DE1922335A1 - Flame retardant threads and fibers - Google Patents
Flame retardant threads and fibersInfo
- Publication number
- DE1922335A1 DE1922335A1 DE19691922335 DE1922335A DE1922335A1 DE 1922335 A1 DE1922335 A1 DE 1922335A1 DE 19691922335 DE19691922335 DE 19691922335 DE 1922335 A DE1922335 A DE 1922335A DE 1922335 A1 DE1922335 A1 DE 1922335A1
- Authority
- DE
- Germany
- Prior art keywords
- threads
- fibers
- solutions
- metal
- compounds
- 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
- 239000000835 fiber Substances 0.000 title claims description 26
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 6
- 239000003063 flame retardant Substances 0.000 title claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 41
- 150000002736 metal compounds Chemical class 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- -1 Polyterephthaloyl Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 2
- GUUTVNSLWGCVFC-UHFFFAOYSA-N 1-n',2-n'-diaminoethanediimidamide Chemical compound NN=C(N)C(N)=NN GUUTVNSLWGCVFC-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical group ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000985694 Polypodiopsida Species 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Inorganic materials [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004031 fumaroyl group Chemical group C(\C=C\C(=O)*)(=O)* 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/22—Halides of elements of Groups 5 or 15 of the Periodic Table
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/24—Flameproof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/21—Nylon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
WuppertalWuppertal
Aus der luxemburgischen Patentschrift Nr. 55 732 sind bereits Fäden aus Polyacyloxalamidrazon mit wiederkehrenden Einheiten der allgemeinen FormelFrom the Luxembourg patent no. 55 732 are already Threads made of polyacyloxalamidrazone with repeating units of the general formula
NH-N-C-C-N-NH-C-R-C-H2N NH2 0 0NH-NCCN-NH-CRCH 2 N NH 2 0 0
in der R einen geradkettigen oder verzweigten gesättigten oder ungesättigten aliphatischen Rest mit 2 bis 12 C-Atomen, einen cycloaliphatisehen, araliphatischen oder aromatischen Rest bedeutet, bekannt. Diese Fäden und Fasern sind nicht schwerentflammbar.in which R is a straight-chain or branched saturated or unsaturated aliphatic radical with 2 to 12 carbon atoms, a cycloaliphatic, araliphatic or aromatic one Remainder means known. These threads and fibers are not flame retardant.
Die vorliegende Erfindung betrifft die Herstellung von schwerentflammbaren Fäden und Fasern aus Polyterephthaloyloxalamidrazon und Polyfumaroyloxalamidrazon.The present invention relates to the production of flame-retardant threads and fibers from polyterephthaloyloxalamidrazone and polyfumaroyloxalamidrazone.
Es wurde gefunden, daß man schwerentflammbare Fäden und Farn aus Polyacyloxalamidrazon erhält, wenn man Fäden und Fa-It has been found that flame-retardant threads and ferns made of polyacyloxalamidrazone are obtained if threads and threads
009882/2038 " 2 "009882/2038 " 2 "
- 2 - Pos. GW 1477 J- 2 - Item GW 1477 J
sern aus Polyacyloxalamidrazonen, die als Säurekomponenten den Terephtaloyl - und/oder Fumaroylrest enthalten, mit der Lösung einer oder mehrerer Verbindungen der Metalle, Zink, Zinn, Cadmium, Barium, Strontium, Calcium, Antimon und Tantal reagieren läßt.acids from polyacyloxalamidrazones, which are used as acid components contain the terephtaloyl and / or fumaroyl radical with which Solution of one or more compounds of metals, zinc, tin, cadmium, barium, strontium, calcium, and antimony Lets tantalum react.
Polyterephthaloyloxalamidrazon und Polyfumaroyloxalamidrazon-Fäden können beispielsweise nach dem Verfahren des luxemburgischen Patentes Nr. 55 732 durch Verspinnen von wäßrigen alkalischen Lösungen der entsprechenden Polyacyloxalamidrazone hergestellt werden.Polyterephthaloyloxalamidrazone and polyfumaroyloxalamidrazone threads can for example by the process of Luxembourg patent No. 55 732 by spinning aqueous alkaline solutions of the corresponding Polyacyloxalamidrazone are produced.
