DE19851774C2 - Process for the preparation of metal salts of aryl-alkylphosphinic acids - Google Patents
Process for the preparation of metal salts of aryl-alkylphosphinic acidsInfo
- Publication number
- DE19851774C2 DE19851774C2 DE19851774A DE19851774A DE19851774C2 DE 19851774 C2 DE19851774 C2 DE 19851774C2 DE 19851774 A DE19851774 A DE 19851774A DE 19851774 A DE19851774 A DE 19851774A DE 19851774 C2 DE19851774 C2 DE 19851774C2
- Authority
- DE
- Germany
- Prior art keywords
- aryl
- olefins
- acids
- alkylphosphinic
- salts
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 25
- 239000002253 acid Substances 0.000 title claims description 23
- 150000007513 acids Chemical class 0.000 title claims description 17
- 150000003839 salts Chemical class 0.000 title claims description 10
- 229910052751 metal Inorganic materials 0.000 title claims description 7
- 239000002184 metal Substances 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- -1 alkali metal salts Chemical class 0.000 claims description 7
- 150000001447 alkali salts Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- CGNKSELPNJJTSM-UHFFFAOYSA-N phenylphosphonous acid Chemical compound OP(O)C1=CC=CC=C1 CGNKSELPNJJTSM-UHFFFAOYSA-N 0.000 claims description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical class CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 2
- PGFZYOCLSPEKSN-UHFFFAOYSA-N 5,5-dimethyl-1,3-diazabicyclo[2.2.0]hex-3-ene dihydrochloride Chemical compound Cl.Cl.CC1(C)CN2CN=C12 PGFZYOCLSPEKSN-UHFFFAOYSA-N 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 229930194542 Keto Natural products 0.000 claims description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N icos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000004291 polyenes Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical class P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- PWXZGIVKGZBIBK-UHFFFAOYSA-O hydroxy-oxo-(4-phenylbutyl)phosphanium Chemical compound O[P+](=O)CCCCC1=CC=CC=C1 PWXZGIVKGZBIBK-UHFFFAOYSA-O 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- PJKNFAICTFGCDT-UHFFFAOYSA-N 2-(2-aminopropan-2-yldiazenyl)propan-2-amine;hydron;dichloride Chemical compound Cl.Cl.CC(C)(N)N=NC(C)(C)N PJKNFAICTFGCDT-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241001656717 Cyclopes Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical class [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical class [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 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
- 238000009835 boiling Methods 0.000 description 1
- 229940087373 calcium oxide Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- UCIYGNATMHQYCT-OWOJBTEDSA-N cyclodecene Chemical compound C1CCCC\C=C\CCC1 UCIYGNATMHQYCT-OWOJBTEDSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- WPYVFMKRHQSQSU-UHFFFAOYSA-N ethyl(phenyl)phosphinic acid Chemical compound CCP(O)(=O)C1=CC=CC=C1 WPYVFMKRHQSQSU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001707 polybutylene terephthalate 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
- 229920002223 polystyrene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/304—Aromatic acids (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Metallsalzen von Aryl- alkylphosphinsäuren sowie die Verwendung der nach diesem Verfahren hergestellten Ver bindungen.The invention relates to a process for the preparation of metal salts of aryl alkylphosphinic acids and the use of the Ver bonds.
Aluminiumsalze von Dialkylphosphinsäuren sind als Flammschutzmittel bekannt (EP 0 699 708 A1). Sie können nach verschiedenen Verfahren hergestellt werden.Aluminum salts of dialkylphosphinic acids are known as flame retardants (EP 0 699 708 A1). They can be made by various methods.
Die DE 24 47 727 A1 beschreibt schwerentflammbare Polyamidformmassen, die ein Salz einer Phosphinsäure oder einer Diphosphinsäure enthalten.DE 24 47 727 A1 describes flame-retardant polyamide molding compositions which are a salt contain a phosphinic acid or a diphosphinic acid.
Die EP-A-0 699 708 beschreibt flammgeschützte Polyesterformmassen, wobei die Poly ester durch den Zusatz von Calcium- oder Aluminiumsalzen von Phosphin- oder Diphos phinsäure flammfest ausgerüstet werden. Die vorgenannten Salze werden durch Umset zung der entsprechenden Dialkylphosphinsäuren mit Calcium- oder Aluminiumhydroxid erhalten.EP-A-0 699 708 describes flame-retardant polyester molding compositions, the poly ester by adding calcium or aluminum salts of phosphine or diphos phinic acid can be made flame-resistant. The aforementioned salts are converted tion of the corresponding dialkylphosphinic acids with calcium or aluminum hydroxide receive.
