultaneously also can influence the plasticity of fiber, uses the coagulating bath fiber and than under has bigger deformability in identical spinneret draft.
Beneficial effect:
1) the spinneret orifice extrusion solution enters in the coagulating bath, guarantees the positive drawing-off of shower nozzle, can realize the positive drawing-off in the coagulating bath and the high speed solvent spinning of fiber;
2) flat fiber prepares by control extrusion solution not exclusively solidifying with high spinneret draft ratio in coagulating bath, rather than the making by special-shaped spinneret orifice, has saved the special facture power consumption of profile spinneret, energy-saving and emission-reduction, environmental protection.
3) the present invention as to going out the drafting rate of coagulating bath strand, has realized the fibre section controllable shapes by setting spinning technology parameter.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The preparation method of flat polyacrylonitrile fibre:
Polyacrylonitrile homopolymers, viscosity average molecular weigh are 4.4 * 10
4
Polymer solution consists of: polyacrylonitrile homopolymers 25wt%, dimethylacetylamide 75wt%; 40 ℃ of following apparent viscosities of spinning solution are 110Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.7mm is extruded be 20 ℃ through diameter, concentration is first coagulating bath of 40wt% dimethylacetylamide and excess water, the time of staying is 20s in coagulating bath, and the spinneret draft ratio is 2 times, and the solvent that goes out in the coagulating bath strand is 40wt%; Be 50 ℃ in temperature then, concentration is to solidify in second coagulating bath of 25wt% dimethylacetylamide and excess water to stretch 2 times; Again through 100 ℃ of boiling water drawing-offs, and under 100 ℃, carry out 1.01 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 3.0cN/dtex;
Elongation at break: 20.6%;
Fiber number: 10dtex;
Flatness: 4.
Embodiment 2
The preparation method of flat polyacrylonitrile fibre:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 85wt%; Second monomer is a methyl acrylate, and content is 7wt%; The 3rd monomer is an itaconic acid, and content is 8wt%.Viscosity average molecular weigh is 6.5 * 10
4
Polymer solution consists of: acrylonitrile copolymer 30wt%, dimethyl formamide 70wt%; 40 ℃ of following apparent viscosities of spinning solution are 320Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.8mm is extruded be 20 ℃ through diameter, concentration is first coagulating bath of 40wt% dimethyl formamide and excess water, the time of staying is 80s in coagulating bath, and the spinneret draft ratio is 6 times, and the solvent that goes out in the coagulating bath strand is 25wt%; Be 70 ℃ in temperature then, concentration is to solidify in second coagulating bath of 20wt% dimethyl formamide and excess water to stretch 2.6 times; Again through 100 ℃ of boiling water drawing-offs, and under 80 ℃, carry out 1.21 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 5.1cN/dtex;
Elongation at break: 16.8%;
Fiber number: 8dtex;
Flatness: 13.
Embodiment 3
The preparation method of flat polyacrylonitrile fibre:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 88wt%; Second monomer is a methyl methacrylate, and content is 7wt%; The 3rd monomer is a sodium allylsulfonate, and content is 5wt%.Viscosity average molecular weigh is 2.5 * 10
5
Polymer solution consists of: acrylonitrile copolymer 5wt%, dimethyl sulfoxide (DMSO) 95wt%; 40 ℃ of following apparent viscosities of spinning solution are 270Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.2mm is extruded be 0 ℃ through diameter, concentration is first coagulating bath of 50wt% dimethyl sulfoxide (DMSO) and excess water, the time of staying is 50s in coagulating bath, and the spinneret draft ratio is 10 times, and the solvent that goes out in the coagulating bath strand is 28wt%; Be 70 ℃ in temperature then, concentration is to solidify in second coagulating bath of 20wt% dimethyl sulfoxide (DMSO) and excess water to stretch 3.5 times; Again through 100 ℃ of boiling water drawing-offs, and under 95 ℃, carry out 1.10 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 6.5cN/dtex;
Elongation at break: 20.5%;
Fiber number: 1.0dtex;
Flatness: 15.
