FIBERS FORMED OF BLENDS OF ETHERIC PHOSPHAZENE POLYMERS AND METAL OXIDES AND THE METHOD OF THEIR FORMATION

Abstract: The invention provides fibers formed of a blend of metal oxide, such as titanium or zirconium oxide, with etheric phosphazene. The invention optionally contains salt for antistatic fibers. The composition of the invention is formed by preparing solutions of etheric phosphazene and inorganic alkoxides, such as titanium isopropoxide. The solutions are then formed into fibers and cured at room temperature or with moderate heating. Fibers produced can be extensible, tough, hard, flexible, or brittle. They are multicomponent blends of the titanium or zirconium oxide and phosphazene. The composite may be doped with low lattice energy salts to form conductive fibers.

Description: FIBERS FORKED OF BLENDS OF ETHERIC PHOSPHAZENE POLYMERS AND METAL OXIDES AND THE METHOD OF THEIR FORMATION Technical Field This invention relates to composite fiber materials that are blends of etheric phosphazenes and metal oxides. Specifically, this invention relates to fibers comprising an etheric phosphazene blended with a metal oxide formed in a sol-gel process by hydrolysis and condensation of a metal alkoxide. Background Art Composites of Etheric Phosphazenes and metal oxides have been proposed in copending and coassigned U.S. Serial No. 329,216 - Coltrain et al filed March 27, 1989. The formation of films Of the composite materials, possibly with antistatic properties, iε proposed in Coltrain et al. Phosphazene polymers have also been suggested for use where higher temperature polymers are desirable such as in gaskets for engines, in friction surfaces, and as membranes for separations of gases or liquids. Such uses would not require the addition of salt as the gasket, or friction materials would not need to be conductive or have antistatic properties. In use as a gasket material, membranes, or friction surface, aε well as in polymer film antistatic surface coats, it is advantageous that the polymer has good abrasion resistance, hardness, and strength. Therefore, it would be desirable if these properties could be improved for phosphazene polymers. It haε been disclosed in U.S. Patent 4,218,556 - Hergenrother et al that chlorophosphazene polymers can be cross-linked with tetraalkylorthoεilicate. Great Britain Patent 1,052,388 - Emblem et al discloses that phosphazene trimeric materials may be cross—linked with similar silicates. However, these cross—linked materials have the disadvantage that they are difficult and expensive to make and are not believed to be abrasion-resistant or tough. U.S. Patent 4,026,839 - Dieck et al discloses polyphosphazene polymer and silicone rubber blends that are fire retardant and may form foams. U.S. Patent 4,6668,762 - Ogata and U.S. Patent 3,304,270 - Dickerson also disclose silicon phosphorus containing polymer compositions. It has been disclosed in Exarhos et al, "31P NMR Studies of Aqueous Colloidal Dispersions Stabilized by Polyphosphazene Adsorption", J. Am. Ceram. SQ - , 71 (9) C-406-C-407 (1988), and Exarhos et al "Molecular Spectroscopic Characterization of Binding Interactions in Phosphazene Stabilized Alumina Dispersions", October 1987, presented at the Materials Research Society 23rd University Conference on Ceramic Science held in Seattle, Washington, August 31, 1987, that polyphosphazenes can be utilized to stabilize alumina dispersions. In the process disclosed in the Exarhoε et al articles, a small amount of polyphosphazene iε mixed with a large amount of large (0.4 micron diameter) aluminum particles. The purpose of the Exarhoε et al processing is to form densified ceramic materials by utilizing polyphosphazene aε a binder. There remains a need for phosphazene polymer fibers that have improved properties of cost, ease " of formation, strength, and toughness. Flame-retardant behavior, biocompatibility, transparency, and dissipation of static charge in phosphazene fiber materials also iε desirable. Polyphosphazene antistatic compositions recently have been proposed in copending and coassigned Application Serial No. 087,480 filed August 20, 1987, by Chen et al. In the copending application polyphoεphazene iε combined with a salt in