US3806528A - Derivatives of perfluorinated hydrocarbons - Google Patents
Derivatives of perfluorinated hydrocarbons Download PDFInfo
- Publication number
- US3806528A US3806528A US00178444A US17844471A US3806528A US 3806528 A US3806528 A US 3806528A US 00178444 A US00178444 A US 00178444A US 17844471 A US17844471 A US 17844471A US 3806528 A US3806528 A US 3806528A
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- substances
- acid
- denotes
- oil
- 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
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- 229930195733 hydrocarbon Natural products 0.000 title abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 5
- 239000000126 substance Substances 0.000 description 37
- -1 aliphatic radicals Chemical class 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 239000005871 repellent Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000004753 textile Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NNTWKXKLHMTGBU-UHFFFAOYSA-N 4,5-dihydroxyimidazolidin-2-one Chemical compound OC1NC(=O)NC1O NNTWKXKLHMTGBU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NQPJDJVGBDHCAD-UHFFFAOYSA-N 1,3-diazinan-2-one Chemical compound OC1=NCCCN1 NQPJDJVGBDHCAD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- YSKUZVBSHIWEFK-UHFFFAOYSA-N ammelide Chemical compound NC1=NC(O)=NC(O)=N1 YSKUZVBSHIWEFK-UHFFFAOYSA-N 0.000 description 1
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- SKKTUOZKZKCGTB-UHFFFAOYSA-N butyl carbamate Chemical compound CCCCOC(N)=O SKKTUOZKZKCGTB-UHFFFAOYSA-N 0.000 description 1
- USIYRFTZKYKHBI-UHFFFAOYSA-N butyl n-ethylcarbamate Chemical compound CCCCOC(=O)NCC USIYRFTZKYKHBI-UHFFFAOYSA-N 0.000 description 1
- OXVVNXMNLYYMOL-UHFFFAOYSA-N carbonyl chloride fluoride Chemical compound FC(Cl)=O OXVVNXMNLYYMOL-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004855 creaseproofing Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SURZCVYFPAXNGN-UHFFFAOYSA-N methyl-carbamic acid ethyl ester Chemical compound CCOC(=O)NC SURZCVYFPAXNGN-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- YNTOKMNHRPSGFU-UHFFFAOYSA-N n-Propyl carbamate Chemical compound CCCOC(N)=O YNTOKMNHRPSGFU-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- BYTFESSQUGDMQQ-UHFFFAOYSA-N octadecanehydrazide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NN BYTFESSQUGDMQQ-UHFFFAOYSA-N 0.000 description 1
- GJNDMSSZEBNLPU-UHFFFAOYSA-N octadecylurea Chemical compound CCCCCCCCCCCCCCCCCCNC(N)=O GJNDMSSZEBNLPU-UHFFFAOYSA-N 0.000 description 1
- YPNZTHVEMNUDND-UHFFFAOYSA-N octyl carbamate Chemical compound CCCCCCCCOC(N)=O YPNZTHVEMNUDND-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- PCIUEQPBYFRTEM-UHFFFAOYSA-N perfluorodecanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PCIUEQPBYFRTEM-UHFFFAOYSA-N 0.000 description 1
- PXUULQAPEKKVAH-UHFFFAOYSA-N perfluorohexanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PXUULQAPEKKVAH-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
-
- 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
- D06M13/322—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 nitrogen
- D06M13/345—Nitriles
- D06M13/348—Nitriles unsaturated, e.g. acrylonitrile
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/68—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for positioning, orientation or alignment
Definitions
- the invention relates to new derivatives of perfluorinated hydrocarbons which essentially contain an alkenylcarboxamido grouping in the molecule.
- the invention also relates to a process for the production of the new substances and their use as oil repellents.
- the new compounds have the Formula I:
- R R R and R which may be identical or difierent
- A denotes a radical of the formula:
- B denotes a radical of the formula: NR or (CHR 0 or a single valency; and R denotes hydrogen or a radical of the formula:
- x denotes one of the integers 0 to 4.
- y denotes one of the integers 0 to 3;
- n denotes one of the integers 0 to 4.
