US3839207A - Allyl 2-carbamoyalkylphosphonates flame retardants - Google Patents
Allyl 2-carbamoyalkylphosphonates flame retardants Download PDFInfo
- Publication number
- US3839207A US3839207A US00374190A US37419073A US3839207A US 3839207 A US3839207 A US 3839207A US 00374190 A US00374190 A US 00374190A US 37419073 A US37419073 A US 37419073A US 3839207 A US3839207 A US 3839207A
- Authority
- US
- United States
- Prior art keywords
- diallyl
- allyl
- phosphonate
- flame
- substrate
- 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.)
- Expired - Lifetime
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 8
- -1 ALLYL Chemical class 0.000 claims description 41
- 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 claims description 25
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 34
- 239000000758 substrate Substances 0.000 abstract description 34
- 239000004753 textile Substances 0.000 abstract description 31
- 230000008569 process Effects 0.000 abstract description 25
- 150000003254 radicals Chemical class 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 6
- 230000000979 retarding effect Effects 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 4
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 description 22
- 239000000835 fiber Substances 0.000 description 21
- 230000005855 radiation Effects 0.000 description 20
- 239000000123 paper Substances 0.000 description 14
- 230000008859 change Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- ABTNKPAZMOYEAS-UHFFFAOYSA-N oxo-bis(prop-2-enoxy)phosphanium Chemical compound C=CCO[P+](=O)OCC=C ABTNKPAZMOYEAS-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- NZRFSLMXTFGVGZ-UHFFFAOYSA-N n-[diethylamino(prop-2-enoxy)phosphoryl]-n-ethylethanamine Chemical compound CCN(CC)P(=O)(N(CC)CC)OCC=C NZRFSLMXTFGVGZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000009988 textile finishing Methods 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000007730 finishing process Methods 0.000 description 4
- 238000004900 laundering Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000011953 free-radical catalyst Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 240000000491 Corchorus aestuans Species 0.000 description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000003685 thermal hair damage Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- KHTDRXGBOWZUAA-UHFFFAOYSA-N (3-amino-3-oxopropyl)phosphonic acid Chemical compound NC(=O)CCP(O)(O)=O KHTDRXGBOWZUAA-UHFFFAOYSA-N 0.000 description 1
- QQAHAGNPDBPSJP-UHFFFAOYSA-N 1,1,1,2,2,3,3,3-octachloropropane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl QQAHAGNPDBPSJP-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 1
- LHHMNJZNWUJFOC-UHFFFAOYSA-N 1-chloro-2-[2-chloroethoxy(ethenyl)phosphoryl]oxyethane Chemical compound ClCCOP(=O)(C=C)OCCCl LHHMNJZNWUJFOC-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- UOZFZTBMPVGXHS-UHFFFAOYSA-N OP(=O)OCCC#N Chemical compound OP(=O)OCCC#N UOZFZTBMPVGXHS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920001617 Vinyon Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- OXLDKMFHLBAHLV-UHFFFAOYSA-N bis(prop-2-enyl) hydrogen phosphite Chemical compound C=CCOP(O)OCC=C OXLDKMFHLBAHLV-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000011093 chipboard Substances 0.000 description 1
- 229910052801 chlorine Chemical group 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- UYDLBVPAAFVANX-UHFFFAOYSA-N octylphenoxy polyethoxyethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCO)C=C1 UYDLBVPAAFVANX-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006298 saran Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6521—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/10—Phosphorus-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/0002—Flame-resistant papers; (complex) compositions rendering paper fire-resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/92—Fire or heat protection feature
- Y10S428/921—Fire or flameproofing
Definitions
- diallyl phosphorus compounds such, for example, as diallyl 2-cyanoethyl phosphonate, 35
- a novel flame retardant finishing process which is suitable for use with textiles made from either natural or synthetic fibers as well as with blends of each of the latter fiber types. It is another object of this invention to provide a flame retardant finishing process for various other flammable, solid substrates such, for example as paper, wood, batting and rope, which are capable of beingimpregnated and/or coated with a flame retardant, resinous finish. It is a further object to provide a flame retardant textile finishing process which is operable at ambient or moderately elevated temperatures and which can employ aqueous systems thereby avoiding fabric degradation and the need for expensive and troublesome organic solvents. Another object is to provide a process for flame retarding textiles which is op- 6 erable with low add-ons of the flame retardant finish thereby providing a pleasing hand to the finished fabrics.
- R is a hydrogen or methyl radical.
- exemplary of those compounds are diallyl 2-carbamoylethylphos- 2-carbamoylisopropylphosphonate, N,N'-methylenebis(diallyl 2-carbamoylethylphosphonate) and N,N'-methylenebis(diallyl Z-carbamoylisopropylphosphonate).
- These flame retardants are applied to a fabric or other substrate at a concentration 20 of from about 5 to 40 percent, as calculated on the dry weight of the substrate, and are thereafter cured, i.e. polymerized, so as to form an insoluble, fire retardant resinous finish by free radical initiation using either a chemical initiator or actinic radiation in, order to in- '25 quiz the desired reaction.
- diallyl compounds used as flame retardants in the process of this invention i.e. diallyl Z-carbamoylethylphosphonate and diallyl 2-carbamoylisopropylphosphonate
- diallyl phosphonate i.e. diallyl Z-carbamoylethylphosphonate and diallyl 2-carbamoylisopropylphosphonate
- diallyl phosphonate i.e. diallyl Z-carbamoylethylphosphonate and diallyl 2-carbamoylisopropylphosphonate
- diallyl compounds are crystalline, colorless solids of negligible odor which are soluble in many organic solvents as well as in water.
- the above listed tetraallyl compounds i.e. N,N'-methylenebis(diallyl 2-carbamoylethylphosphonate) and N,N-methylenebis(diallyl 2- carbamoylisopropylphosphonate
- N,N-methylenebis(diallyl 2- carbamoylisopropylphosphonate) are new compositions of matter which are prepared by means of the base catalyzed addition of at least two moles of diallyl phosphonate per mole of either N,N- methylenebisacrylamide or N,N'-methylenebismethacrylamide.
- diallyl phosphonate and the N,N-methylenebisacrylamide or N,N- '-methylenebismethacrylamide may be combined in the absence of a solvent or, if desired, they may be slurried in a suitable non-interfering solvent such, for example, as methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, acetone or dioxane.
- the selected base catalyst which can be sodium methylate, an alkali metal hydroxide or any other suitable basic material, is then introduced into the reaction mixture in a concentration of from about 0.001 to 10 percent, as based upon the diallyl phosphonate, resulting in an exothermic reaction which may cause the mixture to boil.
- Trace solids are removed from the resulting reaction mixture by filtration yielding the tetraallyl com- 'dant additives and monomers such as those which can be made by the addition of bromine to all or part of the double bonds of these compounds.
- the novel tetraallyl 2-carbamoylakylphosphonates as well as the diallyl 2-carbamoylalkylphosphonates of the prior art will, in this disclosure, be collectively referred to as the allyl phosphonates.”
- aqueous solutions comprises the most economical means of application forthese allyl phosphonate flame retardants, they may also, if desired, be applied to a normally flammable substrate while dissolved in any of the organic solvents commonly used in the solvent finishing of textiles including, for example, trichloroethylene, dischloroethane, trichloroethane, perchloroethylene, methylene chloride, etc. and mixtures thereof.
- the solutions, either aqueous or organic solvent, containing one or more of the selected allyl phosphonates may be applied to textiles or other substrates by the use of any desired procedure.
- diallyl phosphonate evenly absorbed throughout the mass of the textile, or other substrate, and/or to apply it to at least one surface thereof by means of any convenient procedure.
- it may be applied by being sprayed onto one or both surfaces of the substrate or, as is more frequently the case, the substrate may be passed or padded through the solution while the latter is being held in a tank or other suitable container.
- a padding technique is commonly referred to as a padding bath or padding solution.
- the concentration of the allyl phosphonate within the padding bath, or other applicable solution, will be dependent upon a member of factors including, in the case of textile substrates, the nature of the fibers which comprise the textile, the weight and weave of the textile, the degree of flameproofmg that is desired in the flnished textile, as well as other technical and economic considerations known and understood by those skilled in the art.
- the padding bath should contain an amount of the phosphonate such that when the wet uptake is reduced to a dry deposit upon the textile or other substrate, the treated substrate will contain from about 5 to 40 percent of the allyl phosphonate, as based upon the dry weight of the substrate.
- the latter limits are merely illustrative and may be varied so as to provide a finished article having any desired degree of flame retardancy.
- the thus applied allyl phosphonate may be cured in the wet state or it may be completely or, most preferably, partially dried before curing.
