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(12) United States Patent (10) Patent No.: US 7,317.046 B2 Fukuoka Et Al

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(12) United States Patent (10) Patent No.: US 7,317.046 B2 Fukuoka Et Al USOO7317046B2 (12) United States Patent (10) Patent No.: US 7,317.046 B2 Fukuoka et al. (45) Date of Patent: Jan. 8, 2008 (54) CYCLIC PHOSPHAZENES, PROCESS FOR FOREIGN PATENT DOCUMENTS PREPARING THEM, FLAME RETARDANT CONTAINING THEM AS ACTIVE JP 11-263885 * 9/1999 INGREDIENT, AND RESIN COMPOSITION CONTAINING THEM AND MOLDED ARTICLE THEREFROM OTHER PUBLICATIONS (75) Inventors: Naohiko Fukuoka, Koube (JP): Heinosuke Yasuda, Koube (JP); Fukuoka et al. 1999, CAS: 13 1:2441 14.* Masayuki Nishimatsu, Koube (JP); * cited by examiner Yoshinori Ohmae, Koube (JP) Primary Examiner Rei-tsang Shiao (73) Assignee: Chemipro Kasei Kaisha, Limited, (74) Attorney, Agent, or Firm—Oliff & Berridge, PLC Koube (JP) (57) ABSTRACT (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 565 days. The present invention relates to cyclic phosphaZenes of general formula (1) (21) Appl. No.: 10/479,235 (22) PCT Filed: Jun. 5, 2002 (1) (86). PCT No.: PCT/UPO2/O5554 S 371 (c)(1), (2), (4) Date: Dec. 1, 2003 (87) PCT Pub. No.: WO02/098886 wherein Q is a halogen and/or an aryloxy group, and m is an PCT Pub. Date: Dec. 12, 2002 integer of 3 to 10, which are characterized by being sub stantially free from linear phosphaZenes of general formula (65) Prior Publication Data (2) US 2004/0152910 A1 Aug. 5, 2004 (30) Foreign Application Priority Data (2) Q Jun. 5, 2001 (JP) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2001-170228 Jun. 5, 2001 (JP) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2001-1703.19 -n (51) Int. Cl. Q COSK 5/5399 (2006.01) C07F 9/02 (2006.01) wherein Q is a halogen and/or an aryloxy group, and n is an (52) U.S. Cl. ......................................... 524/116; 558/75 integer of 1 to 20 and by having an extremely low content (58) Field of Classification Search .................. 558/75; of halogen, and which are appropriate to flame retardants for 524/116 resins; processes for preparing the same; flame retardants See application file for complete search history. containing the same as an active ingredient; resin composi (56) References Cited tions containing the cyclic phosphaZenes; and molded articles therefrom. U.S. PATENT DOCUMENTS 5,652,285 A * 7/1997 Coggio et al. .............. 524,116 10 Claims, No Drawings US 7,317,046 B2 1. 2 CYCLIC PHOSPHAZENES, PROCESS FOR In addition, Japanese Patent Laid-open No. Sho PREPARING THEM, FLAME RETARDANT 58-219.190 discloses polyhydroxyphenyl phosphonitrilate CONTAINING THEM AS ACTIVE bearing phenolic hydroxy groups characterized by contain INGREDIENT, AND RESIN COMPOSITION ing Substantially no polycondensation products and no CONTAINING THEM AND MOLDED residual chlorine; and a process for preparing the same. This ARTICLE THEREFROM relates to polyhydroxyphenyl phosphonitrilate bearing phe nolic hydroxy groups and a process for preparing the same This application is a 371 of PCT/JP02/05554 filed on Jun. characterized by comprising reacting a phosphonitrile halide 5, 2002. with a sodium or potassium salt of a monomethoxy phenol 10 obtained by protecting one hydroxy group of a dihydric TECHNICAL FIELD phenol with methyl group to produce polyhydroxyphenyl phosphonitrilate, and then reacting the phosphonitrilate with The present invention relates to cyclic phosphaZenes, a a pyridine hydrohalogenic acid to convert the methoxy process for preparing them, a flame retardant containing moiety into a hydroxy group. them as an active ingredient, and a resin composition 15 The present inventors disclose in Japanese Patent Laid containing them and a molded article therefrom. open No. 2001-2691 a process for preparing a cyclic phos phaZene comprising reacting a cyclic halogenated phosp BACKGROUND ART haZene with an alkaline metal phenolate in a solvent containing nitrogen-containing linear and/or cyclic organic One of the prior processes for preparing cyclic aryloxy compound. phosphaZenes is a process of Yokoyama (Journal of the In the prior processes for preparing cyclic aryloxyphos Chemical Society of Japan, Vol. 80, No. 10, p. 118 (1959)) phaZenes, isolated cyclic chlorophosphaZene is used as a raw in which phosphorus pentachloride is reacted with ammo material. When cyclic chlorophosphazenes are obtained in nium chloride in monochlorobenzene to produce a mixture an industrially large amount from a mixture of cyclic and of cyclic chlorophosphazenes represented by formula (3) 25 linear chlorophosphaZenes, a large quantity of halogen gas may be generated and pollute remarkably the environment, and results in very low workability. Even though isolated (3) and purified cyclic chlorophosphaZenes are reacted with a phenol, the intended cyclic phosphaZene is not prepared 30 because linear phosphaZenes are given by ring-opening of cyclic phosphaZenes during the reaction, unsubstituted phos phaZenes having chlorine may remain, or linear phosp haZenes are given by the hydrolysis of cyclic phosphaZenes during its after-treatment. 