POLYMERIZATION OF CYCLIC DIHALOPHOSPHAZENE OLIGOMERS

Abstract: A catalytic method for polymerizing cyclic dihalophosphazene to form linear polydihalophosphazene is provided wherein the catalyst is a solid support of silica or alumina containing supported thereon both a transition metal compound and an organometallic compound.

Description: This invention relates to a process for the polymerization of cyclic dihalophosphazenes oligomers to higher molecular weight substantially linear poly­ dihalophosphazene polymers. The polymerization of cyclic dihalophospha­ zenes such as (NPCl₂)₃ or (NPCl₂)₄ to higher molecular weight linear polydihalophosphazene polymers is well known in the art. Prior known processes for polymer­ izing such cyclic dihalophosphazenes involved the uncatalyzed or catalyzed thermal polymerization of such dihalophosphazenes either in a bulk process or in a solution process employing a solvent. Such processes are taught, for example, in U.S. Patent No. 3,370,020 to Allcock et al., issued February 20, 1968; U.S. Patent No. 3,515,688 to Rose, issued June 2, 1970; U.S. Patent No. 4,005,171 to Reynard et al., issued January 25, 1977; U.S. Patent No. 4,123,503 to Snyder et al., issued October 31, 1978; U.S. Patent No. 4,327,064 to Fieldhouse et al., issued April 27, 1982; U.S. Patent No. 3,917,802 to Allcock et al., issued November 4, 1975; U.S. Patent No. 4,137,330 to Prichard et al., issued January 30, 1979; U.S. Patent No. 4,242,316 to Sinclair, issued December 30, 1980; PTO Patent Speci­ fication Publication No. 0004877, published May 12, 1982, to Snyder et al.; U.S. Patent No. 4,225,567 to Halasa et al., issued September 30, 1980; U.S. Patent No. 3,937,790 to Allcock et al., issued February 10, 1976; and U.S. Patent No. 4,226,840 to Fieldhouse et al., issued October 7, 1980. The present invention concerns an improvement over this prior technology by use of a specifically defined supported coordination catalyst containing both titanium and aluminum. By this method lower temper­ atures and reaction times are possible and starting materials can be employed which are not ultra pure. In the practice of the present invention, cyclic dihalophosphazenes oligomers are polymerized to form linear polydihalophosphazenes by agitating, under an inert gaseous atmosphere, a mixture containing at least one cyclic dihalophosphazene and a polar organic solvent for the cyclic halophosphazene, in the presence of a catalytic amount of a solid catalyst which is composed of a solid support selected from silica gel or alumina and, supported on such support, a transition metal compound and an organo metallic compound, wherein at least a proportion of the transition metal compound has a valence of +3 or less, and maintaining said mixture at a temperature of from 150° to 250°C for a period of time sufficient to form linear polydihalo­ phosphazene. The starting material or monomer of the present invention comprises one or more cyclic dihalo­ phosphazene oligomers represented by the formula (NPX₂) n in which n is from 3 to 7 and wherein X is a halogen selected from chloride, fluoride, and bromide ion. X is preferably chloride. The cyclic dihalo­ phosphazene oligomers which are employed as starting materials are substantially pure oligomers which are obtained by purification of crude cyclic dihalophos­ phazene oligomers. A mixture of these cyclic dihalo­ phosphazenes can be employed in the practice of the invention. For example, a mixture of tri- and tetra­ cyclic dihalophosphazenes are useful. A variety of method for purification are known in the art and include, for example, extraction, crystallization, distillation, saponification, and hydrolysis tech­ niques. Cyclic phosphonitrilic chloride trimer or tetramer are preferred. One or more of these materials can be employed as the starting materials. The solvent employed in the practice of the present invention comprises a materials which is both unreactive to the catalyst and monomer, and preferably is a solvent for the monomer and the polymer at the polymerization temperatures employed. A polar solvent having a dielectric constant high enough to permit cationic polymerization is preferred. Examples of suitable solvents include 1,2,4-trichlorobenzene; 1,2,­ 3-trichlorobenzene; 1,3,5-trichlorobenzene, and mixtures thereof. The solvent should preferably be used in an amount which is sufficient to form a readily agitated slurry mixture containing the particulate catalyst and the monomer. Generally, the solvent should be employed in an amount less than about 50 percent by weight of the reaction mixture. The process is preferably carried out under an inert, dry atmosphere such as nitrogen, helium, or argon. Polymerizations may be conducted under a vacuum, atmospheric or elevated pressure. The catalyst employed in the present inven­ tion comprises a solid support of silica gel or alumina containing supported thereon a catalytically effective amount of a transition metal compound selected from titanium, zirconium, hafnium, vanadium, niobium, tan­ talum, chromium, molybdenum, tungsten or mixtures thereof. Also present on the support is an organo­ metallic compound of aluminum or boron, represented by the formula R a MX b wherein M is either aluminum or boron, a+b is equal to the valence of M, X is a halogen such as chloride or bromide, and R is a hydrocarbon radical selected from alkyl, aryl, cycloalkyl, alkaryl, and arylalkyl, wherein the group contains from one to twenty carbon atoms. The aluminum atom to transition metal atom mole ratio on the supported catalyst is important and should range from 0.1 to 100 aluminum to transition metal, preferably from 1.0 to 65, most preferably from 3 to 8. The transition metal compound is preferably an alkoxide or a halide such as, for example, transi­ tion metal-(OR)₄ and transition metal-(OR)₃ wherein R is selected from a hydrocarbon or transition metal-X₄ and transition metal-X₃ wherein X is a halogen. Pre­ ferred hydrocarbon groups are isobutyl, n-butyl, and isopropyl. The preferred halogen atom is chloride. Preferred transition metal compounds include Ti(OCH₂CH(CH₃)₂)₄, and TiCl₄ and the valence 3 form of these compounds. Preferred organometallic compounds are aluminum alkyl halides such as ethylaluminum dichloride, diethyl aluminum chloride, ethyl aluminum sesqui chloride and mixtures thereof. A catalytically sufficient amount of the supported catalyst should be present. The catalyst, based on the active transition metal, is provided in a molar ratio to "NPCl₂" unit ranging from 1x10⁻⁴ : 1, to 1x10⁻² : 1, preferably from 8x10⁻⁴ : 1 to 8x10⁻³:1. It is preferred to adjust the quantity of active catalyst by changing the amount of catalyst on the support instead of the amount of support and catalyst. It has been discovered that the amount of support in the reaction mixture needs to be minimized in order to reduce the formation of gels in the polymer. The material employed to support the tran­ sition metal compound and organometallic compound comprises alumina or silica. These supports can be prepared in any convenient manner. The supports should generally be in particulate form and range in size from 60 to 200 mesh (U.S. Standard Sieve Series) 250 to 74 microns. The alumina supports can be prepared, for example, by the method taught in U.S. Patent No. 4,428,863. Silica supports can be prepared, for example, by heating silica to a temperature of about 500°C under vacuum for about 5 hours and then cooling under vacuum or nitrogen. Silica supports can also be prepared according to the teachings of U.S. Patent Nos. 4,436,882; 4,384,086; 4,369,295; 4,434,280 and 4,199,475. Supporting the transition metal compound and organometallic compound on the silica or alumina can likewise be accomplished in any manner known in the art. For example, the method taught at column 7, line 40 through line 68 of U.S. Patent No. 4,302,565 can be employed. Other techniques can be used. Uniform heat distribution throughout the reaction mass should be maintained during the polymer­ ization process. Therefore, good mixing is required to reduce crosslinking and gel formation. The polymerization reaction may be carried out within a temperature range of from 150° to 250°C. A preferable temperature range is from 200° to 220°C. The polymers produced according to the prac­ tice of the present invention can range in molecular weight from 3,500 to 35,000. The molecular weight can be controlled by controlling the amount of catalyst present during the polymerization reaction. The molecular weight is determined by the technique set forth in Examples 19-28. The reaction times will vary depending on factors such as polymerization temperatures, the amount of catalysts and the like. Polymerization times rang­ ing from 3 to 6 hours are satisfactory. It has been found that the catalyst does not need to be removed from the polydihalophosphazene polymer prior to converting the dihalophosphazene to a polyorganophosphazene such as taught in U.S. Patent No. 3,370,020. However, if desired the catalyst may be removed from the polymer by diluting the polymer in toluene and removing the solid catalyst particles by centrifuging the mixture. Other techniques may also be employed. In the following examples of the invention the following procedure was employed to prepare the supported catalyst. A titanium compound was reacted with either activated silica gel or alumina at a temp­ erature of 20° to 30°C in hexane solvent. The silica­ -titanium material is then contacted at a temperature of 20° to 30°C. with an aluminum compound dissolved in toluene. The mixture was then heated to reflux for several hours. The solid catalyst was recovered by filtration, washed with hexane and then dried under vacuum. The silica gel or alumina is activated by known techniques such as heating to a temperature of from 400° to 500°C under vacuum or nitrogen purge for about four hours and the solid cooled under vacuum or nitrogen. Examples 1-18 A catalyst was prepared by the following procedure. Silica (60-200 mesh U.S. Standard Sieve Series) -250 to 74 microns was activated and 5.90 