EP1417360B1 - Method for the production of fibres or a fibrous product in an electrostatic spinning method - Google Patents
Method for the production of fibres or a fibrous product in an electrostatic spinning method Download PDFInfo
- Publication number
- EP1417360B1 EP1417360B1 EP02754415A EP02754415A EP1417360B1 EP 1417360 B1 EP1417360 B1 EP 1417360B1 EP 02754415 A EP02754415 A EP 02754415A EP 02754415 A EP02754415 A EP 02754415A EP 1417360 B1 EP1417360 B1 EP 1417360B1
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- EP
- European Patent Office
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- added
- process according
- electron system
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- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 39
- 238000010041 electrostatic spinning Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229920000642 polymer Polymers 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 14
- -1 imino, azo Chemical group 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000012476 oxidizable substance Substances 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 230000010933 acylation Effects 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000006193 diazotization reaction Methods 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000006884 silylation reaction Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000012954 diazonium Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 12
- 239000000654 additive Substances 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002800 charge carrier Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- NUHCTOLBWMJMLX-UHFFFAOYSA-N bromothymol blue Chemical compound BrC1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=C(Br)C(O)=C(C(C)C)C=2)C)=C1C NUHCTOLBWMJMLX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002239 polyacrylonitrile Chemical class 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical class Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Chemical class 0.000 description 1
- 239000004695 Polyether sulfone Chemical class 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000001004 diazonium dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004924 electrostatic deposition Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UWXGZQGGJZDWEG-UHFFFAOYSA-N nitrooxy(oxo)methanediazonium Chemical group [N+](=O)([O-])OC(=O)[N+]#N UWXGZQGGJZDWEG-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Chemical class 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Chemical class 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002635 polyurethane Chemical class 0.000 description 1
- 239000004814 polyurethane Chemical class 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001289 polyvinyl ether Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- 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
Definitions
- the present invention relates to a process for producing fibers or a fiber product in an electrostatic spinning process.
- the production of fibers or fiber products, e.g. of nonwovens, in an electrostatic spinning process has been known in principle from the prior art for some time.
- a polymer solution or a polymer melt is applied to an electrode and charged by a high electrical voltage. If you now bring a counter electrode in the vicinity, then electrical forces act on the polymer solution or on the polymer melt and pull the finest fibers from this electrode.
- Various electrode and applicator devices have already been described for carrying out these methods. Representative here are e.g. DE 20 32 072, EP 1 059 106, US 3,994,258, US 4,144,553, US 4,323,525 and US 4,287,139.
- DE 20 32 072 discloses the fiber diameter of the fiber produced during spinning of a polymer solution in an electrostatic spinning process. In this case, with an improved conductivity of the polymer solution to be spun fibers with a smaller fiber diameter can be obtained.
- DE 20 32 072 discloses the addition of ionizable organic salts.
- EP 1 059 106 likewise discloses additives for controlling the charge, viscosity, surface tension and the conductivity of a polymer solution or polymer melt to be spun in an electrostatic spinning process.
- these additives are expressly used to improve the spinning of the polymer solution or the polymer melt, without a remaining charge or To charge the generated fibers.
- a permanent electrical charging of the fibers or fiber products produced is to be avoided according to the teaching of EP 1 059 106.
- this is disadvantageous for the use of these materials for the filtering of air, since it is only possible to mechanically deposit dust particles without electrically charged fibers.
- the method mentioned in the introduction is inventively further developed in that polymers are spun from solution and / or from the melt and the solution and / or the melt before spinning one or more oxidizable substances or substances are added with a ⁇ -electron system, whereby the charge advantageously increased in the solution to be spun and preserved in the fibers. That the process according to the invention makes it possible to produce electrically charged fibers or a fiber product consisting of such fibers in an electrostatic spinning process.
- the products of the process according to the invention are preferably used in the production of filter materials.
- the added substance or the added substances preferably at least stabilize a positive charge or these Have substances in the corresponding solvent over one or more oxidation potentials, which can be determined by cyclic voltammetry.
- the present invention is based on the finding that a significant procedural improvement is possible when in the to be spun polymer solution or polymer melt a real excess charge is generated, acts on the electric field.
- Bromothymol blue, methyl red, rhodamine B and crystal violet in dichloromethane as solvent and ferrocene as reference were measured cyclovoltammetrically to investigate this phenomenon.
- Bromthymolblau has no oxidation potential in the measuring range, which is accessible in dichloromethane.
- Bromthymolblau has also shown to be completely ineffective as an additive in dichloromethane in the context of the present invention.
- methyl red, rhodamine B and crystal violet have oxidation potentials in the range from 0.9 to 1.14 V and are extremely effective representatives of the additives according to the invention.
- Ferrocene itself with an oxidation potential of 0.38 V is also an effective additive.
- solvents with comparatively high dielectric constants as particularly preferred e.g. Butanone, acetonitrile, dimethyl sulfoxide, water, dimethylformamide, n-methylformamide, acetone, ethanol and ethylene glycol
- solvents with comparatively high dielectric constants as particularly preferred e.g. Butanone, acetonitrile, dimethyl sulfoxide, water, dimethylformamide, n-methylformamide, acetone, ethanol and ethylene glycol
- the content of polymer in the same can vary accordingly, in particular also increase.
- the polarity of the solvent can be further increased or increased by adding a substance with a very high dielectric constant.
- the solvent having a comparatively large dielectric constant has a relative dielectric constant of at least 15.0 at a temperature of 20 ° C.
- the substance used to increase the polarity of the solvent having a very high dielectric constant or substances having very high dielectric constants respectively has or has a relative dielectric constant of at least 20.0, more preferably of at least 30.0 at 20 ° C. . exhibit.