- p denotes one of the integers 0 to 4; and q denotes one of the integers 0 and 1;
- lower alkyl, aryl, aralkyl and cycloalkyl which R R R and R in Formula I denote (in addition to hydrogen) include aliphatic radicals having one to six, aromatic radicals having six to ten, araliphatic radicals having seven to twelve or cycloaliphatic radicals having dive to eight carbon atoms.
- preferred radicals are methyl, ethyl, propyl, phenyl, benzyl or cyclohexyl radicals.
- the perfluorinated alkyl radical R contains three to eleven, preferably five to ten, carbon atoms.
- the alkyl radicals are derived from perfluorinated carboxylic acids whose perfluoroalkyl radical is defined by the abovementioned number of carbon atoms, examples of preferred acids being perfluorocapric, perfluoro caproic and perfluorocaprylic acid because these are the easiest to obtain.
- q denotes zero the alkyl radicals are derived from the amines derived in turn from the abovementioned carboxylic acids, for example by Hoffmann degradation of the corresponding acid amides or by reduction of the corresponding nitriles.
- R of the formula: CF -(CF is of special industrial interest.
- A, B and x have the meanings given for Formula I with a perfluorocarboxylic acid derivative of the formula: R -COU in which R has the meanings given for Formula I and U denotes chlorine or an ester group ing, and with a N-(l-alkenyDcarbamic acid chloride of Formula III:
- a substance which binds acid for example an alkali metal hydroxide, an alkali metal carbonate or preferably a tertiary amine such as triethylamine, tripropylamine, ethyldiisopropylamine or pyridine is added.
- the amounts of the reactants are chosen so that to each mole of compound having Formula II with n OH or NH groups there is available n-l moles of perfluorocarboxylic acid derivative and, when a perfluorocarboxylic acid chloride is used, from 1 to 3 moles of acid-binding substance.
- the reaction mixture is stirred for from one hour to twenty-four hours at room temperature to complete the reaction.
- the intermediates formed may be isolated by stirring the reaction mixture with water, if necessary removing the solvent at subatmospheric pressure, suction filtration and drying of the precipitate.
- N-(l-alkenyD-carbamyl chlorides having Formula III can be prepared in a simple manner by reacting compounds having Formula VI:
- R R (VI) in which R R R and R have the meanings given for Formula I with phosgene.
- the alkenyl isocyanates having Formula IV may then be prepared from the compounds having Formula III (when R denotes hydrogen) by subjecting them to a thermal treatment.
- a direct method of obtaining the alkenyl isocyanates however is by Curtius degradation of azides of a,,B-unsaturated carboxylic acids.
- a compound of Formula V is placed in an inert non-polar solvent such as benzene, toluene, methyl chloride, cyclohexane, ligroin, ether or dioxane and preferably ether and the N-(l-alkenyl) isocyanate is slowly added dissolved in a little solvent at from 0 to 5C.
- the reaction mixture is stirred until reaction is completed for another twelve to fourteen hours at room temperature and the substituted alkenyl-urea or the alkenylurethane formed is suction filtered or the solvent is carefully distilled off at subatmospheric pressure and the end product is isolated in the usual way.
- the advantageous procedure is by reaction of the compounds of Formula III in the presence of an equivalent amount of an acidbinding substance, as for example a tertiary amine, potassium carbonate or sodium carbonate, preferably a tertiary amine, together with the alkenylcarbamyl chloride:
- an acidbinding substance as for example a tertiary amine, potassium carbonate or sodium carbonate, preferably a tertiary amine
- the substituted alkenylureas of Formula I are usually obtained as white crystalline substances and the alkenyl urethanes usually as yellow to brown oils or pastes which are soluble in organic solvents such as acetone, methanol and the like.
- the substances according to the invention are very suitable as oil repellents for surfaces of all types.
- the substances of Formula I may be applied to the surfaces to be treated in the form of their solutions in organic solvents or in the form of aqueous dispersions of these solutions or in the form of the substances themselves.
