EP3414374A1 - Procédé de production de fibres de carbone à partir de fibres de cellulose traitées avec des sels d'acide sulfonique - Google Patents
Procédé de production de fibres de carbone à partir de fibres de cellulose traitées avec des sels d'acide sulfoniqueInfo
- Publication number
- EP3414374A1 EP3414374A1 EP17705035.8A EP17705035A EP3414374A1 EP 3414374 A1 EP3414374 A1 EP 3414374A1 EP 17705035 A EP17705035 A EP 17705035A EP 3414374 A1 EP3414374 A1 EP 3414374A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- weight
- fibers
- cellulose fibers
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical class OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 title claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910052799 carbon Inorganic materials 0.000 title abstract description 15
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 29
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 26
- 239000004917 carbon fiber Substances 0.000 claims abstract description 26
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 31
- 229920002678 cellulose Polymers 0.000 claims description 21
- 239000001913 cellulose Substances 0.000 claims description 21
- 238000009987 spinning Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- GDCXBZMWKSBSJG-UHFFFAOYSA-N azane;4-methylbenzenesulfonic acid Chemical compound [NH4+].CC1=CC=C(S([O-])(=O)=O)C=C1 GDCXBZMWKSBSJG-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000000835 fiber Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 25
- 239000000654 additive Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000000197 pyrolysis Methods 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000010924 continuous production Methods 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 polysiloxane Polymers 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- KBPZVLXARDTGGD-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;iron Chemical compound [Fe].OC(=O)C(O)C(O)C(O)=O KBPZVLXARDTGGD-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- MBDWLVJKYHECGF-UHFFFAOYSA-M azanium;n-sulfonatosulfamate Chemical compound [NH4+].[O-]S(=O)(=O)NS([O-])(=O)=O MBDWLVJKYHECGF-UHFFFAOYSA-M 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Definitions
- the invention relates to a process for the production of carbon fibers from cellulose fibers, which is characterized in that cellulose fibers which are a sulfonic acid salt of the formula I.
- R1 is a hydrocarbon group and K + is a cation, are converted to carbon fibers.
- Carbon fibers can be made by pyrolysis of polyacrylonitrile fibers or cellulose fibers.
- cellulose fibers e.g. Cotton
- synthetically produced cellulose fibers obtained by digesting wood. Because of the large and cheap raw material base, synthetically produced cellulose fibers are particularly interesting starting materials for the production of carbon fibers.
- EP-A 1669480 describes the production of carbon fibers from cellulose fibers. The cellulose fibers used are impregnated with a polysiloxane.
- Viscose fibers are used as cellulose fibers.
- the cellulose fibers are added with an additive which increases the strength.
- PCT / EP2015 / 060479 (PF 76706) describes a process for the production of carbon fibers from cellulosic fibers in which the cellulosic fibers obtained from a spinning bath are not dried before being subsequently treated with additives.
- the viscose fibers contain ammonium compounds.
- Ammoniumimidosulfonate thiourea is also used as the ammonium compound.
- the carbon yield should be as high as possible, that is, the carbon of the starting fiber is transferred as completely as possible into the carbon fiber.
- the carbon yield is not yet satisfactory. Part of the carbon of cellulose is lost through decomposition into ultimately carbon monoxide and carbon dioxide. Too should the mechanical properties of the carbon fibers obtained from cellulose fibers, such as elasticity, are further improved.
- the object of the present invention was therefore an improved process for the production of carbon fibers from cellulose fibers.
- the cellulosic fibers which are converted to carbon fibers contain a sulfonic acid salt of formula I above.
- sulfonic acid salt also includes mixtures of sulfonic acid salts.
- R 1 is a hydrocarbon group having 1 to 20 C atoms, more preferably a hydrocarbon group having 2 to 15 C atoms, and most preferably a hydrocarbon group having 5 to 15 C atoms.
- R 1 is an aromatic group or contains an aromatic group.
- R 1 may be an optionally substituted aryl group, for example an optionally substituted phenyl, diphenyl or naphthyl group, or R 1 may be an alkaryl group, for example an optionally substituted phenyl, diphenyl or naphthyl group bound to the sulfur atom via an alkylene group.
- R 1 is a group of formula III
- R a to R e are independently an H atom or a C 1 to C 4 alkyl group and R x is a C 1 to C 4 alkylene group.
- At least 3 of the radicals R a to R e are an A atom.