grams slurried in 100 ml of hexane. A solution consisting of 1.00 ml (2.85 moles) of Ti[OCH₂-CH-(CH₃)₂]₄ and 50 ml of hexane was added to the activated silica with vigor­ ous stirring. The solution was stirred for one hour at room temperature. The solid was then filtered, washed with three 50 ml portions of hexane and dried under vacuum. A solution consisting of 10 ml (18 mmoles) of ethylaluminum dichloride in 50 ml of toluene was pre­ pared and placed in a dropping funnel. The silica­ -supported Ti compound was then slurried in 50 ml of toluene and ethylaluminum dichloride solution was added to the supported Ti slurry with vigorous stirring. The slurry was then warmed to reflux for two hours, cooled to room temperature and stirred overnight. The solid catalyst (brown in color) was then filtered, washed with four 50 ml portions of hexane, and dried under vacuum. At least a portion of the Ti will be reduced by the aluminum compound to a valence of +3. Several other catalysts were prepared employ­ ing the foregoing procedure but altering the Ti source, mole ratio and support. The catalysts are described in the following Table I. Employing the catalysts identified in Table I, (NPCL₂)₃ trimer was polymerized in the following manner. The catalyst employed, reaction temperature, reaction time, solvent, ratio of Ti to NPCl₂ and yield are set forth in the following Table II. The polymerization was carried out by mixing the reaction components (catalyst, NPCl₂)₃, and solvent) in a 50 ml flask in a dry box. The flask was fitted with a reflux condenser and an adaptor with a 2 mm stopcock placed on the top of the condenser. The apparatus was then removed from the dry box. A tube from a double manifold vacuum/nitrogen line was then attached to the adaptor. The tube was evacuated and refilled with nitrogen five times. The flask was then opened to the nitrogen line. Following this the flask and its contents were placed inside a heating mantle and the contents quickly heated to the reflux temperature of the solvent and the temperature maintained at reflux until the reaction was terminated. To terminate the reaction, the heat source was removed from the flask, and the apparatus allowed to cool to room temperature. The flask was then removed to the dry box and the polymerization yield was determined. The contents of the flask after cooling to room temperature were diluted with toluene and filtered. The solids, which consisted of catalyst and crosslinked polymer (i.e., gel, which is not considered to be a useful product of this reaction) were separated from the liquid. The liquid portion was then added dropwise to hexane. A solid precipitate was formed consisting of the linear polymer. The yield was calculated based on the weight of the solids after they were separated and dried. The results of these polymerization runs are set forth in the following Table II. Examples 19-35 These Examples were conducted in the same general manner as Examples 1-18 except that certain process parameters were varied. These variations are noted below or in Tables, III, IV and V. Silica (60-200 mesh U.S. Standard Sieve Series) -250 to 74 microns was activated prior to use by heating to a temperature of 500°C in a tube furnace with a slow nitrogen purge until no more steam was evolved from the tube. The tube was then evacuated for two hours at a temperature of 500°C, cooled slowly to room temperature, and placed into the dry box. (NPCl₂)₃ was either used as received, recrystallized from hexane, or vacuum sublimed. The purification of this reagent appeared to have no effect on the polymerization reactions. 1,2,4-trichlorobenzene solvent (TCB) was vacuum dis­ tilled from barium oxide and stored under nitrogen prior to use. All other reagents were used as received. All of the supported catalysts were prepared in a manner analogous to that set forth in the Examples 1-18. A slurry of activated silica in hexane was treated with a solution of isobutyl titanate in hexane. The solution was stirred vigorously for several hours. The solid catalyst was collected by decanting the solvent, washing with hexane, and decanting the solvent again. To a slurry of this solid in hexane was added a solution of ethyl aluminum dichloride in toluene. The reaction mixture was heated to reflux for several hours and the slurry was stirred overnight. The solid cata­ lyst was collected and dried under vacuum after several wash/decant steps with hexane. Table III sets forth the ratios of the reagents used to prepare these catalysts. The polymerization reactions were carried out under a variety of conditions. The experimental condi­ tions for each run are given in Table IV. All runs were performed under nitrogen. In a number of Examples reported in Table V, derivatives of linear-phosphonitrilic chloride polymer were prepared according to standard literature pro­ cedures Allcock, H. R., Kugel, R. L., Valen K. J., "Inorganic Chemistry", 1966 5 1709. However, the isolation and purification of the product differed from previously reported procedures in the following