US3875264A - Phosphonous acid esters - Google Patents
Phosphonous acid esters Download PDFInfo
- Publication number
- US3875264A US3875264A US308594A US30859472A US3875264A US 3875264 A US3875264 A US 3875264A US 308594 A US308594 A US 308594A US 30859472 A US30859472 A US 30859472A US 3875264 A US3875264 A US 3875264A
- Authority
- US
- United States
- Prior art keywords
- compound
- carbon atoms
- alkyl
- methyl
- formula
- 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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- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- -1 n-dodecyl Chemical group 0.000 claims description 147
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- 239000004305 biphenyl Substances 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 15
- 239000011368 organic material Substances 0.000 abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 229910052727 yttrium Inorganic materials 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- IJAAVGASNIZXLN-UHFFFAOYSA-N dichlorophosphane;phenoxybenzene Chemical compound ClPCl.C=1C=CC=CC=1OC1=CC=CC=C1 IJAAVGASNIZXLN-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 150000002815 nickel Chemical class 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
- 239000003921 oil Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical class OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006622 cycloheptylmethyl group Chemical group 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
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000006623 cyclooctylmethyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
- C07F9/4841—Aromatic acids or derivatives (P-C aromatic linkage)
-
- 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
- C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
-
- 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
- C08K5/5398—Phosphorus bound to sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
- C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
- C09K15/324—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus containing phosphorus and sulfur
Definitions
- C07f 9/08, C07f 9/16 1 2 3 and 4 are or [58] Field of Search 260/932 1, 2 Raiand are hy r r on i l r ng A and B may be substituted by alkyl groups, [56] I References Cited and inorganic salts of compounds in which any of UNITED STATES PATENTS RrRi are hydrogen- 3,707,565 12/1972 Hofer 260/962 19 Claims, No Drawings 1 PHOSPIIONOUS ACll) E-STERS IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS The present invention relates to phosphonous acid derivatives.
- Y Y Y and Y which may be the same or different, each signifies O or S.
- R R R and R which may be the same or different, each signifies a hydrocarbon radical of up to carbon atoms consisting of aromatic and/or saturated aliphatic units,
- rings A and B may be either further unsubstituted or each further substituted by I or 2 alkyl groups of l to 6 carbon atoms, and inorganic salts of compounds in which any of R to to R is hydrogen.
- X preferably signifies O and n preferably signifies 1.
- Y Y Y and Y are preferably the same, and R R R and R, are preferably also the same. In the preferred compounds, the
- Suitable hydrocarbon radicals for R R R R and R include the following: alkyl radicals, preferably other than tertiary alkyl radicals, of up to 20, preferably up to 12, in particular I to 6 carbon atoms, for example n-alkyl radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecycl and dodecyl, secondary alkyl radicals such as isopropyl, 2- butyl, 3-methyl-2-butyl, 2-pentyl, 2,2-dimethyl-3-butyl, 2-hexyl, 3-hexyl, 2-methyl-3-phenyl, 3 methyl-2- pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-3-pentyl, 2,4-dimethyl-3-pentyl, 2-heptyl, 3 heptyl, 4-heptyl
- l to 6 carbon atoms such as those alkyl radicals mentioned above and also tertiary alkyl radicals, such as tert. butyl, 2-methyl-2-butyl, 2,3-dimethyl-2-butyl, Z-methyl- Z-pentyl, 3-methyl-3-pentyl, 3-ethyl-3-pentyl, 2,4-dimethyl-2-pentyl, 2-methyl'2-hexyl, 3methyl-3- hexyl, 3,4-dimethyl-3-hexyl, 3,5-dimethyl-3-hexyl, 2-methyl-2-heptyl, 3-methyl-3-heptyl, 4-methyl-4- heptyl, 2,3,4-trimethyl-3-pentyl, 2,4,4-trimethyl-2- pentyl, 3-ethyl-3-heptyl, 2-methyl-2-octyl, 4-methyl-4- octyl, 3,6-dimethyl-3-oct
- butyl-4-methylphenyl 4-tert.butyl-2- methylphenyl, 6-tert.butyl-3-methylphenyl, 2,4-ditert.butylphenyl, 4-(1',l',3,3-tetramethylbutyl)- phenyl, 2-methyl-4-( l ,l ',33-tetramethylbutyl)- phenyl, 4-nonylphenyl (mixture of isomers), and 2,4-di-terLoctyl-phenyl; aralkyl radicals, such as phenyl or diphenyl alkyl radicals, the alkyl radicals of which suitably contain 1 to 12, particularly 1 to 6 carbon atoms, and the aryl radicals of which may optionally be alkyl substituted as above, including benzyl, land Z-phenyl-ethyl, l-phenyl-l-propyl, l-phenyl-Z- propyl,
- l to 12 in particular 4 to 12 carbon atoms, such as n-butyl or n-dodecyl, and phenyl and diphenyl radicals, optionally substituted by 1 or 2 alkyl radicals of 1 to 4 carbon atoms, preferably tertiary such alkyl radicals, such as 2,4-di-t-butylphenyl, 2-t-butyl-diphenyl, and 2,4'-di-t-butyldiphenyl.
- the rings A and B may, as indicated, be substituted by l or 2 alkyl groups of up to 6, preferably up to 4 carbon atoms, for example such alkyl groups as mentioned above, but are preferably unsubstituted.
- the invention also provides a process for the production of compounds of formula I and inorganic salts thereof, characterised by reacting a compound of formula II,
- R R Y and Y are as defined above, and, where required, converting the resulting product into an inorganic salt.
- two or more of the compounds III, IV, V and VI may be the same, in which case the molar quantity of the compound is adjusted accordingly.
- the process of the invention may suitably be carried out in conventional manner, for example as described by K. Sasse, Houben-Weyl (eds.), Methoden der organischen Chemie, fourth impression (1963), Vol. XII/l. pp.3 l 8/ff.
- the particular conditions employed depend, to an extent, on the particular compounds III, IV, V or VI being employed. For example, in some instances, it may be advisable to apply external cooling to the reaction mixture to restrain the vigorous reaction.