order to form a conductive composition. This composition has been suggested for use in photographic antistatic layers. While a satisfactory antistatic composition, the material is somewhat tacky and not altogether suitable as an outer coating. Cyclic phosphazenes have also been disclosed for antistatic layers in Japanese Application 129882 - Koπiεhiroku published December 11, 1987. Disclosure of Invention The invention provides fibers that are multicomponent blend of metal oxide, such aε titaniurc oxide or zirconium oxide, with an etheric phosphazene . polymer. The formation of fibers from etheric phosphazenes is significant because these polymers by themselves are amorphous gums that flow at room temperature. The multicomponent blend is produced by a sol-gel process involving the hydrolysis and condensation of a metal alkoxide. The invention fibers optionally contain salt for blendε utilized in forming conductive fiberε. The preferred compositions of the invention are formed by preparing solutions of phosphazene and inorganic monomers, such as titanium isopropoxide, and optionally a salt. The solutions are then extruded or drawn into fibers and cured at room temperature or with moderate heating. There are no covalent cross-links between the phosphazene and the metal oxide. It is also within the invention to form the blends with other metal precursors, ' rather than titanium and zirconium, such as tantalum, silicon, lead, phosphorus, aluminum, boron, tin, iron, copper, lanthanum, germanium, yttrium, or indium. Barium oxide and magnesium oxide mixtures with the above metal oxides also may be utilized in the invention. Modes For Carrying Out the Invention The invention has numerous advantages over other metal oxide and polymer systems and other non metal oxide blended phoεphazene . It is unexpected that an easily formed multicomponent blend of materials produces a strong, fibrous phosphazene material, The invention iε easy to perform in that the two materials are merely blended, not chemically reacted, prior to extrusion. Therefore, there are no difficult to control reactions taking place. The materials of the invention form a fiber that may be handled' without tackiness. The materials make a strong conductive antistatic fiber by addition of a salt. These and other advantages of the invention will be apparent from the description that follows. A preferred method of the invention generally iε carried out by dissolving an etheric phosphazene material in a solvent, such as alcohol, with stirring. Into the stirred solution of polyphosphazene and alcohol is added a metal oxide precursor, such as titanium isopropoxide. Hydrolysis of the solution iε carried out by atmospheric moisture, although acidic water, such as dilute HC1, can also be added. The solution iε then extruded or drawn into- fibers and cured at a temperature of up to about 200 β C. Any suitable polyphosphazene may be utilized in forming the blends of the invention. A preferred composition is an etheric phosphazene comprising repeating units of Formula (I): ^ ? 5 - ^P^ In the above formula, x and y represent molar percentages, with x being 80 to 100"%,, and y being 0 to 20%. R, and e each independently represents the formula ~^2~^ ^- ~ R 3 wnere n is 1 to 50 and R 3 iε hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloakenyl, haloalkynyl, phenyl, substituted aromatic, amine, or thio of from 1 to 18 carbon atoms. In the repeating unit -(R 2 ~0)-, R 2 iε randomly alkylene having from 2 to 4 carbon atoms in the straight chain between oxygen atoms . W, X, and Y each independently represents -0-, -S-, R 6 *7 -SR 10 , -NR llf or -CR 12 ^, R & , R 7 , and R g each independently represents H, alkyl, alkenyl, alkynyl, haloalkyl, haloakenyl, haloalkynyl, phenyl, substituted aromatic, amine, or thio of from 1 to 18 carbon atoms. Q and R, Q each independently represents alkyl, alkenyl, alkynyl, haloalkyl, haloakenyl, haloalkynyl, phenyl, substituted aromatic, amine, or thio of from 1 to 18 carbon atoms or -(R,~-0)--^ I A - R I I and R, 2 each independently represents H, alkyl, alkenyl, alkynyl, haloalkyl, haloakenyl, haloalkynyl, phenyl, substituted aromatic, amine, or thio of from 1 to 18 carbon atoms, or -(R 13 -0) -R,, . R, 3 i.s randomly alkyl of from 2 to 4 carbon atoms, having from 2 to 4 carbon atoms in the straight chain between oxygen atoms. R,, iε H, alkyl, alkenyl, alkenyl, alkynyl, haloalkyl, haloakenyl, haloalkynyl, phenyl, subεtituted aromatic, amine, or thio of from 1 to 18 carbon atomε and m iε 0 to 50. Polyphosphazene compounds that are useful in the present invention are those of Formula (I). In that formula, x and y represent molar percentages, with x being 80 to 1007. and y being 0 to 207.. Preferred valueε for x are from 90 to 100%, and preferred values for y are from 0 to 10%.. R, and R ς are independently represented by the formula ~ (R 2~°^ ~ R 3" useful compounds according to the invention are those where n is from 1 to 50. Especially preferred values for n are from 2 to 10. 2 and R, 3 are each independently randomly alkylene of from 2 to 4 carbon atomε and preferably 2 to 3 carbon atomε, having from 2 to 4 carbon atoms and preferably 2 carbon atoms in the Btraight chain between oxygen atoms. By "randomly alkylene of from 2 to 4 carbon atoms," it is meant that the R 2 or R, g in., each of the repeating units —(R 2 —0)— or -(R, 3 -0)- may be different from other R 2 'ε or as lon as each of the R- 2 'ε or R n ^'ε falls within the overall limitation of being between 2 to 4 carbon atoms, having from 2 to 4 carbon atoms in the straight chain between oxygen atoms. For example, where n=3 and R 3 iε ethyl, R 1 could be -CH 2 CH 2 -0-CHCH 3 CHCH 3 ~0- CH 2 CHCH 3 -0-C 2 H 5 . Exampleε of R ∑ include ethylene, n-propyl, isopropylene, and n—butylene. R~ and R- j , each independently represents (and R Q and R, Q may each independently represent) alkyl, alkenyl, alkynyl, haloalkyl, haloakenyl, haloalkynyl, phenyl, substituted aromatic, amine, or thio typically of from 1 to 18 carbon atomε. Preferably, R 3 iε alkyl, alkenyl, haloalkyl, or aromatic of from 1 to 8 carbon atoms. Useful as 3 and R,, groupε include substituted alkyl-, alkenyl, or aromatic groups of from l to 18 carbon atoms. Examples of substituentε include halogen, such aε F or Cl, amino groups such as H 2 , NHCH 3 , or N CH 3 2 , and thio-containing groups, such as alkylthio (e.g., methylthio, ethylthio) or sulfonate. A preferred substituted R 3 is a terminally halogen substituted alkyl group, such as a perfluoroalkyl. Examples of R-, include -CH 3 , -CH 2 CH 3 , -CH 2 CF 3 , -CH 2 CC1 3 , -(CH 2 ) 5 CH 3 , -(CH 2 ) 4 -CH=CH-CH 3 , -CH 2 -0-CH 3 , and (C 6 H )-(CgH 17 ) . R , R, , R 7 , and Rg each independently representε (and R-, and R, 2 may each independently represent) hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloakenyl, haloalkynyl, phenyl, substituted aromatic, amine, or thio typically of from 1 to 18 carbon atoms. Preferably, they are H or alkyl, or alkenyl of from 1 to 8 carbon atoms . Also uεeful are substituted alkyl or alkenyl groups of from 1 to 18 carbon atoms. Examples of substituents include halogen such as F or Cl, amino groups such aε NH 2 , NHCH 3 , or N(CE 3 ) 2 , and thio-containing groups, such as alkylthio (e.g., ethylthio, ethylthio) of εulfonate: Examples of R,, R, , R-,, R β , R,, , and R-~ include -CH- , -CH 2 CH 3 , -CH 2 CF 3 , -CH 2 CC1 3 , -(CH 2 ) 5 CH 3 , • -(CH 2 ) 4 -CH=CH-CH 3 , -CH 2 -0-CH 3 , and (C 6 H 4 )- C g H 17 ) . The molecular weight of the compound of Formula (I) is preferably between 2 x 10 3 and 1 x 108, and more preferably between 1 x 10 5 and 1 x 107. The salts that are useful when forming antistatic fibers with the multicomponent blends in the present invention are those that complex with the phosphazeneε of Formula (I). Any salt that complexes with the phosphazenes is useful. Whether a salt complexes with the phosphazene can be easily determined by methods known in the art, such as electrical conductivity measurementε , differential scanning calorimetry (DSC) (meaεuring changeε in ' glaεε transition temperature), vibrational spectroscopy, and nuclear magnetic reεonance, or a combination thereof. Further disclosure on phoεphazene/εalt complex formation iε presented in Blonεky, Shriver, Austin, &. Allcock, Solid State Ionics 1986, 18-19. pp. 258-64. A number of factorε can be utilized to determine whether the salt will be likely to complex with