RIGID-ROD POLYMERS

Abstract: Rigid-rod and segmented rigid-rod polymers, methods for preparing the polymers and useful articles incorporating the polymers are provided. The polymers incorporate rigid-rod backbones with pendant solubilizing groups attached thereto for rendering the polymers soluble.

Description: ■ C -1- RIGID-ROD POLYMERS Related Applications 5 This application is a continuation-in-part of U. Application Serial No. 07/397,732, filed 8/23/89, which a continuation-in-part of U.S. Application Serial N 07/157,451, filed February 17, 1988. Applications No 07/397,732 and 07/157,451 are incorporated herein by th 10 reference. Field of the Invention This invention relates to soluble rigid-rod polyme having rigid-rod backbones and pendant,' solubilizi 15 organic groups attached to the backbone, and to metho for preparing the polymers. This invention also relates copolymers comprising rigid-rod segments, havi solubilizing organic groups attached to the rigid-r segments. The rigid-rod polymers can, for example, 20 used as self-reinforced engineering plastics, can be us in combination with flexible coiled polymer binders f the preparation of high tensile strength molecul composites and can be used as matrix resins for fib containing composites. 25 Background of the Invention High-performance fiber-polymer composites are rapi achieving a prominent role in the design and construct of military and commercial aircraft, sports and industr equipment, and automotive components. Composites fill the need for stiffness, strength, and low weight that cannot be met by other materials. The most widely utilized high- performance fiber-polymer composites are composed of oriented carbon (graphite) fibers embedded in a suitabl polymer matrix. To contribute high strength and stiffnes to the composite, the fibers must have a high aspect rati (length to width) . Fibers may be chopped or continuous. The mechanical properties of chopped fiber composite improve greatly as the aspect ratio increases from 1 t about 100. Mechanical properties still improve but at slower rate for further increases in aspect ratio. Therefore, aspect ratios of at least about 25, an preferably of at least about 100 are desirable for choppe fiber composites. Composites prepared with continuou fibers have the highest stiffness and strength Fabricating fiber-containing composites, however, require significant manual labor and such composites cannot b recycled. Furthermore, defe ' ctive and/or damaged composit materials cannot be easily repaired. Molecular composites are high-performance material which are much more economical and easier to process tha conventional fiber-polymer composites. In addition molecular composites can be recycled and are repairable Molecular composites are composed of polymeric material only, i.e., they contain no fibers. Such molecular com posites can be fabricated much more simply than fiber polymer composites. Molecular composites are materials composed of a rigid rod polymer embedded in a flexible polymer matrix. Th rigid-rod polymer can be thought of as the microscopi equivalent of the fiber in a fiber-polymer composit Molecular composites with the optimum mechanic properties will contain a large fraction, at least 3 percent, of rigid-rod polymers, with the balance bei polymeric binder. Molecular composites may contain eith oriented or unoriented rigid-rod polymers. A molecular composite requires that the rigid-ro polymer be effectively embedded in a flexible, possibl coil-like, matrix resin polymer. The flexible polyme serves to disperse the rigid-rod polymer, preventin fj? 5 bundling of the rigid-rod molecules. As in conventiona fiber/resin composites, the flexible polymer in a molecu lar composite helps to distribute stress along the rigid rod molecules via elastic deformation of the flexibl polymer. Thus, the second, or matrix-resin, polymer mus 10 be sufficiently flexible to effectively surround th rigid-rod molecules while still being able to stretch upo stress. The flexible and rigid-rod polymers can als interact strongly via Van der Waals, hydrogen bonding, o ionic interactions. The advantages of molecular com 15 posites can only be realized with the use of rigid-ro polymers. Most of the linear polymers produced commercially toda are coil-like polymers. The chemical structure of th polymer chain allows conformational and rotational motio 20 along the chain so that the entire chain can flex an adopt coil-like structures. This microscopic proper relates directly to the macroscopic properties of flexur strength, flexural moduli, and stiffness. If fewer less extensive conformational changes are possible, 25 stiffer polymer will