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US5356967.Pdf |||||||||||||| USOO53.56967A United States Patent (19) 11 Patent Number: 5,356,967 Böhshar et al. (45) Date of Patent: Oct. 18, 1994 (54 6-ARYL-6H-DIBENZOICE1,2OXAPHOS PHORNE STABILIZERS FOR PLASTICS FOREIGN PATENT DOCUMENTS 75 Inventors: Manfred Böhshar, 60-163890 8/1985 Japan. Kelkheim/Taunus; Hans-Jerg OTHER PUBLICATIONS Kleiner, Kronberg/Taunus; Gerhard Pfahler, Augsburg, all of Fed. Rep. Houben-Weyl's Methods of Organic Chemistry, 4th of Germany Edn., vol. XII/1, Stuttgart, Germany, Georg Thieme Verlag, 1963, pp. 208-211, 221, 296. 73) Assignee: Hoechst Aktiengesellschaft, Encyclopedia of Polymer Science and Engineering, Rev. Frankfurt, Fed. Rep. of Germany Ed., John Wiley & Sons, Inc. 1985, p. 87. 21 Appl. No.: 962,187 Polymer Additives, Guidebook and Directory, Noyes Data Corporation, Park Ridge, N.J., 1972, pp. 127-128. 22) PCT Filed: Jun. 22, 1991 Nippon Ester Co., Ltd., Patent Abs. of JP 132:61-266614 86 PCT No.: PCT/EP91/01158 (1985), abstract of JP 61-266614, Nov. 26, 1986. S 371 Date: Dec. 23, 1992 Primary Examiner-Veronica P. Hoke Attorney, Agent, or Firm-Connolly and Hutz S 102(e) Date: Dec. 23, 1992 87 PCT Pub. No.: WO92/00306 57 ABSTRACT A dibenzo-c,e 1,2) oxaphosphorine of the formula I PCT Pub. Date: Jan. 9, 1992 and process of making said compound 30 Foreign Application Priority Data Jul. 2, 1990 DE Fed. Rep. of Germany ....... 402,195 (I) Jun. 3, 1991 DE Fed. Rep. of Germany ....... 41.18147 51 Int. Cl. ..................... CO7B 49/00; CO7F 9/6574; C08K 5/5377 52 U.S. C. ...................................... 524/117; 558/82; 558/134 58 Field of Search .................. 558/82, 134; 524/117; 430/551, 372 56 References Cited U.S. PATENT DOCUMENTS wherein n = 1 or 2 and in which R is a monovalent or 3,702,878 11/1972 Saito et al. .......................... 524/117 divalent aromatic radical wherein a Grignard com 4,185,006 1/1980 Rasberger et al. 524/17 pound R1(MgHal) is reacted with 6-chloro-6H-diben 4,406,842 9/1983 Spivack ............................... 260/962 zoc,e1,2) oxaphosphorine. 4,474,914 10/1984 Spivack ............................... 524/126 4,732,997 3/1988 Tschoppet al....................... 558/82 This compound optionally with phenolic antioxidants, 5,008,426 4/1991 Kleiner et al. ........................ 558/82 provides stabilization in polymers. 5,109,043 4/1992 Bohshar et al. ..................... 558/134 5,128,495 7/1992 Scheffel et al. ..................... 558/134 16 Claims, No Drawings 5,356,967 1. 2 which R, as a monovalent radical, is a phenyl radical, 6-ARYL-6H-DIBENZOICE)12OXAPHOSPHO which may carry 1 to 3 substituents, or a naphthyl radi RNE STABLIZERS FOR PLASTICS cal, which may carry 1 to 5 substituents, the substituents The present invention relates to novel 6-aryl-6H being identical or different nonaromatic hydrocarbon, dibenzo-c,el1,2loxaphosphorines, to a process for alkoxy, alkylthio or dialkylamino radicals, in each case their preparation, and to their use for stabilizing plastics, having 1 to 8 carbon atoms, aryl or aryloxy, in each case in particular polyolefins. having 6 to 10 carbon atoms, or halogen having an atomic number of from 9 to 35, or, as a divalent radical, It is known that synthetic polymers must be protected is a phenylene or biphenylene radical which is unsubsti by stabilizers or stabilizer systems against undesired 10 tuted or substituted by up to 4 nonaromatic hydrocar oxidative, thermal and photochemical damage during bon radicals having 1 to 8 carbon atoms, or is a naphthy preparation, processing and use. Such stabilizers com lene radical which is unsubstituted or carries 1 to 4 prise, for example, a phenolic antioxidant, which is nonaromatic hydrocarbon radicals having 1 to 8 carbon intended, in particular, to ensure the running time stabil atoms as substituents. ity in use of the finished part, and one or more costabil 15 izers, which regulate the processing stability and in Specific examples of R1 as a monovalent radical are some cases also synergistically increase the action of the the various tolyl radicals, xylyl radicals, mesity1, 2,4,5- phenolic component. trimethylphenyl, the various tert-butylphenyl radicals, Conventional costabilizers include, for example, or di-tert.-butylphenyl radicals, 2,4,6-tri-tert-butylphenyl, tho-alkylated aryl phosphites and phosphonites. 2,4-di-tert.-octylphenyl, and the various biphenyl, me Although the diaryl phosphonites described in Euro 20 thylnaphthyl, dimethylnaphthyl and trimethylnaphthyl pean Patent 5447 have adequate properties as stabilizers radicals. for certain areas of application, their synthesis starts Specific examples of R as a divalent radical are the from organodichlorophosphines which are poorly ac various phenylene radicals, such as 1,3- and 1,4-pheny cessible in industry. In practice, the only industrially lene, the various biphenylene radicals, such as 2',3-, available precursor is dichlorophenylphosphine, which 25 2',4-, 3,3-, 3',4- and 4,4'-biphenylene, and the various is the only possible precursor to derivatives of benzene naphthylene radicals, such as 1,4- and 1,6-naphthylene. phosphonous acid. However, to achieve the desired The invention also relates to a process for the prepa properties, it is frequently desirable to have precisely ration of the phosphinous acid esters of the formula I in compounds containing higher substituted aryl groups which R1 is as defined above, which comprises firstly, in on the phosphorus available. 