Embodiment 4
The preparation method of flat polyacrylonitrile fibre:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 90wt%; Second monomer is a methacrylonitrile, and content is 6wt%; The 3rd monomer is a methylpropene sodium sulfonate, and content is 4wt%.Viscosity average molecular weigh is 5.2 * 10
4
Polymer solution consists of: acrylonitrile copolymer 21wt%, dimethyl sulfoxide (DMSO) 79wt%; 40 ℃ of following apparent viscosities of spinning solution are 190Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.4mm is extruded be 30 ℃ through diameter, concentration is first coagulating bath of 70wt% dimethyl sulfoxide (DMSO) and excess water, the time of staying is 35s in coagulating bath, and the spinneret draft ratio is 4 times, and the solvent that goes out in the coagulating bath strand is 50wt%; Be 40 ℃ in temperature then, concentration is to solidify in second coagulating bath of 40wt% dimethyl sulfoxide (DMSO) and excess water to stretch 4.0 times; Again through 100 ℃ of boiling water drawing-offs, and under 95 ℃, carry out 1.25 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 5.2cN/dtex;
Elongation at break: 18.2%;
Fiber number: 4.3dtex;
Flatness: 6.7.
Embodiment 5
The preparation method of flat polyacrylonitrile fibre:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 87wt%; Second monomer is a vinylacetate, and content is 6wt%; The 3rd monomer is a methylpropene sodium sulfonate, and content is 7wt%.Viscosity average molecular weigh is 7.6 * 10
4
Polymer solution consists of: acrylonitrile copolymer 15wt%, dimethyl sulfoxide (DMSO) 85wt%; 40 ℃ of following apparent viscosities of spinning solution are 196Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.35mm is extruded be 30 ℃ through diameter, concentration is first coagulating bath of 50wt% dimethyl sulfoxide (DMSO) and excess water, the time of staying is 40s in coagulating bath, and the spinneret draft ratio is 5 times, and the solvent that goes out in the coagulating bath strand is 50wt%; Be 50 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethyl sulfoxide (DMSO) and excess water to stretch 5.0 times; Again through 100 ℃ of boiling water drawing-offs, and under 80 ℃, carry out 1.15 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 3.6cN/dtex;
Elongation at break: 21.3%;
Fiber number: 3.2dtex;
Flatness: 7.1.
Embodiment 6
The preparation method of flat polyacrylonitrile fibre:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 87wt%; Second monomer is a vinylacetate, and content is 6wt%; The 3rd monomer is the metering system benzene sulfonic acid sodium salt, and content is 7wt%.Viscosity average molecular weigh is 8.2 * 10
4
Polymer solution consists of: acrylonitrile copolymer 15wt%, dimethyl sulfoxide (DMSO) 85wt%; 40 ℃ of following apparent viscosities of spinning solution are 201Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.15mm is extruded be 30 ℃ through diameter, concentration is first coagulating bath of 50wt% dimethyl sulfoxide (DMSO) and excess water, the time of staying is 40s in coagulating bath, and the spinneret draft ratio is 7 times, and the solvent that goes out in the coagulating bath strand is 50wt%; Be 50 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethyl sulfoxide (DMSO) and excess water to stretch 2.5 times; Again through 100 ℃ of boiling water drawing-offs, and under 85 ℃, carry out 1.3 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 4.2cN/dtex;
Elongation at break: 15.2%;
Fiber number: 2.1dtex;
Flatness: 11.
