PROCESS FOR PREPARING POLYPHOSPHAZENE COPOLYMERS CONTAINING -OZ(OR)M-1 SUBSTITUENTS BONDED TO THE PHOSPHORUS ATOM

Abstract: Polyphosphazene copolymers are prepared which con­ tain randomly distributed units represented by the formulas: wherein X is a -OX(OR) m-1 radical in which Z is B +++ , P +++ , Si ++++ or Ti ++++ , m is the valence of Z, R is a branched, straight chain or cyclic alkyl group containing from 1 to 12 carbon atoms or mixtures thereof and wherein X′ is selected from the group consisting of substituted and unsubstituted alkoxy, aryloxy, amino and mercapto groups. The alkyl groups may vary in carbon chain length or structure within the radical as they may all be the same. The copolymers may contain from about 0.1 to about 55 mole percent of the X substituent and from about 45 to about 99.9 mole percent of the X′ substituent. The copolymers can be utilized to form protective films and may also be utilized in applications such as for moldings, coatings, and the like.

Description: POLYPHOSPHAZENE COPOLYMERS CONTAINING -OZ(OR)m-1 SUBSTITUENTS BONDED TO THE PHOSPHORUS ATOM BACKGROUND OF THE INVENTION This invention relates to polyphosphazene copolymers containing repeating -[P = N]- units in the polymer chain in which -OZ(OR)m-1 substituents (defined below) and other compatible substituents are attached to the phosphorus atom. More particularly, the invention relates to polyphosphazene copolymers containing -OZ(OR)1 1 substituents and substituted or unsubstituted alkoxy, aryloxy, amino and mercapto groups. Polyphosphazene polymers containing repeating -[P = N-]- units in which various alkoxy, substituted alkoxy, aryloxy and substituted aryloxy groups are attached to the phosphorus atom and their method of preparation are described in the prior art as illustrated in the publication "Phosphorus-Nitrogen Compounds", Academic Press, New York, New York 1972 by H. R. Allcock and "Poly(Organophosphazenes)", Chemtech, September 19, 1975 by H. R. Allcock and in such U.S. Patents as 3,515,688; 3,702,833; and 3,856,712. SUMMARY OF THE INVENTION In accordance with this invention, novel polyphosphazene copolymers containing a -OZ(OR)m-1 substituent and a substituted or unsubstituted alkoxy, aryloxy, amino or mercapto substituent are prepared. The copolymers of the Invention contain ran20my distributed repeatinq units represented by the formulas: EMI2.1 wherein X is a -OZ(OR) 1 radical in which Z is B+++, p , 5i , or Ti , m is the valence of Z, R is a branched, straight chain or cyclic alkyl group containing from 1 to 12 carbon atoms and wherein X' is selected from the group consisting of substituted or unsubstituted alkoxy, aryloxy, amino and mercapto radicals, and wherein the polymer can contain from 20 to 50,000 of such units. X substituent radicals represented by the -OZ(OR)m 1 radical include -OB(OR)2, -OP(OR)2, -OSi(OR)3 and -OTi(OR)3 wherein R is as defined above. In the copolymer units represented by the above formulas, all X substituent groups may be the same or they may be mixed and all X' substituent groups may be the same or mixed. In the mixtures, the X substituent groups may be mixtures of different OZ(OR)m1 groups and the X' substituent groups may be mixtures of different alkoxy, aryloxy, amino or mercapto groups. The specific proportion of X to X' substituent groups incorporated in the copolymers of the invention may vary considerably depending upon the particular end use for which the copolymer is intended, chemical and physical properties desired, and the degree of crosslinking desired. In general, the copolymers may contain from about 0.1 to about 55 mole percent of the X substituent and from about 45 to about 99.9 mole percent of the X' substituent. The preferred range is from about 0.5 to about 20 mole percent of the X substituent and from about 80 to about 99.5 mole percent of the X' substituent. For applications such as moldings, coatings, foams and the like, the copolymer should contain