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United States Patent [19] [11] 4,005,171 Reynard Et Al United States Patent [19] [11] 4,005,171 Reynard et al. [45] Jan. 25, 1977 [54] CATALYTIC PREPARATION OF SOLUBLE [56] References Cited POLY( DICHLOROPHOSPHAZENES ) UNITED STATES PATENTS [75] Inventors: Kennard A. Reynard; Arthur H. 3,249,397 5/1966 Nichols .................... .. 423/300 Gerber, both of Cleveland, Ohio 3,370,020 2/1968 Allcock et al. 423/300 3,407,047 10/1968 Paddock et al. ................. .. 423/300 [73] Assignee: Horizons Incorporated, a division of Primary Examiner-O. R. Vertiz Horizons Research Incorporated, Assistant Examiner-Gregory A. Heller Cleveland, Ohio Attorney, Agent, v0r Firm—Lawrence 1. Field [5 7] ABSTRACT [22] Filed: May 28, 1074 Hlgh molecular weight poly(dihalophosphazenes) which exhibit solubility in benzene and in substituted [21] Appl. No.: 474,055 benzenes are prepared in solution or in bulk from dihalophosphazenes such as »(Cl2PN)3_7 at moderate [52] US. Cl. .............................. .. 423/300; 423/30] temperatures by the use of novel polymerization cata [51] Int. Cl.2 ....................................... .. C01B 25/10 lysts. [58] Field of Search ................ .. 423/300, 302, 301; 260/2 P 9 Claims, No Drawings 4,005, 117-1‘ l 2 ditionslhavebeen attended by signi?cant vaporization CATALYTIC PREPARATION OF SOLUBLE. of monomer(s) .with‘concurrent change of monomer(s) POLY(DICHLOROPHOSPHAZENES) tocatalyst ratio, conditions undesirable for reproduc-. ibility and molecular weight control. Other general‘ This invention relates to the preparation of poly(di advantages ofa‘solution polymerization process are chlorophosphazene) which is soluble in various sol that viscosity is more readily controlled and good agita vents including benzene, chlorobenzenes, toluene and tion can be accomplished in very inexpensive equip mixtures of such solvents. '~ ment. - More speci?cally it relates to the polymerization of Still another important advantage in an atmospheric ‘ dichlorophosphazene of the formula (Cl2PN)3.7 to poly 10 solution polymerization’p'rocess is that the [Cl2PN],, mers of the formula [Cl2PN]20.5o;m wherein the poly polymer‘so produced can be purified immediately or merization is accomplished in solution or in bulk in the can' be utilized directly for subsequent derivatization as presence of one or more catalysts. ' ‘ ‘ . in its'reaction with alkoxide, ?uoroalkoxide, or arylox Uncatalyzed bulk polymerization of (Cl-2PN)3, ide salts, orlmixtures thereof. (CI2PN)4, or mixtures thereof, to form soluble Qther advantages of the polymerization process of [Cl2PN],, polymer is described in ‘U.S. Pat. No. this invention will become evident when the process is 3,370,020. This process employs temperatures of compared with the known art which relates to the bulk 200°-300° C, preferably about 250° C. polymerization of hexachlorophosphazene, (Cl2PN)3, Another known process for producing soluble poly( octachlorophosphazene, (CI2PN)4, and mixtures dichlorophosphazenes) is described in Example 1 of 20 thereof as described, for ‘example, in Allcock, “Phos U.S. Pat. No. 3,515,688 and elsewhere in the literature. phorus-Nitrogen Compounds”, Academic Press, N.Y., This is essentially a batch process in which cyclic tri~ _ 1.972 and Chem. Reviews, 72, 315 (1972). The bulk meric (Cl2PN)3 is heated in a sealed tube under an inert polymerizations reported in the prior art are conducted‘ atmosphere for a stated time at polymerizing tempera under vacuum and have further disadvantages. For tures. ' ' example, high temperatures (220°-350° C) are re A simpler process for the large scale production of quiredanonreproducible products are obtained, forma soluble [Cl2PN],, polymer in good yield is- desired be tion of'gelled polymer (particularly at moderate to high cause ‘this polymer can be converted to useful phospha conversions) is experienced, molecular weight is diffi zene derivatives as described for example, in recently cult to control, and a product with a high degree of issued U.S. Pat. Nos. 3,370,020; 3,515,688; 3,700,629 30 polydispersity is obtained. and 3,702,833 and elsewhere. ' . ‘ By the polymerization process of this invention the The primary object of this invention is‘to provide a polymerization of cyclic compounds having the for simple process for the preparation of soluble, high mula (X2PN),,,, where m is a whole positive integer of molecular weight [CLJ’N],I polymer at a signi?cantly from 3 to 7 inclusive and X is a halogen selected from lower temperature than currently "practiced in the art, 35. F, Cl, Br and all of the X’s are not required to be identi said polymer having an intrinsic viscosity of about 0.01 cal, is accomplished at ‘ temperatures from about to about 3.0 dl/g(benze“ne, 30° C), and- asolubility in l30°-220° C in solution or about l30°—200° C in bulk benzene, toluene, xylene, - chlorobenzene and o for periods ranging from 1 hour to several days at any dichlorobenzene. ‘ r i suitable pressure between vacuum and superatmos Another object of this invention is to provide novel 40 pheric pressure. cyclic phosphazenepolymerization catalysts useful in For solution polymerization the concentration of the above process and. a method for their preparation. , monomer can vary from about. 