Embodiment 7
The preparation method of flat polyacrylonitrile fibre:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 87wt%; Second monomer is an acrylamide, and content is 6wt%; The 3rd monomer is a vinylpyridine, and content is 7wt%.Viscosity average molecular weigh is 1.5 * 10
5
Polymer solution consists of: acrylonitrile copolymer 16wt%, dimethyl sulfoxide (DMSO) 84wt%; 40 ℃ of following apparent viscosities of spinning solution are 250Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.25mm is extruded be 30 ℃ through diameter, concentration is first coagulating bath of 50wt% dimethyl sulfoxide (DMSO) and excess water, the time of staying is 40s in coagulating bath, and the spinneret draft ratio is 8 times, and the solvent that goes out in the coagulating bath strand is 30wt%; Be 50 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethyl sulfoxide (DMSO) and excess water to stretch 3.2 times; Again through 100 ℃ of boiling water drawing-offs, and under 85 ℃, carry out 1.4 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 5.2cN/dtex;
Elongation at break: 13.5%;
Fiber number: 2.2dtex;
Flatness: 13.
Embodiment 8
The preparation method of flat polyacrylonitrile fibre:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 87wt%; Second monomer is a methyl acrylate, and content is 6wt%; The 3rd monomer is 2-methyl-5-vinylpyridine, and content is 7wt%.Viscosity average molecular weigh is 5.6 * 10
4
Polymer solution consists of: acrylonitrile copolymer 18wt%, dimethylacetylamide 82wt%; 40 ℃ of following apparent viscosities of spinning solution are 175Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.45mm is extruded be 25 ℃ through diameter, concentration is first coagulating bath of 45wt% dimethylacetylamide and excess water, the time of staying is 50s in coagulating bath, and the spinneret draft ratio is 6 times, and the solvent that goes out in the coagulating bath strand is 30wt%; Be 65 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethylacetylamide and excess water to stretch 4.2 times; Again through 100 ℃ of boiling water drawing-offs, and under 85 ℃, carry out 1.5 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 4.2cN/dtex;
Elongation at break: 15.4%;
Fiber number: 2.8dtex;
Flatness: 9.
Embodiment 9
The preparation method of flat polyacrylonitrile fibre:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 87wt%; Second monomer is a methyl acrylate, and content is 6wt%; The 3rd monomer is an itaconic acid, and content is 7wt%.Viscosity average molecular weigh is 4.5 * 10
4
Polymer solution consists of: acrylonitrile copolymer 22wt%, dimethylacetylamide 78wt%; 40 ℃ of following apparent viscosities of spinning solution are 154Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.65mm is extruded be 15 ℃ through diameter, concentration is first coagulating bath of 55wt% dimethylacetylamide and excess water, the time of staying is 40s in coagulating bath, and the spinneret draft ratio is 4 times, and the solvent that goes out in the coagulating bath strand is 28wt%; Be 65 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethylacetylamide and excess water to stretch 4.4 times; Again through 100 ℃ of boiling water drawing-offs, and under 85 ℃, carry out 1.21 times of dry stretchings and prepare flat polyacrylonitrile fibre.
Product performance index:
Fracture strength: 5.1cN/dtex;
Elongation at break: 14.5%;
Fiber number: 6.2dtex;
Flatness: 8.5.
Embodiment 10
The preparation method of flat fragrant sulfonamide copolymer fibre:
Virtue sulfonamide copolymer: by following two kinds of copolymers that construction unit is formed, wherein the content of structure (1) and structure (2) is than being 3:1.Polymer property viscosity 2.24dL/g.
Structural formula (1)
Structural formula (2)
Polymer solution consists of: fragrant sulfonamide copolymer 1 6wt%, dimethylacetylamide 84wt%, calcium chloride 6wt%; 40 ℃ of following apparent viscosities of spinning solution are 184Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.15mm is extruded be 30 ℃ through diameter, concentration is first coagulating bath of 65wt% dimethylacetylamide, 2wt% calcium chloride and excess water, the time of staying is 30s in coagulating bath, the spinneret draft ratio is 2 times, and the solvent that goes out in the coagulating bath strand is 30wt%; Be 70 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethylacetylamide and excess water to stretch 3.5 times; Again through 100 ℃ of boiling water drawing-offs, and under 160 ℃, carry out 1.5 times of dry stretchings, under 360 ℃, carry out 3 times of elevated temperature heat drawing-offs, prepare flat fragrant sulfonamide copolymer fibre.