- diazonium dyes preferably diazo salts, e.g. Echtblausalz B or BB, Echtviolettsalz B or Echtrotsalz GG suitable.
- charge transfer complexes such as e.g. crystal violet and iodine, or quinone and hydroquinone, have been found to be effective in the present invention.
- much of the cited dyes are attributed to the basic or acid dyes, i. they are salts of negatively or positively charged dye molecules. It can be concluded that dye molecules charged from the outset represent a particularly suitable additive in the process according to the invention.
- substances with an extended ⁇ -electron system which is preferably resonance-stabilized, are particularly well suited as an additive in the process according to the invention if they contain functional groups such as amino, amido, imino, azo, nitro , Carboxy, diazonium, hydroxy, thio, sulfo or halogen groups.
- functional groups such as amino, amido, imino, azo, nitro , Carboxy, diazonium, hydroxy, thio, sulfo or halogen groups.
- the addition of the one or more substances to the polymer solution or polymer melt can take place according to the invention over a relatively broad range.
- the person skilled in the art will easily determine the required proportion by weight based on the desired and desired product properties in the end product. In principle, however, it is preferred if the addition of one or more substances takes place in an amount of from 0.1 to 50% by weight of the polymer solution or polymer melt, more preferably in an amount of from 0.5 to 5% by weight.
- halogens preferably with chlorine, or strong acids or bases, nitrogen oxides or sulfur oxides.
- hydrogen halides e.g. Hydrochloric acid gas
- bases e.g. Ammonia
- polymers can be spun with the process according to the invention, which can be spun from a solution or from the melt.
- polymers soluble in organic solvents are mentioned here, such as polystyrene, polycarbonate, polyvinyl chloride, polyacrylate, polymethacrylate, polyvinyl acetate, polyvinyl acetal, polyvinyl ether, polyurethane, polyamide, polysulfone, polyethersulfone, polyacrylonitrile, cellulose derivatives, and the like Mixtures and copolymers of these polymers.
- thermoplastics here are, for example, polyolefins, polyesters, polyoxymethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyaryletherketone, polyvinylidene fluoride and mixtures and copolymers of these polymers mentioned.
- copolymers of polystyrene such as styrene / acrylonitrile copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / butadiene / styrene copolymer have been found to be particularly suitable.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Fasern oder eines Faserprodukts in einem elektrostatischen Spinnverfahren. Die Herstellung von Fasern oder Faserprodukten, wie z.B. von Vliesstoffen, in einem elektrostatischen Spinnverfahren ist grundsätzlich aus dem Stand der Technik bereits seit geraumer Zeit bekannt. Bei derartigen Verfahren wird ein Polymerlösung oder eine Polymerschmelze auf eine Elektrode aufgebracht und durch eine hohe elektrische Spannung aufgeladen. Bringt man nun eine Gegenelektrode in die Nähe, so wirken elektrische Kräfte auf die Polymerlösung bzw. auf die Polymerschmelze und ziehen feinste Fasern von dieser Elektrode ab. Zur Durchführung dieser Verfahren wurden bereits verschiedene Elektroden- und Auftragungsvorrichtung beschrieben. Stellvertretend sind hier z.B. die DE 20 32 072, EP 1 059 106, US 3,994,258, US 4,144,553, US 4,323,525 und die US 4,287,139 zu nennen.The present invention relates to a process for producing fibers or a fiber product in an electrostatic spinning process. The production of fibers or fiber products, e.g. of nonwovens, in an electrostatic spinning process has been known in principle from the prior art for some time. In such processes, a polymer solution or a polymer melt is applied to an electrode and charged by a high electrical voltage. If you now bring a counter electrode in the vicinity, then electrical forces act on the polymer solution or on the polymer melt and pull the finest fibers from this electrode. Various electrode and applicator devices have already been described for carrying out these methods. Representative here are e.g. DE 20 32 072, EP 1 059 106, US 3,994,258, US 4,144,553, US 4,323,525 and US 4,287,139.
Bereits in der DE 20 32 072 ist offenbart, daß der Faserdurchmesser der erzeugten Faser beim Verspinnen einer Polymerlösung in einem elektrostatischen Spinnverfahren durch die Leitfähigkeit der Lösung beeinflußt werden kann. Dabei sind mit einer verbesserten Leitfähigkeit der zu verspinnenden Polymerlösung Fasern mit einem geringeren Faserdurchmesser zu erhalten. Um dies zu erreichen, offenbart die DE 20 32 072 den Zusatz von in Ionen überführbaren organischen Salzen.It is already disclosed in DE 20 32 072 that the fiber diameter of the fiber produced during spinning of a polymer solution in an electrostatic spinning process can be influenced by the conductivity of the solution. In this case, with an improved conductivity of the polymer solution to be spun fibers with a smaller fiber diameter can be obtained. In order to achieve this, DE 20 32 072 discloses the addition of ionizable organic salts.