- any of the compounds III, IV, V and V1 is water
- the reaction may suitable be carried out at a temperature of from 100 to 150C, in the presence of an acid binding agent such as pyridine or a trialkylamine.
- VIIa VIIb which are acidic and may be converted into inorganic salts.
- Suitable salts include alkali metal, e.g. sodium or potassium, al-
- kaline earth metal e.g. calcium or magnesium, zinc, manganese, aluminium, copper, vanadium, cobalt and nickel salts.
- the salts may be produced by reaction of the free acid with an inorganic hydroxide or salt, such as calcium hydroxide, zinc oxide, sodium carbonate, potassium bicarbonate, aluminium acetate, borium chloride, nickel acetate and zinc chloride.
- the reaction of the compounds II with water and production of salts is carried out in a single operation.
- an excess of water may be provided for hydrolysis of the compound II, and after addition of the appropriate inorganic reagent, the compound II may be slowly added, with stirring, as indicated above.
- compounds of formula II may be produced by reacting the appropriate diphenylmethane, oxide or sulphide, with a phosphorus trihalide, preferably phosphorus trichloride.
- a phosphorus trihalide preferably phosphorus trichloride.
- the process may suitably be effected at an elevated temperature in the gaseous phase, although it is more preferable to react under milder conditions in the presence of a catalyst, e.g. a F riedel-Krafts catalyst, in particular aluminium trichloride. It is preferable to work with phosphorus trichloride at its boiling temperature.
- any aluminium chloride complex of the compound II may be decomposed, for example with phosphorus oxychloride or pyridine.
- the resulting compounds of formula Il may be isolated and purified using conventional techniques.
- the compounds of the invention are useful as stabilisers for organic materials which are sensitive to light, oxygen and heat.
- they may be incorporated in or applied to form a protective surface film on the organic material.
- the new compounds by their stabilizing action protect sensitive materials against degradation.
- plastics materials have a wide area of use in the processing of plastics materials, being suitable, for example, as stabilizers for cellulose acetate, cellulose acetobutyrate, polyethylene, polypropylene, polyvinyl chloride, polyvinyl chloride acetate, polyamides, polystyrene, ethyl cellulose, cellulose nitrate, polyvinyl alcohol, silicon rubber, cellulose propionate, melamine-formaldehyde resins, urea-formaldehyde resins, allyl casting resins, polymethyl methacrylate, polyesters, polyacrylonitrile, and copolymers of these polymers.
- Thecompounds may also be used for the stabilization of natural products such as rubber, cellulose, wool and silk.
- the materials for stabilization may suitably be in the form of film or sheet, rods, coatings, panels, tapes, fibres, granules, powders or other processing forms, or as solutions, emulsions or dispersions.
- the stabilizing compounds may be incorporated in or coated on the materials by conventional methods.
- An important method of application consists in intimately mixing polymeric material, for example polypropylene granules, with the stabilizer in a kneader or other suitable machine, followed by extrusion. This method ensures homogeneous distribution which is important for good protection.
- the material can be extruded, for example, as film, tubing or filament, the latter for conversion into textiles.
- the stabilizer may be incorporated in, for example, the polypropylene prior to textile production.
- the new stabilizers can also be applied to textile yarns and fabrics from an aqueous medium containing a finely dispersed compound of formula (1). This method is particularly suitable for, e.g. textiles of polyethylene terephthalate and cellulose acetate fibres.
- Synthetic polymeric materials need not necessarily be in the final form before incorporation of the compounds of the invention.
- these compounds may be mixed with the monomers or prepolymers prior to the condensation or other polymerization reaction giving the final polymer.
- the new stabilizers are suitable for application to, for example, clear films and plastics, and are also suitable for stabilizing opaque, semi-opaque and translucent materials having a surface susceptible to degradation by ultra-violet radiation, air or heat.
- opaque, semi-opaque and translucent materials having a surface susceptible to degradation by ultra-violet radiation, air or heat.
- the present invention also comprises the sensitive organic materials containing a compound of formula 1 for stabilization.
- the new compounds can be incorporated in the organic materials at any stage of processing using standard methods.
- the amounts of stabilizer employed may vary within wide limits, for example from 0.01 to 5% or preferably from 0.05 to 1% in relation to the weight of the material.
- the stabilized organic materials may contain compounds of formula I alone, or together with further additives, for example ultra-violet absorbers and other stabilizers against degradation by heat and oxygen.
- suitable stabilizers are those belonging to different chemical classes to the compounds of formula I, for example organic compounds of sulphur, tin and pentavalent phosphorus, sterically hindered phenols, 2- hydroxy-benzophenones and hydroxybenzotriazoles. Often, notably high stabilization may be obtained with such mixtures since they may have a synergistic action.
- EXAMPLE 2 At 5, a solution of 33.4 parts of the diphenylether dichloro-phosphine of formula l la, above, in 50 parts of toluene is added to 50.7 parts of 2,4-ditert.butylphenol and parts of triethylamine in 200 parts of toluene in the absence of moisture. The solution is allowed to react overnight at the precipitated product filtered, the filtrate evaporated under vacuum, and the residue crystallized from ether/methanol. m.p. 8889..
- EXAMPLE 4 A solution of parts of 4,4-diphenylether-(bischlorophosphine) in parts of toluene is added, at
- EXAMPLE 6 A solution of 12.5 parts of 4,4-diphenylether-(bisdichlorophosphine) in 50 parts of toluene is added at and the residue triturated with methanol and crystal- 5 99 parts of butane] and 14 parts of triethylam lized from benzene. m.p. 7780.
- Y Y Y and Y which may be the same or different, each signifies -O or -S,
- R R R and R which may be the same or different, each signifies a hydrocarbon radical of up to 20 carbon atoms selected from the group consisting of alkyl; cycloalkyl which may be substituted by up to 3 alkyl groups; cycloalkylalkyl; phenyl which may be substituted by up to 3 alkyl or alkylcycloalkyl groups; diphenyl which may be substituted by up to 3 alkyl or alkylcycloalkyl groups; and phenyl 3.