- the mode of curing in accordance with the process of the invention involves the use of a free radical initiated reaction in order to induce the double bonds, i.e. the ethylenic unsaturation, of the allyl groups present in these compounds to polymerize intermolecularly so as to form a crosslinked, insoluble resin in and/or on the individual fibers, or other structural elements, which comprise the textile or other substrate.
- Free radical initiation of the desired polymerization reaction may be induced either by the use of those chemical catalysts known as free radical initiators or by the use of the actinic radiation.
- Suitable free radical catalysts encompass peroxygen compounds, which may be used as part of a so-called redox system which contain a chemical reducing agent in addition to the peroxygen compound, and azo compounds.
- Suitable peroxygen catalyst are hydrogen peroxide, which is often used in conjunction with ferrous salts; ammonium, sodium or potassium persulfate; t-butyl hydroperoxide; benzoyl peroxide; lauroyl peroxide; dicumyl peroxide; cumene hydroperoxide; t-butyl peroxypivalate; methyl ethyl ketone peroxide; caprylyl peroxide and acetyl peroxide.
- suitable azo catalysts include azobisisobutyronitrile and azobisisovaleronitrile.
- catalysts should be used in an effective amount in the range of from about 0.01 to 5 percent, by weight, of the allyl phosphonate flame retardant; the precise amount required being dependent upon the tightness of the cure, i.e. the degree of crosslinking, which is required as well as the extent to which free radical, chain inhibiting substances such as oxygen have been excluded from the system.
- Actinic radiation encompasses high energy protons and other particles capable of initiating free radical reactions including ultraviolet light, x-rays, gamma rays, alpha rays, beta rays, i.e. electron beam radiation, and plasma, i.e. highly ionized atoms in the vapor state.
- a preferred source of actinic radiation involves the use of an electron beam, i.e. beta radiation, since equipment adaptable for textile and paper mill use is readily available and is eminently suited for rapid, continuous pro cessing.
- the selected catalyst is generally activated by heating up to about 200C. but, preferably, in the range of from about 60 to C. so as to minimize any thermal damage to the substrate.
- the catalyst can be activated, even at ambient temperatures, by applying a ie'ducing agent to the textile or other substrate either before or after applying the flame retardant reagent and catalyst.
- Suitable reducing agents include sulfur dioxide, ferrous salts, such as the halides and sulfates, as well as sulfurous, phosphorous, or hypophosphorous acids and their water soluble salts such, for example, as sodium bisuliite, sodium phosphite and sodium hypophosphite.
- the catalyst may also be activated by actinic radiation.
- actinic radiation When actinic radiation is used, either along or in combination with a free radical catalyst, it is only necessary to expose the substrate to a beam from a radiation source. If desired, this can be done at ambient temperature thus sparing the substrate from thermal damage.
- the exposure can be conveniently conducted by passing the substrate through the beam which may be produced, for example, by a bank of ultraviolet lamps, corona-discharge points, a cobalt-60 source, an X-ray source or an electron beam source.
- a suitable mechanical arrangement of rollers can be employed so that the substrate can be made to repeatedly pass through the radiation field thereby facilitating more complete use of the available radiation flux while also obtaining more uniform irradiation.
- the resulting cure, or polymerization, of the allyl phosphonate which is induced by either a catalyst and- /or actinic radiation generally takes place on the surface and within the body of the fibers, or other structural elements, which comprise the substrate.
- the resulting polymer network may be grafted, or chemically bonded, onto the fiber molecules of the textile or other substrate.
- such grafting is not crucial to the attainment of a durable,
- the irradiation of the substrate is usually carried out subsequent tothe application of the allyl phosphonate although, in the case of cellulosic fibers, which can be irradiated so as to form stable, long lived free radical sites, the allyl compound can be applied subsequent to irradiation whereupon it will proceed to cure.
- Monomers contributing to flame retardancy i.e. monomers having phosphorus, bromine or chlorine atoms-in their molecules including, for example, vinyl and vinylidene halides such as vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide and vinylidene chlorobromide; chloroprene; triallyl phosphate; diallyl allylphosphonate; diallyl cyanoethylphosphonate; diallyl carboxyethylphosphonate; dialkyl vinylphosphonates such as diethyl vinylphosphonate, bis(2-chloroethyl-) vinylphosphonate or its polycondensation products; and, in general all of the unsaturated phosphonate monomers disclosed in my copending applications Ser.
- vinyl and vinylidene halides such as vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide and vinylidene chlorobromide
- chloroprene triallyl
- crosslinked polymers may be further characterized by the fact that they willnot lose more than about 20 percent of their total weight upon being extracted with methanol in a Soxlet extractor.
- fire retardant is intended to refer to that particular property of a material which provides it with a degree of resistance to ignition and burning.
- a fire or flame retardant textile, paper or other solid substrate is one which has a low level of flammability and flame spread. This property may be conveniently evaluated by means of any of the standard flame retardancy tests.
- pre-polymers of these allyl .phosphonates can be prepared without losing the solubility in water which is displayed by the unpolymerized phosphonates by simply limiting the extent of the pre-polymerization so that it does not exceed the gel point. With any given catalyst system, this can be readily determined by a preliminary experiment to define the required heating time and temperature prior to preparing the treating bath for the full-scale finishing operation. However, in general, in preparing these pre-polyomers it may be noted that the solution of the allyl phosphonate should be heated until its viscosity has increased by about 50-500 percent with heating being halted at the first appearance of cloudiness.
- novel tetraallyl phosphonates of this invention have an advantage over the diallyl posphonates since they act like pre-polymers in the sense of being able to cure extremely rapidly to a thermoset condition using amounts of initiator or of radiation which are only about half (or less) of those required with the diallyl compounds;
- the process of this invention is compatible with a wide variety of other textile finishing operations which can be carried out prior, simultaneous with, or subsequent to the process of the invention.
- These other operations include application of durable press, softening, antistatic, abrasion resistance, water-repellent, soilrelease, and antimicrobialfinishes, as well as bleaching, dyeing, printing, flocking, and texturing.
- finishing formulations of the invention may also optionally contain other types of ingredients known in the textile finishing art.
- water and soil repellents, optical brighteners and colorants, softening agents such as polyethylene emulsions, handmodifying agents, buffering agents, pH-controlling agents which may be acidic or basic, emulsified waxes, chlorinated paraffins, polyvinyl chloride, polyvinylidene chloride, homoand copolymers of the alkyl acrylates and other resinous finishing agents may be added in conjunction with the finishing agents of the invention.
- syste ms containing antimony oxide a resinous binder, particularly one containing chloride such as a chlorinated paraffin of polyvinyl chloride, along with the allyl phosphonates required in the process of this invention.
- the fire retardant finishes of this invention may be applied along with and as part of an aminoplastic'binder resin.
- these allyl phosphonates can be used in conjunction with any of the various adhesives, sizes, wet strength additives and other materials which are ordinarily employed in the paper finishing art.
- a hitherto unmentioned advantage of the process of this invention over prior art flame retardant finishing process resides in the fact that the application of the finish does not depend upon the presence in the system of compounds containing readily broken N-CH or O-CH linkages, thereby permitting high levels of durability to be achieved in the resulting flame retardant finishes, including durability to acidic laundry sours which strip the prior art aminoplast finishes from the textile.
- All types of textiles may be treated by means of the process of this invention so as to provide them with durable, fire retardant finishes.
- textiles derived from natural fibers such as cotton, wool, silk, sisal, jute, hemp and linen, wood and from synthetic fibers including nylon and other polyamides; polyolefins such as polypropylene; polyesters such as polyethylene terephthalate; cellulosics such as rayon, cellulose acetate and triacetate; fiber glass (which is flammable when coated with organic sizing agents); acrylics and modacrylics, i.e. fibers based on acrylonitrile copolymers; saran fibers, i.e.
- textile or textiles is meant to encompass woven or knitted fabrics as well as non-woven fabrics which consist of continuous or discontinuous fibers bonded so as to form a fab ric by mechanical entanglement, thermal interfiber bonding or by use of adhesive or bonding substances.
- non-woven fabrics may contain a certain percentage, up to l00 percent, of wood pulp as well as conventional textile fibers in which case part of the bonding process is achieved by means of hydrogen bonding between the cellulosic pulp fibers.
- the finishing agents of this invention can serve not only as flame retardant finishes but can also contribute to the interfiber bonding mechanism by serving as all or part of the adhesive or bonding resin component. This dual role can also be played by the finishing agents of this invention in fabric laminates where the finishing agent can at the same time serve as the interlaminar bonding agent and as the flame retardant. In both of these systems, i.e.
- finishing agents of this invention can also be blended with the usual bonding agents such, for example, as acrylic emulsion polymers, vinyl acetate homoand copolymer emulsions, styrenebutadiene rubber emulsions, urethane resin emulsions, polyvinylchloride emulsions, vinyl chloride-alkyl acrylate copolymer emulsions polyacrylates modified by vinylcarboxylic acid comonomers and the like.