- the solutions or dispersions are then dried at room temperature or preferably at elevated temperature (90 to 150 C.). After the drying of the solutions or dispersions, the surfaces are oil-repellent.
- finishing effects are particularly resistant to washing in the treatment of textile materials when the textiles which have been impregnated with the substances of Formula I are heated for about three to seven, preferably about five, minutes at 80 to 150 C. after they have been dried.
- the effects are very pronounced especially on material consisting of or containing cellulose and reach the optimum at an application of 0.1 to 1.5%, preferably 0.5 to 1.0%, by weight of the substance according to the invention, based on the dry textile material.
- the resistance of the finish can be considerably improved when there are applied to the surfaces to be treated not only the substances having the Formula I but also heatcurable resin-forming substances and if necessary catalysts which support the thermal curing of these resinforming substances, followed by the heat curing.
- heat-curable resin forming substances are those known as aminoplast forming substances, i.e. low molecular weight substances containing N-methylol and/or N- alkoxymethyl groups.
- polymethylol compounds which may if desired be partly or wholly etherified
- aminotriazines such as melamine, ammeline and ammelide
- guanidine dicyanodia'mide
- dicyanodiamidine dicyanodiamidine
- thiourea acetylenediurea
- the catalysts for assisting the heat curing of aminoplast-forming substances include particularly acid and potentially acid catalysts, i.e. strong or medium strength acids, i.e. acids having a dissociation constant K or K of more than such as hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, glycolic acid, maleic acid, monochloroacetic acid, trichloroacetic acid, tartaric acid and citric acid, or substances such as esters 01' particularly salts, which themselves have little or no acidity but which liberate by hydrolysis or thermal influences such an amount of acid that the cure of the aminoplastforming substances is accelerated.
- strong or medium strength acids i.e. acids having a dissociation constant K or K of more than such as hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, glycolic acid, maleic acid, monochloroacetic acid, trichloroacetic acid, tartaric acid and citric acid, or substances such as esters 01' particularly
- cure includes not only the reaction of the molecules of the aminoplast-forming substances with one another but also their reaction with reactive groups of the surface to be finished.
- Salts which are suitable as potentially acid catalysts include for example those of ammonia, amines or polyvalent metals and medium strength or preferably strong acids, for example ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium nitrate, dimonoethanolammonium hydrogen phosphate, ethanolammonium chloride, 1-hydroxy-2-methylpropylammonium- 2-chloride, magnesium chloride, aluminum chloride, zinc chloride, zinc nitrate, zinc fluoroborate and zirconyl chloride. Mixtures of two or more of these catalysts may also be used.
- Curing of the resin-forming substances may for example be carried out by conventional methods by heating the articles bearing on their surfaces the resin-forming substances, the substances of Formula I and the catalysts, for from five to fifteen minutes at a temperature of more than C., preferably at to C.
- oil-repellents in addition to the substance of Formula I, with or without the resin-forming substance and the catalyst, to the surface to be made oil-repellent.
- oil-repellents are parafiin emulsions, stearylurea and condensation products of the same with formaldehyde with or without other aminoplast-forming substances, stearic hydrazide and N-stearoyl-N',N-ethylenurea.
- Textiles finished in this way are strongly oil-repellent and the oil repellency is accompanied by water repellency and soil repellency.
- the substances of Formula I may be applied from an organic phase or from an aqueous phase.
- the substance according to the invention has to be present in a form appropriately emulsified or dispersed in the aqueous phase.
- Two baths are used when the substance of Formula I is applied from an organic phase and it is desired at the same time to achieve a creaseproof finish and oil repellency.
- the substances of Formula I are in the form of aqueous emulsions, it is convenient to use a method having one bath with the creaseproofing agent.
- n is an integer of to 1;
- R R R and R each is hydrogen, methyl, ethyl, propyl, phenyl, benzyl or cyclohexyl.
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Abstract
DERIVATIVES OF PERFLUORINATED HYDROCARBONS HAVING AN ALKENYLCARBOXAMIDO GROUPING IN THE MOLECULE.