at least ten (10) mole percent by weight of the X substituent. The copolymers are prepared by reacting a poly(dichlorophosphazene) having the formula -(NPCl2)n-, in which n is from 20 to 50,000, with a mixture of a Z(OR) m compound, wherein Z and m and R are as defined above, and a substituted or unsubstituted aliphatic alcohol, aromatic alcohol, amino compound or mercaptan compound in the presence of a tertiary amine. The general reaction of the Z(OR) m compound with the poly(dichlorophosphazene) in the presence of the tertiary amine is set out below; the remainder of the reaction with a substituted or unsubstituted aliphatic or aromatic alcohol, an amino compound or mercaptan compound is defined in the prior art. EMI3.1 Illustrative of reactions using specific Z(OR)m compounds to form copolymers of the invention are the following: EMI3.2 The above reactions are illustrative only and show only one chlorine substitution. It is understood that the other chlorine atom may be replaced by one of the other substituent groups (e.g., alkoxy, aryloxy, etc.) defined above and hereinafter. The copolymers can be used to prepare films and may be utilized in applications such as moldings and coatings. They also exhibit a crosslinking reaction at room temperature in the presence of water. DETAILED DESCRIPTION OF THE INVENTION As indicated above, the polyphosphazene copolymers of this invention are prepared by reacting a poly(dichloro phosphazene) polymer having the structure -(NPCl2)n-, in which n is from 20 to 50,000 with a mixture of a Z(OR) m compound and a substituted or unsubstituted aliphatic alcohol, aromatic alcohol, amino compound or mercaptan compound in the presence of a tertiary amine. I. The Poly(Dichlorophosphazene) Polymer Poly(dichlorophosphazene) polymers which are employed as starting materials in the process of this invention are well known in the art as illcstrated in U.S. Patents 3,370,020; 4,005,171; and 4,055,520 and the aforementioned publications of H. R. Allcock, the disclosures of which are incorporated herein by reference. These polymers have the general formula (NPC12)n . in which n may range from 20 to 50,000 or more. As described in the aforementioned references, the polymers are in general prepared by the thermal polymerization of cyclic oligomers having the formula -(NPC2) , in which n is an integer of from 3 to 7, with the cyclic trimer and tetramer often comprising up to 90% of the oligomers. The specific conditions of temperature, pressure and time employed in the thermal polymerization of the cyclic oligomers can vary considerably depending on whether or not the polymerization is catalyzed. Thus, temperatures may range from about 1300C to about 300DC, pressures may range from a vacuum of less than about 10 1 Torr to superatmospheric and times may range from 30 minutes to about 48 hours. A preferred process for preparing the poly (dichlorophosphazene) polymers used in the process of this invention is described in the aforementioned incorporated U.S. Patent 4,005,171. II. The -OZ(OR)m-1 Substituent (i.e., The X Substituent) As indicated, the OZ(OR)m-1 substituent is a radical in which Z is B+++, P+++, Si++++ , or Ti++++, in is the valence of Z and R is a branched, straight chain or cyclic alkyl group containing 1 to 12 carbon atoms. As indicated above, radicals represented by the radical include -OB(OR)2, -OP(OR)2, -OSi(OR)3 and -OTi(OR)3. These radicals may be derived from alkyl borates, alkyiphosphites, tetraalkyl orthosilicates, and tetraalkyl titanates. The alkyl borates which may be employed in forming the copolymers of the invention are the trialkyl borates of the general formla B(OR)3 where R may be a branched, straight chain or cyclic alkyl radical and contain from 1 to 12 carbon stoms. The alkyl groups may vary from one site to another in the borate or the alkyl groups may all be identical in the borate. ,Illustrative examples of alkyl borates which may be suitably employed