- bonding agents such, for example, as acrylic emulsion polymers, vinyl acetate homoand copolymer emulsions, styrenebutadiene rubber emulsions, urethane resin emulsions, polyvinylchloride emulsions, vinyl chloride-alkyl acrylate copolymer emulsions polyacrylates modified by vinylcarboxylic acid comonomers and the like.
- allyl phosphonates can also be employed for the flameproofing of a wide variety of polymeric substrates such as cellulose in the form of paper, wood, plywood, chipboard, jute, batting and the like; urethane foams, coatings, and elastomers; aminoplast resins and phenolic resins as well as their composites with paper, wood flour and the like; alkyd coatings and molding resins; and, paints and varnishes derived from natural or synthetic resins.
- polymeric substrates such as cellulose in the form of paper, wood, plywood, chipboard, jute, batting and the like; urethane foams, coatings, and elastomers; aminoplast resins and phenolic resins as well as their composites with paper, wood flour and the like; alkyd coatings and molding resins; and, paints and varnishes derived from natural or synthetic resins.
- EXAMPLE 2 This example illustrates the preparation of a flame dried at room temperature to a slight degree of moisture retention and thereupon cured by pressing for 3 minutes, at 330F., in a steam heated press
- the thus treated cloths are then washed in water, dried and analyzed for phosphorus by means of X-ray fluorescence. They are then subjected to an accelerated laundering procedure by being boiled for 3 hours in a solution containing 0.5 percent, by weight, of soap and 0.2 percent, by weight, of sodium carbonate.
- the thus treated cloths are then reanalyzed and their flame retardancy evaluated by means of the limiting oxygen index (LOI) method as described in ASTM D-2863.
- LOI limiting oxygen index
- EXAMPLE 3 This example again illustrates the preparation of a flame retardant textile finish by means of the process of this invention which, in this case, utilizes an actinic radiation induced cure. it also provides a comparison with the use of diallyl 2-cyanoethylphosphonate.
- a padding bath is prepared by dissolving 20 parts, by weight, of diallyl 2-carbamoylethylphosphonate in 79 parts of water which also contains 1 part, by weight, of octyl phenoxy polyethoxy ethanol as a wetting agent.
- a padding bath is prepared containing 79 parts of diallyl 2-cyanoethylphosphonate,-l part of octyl phenoxypolyethylene ethanol and, because of the insolubility of the cyanoethyl phosphonate in water, 15 percent, by weight, of methanol is also included.
- An 8 ounce cotton cloth is padded in each of these baths to about a 70 percent, by weight, wet addon. These cloths are then dried to a slightly moist condition and exposed to 4 megarads of electron beam radiation at 1.5 Mev. The flame retardancy of the thus treated cloths is then evaluated by means of the LOI procedure both before and after 5 detergent laundermgs.
- the finishes of this invention display superior fire retardancy when compared with the finishes derived from the cyanoethyl phosphonate compound.
- EXAMPLE 4 This example illustrates the preparation of N,l ⁇ l'-methylenebis(diallyl- 2-carbamoylethylphosphonate), i.e.
- N,- N-methylenebismethacrylamide is, in this instance,
- N,N-methylenebisacrylamide substituted for N,N-methylenebisacrylamide thereby yielding N,N'-methylenebis(dially l 2-carban oyliso propylphosphonate) as he product of the reaction in the form of a viscous syrup.
- EXAMPLE 5 lowing table Cotton cloth having a weight of 32 oz/yd? is padded iri each of thesefbaths, passed through a wringer, dried at room temperature for minutes and than. 99m h tL h edrol s at 2809:29015. fo 5 minutes The LOI of each cloth before and after 5 detergent washes is then determined and these results are also shown in the table.
- EXAMPLE 6 This example illustrates the flame retarding of paper by means of the process or this invention.
- aqueous 7 A diallyl Z-carbamoylethylphosphonate 20% by wt.
- aqueous A diarlyl 2-carbamoylethylphosphonate 10% by 65
- (aqueous) B 0) diallyl 2-cyanoethylphosphonate 10% by wt.
- (alcoholic) (B20) diallyl 2-cyanoethylphosphonate 20% by wt.
- thermoset polymer composition This example illustrates the preparation of a thermoset polymer composition from the diallyl 2-carbamoylethylphosphonate whose preparation is desgribed in Example 1.
- aqueous solution containing 30 percent, by weight, of diallyl 2-carbamoylethylphosphonate and 2 percent, by weight, of ammonium persulfate is gradu- .ph sp qnatel ally warmed to within the range of 6080C.
- a portion of this pre-polymer is removed and is used as a textile finishing agent which, after being applied to the surface of a fabric, is cured by heating the thus treated fabric so as to yield a water insoluble,
- R is selected from the group consisting of hydrogen and methyl radicals.
- allyl' 2-carbamoylalkylphosphonate is selected from the group consisting of diallyl Z-carbamoylethylphosphonate, diallyl 2-carbamoylisopropylphosphonate, N,N'- methylenebis(diallyl 2-carbamoylethylphosponate) and N,N-methylenebis(diallyl 2-carbamoylisopropyl- 3.
- R is selected from the group consisting of hydrogen and methyl radicals.
Abstract
WHERE R is a hydrogen or methyl radical, whereupon the phosphonate is cured by free radical initiation so as to form an insoluble, fire retardant resinous finish.
The present invention provides a process for flame retarding textiles, paper and other flammable, solid substrates by applying to the substrate at least one allyl 2-carbamoylalkylphosphonate corresponding to the formulae:
The present invention provides a process for flame retarding textiles, paper and other flammable, solid substrates by applying to the substrate at least one allyl 2-carbamoylalkylphosphonate corresponding to the formulae:
Description
liiiwihlh,
- United States 111 3,839,207
Weil v 4 1 Oct. 1, 1974 [54] ALLYL' 3,268,292 8/1966 Chance et a1. 8/116 P x 2.CAR MO L Q 3,276,838 10/1966 Chance et al. 8/116 P X 3,725,272 4/1973 Petersen et a1... 8/116 P X FLAME RETARDANTS 3,762,865 10/1973 Weil 8/116 P X [75] Inventor: Edward D. Weil,
Hastin s-on-Hudson, N.Y.
g Primary ExaminerStephen J. Lechert, Jr.
[73] Assignee: Stauffer Chemical Company, New
' York, NY.
[22] Filed: June 27, 1973 [57] ABSTRACT [21] Appl No: 3741190 The present invention provides a process for flame re- R l s li i m tarding textiles, paper and other flammable, solid sub- [62 Division of Ser. NO. 139 222 April 30, 1971, Pat. mat-es by applymg to the Substrate at one any] 3 762 2-carbamoylalkylphosphonate correspondlng to the formulae: [52 us. (:1 252/81, 260/6065 P, 8/116 P, H
106/15 FP, 117/136 1 and [51 1m. (:1 B27k 3/00 1 Y R 0 [58] Field of Search 8/116 P; 252/8.1; H in[(CHFQHCHQhgQHIEgNHlQm 106/ FP; 117/136; 260/60 P where R is a hydrogen or methyl radical, whereupon the phosphonate is'cured by free radical initiation so 5 Referemes C'ted as to form an insoluble, fire retardant resinous finish.
UNITED STATES PATENTS 7/1955 Toy et al. 8/116 P X 6 Claims, N0 Drawings BACKGROUND OF THE INVENTION As shown, for example, in'us. Pat. No. 3,374,292, it is known in the textile and paper finishing art that cellulosic fabrics can be flame retarded by applying compounds such as N-methylol Z-carbamoylethylphosphonates which are then cured on the substrate by means of acid catalysts. However, there are several limitations in this type of process including the fact that the resulting finish is ineffective for flame retarding non-cellulosic fabrics and is also unsatisfactory for blends of cellulosic and synthetic fibers which contain a major proportion of non-cellulosic fibers. In addition, such finishes require the use of acid catalysts at elevated temperatures in the range of about l50l60F. which leads to some acid catalyzed or thermal degradation of cellulosic fabrics with a resultant loss of their .physical properties such as their tear strength. Moreover, because of the elevated temperatures required for their application, sublimation of these phosphonates, or of their decomposition products, can occur causing sticky deposits as well as drippage in the curing oven which often leads to spotting of the cloth and which may require shutting down in order to permit cleaning of the equipment. And, finally, the evolution of formaldehyde vapors from these phosphonates creates an unpleasant atmospheric pollutant.
