EP2861789B1 - Fils discontinus filés ignifuges constitués de mélanges de fibres dérivées de polymères de naphtalène polyoxadiazole sulfonaté - Google Patents
Fils discontinus filés ignifuges constitués de mélanges de fibres dérivées de polymères de naphtalène polyoxadiazole sulfonaté Download PDFInfo
- Publication number
- EP2861789B1 EP2861789B1 EP13783124.4A EP13783124A EP2861789B1 EP 2861789 B1 EP2861789 B1 EP 2861789B1 EP 13783124 A EP13783124 A EP 13783124A EP 2861789 B1 EP2861789 B1 EP 2861789B1
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- EP
- European Patent Office
- Prior art keywords
- fiber
- formula
- yarn
- staple
- molar
- 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.)
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- 239000000835 fiber Substances 0.000 title claims description 384
- 239000000203 mixture Substances 0.000 title claims description 81
- 150000002790 naphthalenes Chemical class 0.000 title claims description 29
- 229920000642 polymer Polymers 0.000 title description 40
- 238000000034 method Methods 0.000 claims description 74
- 239000004753 textile Substances 0.000 claims description 36
- 150000001768 cations Chemical class 0.000 claims description 31
- 238000009987 spinning Methods 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229920002821 Modacrylic Polymers 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- 239000004745 nonwoven fabric Substances 0.000 claims description 6
- 239000002759 woven fabric Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 description 66
- 239000000243 solution Substances 0.000 description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- 229920003235 aromatic polyamide Polymers 0.000 description 31
- 239000004760 aramid Substances 0.000 description 29
- 229920001577 copolymer Polymers 0.000 description 28
- 239000000975 dye Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 24
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 22
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 16
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 14
- 230000015271 coagulation Effects 0.000 description 14
- 238000005345 coagulation Methods 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 229920000742 Cotton Polymers 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920002480 polybenzimidazole Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229920002577 polybenzoxazole Polymers 0.000 description 9
- 238000006277 sulfonation reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000007378 ring spinning Methods 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 238000002166 wet spinning Methods 0.000 description 8
- 241000018242 Obba <basidiomycete fungus> Species 0.000 description 7
- 239000004693 Polybenzimidazole Substances 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 7
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000000981 basic dye Substances 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 239000012493 hydrazine sulfate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 6
- 229920006231 aramid fiber Polymers 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000005605 benzo group Chemical group 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 238000000578 dry spinning Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920000271 Kevlar® Polymers 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 4
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910003202 NH4 Inorganic materials 0.000 description 3
- 229920000784 Nomex Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004772 Sontara Substances 0.000 description 3
- 229920001494 Technora Polymers 0.000 description 3
- 229920000561 Twaron Polymers 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical group 0.000 description 3
- 125000004427 diamine group Chemical group 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000004763 nomex Substances 0.000 description 3
- 238000007383 open-end spinning Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004950 technora Substances 0.000 description 3
- 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 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920012306 M5 Rigid-Rod Polymer Fiber Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000000159 acid neutralizing agent Substances 0.000 description 2
- 238000010042 air jet spinning Methods 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009960 carding Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920003252 rigid-rod polymer Polymers 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- DKSOHQCFPNSKMB-UHFFFAOYSA-N C1=CC=CC2=CC=CC=C12.O1N=NC=C1 Chemical class C1=CC=CC2=CC=CC=C12.O1N=NC=C1 DKSOHQCFPNSKMB-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 240000003759 Erodium cicutarium Species 0.000 description 1
- 235000009967 Erodium cicutarium Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 1
- WRLANGHMVGCSDR-UHFFFAOYSA-N hydrazine;sulfuric acid Chemical compound NN.OS(O)(=O)=O.OS(O)(=O)=O WRLANGHMVGCSDR-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- OIIWPAYIXDCDNL-HGFPCDIYSA-M sodium;2,2,3,3-tetradeuterio-3-trimethylsilylpropanoate Chemical compound [Na+].[O-]C(=O)C([2H])([2H])C([2H])([2H])[Si](C)(C)C OIIWPAYIXDCDNL-HGFPCDIYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/04—Blended or other yarns or threads containing components made from different materials
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/04—Blended or other yarns or threads containing components made from different materials
- D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
Definitions
- the invention relates to flame-resistant spun staple yarns, and fabrics and garments comprising these yarns, and methods of making the same.
- the yarns contain a blend of polymeric staple fiber containing sulfonated naphthalene polyoxadiazole polymers.
- Polyoxadiazole polymers have unique properties and are useful in many fields, for example high performance fibers, such as flame retardant fibers.
- One method to improve flammability is to prepare sulfonated polyoxadiazole polymers. These methods have included the use of sulfonated monomers and post-sulfonation. Gomes et al. (US 20098/0318109 , US2008/0193652 , US2009/0203870 ) reacted hydrazine sulfate and aromatic dicarboxylic acids in phosphoric acid to form monosulfonated polyoxadiazole copolymers, and subsequently post-sulfonated the polymer.
- Another method is the use of oleum during polymerization to sulfonate the polymer as it is prepared.
- Lee et al. (US 7,528,216 and US 7,582,721 ) prepared random polyoxadiazole copolymers by reacting aromatic dicarboxylic acids with hydrazine sulfate in a limited amount of oleum, and prepared sulfonated random polyoxadiazole copolymers using sulfonated monomers ( US 7,528,217 ).
- WO 2009/026482 relates to a flame-resistant yarn comprising a polymeric staple fiber containing a polymer or copolymer derived from a diamino diphenyl sulfone monomer and a polyoxadiazole staple fiber, which does not comprise a sulfonated naphthyl oxadiazole structure of formula (1).
- WO 2008/042115 describes sulfonated polyoxadiazole polymers and fiber polymers, which though do not comprise a sulfonated naphthalene oxadiazole of formula (1) as in the present application.
- a flame-resistant spun yarn comprising 50 to 95 parts by weight of a sulfonated polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa): wherein Formula (I) is present at 5 molar % to 50 molar % , based on the total amount of sulfonated naphthalene polyoxadiazole based staple fiber, and wherein Q is H or SO 3 M, and M is one or more cations; and 5 to 50 parts by weight of a textile staple fiber having limiting oxygen index of 24 or greater and a tenacity of 2 grams per denier or greater, based on the total amount of the polymeric fiber and the textile fiber in the yarn.
- a flame-resistant spun yarn as defined in claim 3 comprising at least 25 parts to 80 parts by weight of a sulfonated polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa), wherein M is a cation; and 20 to 75 parts by weight of a modacrylic fiber, based on the total amount of the polymeric fiber and the textile fiber in the yarn.
- a flame-resistant spun yarn as defined in claim 5 comprising 50 to 95 parts by weight of a sulfonated polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 5 to 50 parts by weight of a high modulus staple fiber having a tensile modulus of 200 grams per denier or greater, based on the total amount of the polymeric fiber and the textile fiber in the yarn.
- a flame-resistant spun yarn as defined in claim 7 comprising 20 to 50 parts by weight of a sulfonated polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 50 to 80 parts by weight of a rigid-rod staple fiber, based on the total amount of the sulfonated polyoxadiazole based fiber and the textile fiber in the yarn.
- a protective garment, woven fabric, nonwoven fabric, belt, or filament comprising the flame-resistant spun yarns.
- a method of producing a spun yarn comprising: a) forming a fiber mixture of 50 to 95 parts by weight of a polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 5 to 50 parts by weight of a textile staple fiber having limiting oxygen index of 24 or greater and a tenacity of 2 grams per denier or greater, based on the total amount of the polymeric fiber and the textile fiber in the yarn; and b) spinning the fiber mixture into a spun staple yarn.
- Also disclosed is a method of producing a spun yarn as defined in claim 10 comprising: a) forming a fiber mixture of 25 to 80 parts by weight of a polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 20 to 75 parts by weight of a modacrylic fiber, based on the total amount of the polymeric fiber and the textile fiber in the yarn; and b) spinning the fiber mixture into a spun staple yarn.
- Also disclosed is a method of producing a spun yarn comprising: a) forming a fiber mixture of 50 to 95 parts by weight of a polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 5 to 50 parts by weight of a high modulus staple fiber having a tensile modulus of 200 grams per denier or greater, based on the total amount of the polymeric fiber and the textile fiber in the yarn; and b) spinning the fiber mixture into a spun staple yarn.
- Also disclosed is a method of producing a spun yarn comprising: a) forming a fiber mixture of 20 to 50 parts by weight of a polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 50 to 80 parts by weight of a rigid-rod staple fiber, based on the total amount of the polymeric fiber and the textile fiber in the yarn; and b) spinning the fiber mixture into a spun staple yarn.
- a flame-resistant spun yarn comprising: 50 to 95 parts by weight of a sulfonated polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa):
- the sulfonated naphthalene polyoxadiazole based staple fiber is present at 50 to 85, or 50 to 75, or 60 to 85, or 70 to 80 parts by weight, and the high modulus staple fiber is present at 15 to 50, or 25 to 40, or 15 to 40, or 20 to 30 parts by weight.
- Suitable textile fibers include meta-aramid fibers, para-aramid fibers, and polyazole fibers.
- a flame-resistant spun yarn comprising at least 25 parts to 80 parts by weight of a sulfonated naphthalene polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 20 to about 75 parts by weight of a modacrylic fiber, based on the total amount of the polymeric fiber and the textile fiber in the yarn.
- Formula (I) is present at 5 molar % to 50 molar %, based on the total amount of sulfonated naphthalene polyoxadiazole based staple fiber.