are trimethyl borate, triethyl borate, tripropyl borate and the like, tris-2-ethyl hexyl borate and the like, and tris-cyclohexyl borate and the like. Alkylphosphites which may be employed in forming the copolyners of the invention are trialkylphosphites having the general formula P(OR)) where R may be a branched, straight chain or cyclic alkyl radical containing from 1 to 12 carbon atoms. The alkyl radicals may vary from one site to another in the phosphite or may be identical at each site. illustrative examples of alkylphosphites which may be suitably employed are trimethyl phosphite, triethyl phosphite, tripropyl phosphite and the like. Tetraalkyl orthosilicates which may be employed in forming the copolymers of the invention are the tetraalkyl orthosilicates of the general formula Si(OR)4 where R may be a branched, straight chain or cyclic alkyl radical with from 1 to 12 carbon atoms. The alkyl radicals may vary from one site to another in the silicate or may be identical at each site. Illustrative examples of the tetraalkyl orthosilicates which may be suitably employed are tetraethyl orthosilicate, tetramethyl orthosilicate, tetrabutyl orthosilicate, tetraoctyl orthosilicate, and the like. A preferred tetraalkyl orthosilicate is tetraethyl orthosilicate. It should be noted here that U.S. Patent 3,702,833 referred to above appears to disclose polyphosphazene terpolymers which contain -OSi(OR1)2R'1 groups. However, copolymers of this invention which contain -OSitOR)3 groups appear to differ in structure from the terpolymers of the patent in that the present copolymers contain the silicate group and other substituent group attached to the same phosphorus atom. Moreover, the patent describes a complicated three-step process for forming the terpolymer which involves first hydrolyzing the polydichlorophosphazenes to form a LNPCl2-NP(OH2)3n copolymer, then reacting that copolymer with a mixture of sodium alkoxide and then reacting the resultant product with a HOSi(OR)3 compound. In contrast, the copolymers of this invention are prepared by a simple process which merely involves reacting the polydichlorophosphazene with a mixture of a Si(OR)4 compound and the other substituent forming compound in the presence of a tertiary amine. Tetraalkyl titanates which may be employed in forming the copolymers of the invention are the tetraalkyl titanates of the general formula Ti(OR)4 where R may be a branched, straight chain or cyclic alkyl radical with from 1 to 12 carbon atoms. The alkyl radicals may vary from one site to another i@ the titanate or may be @@@@@@@@@ at cach @@@@ Ill@@@trative examples of the tetraalkyl titanates which may be suitably employed are teaethyl titanate, tetramethyl titanate, tetrabutyl titanate, tetracityl titanate, and the like. A preferred tetraalkyl titanate is tetrabutyl titanate. III. The Alkoxy, Aryloxy, Amino and Mercapto Substituents (i.e., The X' Substituents) As indicated heretofore, the polyphosphazene copolymers of the invention in addition to the -OZ(OR)m-1 substituent group may contain substituted or unsubstituted alkoxy, aryloxy, amino or mercapto groups. The alkoxy groups (substituted or unsubstituted) may be derived from aliphatic alcohols having from l to 20 carbon atoms such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, hexane, dodecanol and the like; fluoroalcohols, especially those represented by the formula Z(CF2)nCH2OH in which Z is hydrogen or fluorine and n is an integer from 1 to 10 as illustrated by trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3,4,4,4-heptafluorobutanol; 2,2,3,3-tetrafluoropropanol, 2,2;3,3,4,4,5,5-octafluoropentanol, 2,2,3,3,4,4, 5,5,6,6,7,7-dodecafuoroheptanol and the like. In instances where it is desired to incorporate mixed X' substituent groups in the copolymers, mixtures of the foregoing alcohols may be employed. The aryloxy groups (substituted or unsubstituted) may be derived from aromatic alcohols including among others