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 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 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, , 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- 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 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, , - 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 (A): comprises metallic or quaternary ammo 4. Salts where the anion is a complex polyhalide nium salts in which the anion is selected from the group represented by the formula [M'Z,+,]" where M is a consisting of: metal or nonmetal ion having a valence of r and is selected from Al, As, Fe, Mo, V, Nb, Ta, Pd, Pt, Re, Rh, Ti, Zr, Sb, Sn; Z is F or Cl; and r is an integer ' designating the magnitude of the negative charge of 0 OH said complex. ion. Representative complex negative 35 ions are SbFG', SbClJ, AsFa", AIFJ“, FeFf", Til-T6”, RIC o I R2503 v \ and MoClhfs. OH on ' on 5. Alkaline and alkaline earth salts having an anion represented‘by the formula [QX’4_,]"2“" where x is zero or 1; Q is selected from Hg, Zn, Cd; and X’ is bromine or iodine. where R, is a monovalent member selected from the Preferred cations for all the catalyst salts of this in group consisting of polyhaloalkyl where the halogen is vention are Li, Na, K, Mg, Ba, Hg, Ag, and quaternary F, Cl or mixtures thereof, per?uoroaryl and per ammonium ions. chloroaryl; R2 is a monovalent member selected from Group (B): comprises the strong acids of Group (A), the group consisting of F, Cl, lower alkyl (C1-C5), aryl, 45 i.e., the sulfonic acids and polyhalocarboxylic acids substituted alkyl and substituted aryl with the proviso used to prepare the metal salt catalysts of Group (A), that R: is not halogen when bonded to picric acid, and in addition H3P04 and the dehydrated ~ derivatives of H3PO4 such as pyrophosphoric acid, P205 and P2O5--H,-,PO4 mixtures, usually designated “poly 50 phosphoric acid”. Group (C): comprises substituted cyclophospha zenes represented by the formula (X),,(PN),,,(An),, where m is a positive integer of 3 to 7; x and y are positive integers the sum of which equals 2m; x being at Z is F or Cl; M is a metal selected from Groups la, lb, 55 least one and y being not less than zero; each X is va Ila, IIb, and VIII of the Periodic Table, Pb, Mn, or Th; halogen selected from F, C1, or Br; An represents an r is the valence of Metal M; r is an integer designating anion described in Group (A) above, and all the An the magnitude of the negative charge of the complex groups need not be identical to other An groups pre ion [M'Z,+,]"; and Q is a metal selected from} the sent in the cyclophosphazene and for cyclophospha group consisting of Hg, Cd and Zn and X’ .is either Br 60 zenes containing two or more ‘X's, all of the X’s need or I; and x is 0 or 1. not be identical. The following are representative as examples of spey The catalysts of Groups A, vB, and C may be em ci?c catalysts of Group (A): s ._ ployed singly, in combination, or as mixtures with non l. Sulfonic acids where R2 (above) includesthe fol catalyst metal halide salts such as LiCl, LiBr, MgCl2, lowing: - 65 MgBr2, HgCl2, HgBrz, which may be added for the lower alkyl (methyl through butyl) purpose of modifying the polymerization, perfluoromethyl The phosphazene derivatives of Group (C) are pre-' per?uorophenyl pared by substitution reactions of X6P3N3 or X8P4N4, or 4,005,171 5 6 mixtures thereof, or mixtures with higher oligomers, mer, with a, salt of Group (A), adding the remainder of wherein X is a halogen as described above, withone or. monomer, and solvent, if any, and heating at the de more of the salts described in Group (A); Preferred sired polymerization temperature. Incremental addi cations of the salt are silver, alkali metalf‘mercury' and tions of catalyst, monomer, or both, may be made in quaternary ammonium. The interchange is accom the practice of any of the above polymerization meth plished at temperatures from about 25° C to 130° C, or eds. even higher, providing the temperature is such that The remarkable catalytic activity shown by the very little or no polymerization occurs, and reaction times of strong acids utilized in this invention was unexpected in about 1 hour to several days have been used. The reac— view of the results reported with hydrogen chloride. It tion is preferably carried out in a dry polar aprotic has been found that bulk polymerizations of (Cl2PN)3 solvent such as organic ethers [e.g. tetrahydrofuran, in the presence of HCl ( a l-5>

Catalyst (weight Solv Polymerization Ex. % on Monomer) en‘t(s) Conditions Remarks