Description
United States Patent ABSTRACT OF THE DISCLOSURE Derivatives of perfluorinated hydrocarbons having an alkenylcarboxamido grouping in the molecule.
The invention relates to new derivatives of perfluorinated hydrocarbons which essentially contain an alkenylcarboxamido grouping in the molecule.
The invention also relates to a process for the production of the new substances and their use as oil repellents.
The new compounds have the Formula I:
R R (I) in which R denotes perfluorinated alkyl having from three to eleven carbon atoms;
R R R and R which may be identical or difierent,
denote hydrogen, alkyl, aryl, aralkyl or cycloalkyl;
A denotes a radical of the formula:
B denotes a radical of the formula: NR or (CHR 0 or a single valency; and R denotes hydrogen or a radical of the formula:
where x denotes one of the integers 0 to 4;
y denotes one of the integers 0 to 3;
2 denotes one of the integers 0 to 2;
n denotes one of the integers 0 to 4;
p denotes one of the integers 0 to 4; and q denotes one of the integers 0 and 1;
and when q denotes zero, 2: and p denote zero or 1.
3,806,528 Patented Apr. 23, 1974 ice x preferably denotes 1 to 3, 2 preferably denotes 1 or 2, n preferably denotes zero or 1 and p preferably denotes 1 to 3.
In the context of the invention, lower alkyl, aryl, aralkyl and cycloalkyl which R R R and R in Formula I denote (in addition to hydrogen) include aliphatic radicals having one to six, aromatic radicals having six to ten, araliphatic radicals having seven to twelve or cycloaliphatic radicals having dive to eight carbon atoms. Examples of preferred radicals are methyl, ethyl, propyl, phenyl, benzyl or cyclohexyl radicals.
The perfluorinated alkyl radical R contains three to eleven, preferably five to ten, carbon atoms. When q denotes 1, the alkyl radicals are derived from perfluorinated carboxylic acids whose perfluoroalkyl radical is defined by the abovementioned number of carbon atoms, examples of preferred acids being perfluorocapric, perfluoro caproic and perfluorocaprylic acid because these are the easiest to obtain. When q denotes zero, the alkyl radicals are derived from the amines derived in turn from the abovementioned carboxylic acids, for example by Hoffmann degradation of the corresponding acid amides or by reduction of the corresponding nitriles. In both cases R of the formula: CF -(CF is of special industrial interest.
The usual prior art methods of producing these acids result in contamination by up to 15% of higher fluorinated carboxylic acids having a maximum of twelve carbon atoms.
Examples of individual representatives of the new compounds are the substances having the formulae:
Substances of Formula I are accessible by successively reacting a compound of Formula II:
in which A, B and x have the meanings given for Formula I with a perfluorocarboxylic acid derivative of the formula: R -COU in which R has the meanings given for Formula I and U denotes chlorine or an ester group ing, and with a N-(l-alkenyDcarbamic acid chloride of Formula III:
or (when R denotes hydrogen) the alkenyl isocyanate of Formula IV:
R R (IV) ylformamide and then at 0 to 5 C. the perfluorocarboxylic acid derivative with or without a substance which binds acid, for example an alkali metal hydroxide, an alkali metal carbonate or preferably a tertiary amine such as triethylamine, tripropylamine, ethyldiisopropylamine or pyridine is added. When an acid-binding substance is used, the amounts of the reactants are chosen so that to each mole of compound having Formula II with n OH or NH groups there is available n-l moles of perfluorocarboxylic acid derivative and, when a perfluorocarboxylic acid chloride is used, from 1 to 3 moles of acid-binding substance.
Sometimes it is advantageous however to use the compound having the Formula II itself as the acid-binding substance. The reaction mixture is stirred for from one hour to twenty-four hours at room temperature to complete the reaction. The intermediates formed may be isolated by stirring the reaction mixture with water, if necessary removing the solvent at subatmospheric pressure, suction filtration and drying of the precipitate. The intermediate having Formula V:
thus formed (in which the variables have the meanings given for Formula I) may be reacted under the conditions mentioned above with the carbamyl chloride or isocyanate having Formula III or IV.