the etheric phosphazene. The greater the flexibility of the polymer backbone of the polyphosphazene, the more receptive it is to complexing with all salts. Similarly, the higher the concentration of polar groups in the phosphazene, the more receptive it iε to complexing with all saltε. Saltε that have a greater solubility with the phoεphazene will tend to complex with the phoεphazene to a greater extent than εaltε with lower solubility. Saltε with a low lattice energy tend to complex with the etheric phosphazene to a greater extent than εaltε with a high lattice energy. Saltε with bulky anionε tend to complex with the phosphazene to a greater extent than salts with smaller anionε. Also, salts with lower valence chargeε (e.g., mono and divalent salts) tend to complex with the phosphazene to a greater extent than salts with greater valence charges (e.g., trivalent salts). Typical salts suitable for antistatic compositionε of the invention include KCF 3 S0 3 , Ca(CF 3 S0 3 ) 2 , Zn(BF 4 ) 2 , LiBF , NaBF 4 , NaCF 3 S0 3 , CF 3 C0 2 , LiCF 3 C0 2 -, NaCF 3 C0 2 , KC 3 F 7 C0 2 , iC 3 F ? C0 2 , aC 3 F 7 C0 2 , Lil, Nal, KI, C 4 F 9 S0 3 , PF 6 , aB(C 6 H 5 ) 4 , iCF 3 S0 3 , LiC10 4 , KSCN, LiSCN, and NaSCN. One skilled in the art could easily choose a number of additional salts according to the invention, given the salts exemplified above, the factors leading to a likelihood of the salt complexing with the polyphoεphazene, and the above-described tests to determine whether the salt complexes with the polyphoεphazene. The material that forms the metal oxide in the blend of the invention may be derived from highly reactive inorganic monomers having a hydrolyzable leaving group that are soluble in the solvents for the phoεphazene, and that are capable of forming a network via hydrolysis and condensation. The metal of the metal oxide may be defined as any electropositive chemical element characterized by ductility, malleability, luster, conductance of heat, and electricity, which can replace the hydrogen of an acid and forms bases with the hydroxyl radical. According to a particularly preferred embodiment, the oxides employed- are titanium or zirconium heteropolycondenεates that have been prepared by hydrolysis and polycondensation of at least one monomer of the general formula wherein X is hydrogen, halogen, alkoxy, aryloxy, carboxy, or an -NR 2 group, in which R iε hydrogen and/or alkyl, and/or aryl with the proviso that not all of X are hydrogen, and M iε a metal.. Also suitable are heteropolycondensates in which at leaεt εome of the titanium or zirconium haε been substituted by other metals including aluminum, boron, indium, tin, tantalum, lead, phosphoruε , lanthanum, iron, copper, yttrium, and germanium. Barium and magneεium oxide mixtures with above metal oxides also may be utilized in the invention. The preferred subεtituted materialε are titanium alkoxide and zirconium alkoxide, as these materialε appear eaεier to form into fiberε . The polyphoεphazene, metal oxide, and optionally salt, such as potassium triflate, form the required elementε for the invention. It iε alεo possible that the compositions of the invention may contain other materialε such as fillers or materials such as fire retardants or coating aids. Although generally opaque, the compoεite blendε of the invention may be tranεparent aε all or substantially all of the areas of metal oxide have a size of lesε than 2000& and preferable leεs than 500A for the strongest and most tranεparent fibrous materialε. However, in some inεtanceε there may be i puritieε or. deliberately added dyeε or pigmentε that render the products non-transparent. The term "tranεparent" as used herein means that letter quality pica print on white paper can be read through a 0.5 cm thick layer of the compoεite blend material when formed in a layer rather than uεed in fiber formation aε in the invention. The temperature at which curing of the fibers takeε place may be any deεired temperature that provides sufficient condensation of the materialε utilized. Typical curing temperatureε are' between about 25°C and 200 β C. The method of forming the composite fibers of the invention include any conventional polymer fiber forming procesε. Typical