Polyterephthaloyl- und Polyfumaroyloxalamidrazone sind beispielsweise in den luxemburgischen Patentschriften Nr. 54 und 57 177 beschrieben. Man erhält sie durch Umsetzung von Terephthaloyl- bzw. Fumaroylchlorid mit Oxalsäurebisamidrazon. Bekannt sind Polyterephthaloyl- und Fumaroyloxalaasidrazone mit reduzierten Viskositäten von o,2 bia 5,4. Bei dem erfindungsgemäßen Verfahren können jedoch auch Fäden und Fasern aus entsprechenden Polymeren mit höherem Molekulargewicht eingesetzt worden. Es ist nicht unbedingt erforderlich, Fäden "und Fasern aus reinem Polyterephthaloyloxalamidrazon öder" aus" reinem Polyfumaroyloxalamidrazon einzusetzen, obwohl diesem Verfahren der Vorzug gegeben wird. Es ist ebenso möglich. Fäden und Fasern aus Polyacyloxalamidrazonen zu verwenden, die als Säurekomponente sowohl den Terephthaloyl- als auch den Fumaroylrest enthalten. Die Herstellung derartiger Copolyacyloxalamidrazone ist ebenfalls in der luxemburgischen Patentschrift Nr. 54 747 beschrieben. Man erhält sie durch Umsetzung von Terephthaloyl- und Fumaroylchlorid mit Oxalsäurebisamidrazon. Man kann auch Fäden und Fasern einsetzen, die beide Polymere enthalten.Polyterephthaloyl and polyfumaroyloxalamidrazones are for example in Luxembourg Patent Nos. 54 and 57,177. It is obtained by implementing Terephthaloyl or fumaroyl chloride with oxalic acid bisamidrazone. Polyterephthaloyl and fumaroyloxalaasidrazone are known with reduced viscosities of 0.2 to 5.4. In the method according to the invention, however, threads and fibers can also be used from corresponding polymers with higher molecular weight have been used. It is not absolutely necessary to have threads "and fibers made of pure polyterephthaloyloxalamidrazone or" made of " to use pure polyfumaroyloxalamidrazone, although this Method is given preference. It is also possible. To use threads and fibers made of polyacyloxalamidrazones, which contain both the terephthaloyl and the fumaroyl radicals as acid components. The manufacture of such Copolyacyloxalamidrazone is also described in Luxembourg Patent No. 54,747. You get it through Conversion of terephthaloyl and fumaroyl chloride with oxalic acid bisamidrazone. You can also use threads and fibers that contain both polymers.
Ferner ist es bei dem erfindungsgemäßan. Verfahren ebenso möglich von Fäden und Fasern aus PolyterephthalojI- -^*3&r PoIy-It is also within the scope of the present invention. Process also possible from threads and fibers from PolyterephthalojI- - ^ * 3 & r PoIy-
009882/2038 ~3~ I009882/2038 ~ 3 ~ I
r .πr .π
. 3 _ Poe. GW 1477. 3 _ Poe. GW 1477
fumaroyloxalamidrazon auszugehen, die außer den Terephthaloyl- bzw. Fumaroyl-Säureeinheiten noch geringe Mengen anderer Säureeinheiten enthalten.fumaroyloxalamidrazone, which apart from the terephthaloyl or fumaroyl acid units still contain small amounts of other acid units.
Geeignete Metallverbindungen sind anorganische und organische Salze und Komplexverbindungen der Metalle Zink, Zinn, Cadmium, Barium, Strontium, Calcium, Antimon und Tantal.Suitable metal compounds are inorganic and organic salts and complex compounds of the metals zinc, tin, cadmium, Barium, strontium, calcium, antimony and tantalum.