- R 1 is a phenyl, tolyl or xylyl group, in particular a tolyl group.
- the cation in formula I may be any inorganic or organic cation, e.g. a metal cation or a cationic, organic ring system of carbon atoms and optionally heteroatoms such as N, O or S.
- R 2 to R 5 are independently an H atom or an organic group having 1 to 20 C-atoms.
- R 2 to R 5 independently of one another are an H atom or an alkyl group having 1 to 4 C atoms.
- at least two of the radicals R 2 to R 5 are an H atom.
- the cation is ammonium, that is (NH 4 ) + .
- the sulfonic acid salt of the formula I preferably has a solubility in water of at least 10 parts by weight, more preferably of at least 20 parts by weight of sulfonic acid salt per 100 parts by weight of water under normal conditions (20 ° C, 1 bar). In a most preferred embodiment, the sulfonic acid salt is ammonium tosylate.
- the cellulose fiber preferably contains the sulfonic acid salt in such an amount that the sulfur content caused by the sulfonic acid salt is 0.1 to 3% by weight based on the total weight of the dried cellulose fiber;
- the content of sulfur caused by the sulfonic acid salt is particularly preferably at least 0.2% by weight, in particular at least 0.5% by weight, based on the total weight of the dried cellulose fiber.
- the sulfur content caused by the sulfonic acid salt is in the range of 0.5 to 2 weight percent, based on the total weight of the dried cellulose fiber.
- Cellulosic fibers are here understood to mean fibers which consist of more than 60% by weight, in particular more than 80% by weight, particularly preferably more than 90% by weight, of cellulose or modified cellulose.
- the cellulosic fibers consist of more than 98% by weight, most preferably 100% by weight, of cellulose or modified cellulose.
- modified cellulose is meant cellulose in which hydroxyl groups are etherified or esterified, e.g. it may be cellulose acetate, cellulose formate, cellulose propionate, cellulose carbamate or cellulose allophanate.
- the cellulose fibers are preferably fibers which contain more than 60% by weight, in particular more than 80% by weight, more preferably more than 90% by weight and in the particularly preferred embodiments more than 98% by weight. , or consist of 100 wt.% Of cellulose.
- the cellulose fibers may be natural cellulose fibers, eg cotton fibers, or synthetic cellulose fibers.
- Synthetic cellulose fibers are fibers in which cellulose, which has been obtained from any cellulose-containing organic materials, synthetic, that is transferred by a technical process in the fiber form.
- Such synthetic cellulose fibers are in particular: Viscose fibers produced by the viscose process,
- Lyocell® fibers made from a spinning solution containing NMMO (N-methylmorpholine N-oxide) as a solvent and cellulose fibers recovered from ionic liquid spinning solutions as a solvent, e.g. in WO 2007/076979.
- NMMO N-methylmorpholine N-oxide
- it is cellulose fibers which have a water content of more than 20 parts by weight of water, in particular more than 30 parts by weight of water, more preferably more than 50 parts by weight of water, most preferably more than 70 parts by weight of water per 100 parts by weight of cellulose fiber.
- the water content is not higher than 500, especially not higher than 300 parts by weight of water per 100 parts by weight of cellulose fiber.
- the cellulose fiber having the above water content can be easily obtained by, for example, dipping a dried cellulose fiber in water. Both natural cellulose fibers and synthetic cellulose fibers are suitable for this purpose. In a preferred embodiment, synthetic cellulose fibers are used.
- synthetic cellulose fibers are used which were prepared immediately before by a spinning process. The cellulose fibers are then preferably through
- a spin bath is prepared by dissolving cellulose in a solvent. From this spinning bath, the cellulose fiber is obtained by coagulation of the cellulose in the form of a fiber. Thereafter, the obtained cellulose fibers are washed with water to remove adhering solvent or adhesive additives from the spinning bath.
- the contact with water is preferably carried out so that the cellulose fiber absorbs water in the desired amount indicated above.
- the cellulose fiber can be immersed in water for a sufficient time or passed through a sufficiently long water bath in a continuous process.
- cellulose fibers In the production of the cellulose fibers preferably no process measures for drying take place.
- the cellulose fiber obtained in the spinning process is without prior drying washed with water and then, of course, again without prior drying, brought into contact with the solution of the additive. It is therefore a so-called "never dried" cellulose fiber which has the above content of water.