Aus der EP 1 059 106 sind ebenfalls Zusätze zur Kontrolle der Ladung, Viskosität, Oberflächenspannung und der Leitfähigkeit einer in einem elektrostatischen Spinnverfahren zu verspinnenden Polymerlösung oder Polymerschmelze offenbart. Diese Zusätze dienen jedoch ausdrücklich dazu das Verspinnen der Polymerlösung bzw. der Polymerschmelze zu verbessern, ohne zu einer verbleibenden Ladung oder Aufladung der erzeugten Fasern zu führen. Im Gegenteil, eine dauerhafte elektrische Aufladung der erzeugten Fasern bzw. Faserprodukte ist gemäß der Lehre der EP 1 059 106 zu vermeiden. Dies ist jedoch für den Einsatz dieser Materialien für das Filtern von Luft nachteilig, da es ohne elektrisch geladene Fasern nur möglich ist Staubpartikel mechanisch abzuscheiden.EP 1 059 106 likewise discloses additives for controlling the charge, viscosity, surface tension and the conductivity of a polymer solution or polymer melt to be spun in an electrostatic spinning process. However, these additives are expressly used to improve the spinning of the polymer solution or the polymer melt, without a remaining charge or To charge the generated fibers. On the contrary, a permanent electrical charging of the fibers or fiber products produced is to be avoided according to the teaching of EP 1 059 106. However, this is disadvantageous for the use of these materials for the filtering of air, since it is only possible to mechanically deposit dust particles without electrically charged fibers.
Es ist daher Aufgabe der vorliegenden Erfindung das eingangs erwähnte Verfahren zu Bereicherung des Standes der Technik weiterzubilden. Es ist weiterhin Aufgabe der vorliegenden Erfindung ein solches Verfahren so weiterzubilden, daß auf technisch einfache und ökonomische Weise die aus dem Stand der Technik bekannten Nachteile zumindest teilweise überwunden werden, wobei mit diesem Verfahren Produkte mit verbesserten Produkteigenschaften erhältlich sein sollen.It is therefore an object of the present invention to further develop the method mentioned above to enrich the state of the art. It is a further object of the present invention to develop such a process so that in a technically simple and economical manner, the disadvantages known from the prior art are at least partially overcome, with this method products with improved product properties should be available.
Die vorliegende Aufgabe wird durch ein Verfahren mit den Merkmalen des beigefügten Anspruchs 1 gelöst sowie durch eine Verwendung von nach diesem Verfahren hergestellten Fasern oder Faserprodukten mit den Merkmalen des Anspruchs 8. Vorteilhafte Ausgestaltungen der Erfindung sind Gegenstand der Ansprüche 2 bis 7.The present object is achieved by a method having the features of appended claim 1 and by use of fibers or fiber products produced by this method having the features of claim 8. Advantageous embodiments of the invention are subject matter of claims 2 to 7.
Das eingangs erwähnte Verfahren wird erfindungsgemäß dadurch weitergebildet, daß Polymere aus Lösung und/oder aus der Schmelze versponnen werden und der Lösung und/oder der Schmelze vor dem Verspinnen eine oder mehrere oxidierbare Substanzen oder Substanzen mit einem π-Elektronensystem zugesetzt werden, wodurch die Ladung in der zu verspinnenden Lösung vorteilhafterweise erhöht und in den Fasern konservierbar ist. D.h. das erfindungsgemäße Verfahren ermöglicht die Herstellung von elektrisch aufgeladenen Fasern oder eines aus solchen Fasern bestehenden Faserprodukts in einem elektrostatischen Spinnverfahren. Die Erzeugnisse des erfindungsgemäßen Verfahrens finden bevorzugt Anwendung bei der Herstellung von Filtermaterialien.The method mentioned in the introduction is inventively further developed in that polymers are spun from solution and / or from the melt and the solution and / or the melt before spinning one or more oxidizable substances or substances are added with a π-electron system, whereby the charge advantageously increased in the solution to be spun and preserved in the fibers. That the process according to the invention makes it possible to produce electrically charged fibers or a fiber product consisting of such fibers in an electrostatic spinning process. The products of the process according to the invention are preferably used in the production of filter materials.
Es ist dabei weiter bevorzugt, die Polymerlösung oder Polymerschmelze von der Anode zu versprühen, wobei die zugesetzte Substanz bzw. die zugesetzten Substanzen vorzugsweise eine positive Ladung zumindest stabilisieren oder diese Substanzen in dem entsprechenden Lösungsmittel über ein oder mehrere Oxidationspotentiale verfügen, die mittels zyklischer Voltammetrie bestimmbar sind.It is further preferred to spray the polymer solution or polymer melt from the anode, wherein the added substance or the added substances preferably at least stabilize a positive charge or these Have substances in the corresponding solvent over one or more oxidation potentials, which can be determined by cyclic voltammetry.
Im Gegensatz zum Stand der Technik, in dem die Veränderung der Leitfähigkeit der zu verspinnenden Polymerflüssigkeit zur Beeinflussung des Faserdurchmessers durch Zusatz von in Ionenpaare dissoziierbare Salze bewirkt wird, beruht die vorliegende Erfindung auf der Erkenntnis, daß eine wesentliche verfahrenstechnische Verbesserung möglich wird, wenn in der zu verspinnenden Polymerlösung oder Polymerschmelze ein echter Ladungsüberschuß erzeugt wird, auf den das elektrische Feld wirkt.In contrast to the prior art, in which the change in the conductivity of the polymer liquid to be spun for influencing the fiber diameter is effected by the addition of dissociable salts in ion pairs, the present invention is based on the finding that a significant procedural improvement is possible when in the to be spun polymer solution or polymer melt a real excess charge is generated, acts on the electric field.
Überraschenderweise hat sich dabei gezeigt, daß es grundsätzlich viel effektiver ist die Lösung von einer positiv geladenen Düse auf eine negativ geladene Gegenelektrode abzusprühen, als umgekehrt. Der Grund hierfür ist noch nicht vollständig geklärt. Da sich die meisten organischen Substanzen leichter oxidieren als reduzieren lassen wird jedoch angenommen, daß hierfür die entsprechenden Oxidationspotentiale dieser Substanzen entscheidend sind. Aufgrund dieses Sachverhalts ist daher eine positive Ladung effektiver in die zu verspinnende Lösung oder Schmelze einzubringen.Surprisingly, it has been shown that it is basically much more effective spraying the solution of a positively charged nozzle on a negatively charged counter electrode, as opposed to. The reason for this is not completely clear yet. However, since most organic substances oxidize more easily than can be reduced, it is believed that the corresponding oxidation potentials of these substances are crucial for this. Because of this fact, therefore, a positive charge is more effectively to be introduced into the solution or melt to be spun.