Geeignet für die Behandlung des Polyterephthaloyl- bzw. des Polyfumaroyloxalamidrazons sind Lösungen dieser Metallverbindungen in Wasser, verdünnten wäßrigen Basen oder Säuren, sowie in organischen Lösungsmitteln, beispielsweise in Methanol, Äthanol, Dimethylsulfoxid, Hexamethylphosphorsäuretriamid, Sulfolan, Tetramethylharnstoff, Dimethylformamid, Pyridin und anderen Aminen sowie in speziellen Fällen auch in Chlorkohlenwasserstoffen, Estern oder Ketonen. Die Metallverbindungen können auch in Gemischen der genannten Lösungsmittel gelöst angewendet werden. Gut geeignet zur Durchführung des erfindungsgemäßen Verfahrens sind die folgenden Lösungen:Suitable for the treatment of polyterephthaloyl or des Polyfumaroyloxalamidrazons are solutions of these metal compounds in water, dilute aqueous bases or acids, as well in organic solvents, for example in methanol, ethanol, dimethyl sulfoxide, hexamethylphosphoric acid triamide, Sulfolane, tetramethylurea, dimethylformamide, pyridine and other amines and in special cases also in chlorinated hydrocarbons, Esters or ketones. The metal compounds can also be dissolved in mixtures of the solvents mentioned be applied. The following solutions are well suited for carrying out the method according to the invention:
wäßrige Zinn(II)chlorid-Lösungen äthanolische Zinn(II)chlorid-Lösungenaqueous tin (II) chloride solutions ethanolic tin (II) chloride solutions
Lösungen von Zinkverbindungen Zinkchlorid-Lösungen in 2n Ammoniumhydroxid Solutions of zinc compounds Zinc chloride solutions in 2N ammonium hydroxide
Lösungen von Cadmiumverbindungen Cadmiumsulfat-Lösungen in 2n Ammoniumhydroxid Solutions of cadmium compounds Cadmium sulfate solutions in 2N ammonium hydroxide
Lösungen von Bariumverbindungen wäßrige Bariumhydroxidlösungen Solutions of barium compounds aqueous barium hydroxide solutions
009882/2 038 "4" ' |009882/2 038 " 4 "'|
- 4 - Pos. GW 1477- 4 - Item GW 1477
wäßrige ammoniakalische Bariumchloridlösungenaqueous ammoniacal barium chloride solutions
wäßrige Strontiumhydroxidlösungenaqueous strontium hydroxide solutions
wäßrige ammoniakalische Strontiumchloridlösungenaqueous ammoniacal strontium chloride solutions
wäßrige Calciumhydroxidlösungenaqueous calcium hydroxide solutions
wäßrige ammoniakalische Calciumchloridlösungenaqueous ammoniacal calcium chloride solutions
Antimontrichloridlösungen in Dimethylformamid weinsaure Antimon(III)ChloridlösungenAntimony trichloride solutions in dimethylformamide tartaric antimony (III) chloride solutions
Vorteilhafterweise verwendet man gesättigte oder hochkonzentrierte Lösungen.. Es. können ..jedoch, auch, verdünnte. Lösungen β : j Anwendung finden. Zweckmäßig verwendet man Lösungen von Raumtemperatur, es können jedoch auch Lösungen höherer Temperatur verwendet werden.It is advantageous to use saturated or highly concentrated solutions .. Es. can .. however, also, diluted. Solutions β: j apply. Solutions at room temperature are expediently used, but solutions at a higher temperature can also be used.
Die Behandlung der PolyacyloxalamidrazonfSden und Fasern mit den Lösungen der Metallverbindungen kann beispielsweise durch Tauchen der Fäden oder Fasern in einer die Lösung der Metallverbindung enthaltenden Wanne erfolgen. Fasern können beispielsweise lose oder als Garn in Strangform in die Behandlungswanne eingeführt werden. Man kann auch Polyacyloxalamidrazonfäden, aufgewickelt auf einer Spule, in einer geeigneten Spulendruckwäsche der Einwirkung der Metallverbindung aussetzen. .The treatment of the PolyacyloxalamidrazonfSden and fibers with the solutions of the metal compounds can for example by Dipping the threads or fibers in a tub containing the solution of the metal compound. Fibers can, for example, be fed into the treatment tub loosely or as yarn in strand form to be introduced. You can also use polyacyloxalamidrazone threads, wound on a spool, exposed to the action of the metal compound in a suitable spool pressure wash. .