N-(l-alkenyD-carbamyl chlorides having Formula III can be prepared in a simple manner by reacting compounds having Formula VI:
R R (VI) in which R R R and R have the meanings given for Formula I with phosgene. The alkenyl isocyanates having Formula IV may then be prepared from the compounds having Formula III (when R denotes hydrogen) by subjecting them to a thermal treatment.
A direct method of obtaining the alkenyl isocyanates however is by Curtius degradation of azides of a,,B-unsaturated carboxylic acids.
The following method has proved to be very suitable for the production of compounds having Formula I: a compound of Formula V is placed in an inert non-polar solvent such as benzene, toluene, methyl chloride, cyclohexane, ligroin, ether or dioxane and preferably ether and the N-(l-alkenyl) isocyanate is slowly added dissolved in a little solvent at from 0 to 5C. The reaction mixture is stirred until reaction is completed for another twelve to fourteen hours at room temperature and the substituted alkenyl-urea or the alkenylurethane formed is suction filtered or the solvent is carefully distilled off at subatmospheric pressure and the end product is isolated in the usual way. When a carbamyl chloride is used as reactant instead of an isocyanate, the advantageous procedure is by reaction of the compounds of Formula III in the presence of an equivalent amount of an acidbinding substance, as for example a tertiary amine, potassium carbonate or sodium carbonate, preferably a tertiary amine, together with the alkenylcarbamyl chloride: The products formed are then washed with water to free them from the hydrochlorides simultaneously formed.
The substituted alkenylureas of Formula I are usually obtained as white crystalline substances and the alkenyl urethanes usually as yellow to brown oils or pastes which are soluble in organic solvents such as acetone, methanol and the like. The substances according to the invention are very suitable as oil repellents for surfaces of all types.
They have special importance for the oil repellent finishing of textile materials or fibers of natural and artificial material such as wool, silk, polyamide fibers, polyester fibers, polyolefin fibers, cellulose ester fibers and particularly fibers of natural and regenerated cellulose and mixtures thereof with synthetic fibers. The substances of Formula I may be applied to the surfaces to be treated in the form of their solutions in organic solvents or in the form of aqueous dispersions of these solutions or in the form of the substances themselves. The solutions or dispersions are then dried at room temperature or preferably at elevated temperature (90 to 150 C.). After the drying of the solutions or dispersions, the surfaces are oil-repellent.
The finishing effects are particularly resistant to washing in the treatment of textile materials when the textiles which have been impregnated with the substances of Formula I are heated for about three to seven, preferably about five, minutes at 80 to 150 C. after they have been dried. The effects are very pronounced especially on material consisting of or containing cellulose and reach the optimum at an application of 0.1 to 1.5%, preferably 0.5 to 1.0%, by weight of the substance according to the invention, based on the dry textile material.
The resistance of the finish, particularly to the action of water and to washing, can be considerably improved when there are applied to the surfaces to be treated not only the substances having the Formula I but also heatcurable resin-forming substances and if necessary catalysts which support the thermal curing of these resinforming substances, followed by the heat curing. Examples of heat-curable resin forming substances are those known as aminoplast forming substances, i.e. low molecular weight substances containing N-methylol and/or N- alkoxymethyl groups. Examples of such substances are polymethylol compounds (which may if desired be partly or wholly etherified) of urea, monoalkylureas, symmetrical dialkylureas, cyclic ureas such as N,N'-ethylenurea (=imidazolidone-2),
N,N'-1,2-propyleneurea (-=4-methylimidazolidone-2),
N,N'-1,3-propyleneurea (=N,N'-trimethyleneurea or hexahydropyrimidone-Z),
S-hydroxyhexahydropyrimidone-Z,
4-hydroxy-5,5-dialkylhexahydropyrimidone,
4-alkoxy-5,5-dialkylhexahydropyrimidone,
hexahydro-1,3,5-triazinone-2- and its S-alkyl and S-hydroxyalkyl derivatives,
glyoxal monoureine (4,5-dihydroxyimidazolidone-2) and urones,
monocarbamic and dicarbamic esters such as ethyl carbamate,
propyl carbamate,
butyl carbamate,
,B-hydroxyethyl carbamate,
,B-methoxyethyl carbamate,
octyl carbamate,
ethyl N-methylcarbamate, and
butyl N-ethylcarbamate and dicarbamic esters and di-N-ethylcarbamic esters of ethylene glycol,
1,3-butanediol,
1,4-butanediol and 1,6-hexanediol,
of aminotriazines such as melamine, ammeline and ammelide, of guanidine, dicyanodia'mide, dicyanodiamidine, thiourea and acetylenediurea ('=glyoxal diureine).