30 a first step, reacting a hydrocarbon halide R-(Hal) in A further serious disadvantage is the necessity to which R1 is as defined above, n=1 or 2, and the halogen neutralize hydrogen chloride liberated during the syn has an atomic weight of at least 35, but is preferably thesis by means of a suitable auxiliary base. In the recy chlorine or bromine, under Grignard conditions, i.e. cling thereof, the inevitable formation of two equiva 35 expediently with intimate mixing, with an at least stoi lents of the corresponding salt is unavoidable. chiometric amount of finely divided magnesium to give The phosphonites prepared in German Offen the corresponding Grignard compound R(MgHal), legungsschrift 2 034 887 by hydrolysis, esterification, and reacting the latter, in a second step, with 6-chloro transesterification, alkylation or sulfation of 6 6H-dibenzoc,e)1,2)oxaphosphorine. chlorodibenzoc,e)1,2oxaphosphorine have, inter alia, The first step of the process according to the inven disadvantages with respect to shelf life, color behavior tion, which can in principle be carried out in any con and hydrolysis resistance, as has already been described ventional manner, is preferably carried out in an in U.S. Pat. No. 4,185,006. aprotic, organic solvent, such as an ether, for example The object of the present invention was therefore to diethyl ether, dipropyl ether or diisopropyl ether, ethyl provide novel phosphorus stabilizers which, on the one 45 ene glycol dimethyl ether, ethylene glycol diethyl hand, satisfy the high demands of practice and in partic ether, diethylene glycol dimethyl ether, diethylene gly ular do not decompose into a plurality of fragments col diethyl ether, methyl tert-butyl ether, dioxane or and/or acidic secondary products, even on contact with tetrahydrofuran. water, but at the same time can be prepared simply and in high yield by ecologically favorable processes. Since the Grignard compounds are sensitive to hy 50 drolysis and oxidation, it may be expedient to work Surprisingly, it has now been found that cyclic phos under a protective-gas atmosphere. However, a proce phinous acid esters of the formula I dure of this type is in no way essential for the success of the reaction. Particularly suitable protective gases are (I) nitrogen and argon. The reaction temperature is gener 55 ally between 20 and 125 C., but preferably between 30 and 70° C. The use of ultrasound during the forma tion of the Grignard compound is sometimes advanta geous. To prepare the compounds I, the solution or suspen sion of the Grignard reagent is reacted in the second step with a solution of 6-chloro-6H-dibenzoc,e)(1,2)ox aphosphorine. This may be carried out, for example, by metering the solution or suspension of the Grignard meet these requirements very well. reagent into a solution of 6-chloro-6H-dibenzoc,ell, The invention thus relates to dibenzoc,e1,2oxa 65 2)oxaphosphorine with vigorous mixing. However, the phosphorines of the formula I, i.e. aryl-6H-dibenzoic reverse addition is also possible. Suitable diluents are el(1,2}oxaphosphorines where n=1 and arylbis(6H inert, aprotic solvents, for example an aliphatic hydro dibenzo[c,e)(1,2)oxaphosphorines where n=2, in carbon fraction, hexane, heptane, cyclohexane, toluene, 5,356,967 3 4 xylene or one of the abovementioned ethers, or appro tuted or substituted by up to 4 nonaromatic hydrocar priate mixtures. The reaction temperature in this stage is bon radicals having 1 to 8 carbon atoms, or is a naphthy generally between -30 and --50 C., but preferably lene radical which is unsubstituted or carries 1 to 4 between -20 and +20 C. The reaction is generally nonaromatic hydrocarbon radicals having 1 to 8 carbon exothermic; it may accordingly be expedient to control atoms as substituents. the course of the reaction by cooling. The most favor The plastic molding composition according to the able results are achieved if the reactants are employed invention contains athermoplastic or thermoset organic in stoichiometric amounts. However, it is also possible polymer, for example one of the polymers listed below: to employ one reactant in excess; however, this is gener 1. Polymers of mono- or diolefins, for example high-, ally not associated with any particular advantages. The O medium- or low-density polyethylene (which may, mixture is expediently stirred until the reaction is com if desired, be crosslinked), polypropylene, polyiso plete, and precipitated magnesium halide is subse butylene, poly-1-butene, polymethyl-1-pentene, quently separated off.
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