Product performance index:
Fracture strength: 4.6cN/dtex;
Elongation at break: 26.2%;
Fiber number: 2.1dtex;
Flatness: 6.4.
Embodiment 11
The preparation method of flat fragrant sulfonamide homopolymer fibre:
Virtue sulfonamide copolymer: the homopolymers of forming by following construction unit.Polymer property viscosity 3.1dL/g.
Structural formula:
Polymer solution consists of: fragrant sulfonamide copolymer 1 8wt%, dimethyl formamide 82wt%; 40 ℃ of following apparent viscosities of spinning solution are 390Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.2mm is extruded be 0 ℃ through diameter, concentration is first coagulating bath of 50wt% dimethyl formamide and excess water, the time of staying is 40s in coagulating bath, and the spinneret draft ratio is 10 times, and the solvent that goes out in the coagulating bath strand is 30wt%; Be 70 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethyl formamide and excess water to stretch 3.8 times; Again through 100 ℃ of boiling water drawing-offs, and under 140 ℃, carry out 1.5 times of dry stretchings, under 400 ℃, carry out 1.03 times of elevated temperature heat drawing-offs, prepare flat fragrant sulfonamide copolymer fibre.
Product performance index:
Fracture strength: 5.6cN/dtex;
Elongation at break: 18.1%;
Fiber number: 1.7dtex;
Flatness: 15.
Embodiment 12
The preparation method of flat fragrant sulfonamide copolymer fibre:
Virtue sulfonamide copolymer: by following three kinds of copolymers that construction unit is formed, wherein the ratio of structure (1), structure (2) and structure (3) is 1:1:1.Polymer property viscosity 1.0dL/g.
Structural formula (1)
Structural formula (2)
Structural formula (3)
Polymer solution consists of: fragrant sulfonamide copolymer 20wt%, dimethyl sulfoxide (DMSO) 75wt%, lithium chloride 5wt%; 40 ℃ of following apparent viscosities of spinning solution are 100Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.3mm is extruded be 5 ℃ through diameter, concentration is first coagulating bath of 56wt% dimethyl sulfoxide (DMSO), 3wt% lithium chloride and excess water, the time of staying is 40s in coagulating bath, the spinneret draft ratio is 7 times, and the solvent that goes out in the coagulating bath strand is 29wt%; Be 60 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethyl sulfoxide (DMSO) and 1wt% lithium chloride excess water to stretch 3.0 times; Again through 100 ℃ of boiling water drawing-offs, and under 140 ℃, carry out 1.2 times of dry stretchings, under 300 ℃, carry out 2.6 times of elevated temperature heat drawing-offs, prepare flat fragrant sulfonamide copolymer fibre.
Product performance index:
Fracture strength: 5.1cN/dtex;
Elongation at break: 16.2%;
Fiber number: 3.2dtex;
Flatness: 10.
Embodiment 13
The preparation method of flat fragrant sulfonamide copolymer fibre:
Virtue sulfonamide copolymer: by following three kinds of copolymers that construction unit is formed, wherein the ratio of structure (1), structure (2), structure (3) and structure (4) is 1:2:5:3.Polymer property viscosity 1.8dL/g.
Structural formula (1)
Structural formula (2)
Structural formula (3)
Structural formula (4)
Polymer solution consists of: fragrant sulfonamide copolymer 1 2wt%, 1-butyl-3-methylimidazole chlorate 88wt%; 40 ℃ of following apparent viscosities of spinning solution are 345Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.4mm is extruded be 5 ℃ through diameter, concentration is first coagulating bath of 56wt%1-butyl-3-methylimidazole chlorate and excess water, the time of staying is 40s in coagulating bath, the spinneret draft ratio is 7 times, and the solvent that goes out in the coagulating bath strand is 31wt%; Be 60 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt%1-butyl-3-methylimidazole chlorate and excess water to stretch 3.0 times; Again through 100 ℃ of boiling water drawing-offs, and under 140 ℃, carry out 1.2 times of dry stretchings, under 350 ℃, carry out 2.7 times of elevated temperature heat drawing-offs, prepare flat fragrant sulfonamide copolymer fibre.