35 Phenyl phosphonitrilates prepared by the process wherein m is a integer of 3 to 10, with linear chlorophosp described in Journal of the Chemical Society of Japan, Vol. hazenes represented by formula (4) 81, No. 3, p. 481 (1960) are not solid but yellow viscous liquid as they contain linear phosphaZenes prepared by ring-opening of cyclic phosphaZenes, or unsubstituted phos (4) 40 phaZenes having chlorine, and the phosphonitrilates cannot be purified. A preparation process disclosed in Japanese Patent Laid open No. 2001-2691 discloses phosphazenes containing lower content of halogen compared with the conventional 45 processes, but the content of halogen is as much as about 100 ppm. In addition, as cyclic halogenated phosphaZenes are wherein n is an integer of 1 to 20; and the mixture of cyclic used as a raw material, it is unavoidable to result in linear and linear chlorophosphaZenes is recrystallized in a petro phosphaZenes due to ring-opening of a part of the cyclic leum ether, etc. to produce chlorophosphaZenes represented phosphaZenes during the reaction. by formula (3) 50 In addition, in Japanese Patent Laid-open No. Sho 58-219.190 described above, a sodium salt of monomethoxy phenol is used in an amount by a factor of 1.1 based on 1 of (3) chlorine in phosphonitrile halide and the reaction is carried out. However, the reaction is not completed and thus unsub 55 stituted organic halides remain. Consequently, although phosphaZenes represented by the above-mentioned general formula (1) contain no halogen in the structural formula thereof, all substituents thereon cannot be necessarily sub stituted with aryloxy groups, so that halogens still remain on 60 a part of the resulting compounds in the structural formula wherein m is an integer of 3 to 10; and the chlorophosp thereof. In particular, it is difficult to substitute the finally haZenes are reacted with phenols to produce cyclic aryloxy remaining one halogen on a compound, and it is not able to phophaZenes. Concretely, Yokoyama (Journal of the Chemi completely substitute even when the reaction is carried out cal Society of Japan, Vol. 81, No. 3, p. 481 (1960)) reports for about 250 hours. on a condensation reaction of triphosphonitrile chloride with 65 Consequently, although the phosphaZenes represented by alkaline metal phenolates in the presence of pyridine as the above-mentioned general formula (1) are cyclic on the catalyst. structural formula thereof, the cyclic structure on the above US 7,317,046 B2 3 4 mentioned general formula (1) cannot be necessarily main DISCLOSURE OF INVENTION tained in the conventional preparation processes, therefore a part of the products becomes linear compounds. In this connection, the present inventors studied intently Additives for resin include flame retardants, UV light on reaction conditions and purification conditions under absorbers, antioxidants, plasticizers, nucleating agents, etc. which products substantially free from linear phosphazenes Needless to say, they have to satisfy several requirements, can be produced in the preparation of phosphaZenes, and for example they do not deteriorate stability during fabrica consequently found that linear phosphaZenes act as an tion nor pollute molds, further they affect no adverse influ excellent crystallization solvent and dissolve unsubstituted ence on products, in particular they cause no breed-out that halogen-containing phosphaZenes, and then cyclic phosp they exude from the surface of resins. 10 haZenes having an extremely low content of halogen and an In particular, recently it has become problems that flame extremely low content of linear phosphaZenes can be pro retardant compositions containing a resin and a flame retar duced by reacting a mixture of cyclic and linear halogenated dant in which halogen-containing compounds that have been phosphaZenes with alkaline metal phenolate to produce a conventionally main Substances for the flameproofing of mixture of cyclic and linear aryloxyphosphaZenes and sepa wires or cables, etc. are used alone or an admixture with 15 rating and purifying the mixture by crystallization, and that antimony compounds, such as antimony oxide generate the cyclic phosphaZenes free from linear phosphaZenes have halogen gas when the compositions are subjected to com higher flame retardant effect than mixtures of cyclic phos bustion or molding process, etc. It is further said that the phaZenes and linear phosphaZenes, and the inventors com generated gas often deteriorates electrical properties or pleted the present invention. transmission properties.
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