- the sulfonated naphthalene polyoxadiazole based staple fiber is present at 35 to 70, or 50 to 75 parts by weight, or 45 to 60, or 45 to 70 parts by weight, and the modacrylic fiber is present at 30 to 65, or 25 to 50, or 40 to 55, or 30 to 55 parts by weight.
- Suitable modacrylic fibers include copolymers of acrylonitrile combined with vinylidene chloride.
- a flame-resistant spun yarn comprising at least 50 to 95 by weight of a sulfonated naphthalene polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 5 to 50 parts by weight of a high modulus staple fiber having a tensile modulus of 200 grams per denier or greater, based on the total amount of the polymeric fiber and the textile fiber in the yarn.
- the sulfonated naphthalene polyoxadiazole based staple fiber is present at 50 to 85, or 50 to 75, or 60 to 85, or 70 to 80 parts by weight, and the high modulus staple fiber is present at 15 to 50, or 25 to 40, or 15 to 40, or 20 to 30 parts by weight.
- fibers can be used as the high modulus staple fiber, including para-aramid fibers, polyazole fibers, carbon fibers, and mixtures thereof.
- para-aramid fiber can be used in the blend as the high modulus staple fiber.
- aramid is meant a polyamide wherein at least 85% of the amide (-CONH-) linkages are attached directly to two aromatic rings.
- Additives can be used with the aramid and, in fact, it has been found that up to as much as 10 percent, by weight, of other polymeric material can be blended with the aramid or that copolymers can be used having as much as 10 percent of other diamine substituted for the diamine of the aramid or as much as 10 percent of other diacid chloride substituted for the diacid chloride of the aramid.
- the preferred para-aramid is poly(paraphenylene terephthalamide). Methods for making para-aramid fibers useful are generally disclosed in, for example, United States Patent Nos. 3,869,430 ; 3,869,429 ; and 3,767,756 .
- aromatic polyamide organic fibers are sold under the trademarks of Kevlar® and Twaron® by respectively, E. I. du Pont de Nemours and Company, of Wilmington, Delaware; and Teijin, Ltd, of Japan.
- fibers based on copoly(p-phenylene/3,4'-diphenyl ether terephthalamide) are defined as para-aramid fibers as used herein.
- One commercially available version of these fibers is known as Technora® fiber also available from Teijin, Ltd.
- polyazole fibers can be used as the high modulus fiber in the blend.
- suitable polyazoles include polybenzazoles, polypyridazoles, and the like, and can be homopolymers or copolymers. Additives can be used with the polyazoles and up to as much as 10 percent, by weight, of other polymeric material can be blended with the polyazoles. Also copolymers can be used having as much as 10 percent or more of other monomer substituted for a monomer of the polyazoles.
- Suitable polyazole homopolymers and copolymers can be made by known procedures, such as those described in U.S. Patents 4,533,693 (to Wolfe, et al., on Aug.
- the preferred polybenzazoles are polybenzimidazoles, polybenzothiazoles, and polybenzoxazoles. If the polybenzazole is a polybenzimidazole, preferably it is poly[5,5'-bi-1H-benzimidazole]-2,2'-diyl-1,3-phenylene which is called PBI. If the polybenzazole is a polybenzothiazole, preferably it is a polybenzobisthiazole and more preferably it is poly(benzo[1,2-d:4,5-d']bisthiazole-2,6-diyl-1,4-phenylene which is called PBT.
- the polybenzazole is a polybenzoxazole, preferably it is a polybenzobisoxazole and more preferably it is poly(benzo[1,2-d:4,5-d']bisoxazole-2,6-diyl-1,4-phenylene which is called PBO.
- the preferred polypyridazoles are rigid-rod polypyridobisazoles including poly(pyridobisimidazole), poly(pyridobisthiazole), and poly(pyridobisoxazole).
- the preferred poly(pyridobisoxazole) is poly(1,4-(2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d']bisimidazole which is called PIPD.
- Suitable polypyridobisazoles can be made by known procedures, such as those described in U.S. Patent 5,674,969 .
- High modulus carbon fibers are well known in the art and commercially available carbon fibers include Tenax® fibers available from Toho Tenax America, Inc.
- the high modulus staple fiber has a limiting oxygen index (LOI) of 24 or greater, meaning the high modulus staple fiber or fabrics made solely from the high modulus staple fiber will not support a flame in air. In some preferred embodiments the high modulus staple fiber has a LOI of at least 26 or greater.
- LOI limiting oxygen index
- the high modulus staple fiber has a break tenacity of at least 5 grams per denier (4.5 grams per dtex) or greater. In some other embodiments the high modulus staple fiber has a break tenacity of at least 10 grams per denier (9 grams per dtex) or greater.
- the addition of the higher tenacity high modulus staple fiber provides the spun yarn with additional strength that translates into improved strength and durability in the final fabrics and garments made from the spun yarns. Also, in some cases, depending on the blending percentage, it is believed the additional tenacity provided by the high modulus staple fiber to the spun yarn is magnified in the fabrics and garments made from the yarn, resulting in more tenacity improvement in the fabric than in the spun yarn.
- a flame-resistant spun yarn comprising at least 20 to 50 parts by weight of a sulfonated naphthalene polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 50 to 80 parts by weight of a rigid-rod staple fiber based on the total amount of the polymeric fiber and the textile fiber in the yarn.
- the sulfonated naphthalene polyoxadiazole based staple fiber is present at 30 to 40, or 35 to 40, or 30 to about 50, or 20 to 40 parts by weight
- the rigid-rod staple fiber is present at 60 to 70, or 60 to 65, or 50 to 70, or 60 to 80 parts by weight.
- rigid-rod fiber means fibers made from rigid-rod aromatic polymers having what are known in the art as rigid spacer segments; these rigid-rod fibers also form fibrils with abrasion or wear.
- these rigid-rod polymers have highly para-oriented aromatic groups and the fibers made from these polymers have a high tensile modulus.
- rigid-rod fibers With wear or abrasion, rigid-rod fibers readily fibrillate; that is, they form structures having a central fiber stalk with fibrils extending therefrom.
- the stalk is generally columnar and 4 to 50 microns in diameter and the fibrils are hair-like members only a fraction of a micron or a few microns in diameter attached to the stalk and are 10 to 100 microns long.
- para-aramid fiber can be used in the blend as the rigid-rod staple fiber.
- aramid is meant a polyamide wherein at least 85% of the amide (-CONH-) linkages are attached directly to two aromatic rings.
- Additives can be used with the aramid and, in fact, it has been found that up to as much as 10 percent, by weight, of other polymeric material can be blended with the aramid or that copolymers can be used having as much as 10 percent of other diamine substituted for the diamine of the aramid or as much as 10 percent of other diacid chloride substituted for the diacid chloride of the aramid.
- the preferred para-aramid is poly(paraphenylene terephthalamide).
- Methods for making para-aramid fibers useful are generally disclosed in, for example, United States Patent Nos. 3,869,430 ; 3,869,429 ; and 3,767,756 .
- Various forms of such aromatic polyamide organic fibers are sold under the trademarks of Kevlar® and Twaron® by respectively, E. I. du Pont de Nemours and Company, of Wilmington, Delaware; and Teijin, Ltd, of Japan.
- fibers based on copoly(p-phenylene/3,4'-diphenyl ether terephthalamide) are defined as para-aramid fibers as used herein.
- One commercially available version of these fibers is known as Technora® fiber also available from Teijin, Ltd.
- polyazole fibers can be used as the rigid-rod fiber in the blend.
- suitable polyazoles include polybenzazoles, polypyridazoles, and the like, and can be homopolymers or copolymers. Additives can be used with the polyazoles and up to as much as 10 percent, by weight, of other polymeric material can be blended with the polyazoles. Also copolymers can be used having as much as 10 percent or more of other monomer substituted for a monomer of the polyazoles.
- Suitable polyazole homopolymers and copolymers can be made by known procedures, such as those described in U.S. Patents 4,533,693 (to Wolfe, et al., on Aug.
- the preferred polybenzazoles are polybenzimidazoles, polybenzothiazoles, and polybenzoxazoles.
- the polybenzazole is a polybenzimidazole, preferably it is poly[5,5'-bi-1H-benzimidazole]-2,2'-diyl-1,3-phenylene which is called PBI.
- the polybenzazole is a polybenzothiazole, preferably it is a polybenzobisthiazole and more preferably it is poly(benzo[1,2-d:4,5-d']bisthiazole-2,6-diyl-1,4-phenylene which is called PBT.
- the polybenzazole is a polybenzoxazole, preferably it is a polybenzobisoxazole and more preferably it is poly(benzo[1,2-d:4,5-d']bisoxazole-2,6-diyl-1,4-(phenylene) which is called PBO.
- the preferred polypyridazoles are rigid-rod polypyridobisazoles including poly(pyridobisimidazole), poly(pyridobisthiazole), and poly(pyridobisoxazole).
- the preferred poly(pyridobisoxazole) is poly(1,4-(2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d']bisimidazole which is called PIPD.
- Suitable polypyridobisazoles can be made by known procedures, such as those described in U.S. Patent 5,674,969 .
- the spun staple yarns can also include a rigid-rod staple fiber having a limiting oxygen index (LOI) of 21 or greater, meaning the rigid-rod staple fiber or fabrics made solely from the rigid-rod staple fiber will not support a flame in air.
- LOI limiting oxygen index
- the rigid-rod staple fiber has a LOI of at least 26 or greater.
- the rigid-rod staple fiber has a break tenacity of at least 5 grams per denier (4.5 grams per dtex) or greater. In some other embodiments the rigid-rod staple fiber has a break tenacity of at least 10 grams per denier (9 grams per dtex) or greater.