- the cellulose fibers preferably the aqueous cellulose fibers (never dried), are contacted with a solution of the above sulfonic acid salt of formula I.
- hydrophilic solvent especially in water or in a hydrophilic organic solvent, e.g. Alcohols or ethers, or mixtures thereof.
- hydrophilic solvents are water or mixtures of water with other hydrophilic organic solvents which are immiscible with water indefinitely, with the water content in the solvent mixture in a preferred embodiment being at least 50% by weight in the latter case.
- the cellulose fiber can be immersed in the solution for a sufficient time or be passed through a sufficiently long solution bath in a continuous process.
- the cellulose fiber is continuously passed through the solution of sulfonic acid salts.
- the content of the sulfonic acid salts in the solution is, for example, 0.05 to 5 mol / per liter of solution, preferably 0.1 mol to 2 mol / liter of solution.
- the contact time of the cellulose fiber with the solution of the sulfonic acid salts is preferably at least 0.5 seconds, more preferably at least 2 and most preferably at least 10 seconds. In general, it is not longer than 100 seconds, preferably not longer than 30 seconds.
- the cellulose fiber can also be equipped with other additives.
- the solution of the sulfonic acid salt may contain such further additives;
- the cellulose fiber can also be brought into contact with solutions of other additives in further process steps.
- Particularly suitable as further additives are compounds which have a solubility in water of at least 10 parts by weight, preferably of at least 20 parts by weight, in particular of at least 30 parts by weight, per 100 parts by weight of water under normal conditions (20 ° C, 1 bar) own.
- the additives are preferably low molecular weight compounds which have a maximum molecular weight of 1000 g / mol, particularly preferably not more than 500 g / mol, in particular not more than 300 g / mol.
- Suitable further additives are, for example, salts or acids, for example inorganic salts, inorganic acids, organic salts or organic acids, such as carboxylic acids or phosphonic acids.
- salts mentioned are phosphates, hydrogen phosphates, phosphites, hydrogen phosphites, sulfates or sulfites, or chlorides.
- the cations of the above may be, for example, metal cations, preferably alkali metal cations such as Na + or K + , or ammonium (NhV).
- the cellulose fiber contains predominantly or exclusively sulfonic acid salts of the formula I as an additive.
- more than 50% by weight, particularly preferably more than 80% by weight, very particularly preferably more than 90% by weight, of the total amount of additives with which the cellulose fiber is provided is sulfonic acid salts of the formula I.
- the additives with which the carbon fiber is provided are exclusively sulfonic acid salts of the formula I.
- the production of the cellulose fiber in the spinning process and subsequently the further processing by washing the cellulose fiber and contacting the cellulose fiber with the solution of the additives are preferably components of a continuous overall process.
- the cellulose fiber is generally fed to the individual steps of further processing after their production via movable rollers.
- the additized cellulosic fiber may be dried, e.g. at temperatures of 50 to 300 ° C. Drying of this type is recommended when the additized cellulose sebase is first to be stored or transported before it is converted into a carbon fiber.
- the additivated cellulose fiber is converted by pyrolysis in a carbon fiber.
- the pyrolysis is generally carried out at temperatures of 500 to 1600 ° C. It can e.g. under air or under inert gas, e.g. Nitrogen or helium are performed. Preferably, it is carried out under a protective gas.
- the cellulose fiber Before pyrolysis, the cellulose fiber can be dried. For already dried and stored cellulose fibers, the drying may optionally be repeated. It is possible to use a multi-stage process in which the cellulose fiber is dried at temperatures in the range from 50 to 300 ° C. and then the pyrolysis is carried out at temperatures in the range from 500 to 1600 ° C., preferably 700 to 1500 ° C. Both during drying and pyrolysis, the temperature can be increased gradually or continuously.
- drying may take place in two or more stages, for example at 50 to 100 ° C in a first stage and at 100 to 200 ° C in a second stage.
- the contact time in the individual stages can be, for example, 5 to 300 seconds and 10 to 500 seconds in total during the drying.
- pyrolysis in which the temperature is continuously increased, e.g. starting at 200 ° C until finally reaching 1600 or 1400 or 1200 ° C.
- the temperature increase can take place, for example, at 1 to 20 Kelvin / minute.
- the cellulose fiber should preferably be exposed to a temperature in the range of 900 to 1600 ° C. for a period of 10 to 60 minutes.