Product performance index:
Fracture strength: 4.5cN/dtex;
Elongation at break: 16.2%;
Fiber number: 3.5dtex;
Flatness: 9.
Embodiment 14
The preparation method of flat Fanglun 1313:
The inherent viscosity of poly is 1.0dL/g.
Polymer solution consists of: poly 12wt%, dimethylacetylamide 88wt%; 40 ℃ of following apparent viscosities of spinning solution are 90Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.3mm is extruded be 5 ℃ through diameter, concentration is first coagulating bath of 50wt% dimethylacetylamide and excess water, the time of staying is 40s in coagulating bath, and the spinneret draft ratio is 3 times, and the solvent that goes out in the coagulating bath strand is 29wt%; Be 60 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% acetic acid dimethylamide and excess water to stretch 3.4 times; Again through 100 ℃ of boiling water drawing-offs, and under 140 ℃, carry out 1.2 times of dry stretchings, under 350 ℃, carry out 2.6 times of elevated temperature heat drawing-offs, prepare flat Fanglun 1313.
Product performance index:
Fracture strength: 4.9cN/dtex;
Elongation at break: 14.3%;
Fiber number: 4.1dtex;
Flatness: 7.
Embodiment 15
The preparation method of flat Fanglun 1313:
The inherent viscosity of poly is 4.8dL/g.
Polymer solution consists of: poly 30wt%, dimethyl sulfoxide (DMSO) 74wt%; 40 ℃ of following apparent viscosities of spinning solution are 310Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.2mm is extruded be 5 ℃ through diameter, concentration is first coagulating bath of 45wt% dimethyl sulfoxide (DMSO) and excess water, the time of staying is 50s in coagulating bath, and the spinneret draft ratio is 9 times, and the solvent that goes out in the coagulating bath strand is 31wt%; Be 60 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt% dimethyl sulfoxide (DMSO) and excess water to stretch 2.8 times; Again through 100 ℃ of boiling water drawing-offs, and under 140 ℃, carry out 1.2 times of dry stretchings, under 350 ℃, carry out 2.6 times of elevated temperature heat drawing-offs, prepare flat Fanglun 1313.
Product performance index:
Fracture strength: 4.0cN/dtex;
Elongation at break: 10.5%;
Fiber number: 2.1dtex;
Flatness: 13.
Embodiment 16
The preparation method of flat fiber cellulose fiber:
Cellulosic degree of polymerization is 505.
Polymer solution consists of: cellulose 8wt%, 4-methyl morpholine-N-oxide 92wt%; 40 ℃ of following apparent viscosities of spinning solution are 150Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.5mm is extruded be 5 ℃ through diameter, concentration is first coagulating bath of 50wt%4-methyl morpholine-N-oxide and excess water, the time of staying is 50s in coagulating bath, the spinneret draft ratio is 4 times, and the solvent that goes out in the coagulating bath strand is 31wt%; Be 60 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt%4-methyl morpholine-N-oxide and excess water to stretch 2.4 times; Again through 100 ℃ of boiling water drawing-offs, and under 95 ℃, carry out 1.2 times of dry stretchings, prepare the flat fiber cellulose fiber.
Product performance index:
Fracture strength: 2.4cN/dtex;
Elongation at break: 11.1%;
Fiber number: 3.4dtex;
Flatness: 9.
Embodiment 17
The preparation method of flat fiber cellulose fiber:
Cellulosic degree of polymerization is 1100.
Polymer solution consists of: cellulose 30wt%, 1-butyl-3-methylimidazole chlorate 74wt%; 40 ℃ of following apparent viscosities of spinning solution are 410Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.2mm is extruded be 20 ℃ through diameter, concentration is first coagulating bath of 52wt%1-butyl-3-methylimidazole chlorate and excess water, the time of staying is 40s in coagulating bath, the spinneret draft ratio is 9 times, and the solvent that goes out in the coagulating bath strand is 31wt%; Be 60 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt%1-butyl-3-methylimidazole chlorate and excess water to stretch 2.9 times; Again through 100 ℃ of boiling water drawing-offs, and under 90 ℃, carry out 1.2 times of dry stretchings, prepare the flat fiber cellulose fiber.