As is described in the U.S. Pat. Nos. 2,848,507 and 2,867,548, it has also been known in the textile finishing art to use certain diallyl phosphorus compounds such, for example, as diallyl 2-cyanoethyl phosphonate, 35
in preparing flame retarding textile finishes. However, the successful use of such compounds requires their pro-polymerization which complicates the process and necessitates the use of specific organic solvents with a resultant high cost which is uneconomical for large scale commercial textile finishing. Furthermore, these systems require high add-ous, i.e. the deposition of high concentrations of reagents, with a resultant poor hand, i.e. unfavorable tactile qualities, stiffness and harsh surface characteristics, in the resulting treated fabrics. Because of these problems, these diallyl phosphonate finishes have only had limited experimental use, particularly with heavy weight military fabrics.
Thus, it is the prime object of this invention to provide a novel flame retardant finishing process which is suitable for use with textiles made from either natural or synthetic fibers as well as with blends of each of the latter fiber types. It is another object of this invention to provide a flame retardant finishing process for various other flammable, solid substrates such, for example as paper, wood, batting and rope, which are capable of beingimpregnated and/or coated with a flame retardant, resinous finish. It is a further object to provide a flame retardant textile finishing process which is operable at ambient or moderately elevated temperatures and which can employ aqueous systems thereby avoiding fabric degradation and the need for expensive and troublesome organic solvents. Another object is to provide a process for flame retarding textiles which is op- 6 erable with low add-ons of the flame retardant finish thereby providing a pleasing hand to the finished fabrics.
15 phonate, diallyl TECHNICAL DISCLOSURE OF THE INVENTION This process comprises the application to a textile, or other flammable solid substrate, followed by curing, of an effective amount of at least one flame retarding allyl Z-carbamoylalkylphosphonate corresponding to the formulae:
i: cm=oucrno ii omdrriiNnllmn,
where R is a hydrogen or methyl radical. Exemplary of those compounds are diallyl 2-carbamoylethylphos- 2-carbamoylisopropylphosphonate, N,N'-methylenebis(diallyl 2-carbamoylethylphosphonate) and N,N'-methylenebis(diallyl Z-carbamoylisopropylphosphonate). These flame retardants are applied to a fabric or other substrate at a concentration 20 of from about 5 to 40 percent, as calculated on the dry weight of the substrate, and are thereafter cured, i.e. polymerized, so as to form an insoluble, fire retardant resinous finish by free radical initiation using either a chemical initiator or actinic radiation in, order to in- '25 duce the desired reaction.
The diallyl compounds used as flame retardants in the process of this invention, i.e. diallyl Z-carbamoylethylphosphonate and diallyl 2-carbamoylisopropylphosphonate, are known and may be readily prepared 30 by the addition of diallyl phosphonate to either acrylamide or methacrylamide as described, for example, in U.S. Pat. No. 2,754,320, or by the addition of diallyl phosphonate to an alkyl ester of acrylic or methacrylic followed by ammonolysis. These diallyl compounds are crystalline, colorless solids of negligible odor which are soluble in many organic solvents as well as in water.- On the other hand, the above listed tetraallyl compounds, i.e. N,N'-methylenebis(diallyl 2-carbamoylethylphosphonate) and N,N-methylenebis(diallyl 2- carbamoylisopropylphosphonate), are new compositions of matter which are prepared by means of the base catalyzed addition of at least two moles of diallyl phosphonate per mole of either N,N- methylenebisacrylamide or N,N'-methylenebismethacrylamide. In conducting this reaction, the diallyl phosphonate and the N,N-methylenebisacrylamide or N,N- '-methylenebismethacrylamide may be combined in the absence of a solvent or, if desired, they may be slurried in a suitable non-interfering solvent such, for example, as methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, acetone or dioxane. The selected base catalyst, which can be sodium methylate, an alkali metal hydroxide or any other suitable basic material, is then introduced into the reaction mixture in a concentration of from about 0.001 to 10 percent, as based upon the diallyl phosphonate, resulting in an exothermic reaction which may cause the mixture to boil. Trace solids are removed from the resulting reaction mixture by filtration yielding the tetraallyl com- 'dant additives and monomers such as those which can be made by the addition of bromine to all or part of the double bonds of these compounds. For purposes of brevity, the novel tetraallyl 2-carbamoylakylphosphonates as well as the diallyl 2-carbamoylalkylphosphonates of the prior art will, in this disclosure, be collectively referred to as the allyl phosphonates."
While the use of aqueous solutions comprises the most economical means of application forthese allyl phosphonate flame retardants, they may also, if desired, be applied to a normally flammable substrate while dissolved in any of the organic solvents commonly used in the solvent finishing of textiles including, for example, trichloroethylene, dischloroethane, trichloroethane, perchloroethylene, methylene chloride, etc. and mixtures thereof. The solutions, either aqueous or organic solvent, containing one or more of the selected allyl phosphonates may be applied to textiles or other substrates by the use of any desired procedure. It is merely necessary to have the diallyl phosphonate evenly absorbed throughout the mass of the textile, or other substrate, and/or to apply it to at least one surface thereof by means of any convenient procedure. Thus, it may be applied by being sprayed onto one or both surfaces of the substrate or, as is more frequently the case, the substrate may be passed or padded through the solution while the latter is being held in a tank or other suitable container. Such a process is commonly referred to as a padding technique" with the solution being referred to as a padding bath or padding solution.
The concentration of the allyl phosphonate within the padding bath, or other applicable solution, will be dependent upon a member of factors including, in the case of textile substrates, the nature of the fibers which comprise the textile, the weight and weave of the textile, the degree of flameproofmg that is desired in the flnished textile, as well as other technical and economic considerations known and understood by those skilled in the art. However, it is generally desirable that the padding bath should contain an amount of the phosphonate such that when the wet uptake is reduced to a dry deposit upon the textile or other substrate, the treated substrate will contain from about 5 to 40 percent of the allyl phosphonate, as based upon the dry weight of the substrate. Again, it is to be stressed that the latter limits are merely illustrative and may be varied so as to provide a finished article having any desired degree of flame retardancy.
The thus applied allyl phosphonate may be cured in the wet state or it may be completely or, most preferably, partially dried before curing. The mode of curing in accordance with the process of the invention involves the use of a free radical initiated reaction in order to induce the double bonds, i.e. the ethylenic unsaturation, of the allyl groups present in these compounds to polymerize intermolecularly so as to form a crosslinked, insoluble resin in and/or on the individual fibers, or other structural elements, which comprise the textile or other substrate.
Free radical initiation of the desired polymerization reaction may be induced either by the use of those chemical catalysts known as free radical initiators or by the use of the actinic radiation. Suitable free radical catalysts encompass peroxygen compounds, which may be used as part of a so-called redox system which contain a chemical reducing agent in addition to the peroxygen compound, and azo compounds. Examples of suitable peroxygen catalyst are hydrogen peroxide, which is often used in conjunction with ferrous salts; ammonium, sodium or potassium persulfate; t-butyl hydroperoxide; benzoyl peroxide; lauroyl peroxide; dicumyl peroxide; cumene hydroperoxide; t-butyl peroxypivalate; methyl ethyl ketone peroxide; caprylyl peroxide and acetyl peroxide. Examples of suitable azo catalysts include azobisisobutyronitrile and azobisisovaleronitrile. These catalysts should be used in an effective amount in the range of from about 0.01 to 5 percent, by weight, of the allyl phosphonate flame retardant; the precise amount required being dependent upon the tightness of the cure, i.e. the degree of crosslinking, which is required as well as the extent to which free radical, chain inhibiting substances such as oxygen have been excluded from the system.
Actinic radiation encompasses high energy protons and other particles capable of initiating free radical reactions including ultraviolet light, x-rays, gamma rays, alpha rays, beta rays, i.e. electron beam radiation, and plasma, i.e. highly ionized atoms in the vapor state. A preferred source of actinic radiation involves the use of an electron beam, i.e. beta radiation, since equipment adaptable for textile and paper mill use is readily available and is eminently suited for rapid, continuous pro cessing. In any event, regardless of the type of actinic radiation that is used, it should be applied in an effective dosage in the range of from about 0.l.-10 megarads; the exact dosage being dependent on the tightness of cure required, the amount or" inhibitorspresent and the geometry and nature of the substrate.
Where a cure is induced by the use of a free radical catalyst, the selected catalyst is generally activated by heating up to about 200C. but, preferably, in the range of from about 60 to C. so as to minimize any thermal damage to the substrate. Alternatively, the catalyst can be activated, even at ambient temperatures, by applying a ie'ducing agent to the textile or other substrate either before or after applying the flame retardant reagent and catalyst. Suitable reducing agents include sulfur dioxide, ferrous salts, such as the halides and sulfates, as well as sulfurous, phosphorous, or hypophosphorous acids and their water soluble salts such, for example, as sodium bisuliite, sodium phosphite and sodium hypophosphite. The catalyst may also be activated by actinic radiation.