- R,, R R and R each signifies an alkyl radical of l to 12 carbon atoms, a cycloalkyl radical of 3 to 12 carbon atoms, which may be substituted by l, 2 or 3 alkyl groups of l to 4 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl portion contains 5 to 12 carbon atoms and the alkyl portion l to 6 carbon atoms, or a phenyl or diphenyl radical which may be substituted by l, 2 or 3 alkyl radicals of l to 12 carbon atoms.
- R R R and R each signifies an alkyl radical of l to 6 carbon atoms, a cycloalkyl radical of 5 to 8 carbon atoms, which may be substituted by l, 2 or 3 alkyl groups of l to 4 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl portion contains 5 to 8 carbon atoms and the alkyl portion contains 1 to 4 carbon atoms, or a phenyl or diphenyl radical which may be substituted by 1, 2 or 3 alkyl radicals of l to 6 carbon atoms.
- R, R R and R each signifies an alkyl radical of 4 to 12 carbon atoms, or phenyl or diphenyl radical, which may be substituted by l or 2 alkyl radicals of l to 4 carbon atoms.
- R R R and R each signifies n-butyl, n-dodecyl, 2,4-di-tbutylphenyl, 2-t-butylphenyl, or 2,4-di-t-butyldiphenyl.
- a compound f l i 12 i hi h R 12,, R and l to 6 carbon atoms. R are the same.
- X signifies 16' The compound of claim 1 of f ul --O.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Compounds, useful as stablizers for organic materials, of the formula
WHEREIN X is -CH2-, -O- or -S-, Y1, Y2, Y3 and Y4 are -O- or -S-, R1, R2, R3 and R4 are hydrocarbon radicals, rings A and B may be substituted by alkyl groups, AND INORGANIC SALTS OF COMPOUNDS IN WHICH ANY OF R1-R4 are hydrogen.
WHEREIN X is -CH2-, -O- or -S-, Y1, Y2, Y3 and Y4 are -O- or -S-, R1, R2, R3 and R4 are hydrocarbon radicals, rings A and B may be substituted by alkyl groups, AND INORGANIC SALTS OF COMPOUNDS IN WHICH ANY OF R1-R4 are hydrogen.
Description
i United States Patent 1 [111 3,875,264 Hofer et al. Apr. 1, 1975 PHOSPHONOUS ACID ESTERS [75] Inventors: Kurt Hofer, Munchenstein/BL; i ExamuierwLoframe wemberger Guemher Tscheulin Riehen/BS Assistant E.\'ammerRichard L. Raymond both of Switzerland Attorney, Agent, or FirmGerald D. Sharkin; Richard E. Vila; Thomas C. Doyle [73] Assignee: Sandoz Ltd. (also known as Sandoz,
AG), Basie, Switzerland 57 ABSTRACT [22] Filed: Nov. 21, 1972 Compounds, useful as stablizers for organic materials, 21 Appl. No.: 308,594 of fmmula [30] Foreign Application Priority Data T R3 Nov. 24, l97l Switzerland l7l29/7l P p 52 vs. CI 260/932, 260/45.7 PS, 260/45.7 P, R,-Y1 q y R, 260/448 R, 260/502.4 R, 260/502.4 P, Wherffin 260/949, 260/951, 260/962, 260/972, 260/973 X 15 2 0- or S, [51] Int. Cl. C07f 9/08, C07f 9/16 1 2 3 and 4 are or [58] Field of Search 260/932 1, 2 Raiand are hy r r on i l r ng A and B may be substituted by alkyl groups, [56] I References Cited and inorganic salts of compounds in which any of UNITED STATES PATENTS RrRi are hydrogen- 3,707,565 12/1972 Hofer 260/962 19 Claims, No Drawings 1 PHOSPIIONOUS ACll) E-STERS IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS The present invention relates to phosphonous acid derivatives.
More particularly, this invention provides compounds of formula I,
Y Y Y and Y which may be the the same or different, each signifies O or S.
R R R and R which may be the the same or different, each signifies a hydrocarbon radical of up to carbon atoms consisting of aromatic and/or saturated aliphatic units,
and rings A and B may be either further unsubstituted or each further substituted by I or 2 alkyl groups of l to 6 carbon atoms, and inorganic salts of compounds in which any of R to to R is hydrogen.
X preferably signifies O and n preferably signifies 1. Y Y Y and Y, are preferably the same, and R R R and R, are preferably also the same. In the preferred compounds, the
substituent or each substituent is in the para position of the nucleus.
Suitable hydrocarbon radicals for R R R and R include the following: alkyl radicals, preferably other than tertiary alkyl radicals, of up to 20, preferably up to 12, in particular I to 6 carbon atoms, for example n-alkyl radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecycl and dodecyl, secondary alkyl radicals such as isopropyl, 2- butyl, 3-methyl-2-butyl, 2-pentyl, 2,2-dimethyl-3-butyl, 2-hexyl, 3-hexyl, 2-methyl-3-phenyl, 3 methyl-2- pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-3-pentyl, 2,4-dimethyl-3-pentyl, 2-heptyl, 3 heptyl, 4-heptyl, 2-methyl-3-hexyl, 4-methyl-3-hexyl, 5-methyl-3-hexyl, 3-ethyl-4-hexyl, 2,2-dimethyl-3-hexyl, 2,4-dimethyl-3- hexyl, 2,5-dimethyl-3-hexyl, 3,4-dimethyl-2-hexyl, 2-methyl-3-heptyl, 3-methyl-2-heptyl, 3-methyl-4- heptyl, 4-methyl-3-heptyl, 5-methyl-3-heptyl, 6 methyl-2-heptyl, 2-octyl, 3-octyl, 4-octyl, 2,2,4-trimethyl-3- pentyl, S-ethyl-Z-heptyl, .2,2 -dimethyl-3-heptyl, 2,6-dimethyl-4-heptyl, 