. ° C HQ, 1 None A 190 15 No Polymer 2 (cFnsQml-lgl 1%] B 217 3 Soluble polymer [111 = l-4 3 (CF=;SO=1)2Hg[1%] A 190 6 l6: Soluble Polymer 4 (CFnSO¢,),l-lg[1%] C 190 10 Soluble polymer 5 (CF:,SO,-,),Hg(0.3%)' B 217 3 Soluble polymer (75%) [111 = 2.7 6 CF;|SO3Ag(1%) A 190 6 ‘k Soluble and . gelledpolymer 7 AgPF||(3%) A 190 7 Soluble polymer. low conversion 8 (CBF5SOn)2Ba( 1%) A 190 4 " Soluble polymer 9 [2.4-(N00-i‘ A 190 4 Soluble polymer C..H;,SO_1]2Mn( 1%) 1O KSbCl¢(1%) A 190 6 Soluble Polymer l l CO(BF4),(1%) A 190 6 Soluble Polymer 12 CF3COgAg(2%.) A 190 6 F6 12% Conversion. ' "’ .[Tll==0-20 13"’ H31,( 2% )+ C 190 7 19% Conversion Nal (0.7%) 14 Hg12(2%)-l7 j C 190 1 l 2% Conversion Nal(0l7% )“l “ prior to addi ": " tion ofNal) 4,005,171 7 8 -contmued 15 Nal(2’/2) C 190 10 V2 13% Conversion 16 C“H_-,SO-3(CH;.)4N* A 190 11 51% Conversion. (2%) 1n] = 0-06 17 LizTiFuQr/a) A 190 6 25% Conversion 18 CF;,SO;(Na(2%) A 190 10 10% Conversion 19 (CH;,SO_-,Hg)2O( 2%) A 190 2 V; 61% Conversion ~ [1,] = on 20 (CH;(SO;,Hg)2O A 190 15 24% Conversion (0.5%) 11r1= 0.75 21 (CH;,SO;(Hg)2O(2'/¢) A 150-155 17 ‘k Soluble Polymer 22 O A 190 2 V2 40% Conversion

C.;H_-,Hg0SCH_-\( 2‘71)

0 23 (CH;,SO_',)2Zn(2%) A I90 10 7% Conversion 24 CH“SO_-,H(2"/r) A 190 6 V2 21% Conversion 25 CH=.SO;,H(2‘7¢)+ A 190 6 V2 24% Conversion LiC1( 1%) 26 C“F_~,CO2H(2%) A 190 40 53% Conversion 27 CF_-,SO_-,H(2‘7') A 190"" 4 Soluble Polymer 28 Cl_-,CCO,H(2%) A 190 8 30% Conversion 29 n-C_-,F7CO-,H(2“/l) A 150-155 25 15% Conversion 30 n-C7F|.-,CO2H(2%) A 190 13 36% Conversion 31 P105091) A 190 26 63% Conversion, [1;] = 0.24 32 polyphosphoric A 190 23 47% Conversion. acid (2%) [1)] = 0.55 33 polyphosphoric C 190 24 43% Conversion ’ acid (2%) 30 60% Conversion. [1;] = 0.15 34 polyphosphoric C 190 24 15% Conversion acid (2%) + LiCl (2%) 35 KNCS(2%) A 190 25 40% Conversion, [1)] = 0.25 36 picric acid(2%) A 190 10 Soluble Polymer 37 ClSO;,H A 190 6 Soluble Polymer 38"’ (CFuSOnhHg (2%) CuH“ 200 24 Soluble Polymer (90%) “”Derivatized to l(CF;,CH,O),PN_'( HC4F,.CH-_.O)-,PN] by reaction with an equimolar mixture of CFuCH2ONa and HCJRCHgONm [17] 30° acetone = 1.0 dl/g. Calcd: C, 23.5; H. 1.7; C1, 0.0. Found: C, 22.2; H, 1.5; CI. 0.1. ‘"‘NaHgln and Na=Hgl| formed in situ. l"Added 1 1 hours after addition of H312. Gelled polymer formed 10% hours a?er addition of Nul. ""Reaction heated 18 hours at 150° C prior to heating to re?ux. "'Polyrnerization conducted in sealed tube under pressure.

EXAMPLES 39-42 - EXAMPLES .43-50 The procedure of Example 1 was followed using the The procedure of Example 1 was followed without indicated monomer(s) and (CH3SO3l-lg)2O (2% on 45 any solvent. Polymerizations of Examples 43-50 were monomer) as catalyst and 1,2-Cl2C6l-l4-C61-15NO2 conducted in a sealed evacuated pyrex tube. (2w/ 1w) as solvents (50% concentration) at 190° C.

Monomer Polymerization Ex. (% by weight) Time (Hours) Remarks gcl-lPNh (CI-EPN ), 39 25 25 4 27% Conversion, [1;] = 0.10 40"" 25 25 1 11/.» 46% Conversion. [1)] = 0.07 41 0 _ 50 43 19% Conversion 42 30 15 1 1% 40% Conversion + 5% mixture of (Cl2PN)5v (CI2PN)t1 ""LiC1(2%) present with the (CHnSORHghO catalyst.