Die vorgenannten Verfahren haben insbesondere den Nachteil, daß sie von technisch nicht oder nur unter großem Aufwand herzustellenden Ausgangsverbindungen ausgehen.The above-mentioned methods have the particular disadvantage that they are technically not or go out only with great effort to produce starting compounds.
Es ist bisher jedoch kein technisch durchführbares Verfahren bekannt, mit dem sich Me tallsalze von Aryl-alkylphosphinsäuren herstellen lassen.So far, however, no technically feasible method is known with which Me let tall salts of aryl-alkylphosphinic acids be produced.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Metallsal zen von Aryl-alkylphosphinsäuren zur Verfügung zu stellen, das auf einfache Art und Weise zu den gewünschten Endprodukten führt. The invention has for its object a method for producing metal sal to provide zen of aryl-alkylphosphinic acids in a simple manner and Way leads to the desired end products.
Diese Aufgabe wird gelöst durch ein Verfahren der eingangs beschriebenen Art, dadurch
gekennzeichnet, daß man
This object is achieved by a method of the type described in the introduction, characterized in that
- a) Olefine mit Arylphosphonigen Säuren und/oder deren Alkalisalzen in Gegenwart eines kationischen Radikalstarters umsetzt, unda) olefins with arylphosphonous acids and / or their alkali salts in the presence of a cationic radical starter, and
- b) die nach a) erhaltenen Aryl-alkylphosphinsäuren und/oder deren Alkalisalze mit Me tallverbindungen von Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na und/oder K zu den Aryl-alkylphosphinsäuresalzen der Metalle umsetzt.b) the aryl-alkylphosphinic acids obtained according to a) and / or their alkali metal salts with Me tall compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and / or K to the aryl-alkylphosphinic salts of the metals.
Bevorzugt handelt es sich bei den Olefinen um lineare oder verzweigte α-Olefine.The olefins are preferably linear or branched α-olefins.
Bevorzugt handelt es sich bei den Olefinen um Ethylen, n-, i-Propylen, n-, i-Buten, n-, i-Penten, n-, i-Hexen, n-, i-Octen, 1-Decen, 1-Dodecen, 1-Tetradecen, 1-Hexadecen, n-Eicosen, und/oder 2,4,4-Trimethylpenten-Isomerengemisch.The olefins are preferably ethylene, n-, i-propylene, n-, i-butene, n-, i-pentene, n-, i-hexene, n-, i-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, n-eicosen, and / or 2,4,4-trimethylpentene isomer mixture.
Bevorzugt werden als Olefine solche mit innenständiger Doppelbindung, cyclische oder offenkettige Diene und/oder Polyene mit 4 bis 20 Kohlenstoffatomen eingesetzt.Preferred olefins are those with an internal double bond, cyclic or open-chain dienes and / or polyenes with 4 to 20 carbon atoms.
Bevorzugt tragen die Olefine eine funktionelle Gruppe.The olefins preferably carry a functional group.
Als Olefine sind Verbindungen der allgemeinen Formel
Compounds of the general formula are olefins
in der R1-R4 gleich oder verschieden sein können und für Wasserstoff, eine Alkylgruppe mit 1 bis 18 C-Atomen, für Phenyl, Benzyl oder alkylsubtituierte Aromaten stehen, geeignet.in which R 1 -R 4 may be the same or different and represent hydrogen, an alkyl group having 1 to 18 carbon atoms, phenyl, benzyl or alkyl-substituted aromatics.
Geeignet sind ebenfalls Cycloolefine der Formel
Cycloolefins of the formula are also suitable
insbesondere Cyclopen ten, Cyclohexen, Cycloocten und Cyclodecen.especially cyclopes ten, cyclohexene, cyclooctene and cyclodecene.
Eingesetzt werden können auch offenkettige Diene der Formel
Open-chain dienes of the formula can also be used
in der R5-R10 gleich oder verschieden sind und für Wasserstoff oder eine C1 bis C6- Alkylgruppe stehen und R11 für (CH2)n mit n = 0 bis 6 steht. Bevorzugt sind hierbei Butadien, Isopren und 1,5-Hexadien.in which R 5 -R 10 are identical or different and represent hydrogen or a C 1 to C 6 alkyl group and R 11 represents (CH 2 ) n with n = 0 to 6. Butadiene, isoprene and 1,5-hexadiene are preferred.