Zur Untersuchung dieses Phänomens wurden bspw. Bromthymolblau, Methylrot, Rhodamin B und Kristallviolett in Dichlormethan als Lösungsmittel und mit Ferrocen als Referenz cyclovoltammetrisch vermessen. Dabei weist Bromthymolblau in dem Meßbereich, der in Dichlormethan zugänglich ist kein Oxidationspotential auf. In völliger Übereinstimmung mit diesem Untersuchungsergebnis hat sich Bromthymolblau auch als Zusatz in Dichlormethan im Sinne der vorliegenden Erfindung als vollkommen wirkungslos gezeigt. Methylrot, Rhodamin B und Kristallviolett weisen hingegen Oxidationspotential im Bereich von 0,9 bis 1,14 V auf und stellen äußerst wirkungsvolle Vertreter der erfindungsgemäßen Zusätze dar. Auch Ferrocen selbst mit einem Oxidationspotential von 0,38 V ist ein wirkungsvoller Zusatz.Bromothymol blue, methyl red, rhodamine B and crystal violet in dichloromethane as solvent and ferrocene as reference were measured cyclovoltammetrically to investigate this phenomenon. In this case, Bromthymolblau has no oxidation potential in the measuring range, which is accessible in dichloromethane. In complete accordance with this test result Bromthymolblau has also shown to be completely ineffective as an additive in dichloromethane in the context of the present invention. By contrast, methyl red, rhodamine B and crystal violet have oxidation potentials in the range from 0.9 to 1.14 V and are extremely effective representatives of the additives according to the invention. Ferrocene itself with an oxidation potential of 0.38 V is also an effective additive.
Bei der vorliegenden Erfindung ist weiterhin das Zusammenspiel bzw. sind die Wechselwirkungen von Lösungsmittel und zugesetzter Substanz weiterhin von besonderer Bedeutung. Dies wird beim Übergang zu polaren Lösungsmitteln wie Tetrahydrofuran oder Butanon ganz deutlich, da die oben genannten Substanzen in diesen eine noch größere Wirkung im Sinne der Erfindung zeigen. Dies wird allgemein darauf zurückgeführt, daß Ionen im einem Solvens mit höherer Dielektrizitätskonstante besser stabilisiert werden.Further, in the present invention, the interaction of the solvent and the added substance continues to be special meaning. This becomes quite clear in the transition to polar solvents such as tetrahydrofuran or butanone, since the abovementioned substances in these show an even greater effect in the context of the invention. This is generally attributed to better stabilization of ions in a higher dielectric constant solvent.
Vergleichbares gilt auch für Polymerschmelzen, da diese sich wie ein Lösungsmittel für die erfindungsgemäß zugesetzten Substanzen verhalten.The same applies to polymer melts, since they behave like a solvent for the substances added according to the invention.
Durch Verwendung von Lösungsmitteln mit vergleichsweise großen Dielektrizitätskonstanten, wie besonders bevorzugt z.B. Butanon, Acetonitril, Dimethylsulfoxid, Wasser, Dimethylformamid, n-Methylformamid, Aceton, Ethanol und Ethylenglycol ist es möglich mit dem erfindungsgemäßen Verfahren zum elektrostatischen Spinnen noch weiter verbesserte Verfahrensprodukte zu erhalten. Durch die geeignete Wahl des Lösungsmittels und/oder der zugesetzten Substanzen läßt sich vorzugsweise der Faserdurchmesser der in dem erfindungsgemäßen Verfahren erhaltenen Fasern einstellen. Auch läßt sich beim Verspinnen aus einer Lösung der Gehalt an Polymer in derselben entsprechend variieren, insbesondere auch erhöhen. Die Polarität des Lösungsmittels läßt sich ferner auch durch Zusatz einer Substanz mit einer sehr hohen Dielektrizitätskonstante steigern oder erhöhen. Bei einer Lösung von Polystyrol in Dichlormethan oder Essigester ist dies z.B. durch einen Zusatz von Acetamid möglich. Es hat sich jedoch gezeigt, daß es nicht ausreicht die Polarität des Lösungsmittels zu erhöhen. Von entscheidender Bedeutung für die vorliegende Erfindung ist daher, daß sowohl ein Ladungsträger, als auch ein polares Solvens vorliegt, das den Ladungsträger vermutlich stabilisiert.By using solvents with comparatively high dielectric constants, as particularly preferred e.g. Butanone, acetonitrile, dimethyl sulfoxide, water, dimethylformamide, n-methylformamide, acetone, ethanol and ethylene glycol, it is possible with the inventive method for electrostatic spinning to obtain even further improved process products. By suitable choice of the solvent and / or the added substances, it is possible to adjust preferably the fiber diameter of the fibers obtained in the process according to the invention. Also, when spinning from a solution, the content of polymer in the same can vary accordingly, in particular also increase. The polarity of the solvent can be further increased or increased by adding a substance with a very high dielectric constant. For a solution of polystyrene in dichloromethane or ethyl acetate, this is e.g. possible by adding acetamide. However, it has been found that it is not sufficient to increase the polarity of the solvent. Of crucial importance to the present invention is therefore that both a charge carrier, as well as a polar solvent is present, which probably stabilizes the charge carrier.