2-methyl-3-octyl, 3-methyl-4- octyl, 6-ethyl-3-octyl, 2-decyl, 5-decyl, 2,2-dimethyl-3- 2 octyl, 2-methyl-4-nonyl, 3-methyl-4-nonyl, 6-ethyl-3- decyl, 7ethyLZ-methyl-4-nonyl, 2dodecyl, 2,6,8- trimethyl-4-nonyl, Z-tridecyl, 2-tetradecyl, 2- pentade'cyl, 2-hexadecyl, 2-nonadecyl, alkyl radicals bound through a primary carbon atom but otherwise branched, for example Z-methyl-l-propyl, 2,2-dimethyl-l-propyl, Z-methyl-l-butyl, 2-ethyl-1-butyl, 2,2- dimethyl-l-butyl, Z-methyl-l-pentyl, 3-methyl-1- pentyl, 4-methyl-l-pentyl, 2,4-dimethyl-l-pentyl, 2- ethyl-l-hexyl, 2,2-dimethyl-1-hexyl, 2,2,4-trimethyl-1- pentyl, 4-methyl-2propyl-l-pentyl, 3,7-dimethyl-loctyl, 2,2-dimethyl-l-decyl; cycloalkyl radicals of up to 20, preferably 3 to 12, in particular 5 to 8 carbon atoms, optionally substituted by l, 2 or 3 alkyl radicals, for example of l to 4 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, 2-, 3- or 4-methylcyclohexyl, cyclooctyl, 2,5-, 2,6-, 3,4- or 3,5-dimethylcyclohexyl, l-cyclohexylpropyl, Z-propylcyclohexyl, 3,3,5-trimethylcyclohexyl, Z-butylcyclohexyl, 4-tert- .butylcyclohexyl, 3-methyl-6-iso-propylcyclohexyl, cyclododecyl, l-methylcyclopentyl, l-methylcyclohexyl, l-methylcycloheptyl, l-propylcyclopentyl, l-butylcyclopentyl, l-butylcyclohexyl and l-pentylcyclopentyl; cycloalkylalkyl radicals, in particular C cycloalkyl C alkyl radicals, for example cyclohexyl-methyl, 2- cyclohexyl-ethyl, cycloheptylmethyl, 3- cyclohexylpropyl, cyclooctylmethyl, cycloundecylmethyl and cyclododecylmethyl; aryl radicals, for example phenyl or diphenyl, optionally substituted by l, 2 or 3 alkyl radicals, e.g. of 1 to 12, preferably l to 6 carbon atoms, such as those alkyl radicals mentioned above and also tertiary alkyl radicals, such as tert. butyl, 2-methyl-2-butyl, 2,3-dimethyl-2-butyl, Z-methyl- Z-pentyl, 3-methyl-3-pentyl, 3-ethyl-3-pentyl, 2,4-dimethyl-2-pentyl, 2-methyl'2-hexyl, 3methyl-3- hexyl, 3,4-dimethyl-3-hexyl, 3,5-dimethyl-3-hexyl, 2-methyl-2-heptyl, 3-methyl-3-heptyl, 4-methyl-4- heptyl, 2,3,4-trimethyl-3-pentyl, 2,4,4-trimethyl-2- pentyl, 3-ethyl-3-heptyl, 2-methyl-2-octyl, 4-methyl-4- octyl, 3,6-dimethyl-3-octyl, 3,7-dimethyl-3-octyl, 4,4,- 4,6,6-pentamethyl-Z-heptyl, as well as l-alkyl substituted cycloalkyl radicals, such as those mentioned above; examples of such substituted aryl radicals include 2-, 3- and 4-methylphenyl, 2,3-, 2,4-, 2,5-, 3,4- and 3,5-dimethylphenyl, 2-, 3 and 4-ethylphenyl, 2,3,5- and 2,4,5-trimethylphenyl, 3-ethyl-5- methylphenyl, 4-sec.butyl-phenyl, 2- and 4- tert.butylphenyl, 5isopropyl-2-methylphenyl, 2-isopropyl-5- methylphenyl, 3-isopropyl-5methylphenyl, 4-tert.pentylphenyl, 2-tert. butyl-4-methylphenyl, 4-tert.butyl-2- methylphenyl, 6-tert.butyl-3-methylphenyl, 2,4-ditert.butylphenyl, 4-(1',l',3,3-tetramethylbutyl)- phenyl, 2-methyl-4-( l ,l ',33-tetramethylbutyl)- phenyl, 4-nonylphenyl (mixture of isomers), and 2,4-di-terLoctyl-phenyl; aralkyl radicals, such as phenyl or diphenyl alkyl radicals, the alkyl radicals of which suitably contain 1 to 12, particularly 1 to 6 carbon atoms, and the aryl radicals of which may optionally be alkyl substituted as above, including benzyl, land Z-phenyl-ethyl, l-phenyl-l-propyl, l-phenyl-Z- propyl, 2-phenyl-1-propyl, 3-phenyl-l-propyl, l-(otolyl)-ethyl, 1-(m-tolyl) ethyl, l-(p-tolyl)-ethyl, lphenyl-l-butyl, 2-(2,4;6-trimethyl-phenyl)-ethyl, l-phenyl- 1 pentyl, l-(4-tert.butyl-phenyl )-ethyl, 4-methyl-l-phenyl-2-pentyl and benzohydryl. The preferred hydrocarbon radicals for R R R and R include alkyl radicals, other than tertiary alkyl radicals,
of l to 12, in particular 4 to 12 carbon atoms, such as n-butyl or n-dodecyl, and phenyl and diphenyl radicals, optionally substituted by 1 or 2 alkyl radicals of 1 to 4 carbon atoms, preferably tertiary such alkyl radicals, such as 2,4-di-t-butylphenyl, 2-t-butyl-diphenyl, and 2,4'-di-t-butyldiphenyl.
The rings A and B may, as indicated, be substituted by l or 2 alkyl groups of up to 6, preferably up to 4 carbon atoms, for example such alkyl groups as mentioned above, but are preferably unsubstituted.
The invention also provides a process for the production of compounds of formula I and inorganic salts thereof, characterised by reacting a compound of formula II,
a /Hal Hal X Hal in which X, n and rings A and B are as defined above,
and
the radicals Hal, which may be the same or different, each signify a halogen atom, with compounds of formula III and IV,
in which R,, R Y, and Y 2 are as defined above, and, if n signifies l, with compounds of formula V and VI.
v VI
in which R R Y and Y, are as defined above, and, where required, converting the resulting product into an inorganic salt. As will be appreciated, two or more of the compounds III, IV, V and VI may be the same, in which case the molar quantity of the compound is adjusted accordingly.