Als Cyclodiene sind 1,3 Cyclopentadien, Dicyclopentadien und 1,5-Cyclooctadien sowie Norbornadien bevorzugt.As cyclodienes are 1,3 cyclopentadiene, dicyclopentadiene and 1,5-cyclooctadiene as well Norbornadiene preferred.
Bevorzugt handelt es sich bei der Arylphosphonigen Säure und/oder deren Alkalisalze um Phenylphosphonige Säure und/oder deren Alkalisalze.The arylphosphonous acid and / or its alkali metal salts are preferred Phenylphosphonous acid and / or its alkali salts.
Bevorzugt handelt es sich bei dem Aryl-Rest der Aryl-alkylphosphinsäuren und Arylphos phonigen Säuren um Aromaten mit 6 bis 12 C-Atomen, die mit Halogenen, Hydroxyl-, Aryl-, Alkyl-, Ether-, Ester-, Keto-, Carboxyl-, Sulfonyl- und/oder Chloralkylgruppen ein fach oder mehrfach substituiert sein können.The aryl radical of the aryl-alkylphosphinic acids and arylphos is preferred Phonic acids around aromatics with 6 to 12 carbon atoms, which are combined with halogens, hydroxyl, Aryl, alkyl, ether, ester, keto, carboxyl, sulfonyl and / or chloroalkyl groups may be substituted multiple or more times.
Bevorzugt handelt es sich bei den Azo-Verbindungen um kationische und/oder nicht kationische Azo-Verbindungen.The azo compounds are preferably cationic and / or not cationic azo compounds.
Bevorzugt werden als kationische Azo-Verbindungen 2,2'-Azobis(2-amidinopropan)- dihydrochlorid oder 2,2'-Azobis(N,N'-dimethylenisobutyramidin)dihydrochlorid einge setzt.Preferred cationic azo compounds are 2,2'-azobis ( 2- aminopropane) dihydrochloride or 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride.
Erfindungsgemäß geeignet sind auch nichtkationische Azo-Verbindungen wie Azo bis(isobutyronitril), 4,4'Azobis(4-cyano-pentansäure) und, 2,2'Azobis(2-methyl butyronitril).Non-cationic azo compounds such as azo are also suitable according to the invention bis (isobutyronitrile), 4,4'Azobis (4-cyano-pentanoic acid) and, 2,2'Azobis (2-methyl butyronitrile).
Erfindungsgemäß geeignet sind ebenfalls als Radikalstarter peroxidische anorganische Radikalstarter (Wasserstoffperoxid, Ammoniumperoxodisulfat, Kaliumperoxodisulfat etc.) und/oder peroxidische organische Radikalstarter (Dibenzoylperoxid, Di-tert.-butylperoxid, Peressigsäure etc.). Peroxidic inorganic radicals are also suitable as radical initiators Radical starters (hydrogen peroxide, ammonium peroxodisulfate, potassium peroxodisulfate etc.) and / or peroxidic organic radical initiators (dibenzoyl peroxide, di-tert-butyl peroxide, Peracetic acid etc.).
Eine breite Auswahl geeigneter Radikalstarter findet sich beispielsweise in Houben-Weyl, Ergänzungsband 20, im Kapitel "Polymerisation durch radikalische Initiierung" auf den Seiten 15-74.A wide selection of suitable radical initiators can be found, for example, in Houben-Weyl, Supplement 20 , in the chapter "Polymerization by Radical Initiation" on pages 15-74.
Bevorzugt handelt es sich bei den Metallverbindungen um Metalloxide, -hydroxide, -oxidhydroxide, -sulfate, -acetate, -nitrate, -chloride und/oder -alkoxide.The metal compounds are preferably metal oxides, metal hydroxides, Oxide hydroxides, sulfates, acetates, nitrates, chlorides and / or alkoxides.
Besonders bevorzugt handelt es sich bei den Metallverbindungen um Aluminiumhydroxid oder um Aluminiumsulfate.The metal compounds are particularly preferably aluminum hydroxide or aluminum sulfates.
Bevorzugt erfolgt die Umsetzung in Gegenwart von Carbonsäuren.The reaction is preferably carried out in the presence of carboxylic acids.