009882/2038 009882/2038
ι—ι—
- 5 - Pos. GW 1477- 5 - Item GW 1477
Bei der Behandlung der Fäden und Fasern mit den Lösungen der Metallverbindungen reagiert das den Faden oder die Faser bildende Polyterephthaloyl- bzw. Polyfumaroyloxalamidrazon chemisch mit der Metallverbindung. Dabei bindet das Polyacyloxalamidrazon das entsprechende Metall, vermutlich in komplexer Form bzw. als Enolat.When the threads and fibers are treated with the solutions of the metal compounds, that which forms the thread or the fiber reacts Polyterephthaloyl or polyfumaroyloxalamidrazone chemically with the metal compound. The polyacyloxalamidrazone binds here the corresponding metal, presumably in complex form or as an enolate.
Die Umsetzungsgeschwindigkeit und die aufgenommene Metallmenge sind von mehreren Faktoren abhängig. Die Geschwindigkeit der Metallaufnahme hängt u.a. von der Art des Polyacyloxalamldrazons, von dem jeweiligen Metall, der Metallverbindung, deren Konzentration in der Lösung, dem Lösungsmittel bzw. dem Lösungsmittelgemisch, der Temperatur und dem pH-Wert der Lösung ab. Der Faden nimmt im Verlaufe der Behandlung solange Metall aus der Lösung auf, bis die Sättigungsgrenze des entsprechenden Polyacyloxalamidrazons erreicht ist. Für die Herstellung eines Polyterephthaloyl- bzw. eines Polyfumaroyloxalamidrazons mit einem bestimmten Metallgehalt besonders geeignete Verfahrensweise, Insbesondere die erforderliche Reaktionszeit, läßt sich durch eine einfache Testreihe leicht ermittelnv" ·*"-'·'"· ·-"*-·-«-·—*·«"<·*—-~...,-~—w.-.,,.. .... ............... . ,.. The rate of conversion and the amount of metal absorbed depend on several factors. The rate of metal uptake depends, among other things, on the type of polyacyloxalamldrazone, on the respective metal, the metal compound, their concentration in the solution, the solvent or solvent mixture, the temperature and the pH of the solution. In the course of the treatment, the thread absorbs metal from the solution until the saturation limit of the corresponding polyacyloxalamidrazone is reached. For the production of a Polyterephthaloyl- or a Polyfumaroyloxalamidrazons with a specific metal content particularly suitable procedure, particularly the required reaction time can easily through a simple series of tests ermittelnv "· *" - '·''· · - "* - * -" - · - * · «"<· * —- ~ ..., - ~ —w .-. ,, .. .... ................ , ..
Die nach dem erfindungsgemäßen Verfahren erhältlichen schwerentflammbaren Fäden und Fasern können auch nach einem weiteren, allerdings weniger vorteilhaften Verfahren hergestellt werden. Bei dieser Verfahrensweise geht man nicht von fertigen Fäden und Fasern aus, sondern von alkalischen Lösungen der PoIyacyloxalamidrazone· Diese Lösungen werden in einem Bad versponnen, welches neben der für die Bildung des Fadens erforderlichen Säure und/oder Salzendie Metallverbindung in gelöster Form enthält. In diesem Falle setzt die Behandlung der Polyacyloxalamidrazon-Fäden bereits während ihrer Entstehung ein.The flame-retardant threads and fibers obtainable by the process according to the invention can also be produced by a further, albeit less advantageous, process. In this procedure, it is not based on the finished filaments and fibers, but from alkaline solutions of PoIyacyloxalamidrazone · These solutions are spun in a bath which in addition to the time required for the formation of the thread acid and / or salts of the metal compound in dissolved form n contains. In this case, the treatment of the polyacyloxalamidrazone threads begins as soon as they are formed.
Die nach dem erfindungsgemäßen Verfahren hergestellten FädenThe threads produced by the method according to the invention
~6- ι~ 6 - ι
009882/2038 I009882/2038 I.