phenol; alkylphenols such as cresols, xylenols, p-, o-, and m- ethyl and propyl phenols and the like; halogen-substituted phenols such as p-, o-, and m-chloro and bromo phenols and di- or tri-halogen substituted phenols and the like; and alkoxy-substituted phenols such as 4-methoxyphenol, 4-(n-butoxy) phenol and the like. Mixtures of the foregoing aromatic alcohols may also be employed. The amino groups may be derived from any of the amino compounds heretofore employed in the polyphosphazene polymer art. Thus, the amino groups may be derived from aliphatic primary and secondary amines such as methylamine, ethylamine, dimethylamine, ethylmethylamine and the like and aromatic amines such as those described in U.S. Patent 4,042,561, incorporated herein by reference, as illustrated by aniline, halogen-substituted anilines, alkyl-substituted anilines, alkoxy-substituted anilines and the like. The mercapto groups may be derived from any of the mercaptan compounds heretofore employed in the polyphosphazene polymer art. Thus, for example, the mercaptan compounds described in U.S. Patent 3,974,242 to Lanier et al, incorporated herein by reference, may be utilized. Representative of suitable mercaptan compounds as described in the aforementioned patent are methyl mercaptan and its hor6logs ethyl, propyl, butyl, aryl and hexyl mercaptans, thiophenol, thionaphthols, benzyl mercaptan, cyclohexyl mercaptan and the like. Preferred substituent groups represented by X' are alkoxy, especially fluoroalkoxy, and aryloxy, especially substituted phenols such as halogen-substituted phenols. IV. The Tertiary Amine The use of the tertiary amine minimizes undesirable side reactions and at the same time acts as an effective acid scavenger. Tertiary amines which may be employed in preparing the polymers of the invention are those represented by the general structure: EMI8.1 wherein R'l, R'2, and '3 may each be alkyl containing from 1 to 8 carbon atoms. Thus, for example, the tertiary amine may be a trialkyl amine such as trimethyl- amine, triethylamine, tri-isopropylamine, tri-n-propylamine, tri-isobutylamine, tri-n-butylamine, and the like. In addition, tertiary amines such as pyridine, N,N,N',N'-tetramethylethylene diamine (TMEDA), dipipyridyl ethane, 1,4 diaza bicyclo (2.2.2) octaine (DABCO), Nmethyl pyrolle and N-methyl morpholine can also be utilized. The preferred tertiary amines for use in preparing the polymers of the invention are triethylamine, N,N,N',N'-tetramethylethylene diamine and pyridine. As indicated above, the copolymers of the present invention are prepared by reacting the poly (dichlorophosphazene) polymer and the substituent mixture of the Z(OR) m compound and a substituted or unsubstituted aliphatic alcohol, aromatic alcohol, amino compound or mercaptan compound in the presence of a tertiary amine. The specific reaction conditions and proportion of ingredients employed in preparing these copolymers can vary somewhat depending on factors such as the reactivity of the specific substituent mixtures utilized, the particular tertiary amine employed, and the degree of substitution desired in the finished polymer. In general, reaction temperatures may range from about 25"C to about 2000C and times may range from 3 hours up to 7 days; lower temperatures necessitating longer reaction times and higher temperatures allowing shorter reaction times. These conditions are, of course, utilized in order to obtain the most complete reaction possible, i.e., in order to insure substantially complete conversion of the chlorine atoms in the polymer to the corresponding esters of the substituent mixture. The above reaction is ordinarily carried out in the presence of a solvent The solvent employed in the reaction should be a solvent for the poly(dichlorophosphazene) polymer, the substituent mixture and the tertiary amine. Examples of suitable solvents which may be employed include