Product performance index:
Fracture strength: 3.9cN/dtex;
Elongation at break: 12.8%;
Fiber number: 2.0dtex;
Flatness: 12.
Embodiment 18
The preparation method of flat fiber element/protein blended fiber:
Cellulosic degree of polymerization is 760, protein molecular weight is 5.1 * 10
5
Polymer solution consists of: protein 4wt%, cellulose 13wt%, 1-butyl-3-methyl-imidazoles Bromide 83wt%; 40 ℃ of following apparent viscosities of spinning solution are 140Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.8mm is extruded be 25 ℃ through diameter, concentration is first coagulating bath of 42wt%1-butyl-3-methyl-imidazoles Bromide and excess water, the time of staying is 50s in coagulating bath, the spinneret draft ratio is 2 times, and the solvent that goes out in the coagulating bath strand is 40wt%; Be 60 ℃ in temperature then, concentration is to solidify in second coagulating bath of 33wt%1-butyl-3-methyl-imidazoles Bromide and excess water to stretch 3.4 times; Again through 100 ℃ of boiling water drawing-offs, and under 80 ℃, carry out 1.1 times of dry stretchings, prepare flat protein fibre.
Product performance index:
Fracture strength: 3.8cN/dtex;
Elongation at break: 15.7%;
Fiber number: 10.0dtex;
Flatness: 5.
Embodiment 19
The preparation method of flat polyacrylonitrile/protein blended fiber:
The acrylonitrile homopolymer molecular weight is 8.2 * 10
4, protein molecular weight is 1.2 * 10
5
Polymer solution consists of: protein 4wt%, polyacrylonitrile 20wt%, 1-allyl-3-methyl-imidazoles chlorate 76wt%; 40 ℃ of following apparent viscosities of spinning solution are 400Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.4mm is extruded be 11 ℃ through diameter, concentration is first coagulating bath of 53wt%1-allyl-3-methyl-imidazoles chlorate and excess water, the time of staying is 70s in coagulating bath, the spinneret draft ratio is 10 times, and the solvent that goes out in the coagulating bath strand is 31wt%; Be 70 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt%1-allyl-3-methyl-imidazoles chlorate and excess water to stretch 4.5 times; Again through 100 ℃ of boiling water drawing-offs, and under 90 ℃, carry out 1.2 times of dry stretchings, prepare flat protein fibre.
Product performance index:
Fracture strength: 4.0cN/dtex;
Elongation at break: 18.3%;
Fiber number: 4.0dtex;
Flatness: 15.
Embodiment 20
The preparation method of flat polyacrylonitrile/chitin blended fiber:
Acrylonitrile copolymer: first monomer is a polyacrylonitrile, and content is 87wt%; Second monomer is a methyl acrylate, and content is 6wt%; The 3rd monomer is an itaconic acid, and content is 7wt%.Viscosity average molecular weigh is 4.5 * 10
4Chitin molecule amount 5.6 * 10
4
Polymer solution consists of: acrylonitrile copolymer 16wt%, chitin 3wt%, 1-butyl-3-methyl-imidazoles Bromide 81wt%; 40 ℃ of following apparent viscosities of spinning solution are 207Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.4mm is extruded be 11 ℃ through diameter, concentration is first coagulating bath of 53wt%1-butyl-3-methyl-imidazoles Bromide and excess water, the time of staying is 70s in coagulating bath, the spinneret draft ratio is 7 times, and the solvent that goes out in the coagulating bath strand is 31wt%; Be 70 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt%1-butyl-3-methyl-imidazoles Bromide and excess water to stretch 4.0 times; Again through 100 ℃ of boiling water drawing-offs, and under 90 ℃, carry out 1.2 times of dry stretchings, prepare flat chitin fiber.