ORIGINAL INSPECTEDORIGINAL INSPECTED
I - 6 - Pos. GW 1477 |I - 6 - Item GW 1477 |
und Fasern sind umso schwerer entflammbar, je mehr Metall sie enthalten. Derartige Fäden ur:d Fasern, die einen für jedes Metall charakteristischen Metall-Mindestgehalt besitzen, sind sogar nichtentflammbar gemäß DIN 53 906. Dieser Metall-Mindestgehalt liegt bei den Polyterephthaloyloxalamidrazon-Fäden im Bereich von 4 bis 8 Gew.-%. Beispielsweise beträgt der Slnk-Mindestgehalt ca. 5 Gew.-%, der Zinn-Mindestgehalt ca. 3,5 Gew.-% und der Calcium-Mindestgehalt ca.4 Gew.-%. Die erforderlichen Mindest-Metallgehalte bei Polyfumaroyloxalamidrazon-Fäden entsprechen den bei den Polyterephthaloyloxalamidrazon-Fäden gemessenen Werten. Fäden und Fasern, deren Mindestgehalt zwischen 3,5 bis 8 Gew.-% und der Sättigungsgrenze liegt, sind nicht nur "nichtentflammbar" im Sinne der DIN 53 906, sondern widerstehen unbeschadet auch der längeren Einwirkung von Flammen-? Es werden daher nach dem erflndungsgemäßen Verfahren vorzugsweise Fäden und Fasern mit einem Metallgehalt von 3ff5%bis zur Sättigungsgrade hergestellt.and the more metal they contain, the more difficult it is to ignite fibers. Such threads ur: d fibers, which have a minimum metal content characteristic for each metal, are even non-flammable according to DIN 53 906. This minimum metal content for the polyterephthaloyloxalamidrazone threads is in the range from 4 to 8% by weight. For example, the minimum Slnk content is approx. 5% by weight, the minimum tin content is approx. 3.5% by weight and the minimum calcium content is approx. 4% by weight. The minimum metal content required for polyfumaroyloxalamidrazone threads corresponds to the values measured for polyterephthaloyloxalamidrazone threads. Threads and fibers, the minimum content of which is between 3.5 to 8% by weight and the saturation limit, are not only "non-flammable" in the sense of DIN 53 906, but also withstand prolonged exposure to flames without prejudice to? There are therefore prepared according to the method preferably erflndungsgemäßen filaments and fibers having a metal content of 3 ff 5% to saturation levels.
Die nach dem erfindungsgemäßen Verfahren hergestellten schwer- oder nichtentflammbaren Fäden und Fasern besitzen gute textile Eigenschaften. Sie lassen sich ohne Schwierigkeiten zu Garnen, " " Stapelfasermischgarnen/ Geweben; Gewirken, Vliesen etc -verar-' bei ten. Im allgemeinen sind die Festigkeitswerte und die Dehnungswerte von Fäden mit einem Metallgehalt von ca. 15 bis 50 Gew.-% nur etwa 10 bis 20% 'niedriger als die Werte der entsprechenden Polyacyloxalamidrazon-Fäden. Fäden mit geringerein Metallgehalt besitzen nur wenig geringere Festigkeiten und Dehnungen als die entsprechenden Polyaeyloxalamidrazon-Fäden. Nach dem erfindungcgemäßen Verfahren läßt sich beispielsweise ein Polyterephthaloyloxalamidrazon-Faden mit einem ^ink-Gehalt von 15 Gew.-» herstellen, dessen Trockenfestigkeit 17 Rkm, dessen Trockendehnung 15%, dessen Naßfestigkeit 6 Rkm, dessen Naßdehnung 8 bis 16% und dessen relative Schiisigenfestigkelt. 75% beträgt.The difficult- or non-flammable threads and fibers have good textile properties. They can be easily made into yarns, "" Staple fiber blended yarns / woven fabrics; Knitted, nonwovens etc -verar- 'at th. In general, the strength values and the elongation values of threads with a metal content of approx. 15 to 50% by weight only about 10 to 20% lower than the values of the corresponding Polyacyloxalamidrazone threads. Threads with lesser one Metal content have only slightly lower strengths and elongations than the corresponding polyaeyloxalamidrazone threads. According to the method according to the invention, for example a polyterephthaloyloxalamidrazone thread with an ink content can be used of 15 wt. », its dry strength 17 Rkm, its dry elongation 15%, its wet strength 6 Rkm, its Wet elongation 8 to 16% and its relative ski strength. 75%.