result. Two technical difficulties have limited molecul composites to laboratory curiosities. Firstly, the pri art relating to molecular composites calls for mere blending or mixing a rigid-rod polymer with a flexib 30 polymer. It is well known in the art, however, that, general, polymers of differing types do not mix. That i homogeneous single phase blends cannot be obtained. Th rule also applies to rigid-rod polymers and, thus, t early molecular composites could be made with only sma 35 weight fractions of a rigid-rod component. In the systems, an increase in the fraction of the rigid-r component led to phase separation, at which point molecular composite could no longer be obtained. The second technical difficulty is that rigid-rod polymers of significant molecular weight are exceedingly difficult to prepare. The technical problem is exemplified by the rigid-rod polymer, polyparaphenylene. During the polymerization of benzene, or other monomer leading to polyparaphenylene, the growing polymer chain becomes decreasingly soluble and precipitates from solution causing the polymerization to cease. This occurs after the chain has grown to a length of only six to ten monomer units. These oligomers, i.e., rigid-rod polymers, are too short to contribute to the strength of a composite. A lack of solubility is a general property of rigid-rod polymers, hence, synthesis of all such rigid-rod polymers is difficult. The solubility problem may be avoided in the special case in which the product polymer contains basic groups which can be protonated in strong acid and the polymerization can be conducted in strong acid. For example, rigid-rod polyquinoline can be prepared in the acidic solvent system dicresylhydrogenphosphate/m-cresol, because the quinoline group interacts with the acidic solvent, preventing precipitation. However, the resulting polymers are soluble only in strong acids, making further processing difficult. Before molecular composites can become a practica reality, the problems of (a) blending the rigid-rod an flexible components into a stable homogeneous phase, an (b) the low solubility of the polymer, must be overcome. Su marv of the Invention In one embodiment, rigid-rod polyphenylenes provided accordance with the present invention are line 5 polyphenylenes in which the polymer chain has at lea about 95% 1,4 linkages, and incorporates penda solubilizing side groups. Rigid-rod polyphenylenes may ho opolymers or copolymers having more than one type 1,4-phenylene monomer unit. The number average degree 10 polymerization (DP n ) is greater than about 25. As used herein, DP n is defined as follows: DP n = (number of monomer molecules present initially) / (number of polymer chains in the system) 15 In another embodiment of the present inventio segmented rigid-rod polyphenylene copolymers are provide The segmented copolymers of the present invention compri one or more rigid-rod polyphenylene segments and one more non-rigid segments, wherein the rigid- 20 polyphenylene segments have a number average segm . length (SL n ) of greater than about eight. As used herein, the number average segment length defined by: 25 SL n = (number of rigid monomer molecules pres initially)/(the total number of rigid segments at the of the reaction) and is essentially the average number of monomer units 30 each rigid segment. Each polymer chain typically conta many rigid segments. However, some may contain less t others, or only one rigid segment. The number aver segment length may be approximated by: '* 35 SL n - (number • of rigid monomer molecules pres initially) /(number of kinked or flexible monomer molecu present initially + number of polymer chains at the en the reaction) The rigid-rod and segmented rigid-rod polymers of th present invention are unique in that they are soluble i one or more organic solvents. The polymer and th monomers demonstrate a significant degree of solubility i a common solvent system so that the polymer will remain i a dissolved state in the polymerization solvent system. The rigid-rod and segmented rigid-rod polymers of th present invention are made soluble by pendant solubilizin organic groups (side groups or side chains) which ar attached to the backbone, that is, to the monomer units The pendant organic groups impart increased solubility an meltability to the polymer by disrupting interaction between the rigid chains, providing favorable interaction with organic solvents, increasing the entropy (disorder of the chains, and causing steric interactions which twis the phenylene units out of planarity. Therefore, suc polymers can be considered to be self-reinforced plastic or single-component molecular composites. Thus, th