Gemäß einer bevorzugten Ausführungsform weist das Lösungsmittel mit einer vergleichsweisen großen Dielektrizitätskonstanten eine relative Dielektrizitätskonstante von wenigstens 15,0 bei einer Temperatur von 20 °C auf. Des weiteren ist bevorzugt, daß die zur Erhöhung der Polarität des Lösungsmittels verwendete Substanz mit sehr hoher Dielektrizitätskonstante bzw. verwendeten Substanzen mit sehr hohen Dielektrizitätskonstanten jeweils eine relative Dielektrizitätskonstante von wenigstens 20,0, weiter bevorzugt von wenigstens 30,0 bei 20 °C aufweist bzw. aufweisen.According to a preferred embodiment, the solvent having a comparatively large dielectric constant has a relative dielectric constant of at least 15.0 at a temperature of 20 ° C. Furthermore, it is preferred that the substance used to increase the polarity of the solvent having a very high dielectric constant or substances having very high dielectric constants respectively has or has a relative dielectric constant of at least 20.0, more preferably of at least 30.0 at 20 ° C. . exhibit.
Im Zusammenspiel mit den oben aufgeführten polaren Lösungsmitteln sind erstaunlicherweise sehr viele Substanzen als Ladungsträger geeignet, die dann nicht unbedingt über ein Oxidationspotential verfügen müssen.In combination with the polar solvents listed above, surprisingly many substances are suitable as charge carriers, which then do not necessarily have to have an oxidation potential.
Von besonderer Bedeutung für die Verwendung der gemäß dem erfindungsgemäßen Verfahren hergestellten Fasern bzw. des nach dem erfindungsgemäßen Verfahren hergestellten Fasermaterials zur Herstellung von Luftfiltern ist, daß diese Ladungen stabil über einen langen Zeitraum beibehalten, um neben einer rein mechanischen Abscheidung von Staubpartikeln auch eine elektrostatische Abscheidung von Staubpartikeln zu ermöglichen. Hierfür haben sich insbesondere Subtanzen als äußerst wirkungsvolle Zusätze erwiesen, die große π-Elektronensysteme besitzen, welche vorteilhafterweise mit Aminogruppen bzw. Aminofunktionen wechselwirken können. Als Beispiele sind Farbstoffderivate des Fuchsins, wie Kristallviolett und Malachingrün, Rhodamine, Azofarbstoffe mit zusätzlichen Amingruppen, wie Methylrot, und andere, wie bspw. Auramin, Safranin oder Oracetblau zu nennen. Neben Azo-Farbstoffen sind auch Diazonium-Farbstoffe, vorzugsweise Diazoechtsalze, wie z.B. Echtblausalz B bzw. BB, Echtviolettsalz B oder Echtrotsalz GG, geeignet. Ebenso haben sich Charge-Transfer-Komplexe, wie z.B. aus Kristallviolett und lod oder aus Chinon und Hydrochinon, als wirkungsvoll im Sinne der vorliegende Erfindung erwiesen. Überraschenderweise ist ein Großteil der angeführten Farbstoffe den basischen- bzw. sauren Farbstoffen zuzuordnen, d.h. es handelt sich um Salze aus negativ bzw. positiv geladenen Farbstoffmolekülen. Hieraus ist zu schließen, daß von vornherein geladene Farbstoffmoleküle einen besonders geeigneten Zusatz bei dem erfindungsgemäßen Verfahren darstellen.Of particular importance for the use of the fibers produced by the process according to the invention or the fiber material produced by the process according to the invention for the production of air filters is that these charges stable over a long period maintained in addition to a purely mechanical deposition of dust particles and an electrostatic deposition to allow dust particles. For this purpose, in particular substances have been found to be extremely effective additives that have large π-electron systems, which can advantageously interact with amino groups or amino functions. Examples include dye derivatives of fuchsin such as crystal violet and malachine green, rhodamines, azo dyes with additional amine groups such as methyl red, and others such as auramine, safranine or oracetic blue. In addition to azo dyes, diazonium dyes, preferably diazo salts, e.g. Echtblausalz B or BB, Echtviolettsalz B or Echtrotsalz GG suitable. Likewise, charge transfer complexes such as e.g. crystal violet and iodine, or quinone and hydroquinone, have been found to be effective in the present invention. Surprisingly, much of the cited dyes are attributed to the basic or acid dyes, i. they are salts of negatively or positively charged dye molecules. It can be concluded that dye molecules charged from the outset represent a particularly suitable additive in the process according to the invention.
Auch bei diesen Substanzen läßt sich die Wirkung beim Einsatz von stärker polaren Lösungsmitteln oder beim Einsatz von Lösungsmitteln mit polaritätssteigernden Zusätzen verstärken. Dabei hat sich unerwarteter Weise gezeigt, daß Substanzen mit einem ausgedehnten π-Elektronensystem, das vorzugsweise resonanzstabilisiert ist, besonders gut als Zusatz beim erfindungsgemäßen Verfahren geeignet sind, wenn sie funktionelle Gruppen wie Amino-, Amido- , Imino-, Azo-, Nitro-, Carboxy-, Diazonium-, Hydroxy-, Thio-, Sulfo- oder Halogengruppen enthalten. Sie können aber auch ausgewählt sein aus der Gruppe der organischen Farbstoffe, deren Vorstufen oder Derivate, der Metallocene und der Phthalocyanine sowie aus der Gruppe der optischen Aufheller, wie bspw. Blankophor R.Even with these substances, the effect can be enhanced when using more polar solvents or when using solvents with polarity-enhancing additives. It has unexpectedly been found that substances with an extended π-electron system, which is preferably resonance-stabilized, are particularly well suited as an additive in the process according to the invention if they contain functional groups such as amino, amido, imino, azo, nitro , Carboxy, diazonium, hydroxy, thio, sulfo or halogen groups. You can but also be selected from the group of organic dyes, their precursors or derivatives, metallocenes and phthalocyanines and from the group of optical brighteners, such as, for example, Blankophor R.