Product performance index:
Fracture strength: 4.2cN/dtex;
Elongation at break: 14.5%;
Fiber number: 4.9dtex;
Flatness: 10.
Embodiment 21
The preparation method of flat fragrant sulfonamide copolymer/chitin blended fiber:
Virtue sulfonamide copolymer: by following two kinds of copolymers that structure is formed, the ratio 1:9 of structure (1) and structure (2) wherein.Polymer property viscosity 2.34dL/g, the chitin molecule amount is 6.7 * 10
4
Structural formula (1)
Structural formula (2)
Polymer solution consists of: chitin 18wt%, 1-butyl-3-methyl-imidazoles Bromide 82wt%; 40 ℃ of following apparent viscosities of spinning solution are 400Pas.Polymer solution is that to enter temperature after the circular spinneret orifice of 0.1mm is extruded be 30 ℃ through diameter, concentration is first coagulating bath of 41wt%1-butyl-3-methyl-imidazoles Bromide and excess water, the time of staying is 70s in coagulating bath, the spinneret draft ratio is 9 times, and the solvent that goes out in the coagulating bath strand is 26wt%; Be 68 ℃ in temperature then, concentration is to solidify in second coagulating bath of 30wt%1-butyl-3-methyl-imidazoles Bromide and excess water to stretch 2.5 times; Again through 100 ℃ of boiling water drawing-offs, and under 90 ℃, carry out 1.2 times of dry stretchings, prepare flat chitin fiber.
Product performance index:
Fracture strength: 3.0cN/dtex;
Elongation at break: 15.6%;
Fiber number: 2.1dtex;
Flatness: 9.
Claims (10)
1. the preparation method of a flat fiber adopts dry-jet wet spinning technology, and it is characterized in that: polymer solution enters first coagulating bath after circular spinneret orifice is extruded, and the spinneret draft ratio is 2～10 times, and the solvent that goes out in the coagulating bath strand is 25～50wt%; In second coagulating bath, solidify stretching then, described solidify to stretch be meant in continuing process of setting and stretch; Process washing again, and carry out the drying stretching, prepare flat fiber.
2. the preparation method of a kind of flat fiber according to claim 1 is characterized in that, the concentration of described polymer solution is 5～30wt%; Described first and second coagulation bath compositions are solvent and the excess water consistent with polymer solution, and described first coagulation bath temperature is 0～30 ℃, and the described first coagulating bath concentration is 40～70wt%; Described second coagulation bath temperature is 40～70 ℃, and the described second coagulating bath concentration is 20～40wt%.
3. the preparation method of a kind of flat fiber according to claim 1 is characterized in that, the setting time of described strand in described first coagulating bath is 20～80s.
4. the preparation method of a kind of flat fiber according to claim 1, it is characterized in that described polymer is one or more the combination in polyacrylonitrile, fragrant sulfonamide homopolymers or copolymer, poly, cellulose, protein or the chitin; Described polyacrylonitrile is polyacrylonitrile homopolymers and the acrylonitrile copolymer that contains first monomer, second monomer and the 3rd monomer, wherein, first monomer is an acrylonitrile, second monomer is taken from a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate or the acrylamide, and the 3rd monomer is taken from a kind of in itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine or the 2-methyl-5-vinylpyridine; Described fragrant sulfonamide copolymer is the homopolymers be made up of a kind of construction unit in structural formula (1)～(4) or the random copolymer be made up of any two kinds or above construction unit in structural formula (1)～(4);
Structural formula (1)
Structural formula (2)
Structural formula (3)
Structural formula (4)
When described polymer is fragrant sulfonamide homopolymers or copolymer (or poly), after described dry the stretching, also needs to carry out elevated temperature heat and stretch.