The process of the invention may suitably be carried out in conventional manner, for example as described by K. Sasse, Houben-Weyl (eds.), Methoden der organischen Chemie, fourth impression (1963), Vol. XII/l. pp.3 l 8/ff. As will also be appreciated, however, the particular conditions employed depend, to an extent, on the particular compounds III, IV, V or VI being employed. For example, in some instances, it may be advisable to apply external cooling to the reaction mixture to restrain the vigorous reaction. Thus, for example, when any of the compounds III, IV, V and V1 is water, then it is preferable to charge the reaction mixture with an excess of water and to add the compound II with cooling and stirring and at a rate slow enough to ensure that the exothermic reaction does not lead to an unduly high temperature. Where the compounds III, IV, V or VI are alcohols or phenols, the reaction may suitable be carried out at a temperature of from 100 to 150C, in the presence of an acid binding agent such as pyridine or a trialkylamine.
Where the compound II is reacted with water, products are formed containing radicals of formula VIIa and VII b,
VIIa VIIb which are acidic and may be converted into inorganic salts.
Conversion of the acidic compounds into inorganic salts may be effected in conventional manner. Suitable salts include alkali metal, e.g. sodium or potassium, al-
kaline earth metal, e.g. calcium or magnesium, zinc, manganese, aluminium, copper, vanadium, cobalt and nickel salts. The salts may be produced by reaction of the free acid with an inorganic hydroxide or salt, such as calcium hydroxide, zinc oxide, sodium carbonate, potassium bicarbonate, aluminium acetate, borium chloride, nickel acetate and zinc chloride.
Preferably, however, the reaction of the compounds II with water and production of salts is carried out in a single operation. For this purpose, an excess of water may be provided for hydrolysis of the compound II, and after addition of the appropriate inorganic reagent, the compound II may be slowly added, with stirring, as indicated above.
The resulting compounds of formula I and inorganic salts thereof may be isolated and purified using conventional techniques.
The compounds of formula II, employed as starting materials are either known or may be produced in conventional manner from available materials, for example as described by K. Sasse, Houben-Wehl (eds), Methoden der organischen Chemie, fourth impression 1963), Vol. XII/l organische Phosphorverbindungen, Part I, pp.302-3 18. Thus, for example, the compound IIa,
is described in Journal of the Chemical Society, 1932, 2880. In general, compounds of formula II may be produced by reacting the appropriate diphenylmethane, oxide or sulphide, with a phosphorus trihalide, preferably phosphorus trichloride. The process may suitably be effected at an elevated temperature in the gaseous phase, although it is more preferable to react under milder conditions in the presence of a catalyst, e.g. a F riedel-Krafts catalyst, in particular aluminium trichloride. It is preferable to work with phosphorus trichloride at its boiling temperature. After reaction, any aluminium chloride complex of the compound II may be decomposed, for example with phosphorus oxychloride or pyridine.
The resulting compounds of formula Il may be isolated and purified using conventional techniques.
The compounds of the invention are useful as stabilisers for organic materials which are sensitive to light, oxygen and heat. For this purpose, they may be incorporated in or applied to form a protective surface film on the organic material. When thus applied, the new compounds by their stabilizing action protect sensitive materials against degradation. They have a wide area of use in the processing of plastics materials, being suitable, for example, as stabilizers for cellulose acetate, cellulose acetobutyrate, polyethylene, polypropylene, polyvinyl chloride, polyvinyl chloride acetate, polyamides, polystyrene, ethyl cellulose, cellulose nitrate, polyvinyl alcohol, silicon rubber, cellulose propionate, melamine-formaldehyde resins, urea-formaldehyde resins, allyl casting resins, polymethyl methacrylate, polyesters, polyacrylonitrile, and copolymers of these polymers. Thecompounds may also be used for the stabilization of natural products such as rubber, cellulose, wool and silk.
The materials for stabilization may suitably be in the form of film or sheet, rods, coatings, panels, tapes, fibres, granules, powders or other processing forms, or as solutions, emulsions or dispersions. The stabilizing compounds may be incorporated in or coated on the materials by conventional methods. An important method of application consists in intimately mixing polymeric material, for example polypropylene granules, with the stabilizer in a kneader or other suitable machine, followed by extrusion. This method ensures homogeneous distribution which is important for good protection. The material can be extruded, for example, as film, tubing or filament, the latter for conversion into textiles. In this method of application, the stabilizer may be incorporated in, for example, the polypropylene prior to textile production. The new stabilizers, however, can also be applied to textile yarns and fabrics from an aqueous medium containing a finely dispersed compound of formula (1). This method is particularly suitable for, e.g. textiles of polyethylene terephthalate and cellulose acetate fibres.
Synthetic polymeric materials need not necessarily be in the final form before incorporation of the compounds of the invention. Thus, these compounds may be mixed with the monomers or prepolymers prior to the condensation or other polymerization reaction giving the final polymer.
The new stabilizers are suitable for application to, for example, clear films and plastics, and are also suitable for stabilizing opaque, semi-opaque and translucent materials having a surface susceptible to degradation by ultra-violet radiation, air or heat. Examples of such materials are foam plastics, opaque films and coatings, opaque papers, opaque and transparent pigmented plastics, fluorescent pigments, automobile and furniture polishes, creams, lotions and related products, which may be opaque, clear or translucent.
As regards the constitution of compounds of formula I and their action, it may be mentioned that particularly good stabilization is obtained in polyalkylenes, notably polypropylene, when the molecule of the compound of the invention consists to a large extent of saturated aliphatic groups. When phosphonous acids of formula I in which R R R and R represent hydrogen are employed in the form of the nickel salts, the stabilizing action against visible light and ultra-violet radiation is particularly effective, especially in polyalkylenes. The manganese and copper salts are particularly suitable for stabilizing polyamides against degradation by ultraviolet radiation, while the salts of other transition metals such as vanadium and cobalt, are suitable as ultraviolet absorbers in a number of substrates.