- the addition of the higher tenacity rigid-rod staple fiber provides the spun yarn with additional strength that translates into improved strength and durability in the final fabrics and garments made from the spun yarns. Also, in some cases, it is believed the additional tenacity provided by the rigid-rod staple fiber to the spun yarn is magnified in the fabrics and garments made from the yarn, resulting in more tenacity improvement in the fabric than in the spun yarn.
- a flame-resistant spun yarn comprising at least 50 to 95 parts by weight of a sulfonated naphthalene polyoxadiazole based staple fiber comprising repeat units of Formula (I) and one or both of Formula (II) and (IIa) wherein M is a cation; and 5 to 50 parts by weight of a textile staple fiber having limiting oxygen index of 21 or greater and a tenacity of 4 grams per denier or greater, based on the total amount of the polymeric fiber and the textile fiber in the yarn.
- the sulfonated naphthalene polyoxadiazole based staple fiber is present at 50 to 85, or 50 to 75, or 60 to 85, or 70 to 80 parts by weight, and the high modulus staple fiber is present at 15 to 50, or 25 to 40, or 15 to 40, or 20 to 30 parts by weight.
- M is typically a monovalent cation such as H, Li, Na, K, or NH 4 .
- Formula (I) is present at 5 molar% to 50 molar%, based on the total amount of sulfonated naphthalene polyoxadiazole based staple fiber.
- Formula (I) is present at 5 molar % to 40 molar %, or 10 molar % to 30 molar %, and one or both of Formula (II) and (IIa) is present at 50 molar % to 95 molar %, or 60 molar % to 95 molar %, or 70 molar % to 90 molar %, based on the total amount of sulfonated naphthalene polyoxadiazole based staple fiber.
- Formula (II) is used in 60 to 95 molar %, or 70 to 90 molar %; and Formula (IIa) is used in 0 to 30 molar %, or 0 to 20 molar %. In yet other embodiments, Formula (II) is not present or Formula (IIa) is not present.
- M can be converted to another M at any time, either before or after spinning or formation into a shaped article.
- M is H
- the polymer can be neutralized by contact with a salt, such as but not limited to sodium bicarbonate, sodium hydroxide, cesium hydroxide, lithium hydroxide, potassium hydroxide, or potassium carbonate.
- a salt such as but not limited to sodium bicarbonate, sodium hydroxide, cesium hydroxide, lithium hydroxide, potassium hydroxide, or potassium carbonate.
- the ion exchange and/or neutralization can be performed by any method known in the art.
- the sulfonated naphthalene polyoxadiazole based staple fiber can further comprise repeat units of other moieties in the polymer chain. These repeat units can comprise one or both of Formula (III) and Formula (IIIa): wherein M is one or more cations.
- the sulfonated naphthalene polyoxadiazole based staple fiber can have at least 2 weight %, 4 weight %, or 6 weight % sulfur content.
- the amount of sulfur can be increased by sulfonation of the monomers before polymerization, or sulfonation of the polymer.
- the polymers disclosed herein can be made by any method or process known in the art.
- One suitable method comprises the steps of:
- the process described herein can prepare sulfonated polyoxadiazole copolymers that comprise at least 2 weight %, 4 weight %, or 6 weight % sulfur content.
- the amount of sulfur can be increased by additional process steps in which the NDA and/or the OBBA, or one or both of terephthalic acid and isophthalic acid are further sulfonated before polymerization, and/or process steps in which the polyoxadiazole copolymer product is sulfonated.
- This sulfonation can be performed by any method known in the art that is not detrimental to the final product, such as contact with oleum, sulfuric acid, or other sulfonation agent.
- Hydrazine can be used directly, or used in the form of a solid hydrazine salt.
- One suitable solid salt is hydrazine sulfate, [N 2 H 5 ]HSO 4 , also called hydrazinium sulfate.
- Oleum also known as fuming sulfuric acid, disulfuric acid or pyrosulfuric acid, refers to a solution of various compositions of sulfur trioxide (SO 3 ) in sulfuric acid. Typically about 15% or 18%, to about 30%, or about 22% oleum is used, which refers to the weight % of SO 3 in the sulfuric acid. The oleum is added in an amount of at least about 4 molar equivalents of SO 3 , or at least about 5 molar equivalents, based on the number of moles of hydrazine.
- SO 3 sulfur trioxide
- the amounts of the reagents used is dependent on the desired percentage of the repeat units in the final polymer. Based on the total amount of dicarboxylic acids used, 2,6-naphthalene dicarboxylic acid is used in amounts of at 1 molar % to less than 100 molar %, or 5 molar % to 50 molar %, or 5 molar % to 30 molar %, and one or both of terephthalic acid and isophthalic acid is used in amounts of 1 molar % or less than 100 molar %, or 50 molar % to 99 molar %, or 70 molar % to 95 molar %,.
- OBBA is present at 1 molar % to 30 molar %, or 2 molar % to 20 molar %.
- terephthalic acid is used in 50 to 95 molar %, or 80 to 90 molar %; and isophthalic acid is used in 0 to 30 molar %, or 0 to 20 molar %.
- terephthalic acid is not present or isophthalic acid is not present.
- Various ratios of hydrazine can be could be used, but is typically used at about a 1:1 molar ratio of dicarboxylic acids : hydrazine.
- the ingredients can be combined in any order, but typically the solid ingredients are first thoroughly mixed together and then combined with the oleum.
- the oleum is added in a single step; that is, added in one aliquot.
- the oleum and NDA and optionally OBBA can be mixed together prior to the addition of the other dicarboxylic acids and hydrazine.
- the mixture is then thoroughly mixed by stirring or other agitation means until sufficiently dissolved, typically at least five minutes. This dissolution can be performed at room temperature up to 100 °C.
- the process comprises the steps of:
- the mixture is allowed to react until sufficient polymer has formed.
- the polymerization reaction is performed at a temperature of 100 °C to 180 °C, or 120 °C to 140 °C, for at least 0.5 hours.
- the temperature can be maintained or increased or ramped up during the reaction.
- the temperature can be used to control the amounts of sulfonation and type of sulfonated repeating units in the final polymer. For instance, if more sulfonation and/or ring-closed repeating units are desired then the temperature should be increased, typically to greater than 120 °C. If less sulfonation and/or ring-closed repeating units are desired then the temperature should be lower, typically less than 100 °C.
- the sulfonated naphthalene polyoxadiazole polymers prepared by the process disclosed above can be neutralized either before or after formation into a shaped article, so that the H cation is replaced by another cation, typically a monovalent cation such as Li, Na, K, or NH 4 .
- a neutralization agent typically a basic salt such as sodium bicarbonate or other ion exchange agent.
- the polymers described herein can be formed into a shaped article, such as films, fibrids, fibers for floc, and fibers for textile uses, and for use in protective garments, woven fabrics, nonwoven fabrics, papers, belts, or filaments. It can be spun into fibers via solution spinning, using a solution of the polymer in either the polymerization solvent or another solvent for the polymer. Fiber spinning can be accomplished through a multi-hole spinneret by dry spinning, wet spinning, or dry-jet wet spinning (also known as air-gap spinning) to create a multi-filament yarn or tow as is known in the art.
- Shaped articles as described herein include extruded or blown shapes or films, molded articles, and the like.
- Films can be made by any known technique such as casting the dope onto a flat surface, extruding the dope through an extruder to form a film or extruding and blowing the dope film to form an extruded blown film.
- Typical techniques for dope film extrusion include processes similar to those used for fibers, where the solution passes through a spinneret or die into an air gap and subsequently into a coagulant bath. More details describing the extrusion and orientation of a dope film can be found in Pierini et al. (U. S. Pat. No.
- the dope film prepared is preferably no more than about 250 mils (6.35 mm) thick and more preferably it is at most about 100 mils (2.54 mm) thick.
- Fiber is defined as a relatively flexible, unit of matter having a high ratio of length to width across its cross-sectional area perpendicular to its length.
- fiber is used interchangeably with the term “filament” or “end” or “continuous filament”.
- the cross section of the filaments described herein can be any shape, such as circular or bean shaped, but is typically generally round, and is typically substantially solid and not hollow. Fiber spun onto a bobbin in a package is referred to as continuous fiber. Fiber can be cut into short lengths called staple fiber. Fiber can be cut into even smaller lengths called floc.
- Yarns, multifilament yarns or tows comprise a plurality of fibers. Yarn can be intertwined and/or twisted.
- Fibers may be spun from solution using any number of processes, however, wet spinning and air-gap spinning are the best known.
- wet spinning the spinneret extrudes the fiber directly into the liquid of a coagulation bath and typically the spinneret is immersed or positioned beneath the surface of the coagulation bath.
- air-gap spinning also sometimes known as "dry-jet” wet spinning
- the spinneret extrudes the fiber first into a gas, such as air, for a very short duration and then the fiber is immediately introduced into a liquid coagulation bath.
- the spinneret is positioned above the surface of the coagulation bath, creating an "air-gap" between the spinneret face and the surface of the coagulation bath.
- “Dry spinning” means a process for making a filament by extruding a solution into a heated chamber having a gaseous atmosphere to remove the solvent, leaving a solid filament.
- the solution comprises a fiber-forming polymer in a solvent which is extruded in a continuous stream through one or more spinneret holes to orient the polymer molecules.
- This is distinct from “wet spinning” or “air-gap spinning” wherein the polymer solution is extruded into a liquid precipitating or coagulating medium to regenerate the polymer filaments.
- a gas is the primary solvent extraction medium
- wet spinning a liquid is the primary solvent extraction medium.
- the filaments can then be treated with a liquid to either cool the filaments or wash the filaments to further extract remaining solvent.