diglyme, triglyme, tetraglyme, toluene, xylene, cyclohexane, chloroform, dioxane, dioxalene, methylene chloride, tetrachloroethane, and tetrahydrofuran. The amount of solvent employed is not critical and any amount sufficient to solubilize the reaction mixture materials can be employed. In addition, the materials in the reaction zone should be reasonably free of water, most preferably containing 0.01 percent by weight of water or less. The avoidance of water in the reaction system is necessary in order to inhibit the reaction of the available chlorine atoms in the chloropolymer therewith. Also the presence of water yields crosslinks with the X substituent groups of the copolymers of this invention at room temperature and therefore, the absence of water is vital until this reaction is desired. Thus, for example, when the X substituent group of the copolymer is derived from an alkyl borate ri.e., B(OR)3J, the alkyl groups in the borate linkage in the copolymer will react with water to yield BOH on the copolymer. The BOH site will react with other borate linkages to yield B-O-B, the crosslink structure. Copolymers containing X substituents derived from alkyl phosphites, tetraalkyl orthosilicates and tetraalkyl titanates react in similar manner with water. Thus, the alkyl groups in the phosphite linkages react with water (hydrolyze) to yield POH groups which subsequently react with additional POR or POH to give P-O-P crosslinks; the alkyl groups in the silicate linkages react with water to yield SiOH groups which subsequently react with additional SiOR or SiOH to give Si-O-Si crosslinks; and the alkyl groups in the titanate linkages react with water to yield TiOH groups which subsequently react with additional TiOR or TiOH to give Ti-o-Ti crosslinks. This reaction occurs at room temperature. Its rate is controlled by the amount of X substituent and water present. The resulting crosslinked product is readily realized and due to its highly inorganic character, yields improved flame retardant, heat stability and solvent resistance properties. In general, the amount of-the substituent mixture employed in the process should be at least molecularly equivalent to the number of available chlorine atoms in the polymer mixture. However, if desired, an excess of such compounds may be employed in order to insure substantially complete reaction of all the available chlorine atoms. The following examples are submitted for the purpose of further illustrating the nature of the present invention and are not intended as a limitation on the scope thereof. Parts and percentages referred to in the examples are by weight unless otherwise indicated. The following examples (i.e., 1-3) illustrate copolymers of the invention in which the X substituent is -OB(OR)2. rAtIPLE i Preparation of EMI12.1 <tb> <SEP> B(Cs17!2 <tb> <SEP> b <tb> = <SEP> N <SEP> Nt <SEP> Copolymer <tb> <SEP> n <tb> <SEP> O-CH2CF3 <tb> To a 10 ounce beverage bottle was charged 13.13 gms. (44 millimoles) tris-2-ethyl hexyl borate, B(OC8H17)3, 100 cc of dry tetrahydrofuran (hereinafter THF), 12.3 cc (88 millimoles) of triethylamine, 3.2 cc (44 millimoles) of trifluoroethanol, and 30.3 gms. of a 15.3% poly(dichlorophosphazene) polymer in THE (4.64 gms., 40.0 millimoles) having a degree of polymerization of about 2600. After 20 hrs. in a 1200C rotary bath, the reaction was cooled and the triethylamine salt of 2ethyl.hexyl chloride and triethylamine hydrochlorate settled out of solution and-no PCL bonds could be detected by Infrared spectroscopy. A film of this copolymer was cast on a glass plate which was soluble in THE after two weeks exposure to air. After six weeks exposure to air the film was crosslinked as evidenced by its insolubility in THF. A coagulation in hexane gave 2.94 gms. of a tan rubbery material which became hard on standing. An analysis of the crosslinked product gave: C H N P Cl 28.638 5.04% 8.658 14.09* 3.26% It was calculated that this product contained 12.67% triethylamine hydrochloride and 