rigid-rod and segmented rigid-rod polymers of the presen invention have incorporated rod-like and coil-like com ponents into a single molecular species. The rigid-rod o segmented rigid-rod polymer can also be mixed with a coil like matrix resin to form a blend, wherein the pendan organic. groups act as compatibilizers to inhibit phas separation. Rigid—rod polymers produced in the past are, i general, highly insoluble (except in the special case o polymers with basic groups which may be dissolved strong acid) and are infusible. These properties ma them difficult, and often impossible, to prepare a process. We have found, surprisingly, that t incorporation of appropriate pendant organic side grou to the polymer substantially improves solubility a fusibility. Earlier work has suggested that such penda side groups do not increase the solubility of rigid-r polymers. However, by increasing the size of the si chain, by placing side chains so that steric repulsio prevent adjacent phenylene ring from lying in the sa plane, by placing side chains in a non-regular (rando stereochemical arrangement, and/or by matching i properties (principally, polarity and dielectric constan to the polymerization solvent, rigid-rod and segment rigid-rod polymers of substantial molecular weight can prepared. For example, when the polymerization is carri out in a polar solvent, such as dimethylacetamide (DMA or N-methylpyrrolidinone (NMP) , the solubilizing organ side groups will preferably be polar and will have hi dielectric constants, such as ketones, amides, esters a the like. The rigid-rod backbone/flexible side-chain polymers the present invention can be prepared in common solve and can be processed with standard methods to give stable, single-component,' molecular composite or s reinforced polymer useful for structural and ot applications requiring high strength and modulus. The rigid-rod and segmented rigid-rod polymers of present invention when used in a blend with a flexi polymer are the primary source of tensile strength modulus of the resulting molecular composite. S molecular composites may be homogeneous single ph blends, blends having microphase structure, or multi-ph blends having macroscopic structure. Pendant side gro can be chosen to increase compatibility between the rig rod or segmented rigid-rod polymer and the flexi polymer. The more compatible system will have finer ph structure. The most compatible will be miscible homogeneous single phase. The rigid-rod and segmen rigid-rod polymers of the present invention can be blen with thermoplastics, thermosets, liquid crystall polymers (LCP's) , rubbers, elastomers, or any natural synthetic polymeric material. It is known in literature that the properties of chopped fiber composites improve as the aspect ratio of the fiber increases from 1 to about 100, with less relative additional improvement on further increases of ' aspect ratio. It is also known in the literature that in simple blends of rigid-rod and flexible polymers, the strength and moduli of the molecular composite blend is a function of the aspect ratio of the rigid-rod component, and that these blends phase separate on heating (W. F. Hwang, D. R. Wiff, C. L. Benner, and T. E. Hel iniak, Journal of Macromolecular Science - Physics, B22, pp. 231-257 (1983)). Preferably, when employed as a self-reinforcing plastic, the rigid-rod polymer of the present invention will have an aspect ratio of at least 100, that is, the backbone of the polymer (not including side groups) will have straight segments with an average aspect ratio of at least 100. For structural and aerospace uses, for example, aspect ratios greater than 100 are desirable. For other less demanding uses, such as cabinets, housings, boat hulls, circuit boards and many others, the rigid-rod polymer backbone can have an aspect ratio of 25 or more. Similarly the segmented rigid-rod polymers of the present invention when employed in structural applications will have segments with aspect ratios greater than about 6, preferably greater than about 8. The high strength and stiffness of the soluble rigid- rod and segmented rigid-rod polymers of the present invention are directly related to the aspect ratio of the straight segments comprising the polymer chains. For the purposes of the present invention, by aspect ratio of a monomer unit is meant the length to diameter ratio of the smallest diameter cylinder which will enclose the monomer unit, including half the length of each connecting bond, but not including any solubilizing side group(s) , such that the connecting bonds are parallel to the axis of the cylinder. For example, the aspect ratio of a polyphenylene monomer