Die nach dem erfindungsgemäßen Verfahren heraeetoiite^ FädenThe threads produced by the method according to the invention
· 009682/2038 " Ί " I· 009682/2038 " Ί " I.
r . .πr. .π
Pos. GW 1477Item GW 1477
und Fasern besitzen eine vom jeweils gebundenen Metall abhängige kräftige Eigenfarbe, die eine weitere Einfärbimg unnötig nacht. Es ist jedoch auch möglich, die Fäden und Fasern mit den üblichen Farbstoffen, wie z.B. Dispersionsfarbstoffen, Metallkomplexfarbstoffen, Substantiven-, basischen oder sauren Farbstoffen nachzutönen. Fäden und Fasern, die die Metalle Zink, Zinn, Cadmium, Barium, Calcium und Strontium besitzen, sind orange bis braun. Solche, die Antimonverbindungen enthalten, sind rot und solche, die Tantal enthalten, gelborange.and fibers have a dependent metal bond strong intrinsic color that makes further coloring unnecessary. However, it is also possible to use the threads and fibers the usual dyes, such as disperse dyes, Metal complex dyes, nouns, basic or acidic To recreate dyes. Threads and fibers containing the metals zinc, tin, cadmium, barium, calcium and strontium, are orange to brown. Those that contain antimony compounds are red and those that contain tantalum are yellow-orange.
In den Beispielen 1 bis 14 wurde ein Polyacyloxalamidrazonfaden verwendet, der nach dem folgenden Verfahren hergestellt wurde.In Examples 1 to 14, a polyacyloxalamidrazone thread was used, which was produced according to the following procedure became.
Durch ca 2-stündiges Rühren von 8 Gewichtstellen Polyterephthaloyloxalamidrazon, 6 Gewichtsteilen Kaliumhydroxid, 86 Gewichtsteilen Hasser und 0,45 Gewichtsteilen eines äthoxylierten Kokosfettamins bei Raumtemperatur-wurde eine Lösung-erhalten,-welche nach dem Filtrieren und Entlüften eine Viskosität von 9,5 see. Kugelfall aufwies. Diese Spinnmasse wurde in einer 20 tlgen wäßrigen Ammoniumchlorid-Lösung von 30°C versponnen. Der erhaltene Polyterephthaloyloxalamidrazon-Faden besaS die folgenden textlien Daten:By stirring 8 weight points of polyterephthaloyloxalamidrazone for about 2 hours, 6 parts by weight of potassium hydroxide, 86 parts by weight of hasser and 0.45 parts by weight of an ethoxylated coconut fatty amine at room temperature a solution was obtained, which after filtering and deaerating, a viscosity of 9.5 seconds. Ball drop showed. This spinning mass was spun in a 20 parts aqueous ammonium chloride solution at 30.degree. The received Polyterephthaloyloxalamidrazone filament had the following textile data:
Gesamttiter: 190 dtex
Trockenfestigkeit: 20,0 Rkm
Trockendehnung: 20,0 %
Naßfestigkeit: 8,5 Rkm
Naßdehnung: 23,0 %Total titre: 190 dtex
Dry strength: 20.0 Rkm
Dry elongation: 20.0%
Wet strength: 8.5 Rkm
Wet elongation: 23.0%
Der Polyterephthaloyloxalamidrazon-Faden wurde anschließend in der Lösung einer Metallverbindung getaucht· Vereuchsbe-The polyterephthaloyloxalamidrazone filament was then immersed in a solution of a metal compound
009882/20 3 8 " · "009882/20 3 8 "·"
f— —ιf - - 1
• - fl - Ρηβ. fiW 1477 I• - fl - Ρηβ. fiW 1477 I.
dingungen und Ergebnisse sind in Tabelle 1 dargestellt.Conditions and results are shown in Table 1.
Die Bestimmung der Entflammbarkeit erfolgt nach der Vorschrift der DIN 53 906.The determination of the flammability takes place according to the regulation the DIN 53 906.