Besonders bevorzugt handelt es sich bei der Carbonsäure um Essigsäure.The carboxylic acid is particularly preferably acetic acid.
Bevorzugt erfolgt die Umsetzung bei einer Temperatur von 40 bis 130°C.The reaction is preferably carried out at a temperature of 40 to 130 ° C.
Besonders bevorzugt erfolgt die Umsetzung bei einer Temperatur von 60 bis 100°C.The reaction is particularly preferably carried out at a temperature of 60 to 100.degree.
Insbesondere wird das Verfahren bevorzugt bei einer Temperatur von 80 bis 95°C ausge führt.In particular, the process is preferably carried out at a temperature of 80 to 95 ° C leads.
Bevorzugt erfolgt die Umsetzung in einem Druckreaktor. Dies gilt insbesondere, wenn der Siedepunkt der Olefine unterhalb der Reaktionstemperatur liegt.The reaction is preferably carried out in a pressure reactor. This applies in particular if the Boiling point of the olefins is below the reaction temperature.
Dabei erfolgt die Umsetzung im Schritt b) nach Einstellung eines für das jeweilige System Aryl-alkylphosphinsäure/Metallverbindung optimalen pH-Bereichs für die Salzfällung.The implementation in step b) takes place after setting one for the respective system Aryl-alkylphosphinic acid / metal compound optimal pH range for salt precipitation.
Die Erfindung betrifft auch die Verwendung der nach dem vorstehend beschriebenen Ver fahren erhaltenen Aryl-alkylphosphinsäuren und/oder deren Alkalisalzen zur Herstellung von Flammschutzmitteln.The invention also relates to the use of the Ver drive obtained aryl-alkylphosphinic acids and / or their alkali salts for the preparation of flame retardants.
Die Erfindung betrifft ebenfalls die Verwendung der nach dem vorstehend beschriebenen Verfahren erhaltenen Aryl-alkylphosphinsäuren und/oder deren Alkalisalzen zur Herstel lung von Flammschutzmitteln für thermoplastische Polymere wie Polyethylenterephthalat, Polybutylenterephthalat, Polystyrol oder Polyamid und für Duroplaste.The invention also relates to the use of those described above Process obtained aryl-alkylphosphinic acids and / or their alkali salts for their preparation development of flame retardants for thermoplastic polymers such as polyethylene terephthalate, Polybutylene terephthalate, polystyrene or polyamide and for thermosets.
Die nach dem vorstehend beschriebenen Verfahren erhaltenen Aryl-alkylphosphinsäuren und/oder deren Metallsalze finden auch Verwendung als Additive in polymeren Massen, als Extraktionsmittel und oberflächenaktive Mittel.The aryl-alkylphosphinic acids obtained by the process described above and / or their metal salts are also used as additives in polymeric compositions, as extractants and surfactants.
Die Erfindung wird durch die nachstehenden Beispiele erläutert.The invention is illustrated by the examples below.
500 g (3,5 Mol) Phenylphosphonige Säure wurden zusammen mit 4 kg Essigsäure in ei nem 16-L-Druckreaktor eingefüllt. Anschließend wurde unter Rühren bis auf 85°C In nentemperatur aufgeheizt und soviel Ethylen aufgedrückt, bis bei 5 bar eine Sättigung er reicht war. Danach wurden 27 g (100 mMol, entspricht 3 Mol%, bezogen auf die einge setzte Phenylphosphonige Säure) 2,2'-Azobis(2-amidinopropan)dihydrochlorid, gelöst in 100 ml Wasser innerhalb 3 Stunden zudosiert. Die exotherme Reaktion wurde mittels der Dosiergeschwindigkeit der vorgenannten Radikalstarterlösung so gesteuert, daß max. 95°C Reaktionstemperatur erreicht wurde. Während der weiteren Reaktion wurde Ethylen so nachgeführt, daß der Druck über die gesamte Dauer des Versuchs auf etwa 5 bar gehalten wurde. Anschließend ließ man noch 3 h bei 85°C nachreagieren. Dann wurde der Reaktor entspannt und abgekühlt. Die Auswaage betrug 4,7 kg (100% der Theorie).500 g (3.5 mol) of phenylphosphonous acid together with 4 kg of acetic acid in egg filled in a 16 L pressure reactor. Then In. Was stirred up to 85 ° C. heated to the required temperature and enough ethylene was pressed in until it reached saturation at 5 bar was enough. Then 27 g (100 mmol, corresponds to 3 mol%, based on the set phenylphosphonous acid) 2,2'-azobis (2-amidinopropane) dihydrochloride, dissolved in 100 ml of water are metered in within 3 hours. The exothermic reaction was determined using the Dosing speed of the aforementioned radical starter solution controlled so that max. 95 ° C reaction temperature was reached. During the further reaction Ethylene so adjusted that the pressure over the entire duration of the experiment is approximately 5 bar was kept. Then allowed to react for a further 3 h at 85 ° C. Then the reactor was depressurized and cooled. The weight was 4.7 kg (100% of the Theory).