respect. Excess sodium alkoxides and/or phenoxides were neutralized to pH ≦3.0 by the dropwise addition of concentrated HCl. The polymer was then precipitated by slow addition of the reaction mixture to water with vigorous stirring. The water was decanted and the polymer was washed with excess water to remove most of the salts and organic solvents. The polymer was then washed with n-propanol, then water, and finally with n-propanol. The solvent was then decanted from the polymers. Toluene was then added and the mixture was heated to boiling. The water and n-propanol were removed as the toluene azeotropes. As the boiling point of the mixture reached 110°C, the polymer dissolved to form a viscous, cloudy solution. The solution was cooled to room temperature, poured into centrifuge tubes, and spun at 10,000 rpm for 15 minutes to remove insoluble salts and gels. The clear solution was decanted from the centrifuge tubes into a beaker. The toluene was evaporated by heating under an air purge. The final traces of solvent were removed by placing the beaker in a vacuum oven (90°C, 20 mm Hg) until a constant weight was obtained. Yields were determined gravimetrically, and are based on the moles of (NPCl₂) in the starting reagent (NPCl₂)₃. Solution viscosity data is reported as the inherent viscosity, where t is the time for the polymer solution, t o is the time for the pure solvent, and c is the concentration of polymer (grams/deciliter). All viscosity data was obtained at a temperature of 25°C using a Ubbelohde viscometer. Polymer solutions were prepared in either tetrahydrofuran or toluene. Determination of the same polymer sample in the two solvents showed less than a 5 percent difference in the viscosity values. Approximations to Mv, the viscosity average molecular weight, were made using the Mark-Houwink equation, [n] = K¹ Mv a with the constants K¹ = 2.50 x 10⁻³ dl · mole/g² and a = 1/2, as reported by Allcock in Allcock, H. R.; Kugel, R. L.; Valen, K. J.; "Macromolecules", 1978, 11 , 179.

Claims: 1. A process for the polymerization of cyclic dihalophosphazene oligomer to form linear poly­ dihalophosphazene comprising the step of: agitating, under an inert gaseous atmos­ phere, a mixture containing at least one cyclic dihalo­ phosphazene, a polar organic solvent for said cyclic halophosphazene, a catalytic amount of a solid catalyst comprising a solid support selected from silica or alumina containing supported thereon a transition metal compound and an organometallic compound, wherein at least a portion of the transition metal compound has a valence of +3 or lower, and maintaining said mixture at a temperature of from 150° to 250°C for a period of time sufficient to form linear polydihalophosphazene. 2. The process of Claim 1, wherein the transi­ tion metal of the transmission metal compound is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or mixtures thereof, and wherein said organometallic compound corresponds to the formula RaMXb in which M is aluminum or boron, a + b is equal to the valence of M, X is a halogen selected from chloride or bromide and R is a hydrocarbon selected from alkyl, aryl, cycloalkyl, alkaryl or arylalkyl wherein the group contains from 1 to 20 carbon atoms. 3. The process of Claim 2, wherein the transi­ tion metal is titanium and the metal of the organo­ metallic compound is aluminum. 4. The process of Claim 2, wherein the atom mole ratio of aluminum or boron to transition metal ranges from 0.08 to 100. 5. The process of Claim 2, wherein the atom mole ratio of the aluminum ion to titanium ion present in the catalyst ranges from 0.1 to 65. 6. The process of any one of the preceding claims, wherein said cyclic dihalophosphazene corres­ ponds to the formula (NPX₂)n wherein X is a halogen selected from chloride, bromide or fluoride and n is an integer of from 3 to 7. 7. The process of Claim 6, wherein the cyclic dihalophosphazine corresponds to the formula NPCl₂ and wherein the mole ratio of titanium to NPCl₂ in the initial reaction mixture ranges from 1x10⁻⁴:1 to 1x10⁻²:1. 8. The process of Claim 6, wherein the mole ratio of titanium to NPCl₂ in the initial reaction mixture ranges from 8x10⁻⁴:1 to 8x10⁻³:1. 9. The process of any one of the preceding claims, wherein the solvent is 1,2,4-trichlorobenzene. 10. The process of of any one of the pre­ ceding claims, wherein the source from which titanium is present is Ti(OR)₄ wherein R is selected from isobutyl, n-butyl or isopropyl. 11. The process of any one of Claims 1 to 9, wherein the titanium metal compound is Ti(OR)₃ and Ti(OR)₄ wherein R is selected from the group consisting of isobutyl, n-butyl or isopropyl. 12. The process of Claim 6, wherein X in (NPX₂)n is chloride. 13. The process of any one of the preceding claims, wherein said mixture is maintained at a temper­ ature of from 200° to 220°C, and including the step of recovering polydihalophosphazene.

Inventors: KIRKPATRICK, CHARLES C.
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1986
Main classification: C08G79
IPC codes: C01B21, B01J31, C08G79