unit (-C 6 H 4 -) is about 1. The aspect ratio of a polymer segment is taken to be the length to diameter ratio of the smallest diamete cylinder which will enclose the polymer segment, includin half the length of the terminal connecting bonds, but no including any attached side groups, such that the axis o the cylinder is parallel to the connecting bonds in th straight segment. For the purposes of the present invention, aspect rati will only be applied to rigid-rod polymers, rigid-ro monomer units, or straight segments of rigid-rod polymers The aspect ratio of a rigid-rod polymer will be taken t mean the average aspect ratio of its straight segments The above definition of aspect ratio is intended t provide a close analogy to its common usage with respec to fiber-containing composites. The polymer backbone of rigid-rod polymers provided i accordance with one embodiment of this invention will b substantially straight, with no flexibility that coul result in bends or kinks in the backbone, that is, the will have a high aspect ratio. Accordingly, the polymer should be made employing processes which are not prone t the formation of occasional kinks or other' imperfectio which may interfere with the rigidity of the backbone Nonetheless, almost all chemical reactions have sid reactions, and, accordingly, some phenylene monomer unit incorporated in the final polymer will not have 1, linkages, but rather, will have 1,2 or 1,3 linkages (non parallel covalent bonds) . Other side reactions are als possible leading to non-phenylene linkages, for example ether linkages or phosphorous linkages. However, t rigid-rod polymers provided in accordance with practice the present invention will have at least 95% 1,4 linkag and preferably, at least 99% 1,4 linkage. Any 1,2 or 1, linkage in the polymer chain will reduce the avera length of straight segments. Thus, a polymer chain length 1000 monomer units having 99% 1,4 linkage and wi contain, on average, 11 straight segments with a numb average segment length (SL n ) equal to approximately 91. Rigid-rod polymers provided in accordance with this invention which have greater than 99% parallel covalent bonds, i.e., where greater than 99% of the backbone linkages are 1,4 linkages, will be exceptionally stiff and strong and will be useful where high tensile and flexural strengths and moduli are required, as in aerospace applications. Rigid-rod polymers having between about 95% and 99% parallel covalent bonds will be useful for less stringent applications, such as body panels, molded parts, electronic substrates, and myriad others. In one embodiment of the present invention, non-rigid-rod monomer units may intentionally be introduced into the polymer, to promote solubility or to modify other properties such as T or elongation to break. The polymers provided in accordance with practice of the present invention can be homopolymers or can be copolymers of two or more different monomers. The polymers of the present invention comprise a rigid-rod backbone comprising at least about 25 phenylene units, preferably at least about 100 phenylene units, wherein at least about 95%, and preferably 99%, of the monomer units are coupled together via 1,4 linkages and the polymer an its monomers are soluble in a common solvent system. Solubility is provided by solubilizing groups which ar attached to the rigid-rod backbone, that is, to at leas some of the monomer units of the backbone. Preferably, solubilizing group is attached to at least 1 out of 10 monomer units. For the purposes of the present invention, the ter "soluble" will mean that a solution can be prepared con taining greater than 0.5% by weight of the polymer an greater than about 0.5% of the monomer(s) being used t form the polymer. By "solubilizing groups" is meant functional group which, when attached as side chains to the polymer i question, will render it soluble in an appropriate solven system. It is understood that various factors must considered in choosing a solubilizing group for particular polymer and solvent, and that, all else bei the same, a larger or higher molecular weight solubilizi group will induce a higher degree of solubilit Conversely, for smaller solubilizing groups, matching t properties of the solvent and solubilizing groups is mo critical, and it may be necessary to have, in additio other favorable interactions inherent in the structure the polymer to aid in solubilization. By the term "rigid-rod monomer unit" it is meant t basic, organic, structural units of the polymer rigid-r backbone chain in which the covalent bonds connecting th to adjacent monomer units are parallel regardless conformational changes within the rigid-rod