When actinic radiation is used, either along or in combination with a free radical catalyst, it is only necessary to expose the substrate to a beam from a radiation source. If desired, this can be done at ambient temperature thus sparing the substrate from thermal damage. The exposure can be conveniently conducted by passing the substrate through the beam which may be produced, for example, by a bank of ultraviolet lamps, corona-discharge points, a cobalt-60 source, an X-ray source or an electron beam source. Reasonably homogeneous radiation flux is desirable where an electron beam is used, thus the beam can be transversely scanned at a rapid rate across the substrate so as to evenly irradiate all points thereon. If desired, a suitable mechanical arrangement of rollers can be employed so that the substrate can be made to repeatedly pass through the radiation field thereby facilitating more complete use of the available radiation flux while also obtaining more uniform irradiation.
The use of radiation initiation does not generally require the use of a chemical activator. However, the efficiency of the radiation can frequently be improved by use of such an activator. Suitable activators for this compounds such as azobisisobutyronitrile. Where an electron beam is used, the application of about 01-10 megarads, at a voltage sufficient to substantially penetrate the substrate to the depth to which the flame retardant polymer is to be formed, generally sufflcies to effect the desired cure.
The resulting cure, or polymerization, of the allyl phosphonate which is induced by either a catalyst and- /or actinic radiation generally takes place on the surface and within the body of the fibers, or other structural elements, which comprise the substrate. Moreover, in some cases the resulting polymer network may be grafted, or chemically bonded, onto the fiber molecules of the textile or other substrate. However, such grafting is not crucial to the attainment of a durable,
flame retardant finish.
The irradiation of the substrate is usually carried out subsequent tothe application of the allyl phosphonate although, in the case of cellulosic fibers, which can be irradiated so as to form stable, long lived free radical sites, the allyl compound can be applied subsequent to irradiation whereupon it will proceed to cure.
The process of this invention may, if desired, include the use of other free radical curable, i.e. polymerizable, comonomers along with the selected allyl phosphonate as a means of achievingvariations in the properties of the resulting treated textiles. Thus, suitable optional comonomers for use in conjunction with the allyl phosphonates include:
1. Monomers containing an amide nitrogen such as acrylamide, methacrylamide, N-methylolacrylamide, diacetonylacrylamide, methylenebisacrylamide, triacrylolhexahydrotriazine, N -vinylpyrrolidone and cellulose-grafted N-methylolacrylamide, the use of the latter monomer being disclosed in US. Pat. No. 3,434,161. The use of these amide nitrogen containing comonomers at a concentration of about 0.1-6 moles per mole of the allyl phosphonate, permits a more economical finish, particularly with cellulosic fibers, since less of the more costly phosphonate monomer needs to be used in order to achieve a given level of flame retardancy.
2. Monomers containing more than one polymerizable double bond such, for example, as the polyol polyacrylates or methacrylates, the glycol diacrylates, the glycol dimethacrylates, methylenebisacrylamide, triacryloylhexahydrotriazine, triallylphosphonate, diallyl allylphosphonate and triallyl cyanurate. By using this class of comonomers, the crosslink density of the resulting finish can be increased thereby enhancing its durability with respect to wear and laundering.
3. Monomers contributing to flame retardancy, i.e. monomers having phosphorus, bromine or chlorine atoms-in their molecules including, for example, vinyl and vinylidene halides such as vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide and vinylidene chlorobromide; chloroprene; triallyl phosphate; diallyl allylphosphonate; diallyl cyanoethylphosphonate; diallyl carboxyethylphosphonate; dialkyl vinylphosphonates such as diethyl vinylphosphonate, bis(2-chloroethyl-) vinylphosphonate or its polycondensation products; and, in general all of the unsaturated phosphonate monomers disclosed in my copending applications Ser. Nos. 23,493 (now abandoned) and 23,499 (now US. Pat. No. 3,695,925, issued Oct. 3, 1973) both filed Mar. 27, 1970. Other suitable flame retardant comonomers are the compounds made by base catalyzed addition of l to 2 moles of dialkyl phosphite and/or 1 to 3 moles of diallyl phosphite to the double bonds-of triacryloylhexahydrotriazine. When utilized in the process of this invention, these optional comonomers should be present in the system in a concentration of up to about 10 percent, by weight, of the diallyl phosphonate.
It should be noted, at this point, that the use of the term crosslinked in describing the cured, fire retardant resins resulting from the polymerization of the selected allyl phosphonate in the finishing process of this invention will indicate to those skilled in the art that these resins possess a highly intermeshed, threedimensional configuration or network rather than a simple linear or branched structure of the type found in non-crosslinked copolymers. Thus, such crosslinked polymers may be further characterized by the fact that they willnot lose more than about 20 percent of their total weight upon being extracted with methanol in a Soxlet extractor. Moreover, as used in this disclosure, the term fire retardant is intended to refer to that particular property of a material which provides it with a degree of resistance to ignition and burning. Thus, a fire or flame retardant textile, paper or other solid substrate is one which has a low level of flammability and flame spread. This property may be conveniently evaluated by means of any of the standard flame retardancy tests.
In contrast to the known diallyl 2-cyanoethyl phosphonate finishes, pre-polymerization of the above described allyl phosphonates is not necessary in the process of this invention. However, it is within the purview of this process to permit such pre-polymerization for the purpose of permitting extremely rapid cures of the flame retardant finish on the textile or other substrate since some of the polymer links will have been formed prior to its application to the cloth. Advantageously,
pre-polymers of these allyl .phosphonates can be prepared without losing the solubility in water which is displayed by the unpolymerized phosphonates by simply limiting the extent of the pre-polymerization so that it does not exceed the gel point. With any given catalyst system, this can be readily determined by a preliminary experiment to define the required heating time and temperature prior to preparing the treating bath for the full-scale finishing operation. However, in general, in preparing these pre-polyomers it may be noted that the solution of the allyl phosphonate should be heated until its viscosity has increased by about 50-500 percent with heating being halted at the first appearance of cloudiness. Moreover, it is to be noted that the novel tetraallyl phosphonates of this invention have an advantage over the diallyl posphonates since they act like pre-polymers in the sense of being able to cure extremely rapidly to a thermoset condition using amounts of initiator or of radiation which are only about half (or less) of those required with the diallyl compounds;
The process of this invention is compatible with a wide variety of other textile finishing operations which can be carried out prior, simultaneous with, or subsequent to the process of the invention. These other operations include application of durable press, softening, antistatic, abrasion resistance, water-repellent, soilrelease, and antimicrobialfinishes, as well as bleaching, dyeing, printing, flocking, and texturing.
Thus, the finishing formulations of the invention may also optionally contain other types of ingredients known in the textile finishing art. For example, water and soil repellents, optical brighteners and colorants, softening agents such as polyethylene emulsions, handmodifying agents, buffering agents, pH-controlling agents which may be acidic or basic, emulsified waxes, chlorinated paraffins, polyvinyl chloride, polyvinylidene chloride, homoand copolymers of the alkyl acrylates and other resinous finishing agents may be added in conjunction with the finishing agents of the invention. And, where an extremely high degree of flame retardance is required, it is also possible to employ syste ms containing antimony oxide, a resinous binder, particularly one containing chloride such as a chlorinated paraffin of polyvinyl chloride, along with the allyl phosphonates required in the process of this invention. Moreover, in treating wood and paper substrates, the fire retardant finishes of this invention may be applied along with and as part of an aminoplastic'binder resin. And, when used for finishing paper, these allyl phosphonates can be used in conjunction with any of the various adhesives, sizes, wet strength additives and other materials which are ordinarily employed in the paper finishing art.
A hitherto unmentioned advantage of the process of this invention over prior art flame retardant finishing process resides in the fact that the application of the finish does not depend upon the presence in the system of compounds containing readily broken N-CH or O-CH linkages, thereby permitting high levels of durability to be achieved in the resulting flame retardant finishes, including durability to acidic laundry sours which strip the prior art aminoplast finishes from the textile.
All types of textiles may be treated by means of the process of this invention so as to provide them with durable, fire retardant finishes. Thus, one may treat textiles derived from natural fibers such as cotton, wool, silk, sisal, jute, hemp and linen, wood and from synthetic fibers including nylon and other polyamides; polyolefins such as polypropylene; polyesters such as polyethylene terephthalate; cellulosics such as rayon, cellulose acetate and triacetate; fiber glass (which is flammable when coated with organic sizing agents); acrylics and modacrylics, i.e. fibers based on acrylonitrile copolymers; saran fibers, i.e. fibers based on vinylidene chloride copolymers; rubber based fibers; spandex fibers, i.e. fibers based on a segmented polyurethane; vinal fibers, i.e. fibers based on vinyl alcohol copolymers; vinyon fibers, i.e. fibers based on vinyl chloride copolymers and, metallic fibers. Textiles derived from blends of any of the above listed natural and/or synthetic fibers may also be treated by means of the process of this invention.