In den Beispielen 15 und 16 wurde ein Polyfumaroyloxalamidrazon-Faden verwendet, der durch Verspinnen einer Lösung aus 8 Gewichtstellen Polyfumaroyloxalamidrazon, 6 Gewichtsteilen Kaliumhydröxid und 86 Gewichtsteilen Wasser in eine 20 gewichtsprozentige wäßrige Ammoniumchloridlösung bei 300C erhalten wurde. Der erhaltene Polyfumaroyloxalamidrazon-Faden besaß die folgenden textlien Eigenschaften:In Examples 15 and 16 Polyfumaroyloxalamidrazon yarn was used which was obtained by spinning a solution of 8 weight bodies Polyfumaroyloxalamidrazon, 6 parts by weight Kaliumhydröxid and 86 parts by weight of water into a 20 weight percent aqueous ammonium chloride solution at 30 0C. The polyfumaroyloxalamidrazone thread obtained had the following textile properties:
Trockenfestigkeit: 4,5 Rkm Trockendehnung: 1,5 %
absolute Schiingenfestigkeit: 3,4 Rkm Quellwert! 67 %Dry strength: 4.5 Rkm dry elongation: 1.5%
absolute loop strength: 3.4 Rkm swelling value! 67%
Die Polyfumaroyloxaiamidrazon-Fäden wurden anschließend in der Lösung einer Metallverbindung getaucht. VersuchsbedingungenThe Polyfumaroyloxaiamidrazone threads were then in immersed in the solution of a metal compound. Test conditions
und Ergebnisse sind in Tabelle 2 dargestellt.and results are shown in Table 2.
ORIGINAL INSPECTEDORIGINAL INSPECTED
009882/2038009882/2038
T a b e T a b e
1 e 1 1 e 1
Pos. GW 1477 Item GW 1477
Beisp, Nr.Example, No.
Metallverbindung Lösungsmittel Konz. Metal compound solvent conc.
Gew.-%Wt%
Zeit Aufgenommene
S td. Metallmenge
Gew.-%Recorded time
S td. Amount of metal
Wt%
Eigenschaften des Fadens gemäß DIN 53 9Ο6 Properties of the thread according to DIN 53 9Ο6
O CD CD COO CD CD CO
1 21 2
SnCl2-2 H2O *2 H2OSnCl 2 -2 H 2 O * 2 H 2 O
Wasser v 20Water v 20
2,5%ige wäßrige NH4Cl-rLösung342.5% aqueous NH 4 Cl solution34
ÄthanolEthanol
2n2n
2n2n
2n NH4OH;1 2n NH4OH: !2n NH 4 OH; 1 2n NH 4 OH:!
2n 4 Wasser 2n NH4OHJ Wasser · 2n 4f Wasser DMF2n 4 water 2n NH 4 OHJ water · 2n 4 f water DMF
10 20 23 20 2010 20 23 20 20
gesättigt 10saturated 10
gesättigt 16 gesättigtsaturated 16 saturated
0,75 72 48 24 29 240.75 72 48 24 29 24
34,534.5
1212th
16,2 21,5 36,216.2 21.5 36.2
5,1 49,0 29,4 15,5 12,5 125.1 49.0 29.4 15.5 12.5 12th
6,1 11,86.1 11.8
5,45.4
nichtentflammbarnon-flammable
nichtentflammbar ni chtentflammbar nichtentflammbar nichtentflammbar nichtentflammbar nichtentflammbar ι nichtentflammbar nichtentflammbar nichtentflammbar ni ch tent flammbar nichtentflammbar nichtentflammbar ni chtentflammbarnon-flammable non-flammable non-flammable non-flammable non-flammable non-flammable ι non-flammable non-flammable non-flammable non-flammable non-flammable non-flammable non-flammable
- 10 -- 10 -
Pos. GW 1477Item GW 1477
Beisp, Nr.Example, no.