- the fibers in the multi-filament yarn, or tow, after spinning can then be treated to neutralize, wash, dry, or heat treat the fibers as needed using conventional technique to make stable and useful fibers.
- the fibers formed from the polymers described herein are useful in a variety of applications. They are colorless, or colorless to white in color, although impurities can impart discoloration, and are particularly useful as flame retardant fibers as the polymers have a limiting oxygen index of about 24 or greater, or about 26 or greater, or about 28 or greater.
- fibers can be spun from sulfuric acid solutions ranging in concentration from 5 to 25 wt % polymer using a spinneret with 5-50 holes having diameter of 0.003" or 0.008".
- the volumetric flow rate of spinning solution is typically 0.3-2 mL/min.
- the fiber is then extruded directly into a coagulation bath filled with a room temperature or elevated temperature or sub-ambient temperature solution containing 0-70 wt. % sulfuric acid, saturated salt solutions, or basic aqueous solutions.
- the number, size, shape, and configuration of the orifices can be varied to achieve the desired fiber product.
- the extruded dope is fed into a coagulation bath with or without prior passage through a noncoagulating fluid layer.
- the noncoagulating fluid layer is generally air but can be any other inert gas or liquid which is a noncoagulant for the dope.
- the fibers and/or film can contain common additives such as dyes, pigments, antioxidants, delusterants, antistatic agents, and U.V. stabilizers, added either to the spin solution, dope or to the coagulation bath, or coated on the fiber during or after the spinning process.
- the fibers would exhibit good dyeability, especially cationic dyes.
- Basic or cationic dyes are water soluble and dissociate into anions and colored cations.
- the cations have a strong affinity for the sulfonic group in the polymer masterbatch, and forms salts.
- the sulfonated polyoxadiazole copolymers prepared by the process disclosed above can be neutralized either before or after formation into a shaped article, so that the H cation is replaced by another cation, typically a monovalent cation such as Li, Na, K, or NH 4 .
- a neutralization agent typically a basic salt such as sodium bicarbonate or other ion exchange agent.
- staple fibers refers to fibers that are cut to a desired length or are stretch broken, or fibers that occur naturally with or are made having a low ratio of length to the width of the cross-sectional area perpendicular to that length when compared with filaments.
- Man-made staple fibers are cut or made to a length suitable for processing on cotton, woolen, or worsted yarn spinning equipment.
- the staple fibers can have (a) substantially uniform length, (b) variable or random length, or (c) subsets of the staple fibers have substantially uniform length and the staple fibers in the other subsets have different lengths, with the staple fibers in the subsets mixed together forming a substantially uniform distribution.
- suitable staple fibers have a length of 0.25 centimeters (0.1 inches) to 30 centimeters (12 inches). In some embodiments, the length of a staple fiber is from 1 cm (0.39 in) to 20 cm (8 in). In some preferred embodiments the staple fibers made by short staple processes have a staple fiber length of 1 cm (0.39 in) to 6 cm (2.4 in).
- the staple fibers can be made by any process.
- the staple fibers can be cut from continuous straight fibers using a rotary cutter or a guillotine cutter resulting in straight (i.e., non crimped) staple fiber, or additionally cut from crimped continuous fibers having a saw tooth shaped crimp along the length of the staple fiber, with a crimp (or repeating bend) frequency of preferably no more than 8 crimps per centimeter.
- the staple fibers can also be formed by stretch breaking continuous fibers resulting in staple fibers with deformed sections that act as crimps.
- Stretch broken staple fibers can be made by breaking a tow or a bundle of continuous filaments during a stretch break operation having one or more break zones that are a prescribed distance creating a random variable mass of fibers having an average cut length controlled by break zone adjustment.
- Spun staple yarn can be made from staple fibers using traditional long and short staple ring spinning processes that are well known in the art.
- cotton system spinning fiber lengths from 1.9 to 5.7 cm (0.75 in to 2.25 in) are typically used.
- worsted or woolen system spinning fibers up to 16.5 cm (6.5 in) are typically used.
- this is not intended to be limiting to ring spinning because the yarns may also be spun using air jet spinning, open end spinning, and many other types of spinning which converts staple fiber into useable yarns.
- Spun staple yarns can also be made directly by stretch breaking using stretch-broken tow to top staple processes.
- the staple fibers in the yarns formed by traditional stretch break processes typically have length of up to 18 cm (7 in) long.
- spun staple yarns made by stretch breaking can also have staple fibers having maximum lengths of up to 50 cm (20 in.) through processes as described for example in PCT Patent Application No. WO 0077283 .
- Stretch broken staple fibers normally do not require crimp because the stretch-breaking process imparts a degree of crimp into the fiber.
- the staple fibers can also be formed by stretch breaking continuous fibers resulting in staple fibers with deformed sections that act as crimps.
- Stretch broken staple fibers can be made by breaking a tow or a bundle of continuous filaments during a stretch break operation having one or more break zones that are a prescribed distance creating a random variable mass of fibers having an average cut length controlled by break zone adjustment.
- continuous filament refers to a flexible fiber having relatively small-diameter and whose length is longer than those indicated for staple fibers.
- Continuous filament fibers and multifilament yarns of continuous filaments can be made by processes well known to those skilled in the art.
- aramid fiber can be used in the blend as the textile staple fiber.
- meta-aramid fibers are used in the blend as the textile staple fiber.
- aramid is meant a polyamide wherein at least 85% of the amide (-CONH-) linkages are attached directly to two aromatic rings.
- a meta-aramid is such a polyamide that contains a meta configuration or meta-oriented linkages in the polymer chain. Meta-aramid fibers are currently available under the trademarks Nomex® from E. I. du Pont de Nemours of Wilmington, Delaware.
- Additives can be used with the aramid and, in fact it has been found that up to as much as 10 percent, by weight, of other polymeric material can be blended with the aramid or that copolymers can be used having as much as 10 percent of other diamine substituted for the diamine of the aramid or as much as 10 percent of other diacid chloride substituted for the diacid chloride of the aramid.
- the preferred meta-aramid fiber is poly(meta-phenylene isophthalamide) (MPD-I). This fiber may be spun by dry or wet spinning using any number of processes; United States Patent Nos. 3,063,966 and 5,667,743 are illustrative of useful processes.
- para-aramid fibers can be used as the textile staple fiber in the blend for increased flame strength and reduced thermal shrinkage.
- Para-aramid fibers are currently available under the trademarks Kevlar® from E. I. du Pont de Nemours of Wilmington, Delaware and Twaron® from Teijin Ltd. of Tokyo, Japan.
- Technora® fiber which is available from Teijin Ltd. of Tokyo, Japan, and is made from copoly(p-phenylene/3,4'diphenyl ester terephthalamide), is considered a para-aramid fiber.
- polyazole fibers can be used as the textile fiber in the blend.
- suitable polyazoles include polybenzazoles, polypyridazoles, and the like, and can be homopolymers or copolymers. Additives can be used with the polyazoles and up to as much as 10 percent, by weight, of other polymeric material can be blended with the polyazoles. Also copolymers can be used having as much as 10 percent or more of other monomer substituted for a monomer of the polyazoles.
- Suitable polyazole homopolymers and copolymers can be made by known procedures, such as those described in U.S. Patents 4,533,693 (to Wolfe, et al., on Aug.
- the preferred polybenzazoles are polybenzimidazoles, polybenxothiazoles, and polybenzoxazoles. If the polybenzazole is a polybenzimidazole, preferably it is poly[5,5'-bi-1H-benzimidazole]-2,2'-diyl-1,3-phenylene which is called PBI. If the polybenzazole is a polybenxothiazole, preferably it is a polybenxobisthiazole and more preferably it is poly(benxo[1,2-d:4,5-d']bisthiazole-2,6-diyl-1,4-phene which is called PBT.
- the polybenzazole is a polybenzoxazole, preferably it is a polybenzobisoxazole and more preferably it is poly(benzo[1,2-d:4,5-d']bisoxazole-2,6-diyl-1,4-phenylene which is called PBO.
- the preferred polypyridazoles are rigid rod polypyridobisazoles including poly(pyridobisimidazole), poly(pyridobisthiazole), and poly(pyridobisoxazole).
- the preferred poly(pyridobisoxazole) is poly(1,4-(2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d']bisimidazole which is called PBI.
- Suitable polypyridobisazoles can be made by known procedures, such as those described in U.S. Patent 5,674,969 .
- modacrylic fibers can be used.
- the preferred modacrylic fibers used in this invention are copolymers of acrylonitrile combined with vinylidene chloride.
- the copolymer can have, in addition, an antimony oxide or antimony oxides for improved fire retardancy.
- Such useful modacrylic fibers include, but are not limited to, fibers disclosed in United States Patent No. 3,193,602 having 2 weight percent antimony trioxide, fibers disclosed in United States Patent No. 3, 748,302 made with various antimony oxides that are present in an amount of at least 2 weight percent and preferably not greater than 8 weight percent, and fibers disclosed in United States Patent Nos. 5,208,105 & 5,506,042 having 8 to 40 weight percent of an antimony compound.
- the preferred modacrylic fiber is commercially available from Kaneka Corporation, Japan, in various forms, some containing no antimony oxides while others such as Protex C are said to contain 10 to 15 weight percent of those compounds.
- the various types of staple fibers are present as a staple fiber blend.
- fiber blend it is meant the combination of two or more staple fiber types in any manner.
- the staple fiber blend is an "intimate blend", meaning the various staple fibers in the blend form a relatively uniform mixture of the fibers.
- the two or more staple fiber types are blended prior to or while the yarn is being spun so that the various staple fibers are distributed homogeneously in the staple yarn bundle.