of such processes are- extruding, spinning, and drawing of the fibers. Further, many of the materials may be cast on water and fiberε drawn from materials on the surface of the water, or they can be wet spun from solution into a water or steam bath. The phosphazene and metal oxide of the invention may be combined in any amounts that give a suitable fiber. Typical of such combinations are those of between about 20% and about 95% by weight of the phosphazene combined with between about 5% and about 80% by weight of the material forming the metal oxide. It has been found that an amount of between about 40 and about 60 weight percent of phosphazene in combination with between about 40 and about 60% by weight of the inorganic oxide precursor ' is suitable to give products of desirable strength. A preferred blend has been found to be about 70% of the metal alkoxide for the beεt balance of strength, hardness, flexibility, and conductivity. The finished composite material after curing typically has a metal oxide content of between about 1 and about 607. by weight. At higher oxide contentε the fiberε become brittle and may fall apart when flexed or handled. A preferred amount of metal oxide content iε between about 10% and about 40% by weight to form a strong and continuous network of the metal oxide in the fiberε. The optimum amount of metal oxide for oxides of titanium, and zirconium haε been found to be between about 15% and about 25% by weight for the strongest and most flexible materials. The amount of salt utilized in the conductive fibers may be any amount that gives a suitable amount of conductivity in the product being formed. Typical weight of salt is between about 5 and about 20 weight percent of the finished product. EXAMPLES The practice of the invention is further illustrated by the following examples : Preparation 1 - Poly(dichlorophosphazene) Poly(dichlorophosphazene) waε prepared by the thermal polymerization of hexachlorocyclotriphoεphazene [(NPC1,)-] at 250 β C. Polymerization of (NPC1,).-, was carried out m . sealed PyrexTM glass tubes of size 23 x 3.5 cm (200 g scale). Crushed Pyrex glasε (2 g) waε added to the tube to facilitate initiation. The tubeε were evacuated on a vacuum line for 30 minuteε before they were sealed. The sealed tubes were heated at 250 β C until the contents became viscous, about 24 hours. After the tubes had cooled to room temperature, they were placed in a glove bag filled with argon, the Pyrex tube broken open, and the contentε placed in a εublimator. The bulk of the starting trimer (50 g) waε removed from the polymer during the sublimation (50 β C, 16 hours). The remaining polymer was a white material that was highly elaεtomeric and formed clear viεcous εolutionε in tetrahydrofuran and toluene. Preparation 2 - Poly[bis(2-(2-methoxyethoxy)ethoxy) phosphazene] (MEEP). A solution of poly(dichlorophosphazene) (33 g, 0.28 mol) in tetrahydrofuran (500 ml) was added over a 3-hour period to a stirred suspension of todium 2-(2-methoxyethoxy)ethoxide, prepared from sodium hydride (40 g, 0.83 mol) and 2-(2-methoxyethoxy)- ethanol (150 g, 1.25 mol) in THF (500 ml). Tetra-n-butylammonium bromide (0.5 g) was added. The reaction was stirred for 48 hours at room temperature and then waε refluxed for one hour to finish the substitution. The reaction was neutralized with ' 5% HC1. The reaction mixture waε dialyzed against water and freeze—dried . The freeze—dried polymer- (60 g) was diεεolved in acetone- (800 ml) and filtered through a coarεe glaεε frit. It was then precipitated .into heptane (4 x 1500 ml). The polymer was redisεolved in acetone and reprecipitated into heptane aε before. A 31P(1H) NMR spectrum conεi.sted of a shar " p singlet at -7.6 PPM, which was indicative of total halogen replacement. Yield waε 23%. IR (P=N) , 1240 cm -1 . Intrinεic viscoεity waε 1.06 dl/g. Low angle laεer light scattering gave an apparent weight average molecular weight of 5.4 x 10 gm/mol. Elemental analyεiε (found/theoretical, %) : N (5.0/4.9), C (41.8/42.4), H (7.6/7.8), P (11.3/10.9), Cl (<0.3/0.0). EXAMPLES A MEEP solution for Exampleε 1—4 waε formed by combining the MEEP of Preparation 2 with tetrahydrofuran (THF) at the rate of 10 grams MEEP per 100 