Der Zusatz der einen oder mehreren Substanzen zu der Polymerlösung oder Polymerschmelze kann erfindungsgemäß über einen relativ breiten Bereich erfolgen. Der Fachmann wird hier anhand der angestrebten und gewünschten Produkteigenschaften im Endprodukt problemlos den erforderlichen Gewichtsanteil ermitteln. Grundsätzlich ist aber bevorzugt, wenn der Zusatz bei einem oder mehreren Substanzen in einer Menge von 0,1 bis 50 Gew.-% der Polymerlösung oder Polymerschmelze erfolgt, stärker bevorzugt in einer Menge von 0,5 bis 5 Gew.-%.The addition of the one or more substances to the polymer solution or polymer melt can take place according to the invention over a relatively broad range. The person skilled in the art will easily determine the required proportion by weight based on the desired and desired product properties in the end product. In principle, however, it is preferred if the addition of one or more substances takes place in an amount of from 0.1 to 50% by weight of the polymer solution or polymer melt, more preferably in an amount of from 0.5 to 5% by weight.
In Bezug auf die Produkteigenschaften der nach dem erfindungsgemäßen Verfahren hergestellten Fasern bzw. des Faserprodukts ist anzumerken, daß Farbstoffe häufig bereits in sehr geringen Konzentrationen eine vergleichsweise intensive Färbung hervorrufen. Da mit Ausnahme von Anwendungen in Spezialgebieten häufig erwünscht ist, daß Luftfilter weiß oder bestenfalls schwach gefärbt sind, ist es erfindungsgemäß bevorzugt, wenn die der Polymerlösung bzw. der Polymerschmelze zugesetzten Substanzen farblos sind. Alternativ ist es bevorzugt, die vorstehend aufgeführten Zusätze, sofern sie farbig sind, so zu verändern, daß sie farblos erscheinen, ohne dabei ihre Wirkung zu verlieren. Dem Fachmann stehen hierfür allgemein bekannte chemische Umsetzungen zur Verfügung, wie z.B. die Alkylierung, Acylierung, Veresterung, Silylierung, Diazotierung, Oxidation oder die Umsetzung mit Halogenen, bevorzugt mit Chlor, oder starken Säuren oder Basen, Stickoxiden oder Schwefeloxiden. Hier haben sich Halogenwasserstoffe, wie z.B. Salzsäuregas, oder Basen, wie z.B. Ammoniak, besonders bewährt.With regard to the product properties of the fibers or the fiber product produced by the process according to the invention, it is to be noted that dyes often cause comparatively intense dyeing even at very low concentrations. Since, with the exception of applications in special fields, it is often desirable for air filters to be white or at best slightly colored, it is preferred according to the invention for the substances added to the polymer solution or the polymer melt to be colorless. Alternatively, it is preferable to change the additives listed above, if they are colored, so that they appear colorless without losing their effect. For this purpose, generally known chemical reactions are available to the person skilled in the art, e.g. the alkylation, acylation, esterification, silylation, diazotization, oxidation or the reaction with halogens, preferably with chlorine, or strong acids or bases, nitrogen oxides or sulfur oxides. Here, hydrogen halides, e.g. Hydrochloric acid gas, or bases, e.g. Ammonia, especially proven.
Grundsätzlich lassen sich sämtliche Polymere mit dem erfindungsgemäßen Verfahren verspinnen, die aus einer Lösung oder aus der Schmelze heraus verspinnbar sind. Hier sind insbesondere in organischen Lösungsmitteln lösliche Polymere zu erwähnen, wie Polystyrol, Polycarbonat, Polyvinylchlorid, Polyacrylat, Polymethacrylat, Polyvinylacetat, Polyvinylacetal, Polyvinylether, Polyurethan, Polyamid, Polysulfon, Polyethersulfon, Polyacrlynitril, Cellulosederivate sowie Mischungen und Copolymere dieser Polymere. Als Thermoplaste sind hier bspw. Polyolefine, Polyester, Polyoxymethylen, Polychlortrifluorethylen, Polyphenylensulfid, Polyaryletherketon, Polyvinylidenfluorid sowie Mischungen und Copolymere dieser Polymere zu nennen. Weiterhin haben sich die Copolymere von Polystyrol, wie z.B. Styrol/Acrylnitril-Copolymer, Styrol/Butadien/Styrol-Copolymer, Acrylnitril/Butadien/Styrol-Copolymer, als besonders geeignet erwiesen.In principle, all polymers can be spun with the process according to the invention, which can be spun from a solution or from the melt. In particular, polymers soluble in organic solvents are mentioned here, such as polystyrene, polycarbonate, polyvinyl chloride, polyacrylate, polymethacrylate, polyvinyl acetate, polyvinyl acetal, polyvinyl ether, polyurethane, polyamide, polysulfone, polyethersulfone, polyacrylonitrile, cellulose derivatives, and the like Mixtures and copolymers of these polymers. As thermoplastics here are, for example, polyolefins, polyesters, polyoxymethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyaryletherketone, polyvinylidene fluoride and mixtures and copolymers of these polymers mentioned. Furthermore, the copolymers of polystyrene, such as styrene / acrylonitrile copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / butadiene / styrene copolymer have been found to be particularly suitable.