The present invention also comprises the sensitive organic materials containing a compound of formula 1 for stabilization. As previously indicated, the new compounds can be incorporated in the organic materials at any stage of processing using standard methods. The amounts of stabilizer employed may vary within wide limits, for example from 0.01 to 5% or preferably from 0.05 to 1% in relation to the weight of the material. The stabilized organic materials may contain compounds of formula I alone, or together with further additives, for example ultra-violet absorbers and other stabilizers against degradation by heat and oxygen. As regards the latter, suitable stabilizers are those belonging to different chemical classes to the compounds of formula I, for example organic compounds of sulphur, tin and pentavalent phosphorus, sterically hindered phenols, 2- hydroxy-benzophenones and hydroxybenzotriazoles. Often, notably high stabilization may be obtained with such mixtures since they may have a synergistic action.
In the following Examples the parts and percentage are by weight and the temperatures in degrees centigrade.
EXAMPLE A Production of an Intermediate of Formula I] c1 P IIc c1 is obtained in the form of a pale red oil with a pungent odour.
EXAMPLE 1 In the absence of moisture, a solution of 20 parts of the diphenylether dichlorophosphine of formula Ila, above, in 50 parts of toluene is added at 0-5 to 29.9 parts of dodecyl mercaptan and 15 parts of triethylamine in parts of toluene. The solution is allowed to react overnight at 40. Subsequently, the precipitated salt is filtered, the filtrate evaporated under vacuum, and the residue crystallized from absolute ether. mp. 25 -26 Elementary analysis mi SH H found 9.9 calculated 9.8
EXAMPLE 2 At 5, a solution of 33.4 parts of the diphenylether dichloro-phosphine of formula l la, above, in 50 parts of toluene is added to 50.7 parts of 2,4-ditert.butylphenol and parts of triethylamine in 200 parts of toluene in the absence of moisture. The solution is allowed to react overnight at the precipitated product filtered, the filtrate evaporated under vacuum, and the residue crystallized from ether/methanol. m.p. 8889..
Elementary analysis P w sr a found calculated EXAMPLE 3 A solution of 95.5 parts of 4,4-diphenylether-(bisdichloro-phosphine offormula 11c, above, in 50 parts of toluene is added, at 05, in the absence of moisture, to 21 1 parts of 2,4-di-tert.butylphenol and 104 parts of triethylamine in 300 parts of toluene. The solution is allowed to react overnight at 40, the precipitated product filtered, the filtrate evaporated under vacuum,
EXAMPLE 4 EXAMPLE 5 A solution of parts of 4,4-diphenylether-(bischlorophosphine) in parts of toluene is added, at
15 0.-5, to 136.3 parts of 2,4-di-tert.butyl-4-phenyl phenol and 49 parts of triethylamine in 300 parts of toluene, in the absence of moisture. The solution is allowed to react overnight at 40, the precipitated salt filtered, the filtrate evaporated under vacuum, and the residue triturated to a white powder. m.p. 8285.
EXAMPLE 6 A solution of 12.5 parts of 4,4-diphenylether-(bisdichlorophosphine) in 50 parts of toluene is added at and the residue triturated with methanol and crystal- 5 99 parts of butane] and 14 parts of triethylam lized from benzene. m.p. 7780.
ine in parts of toluene in the absence of moisture. The solution is allowed to react overnight at 40, the precipitated salt filtered and the filtrate evaporated Element! analysis C H P under vacuum to yield a pale yellow oil. (Mil-205p: f 84 30 The structural formulae of the compounds produced calculated 77.6 8.8 5.9
m Examples 1 to 6 are shown in Table 1 below.
Table 1 Example 0 O P) NO. Q n
Significance of Q n l C H S- O 2 (tert.)H C 0 (tert. H C
3 do. l
(tert. H9C4 5 (teIt.)l'I9C4 O l (tert. H 6
USE EXAMPLE Polypropylene, which contains, as antioxidant, 0.2%
of 4,4'-Methylen-bis-(2,6-di-tert.butylphenol) is intimately mixed with 0.1% of a compound produced in any one of Examples 1 to 6. The plastic is stored, in the form of thin discs, under oxygen in a closed system after removal of air. The system is then warmed to 190, whereby an excess pressure of about mm Hg arises. The oxidation of the plastic is followed by fall in pressure. The speed of the fall in pressure is low if the activity or the stabiliser or stabiliser mixture is high. Significantly improved results are obtained with poly propylene which contains in addition to 4,4- methylene-bis-(2,6-di-tert.butylphenol), a compound according to any one of Examples 1 to 6.
What is claimed is:
1. A compound of the formula P P QV R2 Y2 Y4 -r inwhich X signifies CH O, or -S,
Y Y Y and Y,, which may be the same or different, each signifies -O or -S,
R R R and R which may be the same or different, each signifies a hydrocarbon radical of up to 20 carbon atoms selected from the group consisting of alkyl; cycloalkyl which may be substituted by up to 3 alkyl groups; cycloalkylalkyl; phenyl which may be substituted by up to 3 alkyl or alkylcycloalkyl groups; diphenyl which may be substituted by up to 3 alkyl or alkylcycloalkyl groups; and phenyl 3. A compound of claim 1, in which Y Y Y and Y, are the same.
4. A compound of claim 1, in which R,, R R and R are the same.
5. A compound of claim 1, in which the substituent or each substituent is in the para position of the nucleus.
6. A compound of claim 1, in which rings A and B are I each further unsubstituted.
7. A compound of claim 1, in which R,, R R and R each signifies an alkyl radical of l to 12 carbon atoms, a cycloalkyl radical of 3 to 12 carbon atoms, which may be substituted by l, 2 or 3 alkyl groups of l to 4 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl portion contains 5 to 12 carbon atoms and the alkyl portion l to 6 carbon atoms, or a phenyl or diphenyl radical which may be substituted by l, 2 or 3 alkyl radicals of l to 12 carbon atoms.
8. A compound of claim 1, in which R R R and R, each signifies an alkyl radical of l to 6 carbon atoms, a cycloalkyl radical of 5 to 8 carbon atoms, which may be substituted by l, 2 or 3 alkyl groups of l to 4 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl portion contains 5 to 8 carbon atoms and the alkyl portion contains 1 to 4 carbon atoms, or a phenyl or diphenyl radical which may be substituted by 1, 2 or 3 alkyl radicals of l to 6 carbon atoms.