\ Gew.-% \ % By weight
Zeit Aufgenommene
Std. Metallmenge
Gew.-%Recorded time
Hrs. Amount of metal
Wt%
Eigenschaften
des Fadensproperties
of the thread
grmäß PIN 53 906size PIN 53 906
15 1615 16
ZnCl2 ZnCl 2
3 CdSO4*8H2O3 CdSO 4 * 8H 2 O
2n NH4OH 2n NH4OH2n NH 4 OH 2n NH 4 OH
10 1010 10
21,7
27,521.7
27.5
nichtentflammbar
nichtentflammbarnon-flammable
non-flammable
55 Ο 55 Ο
γ-γ-
0)0)
- 11 -- 11 -
CD NJ NJ CO GJCD NJ NJ CO GJ
Claims (1)
Priority Applications (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691922335 DE1922335C3 (en) | 1969-05-02 | Process for the production of flame-retardant threads and fibers from polyacyloxalamidrazones | |
| ZA701993A ZA701993B (en) | 1969-05-02 | 1970-03-23 | Flame-resistant filaments and fibres |
| GB1252385D GB1252385A (en) | 1969-05-02 | 1970-03-24 | |
| CS7000002179A CS184307B2 (en) | 1969-05-02 | 1970-04-02 | |
| BE748358D BE748358A (en) | 1969-05-02 | 1970-04-02 | HIGHLY FLAMMABLE THREADS AND FIBERS |
| RO63018A RO57974A (en) | 1969-05-02 | 1970-04-07 | |
| ES378502A ES378502A1 (en) | 1969-05-02 | 1970-04-13 | Flame-resistant polyacyloxalamidrazone filaments |
| BG14496A BG17638A3 (en) | 1969-05-02 | 1970-04-15 | |
| AT347970A AT301740B (en) | 1969-05-02 | 1970-04-16 | Process for the production of flame-retardant threads and fibers |
| CH573970D CH573970A4 (en) | 1969-05-02 | 1970-04-17 | |
| CH573970A CH515378A (en) | 1969-05-02 | 1970-04-17 | Process for the production of permanently flame retardant threads and fibers from polyacyloxalamidrazone |
| US32394A US3661502A (en) | 1969-05-02 | 1970-04-27 | Flame-resistant polyacyloxalamidrazone filaments |
| HUGA1006A HU168216B (en) | 1969-05-02 | 1970-04-28 | |
| LU60826D LU60826A1 (en) | 1969-05-02 | 1970-04-29 | |
| SE05946/70A SE351870B (en) | 1969-05-02 | 1970-04-29 | |
| NL7006292A NL7006292A (en) | 1969-05-02 | 1970-04-29 | |
| FR7016047A FR2047206A5 (en) | 1969-05-02 | 1970-04-30 | |
| BG098605A BG98605A (en) | 1969-05-02 | 1994-02-28 | ANTI-TUMOR PEPTIDES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691922335 DE1922335C3 (en) | 1969-05-02 | Process for the production of flame-retardant threads and fibers from polyacyloxalamidrazones |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1922335A1 true DE1922335A1 (en) | 1971-01-07 |
| DE1922335B2 DE1922335B2 (en) | 1976-05-26 |
| DE1922335C3 DE1922335C3 (en) | 1977-01-13 |
Family
ID=
Also Published As
| Publication number | Publication date |
|---|---|
| CH573970A4 (en) | 1971-07-30 |
| AT301740B (en) | 1972-09-11 |
| GB1252385A (en) | 1971-11-03 |
| CH515378A (en) | 1971-07-30 |
| SE351870B (en) | 1972-12-11 |
| BG98605A (en) | 1996-03-29 |
| DE1922335B2 (en) | 1976-05-26 |
| LU60826A1 (en) | 1970-06-29 |
| NL7006292A (en) | 1970-11-04 |
| BE748358A (en) | 1970-09-16 |
| ES378502A1 (en) | 1977-05-16 |
| BG17638A3 (en) | 1973-11-10 |
| HU168216B (en) | 1976-03-28 |
| RO57974A (en) | 1975-06-15 |
| FR2047206A5 (en) | 1971-03-12 |
| ZA701993B (en) | 1971-01-27 |
| CS184307B2 (en) | 1978-08-31 |
| US3661502A (en) | 1972-05-09 |
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|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| EHJ | Ceased/non-payment of the annual fee |