- Fabrics can be made from the spun staple yarns and can include, but is not limited to, woven or knitted fabrics.
- General fabric designs and constructions are well known to those skilled in the art.
- woven fabric is meant a fabric usually formed on a loom by interlacing warp or lengthwise yarns and filling or crosswise yarns with each other to generate any fabric weave, such as plain weave, crowfoot weave, basket weave, satin weave, twill weave, and the like. Plain and twill weaves are believed to be the most common weaves used in the trade and are preferred in many embodiments.
- knitted fabric is meant a fabric usually formed by interlooping yarn loops by the use of needles.
- spun staple yarn is fed to a knitting machine which converts the yarn to fabric.
- multiple ends or yarns can be supplied to the knitting machine either plied of unplied; that is, a bundle of yarns or a bundle of plied yarns can be co-fed to the knitting machine and knitted into a fabric, or directly into a article of apparel such as a glove, using conventional techniques.
- it is desirable to add functionality to the knitted fabric by co-feeding one or more other staple or continuous filament yarns with one or more spun staple yarns having the intimate blend of fibers.
- the tightness of the knit can be adjusted to meet any specific need.
- a very effective combination of properties for protective apparel has been found in for example, single jersey knit and terry knit patterns.
- the spun staple yarns can be used to make flame-resistant garments.
- the garments can have essentially one layer of the protective fabric made from the spun staple yarn.
- Exemplary garments of this type include jumpsuits and coveralls for fire fighters or for military personnel. Such suits are typically used over the firefighters clothing and can be used to parachute into an area to fight a forest fire.
- Other garments can include pants, shirts, gloves, sleeves and the like that can be worn in situations such as chemical processing industries or industrial electrical/utility where an extreme thermal event might occur.
- the fabrics have an arc resistance of at least 0.8 calories per square centimeter per ounce per square yard.
- the fiber mixture of the sulfonated naphthalene polyoxadiazole based staple fiber and the textile staple fiber is formed by making an intimate blend of the fibers. If desired, other staple fibers can be combined in this relatively uniform mixture of staple fibers.
- the blending can be achieved by any number of ways known in the art, including processes that creel a number of bobbins of continuous filaments and concurrently cut the two or more types of filaments to form a blend of cut staple fibers; or processes that involve opening bales of different staple fibers and then opening and blending the various fibers in openers, blenders, and cards; or processes that form slivers of various staple fibers which are then further processed to form a mixture, such as in a card to form a sliver of a mixture of fibers.
- Other processes of making an intimate fiber blend are possible as long as the various types of different fibers are relatively uniformly distributed throughout the blend. If yarns are formed from the blend, the yarns have a relatively uniform mixture of the staple fibers also.
- the individual staple fibers are opened or separated to a degree that is normal in fiber processing to make a useful fabric, such that fiber knots or slubs and other major defects due to poor opening of the staple fibers are not present in an amount that detract from the final fabric quality.
- the intimate staple fiber blend is made by first mixing together staple fibers obtained from opened bales, along with any other staple fibers, if desired for additional functionality.
- the fiber blend is then formed into a sliver using a carding machine.
- a carding machine is commonly used in the fiber industry to separate, align, and deliver fibers into a continuous strand of loosely assembled fibers without substantial twist, commonly known as carded sliver.
- the carded sliver is processed into drawn sliver, typically by, but not limited to, a two-step drawing process.
- Spun staple yarns are then formed from the drawn sliver using techniques including conventional cotton system or short-staple spinning processes such as open-end spinning and ring-spinning; or higher speed air spinning techniques such as Murata air-jet spinning where air is used to twist the staple fibers into a yarn.
- the formation of spun yarns can also be achieved by use of conventional woolen system or long-staple processes such as worsted or semi-worsted ring-spinning or stretch-break spinning. Regardless of the processing system, ring-spinning is the generally preferred method for making the spun staple yarns.
- pre-reacted NDA is used.
- 2,6-NDA was dissolved in 18.7% oleum, and the reaction was allowed to proceed for 6.5 hours at 130 °C.
- the reactor was charged with hydrazine sulfate and the other dicarboxylic acids, in the same ratios as above.
- the mixture of sulfonated 2,6-NDA was then added.
- the mixture contained a lot of solid chunks which did not incorporate into the reaction mixture.
- the polymerization was allowed to proceed for 4 hours at 130 °C.
- the polymer reaction mixture was diluted with sulfuric acid (95-98%). Sufficient sulfuric acid was added so that the solution viscosity was high enough such that a thin continuous stream could be dropped into a blender containing water while rotating at a rate, to ensure that the coagulated fiber not be pulled apart. Optimization of this process was determined for each polymerization.
- a rubber septum was added to the top of the blender blade, which allowed for the fiber to be wound around and collected.
- the fiber was then rewound onto a glass vial, typically by hand, washed with water, and then soaked in dilute sodium bicarbonate until fully neutralized.
- the fiber was then washed and soaked with water to remove any residual sodium bicarbonate.
- the fibers were allowed to dry at ambient conditions. In some examples, a sample of the fiber was dried under high vacuum at room temperature for molecular weight determination by size exclusion chromatography (SEC) in methane sulfonic acid.
- SEC size exclusion chromatography
- the fibers were spun from sulfuric acid solutions that ranged in concentration from 6-9 wt % polymer.
- the solution was delivered by a gear pump through a spinneret with 5-20 holes having diameter of 0.003" or 0.008".
- the volumetric flow rate of spinning solution was 0.2-2 mL/min.
- the fiber was extruded directly into a coagulation bath filled with a room temperature solution that was 0-70 wt. % sulfuric acid.
- the fiber emerged from the coagulation bath through a ceramic guide into a wash bath of room temperature water. In the wash bath the fiber was wrapped around two speed-controlled driven rolls and then drawn 50-600%. Three wraps were usually made around each of these rolls.
- the fiber was wound onto a phenolic core.
- the wound fiber bobbins were then neutralized in 0.5 wt % sodium bicarbonate or sodium hydroxide solution, washed in de-ionized water and air dried at room temperature in a series of batch steps.
- the polymerization solution was diluted with sulfuric acid (95-98%) until the viscosity achieved would allow pouring onto a glass plate to give a uniform film. This viscosity was typically less than the viscosity required to coagulate fiber.
- the polymer and glass plate were immersed into a water bath in order to coagulate the film.
- the coagulated film was washed with water and then soaked in dilute sodium bicarbonate until fully neutralized.
- the film was then washed and soaked with water to remove any residual sodium bicarbonate.
- the film was pressed under varying amounts of pressure between paper towels, repeatedly, until mostly dry by touch.
- the film was then placed between aluminum foil sheets and pressed at 10,000 lb for 5 minutes.
- the resulting film was dried under high vacuum at room temperature for 24 hours.
- Limiting Oxygen Index is the minimum concentration of oxygen, expressed as a volume percent, in a mixture of oxygen and nitrogen that will just support the flaming combustion of a material initially at room temperature under the conditions of ASTM G125 / D2863.
- LOI was measured using a modified ASTM method (ASTM D 2863) to allow for rapid screening of the samples. Films were mounted in sample holder which was inserted in the LOI apparatus and covered with a glass chimney. The oxygen content within the glass chimney was controlled digitally. The film was exposed to a flame, and the oxygen level in the chimney was increased until the sample burns. The LOI of any given sample was measured at the point at which candle-like burning can be sustained.
- Oleum was replaced by polyphosphoric acid and sulfuric acid was replaced by phosphoric acid (2) Comparative example. Reaction temperature was increased to 140°C instead of 130°C as described in the general procedure. All other specifications are the same. (3) Comparative example. Reaction temperature was increased to 150°C instead of 130°C as described in the general procedure. All other specifications are the same. (4) Comparative example. Reaction temperature was increased to 160°C instead of 130°C as described in the general procedure. All other specifications are the same. (5) Pre-reacted (sulfonated) 2,6-NDA was used. (6) Isophthalic acid: IA. 5 molar equivalents of oleum used.
- 2,6-Naphthalene dicarboxylic acid (0.5053 g, Aldrich 99%) was added to 27.9g of 18.7 % oleum.
- the material was heated to 130°C and reacted with stirring by magenetic bar for 30 minutes. The reaction was removed from heat and allowed to cool to room temperature.
- 1 H NMR spectrum and LC/MS were performed and indicate that the desired sulfonated products were formed.
- a saturated solution of the monosulfonated sulfone product was prepared in water-d 2 containing a trace of sodium 3-trimethylsilylpropionate-d 4 as a chemical shift referent. The solution was inserted in a NMR probe.
- Literature comparison permitted assignment of the 1 H resonances of the primary disulfonated product.
- the 1 H assignments (in ppm relative to chemical shift referent at 0.00 ppm) are shown in the following below.
- Fibers were made from the polymer of Example 1 using the following procedure.
- the fibers were spun from sulfuric acid solutions with a concentration of 7.2 wt % (15 mol% NDA) POD co-polymer.
- the solution was delivered by a gear pump through a spinneret with 10 holes having diameter of 0.005".
- the volumetric flow rate of spinning solution was 1.8 mL/min.
- the fiber was extruded directly into a coagulation bath filled with a room temperature solution that was 56 wt. % sulfuric acid.
- the fiber emerged from the coagulation bath through a ceramic guide into a wash bath of room temperature solution of NaOH in water maintained at a pH ⁇ 12.0.
- the fiber was wrapped around two speed-controlled driven rolls and then drawn 400%. Three wraps were usually made around each roll.
- the fiber was wound onto a phenolic core.
- the wound fiber bobbins were then washed in de-ionized water and air dried at room temperature in a series of
- Fibers were made from the polymer of Example 2 using the following procedure.