21.42% hydrolyed chloropolymer. The solid polymer when pressed at 1750C under a pressure of 2000 psi formed a smooth, clear continuous film. EXAMPLE 2 Preparation of EMI13.1 <tb> B( <SEP> OCH3)2 <tb> 0 <tb> 1N <SEP> Copolymer <tb> <SEP> n <tb> O-CH2CF3 <tb> The experiment of Example 1 was repeated substituting 4.58 gms. (44 millimoles) of trimethyl borate, B(OCH3)3 for the tris-2-ethyl hexyl borate. The other ingredients and conditions were identical. After methanol washing 3.5 gms. of insoluble products was realized In this example, the trifluoroethanol was added prior to the trimethyl borate. This was necessary as the borate would react too fast and crosslinkage would occur in the reaction vessel with a resulting unusable product. EXAMPLE 3 Preparation of EMI13.2 <tb> <SEP> B(OC8H17)2 <tb> <SEP> 0 <tb> = <SEP> = <SEP> N- <SEP> Copolymer <tb> <SEP> le <SEP> n <tb> <SEP> C6H4 <tb> To a 10 ounce beverage bottle was charged 6.57 gms. (22 millimoles) tris-2-ethyl hexyl borate, B(OC8E17)3, 100 cc of dry alcohol free chloroform, 12.3 cc (88 millimoles) of triethylamine, 8.49 gms. (66 millimoles) of p-chlorophenol, and 42.5 gms. of a 10.93% poly(dichlorophosphazene) polymer in cyclohexane (40.1 millimoles) having a degree of polymerization of about 2600. After 20 hrs. in a 1200C oven, a clear, yellow viscous resulted. After cooling to 250C, triethylamine hydrochloride crystalized out. Infrared spectroscopy showed no PCL band at 600 cm and strong, new bands at 558, 540 and 480 cm The solution was cast and, after drying two days in air, a rubbery, tetrahydrofuran insoluble, film resulted. The following examples (i.e., 4-5) illustrate copolymers of the invention in which the X substituent is -OP(OR)2. EXAMPLE 4 Preparation of EMI14.1 <tb> <SEP> Cm <SEP> 2 <SEP> 3 <tb> <SEP> 0 <tb> <SEP> = <SEP> ±] <SEP> Copo <SEP> lymer <tb> I <SEP> n <SEP> <tb> <SEP> 0 <tb> <SEP> P(0CH3)2 <tb> <SEP> P(OCH3)2 <tb> To a 10 ounce beverage bottle was charged 5.2 cc (44 millimoles) of trimethyl phosphite, P(OCH3)3, 100 cm of dry tetrahydrofuran (hereinafter THF, 12.3 cc (88 millimoles) of triethylamine, 3.2 cc (44,millimoles) of trifluoroethanol, and 35.9 gms. of a 12.B5 THF solution of poly(dichlorophosphazene) (39.9 millimoles) having a degree of polymerization of about 2600. After 68 hours at 800C in a-rotary bath and cooling, no PCL bonds could be detected by Infrared spectroscopy. The THE insoluble chloride salts settled out as needle crystals. The remaining solution was evaporated to yield a hard, brittle film that was insoluble in THF. An analysis of the polymeric product showed the following results: C H N P Cl Actual (8) 18.60 2.12 8.13 19.01 2.54 From this the composition of the film was assumed to be 19.6% hydrolyzed chloropolymer, 9.08 triethylamine methylchloride, 59.0% trifluoroethoxy derivative and 10.4% dimethyl phosphite derivative. This composition has a calculated analysis of: C H N P C1 Calculated(%) 18.56 3.04 8.26 18.89 2.11 EXAMPLE 5 Preparation of EMI15.1 <tb> <SEP> p,C6H4Cl <tb> [P <SEP> = <SEP> N] <SEP> Copolymer <tb> <SEP> 0 <tb> <SEP> P(OCH3)2 <tb> To a 10 ounce beverage bottle was charged 2.60 cc (22 millimoles) of trimethyl phosphite, P(OCH3)3, 100 cc of dry THF, 8.49 grams (66 millimoles) of p-chlorophenol, 12.3 cc (88 millimoles) of triethylamine and 42.7 grams (40.3 millimoles) of a 10.93% cyclohexane solution of poly(dichlorophosphazene) having a degree of polymerization of about 26000. Heating in an oven for 20 hours at 1200C gave a colorless solution with insoluble amine salts. Infrared spectroscopy showed no PCl band at 600 cm 1 and new bands at 543, 512 and 492 cm 1 Casting a film gave a white rubbery film that was insoluble in THF after standing in air after 2 days. The following-examples (i.e., 6-7) illustrate copolymers of the invention in which the X substituent is -OSi(OR)3. EXAMPLE 6 Preparation of oSi(OC2H5)3)2PN+, +(OSi(OC2H5)3) (CF3CH2O)PN]-, (CF3CH20)2PNs Copolymer To a 10 ounce beverage bottle