Catalyst (weight % on Polymerization Ex. monomer) Conditions Remarks ._.;C_ is. 43 None 217 3 No high polymer 44 (CF_-,S0;,),l-lg(3%) 230-240 3 Gelled polymer 45 (CFaSOn)-¢Hg(0.5%) 190 5 Soluble polymer 4,005,171 » 9 ‘10

-continued ' Catalyst (weight % on ‘Polymerization Ex. monomer) Conditions ‘ Remarks

. a. . . r‘ . 46 CFnSOnAg(l%) I80 3 Soluble polymer 47 HgCl,(l%) 250 8 24% Conversion, in] "M "=0.46 dl/g 48 HgBr,( 1%) 250 8 29% Conversion, ‘ ‘ [1;] H“ "=0.s2 dl/g 49 RC] 190 - 24 No high polymer 50 polyphosphoric(l%) I90 20 Soluble polymer

" chromato‘ra h was indicative of a si ni?cant chan e EXAMPLE 5: 15 in (Cl2PN)3g concentration.p y The mixtureg - was added gto A l-liter ?ask was charged undera nitrogen atmo additional (Cl2PN)_-, (14.0 g) and o-dichlorobenzene sphere with (Cl2PN)3 (450g), o-dichlorobenzene (50 and heated at gentle re?ux (Ca.190° C) for 4 hours. g), and polyphosphoric acid (3.0 g,.Matheson Coleman Soluble polymer (33% conversion) was formed which & BelI Company). The mixture was heated with good had an intrinsic viscosity ofO. 10 dl/g (benzene, 30° C). agitation 1 hour at l50°-l70° C and then at about 195° 20 C for 45 hours to give a very viscous mixture. Unre- - EXAMPLE 55 acted (Cl2PN)3 was removed by extracting twice with Preparation of a Poly(chloro-tri?uoroacetoxy) 500 ml dry heptane, and then by stirring overnight at Cyclophosphazene 40° C with 500 ml dry‘ petroleum ether. Solvent was To a solution of (Cl2PN)3 (2.5 g, 7.19 mmol) in dry decanted off and the [ClzPNln .polymer (184 g, 41% tetrahydrofuran (‘50 ml) was added, with good stirring yield), which had an intrinsic viscosity of 0.9 dl/g (ben under nitrogen, silver trifluoroacetate ( 5.0 g, 22.6 zene, 30° C), was dissolved in 500ml dry benzene. This polymer solution was reacted with an equimolar mix mmol). The reaction'was covered with ‘aluminum foil, stirred‘ 18 hours at'room temperature and re?uxed¢4 ture of CF3Cl-l-2ONa' and>HCF2C3F6CH2ONa in tetrahy~ hours‘. The ‘mixture was cooled, centrifuged, liquor drofuran for 1 day at room temperature to give, after _30 removed, andsolids reslurred with tetrahydrofuran (40 purification, an elastomeric po1y(?uoroalkoxyphos ml) .and centrifuged. The combined clear liquor was phazene) copolymer with an inrinsic viscosity. 1.1 dl/g evaporated under vacuum and then dried to constant in acetone (30° C) and a chlorine content of 0.03%. weight under high vacuum. A whitish semi-solid mix EXAMPLES 52~53 35 ture [4.1 g, theory for (Cl)_-,(CF3CO2)3P3N3 is 4.19 glwas obtained. The tetrahydrofuran insoluble solids Polymerization of (Cl2PN)3 Using Phosphazene were washed with acetone and dried to give 3.25 g. Catalyst ~ . Further treatment of this solid with 15% HNO3 (60 ml) Example 52: Via (CIZPNL; (CF3CO2Ag is insoluble in this acid) followed by wash The phosphazene catalyst was prepared by reaction, 40 ing with water and methanol gave, after vacuum drying, under dry nitrogen, of (Cl2PN)3 (3.0 g), (Cl-l3S031-1g 3.14 g (theory = 3.24 g for AgCl). The soluble semi );O (0.5 g), in nitrobenzene (7.5 g) for 4 hours at 135° solid showed several signi?cant. volatile components in C. The mixture was cooled to room temperature and vapor-phase-liquid chromatography indicative of a insoluble solids removed by centrifuging. An aliquot mixture of poly(chloro-tri?uoroacetoxy) cyclophos (4.0 g) of the clear yellow liquor was added to (Cl2PN )3 45 phazenes. (13.8 g) and 1,2-Cl2C6H4/C61-l5NO2 (2w/1w, 12.2 g) EXAMPLE 56 which was polymerized under nitrogen for 6 léhours at 190° C. The [Cl2PN],I polymer which was produced Preparation of (CI-1350311920 (53% yield by vapor-phase-liquid chromatography) A ?ask was charged with methanol (500 ml), HgO had an intrinsic viscosity of 0.40 dl/g (benzene, 30° C). (108 g, 0.50 mol); and CH3SO3H ( 101 g, 0.57 mol) and stirred well under re?ux for 2 hours. Methanol ( 150 EXAMPLE 53: Via (Cl2PN)4 ml) was removed by‘ distillation and benzene (200 ml) The phosphazene catalyst was