gramε THF. Example 1 1:3 MEEP:zirconium alkoxide by weight of the εtock MEEP solution (2 g) was stirred with a magnetic εtirrer in a 4 dram vial. Zirconium butoxide n-butanol complex (0.64 g) waε added, the solution shaken vigorouεly by hand, followed by heating in a 65 β C oil bath for five minute . The clear, viscous fluid was poured into a 2 mL syringe and expelled through an 18 gauge one-inch needle to produce a clear fiber with a slight yellow color. The fiber turned opaque and became brittle over a period of four days. Example 2 1:1.5 MEEP:zirconium alkoxide by weight. The same procedure was followed as described in Example 1 using the MEEP solution (2 g) and zirconium butoxide n-butanol complex (0.32 g). The fiber waε similar in appearance to the one described above but remained flexible after four days . Example 3 1:1.5:0.05 MEEP:zirconium alkoxide:salt antistat. The εame procedure waε followed aε deεcribed in Example 1 uεing the MEEP solution (2 g) and zirconium alkoxide (0.32 g), except that lithium triflate (0.01 g) was added after warming the sample. Clear fiberε were extruded from a Pasteur pipet. Example 4 1:3 MEEP.-titanium alkoxide. The same procedure was followed as in Example 1. The MEEP solution (0.1 g) waε mixed with titanium isopropoxide (0.33 g). The fibers were opaque immediately after forming. Example 5 Dry spinning of a MEEP(polyphosphazene)/- titanium isopropoxide fiber. A 10 weight percent solution of polyphosphazene (MEEP) in acetone waε prepared using 9 gramε of MEEP. To thiε solution,- 18 gramε of titanium isopropoxide waε added while mixing. The resulting solution was concentrated to an appropriate spinning viscosity by pulling off acetone in a rotor-vap at 25 β C. The solution waε then loaded into an Inεtron extruder equipped with a capillary outlet from a barrel held at 29°C. Fibers were extruded by applying preεεure to the top of the barrel. Theεe fiberε, when dry, were rubbery, flexible, self—supporting, and could endure a high degree of extension before breaking. Thiε example demonstrateε that high quality fiberε of etheric phoεphazeneε with metal oxideε can be obtained by the uεe of proper fiber extruεion techniqueε . The above exampleε illustrate that fibers may be succeεεfully prepared from zirconium and titanium oxide blendε with the etheric phoεphazene. Utilized in the Examples 1-4 was about a 10% solution of MEEP in tetrahydrafuran (THF). Attempts were made using procesεeε εimilar to thoεe of Exampleε 1—4 to form zirconium and titanium fiberε from solutions of about 2% MEEP and 20% MEEP. These attempts were unεuccesεful utilizing the syringe and Pasteur pipet. However, thiε iε not believed to be determinative that the invention can only be formed at about- a 10% solution, as the non-sophisticated fiber-forming techniques utilized in the Examples 1—4 do not exhaust the posεibilitieε of εtandard fiber formation techniqueε. It would be recognized by one ordinarily skilled in the art that proper fiber extrusion techniques would result in fiberε from other solution concentrations. Similarly, attempts to make silicon by techniques such as in Examples 1-4 also were unεucceεεful; however, it iε again conεidered that thiε iε only a failure of the primitive fiber-forming techniqueε and failure to experiment with fiber-forming conditionε, aε there does not appear to be any technological reason why fibers could not be formed by extrusion of these materialε. It iε surprising that silicon alkoxides failed to yield fibers, probably due to the slower rate of oxide formation of tetraethoxyεilane. We believe that increasing the rate of hydrolysis and/or condensation by the addition of acid or baεe, or υεing a more reactive oxide precurεor, would yield other phoεphazene metal oxide fiberε. The important factor appearε to be controlling the sol—gel rate of reaction. By increaεing the rate of reaction for silicon, one should be able to obtain fibers . Thiε invention has been deεcribed in detail with particular reference to particular embodimentε thereof, but it will be underεtood that variations and modificationε can be effected within the scope and spirit of the invention. The invention is only intended to be limited by the breadth of the claims.