The catalysts for assisting the heat curing of aminoplast-forming substances include particularly acid and potentially acid catalysts, i.e. strong or medium strength acids, i.e. acids having a dissociation constant K or K of more than such as hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, glycolic acid, maleic acid, monochloroacetic acid, trichloroacetic acid, tartaric acid and citric acid, or substances such as esters 01' particularly salts, which themselves have little or no acidity but which liberate by hydrolysis or thermal influences such an amount of acid that the cure of the aminoplastforming substances is accelerated. In this context, cure includes not only the reaction of the molecules of the aminoplast-forming substances with one another but also their reaction with reactive groups of the surface to be finished. Salts which are suitable as potentially acid catalysts include for example those of ammonia, amines or polyvalent metals and medium strength or preferably strong acids, for example ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium nitrate, dimonoethanolammonium hydrogen phosphate, ethanolammonium chloride, 1-hydroxy-2-methylpropylammonium- 2-chloride, magnesium chloride, aluminum chloride, zinc chloride, zinc nitrate, zinc fluoroborate and zirconyl chloride. Mixtures of two or more of these catalysts may also be used.
Curing of the resin-forming substances may for example be carried out by conventional methods by heating the articles bearing on their surfaces the resin-forming substances, the substances of Formula I and the catalysts, for from five to fifteen minutes at a temperature of more than C., preferably at to C.
It has also proved to be very suitable to apply an ad ditional oil-repellent, in addition to the substance of Formula I, with or without the resin-forming substance and the catalyst, to the surface to be made oil-repellent. Examples of oil-repellents are parafiin emulsions, stearylurea and condensation products of the same with formaldehyde with or without other aminoplast-forming substances, stearic hydrazide and N-stearoyl-N',N-ethylenurea.
Textiles finished in this way are strongly oil-repellent and the oil repellency is accompanied by water repellency and soil repellency.
The substances of Formula I may be applied from an organic phase or from an aqueous phase. In the latter case, the substance according to the invention has to be present in a form appropriately emulsified or dispersed in the aqueous phase.
Two baths are used when the substance of Formula I is applied from an organic phase and it is desired at the same time to achieve a creaseproof finish and oil repellency.
1st bath.-Oil-repellent agent according to the invention (organic phase);
2nd bath.Heat-curable (aqueous phase).
When the substances of Formula I are in the form of aqueous emulsions, it is convenient to use a method having one bath with the creaseproofing agent.
Not only textiles, but also other materials such as wood, paper, leather and plastics may be given an oil-repellent impregnation or coating with the compounds of the invention.
,The following examples illustrate the invention. The parts specified are by weight.
'EXAMPLES 1 TO 14 resin-forming substance I.-Production of the perfluorinated hydrocarbons 0.1 mole of the perfluoro compound of Formula V is dissolved in 600 to 800 parts of dry ether and while stirring 0.1 mole of vinyl isocyanate per free reactive -NH or -OH group, dissolved in 80 to 100 parts of absolute ether, is added at a temperature of 0 to 5 C. in the course of 20 to 30 minutes. To complete the reaction, the whole is stirred first for another hour at 0 C. and then for another twelve to fifteen hours at room temperature. The solvent is then removed under mild conditions at subatmospheric pressure and the viscous residue is dried for a short time or the crystalline product suction filtered and washed with a little dry ether.
In the table:
E=Example No. SP=Starting product EB=End product Y=Yield in percent mp=Melting point in C. AR=Analytical results C H N =C H N calculated Cf Hg N1=C H N found.