9. A compound of claim 1, in which R,, R R and R, each signifies an alkyl radical of 4 to 12 carbon atoms, or phenyl or diphenyl radical, which may be substituted by l or 2 alkyl radicals of l to 4 carbon atoms.
10; A compound of claim 1, in which R,, R R and R, each signifies other then a tertiary alkyl radical.
11. A compound of claim 1, in which R R R and R each signifies n-butyl, n-dodecyl, 2,4-di-tbutylphenyl, 2-t-butylphenyl, or 2,4-di-t-butyldiphenyl.
12. A compound of claim 2 in which Y Y Y and Y, are the same.
13. A compound of claim 2 wherein R R R and and diphenylalkyl, the aryl portions of which may R4 are h same be substituted by up to 3 alkyl groups. 14. A compound of claim 3 wherein R R R and and rings A and B maybe either unsubstituted or R4 are the Same each further substituted by 1 or 2 alkyl groups of 15 A compound f l i 12 i hi h R 12,, R and l to 6 carbon atoms. R are the same. 2. A compound of claim 1, in which X signifies 16' The compound of claim 1 of f ul --O.
t-C l l t-C H u l u u 9 3; c n o\ 1/0 3;, (2 x1 /P- -op\ a j; C H =[-O O H 1; C 3
17. The compound of claim 1 of formula PQO-QQQ 18. The compound of claim 1 of formula gc H 19. The compound of claim 1 of formula
Claims (19)
1. A COMPOUND OF THE FORMULA
2. A compound of claim 1, in which X signifies -O-.
3. A compound of claim 1, in which Y1, Y2, Y3 and Y4 are the same.
4. A compound of claim 1, in which R1, R2, R3 and R4 are the same.
5. A compound of claim 1, in which the
6. A compound of claim 1, in which rings A and B are each further unsubstituted.
7. A compound of claim 1, in which R1, R2, R3 and R4 each signifies an alkyl radical of 1 to 12 carbon atoms, a cycloalkyl radical of 3 to 12 carbon atoms, which may be substituted by 1, 2 or 3 alkyl groups of 1 to 4 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl portion contains 5 to 12 carbon atoms and the alkyl portion 1 to 6 carbon atoms, or a phenyl or diphenyl radical which may be substituted by 1, 2 or 3 alkyl radicals of 1 to 12 carbon atoms.
8. A compound of claim 1, in which R1, R2, R3 and R4 each signifies an alkyl radical of 1 to 6 carbon atoms, a cycloalkyl radical of 5 to 8 carbon atoms, which may be substituted by 1, 2 or 3 alkyl groups of 1 to 4 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl portion contains 5 to 8 carbon atoms and the alkyl portion contains 1 to 4 carbon atoms, or a phenyl or diphenyl radical which may be substituted by 1, 2 or 3 alkyl radicals of 1 to 6 carbon atoms.
9. A compound of claim 1, in which R1, R2, R3 and R4 each signifies an alkyl radical of 4 to 12 carbon atoms, or phenyl or diphenyl radical, which may be substituted by 1 or 2 alkyl radicals of 1 to 4 carbon atoms.
10. A compound of claim 1, in which R1, R2, R3 and R4 each signifies other then a tertiary alkyl radical.
11. A compound of claim 1, in which R1, R2, R3 and R4 each signiFies n-butyl, n-dodecyl, 2,4-di-t-butylphenyl, 2-t-butylphenyl, or 2,4-di-t-butyldiphenyl.
12. A compound of claim 2 in which Y1, Y2, Y3, and Y4 are the same.
13. A compound of claim 2 wherein R1, R2, R3, and R4 are the same.
14. A compound of claim 3 wherein R1, R2, R3, and R4 are the same.
15. A compound of claim 12 in which R1, R2, R3, and R4 are the same.
16. The compound of claim 1 of formula
17. The compound of claim 1 of formula
18. The compound of claim 1 of formula
19. The compound of claim 1 of formula
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US455597A US3903208A (en) | 1971-11-24 | 1974-03-28 | Phosphonous and thiophosphonous acid esters |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1712971A CH557389A (en) | 1971-11-24 | 1971-11-24 | PROCESS FOR THE PRODUCTION OF NEW DIPHENYLMETHANE, DIPHENYLOXIDE AND DIPHENYLSULFIDE PHOSPHONY AND THIOPHOSPHONIC ACIDS, THEIR ESTERS AND THIOESTERS. |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/575,524 Continuation-In-Part US4107138A (en) | 1971-11-24 | 1975-05-08 | Phosphonous and thiophosphonous acid ethers as stabilizers for organic materials |
Publications (1)
Publication Number | Publication Date |
---|---|
US3875264A true US3875264A (en) | 1975-04-01 |
Family
ID=4422988
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US308594A Expired - Lifetime US3875264A (en) | 1971-11-24 | 1972-11-21 | Phosphonous acid esters |
Country Status (13)
Country | Link |
---|---|
US (1) | US3875264A (en) |
JP (1) | JPS5645919B2 (en) |
AT (1) | AT327944B (en) |
BE (1) | BE791767A (en) |
BR (1) | BR7208256D0 (en) |
CA (1) | CA989414A (en) |
CH (1) | CH557389A (en) |
DE (1) | DE2256783C2 (en) |
ES (1) | ES408865A1 (en) |
FR (1) | FR2161052B1 (en) |
GB (1) | GB1415532A (en) |
IT (1) | IT971154B (en) |
NL (1) | NL7215623A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2701638A1 (en) * | 1976-01-16 | 1977-07-21 | Raychem Corp | INSULATING COMPOUNDS CONTAINING PHOSPHORUS COMPOUNDS |
US4219607A (en) * | 1978-01-13 | 1980-08-26 | Raychem Corporation | High voltage insulating compositions containing phosphorus compounds |
US4223071A (en) * | 1978-01-13 | 1980-09-16 | Raychem Corporation | High voltage insulating compositions containing phosphorus compounds |