Claims: CLAIMS : 1. A proceεε of forming a blended compoεite fiber comprising combining etheric phosphazene and a metal oxide precursor in a solvent solution, mixing until the materials are disεolved, forming the dissolved materials into fiber and curing to recover a blended composite of etheric phosphazene and metal oxide that iε not covalently crosε-linked between the etheric phoεphazene and metal oxide. 2. The procesε of Claim 1 wherei'n said forming is by extrusion. 3. The procesε of Claim 2 wherein said extruεion is into a liquid. 4. The procesε of Claim 1 wherein εaid forming is by drawing said fiber. 5. The process of Claim 4 wherein εaid fiber is drawn from εaid diεsolved materials floating on a liquid. 6. The procesε of Claim 1 wherein εaid curing is by heating to between about 25 β C and about 200 β C and εaid metal oxide . precurεor comprises a metal alkoxide. 7. The procesε of Claim 1 wherein said metal oxide precursor compriseε metal oxide with the metal portion of said metal oxide titanium or zirconium. 8. The process of Claim 1 wherein said metal oxide precursor compriseε metal oxide with the metal portion of said metal oxide selected from at least one member of the group consisting of titanium, boron, aluminum, zirconium, tin, germanium, tantalum, phoεphorus , lead, arεenic, lanthanum, iron, indium, copper, yttrium, barium, magneεium and mixtureε thereof. 9. The process of Claim 1 wherein laid phoεphazene polymer compriseε at least one material selected from the group consiεting of: I. A polyphosphazene comprising repeating units for the formula: wherein x and y represent molar percentages , with x being 80 to 100% and y being 0 to 20%. . R, and R. each independently represents the formula ~(R 2 ~ ^ ~ 3 w ^ ere n n iε 1 to 50, R 2 iε randomly alkyl of from 2 to 4 carbon atomε, having from 2 to 4 carbon atoms in the straight chain between oxygen atoms, and R 3 is alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, substituted aromatic, amine or thio of from 1 to 18 carbon atoms , W, X, and Y each independently repreεentε R ,*6 R ,77 -0-, -S-, -N-, or -C-, R ,f6S R ,77 Z repreεentε -ORQ, _ S 10 . ~ NR H> OΓ ~ CR i2' wherein R , R, , R-, , and R g each independently repreεentε H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, εubεtituted aromatic, - amine, or thio of from 1 to 18 carbon atomε, R q and R, Q each independently repreεentε alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, substituted aromatic, amine, or thio of from 1 to 18 carbon atoms or ~( R i3"-0) ιn _R > R,, and R, 2 each independently represents H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, substituted aromatic, amine or thio of from 1 to 18 carbon atomε, or -(R,.,—0) -R 1 . , 3 iε randomly alkyl of from 2 to 4 carbon atomε, having from 2 to 4 carbon atomε in the straight 5 chain between oxygen atomε , R, iε alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, subεtituted aromatic, amine, or thio of from 1 to 18 carbon atoms, and m iε 0 to 50. 10 10. A proceεε of Claim 9 wherein R 2 haε 2 carbon atomε in the straight chain between oxygen atoms, and n is from 2 to 10. 15 11. The process of Claim 10 wherein W and X each independently representε —0—. 12. The proceεε according to Claim 11 wherein R 2 and R 3 are each independently methyl or ethyl. 20 13. The proceεε of Claim 10 wherein a salt is combined with said phosphazene and said metal oxide and wherein εaid salt iε selected from the group consisting of KCF 3 S0, Ca(CF 3 S0 3 ) 2 , Zn(BF 4 ) 2 , LiBF 4 , NaBF 4 , aCF 3 S0 3 , 25 KCF 3 C0 2 , LiCF 3 C0 2 , NaCF 3 C0 2 , KC 3 F ? C0 2 , LiC 3 F ? C0 2 , NaC 3 F ? C0 2 , Lil, Nal, KI, C 4 F 9 S0 3 K, KPF 6 , aB(C 6 H 5 ) 4 , LiCF 3 S0 3 , LiCa0 4 , KSCN, LiSCN, and NaSCN. 14. The procesε of Claim 9 wherein " 30 3 iε substituted alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, subεtituted aromatic, amine, or thio of from 1 to 18 carbon atomε. 15. The proceεε of Claim 14 wherein R 3 35 repreεentε a halogen εubεtituted alkyl or phenyl group. 