5. the preparation method of a kind of flat fiber according to claim 1, it is characterized in that the solvent of described polymer solution is following one or more: dimethyl formamide, dimethyl sulfoxide (DMSO), dimethylacetylamide, 4-methyl morpholine-N-oxide, 1-butyl-3-methylimidazole chlorate, 1-butyl-3-methyl-imidazoles Bromide or 1-allyl-3-methyl-imidazoles chlorate.
6. the preparation method of a kind of flat fiber according to claim 5 is characterized in that, also contains inorganic salts in the solvent of described polymer solution, and described inorganic salts are calcium chloride or lithium chloride, and content is smaller or equal to 6wt%.
7. the preparation method of a kind of flat fiber according to claim 1 is characterized in that, the diameter of described circular spinneret orifice is 0.1～0.8mm; The described draw ratio that solidifies stretching is 2～5 times.
8. the preparation method of a kind of flat fiber according to claim 1 is characterized in that, 80～160 ℃ of described dry draft temperatures, and draw ratio is 1.01～1.5 times.
9. the preparation method of a kind of flat fiber according to claim 4 is characterized in that, described elevated temperature heat stretches, 300～400 ℃ of temperature, and draw ratio is 1.03～3 times.
10. the preparation method of a kind of flat fiber according to claim 1 is characterized in that, the flatness of described flat fiber is 4～15; The fiber number of described flat fiber is 1～10dtex.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080221A (en) * | 2014-05-22 | 2015-11-25 | 东丽纤维研究所（中国）有限公司 | Heatproof filtering material, and production method and application thereof |
| CN108641102A (en) * | 2018-06-20 | 2018-10-12 | 北京林业大学 | A kind of highly effective cellulose dicyandiamide solution and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1449495A (en) * | 1964-10-12 | 1966-03-18 | Monsanto Co | Wet spinning process with non-submerged acrylonitrile filament spinneret |
| JPH07305222A (en) * | 1994-05-09 | 1995-11-21 | Unitika Ltd | Method for producing polyvinyl alcohol fiber |
| JP2004052129A (en) * | 2002-07-17 | 2004-02-19 | Toray Ind Inc | Dry-wet type spinning apparatus |
| CN101429682A (en) * | 2008-11-28 | 2009-05-13 | 东华大学 | Method for producing regenerated cellulose fiber by dual-bath coagulation |
| CN102358958A (en) * | 2011-07-27 | 2012-02-22 | 东华大学 | Method for preparing aromatic polysulphonamide fibers |
-
2013
- 2013-05-03 CN CN201310159331.5A patent/CN103215673B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1449495A (en) * | 1964-10-12 | 1966-03-18 | Monsanto Co | Wet spinning process with non-submerged acrylonitrile filament spinneret |
| JPH07305222A (en) * | 1994-05-09 | 1995-11-21 | Unitika Ltd | Method for producing polyvinyl alcohol fiber |
| JP2004052129A (en) * | 2002-07-17 | 2004-02-19 | Toray Ind Inc | Dry-wet type spinning apparatus |
| CN101429682A (en) * | 2008-11-28 | 2009-05-13 | 东华大学 | Method for producing regenerated cellulose fiber by dual-bath coagulation |
| CN102358958A (en) * | 2011-07-27 | 2012-02-22 | 东华大学 | Method for preparing aromatic polysulphonamide fibers |
Non-Patent Citations (2)
| Title |
|---|
| 尹平平: "喷丝板微孔中熔体流动及异形纤维成形过程的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 07, 15 July 2006 (2006-07-15), pages 016 - 68 * |
| 本书编写组: "《石油和石化工业概述》", 31 July 2010, article "腈纶", pages: 150 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080221A (en) * | 2014-05-22 | 2015-11-25 | 东丽纤维研究所（中国）有限公司 | Heatproof filtering material, and production method and application thereof |
| CN108641102A (en) * | 2018-06-20 | 2018-10-12 | 北京林业大学 | A kind of highly effective cellulose dicyandiamide solution and application thereof |
| CN108641102B (en) * | 2018-06-20 | 2020-12-08 | 北京林业大学 | High-efficiency cellulose solvent system and application thereof |
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