Die vorliegende Erfindung wird nachfolgend anhand von Beispielen näher erläutert, die ausschließlich dem besseren Verständnis der Erfindung dienen sollen und keinesfalls zu deren Einschränkung.The present invention will be explained in more detail by way of examples, which are intended solely for the better understanding of the invention and in no way to limit it.
In einer Laboranlage, bei der die Polymerlösung sehr langsam aus einer 5 ml Kolbenspritze durch eine Stahlnadel gedrückt wird, wird eine Lösung von 5 Gew.-% Polystyrol in Dichlormethan mit ca. 0,5 bis 2 g/l Rhodamin G6 zugesetzt. Bei einer an den Elektroden anliegenden Potentialdifferenz von 15 bis 50 kV entstehen Fasern mit einem Durchmesser von ca. 200 bis 1500 nm, wobei der maximale Anteil einen Durchmesser von etwa 600 nm besitzt.In a laboratory plant in which the polymer solution is very slowly forced out of a 5 ml syringe through a steel needle, a solution of 5% by weight of polystyrene in dichloromethane with about 0.5 to 2 g / l rhodamine G6 is added. With a potential difference of 15 to 50 kV applied to the electrodes, fibers with a diameter of approximately 200 to 1500 nm are formed, the maximum portion having a diameter of approximately 600 nm.
Mit dem erfindungsgemäßen Verfahren lassen sich auf diese Weise 3 ml und mehr Polymerlösung pro Stunde verspinnen. Im Gegensatz dazu war es mit dem aus dem Stand der Technik bekannten Verfahren nur möglich 0,32 ml Polymerlösung pro Stunde zu verspinnen. Ebenso war es nicht möglich Polystyrollösungen in Dichlormethan mit einem Anteil von weniger als 10 Gew.-% elektrostatisch zu verspinnen. Aufgrund der hohen Konzentration erhält man im Stand der Technik darüberhinaus auch deutlich dickere Fasern mit einem Durchmesser von etwa 20 µm. Die vorliegende Erfindung erlaubt es daher vorteilhafterweise auch Polymere in einem elektrostatischen Spinnverfahren zu verspinnen, die bisher nicht bzw. bisher nicht in Konzentrationen von weniger als 10 % zu verspinnen waren. Dies ist insbesondere mit Lösungen von Polystyrol, Polycarbonat, Polyacrylonitril, Polymethylmethacrylat möglich, wobei diese Polymere auch bei Konzentrationen unter 10 Gew.-% Polymeranteil an der Lösung versponnen werden können, insbesondere bis zu einer Konzentration von etwa 3 Gew.-%.With the method according to the invention, 3 ml and more polymer solution per hour can be spun in this way. In contrast, with the method known from the prior art, it was only possible to spin 0.32 ml of polymer solution per hour. Likewise, it was not possible to electrostatically polystyrene solutions in dichloromethane with a proportion of less than 10 wt .-%. Due to the high concentration obtained in the prior art beyond also much thicker fibers with a diameter of about 20 microns. The present invention therefore advantageously also allows polymers to be spun in an electrostatic spinning process which have hitherto not or until now not been able to be spun in concentrations of less than 10%. This is possible, in particular, with solutions of polystyrene, polycarbonate, polyacrylonitrile, polymethyl methacrylate, these polymers also being able to be spun onto the solution at concentrations below 10% by weight of polymer content, in particular up to a concentration of about 3% by weight.
Claims (8)
- Process for producing fibres or a fibrous product in an electrostatic spinning process, wherein polymers are spun from solution and/or from the melt and the solution and/or the melt has or have added to it or them before spinning one or more oxidizable substances or substances having a π-electron system and a polar solvent and/or a substance for increasing the polarity of the solvent and the polymer solution or polymer melt is spray dispensed by the anode, the added oxidizable substance(s) or substance(s) having a π-electron system at least stabilizing any positive charge, so that the fibres or the fibrous product bear(s) an electric charge after spinning.
- Process according to any one of the preceding claims, characterized in that the added oxidizable substance(s) or substance(s) having a π-electron system is or are selected from the group consisting of the organic dyes, preferably the basic or acidic dyes, their precursors or derivatives, the charge transfer complexes, the metallocenes and the phthalocyanines and the optical brighteners.
- Process according to any one of the preceding claims, characterized in that the added oxidizable substance(s) or substance(s) having a π-electron system has at least one functional group having charge-stabilizing properties, especially an amino, amido, imino, azo, diazonium, nitro, carboxyl, hydroxyl, thio, sulpho or halo group.
- Process according to any one of the preceding claims, characterized in that the spinning is effected from a solution in especially butanone, acetonitrile, dimethyl sulphoxide, water, dimethylformamide, formamide, N-methylformamide, dichloromethane, ethyl acetate, acetone, ethanol or ethylene glycol solvent.
- Process according to any one of the preceding claims, characterized in that the one or more oxidizable substance (5) or substance(s) having a π-electron system are added in an amount of 0.1% to 50% by weight of the polymer solution or polymer melt, preferably in an amount of 0.5% to 5% by weight.
- Process according to any one of the preceding claims, characterized in that the added oxidizable substance(s) or substance(s) having a π-electron system are colourless.
- Process according to any one of Claims 1 to 7, characterized in that the added oxidixable substance(s) or substance(s) having a π-electron system is or are decolourized by chemical reaction, especially by alkylation, acylation, esterification, silylation, diazotization, oxidation or by reaction with halogens, preferably with chlorine, or strong acids or bases, nitrogen oxides or sulphur oxides, before being added to the polymer solution or polymer melt.