16. The process according to Claim 9 wherein said polymeric phosphazene compriseε poly[biβ(2—(2— methoxyethoxy)ethoxy)phoεphazene] . 17. The procesε of Claim 1 wherein βaid etheric phosphazene iε utilized in the amount of between about 20 and 95 percent by weight and εaid metal oxide precursor is used in an amount between 5 and about 80 percent by weight. 18. Composite fiber comprising a multicomponent blend of etheric phoεphazene and metal oxide wherein εaid metal oxide compriseε between about 1 and about 80 percent by weight of said composite. 19. The composite fiber of Claim 18 wherein εaid metal oxide compriεeε between about 10 and about 60 percent by weight of εaid composite. 20. The compoεite fiber of Claim 19 wherein the metal of εaid metal oxide is selected from the group conεiεting of titanium, zirconium, and mixtures thereof, and εaid metal oxide iε present in an amount of between about 10 and about 30 percent by weight of εaid compoεite. 21. The compoεite fiber of Claim 19 wherein the metal portion of εaid metal oxide is selected from at least one member of the group consisting of titanium, boron, aluminum, zirconium, tin, germanium, indium, tantalum, phosphoruε , lead, lanthanum, iron, copper, yttrium, barium, magneεium and ixtureε thereof. 22. The composite fiber of Claim 18 wherein εaid etheric phosphazene comprises at least one material selected from those consisting of A phosphazene polymer comprising repeating units for the formula: wherein x and y represent molar percentages , with x being 80 to 100% and y being 0 to 20%. wherein x and y represent molar percentages, with x being 80 to 100% and y being 0 to 20%. R, and e each- independently representε the formula "~( R 2" ~ ^n~"^3 wnere i n n iε 1 to 50, R 2 iε randomly alkyl of from 2 to 4 carbon atomε, having from 2 to 4 carbon atomε in the straight chain between oxygen atoms, and R 3 iε alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, εubεtituted aromatic, amine or thio of from 1 to 18 carbon atomε, repreεentε > or ' independently repreεentε H, alkyl, or alkenyl of from 1 to 18 carbon atomε , R Q and R, Q each independently repreεentε alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, subεtituted aromatic, amine, or thio of from 1 to 18 carbon atomε or ~( R i3""° m ~ R ι4> R,, and R, 2 each independently representε H, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, εubεtituted aromatic, amine or thio of from 1 to 18 carbon atomε, or -( R ι3~°) m ~ R i4' R, 3 is randomly alkyl of from 2 to 4 carbon atoms, having from 2 to 4 carbon atoms in the straight chain between oxygen atoms, 14 iε alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, phenyl, substituted aromatic, amine, or thio of from 1 to 18 carbon atomε, and is 0 to 50. • 23. The composite fiber of Claim 18 further comprising a salt. 24. The composite fiber of Claim 23 wherein the salt is selected from the group consiεting of CF 3 S0, Ca(CF 3 S0 3 ) 2 , Zn(BF ) 2 , LiBF , NaBF 4 , aCF 3 S0 3 , - CF 3 C0 2 , LiCF 3 C0 2 , NaCF 3 C0 2 , KC 3 F 7 C0 2 , LiC 3 F.-C0 2 ., • NaC 3 F 7 C0 2 , Lil, Nal, I , C 4 F 9 S0 3 K, KPF 6 , NaB(C 6 H 5 ) 4 , LiCF 3 S0 3 , LiCa0 4 , SCN, LiSCN, and NaSCN. 25. The composite according to Claim 22 wherein n is from 2 to 10, wherein W and X each independently represent -0-, and wherein R 2 and R 3 are each independently methyl, ethyl, or perfluoroethyl. 26. The composite fiber of Claim 22 wherein R 2 and R *3 are each ethyl, and R 3 , R , and R-, are each independently methyl, ethyl, or perfluoroethyl. 27. The composite fiber according to Claim 18 wherein said polymeric phosphazene compriseε poly[bis(2-(2-methoxyethoxy)ethoxy)phosphazene] .

Inventors: COLTRAIN BRADLEY KEITH, FERRAR WAYNE THOMAS, LANDRY CHRISTINE JOANNE THERES, COLTRAIN, BRADLEY, KEITH, FERRAR, WAYNE, THOMAS, LANDRY, CHRISTINE, JOANNE, THERESA
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1990
Main classification: C08K3
IPC codes: C08G79, C08K3, C08K5, C08L85, D01F1, D01F6, D01F9