- the carbon yield in the pyrolysis is generally 20 to 95% by weight; that is, the carbon fiber contains 20 to 95 percent by weight of the carbon contained in the cellulose fiber.
- the carbon yield is in particular from 70 to 95, particularly preferably from 70 to 90, very particularly preferably from 70 to 85,% by weight.
- the resulting carbon fiber has very good mechanical properties, in particular good strength and elasticity.
- a synthetic, tear-resistant cellulose fiber used for the production of car tires is used.
- Such cellulose fibers are known as tire cord fibers.
- the cellulose fiber used was made of cellulose dissolved in an ionic liquid.
- the cellulose fiber was obtained by coagulation of the cellulose from the spinning bath and not dried since its preparation. It had a water content greater than 70 parts by weight of water per 100 parts by weight of cellulose, hence the term "never-dried tire cord fiber".
- the equipment and drying of the cellulose fiber takes place in a continuous process on godets. Godets are rollers that allow the continuous flow of fiber along the system. There are 4 of these godets used.
- the loading of the fiber with the additives takes place via a dip bath.
- a hot air duct Between the third and fourth galette is a hot air duct, in which a drying takes place.
- a tension controlled winder winds up the finished and dried fiber material.
- Example 1 The carbonization of the dried cellulose fiber obtained was carried out in Example 1 and Comparative Example 1 also in a continuous process; in Comparative Examples 2 and 3, it was carried out batchwise
- Example 1 The never-dried tire cord fiber was wrapped in 2 turns around Galette 1 (room temperature,
- the sulfur content of the dried fiber was 1% by weight.
- the cellulose fiber thus produced was continuously derivatized and stabilized under protective gas.
- the residence times were 13.8 min at 200 ° C, 27.7 min at 210 ° C and 13.8 min at 240 ° C.
- the total residence time in the stabilization was corresponding to 55.2 min.
- the thread tension was 0.34 cN / tex.
- the resulting stabilized fiber was then carbonated continuously under inert gas. For this purpose, the fiber was subjected to tensile stress.
- the thread tension was 2.6 cN / tex.
- the residence times were 1.58 min at 310 and 510 ° C, 4.74 min at 750 ° C, 1 .58 min at 971 ° C and 4.74 min at 1400 ° C and a total of 12.65 min.
- Comparative Example 1 was carried out in exactly the same way as Example 1, except for the following.
- the never-dried tire cord fiber was not pulled through a 0.3 molar solution of ammonium tosylate but through a 1 molar solution of ammonium hydrogen phosphate.
- the phosphorus content of the dried fiber was 1% by weight.
- the total residence time in the stabilization was corresponding to 55.2 min.
- the thread tension was 0.38 cN / tex.
- the thread tension in the carbonization was 1.1 cN / tex. As the thread tension increased, the fiber ripped.
- Comparative Example 2 was carried out in exactly the same way as Example 1, except for the following
- the never-dried tire cord fiber was not pulled through a 0.3 molar solution of ammonium tosylate, but through a 0.3 molar solution of p-toluenesulfonic acid.
- the sulfur content of the dried fiber was 1% by weight.
- the cellulose fiber thus produced was very brittle and brittle. It could not be further processed in a continuous process as it does not withstand any tensile load.
- the cellulose fiber was therefore batch derivatized, stabilized and carbonized. The following temperature program is used:
- Comparative Example 3 was carried out in the same way as Comparative Example 2 except that the never-dried tire cord fiber was treated with no additive, neither ammonium tosylate nor toluenesulfonic acid, before it was dried.
- the never-dried tire cord fiber was dried in 7 turns around Galette 1 (80 ° C, 6.5 m / min) and through a heating channel (120 ° C, length:) on Galette 2 (room temperature, 6.5 m / min) and then on a coil wound.
- the carbonation yield indicates how much carbon of the cellulose in the cellulose fiber has been converted to carbon of the carbon fiber.