As used in this disclosure, the term textile or textiles" is meant to encompass woven or knitted fabrics as well as non-woven fabrics which consist of continuous or discontinuous fibers bonded so as to form a fab ric by mechanical entanglement, thermal interfiber bonding or by use of adhesive or bonding substances.
Such non-woven fabrics may contain a certain percentage, up to l00 percent, of wood pulp as well as conventional textile fibers in which case part of the bonding process is achieved by means of hydrogen bonding between the cellulosic pulp fibers. In non-woven fabrics, the finishing agents of this invention can serve not only as flame retardant finishes but can also contribute to the interfiber bonding mechanism by serving as all or part of the adhesive or bonding resin component. This dual role can also be played by the finishing agents of this invention in fabric laminates where the finishing agent can at the same time serve as the interlaminar bonding agent and as the flame retardant. In both of these systems, i.e. non-woven fabrics and laminated fabrics, the finishing agents of this invention can also be blended with the usual bonding agents such, for example, as acrylic emulsion polymers, vinyl acetate homoand copolymer emulsions, styrenebutadiene rubber emulsions, urethane resin emulsions, polyvinylchloride emulsions, vinyl chloride-alkyl acrylate copolymer emulsions polyacrylates modified by vinylcarboxylic acid comonomers and the like.
It should also be noted, at this point, that in addition to being used to provide flame retardant finishes for textiles, the above described allyl phosphonates can also be employed for the flameproofing of a wide variety of polymeric substrates such as cellulose in the form of paper, wood, plywood, chipboard, jute, batting and the like; urethane foams, coatings, and elastomers; aminoplast resins and phenolic resins as well as their composites with paper, wood flour and the like; alkyd coatings and molding resins; and, paints and varnishes derived from natural or synthetic resins.
The following examples will further illustrate the embodiment of this invention. In these examples all parts given are by weight unless otherwise noted.
EXAMPLE I This example illustrates the preparation of diallyl Z-carbamoylethylphosphonate,
0 ll i.e. (CH -CHCH OhPCI-I CH AINH To a stirred mixture of 162 g. of diallyl phosphonate and 71 g. of acrylamide, there is slowly added a 4 percent, by weight, solution of sodium in allyl alcohol. The mixture is cooled during and subsequent to its preparation so as to maintain its temperature below 65C. When no further temperature rise occurs, the reaction mixture proceeds to form a solid, mp. 512C, the infra-red spectrum of which shows no P-I-I band. The nuclear magnetic resonance spectrum shows protons characteristic of PCI-I CI-I C(=0)-- (8 2.33), CH-OP (8 4.5), CH,=CH-- (8 5.6) and NH (two NHs) in the correct area ratio of 4:4:6:2.
EXAMPLE 2 This example illustrates the preparation of a flame dried at room temperature to a slight degree of moisture retention and thereupon cured by pressing for 3 minutes, at 330F., in a steam heated press The thus treated cloths are then washed in water, dried and analyzed for phosphorus by means of X-ray fluorescence. They are then subjected to an accelerated laundering procedure by being boiled for 3 hours in a solution containing 0.5 percent, by weight, of soap and 0.2 percent, by weight, of sodium carbonate. The thus treated cloths are then reanalyzed and their flame retardancy evaluated by means of the limiting oxygen index (LOI) method as described in ASTM D-2863. In brief, this procedure directly relates flame retardancy to a measurement of the minimum percentage concentration of oxygen in a oxygenznitrogen mixture which permits the sample to burn; the LOl being calculated as follows:
L hi/[ 2] 2] X 100 Thus, a higher LOl is indicative of a higher degree of flame retardancy.
The following table presents the results of these evaluations.
These results show excellent durability to laundering and good flame retardancy on the part of fabrics treated with the flame retardant finish ofthis invention. Moreover, the thus treated cloths exhibit a good hand," good tear strength as well as a retention of their original white color.
EXAMPLE 3 This example again illustrates the preparation of a flame retardant textile finish by means of the process of this invention which, in this case, utilizes an actinic radiation induced cure. it also provides a comparison with the use of diallyl 2-cyanoethylphosphonate.
A padding bath is prepared by dissolving 20 parts, by weight, of diallyl 2-carbamoylethylphosphonate in 79 parts of water which also contains 1 part, by weight, of octyl phenoxy polyethoxy ethanol as a wetting agent. For comparative purposes, a padding bath is prepared containing 79 parts of diallyl 2-cyanoethylphosphonate,-l part of octyl phenoxypolyethylene ethanol and, because of the insolubility of the cyanoethyl phosphonate in water, 15 percent, by weight, of methanol is also included. An 8 ounce cotton cloth is padded in each of these baths to about a 70 percent, by weight, wet addon. These cloths are then dried to a slightly moist condition and exposed to 4 megarads of electron beam radiation at 1.5 Mev. The flame retardancy of the thus treated cloths is then evaluated by means of the LOI procedure both before and after 5 detergent laundermgs.
Fire Retardant 7c Dry Add-on LOl Before LOl After Washing Washing diallyl 12.79 25 24 carbamoylethyl phosphonate diallyl ll.83 24 l9 Z-cyanoethyl phosphonate Control l8 Untreated Cotton Thus, the above given data reveal that the carbamoyl compound required for use in the process of this invention provides durable, flame retardant properties in the treated fabric whereas the finish derived from the cyanoethyl compound is substantially all removed by laundering.
In another comparison of intrinsic flame retardant properties, aside from the question of durability, the carbamoyl and cyano compounds are again compared at varying levels of add-on on 3.2 oz. cotton cloths which are treated in the manner described hereinabove. The following table provides ,the results of this comparison.
The above data clearly indicate that at all add-on levels, the finishes of this invention display superior fire retardancy when compared with the finishes derived from the cyanoethyl phosphonate compound.
EXAMPLE 4 This example illustrates the preparation of N,l\l'-methylenebis(diallyl- 2-carbamoylethylphosphonate), i.e.
To a slurry of 154 gms. of N,N'- methylenebisacrylamide and 324 gms. of diallyl phosphonate in 800 ml. of methylene chloride there is added, with stirring, 2.9 gms. of sodium methylate. The reaction mixture spontaneously boils and methylene chloride is allowed to distill off until the reaction subsides. The resulting reaction mixture is homogeneous except for trace solids which are removed by filtration. The infrared spectrum of the filtrate shows no remaining P-H compound. The solution is then stripped to SQjQ under vacuum leaving a substantially quantitative yield of 'the' product as ayellowish syrup,'n 1.4998 which is completely soluble in water. H ..../..?1$ C C HeQ P2 2 13.0% P
Found: 12.9% P 7 The above given structure is confirmed by nmr spectroscopy.,When this monomer is directly exposed to the'radiation froma mercury vapor lamp for a period of several hours, it cures to form a clear, "solid, extremely hard polymer having a Barcol hardness value of 50. This polymer also has good impact strength as demonstrated by the fact that a 1/8f" 2 inch diameter plaque survivesseveral 40ft. falls without shattering.
In a repetition of the above described procedure, N,- N-methylenebismethacrylamide is, in this instance,
, substituted for N,N-methylenebisacrylamide thereby yielding N,N'-methylenebis(dially l 2-carban oyliso propylphosphonate) as he product of the reaction in the form of a viscous syrup.
EXAMPLE 5 lowing table. Cotton cloth having a weight of 32 oz/yd? is padded iri each of thesefbaths, passed through a wringer, dried at room temperature for minutes and than. 99m h tL h edrol s at 2809:29015. fo 5 minutes The LOI of each cloth before and after 5 detergent washes is then determined and these results are also shown in the table.
' Padding Bath A B C N,N-methylenebis(;dial l yl 7 35 25 15 z c arlfirnoylefiiylphosphonate) i Acrylamide (con1onomer) 1O Ammonium persulfate (catalyst) '7 0.5 0.5 0.5
Octyl phenoxypolyethyle'ne 0.4 0.4 0.4 ethanol (wetting agent) Water 7 64.1 64.1 64.1
Dry add-on (2) 26.3 25.2 23.6
LOI Before washing 30.69 30.27 27.38 24.23 25.74 24.2]
LOl after 5 detergent washings Since the untreated cloth has an LOI of only l8, it is seen that the process of this invention imparts a substantial degree of durable flame retardancy.
EXAMPLE 6 This example illustrates the flame retarding of paper by means of the process or this invention.
Weighed pieces of paper are impregnated with each of the 'below described solutions:
.wt. (aqueous) 7 (A diallyl Z-carbamoylethylphosphonate 20% by wt. (aqueous) (A diarlyl 2-carbamoylethylphosphonate 10% by 65 (A diallyl Z-carbamoylethylphosphonate 40% by wt: (aqueous) (B 0) diallyl 2-cyanoethylphosphonate 10% by wt. (alcoholic) (B20) diallyl 2-cyanoethylphosphonate 20% by wt.