US4263230A (en) * | 1979-10-11 | 1981-04-21 | Stauffer Chemical Company | Bisphosphonites |
EP0158501A2 (en) * | 1984-04-02 | 1985-10-16 | Polyplastics Co. Ltd. | Method of preparation of polyester |
US4551527A (en) * | 1981-07-02 | 1985-11-05 | Borg-Warner Chemicals, Inc. | Salts of 5,5-bis-(bromomethyl)-2-hydroxy-2-oxo-1,3,2-dioxaphosphorinane and process for preparing same |
US5298541A (en) * | 1989-05-20 | 1994-03-29 | Hoechst Aktiengesellschaft | Aryl phosphonites, a process for their production and their use for stabilizing plastics |
US5342869A (en) * | 1991-07-03 | 1994-08-30 | Sandoz Ltd. | Stabilized polymeric compositions |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2962673D1 (en) * | 1978-04-20 | 1982-06-24 | Ciba Geigy Ag | Ortho-alkylated phenylphosphonites, process for their preparation and stabilized compositions |
CA1276344C (en) * | 1980-12-17 | 1990-11-13 | Markus Matzner | Processing of heat stabilized polyarylates |
JPS5813653A (en) * | 1981-07-17 | 1983-01-26 | Teijin Ltd | Resin composition |
JPS638453A (en) * | 1986-06-27 | 1988-01-14 | Polyplastics Co | Thermoplastic polyester resin composition |
JPS63105053A (en) * | 1986-10-20 | 1988-05-10 | Kuraray Co Ltd | Polyester resin having excellent light resistance |
GB8901517D0 (en) * | 1989-01-24 | 1989-03-15 | Sandoz Ltd | Improvements in or relating to organic compounds |
JPH02287165A (en) * | 1989-04-27 | 1990-11-27 | Nec Kansai Ltd | Measurement of electrical characteristic of semiconductor integrated circuit device |
WO2000012518A1 (en) * | 1998-09-01 | 2000-03-09 | Clariant Finance (Bvi) Limited | Process for the production of phosphor organic compounds |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3707565A (en) * | 1968-08-28 | 1972-12-26 | Sandoz Ltd | Phenol sulfide derivatives |
-
0
- BE BE791767D patent/BE791767A/en unknown
-
1971
- 1971-11-24 CH CH1712971A patent/CH557389A/en not_active IP Right Cessation
-
1972
- 1972-11-17 NL NL7215623A patent/NL7215623A/xx not_active Application Discontinuation
- 1972-11-20 DE DE2256783A patent/DE2256783C2/en not_active Expired
- 1972-11-21 US US308594A patent/US3875264A/en not_active Expired - Lifetime
- 1972-11-21 GB GB5368172A patent/GB1415532A/en not_active Expired
- 1972-11-22 JP JP11760972A patent/JPS5645919B2/ja not_active Expired
- 1972-11-22 ES ES408865A patent/ES408865A1/en not_active Expired
- 1972-11-23 IT IT32015/72A patent/IT971154B/en active
- 1972-11-23 AT AT997272A patent/AT327944B/en not_active IP Right Cessation
- 1972-11-23 CA CA157,234A patent/CA989414A/en not_active Expired
- 1972-11-23 BR BR008256/72A patent/BR7208256D0/en unknown
- 1972-11-24 FR FR7241835A patent/FR2161052B1/fr not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3707565A (en) * | 1968-08-28 | 1972-12-26 | Sandoz Ltd | Phenol sulfide derivatives |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2338555A1 (en) * | 1976-01-16 | 1977-08-12 | Raychem Corp | INSULATING COMPOSITIONS CONTAINING PHOSPHORUS COMPOUNDS |
US4100089A (en) * | 1976-01-16 | 1978-07-11 | Raychem Corporation | High-voltage insulating material comprising anti-tracking and erosion inhibiting compounds with insulating polymers |
DE2701638A1 (en) * | 1976-01-16 | 1977-07-21 | Raychem Corp | INSULATING COMPOUNDS CONTAINING PHOSPHORUS COMPOUNDS |
US4219607A (en) * | 1978-01-13 | 1980-08-26 | Raychem Corporation | High voltage insulating compositions containing phosphorus compounds |
US4223071A (en) * | 1978-01-13 | 1980-09-16 | Raychem Corporation | High voltage insulating compositions containing phosphorus compounds |
US4263230A (en) * | 1979-10-11 | 1981-04-21 | Stauffer Chemical Company | Bisphosphonites |
US4551527A (en) * | 1981-07-02 | 1985-11-05 | Borg-Warner Chemicals, Inc. | Salts of 5,5-bis-(bromomethyl)-2-hydroxy-2-oxo-1,3,2-dioxaphosphorinane and process for preparing same |
EP0158501A2 (en) * | 1984-04-02 | 1985-10-16 | Polyplastics Co. Ltd. | Method of preparation of polyester |
JPS60208325A (en) * | 1984-04-02 | 1985-10-19 | Polyplastics Co | Production of polyester |
EP0158501A3 (en) * | 1984-04-02 | 1986-10-08 | Polyplastics Co. Ltd. | Method of preparation of polyester |
JPH0341091B2 (en) * | 1984-04-02 | 1991-06-21 | ||
US5298541A (en) * | 1989-05-20 | 1994-03-29 | Hoechst Aktiengesellschaft | Aryl phosphonites, a process for their production and their use for stabilizing plastics |
US5342869A (en) * | 1991-07-03 | 1994-08-30 | Sandoz Ltd. | Stabilized polymeric compositions |
Also Published As
Publication number | Publication date |
---|---|
CA989414A (en) | 1976-05-18 |
JPS5645919B2 (en) | 1981-10-29 |
IT971154B (en) | 1974-04-30 |
AT327944B (en) | 1976-02-25 |
CH557389A (en) | 1974-12-31 |
NL7215623A (en) | 1973-05-28 |
FR2161052B1 (en) | 1977-12-23 |
DE2256783C2 (en) | 1982-04-01 |
JPS4862741A (en) | 1973-09-01 |
BE791767A (en) | 1973-05-22 |
BR7208256D0 (en) | 1973-08-23 |
FR2161052A1 (en) | 1973-07-06 |
DE2256783A1 (en) | 1973-05-30 |
GB1415532A (en) | 1975-11-26 |
ATA997272A (en) | 1975-05-15 |
ES408865A1 (en) | 1976-03-16 |
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