was charged 9.17 gms. (44 millimoles; 9.82 cc) of tetraethyl orthosilicate, Si(OC2H5)4 100 cc of dry tetrahydrofuran (hereinafter THF), 12.3 cc (88 millimoles) of triethylamine, 3.2 cc (44 millimoles) of trifluoroethanol, and 36.0 gms. of a 12.85% THF solution of poly(dichlorophosphazene) 4.626 gms., (39.9 millimoles having a degree of polymerization of about 2600. After 20 hours in a 80 C rotary bath and cooling, no PCl bonds could be detected by Infrared spectroscopy. The THF insoluble chloride salts (triethylamine hydrochloride and tetraethylamine chloride) settled out as crystals. The remaining solution was evaporated to yield a hard, brittle film that was insoluble in THE. An analysis of the polymeric product showed the following results: C H N P C1 Calculated (%) 18.33 2.22 7.08 15.65 2.54 Actual (%) 18.33 2.22 8.16 15.16 2.54 The calculated results were based on 72.3% [(CF3CH2O)2PN]n, 4.20% [Cl2PN]n, 21.4% [(OSi(OC2H5)3)2PN]n and 6.9% [(HO2)PN]n which were assumed products although it is recognized that the actual products represent mixtures thereof, specifically those identified above. The mole percent for the above assumed products from trifluoroethanol and tetraethyl orthosilicate were: Weight % Mole % 21.4 15.7 [(OSi(OC2H5)3)2PN]x 72.3 59.6 ((CF3CH2O )2PN]x 4.2 7.3 (Cl2PN)x 6.9 17.5 [(XO)2PN]x EXAMPLE 7 Preparation of XOSi(OC2H5)3)2PNk, +(OSi(OC2H5)3) (ClC6H4O)PN 4(ClC6H4O) 2PN Copolymer To a 10 ounce beverage bottle was charged 9.17 gms. (44 millimoles; 9.82 cc) of tetraethyl orthosilicate, Si(OC2H5)4 100 cc of dry, alcohol free chloroform, 12.3 cc (88 millimoles) of triethylamine, 5.66 gms. (44 Willinoles) of p-chlorophenol, and 55.6 gms. of 8.35% cycloWexane solution of poly(dichlorophosphazene), (40.1 millimoles) having a degree of polymerization of about 2600. After 20 hours in a 1200C oven, a viscous yellow 91utlon with crystals of amino salts was obtained. InfrBtea Spectroscopy showed no PCL bonds at 600 and strong, new bonds at 568, 540 and 478 cm 1 A solution was cast and, after drying three days in the air, a rubbery, tetrahydrofuran insoluble, film resulted. The following examples (i.e., 8-9) illustrate copolymers of the invention in which the X substituent is -O@i(OR)3. EXAMPLE 8 Preparation of NP(OCH2CF3) (OTi(OC4H9)3] Copolymer To a 10 ounce beverage bottle was charged 14.97 gms (44 millimoles; 15.06 cc) of tetrabutyl titanate, Ti(OC4H9)4, 100 cc of dry tetrahydrofuran (hereinafter THF), 12,3 cc (88 millimoles) of triethylamine, 3.2 cc (44 millimoles) of trifluoroethanol, and 35.9 gms of a 12.85% THF solution of poly(dichlorophosphazene) (39.9 millimoles) having a degree of polymeriation of about 2600. After 68 hours at 800C in a rotary bath and cooling, no PCL bonds could be detected by Infrared spectroscopy. The THE insoluble chloride salts settled out as needle crystals. The remaining solution was evaporated to yield a hard, brittle film that was insoluble in THE. EXA:APLE 9 Preparation of [NP(OH4C6-Cl-p)(OTi(OC4H9)3) Copolymer To a 10 ounce beverage bottle was charged 7.53 cc (22 millimoles) of tetrabutyl titanate, Ti(oC4Hg)4, 100 cc of alcohol free chloroform, 8.49 gms (88 millimoles) of p-chlorophenol, 12.3 cc (88 millimoles) of triethylamine and 42.3 gms. of a 10.93% cyclohexane solution of poly(dichlorophosphazene) (39.9 millimoles) having a degree of polymerization of about 2600. Heating the mixture for 20 hours at 1200C in an oven produced a solution with insoluble amine salts. I.R. showed no P- Cl bonds at 600 cm 1 and new bonds at 500+500 cm-1. A film cast from the solution was rubbery in nature and was insoluble in THE after standing for 2 days in air. Elemental analysis of the film showed the following results: C H N P Cl Actual (%) 38.55 5.78 5.01 6.37 20.05 Calculated*(%) 38.59 5.14 5.86 6.26 19.93 *Based on a composition consisting of 29.8 percent triethylemine, 3.8 percent chloropolymer, 42.1 percent p-chlorophenol derivative and 10.7 percent titanate derivative.