(alcholic) (B diallyl 2-cyanoethylphosphonate 40% by wt.
(alcholic) ((116) N,N-methylenebis(diallyl) 2-c arbamoylethylphosphonate) 10% by wt. (aqueous) (C20) N,N-methylenebis(diallyl Z-carbamoylethylphosphonate) 20% by wt. (aqueous) (C40) N,N methylenebis(diallyl 2-carbamoylethylphosphonate) 40% by wt. (aqueous) In each case, the paper is saturated to a wet-uptake of approximately 200 percent, by weight. The thus treated papers are dried for 15 minutes in an oven set at 70 C. and then irradiated by exposure to a 400-watt 29 high pressure mercury'arc lamp for a period of 24 hours. The dry add-ons, i.e. the weight of the treated paper less its original Weight IOO/original weight,
are determined both before and after a 15 minute wash with running water, and the flame retardancy of each 25 sample is'evaluated both before and after the water wash. The flame retardancy of these sheets is expressed on the following scale:
+++ (excellent retardancy) self-extinguishing when its lower edge is ignited while the strip is suspended in the vertical position;
++ (good retardancy) self-extinguishing when its lower edge is ignited while suspended at an inclination of 45;
+ (slight retardancy) self-extinguishing where one end is ignited while the strip is suspended in a horizontal position; and
(not self-extinguishing in any position).
The results of this evaluation are presented in the following table:
Dry Add-on (/1) H Flame Rctardanee Treating Before After Before After H Solution Washing w hin Washing washing A. 16.2 2.1 4+
2., 30.3 14.1 4+1 A,0 62.5 42.4 44+ B111 35 0,9 B20 7.4 L0 B it) l -S 1.9 -|fc... 16.1 9.6 020 37.1 22.1 +1+ 4+ These results reveal that the finish derived from diallyl cyanoethylphosphonate is substantially lost during the curing whereas the finishes of this invention are retained. It is also seen that the novel tetraallyl compound provides afinish which is exceedingly durable to water washing.
EXAMPLE 7 This example illustrates the preparation of a thermoset polymer composition from the diallyl 2-carbamoylethylphosphonate whose preparation is desgribed in Example 1.
An aqueous solution containing 30 percent, by weight, of diallyl 2-carbamoylethylphosphonate and 2 percent, by weight, of ammonium persulfate is gradu- .ph sp qnatel ally warmed to within the range of 6080C. During thisws tmin ppriqdi th so t q qntlsayiscgt PIP polymer. A portion of this pre-polymer is removed and is used as a textile finishing agent which, after being applied to the surface of a fabric, is cured by heating the thus treated fabric so as to yield a water insoluble,
flame retardant finish. Prolonged heating of the balance of the pre-polymer solution causes it to gel and thereafter a white, odorless water insoluble polymer is precipitated. This polymeric product is then dried and used as a flame retardant additive for flammable polymers.
Variations may be made in proportions, procedures and materals without departing from the scope of this invention as defined in the following claims.
What is claimed is:
l. A flame retardant of an ally] polymer 2-carbamoylalkylphosphonate corresponding to the formulae:
where R is selected from the group consisting of hydrogen and methyl radicals.
2. The polymer of claim 20, wherein said allyl' 2-carbamoylalkylphosphonate is selected from the group consisting of diallyl Z-carbamoylethylphosphonate, diallyl 2-carbamoylisopropylphosphonate, N,N'- methylenebis(diallyl 2-carbamoylethylphosponate) and N,N-methylenebis(diallyl 2-carbamoylisopropyl- 3. The polymer of'claim 1 wherein at least one other I where R is selected from the group consisting of hydrogen and methyl radicals.
5. The compound according to claim 4. 6.. The compound according to claim 4.
UNITED STATES PATENT OFFICE CETIFICATE OF CORRECTION Patent No. 5,859,207 Da October 1, 197A to Edward D. Weil It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
a In the Title, change "ALLYL Z-CARBAMOYALKYLPHOSPHONATES FLAME RETARDANTS" to ALLYL 2-CARBAMOYLALKYLPHOSPHONATE FLAME RETARDANTS Signed and Scaled this ninth Day Of September 1975 [SEAL] Attest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer (ummissiunor uflat'llls and Tradcmurkx FORM PO-1050(10-69) USCOMM-DC 60376-P69 uvs covERNMENY PRINYING OFFICE: 8 930 Poem UNITED STATES PATENT. OFFICE 569 CERTIFICATE OF CORRECTION Patent No- 3,839,207 Dated June 27, 1973 Inven fl?) Edward- Weil It is certified that errcir appears in the aboveidentified patent and thatsaid Letters Patent are hereby corrected as shpwn below:
Col. 2, line 14, change "those" to these Col. 3, line 16, change "dischlorethane to dichloroethane--; Col. 3, line 36, change "member" to --number;
Col. 7, line 22, change "of" to -or--;
Col. 8, line 51, change "51.2" to 5l2-;
Col. 8, line 56, change "CH'O-P" to CH -OP' "and change ||CH1=CH I| to C'H2=CH D Col. 11, line 5, change "n" to n 3 Col. 12, line 10, change "(diallyh in the formula to -(dia] lylv; Col. 12, lines 28, 31 and 34, ,ins'ert before selfextinguishing";
Col.- 12, line 33,- change "45" to 45 Col. 12, line 55, change "cyanoethylphosphonate" to 2- cyanoethylphosponate;
Col. 13, line 27, change claim 20" to --claim l--;
Signed and sealed this 11th day of March 1975.
(SEAL) Attest:
' v C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Office; and Trademarks.
Claims (6)
1. A FLAME RETARDANT POLYMER OF AN ALLYL 2-CARBAMOYLALKYLPHOSPHONATE CORRESPONDING TO THE FORMULAE:
2. The polymer of claim 20, wherein said allyl 2-carbamoylalkylphosphonate is selected from the group consisting of diallyl 2-carbamoylethylphosphonate, diallyl 2-carbamoylisopropylphosphonate, N,N''-methylenebis(diallyl 2-carbamoylethylphosponate) and N,N''-methylenebis(diallyl 2-carbamoylisopropylphosphonate).
3. The polymer of claim 1 wherein at least one other comonomer is present in the polymer, said comonomer being selected from the group consisting of amide nitrogen-containing monomers, monomers containing more than one polymerizable double bond, and monomers which contribute to flame retardancy and which have phosphorus, bromine or chlorine atoms in their molecules.