- the fibers were spun from sulfuric acid solutions with a concentration of 7.8 wt % (20 mol% NDA) POD co-polymer.
- the solution was delivered by a gear pump through a spinneret with 20 holes having diameter of 0.005".
- the volumetric flow rate of spinning solution was 1.8 mL/min.
- the fiber was extruded directly into a coagulation bath filled with a room temperature solution that was 58 wt. % sulfuric acid.
- the fiber emerged from the coagulation bath through a ceramic guide into a wash bath of room temperature solution of NaOH in water maintained at a pH ⁇ 12.0.
- the fiber was wrapped around two speed-controlled driven rolls and then drawn 340%. Three wraps were usually made around each roll.
- the fiber was wound onto a phenolic core.
- the wound fiber bobbins were then washed in de-ionized water and air dried at room temperature in a series
- the mixture was further heated to 70 °C for 15 minutes, and then to 100-130 °C for 60 minutes, it took ⁇ 5-10 minutes to increase the heat.
- the solution was removed leaving the fiber behind in the flask.
- the fiber was then washed with hot de-ionized water ( ⁇ 70 °C), and again with room temperature de-ionized water.
- a solution of MERPOL® HCS 0.061 g of a 0.1 wt% solution
- de-ionized water 50g
- the fiber was then washed with hot de-ionized water ( ⁇ 70°C) and room temperature de-ionized water sequentially.
- the fiber was wrapped in a Sontara® SPSTM towel to dry. Fibers were analyzed by cross-section. Images indicate distribution of each dye to the core of the fiber. (Fibers dyed at lower concentration of dye showed dye penetration to the core, but the absence of dye around the sheath; fibers dyed at higher concentrations of dye showed uniform dye penetration.)
- the mixture was further heated to 70 °C for 15 minutes, and then to 100-130 °C for 60 minutes, it took ⁇ 5-10 minutes to increase the heat.
- the solution was removed leaving the fiber behind in the flask.
- the fiber was then washed with hot de-ionized water ( ⁇ 70 °C), and again with room temperature de-ionized water.
- a solution of MERPOL® HCS 0.061 g of a 0.1 wt% solution
- de-ionized water 50g
- the fiber was then washed with hot de-ionized water ( ⁇ 70 °C) and room temperature de-ionized water sequentially.
- the fiber was wrapped in a Sontara® SPSTM towel to dry. Fibers were analyzed by cross-section. Images indicate distribution of each dye to the core of the fiber. (Fibers dyed at lower concentration of dye showed dye penetration to the core, but the absence of dye around the sheath; fibers dyed at higher concentrations of dye showed uniform dye penetration.)
- the mixture was further heated to 70 °C for 15 minutes, and then to 25-100 °C for 60 minutes, it took ⁇ 5-10 minutes to increase the heat.
- the solution was removed leaving the fiber behind in the flask.
- the fiber was then washed with hot de-ionized water ( ⁇ 70°C), and again with room temperature de-ionized water.
- a solution of MERPOL® HCS 0.061 g of a 0.1 wt% solution
- de-ionized water 50g
- the fiber was then washed with hot de-ionized water ( ⁇ 70 °C) and room temperature de-ionized water sequentially.
- the fiber was wrapped in a Sontara® SPSTM towel to dry. Fibers were analyzed by cross-section. Images indicate distribution of each dye to the core of the fiber. (Fibers dyed at lower concentration of dye showed dye penetration to the core, but the absence of dye around the sheath; fibers dyed at higher concentrations of dye showed uniform dye penetration.)
- POD-NDA yarns were then separated into single filaments and mounted to a cardboard frame to provide full exposure to light.
- the cardboard frames were placed into a Xe arc chamber and the test was conducted for 96 hrs following AATCC 16E: Colorfastness to Light standardized test. Filaments were conditioned at 70F & 60% humidity for 18 hrs.
- Denier was measured using the TEXTTECHNO Vibromat. Samples were cut into 9 cm segments and approximate denier were calculated by weight when appropriate (1den 1g/9000m). This approximate denier was programmed into the Vibromat to determine the appropriate balance weight. Denier was determined by TEXTECHNO vibromat software and analysis was replicated 5-6 times.
- This example illustrates flame-resistant spun yarns and fabrics of intimate blends of the NDA-POD fiber from Example 25 and a textile staple fiber having limiting oxygen index of 24 or greater and a tenacity of about 4 grams per denier or greater, such as poly(meta-phenylene isophthalamide) (MPD-I) fiber available from E. I. duPont de Nemours & Company under the trademark Nomex® fiber.
- MPD-I poly(meta-phenylene isophthalamide)
- a picker blend sliver of 50 weight percent of NDA-POD staple fiber and 50 weight percent of MPD-I staple fiber is prepared and processed by conventional cotton system equipment and spun into a flame resistant spun staple yarn having a twist multiplier of about 4.0 and a single yarn size of about 21 tex (28 cotton count) using a ring spinning frame. Two such single yarns are then plied on a plying machine to make a two-ply flame resistant yarn for use as a fabric warp yarn. Using the same blend and a similar process, including the same twist and blend ratio, a 24 tex (24 cotton count) singles yarn is made, and two of these single yarns are plied to form a two-ply flame resistant yarn for use as a fabric fill yarn.
- Both of these two-ply warp and two-ply fill yarns have a tenacity greater than the tenacity of a two-ply 100% NDA-POD staple fiber yarn made under similar conditions, i. e., the two-ply yarns have a tenacity of at least 3 grams per denier (2.7 grams per dtex).
- the ring-spun warp and fill yarns are woven into a fabric on a shuttle loom, making a greige fabric having a 2x1 twill weave and a construction of 26 ends x 17 picks per cm (72 ends x 52 picks per inch), and a basis weight of about 215 g/m 2 (6.5 oz/yd 2 ).
- the greige twill fabric is then scoured in hot water and is dried under low tension.
- the scoured fabric is then jet dyed using basic dye.
- the resulting fabric has a basis weight of about 231 g/m 2 (7 oz/yd 2 ) and an LOI in excess of 28.
- a portion of the fabric is cut into various shapes and the shapes are sewn together to convert the fabric into single-layer protective garments useful for those exposed to thermal hazards.
- ring-spun yarns, and associated fabric and garment are made from 100% NDA-POD staple fiber as a control.
- Table 2 illustrates the properties of the resulting fabric and garments. A “+” indicates superior properties to those of the control, while the notation "0" indicates the performance of the control or performance equivalent to the control.
- Table 2 Property 100% NDA-POD Example 27 Grab Test Break Strength (lbf) W/F 0 + Trap Tear (lbf) W/F 0 + Taber Abrasion (Cycles)CS-10/1000 g 0 + TPP (cal/cm 2 ) 0 0 0 Vertical Flame (in) W/F 0 0 Instrumented Thermal Manikin Test (% of body burn) 0 - ARC rating(cal/cm 2 ) 0 -
- This example illustrates flame-resistant spun yarns and fabrics of intimate blends of the NDA-POD fiber from Example 24 and a modacrylic fiber, such as modacrylic fiber made by Kaneka Corporation under the trademark of Protex C®.
- a picker blend sliver of 65 weight percent of NDA-POD staple fiber and 35 weight percent of modacrylic staple fiber is prepared and processed by the conventional cotton system equipment and spun into a flame resistant spun staple yarn having a twist multiplier of about 4.0 and a single yarn size of about 21 tex (28 cotton count) using a ring spinning frame. Two such single yarns are then plied on a plying machine to make a two-ply flame resistant yarn for use as a fabric warp yarn. Using the same blend and a similar process, and the same twist and blend ratio, a 24 tex (24 cotton count) singles yarn is made, and two of these single yarns are plied to form a two-ply flame resistant yarn for use as a fabric fill yarn.
- Both of these two-ply warp and two-ply fill yarns have a tenacity greater than the tenacity of a two-ply 100% NDA-POD staple fiber yarn made under similar conditions, i. e., the two-ply yarns have a tenacity of at least 3 grams per denier (2.7 grams per dtex).
- the ring-spun warp and fill yarns are woven into a fabric on a shuttle loom, making a greige fabric having a 2x1 twill weave and a construction of 26 ends x 17 picks per cm (72 ends x 52 picks per inch), and a basis weight of about 215 g/m 2 (6.5 oz/yd 2 ).
- the greige twill fabric is then scoured in hot water and is dried under low tension.
- the scoured fabric is then jet dyed using basic dye.
- the resulting fabric has a basis weight of about 231 g/m 2 (7 oz/yd 2 ) and an LOI in excess of 28.
- a portion of the fabric is cut into various shapes and the shapes are sewn together to convert the fabric into single-layer protective garments useful for those exposed to thermal hazards.
- ring-spun yarns, and associated fabric and garment are made from 100% NDA-POD staple fiber as a control.
- Table 3 illustrates the properties of the resulting fabric and garments. A “+” indicates superior properties to those of the control, while the notation "0" indicates the performance of the control or performance equivalent to the control. Table 3 Property 100% NDA-POD Example 28 Grab Test Break Strength (lbf) W/F 0 + Trap Tear (lbf) W/F 0 + Taber Abrasion (Cycles)CS-10/1000 g 0 - TPP (cal/cm 2 ) 0 0 Vertical Flame (in) W/F 0 0 Instrumented Thermal Manikin Test (% of body burn) 0 - ARC rating(cal/cm 2 ) 0 +
- This example illustrates flame-resistant spun yarns and fabrics of intimate blends of the NDA-POD fiber from Example 25 and a fiber having high modulus, specifically a tensile modulus of 200 grams per denier or greater, such as poly(paraphenylene terephthalamide) (PPD-T) fiber available from E. I. duPont de Nemours & Company under the trademark Kevlar® fiber.