- the carbon content indicates to what weight% the carbon fiber consists of carbon.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16155261 | 2016-02-11 | ||
PCT/EP2017/052079 WO2017137285A1 (fr) | 2016-02-11 | 2017-02-01 | Procédé de production de fibres de carbone à partir de fibres de cellulose traitées avec des sels d'acide sulfonique |
Publications (4)
Publication Number | Publication Date |
---|---|
EP3414374A1 true EP3414374A1 (fr) | 2018-12-19 |
EP3414374B1 EP3414374B1 (fr) | 2023-06-07 |
EP3414374C0 EP3414374C0 (fr) | 2023-06-07 |
EP3414374B8 EP3414374B8 (fr) | 2023-07-19 |
Family
ID=55353080
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17705035.8A Active EP3414374B8 (fr) | 2016-02-11 | 2017-02-01 | Procédé de production de fibres de carbone à partir de fibres de cellulose traitées avec des sels d'acide sulfonique |
Country Status (6)
Country | Link |
---|---|
US (1) | US10995429B2 (fr) |
EP (1) | EP3414374B8 (fr) |
CA (1) | CA3014258C (fr) |
ES (1) | ES2954633T3 (fr) |
PL (1) | PL3414374T3 (fr) |
WO (1) | WO2017137285A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3083547B1 (fr) * | 2018-07-09 | 2021-07-30 | Inst De Rech Tech Jules Verne | Fibre de carbone et procede de fabrication d’une telle fibre de carbone a partir de cellulose |
TW202022182A (zh) * | 2018-10-10 | 2020-06-16 | 德商商先創國際股份有限公司 | 穩定先質纖維或薄膜以生產碳纖維或薄膜的方法 |
DE102020113807A1 (de) | 2020-05-22 | 2021-11-25 | centrotherm international AG | Endlosfasern auf Basis von Cellulose und/oder Cellulosederivaten, Verfahren zu deren Herstellung sowie deren Verwendung |
CN115368474B (zh) * | 2022-09-06 | 2023-11-28 | 绍兴文理学院 | 一种酒糟基莱赛尔纤维浆粕的制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3179605A (en) | 1962-10-12 | 1965-04-20 | Haveg Industries Inc | Manufacture of carbon cloth |
JPS5330810B2 (fr) | 1974-05-16 | 1978-08-29 | ||
JPS61113826A (ja) | 1984-11-07 | 1986-05-31 | Nitto Boseki Co Ltd | 不燃性繊維材料の製造方法 |
AT413824B (de) * | 2001-11-02 | 2006-06-15 | Chemiefaser Lenzing Ag | Verfahren zur behandlung von lösungsmittelgesponnenen cellulosischen fasern |
EP2984214A1 (fr) | 2013-04-12 | 2016-02-17 | The Procter & Gamble Company | Structures à fibres de polymères hydroxylés comprenant des sels de sulfonate d'alkyle d'ammonium et procédés de fabrication correspondants |
WO2015173243A1 (fr) | 2014-05-16 | 2015-11-19 | Basf Se | Procédé de production de fibres de carbone à partir de fibres de cellulose |
-
2017
- 2017-02-01 PL PL17705035.8T patent/PL3414374T3/pl unknown
- 2017-02-01 WO PCT/EP2017/052079 patent/WO2017137285A1/fr active Application Filing
- 2017-02-01 US US16/077,356 patent/US10995429B2/en active Active
- 2017-02-01 ES ES17705035T patent/ES2954633T3/es active Active
- 2017-02-01 EP EP17705035.8A patent/EP3414374B8/fr active Active
- 2017-02-01 CA CA3014258A patent/CA3014258C/fr active Active
Also Published As
Publication number | Publication date |
---|---|
CA3014258C (fr) | 2023-12-19 |
PL3414374T3 (pl) | 2023-09-25 |
EP3414374B1 (fr) | 2023-06-07 |
CA3014258A1 (fr) | 2017-08-17 |
ES2954633T3 (es) | 2023-11-23 |
EP3414374C0 (fr) | 2023-06-07 |
EP3414374B8 (fr) | 2023-07-19 |
US10995429B2 (en) | 2021-05-04 |
WO2017137285A1 (fr) | 2017-08-17 |
US20190062954A1 (en) | 2019-02-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE974057C (de) | Verfahren zur Herstellung von hochfesten Faeden oder Stapelfasern durch Verspinnen von Viscose | |
EP0797694B2 (fr) | Filaments cellulosiques files dans un solvant | |
EP3414374B1 (fr) | Procédé de production de fibres de carbone à partir de fibres de cellulose traitées avec des sels d'acide sulfonique | |
AT514475B1 (de) | Polysaccharidfaser und Verfahren zu ihrer Herstellung | |
EP3143187B1 (fr) | Procédé de production de fibres de carbone à partir de fibres de cellulose | |
DE102013002833B4 (de) | Verfahren zur Herstellung von Celluloseregeneratfasern und Verwendung der nach dem Verfahren hergestellten Celluloseregeneratfasern | |
DE202013011959U1 (de) | Direktgesponnene Cellulosefasern, deren Herstellung und Verwendung | |
DE69813276T2 (de) | Verfahren zur herstellung von fasern oder filamenten aus regenerierter zellulose | |