prepared by reaction, was added. The mixture was concentrated to about ‘1% under dry nitrogen, of (C12PN)4 (3.0 g, 6.5 mmol), the volume and a mixture of isopropyl alcohol ( 150 m1) CFaCOgAg (4.0 g, 18.0 mmol) in nitrobenzene (18 g) 55 and benzene (250 ml) was added. The mixture was for 2 hours at 75° C. The immobile mass was shaken cooled, solid ?ltered off and washed with isopropyl with 1,2-Cl2Cal-14 (36 g) and solids removed by subse alcohol-benzene (1v/ 1v) and vacuum dried at 130° C quent centrifuging. An aliguot (7.5 g) of the clear light for 18 hours. The product ( 141 g, 93% yield) was ob Iyellow solution was added Cl2PN)3( 15 g) and 1,2 tained as a whitish solid. Anal. ‘Calcd. for (Cl-l3SO3l-lg Cl2C6H4/CBH5NO2 (2w/1W, 7.5 g) which was polymer 60 )2(): C, 4.0; H, 1.0; S, 10.5 Found: C, 4.1; H, 1.0; S, ized under nitrogen for 6 hours at 190° C. The 10.7. Anal. Calcd. for (Cl-1380311920: C, 6.1; H, 1.5; [Cl2PN1? polymer which was produced (29% yield) S, 16.4. . had an intrinsic viscosity of 0.22 dl/g (benzene 30° C). We claim: EXAMPLE 54 1. A process for the preparation of soluble polyhalo 65 phosphazene polymer consisting essentially of recur A mixture of (CH3SO3HghO (0.3 g), (C12PN)3 (1.0 ring structural units represented by the formula g), and nitrobenzene (5.0 g) was heated under nitrogen [X2PN] and having an intrinsic viscosity of about 0.01 with stirring at 135° C for 2 hours. Vapor-phaseJiquid to about 3.0 dl/g (benzene, 30° C), said polymer being 4,005,171 11 12 soluble in benzene, toluene, chlorobenzene, and di and the metal of the salt is a metal selected from chlorobenzene, which comprises heating at least one the group consisting of Li, Na, K, Mg, Ba, Hg, Ag, cyclic oligomer represented by the formula (X-ZPN)", Mn and Zn; Group B consists of at least one acid selected from where m is 3-7, wherein X is a halogen selected from 5 the group consisting of acids represented by the the group consisting of F, Cl, and Br and all of the X’s following formulae: are not required to be identical, at temperatures of about 130° C to 220° C in the presence of an effective O_ amount of at least one catalyst which is selected from OH OH the group consisting of A and B and mixtures thereof 10 I wherein: Group A consists of metallic or quaternary ammo OH OH nium salts in which the anion is represented by one of the following formulae: H3PO4 and its dehydrated derivatives and wherein R, and R2 are as de?ned in Group A. 2. The process of claim 1 wherein the polymerization is carried out in a solvent. 3. The process of claim 2 in which the solvent is selected from the group consisting of benzene, chloro 20 benzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, and mixtures thereof. 4. The process of claim 1 which including in addition the step of heating the reactants and catalyst to a tem perature significantly below the polymerization tern~ where RI is a monovalent member selected from 25 perature prior to raising the temperature to effect poly the group consisting of polyhaloalkyl, where the merization. halogen is F, Cl or mixtures thereof, perfluoroaryl 5. The process of claim 1 in which a dehydrated and perchloroaryl; R2 is a monovalent member derivative of H3PO4 is employed as catalyst. selected from the group consisting of F, Cl, lower 6. The process of claim 1 in which the polymerization 30 is effected in the presence of an alkali or alkaline earth alkyl (C1-C5), aryl, substituted alkyl and substi chloride or bromide and the polymerization catalyst is tuted aryl with the proviso that R2 is not halogen "31:04 or dehydrated derivative of H3PO4. when bonded to 7. The process of claim 1 wherein the concentration of catalyst is between 0.1% and 20%. 35 8. The process of claim 1 wherein the initial concen tration of monomer is between 5 and 95%. 9. The process of claim 1 wherein the polymerization is effected in the temperature range from 130° C to 220° C. 40 *****

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