II.-Making textile material oil-repellent:
10 parts of any of the products of Formula I obtained as described above is dissolved in 1000 parts of acetone. Cotton poplin is padded at room temperature with the solution so that the liquor take-up is 80%. Thus 0.8% of substance remains on the textile material after it has been dried at 80 C. and condensed for five minutes at 150 C. The cloth finished in this way has good oil repellency. A mixture of 10 parts of mineral oil having a viscosity of 78 to 84 centistokes (at 50 C.) and 90 parts of n-heptane is prevented from spreading.
We claim:
1. A compound of the formula wherein R is perfluorinated alkyl of 3 to 11 carbon atoms;
'R R R and R each is hydrogen, lower alkyl, phenyl,
benzyl or cycloalkyl of 5 to 8 carbon atoms;
as is an integer of 1 to 3;
n is an integer of to 1; and
p is an integer of l to 3.
2. A compound as claimed in claim 1 wherein R R R and R each is hydrogen, methyl, ethyl, propyl, phenyl, benzyl or cyclohexyl.
3. A compound as claimed in claim 1 wherein R R R and R each is hydrogen or methyl.
References Cited UNITED STATES PATENTS ELBERT L. ROBERTS, Primary Examiner E. G. LOVE, Assistant Examiner US. Cl. X.R.
8115.6, 116.2, 127.5, 128 R; 117-121, 138.8 B, 138.8 F, 138.8 N, 141, 144; 260-70, 243 B, 268 C, 268 R,
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,806,528 DATED April 23, 1974 \NVENTOR(S) 1 Heinz Eilingsfeld et a1.
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In Column 1, after Line 8, insert "Claims priority, application Germany, September 9, 1970, P 20 44 656.4"
Signed and Scaled this twenty-second D3) Of June 1976 [SEAL] Arrest:
RUTH c. MASON a c. MARSHALL mum Arresting Officer Commissioner of Patents and Trademarks
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1187671D CH1187671D (en) | 1970-09-09 | ||
DE19702044656 DE2044656A1 (en) | 1970-09-09 | 1970-09-09 | Derivatives of perfluorinated hydrocarbons |
US00178444A US3806528A (en) | 1970-09-09 | 1971-09-07 | Derivatives of perfluorinated hydrocarbons |
FR7132391A FR2106269A5 (en) | 1970-09-09 | 1971-09-08 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19702044656 DE2044656A1 (en) | 1970-09-09 | 1970-09-09 | Derivatives of perfluorinated hydrocarbons |
US00178444A US3806528A (en) | 1970-09-09 | 1971-09-07 | Derivatives of perfluorinated hydrocarbons |
Publications (1)
Publication Number | Publication Date |
---|---|
US3806528A true US3806528A (en) | 1974-04-23 |
Family
ID=25759704
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US00178444A Expired - Lifetime US3806528A (en) | 1970-09-09 | 1971-09-07 | Derivatives of perfluorinated hydrocarbons |
Country Status (4)
Country | Link |
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US (1) | US3806528A (en) |
CH (1) | CH1187671D (en) |
DE (1) | DE2044656A1 (en) |
FR (1) | FR2106269A5 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4539006A (en) * | 1983-09-13 | 1985-09-03 | Minnesota Mining And Manufacturing Company | Leather treatment |
AU582346B2 (en) | 1983-09-13 | 1989-03-23 | Minnesota Mining And Manufacturing Company | Fluorohydrocarbon sulfonamide compounds and use thereof in treatment of leather, textiles and cellusosic materials |
-
0
- CH CH1187671D patent/CH1187671D/xx unknown
-
1970
- 1970-09-09 DE DE19702044656 patent/DE2044656A1/en active Pending
-
1971
- 1971-09-07 US US00178444A patent/US3806528A/en not_active Expired - Lifetime
- 1971-09-08 FR FR7132391A patent/FR2106269A5/fr not_active Expired
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FR2106269A5 (en) | 1972-04-28 |
DE2044656A1 (en) | 1972-03-30 |
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