1 kg der nach Schritt a) erhaltenen Lösung wurde mit einer Lösung von 165 g (0,25 Mol) Aluminiumsulfat-Hydrat in 300 ml Wasser versetzt und unter Rühren auf 45°C erwärmt. 1 kg of the solution obtained after step a) was mixed with a solution of 165 g (0.25 mol) Aluminum sulfate hydrate in 300 ml of water and heated to 45 ° C with stirring.
Anschließend fügte man soviel 25%ige Natronlaugelösung zu, daß der pH-Wert zwischen 4,5 und 4,9 lag. Die Ausfällung der Aluminiumphosphinate wurde dann durch zweistündi ges Erhitzen der Suspension auf 85°C vervollständigt.Then enough 25% sodium hydroxide solution was added to bring the pH between 4.5 and 4.9. The precipitation of the aluminum phosphinates was then carried out for two hours The heating of the suspension to 85 ° C. was completed.
Nach Abkühlung auf Raumtemperatur wurde über eine Nutsche filtriert und der Rückstand
mit Wasser und Aceton gewaschen. Nach Trocknung des Produktes im Vakuumtrocken
schrank bei 120°C wurden 116 g eines farblosen Pulvers erhalten. Die Ausbeute betrug
91% der Theorie.
Analysenwerte:
Phosphor: gef. 16,9%, ber. 17,2% (w/w),
Aluminium: gef. 5,2%, ber. 5,0% (w/w).After cooling to room temperature, the mixture was filtered through a suction filter and the residue was washed with water and acetone. After drying the product in a vacuum drying cabinet at 120 ° C., 116 g of a colorless powder were obtained. The yield was 91% of theory.
Analysis values:
Phosphorus: found 16.9%, calc. 17.2% (w / w),
Aluminum: found 5.2%, calc. 5.0% (w / w).
Claims (16)
- a) Olefine mit Arylphosphonigen Säuren und/oder deren Alkalisalzen in Gegenwart eines Radikalstarters umsetzt, und
- b) die nach a) erhaltenen Aryl-alkylphosphinsäuren und/oder deren Alkalisalze mit Me tallverbindungen von Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na und/oder K zu den Aryl-alkylphosphinsäuresalzen der Metalle umsetzt.
- a) reacting olefins with arylphosphonous acids and / or their alkali salts in the presence of a radical initiator, and
- b) the aryl-alkylphosphinic acids obtained according to a) and / or their alkali metal salts with metal compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and / or K to the aryl-alkylphosphinic salts of the metals.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19851774A DE19851774C2 (en) | 1997-11-28 | 1998-11-10 | Process for the preparation of metal salts of aryl-alkylphosphinic acids |
| EP98121820A EP0919560B1 (en) | 1997-11-28 | 1998-11-17 | Process for the preparation of metal salts of aryl-alkylphosphinic acids |
| DE59810838T DE59810838D1 (en) | 1997-11-28 | 1998-11-17 | Process for the preparation of metal salts of aryl-alkylphosphinic acids |
| US09/198,539 US6232493B1 (en) | 1997-11-28 | 1998-11-24 | Process for preparing metal salts of arylalkylphosphinic acids |
| JP10337986A JPH11236392A (en) | 1997-11-28 | 1998-11-27 | Production of metal salt of arylalkylphosphinic acid |
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|---|---|---|---|
| DE19752727 | 1997-11-28 | ||
| DE19851774A DE19851774C2 (en) | 1997-11-28 | 1998-11-10 | Process for the preparation of metal salts of aryl-alkylphosphinic acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0699708A2 (en) * | 1994-08-31 | 1996-03-06 | Hoechst Aktiengesellschaft | Flame retardant polyester moulding compositions |
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| DE19851774A1 (en) | 1999-07-01 |
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