- PPD-T poly(paraphenylene terephthalamide)
- a picker blend sliver of 85 weight percent of the NDA-POD staple fiber and 15 weight percent of PPD-T staple fiber is prepared and processed by conventional cotton system equipment and spun into a flame resistant spun staple yarn having a twist multiplier of about 4.0 and a single yarn size of about 21 tex (28 cotton count) using a ring spinning frame.
- Two such single yarns are then plied on a plying machine to make a two-ply flame resistant yarn for use as a fabric warp yarn Using the same blend and a similar process, including the same twist and blend ratio, a 24 tex (24 cotton count) singles yarn is made, and two of these single yarns are plied to form a two-ply flame resistant yarn for use as a fabric fill yarn.
- Both of these two-ply warp and two-ply fill yarns have a tenacity greater than the tenacity of a two-ply 100% NDA-POD staple fiber yarn made under similar conditions, i. e., the two-ply yarns have a tenacity of at least 3 grams per denier (2.7 grams per dtex).
- the ring-spun warp and fill yarns are woven into a fabric on a shuttle loom, making a greige fabric having a 2x1 twill weave and a construction of 26 ends x 17 picks per cm (72 ends x 52 picks per inch), and a basis weight of about 215 g/m 2 (6.5 oz/yd 2 ).
- the greige twill fabric is then scoured in hot water and is dried under low tension.
- the scoured fabric is then jet dyed using basic dye.
- the resulting fabric has a basis weight of about 231 g/m 2 (7 oz/yd 2 ) and an LOI in excess of 28.
- a portion of the fabric is cut into various shapes and the shapes are sewn together to convert the fabric into single-layer protective garments useful for those exposed to thermal hazards.
- ring-spun yarns, and associated fabric and garment are made from 100% NDA-POD staple fiber as a control.
- Table 4 illustrates the properties of the resulting fabric and garments. A “+” indicates superior properties to those of the control, while the notation "0" indicates the performance of the control or performance equivalent to the control.
- Table 4 Property 100% NDA-POD Example 29 Grab Test Break Strength (lbf) W/F 0 - Trap Tear (lbf) W/F 0 + Taber Abrasion (Cycles)CS-10/1000 g 0 + TPP (cal/cm 2 ) 0 0 0 Vertical Flame (in) W/F 0 + Instrumented Thermal Manikin Test (% of body burn) 0 0 ARC rating(cal/cm 2 ) 0 0 0
- Example 29 is repeated, except the picker blend sliver contains 40 weight percent of the NDA-POD staple fiber and 60 weight percent of the PPD-T staple fiber. As in Example 29, ring-spun yarns, and associated fabric and garment are made from 100% NDA-POD staple fiber as a control.
- Table 5 illustrates the properties of the resulting fabric and garments. A “+” indicates superior properties to those of the control, while the notation "0" indicates the performance of the control or performance equivalent to the control.
- Table 5 Property 100% NDA-POD Example 30 Grab Test Break Strength (lbf) W/F 0 + Trap Tear (lbf) W/F 0 + Taber Abrasion (Cycles)CS-10/1000 g 0 + TPP (cal/cm 2 ) 0 0 0 Vertical Flame (in) W/F 0 + Instrumented Thermal Manikin Test (% of body burn) 0 0 ARC rating(cal/cm 2 ) 0 0 0
- Example 29 is repeated, except the picker blend sliver contains 60 weight percent of the NDA-POD staple fiber and 40 weight percent of the FR rayon. As in Example 29, ring-spun yarns, and associated fabric and garment are made from 100% NDA-POD staple fiber as a control.
- Table 6 illustrates the properties of the resulting fabric and garments. A “+” indicates superior properties to those of the control, while the notation "0" indicates the performance of the control or performance equivalent to the control.
- Table 6 Property 100% NDA-POD Example 30 Grab Test Break Strength (lbf) W/F 0 0 Trap Tear (lbf) W/F 0 0 Taber Abrasion (Cycles)CS-10/1000 g 0 0 TPP (cal/cm 2 ) 0 0 Vertical Flame (in) W/F 0 + Instrumented Thermal Manikin Test (% of body burn) 0 + Afterglow 0 +
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Claims (12)
- Fil filé résistant aux flammes comprenant:
de 50 à 95 parties en poids d'une fibre discontinue à base de polyoxadiazole sulfoné comprenant des motifs de répétition de Formule (I) et une ou les deux des Formules (II) et (IIa):dans lequel la Formule (I) est présente sous 5 % molaire à 50 % molaire, sur la base de la quantité totale de la fibre discontinue à base de polyoxadiazole de naphtalène sulfoné, etdans lequel Q est H ou SO3M, et M est un ou plusieurs cations;et de 5 à 50 parties en poids d'une fibre discontinue textile ayant un indice limitant d'oxygène de 24 ou plus et une ténacité de 2 grammes par denier ou plus, sur la base de la quantité totale de la fibre polymère et de la fibre textile dans le fil. - Vêtement protecteur, textile tissé, textile non-tissé, courroie, ou filament comprenant le fil filé résistant aux flammes selon la revendication 1.
- Fil filé résistant aux flammes comprenant:
au moins 25 parties à 80 parties en poids d'une fibre discontinue à base de polyoxadiazole sulfoné comprenant des motifs de répétition de Formule (I) et une ou les deux des Formules (II) et (IIa):dans lequel la Formule (I) est présente sous 5 % molaire à 50 % molaire, sur la base de la quantité totale de la fibre discontinue à base de polyoxadiazole de naphtalène sulfoné, etdans lequel Q est H ou SO3M, et M est un ou plusieurs cations;et de 20 à 75 parties en poids d'une fibre modacrylique, sur la base de la quantité totale de la fibre polymère et de la fibre textile dans le fil. - Vêtement protecteur, textile tissé, textile non-tissé, courroie, ou filament comprenant le fil filé résistant aux flammes selon la revendication 3.
- Fil filé résistant aux flammes comprenant:
de 50 à 95 parties en poids d'une fibre discontinue à base de polyoxadiazole sulfoné comprenant des motifs de répétition de Formule (I) et une ou les deux des Formules (II) et (IIa):dans lequel la Formule (I) est présente sous 5 % molaire à 50 % molaire, sur la base de la quantité totale de la fibre discontinue à base de polyoxadiazole de naphtalène sulfoné, etdans lequel Q est H ou SO3M, et M est un ou plusieurs cations;et de 5 à 50 parties en poids d'une fibre discontinue de module élevé ayant un module sous traction de 200 grammes par denier ou plus, sur la base de la quantité totale de la fibre polymère et de la fibre textile dans le fil. - Vêtement protecteur, textile tissé, textile non-tissé, courroie, ou filament comprenant le fil filé résistant aux flammes selon la revendication 5.
- Fil filé résistant aux flammes comprenant:
de 20 à 50 parties en poids d'une fibre discontinue à base de polyoxadiazole sulfoné comprenant des motifs de répétition de Formule (I) et une ou les deux des Formules (II) et (IIa):dans lequel la Formule (I) est présente sous 5 % molaire à 50 % molaire, sur la base de la quantité totale de la fibre discontinue à base de polyoxadiazole de naphtalène sulfoné, etdans lequel Q est H ou SO3M, et M est un ou plusieurs cations;et de 50 à 80 parties en poids d'une fibre discontinue à tige rigide, sur la base de la quantité totale de la fibre à base de polyoxadiazole sulfoné et de la fibre textile dans le fil. - Vêtement protecteur, textile tissé, textile non-tissé, courroie, ou filament comprenant le fil filé résistant aux flammes selon la revendication 7.
- Procédé de production d'un fil filé comprenant:a) la formation d'un mélange de fibres de 50 à 95 parties en poids d'une fibre discontinue à base de polyoxadiazole comprenant des motifs de répétition de Formule (I) et une ou les deux des Formules (II) et (IIa):dans lequel la Formule (I) est présente sous 5 % molaire à 50 % molaire, sur la base de la quantité totale de la fibre discontinue à base de polyoxadiazole de naphtalène sulfoné, etdans lequel Q est H ou SO3M, et M est un ou plusieurs cations;et de 5 à 50 parties en poids d'une fibre discontinue textile ayant un indice limitant d'oxygène de 24 ou plus et une ténacité de 2 grammes par denier ou plus, sur la base de la quantité totale de la fibre polymère et de la fibre textile dans le fil; etb) le filage du mélange de fibres en un fil discontinu filé.
- Procédé de production d'un fil filé comprenant:a) la formation d'un mélange de fibres de 25 parties à 80 parties en poids d'une fibre discontinue à base de polyoxadiazole comprenant des motifs de répétition de Formule (I) et une ou les deux des Formules (II) et (IIa):dans lequel la Formule (I) est présente sous 5 % molaire à 50 % molaire, sur la base de la quantité totale de la fibre discontinue à base de polyoxadiazole de naphtalène sulfoné, etdans lequel Q est H ou SO3M, et M est un ou plusieurs cations;et de 20 à 75 parties en poids d'une fibre modacrylique, sur la base de la quantité totale de la fibre polymère et de la fibre textile dans le fil; etb) le filage du mélange de fibres en un fil discontinu filé.