Claims: Claims: 1. A polyphosphazene copolymer containing randomly distributed units represented by the formulas: EMI19.1 wherein X is a -OZ(OR)m-l radical in which Z is B++s, P+++, Si++++ or Ti++++, m is the valence of Z and R is a branched, straight chain or cyclic alkyl group containing from 1 to 12 carbon atoms; wherein X' is selected from the group consisting of substituted and unsubstituted- alkoxy, aryloxy, amino and mercapto groups and wherein said copolymer contains from 20 to 50,000 of said units. 2. The copolymer of claim 1 wherein the X substituent is between about 0.1 and about 55 mole percent and the X' substituent is between about 45 and 99.9 mole percent. 3. The copolymer of claim I wherein X is -OB(OR)2. 4. The copolymer of claim 3 wherein the X substituent is -OB(OC8E17)2 and the X' substituent is -OCH2CF3. 5. The copolymer of claim 3 wherein the X substituent is -OB(OC8H17) and the X' substituent is -OC6H4Cl. 6. The copolymer of claim 3 wherein the X substituent is -OB(OCH3)2 and the X' substituent is OCH2CF3 ' 7. The copolymer of claim 1 wherein X is -OP(OR)2. 8. The copolymer of claim 7 wherein X is -OP(OCH3)2 and X' is -OCH2CF3. 9. The copolymer of claim 7 wherein X is -OP(OCH3)2 and X' is -OC6H4Cl. 10. The copolymer of claim 1 wherein X is -OSi(OR)3. 11. The copolymer of claim 10 wherein X is -OSi(oc2H5)3 and X' is -OCH2CF3. 12. The copolymer of claim 10 wherein X is -OSi(OC2H5)3 and X' is -OC6H4Cl. 13. The copolymer of claim 1 wherein X is -OTi(OR)3. 14. The copolymer of claim 13 wherein X is -OTi(OC4H9)3 and X' is -OCH2CF3. 15. The copolymer of claim 13 wherein X is -OTi(OC4Hg)3 and X is p-ClC6H4O-. 16. A method of preparing polyphosphazene copolymers containing randomly distributed units represented by the formulas: EMI20.1 wherein X is a -OZ(OR)m-1 radical in which Z is B+++, P+++, Si++++ or Ti++++, m is the valence of Z and R is branched, straight chain or cyclic alkyl radical containing from 1 to 12 carbon atoms or mixtures thereof, and wherein X' is selected from the group consisting of substituted and unsubstituted alkoxy, aryloxy, amino or mercapto groups and mixtures thereof; said method comprising reacting a poly(dichlorophosphazene) polymer having the formula -(NPCl2)n-, wherein n is from 20 to 50,000, with a mixture consisting of a Z(OR) m compound where Z, m and R are as defined above and a substituted or unsubstituted aliphatic or aromatic alcohol, an amino compound or a mercapto compound in the presence of a tertiary amine. 17. The method of claim 16 wherein said Z(OR) compound is a trialkyl borate represented by the m formula 3(OR)3. 18. The method-of claim 16 wherein said mixture consists of a trialkftl borate and an aliphatic or aromatic alcohol. 19. The method of claim 18 where said mixture consists of tris-2-ethyl hexyl borate and trifluoroethanol. 20. The method of claim 8 wherein said mixture consists of trimethyl borate and trifluoroethanol. 21. The method of claim 18 wherein said mixture consists of tris-2-ethyl hexyl borate and pchlorophenol. 22. The method of claim 16 wherein said Z(OR) m compound is a trialkyl phosphite represented by the formula P(OR)3. 23. The method of claim 16 wherein said mixture consists of a trialkyl phosphite and an aliphatic or aromatic alcohol. 24. The method of claim 23 wherein said mixture consists of trimethyl phosphite and trifluoroethanol. 25. The method of claim 23 wherein said mixture consists of trimethyl phosphite and p-chlorophenol. 26. The method of claim 16 wherein said Z(OR) m compound is a tetraalkyl orthosilicate represented by the formula Si(OR)4. 27. The method of claim 16 wherein said mixture consists of a tetraalkyl orthosilicate and an aliphatic or aromatic alcohol. 28. The method of claim 27 wherein said mixture consists of tetraethyl orthosilicate and trifluoroethanol. 29. The method of claim 27 wherein said mixture consists of tetraethyl orthosilicate and pchlorophenol. 30. The method of claim 16 wherein said Z(OR) m compound is a tetraalkyl titanate represented by the formula Ti(OR)4. 31. The method of claim 16 wherein said mixture consists of a tetraalkyl titanate and an aliphatic or aromatic alcohol. 32. The method of claim 31 wherein said mixture consists of tetrabutyl titanate and trifluoroethanol. 33. The method of claim 31 wherein said mixture consists of tetrabutyl titanate and p-chlorophenol. 34. The method of claim 16 wherein said tertiary amine is triethylamine.

Inventors: HALASA, ADEL FARHAN, HERGENROTHER, WILLIAM LEE
Applicants: THE FIRESTONE TIRE & RUBBER COMPANY
Application year: 1979
Main classification: C08G79
IPC codes: C08L85, C08G79