EP2460843B1 (fr) | Solutions polymères dans des liquides ioniques ayant une stabilité thermique et rhéologique améliorée | |
DE1469058A1 (de) | Verfahren zur Herstellung von Kunstfaeden | |
DE2752743C2 (de) | Verfahren zur Herstellung von Filamenten oder Folien durch Verspinnen einer Celluloselösung | |
EP0726974B1 (fr) | Procede de fabrication d'objets moules en cellulose | |
DE3336584A1 (de) | Verfahren zur herstellung von kohlenstoffasern oder grafitfasern | |
DE102004007616B4 (de) | Verfahren zur Herstellung von Fasern und anderen Formkörpern aus Cellulosecarbamat und/oder regenerierter Cellulose | |
DE212015000267U1 (de) | Carbonfasern aus Phosphor enthaltenden Cellulosefasern | |
WO1997004148A1 (fr) | Fibres de cellulose | |
EP2294259B1 (fr) | Fibre de cellulose et son procédé de fabrication | |
WO2021234152A1 (fr) | Fibres continues à base de cellulose et/ou de dérivés de cellulose, leur procédé de production et leur utilisation | |
DE3015565A1 (de) | Verfahren zur herstellung von geformten koerpern aus regenerierter cellulose aus spinnloesungen | |
DE876886C (de) | Verfahren zur Herstellung von Cellulosehydratfaeden durch Verspinnen von Viscose | |
DE2031308B2 (de) | Verfahren zur Herstellung von gekräuselten, regenerierten Cellulosefasern | |
DE1469064C (de) | Verfahren zum Herstellen von aus regenerierter Cellulose bestehenden Fäden, Fasern oder Folien | |
AT235463B (de) | Verfahren zur Herstellung von künstlichen Stapelfasern aus regenerierter Cellulose | |
WO2001062845A1 (fr) | Corps moule en cellulose et procede permettant de le produire | |
AT201226B (de) | Verfahren zur Herstellung von Fäden nach dem Viskose-Spinnverfahren |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20180904 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: HERMANUTZ, FRANK Inventor name: CWIK, TOMASZ Inventor name: ABELS, FALKO Inventor name: BUCHMEISER, MICHAEL R. Inventor name: MASSONNE, KLEMENS Inventor name: SPOERL, JOHANNA Inventor name: MERGER, MARTIN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: TECHNIKUM LAUBHOLZ GMBH |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BUCHMEISER, MICHAEL R. Inventor name: HERMANUTZ, FRANK Inventor name: SPOERL, JOHANNA Inventor name: MASSONNE, KLEMENS Inventor name: CWIK, TOMASZ Inventor name: MERGER, MARTIN Inventor name: ABELS, FALKO |
|
INTG | Intention to grant announced |
Effective date: 20220506 |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
INTC | Intention to grant announced (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20221110 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1575245 Country of ref document: AT Kind code of ref document: T Effective date: 20230615 Ref country code: DE Ref legal event code: R096 Ref document number: 502017014823 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PK Free format text: BERICHTIGUNG B8 |
|
RAP4 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: TECHNIKUM LAUBHOLZ GMBH |
|
U01 | Request for unitary effect filed |
Effective date: 20230705 |
|
U07 | Unitary effect registered |
Designated state(s): AT BE BG DE DK EE FI FR IT LT LU LV MT NL PT SE SI Effective date: 20230718 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: NO Ref legal event code: T2 Effective date: 20230607 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230908 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231007 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231007 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502017014823 Country of ref document: DE |
|
U20 | Renewal fee paid [unitary effect] |
Year of fee payment: 8 Effective date: 20240215 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20240319 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240222 Year of fee payment: 8 Ref country code: CH Payment date: 20240301 Year of fee payment: 8 |
|
26N | No opposition filed |
Effective date: 20240308 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20240131 Year of fee payment: 8 Ref country code: NO Payment date: 20240220 Year of fee payment: 8 |