4. The allyl 2-carbamoylalkylphosphonates corresponding to the formula:
5. The compound
6. The compound
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00374190A US3839207A (en) | 1971-04-30 | 1973-06-27 | Allyl 2-carbamoyalkylphosphonates flame retardants |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13922271A | 1971-04-30 | 1971-04-30 | |
US00374190A US3839207A (en) | 1971-04-30 | 1973-06-27 | Allyl 2-carbamoyalkylphosphonates flame retardants |
Publications (1)
Publication Number | Publication Date |
---|---|
US3839207A true US3839207A (en) | 1974-10-01 |
Family
ID=26836996
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00374190A Expired - Lifetime US3839207A (en) | 1971-04-30 | 1973-06-27 | Allyl 2-carbamoyalkylphosphonates flame retardants |
Country Status (1)
Country | Link |
---|---|
US (1) | US3839207A (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3969230A (en) * | 1974-12-30 | 1976-07-13 | Hooker Chemicals & Plastics Corporation | Brominated carbamoyl derivatives useful to impart flame retarding property to combustible substrates |
US4143206A (en) * | 1974-12-20 | 1979-03-06 | Ciba-Geigy Corporation | Method of finishing synthetic organic fibrous material, in particular of providing it with an antistatic finish |
US5062996A (en) * | 1990-04-20 | 1991-11-05 | Jannette G. Kaylor | Methods and compositions for sorbing flammable liquids |
US5562739A (en) * | 1994-06-01 | 1996-10-08 | Courtaulds Fibres (Holdings) Limited | Lyocell fiber treatment method |
US5580356A (en) * | 1993-03-10 | 1996-12-03 | Courtaulds Fibres (Holdings) Limited | Fibre treatment method |
US5882356A (en) * | 1992-10-21 | 1999-03-16 | Courtaulds Fibres (Holdings) Limited | Fibre treatment |
EP1537130A1 (en) * | 2002-09-11 | 2005-06-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Carboxylic acid derivatives containing phosphorous groups and organically polymerisable groups |
US7127878B1 (en) | 2003-12-16 | 2006-10-31 | Samson Rope Technologies | Controlled failure rope systems and methods |
US7168231B1 (en) | 2002-09-05 | 2007-01-30 | Samson Rope Technologies | High temperature resistant rope systems and methods |
US8511053B2 (en) | 2008-06-04 | 2013-08-20 | Samson Rope Technologies | Synthetic rope formed of blend fibers |
US8689534B1 (en) | 2013-03-06 | 2014-04-08 | Samson Rope Technologies | Segmented synthetic rope structures, systems, and methods |
US8707668B2 (en) | 2003-12-16 | 2014-04-29 | Samson Rope Technologies | Wrapped yarns for use in ropes having predetermined surface characteristics |
US9003757B2 (en) | 2012-09-12 | 2015-04-14 | Samson Rope Technologies | Rope systems and methods for use as a round sling |
US9074318B2 (en) | 2005-09-15 | 2015-07-07 | Samson Rope Technologies | Rope structure with improved bending fatigue and abrasion resistance characteristics |
US9573661B1 (en) | 2015-07-16 | 2017-02-21 | Samson Rope Technologies | Systems and methods for controlling recoil of rope under failure conditions |
US10377607B2 (en) | 2016-04-30 | 2019-08-13 | Samson Rope Technologies | Rope systems and methods for use as a round sling |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2714100A (en) * | 1952-08-05 | 1955-07-26 | Victor Chemical Works | Diallyl monochloromethanephosphonate and polymers |
US3268292A (en) * | 1963-02-08 | 1966-08-23 | Leon H Chance | Process of treating cellulosic textiles with nu-methylol derivatives of tris (2-carbamoylethyl) phosphine oxide and products thereof |
US3276838A (en) * | 1963-02-08 | 1966-10-04 | Leon H Chance | Process of treating cellulosic textiles with methylol derivatives of tris(2-carbamoylethyl) phosphine and products thereof |
US3725272A (en) * | 1970-07-21 | 1973-04-03 | Basf Ag | Flameproofing agent for textile materials |
US3762865A (en) * | 1971-04-30 | 1973-10-02 | Stauffer Chemical Co | Flame retarding of solid substrates with allyl 2-carbamoylalkylphosphonates |
-
1973
- 1973-06-27 US US00374190A patent/US3839207A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2714100A (en) * | 1952-08-05 | 1955-07-26 | Victor Chemical Works | Diallyl monochloromethanephosphonate and polymers |
US3268292A (en) * | 1963-02-08 | 1966-08-23 | Leon H Chance | Process of treating cellulosic textiles with nu-methylol derivatives of tris (2-carbamoylethyl) phosphine oxide and products thereof |
US3276838A (en) * | 1963-02-08 | 1966-10-04 | Leon H Chance | Process of treating cellulosic textiles with methylol derivatives of tris(2-carbamoylethyl) phosphine and products thereof |
US3725272A (en) * | 1970-07-21 | 1973-04-03 | Basf Ag | Flameproofing agent for textile materials |
US3762865A (en) * | 1971-04-30 | 1973-10-02 | Stauffer Chemical Co | Flame retarding of solid substrates with allyl 2-carbamoylalkylphosphonates |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4143206A (en) * | 1974-12-20 | 1979-03-06 | Ciba-Geigy Corporation | Method of finishing synthetic organic fibrous material, in particular of providing it with an antistatic finish |
US3969230A (en) * | 1974-12-30 | 1976-07-13 | Hooker Chemicals & Plastics Corporation | Brominated carbamoyl derivatives useful to impart flame retarding property to combustible substrates |
US5062996A (en) * | 1990-04-20 | 1991-11-05 | Jannette G. Kaylor | Methods and compositions for sorbing flammable liquids |
US5882356A (en) * | 1992-10-21 | 1999-03-16 | Courtaulds Fibres (Holdings) Limited | Fibre treatment |
US5580356A (en) * | 1993-03-10 | 1996-12-03 | Courtaulds Fibres (Holdings) Limited | Fibre treatment method |
US5562739A (en) * | 1994-06-01 | 1996-10-08 | Courtaulds Fibres (Holdings) Limited | Lyocell fiber treatment method |
US7437869B1 (en) | 2002-09-05 | 2008-10-21 | Samson Rope Technologies | High temperature resistant rope systems and methods |
US7168231B1 (en) | 2002-09-05 | 2007-01-30 | Samson Rope Technologies | High temperature resistant rope systems and methods |
US7743596B1 (en) | 2002-09-05 | 2010-06-29 | Samson Rope Technologies | High temperature resistant rope systems and methods |
US7777080B2 (en) | 2002-09-11 | 2010-08-17 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Carboxylic acid derivatives containing phosphorous groups and organically polymerizable groups |
US20060142515A1 (en) * | 2002-09-11 | 2006-06-29 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Carboxylic acid derivatives containing phosphorous groups and organically polymerisable groups |
EP1537130A1 (en) * | 2002-09-11 | 2005-06-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Carboxylic acid derivatives containing phosphorous groups and organically polymerisable groups |
US8707668B2 (en) | 2003-12-16 | 2014-04-29 | Samson Rope Technologies | Wrapped yarns for use in ropes having predetermined surface characteristics |
US7127878B1 (en) | 2003-12-16 | 2006-10-31 | Samson Rope Technologies | Controlled failure rope systems and methods |
US9404203B2 (en) | 2003-12-16 | 2016-08-02 | Samson Rope Technologies | Wrapped yarns for use in ropes having predetermined surface characteristics |
US9074318B2 (en) | 2005-09-15 | 2015-07-07 | Samson Rope Technologies | Rope structure with improved bending fatigue and abrasion resistance characteristics |
US9982386B2 (en) | 2005-09-15 | 2018-05-29 | Samson Rope Technologies | Rope structure with improved bending fatigue and abrasion resistance characteristics |
US8511053B2 (en) | 2008-06-04 | 2013-08-20 | Samson Rope Technologies | Synthetic rope formed of blend fibers |
US9003757B2 (en) | 2012-09-12 | 2015-04-14 | Samson Rope Technologies | Rope systems and methods for use as a round sling |
US8689534B1 (en) | 2013-03-06 | 2014-04-08 | Samson Rope Technologies | Segmented synthetic rope structures, systems, and methods |
US9261167B2 (en) | 2013-03-06 | 2016-02-16 | Samson Rope Technologies | Segmented synthetic rope structures, systems, and methods |
US9573661B1 (en) | 2015-07-16 | 2017-02-21 | Samson Rope Technologies | Systems and methods for controlling recoil of rope under failure conditions |
US10377607B2 (en) | 2016-04-30 | 2019-08-13 | Samson Rope Technologies | Rope systems and methods for use as a round sling |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3839207A (en) | Allyl 2-carbamoyalkylphosphonates flame retardants | |
US3855359A (en) | Copolycondensed vinylphosphonates | |
US3906136A (en) | Process of flame retarding substrates by applying hexahydratriazine phosphonate derivatives | |
US3762865A (en) | Flame retarding of solid substrates with allyl 2-carbamoylalkylphosphonates | |
US2891877A (en) | Flame resistant organic textiles and method of production | |
US3671304A (en) | Process for flameproofing and resultant product | |
US3607356A (en) | Imparting flame resistance to fibrous textiles from an alkaline medium | |
US3577270A (en) | Process for rendering cellulosic fibers flame resistant | |
US3695925A (en) | Process for flameproofing textiles | |
US2814573A (en) | Organic polymeric compositions containing nitrilo methylol-phosphorus polymers and bromine compounds | |
US3670048A (en) | Graft copolymers of unsaturated polyethers on polyamide and polyester substrates | |
US2901444A (en) | Polymers made from 1-aziridinyl phosphine oxides and sulfides and flame resistant organic textiles | |
AU642465B2 (en) | Flame retardant composition and method of use | |
US3799738A (en) | Flame retardant process for cellulosics | |
US4017257A (en) | Textiles fire-retardant treated with copolycondensed vinylphosphonates and process | |
US4067927A (en) | Copolycondensed vinylphosphonates and their use as flame retardants | |
US4063885A (en) | Single-treatment radiation process for imparting durable soil-release properties to cotton and cotton-polyester blend fabrics | |
US3849409A (en) | Hexahydrotriazine phosphonate derivatives | |
US4483689A (en) | Abrasion-resistant durable-press acrylic finishes for cotton textiles by use of nonoxidative polymerization initiators and accelerators in two-stage heat curing | |
US2537064A (en) | Treatment of organic textile materials and products thereof | |
US4211622A (en) | Process for imparting durable flame retardancy to fabric, fibers and other materials and improved product produced thereby | |
US3065041A (en) | Method of graft-polymerizing acrylate monomers onto paper in presence of ethylene dimethacrylate, and resulting product | |
US3926555A (en) | Modification of cotton textiles and cotton/polyester textile blends by photo-initiated polymerization of vinylic monomers | |
US3219478A (en) | Flameproofing of cellulosic material | |
US3816068A (en) | Flame retardant for cellulosic fabrics |