- Use of fibres or of a fibrous product produced by a process according to any one of the preceding claims, for producing air filter media, especially for producing cabin air filters, circulating air filters, cleanroom filters, waste air filters, living room filters or vacuum cleaner filters.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10137160 | 2001-07-30 | ||
| DE10137160 | 2001-07-30 | ||
| DE10155448A DE10155448A1 (en) | 2001-07-30 | 2001-11-12 | Process for the production of fibers or a fiber product in an electrostatic spinning process |
| DE10155448 | 2001-11-12 | ||
| PCT/DE2002/002704 WO2003014430A1 (en) | 2001-07-30 | 2002-07-23 | Method for the production of fibres or a fibrous product in an electrostatic spinning method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1417360A1 EP1417360A1 (en) | 2004-05-12 |
| EP1417360B1 true EP1417360B1 (en) | 2004-12-22 |
Family
ID=26009812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02754415A Expired - Lifetime EP1417360B1 (en) | 2001-07-30 | 2002-07-23 | Method for the production of fibres or a fibrous product in an electrostatic spinning method |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20040207126A1 (en) |
| EP (1) | EP1417360B1 (en) |
| WO (1) | WO2003014430A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6743273B2 (en) | 2000-09-05 | 2004-06-01 | Donaldson Company, Inc. | Polymer, polymer microfiber, polymer nanofiber and applications including filter structures |
| EP1590066A2 (en) * | 2003-02-05 | 2005-11-02 | HELSA-WERKE Helmut Sandler GmbH & Co. KG | Filter element and method for the production thereof |
| DE102008022759B4 (en) * | 2007-05-17 | 2019-03-07 | Sumitomo Chemical Co. Ltd. | Process for producing a polyethersulfone fiber, polyethersulfone fiber and their use |
| ES2932986T3 (en) | 2009-03-19 | 2023-01-30 | Emd Millipore Corp | Removal of microorganisms from liquid samples by using nanofiber media for filtration |
| EP2603611B1 (en) | 2010-08-10 | 2019-12-18 | EMD Millipore Corporation | Method for retrovirus removal |
| CN105413480B (en) | 2011-04-01 | 2019-03-29 | Emd密理博公司 | Composite structure containing nanofiber |
| US9365951B2 (en) | 2014-01-30 | 2016-06-14 | Kimberly-Clark Worldwide, Inc. | Negative polarity on the nanofiber line |
| WO2015200239A1 (en) | 2014-06-26 | 2015-12-30 | Emd Millipore Corporation | Filter structure with enhanced dirt holding capacity |
| KR102206963B1 (en) | 2015-04-17 | 2021-01-25 | 이엠디 밀리포어 코포레이션 | Method of purifying a biological material of interest in a sample using nanofiber ultrafiltration membranes operated in tangential flow filtration mode |
| US9951443B2 (en) * | 2015-12-31 | 2018-04-24 | University Of Tartu | Separators, electrodes, half-cells, and cells of electrical energy storage devices |
| US11180867B2 (en) | 2019-03-20 | 2021-11-23 | University Of Kentucky Research Foundation | Continuous wet-spinning process for the fabrication of PEDOT:PSS fibers with high electrical conductivity, thermal conductivity and Young's modulus |
| CN116043339B (en) * | 2022-07-19 | 2024-05-31 | 国家粮食和物资储备局科学研究院 | Nanofiber delivery carrier and preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US705691A (en) * | 1900-02-20 | 1902-07-29 | William James Morton | Method of dispersing fluids. |
| US1935205A (en) * | 1927-12-13 | 1933-11-14 | Celanese Corp | Manufacture of new dyestuffs and the application thereof |
| US2197896A (en) * | 1937-02-15 | 1940-04-23 | Du Pont | Artificial wool |
| US3411903A (en) * | 1964-11-23 | 1968-11-19 | Xerox Corp | Xerographic method and plate comprising photoconductive insulating fibers |
| US4657793A (en) * | 1984-07-16 | 1987-04-14 | Ethicon, Inc. | Fibrous structures |
| DE3837345A1 (en) * | 1988-11-03 | 1990-05-10 | Hoechst Ag | USE OF COLORLESS HIGH GRADE FLUORATED AMMONIUM AND IMMONIUM COMPOUNDS AS LOADING AGENTS FOR ELECTROPHOTOGRAPHIC RECORDING METHODS |
| ES2218521T3 (en) * | 1993-03-09 | 2004-11-16 | Trevira Gmbh | ELECTREPE FIBERS WITH AN IMPROVED LOAD STABILITY, THE PROCESS FOR THEIR PRODUCTION AND TEXTILE MATERIALS CONTAINING THESE ELECTREPE FIBERS. |
| US6800155B2 (en) * | 2000-02-24 | 2004-10-05 | The United States Of America As Represented By The Secretary Of The Army | Conductive (electrical, ionic and photoelectric) membrane articlers, and method for producing same |
| DE10063518C2 (en) * | 2000-12-20 | 2003-11-20 | Sandler Helmut Helsa Werke | Process for the electrostatic spinning of polymers to obtain nano and microfibers |
-
2002
- 2002-07-23 US US10/481,805 patent/US20040207126A1/en not_active Abandoned
- 2002-07-23 WO PCT/DE2002/002704 patent/WO2003014430A1/en not_active Application Discontinuation
- 2002-07-23 EP EP02754415A patent/EP1417360B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US20040207126A1 (en) | 2004-10-21 |
| EP1417360A1 (en) | 2004-05-12 |
| WO2003014430A1 (en) | 2003-02-20 |
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