5—95%.'Preferred sol Still another object of this invention is to form the vents for solution polymerization are those whichare [CIZPN],l polymer by a process in which the polymer unreac'tive to both catalyst and (X2PN),,. monomer and, produced is ready for reaction or puri?cation immedi 45 which preferably are solvent for both monomer and ately following polymerization, thereby avoiding the polymer at polymerization temperature. Suitable sol_. delay normally encountered when ‘high molecular vents‘include nitro or halo. aromatics'such as chloro weight materials are dissolved. benzene, l,2-dichlorobenzene, 1,2,4-trichlorobenzene, These and other‘ objects, whichwill'be apparent from bromobenzene, m- or p-bromochlorobenzene, nitro the description which follows, are achieved by the use benzene, o- or m-nitrotoluene, m-chloronitrobenzene, of speci?c catalysts which make possible the polymeri and mixtures of these solvents. These and other sol zation of cyclic phosphazene oligomers in solution or in vents which may also be employed singly or in combi bulk to form the desired‘ poly(dichlorophosphazene) nation include benzene, biphenyl, toluene, xylene, ha polymer. logenated biphenyls, carbon tetrachloride, hexachloro The catalyzed polymerization when conducted in_ ethane,‘ tetrachloroethane, pentachloroethane, and accordance with this invention is conducted with ease ‘hex‘achlorobutadiene. The ‘methylated benzenes are in solution or in ‘bulk and at temperatures which are preferably used ‘at temperatures below 195° C and ‘signi?cantly lower than those previously employed. benzene and biphenyl are preferably used at tempera~ ,The use of lower temperatures result in a more efficient tures below 220° C. polymerization and also diminish the tendency to form 60 When the’ ‘polymerization is conducted ‘at atmo "gel. spheric pressure or above, a dry inert atmosphere such For solution or bulk polymerization any convenient asnitrogen, helium, or argon is preferably employed. pressure can used from‘vacuum up to atmospheric Polymerizations may be conducted under vacuum or pressures and above. Vaporization of starting mono under pressure. The concentration of catalyst(s) can mer(s) in systems which are not closed, can be.:-re 65‘ vary from 0.l-20% but is preferably in the range of pressed by employing 10 weight % or even less of a 0.l-5%. suitable solvent; Previously reported bulkJpolymeriza Conversions of up to about 80% of soluble [ClgPNln tions at elevated‘ temperature under "atmospheric con polymer have been achieved wherein the polymer is 4,005,171 3 characterized by an intrinsic viscosity as measured in fluoro benzene at 30° C of from about 0.01 to about 3.0 dl/g. chloro- - High percent conversionsto polymer are favored-by an phenyl increase in temperature, catalyst(s) "concentration; toluoyl monomer concentration, and polymerization ‘timerThe 5 naphthyl [Cl2PN],, polymer so produced is characterized by very p-bromophenyl- ‘ little or no gelled material and is thus, ideally suited for nitrophenyl the subsequent preparation of other substituted poly 2,4-dinitrophenyl- v phosphazenes which have a wide range of utility._ biphenyl Although polymerizations are preferably carried out with compounds of formula (Cl2PN),,,, polymerization 2. Polyhalocarboxylic acids where R, (above) in of ?uoro-, bromo-, and even mixed halo- cyclophos cludes the following: phazenes have been effected. in general, the ?uoro trifluoromethyl derivatives require higher polymerization temperatures trichloromethyl and the bromo derivatives require lower polymeriza~ di?uoromethyl tion temperatures than those used to polymerize the di?uorochloromethyl corresponding chloro derivatives. per?uoropropyl The catalysts employed in the practice of the poly per?uorobutyl merization process of this invention to form soluble, 3. Salts of miscellaneous acids: high molecular weight [CIQPNLI Polymer are selected 20 ?uoroboric from three groups, namely metal or organo metal‘salts ?uorophosphoric derived from very strong acids (Group A), strong acids picric (Group B), and derivatives of halocyclicphosphazenes phosphoric (Group C). Catalysts may be employed singly or in pyrophosphoric - 25 polyphosphoric combination. ’ ' Representative members from each group include hydriodic (alkali, alkaline earth and quaternary ammo the following: ' ' nium salts only) Group
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