- Procédé de production d'un fil filé comprenant:a) la formation d'un mélange de fibres de 50 à 95 parties en poids d'une fibre discontinue à base de polyoxadiazole comprenant des motifs de répétition de Formule (I) et une ou les deux des Formules (II) et (IIa):dans lequel la Formule (I) est présente sous 5 % molaire à 50 % molaire, sur la base de la quantité totale de la fibre discontinue à base de polyoxadiazole de naphtalène sulfoné, etdans lequel Q est H ou SO3M, et M est un ou plusieurs cations;et de 5 à 50 parties en poids d'une fibre discontinue de module élevé ayant un module sous traction de 200 grammes par denier ou plus, sur la base de la quantité totale de la fibre polymère et de la fibre textile dans le fil; etb) le filage du mélange de fibres en un fil discontinu filé.
- Procédé de production d'un fil filé comprenant:a) la formation d'un mélange de fibres de 20 à 50 parties en poids d'une fibre discontinue à base de polyoxadiazole comprenant des motifs de répétition de Formule (I) et une ou les deux des Formules (II) et (IIa):dans lequel la Formule (I) est présente sous 5 % molaire à 50 % molaire, sur la base de la quantité totale de la fibre discontinue à base de polyoxadiazole de naphtalène sulfoné, etdans lequel Q est H ou SO3M, et M est un ou plusieurs cations;et de 50 à 80 parties en poids d'une fibre discontinue à tige rigide, sur la base de la quantité totale de la fibre polymère et de la fibre textile dans le fil; etb) le filage du mélange de fibres en un fil discontinu filé.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261660115P | 2012-06-15 | 2012-06-15 | |
PCT/US2013/045127 WO2014007948A2 (fr) | 2012-06-15 | 2013-06-11 | Fils discontinus filés ignifuges constitués de mélanges de fibres dérivées de polymères de naphtalène polyoxadiazole sulfonaté |
Publications (2)
Publication Number | Publication Date |
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EP2861789A2 EP2861789A2 (fr) | 2015-04-22 |
EP2861789B1 true EP2861789B1 (fr) | 2020-09-09 |
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EP13783124.4A Active EP2861789B1 (fr) | 2012-06-15 | 2013-06-11 | Fils discontinus filés ignifuges constitués de mélanges de fibres dérivées de polymères de naphtalène polyoxadiazole sulfonaté |
Country Status (4)
Country | Link |
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EP (1) | EP2861789B1 (fr) |
JP (1) | JP6112683B2 (fr) |
CN (1) | CN104540987B (fr) |
WO (1) | WO2014007948A2 (fr) |
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CN109576843A (zh) * | 2018-12-29 | 2019-04-05 | 江苏宝德新材料有限公司 | 一种阻燃耐高温pod纤维赛络纺纺纱工艺 |
CN111424353A (zh) * | 2020-02-24 | 2020-07-17 | 山东宏业纺织股份有限公司 | 一种阻燃缝纫线及其生产工艺 |
Family Cites Families (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3063966A (en) | 1958-02-05 | 1962-11-13 | Du Pont | Process of making wholly aromatic polyamides |
US3227793A (en) | 1961-01-23 | 1966-01-04 | Celanese Corp | Spinning of a poly(polymethylene) terephthalamide |
US3193602A (en) | 1962-08-13 | 1965-07-06 | Monsanto Co | Process for the production of flame retarded acrylic fibers |
US3414645A (en) | 1964-06-19 | 1968-12-03 | Monsanto Co | Process for spinning wholly aromatic polyamide fibers |
US3869430A (en) | 1971-08-17 | 1975-03-04 | Du Pont | High modulus, high tenacity poly(p-phenylene terephthalamide) fiber |
US3869429A (en) | 1971-08-17 | 1975-03-04 | Du Pont | High strength polyamide fibers and films |
US3748302A (en) | 1971-11-17 | 1973-07-24 | Du Pont | Flame-retarded acrylonitrile fibers |
US3767756A (en) | 1972-06-30 | 1973-10-23 | Du Pont | Dry jet wet spinning process |
GB1527352A (en) * | 1974-09-17 | 1978-10-04 | Ici Ltd | Shaped articles of polyoxadiazoles |
JPS5158521A (en) * | 1975-09-17 | 1976-05-21 | Ici Ltd | Horifueniren 1 3 44 okisajiazooruno enshinfuiramentono seizoho |
JPS5881637A (ja) * | 1981-11-11 | 1983-05-17 | 帝人株式会社 | 耐熱性紡績糸 |
US4533693A (en) | 1982-09-17 | 1985-08-06 | Sri International | Liquid crystalline polymer compositions, process, and products |
US4772678A (en) | 1983-09-15 | 1988-09-20 | Commtech International Management Corporation | Liquid crystalline polymer compositions, process, and products |
US4703103A (en) | 1984-03-16 | 1987-10-27 | Commtech International | Liquid crystalline polymer compositions, process and products |
EP0183014B1 (fr) | 1984-10-05 | 1994-02-02 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Mélange de fibres retardant la flamme |
US5208105A (en) | 1984-10-05 | 1993-05-04 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Flame-retarded composite fiber |
US4939235A (en) | 1985-09-26 | 1990-07-03 | Foster-Miller, Inc. | Biaxially oriented ordered polybenzothiazole film |
US4973442A (en) | 1985-09-26 | 1990-11-27 | Foster Miller Inc. | Forming biaxially oriented ordered polymer films |
US4847350A (en) | 1986-05-27 | 1989-07-11 | The Dow Chemical Company | Preparation of aromatic heterocyclic polymers |
US4898924A (en) | 1989-01-11 | 1990-02-06 | Hoechst Celanese Corporation | Process for the production of biaxially oriented rigid rod heterocyclic liquid crystalline polymer films |
US5089591A (en) | 1990-10-19 | 1992-02-18 | The Dow Chemical Company | Rapid advancement of molecular weight in polybenzazole oligomer dopes |
US5276128A (en) | 1991-10-22 | 1994-01-04 | The Dow Chemical Company | Salts of polybenzazole monomers and their use |
US5367042A (en) | 1992-08-27 | 1994-11-22 | The Dow Chemical Company | Process for fabricating oriented polybenzazole films |
DE69412250T2 (de) | 1993-04-28 | 1999-02-11 | Akzo Nobel N.V., Arnheim/Arnhem | Pyridobismidazole enthaltendes rigid-rod-Polymer |
US5667743A (en) | 1996-05-21 | 1997-09-16 | E. I. Du Pont De Nemours And Company | Wet spinning process for aramid polymer containing salts |
KR100754706B1 (ko) | 1999-06-14 | 2007-09-03 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 신장 분할 방법 및 제품 |
US7528216B2 (en) | 2006-05-01 | 2009-05-05 | E.I. Du Pont De Nemours And Company | Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom |
US7582721B2 (en) * | 2006-05-01 | 2009-09-01 | E.I. Du Pont De Nemours And Company | Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom |
US20080014440A1 (en) * | 2006-07-13 | 2008-01-17 | Kiu-Seung Lee | Polyoxadiazole composite fibers |
US7528217B2 (en) * | 2006-10-06 | 2009-05-05 | E.I. Du Pont De Nemours And Company | Polymers and fibers formed therefrom |
DE102007007879A1 (de) | 2007-02-14 | 2008-08-21 | Gkss-Forschungszentrum Geesthacht Gmbh | Beschichtung eines Bauteils |
DE102007029542A1 (de) | 2007-06-25 | 2009-01-02 | Gkss-Forschungszentrum Geesthacht Gmbh | Verfahren zur Herstellung eines sulfonierten Poly (1,3,4-oxadiazol)-Polymers |
US7618707B2 (en) * | 2007-08-22 | 2009-11-17 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and modacrylic fibers and fabrics and garments made therefrom and methods for making same |
US7537830B2 (en) * | 2007-08-22 | 2009-05-26 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone, low thermal shrinkage fibers, flame resistant fibers, and antistatic fibers and fabrics and garments made therefrom and methods for making same |
US7700191B2 (en) * | 2007-08-22 | 2010-04-20 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and high modulus fibers and fabrics and garments made therefrom and methods for making same |
US7700190B2 (en) * | 2007-08-22 | 2010-04-20 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and textile fibers and fabrics and garments made therefrom and methods for making same |
US7537831B2 (en) * | 2007-08-22 | 2009-05-26 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and modacrylic fibers and fabrics and garments made therefrom and methods for making same |
DE102008009068A1 (de) | 2008-02-13 | 2009-08-27 | Gkss-Forschungszentrum Geesthacht Gmbh | Verfahren zur Herstellung eines Polyoxadiazol-Polymers |
EP2652010A1 (fr) * | 2010-12-16 | 2013-10-23 | E.I. Du Pont De Nemours And Company | Fils de fibres courtes, filées-liées, ignifuges, faits de mélanges de fibres issues de polymères de polyoxadiazole sulfoné |
US9370212B2 (en) * | 2011-09-02 | 2016-06-21 | E I Du Pont De Nemours And Company | Article of thermal protective clothing |
US8695319B2 (en) * | 2011-12-05 | 2014-04-15 | E I Du Pont De Nemours And Company | Yarns of polyoxadiazole and modacrylic fibers and fabrics and garments made therefrom and methods for making same |
-
2013
- 2013-06-11 EP EP13783124.4A patent/EP2861789B1/fr active Active
- 2013-06-11 CN CN201380041417.6A patent/CN104540987B/zh active Active
- 2013-06-11 JP JP2015517350A patent/JP6112683B2/ja active Active
- 2013-06-11 WO PCT/US2013/045127 patent/WO2014007948A2/fr active Application Filing
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
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JP6112683B2 (ja) | 2017-04-12 |
EP2861789A2 (fr) | 2015-04-22 |
WO2014007948A3 (fr) | 2014-05-30 |
CN104540987A (zh) | 2015-04-22 |
WO2014007948A2 (fr) | 2014-01-09 |
JP2015526601A (ja) | 2015-09-10 |
CN104540987B (zh) | 2018-08-28 |
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