monomer uni For the purposes of this invention rigid-rod monomer uni will be limited to 1,4-phenylene units, including a attached side chain, i.e., solubilizing groups. The term "monomer unit"' will always be used in t present invention to mean "rigid-rod monomer unit." the instances where, a flexible or non-rigid-rod monom unit is discussed, it will be indicated as a "non-rig monomer unit." Most non-rigid monomer units cannot atta a conformation in which the bonds to the polymer chain a parallel, for example, the 1,3-phenylene group or t 4,4'-diphenylether group. However, some non-rigid monom units will admit a conformation in which the bonds to t polymer chain are parallel, such as the phenylene ami type non-rigid monomer units of a polymer provided DuPont Company under the trademark KFNLAR (polyamide 1,4-phenylenediamine and terephthalic acid) . Polym comprised of such non-rigid monomer units are "pseu rigid" due to the possibility of bent or kinked confor tions. Rigid-rod polymers are, in general, stiffer t pseudo-rigid polymers. By the term "monomers," for the purposes of the pres invention, it is meant the immediate chemical precurs to the polymer. Because most of the polymerization reactions described herein are condensation polymerizations, a monomer will typically lose one or more functional group(s) with respect to the corresponding monomer unit. For example, the monomer dichlorobenzene (C 6 H 4 C1 2 ) polymerizes to a polymer with phenylene (C 6 H 4 ) monomer units. The solubility of rigid-rod and segmented rigid-rod polymers provided in accordance with this invention is achieved by the attachment of pendant, solubilizing organic groups to at least some of the monomer units of the polymers. One who is skilled in the art will recognize that it is difficult to determine a priori what combinations of organic substituent (pendant organic group) , po-lymer backbone, polymer configuration, solvent system, and other environmental factors (e.g., temperature, pressure) will lead to solubility due to the many complex interactions involved. Indeed, as is mentioned above, other workers have found that pendant organic side groups do not provide a substantial increase in the solubility of rigid-rod oligomers and polymers. We, however, have discovered general strategies for the rational design of soluble rigid-rod and segmented rigid- rod polymer systems. For example, if the rigid-rod or segmented rigid-rod polymers are to be synthesized in polar solvents, the pendant solubilizing organic groups of the polymer and the monomer starting material will be a group that is soluble in polar solvents. Similarly, if the rigid-rod or segmented rigid-rod polymers are to be synthesized in non-polar solvents, the pendant solubilizing organic group on the rigid-rod polymer backbone and the monomer starting material will be a group that is soluble in non-polar solvents. Various factors dependent on the nature of the backbon itself also affect the inherent solubility of the polymer. The orientation of the individual monomer units, especially with regard to the positioning of pendan organic substituents, has been shown to have an effect on the solubility properties of polymers. In particular, 2,2'-disubstituted biphenylene units incorporated into aromatic polyesters (H.G. Rogers et al, U.S. Patent No. 4,433,132; February 21, 1984), rod-like polya ides (H.G. Rogers et al, Macromolecules 1985, 18, 1058) and rigid polyimides (F.W. Harris et al. High Performance Polymers 1989, 1, 3) generally lead to enhanced solubility, presumably not due to the identity of the substituents themselves but to sterically enforced non-coplanarity of the biphenylene aromatic rings. Extended, planar chains and networks of conjugated aromatics exhibit good stacking and strong intermolecular interactions and are generally expected to exhibit high crystallinity and, thus, poor solubility. Random distribution of side chains in homo- polymers and especially copolymers will enhance solubilit by lowering the symmetry of the polymer chain, thereb decreasing crystallinity. The rigid-rod and segmented rigid-rod polymer (homopolymers and copolymers) provided in accordance wit the present invention will have at least one monomer uni for each 100 monomer units in the rigid-rod backbon substituted with a solubilizing organic group, o preferably one monomer unit for each ten monomer units i the rigid-rod backbone substituted with a solubilizin organic group. In general, for relatively smal solubilizing side groups a higher degree of substitutio is needed for good solubility. In many instances no mor than 50% of the monomer units should be unsubstituted, fo example copolymers of 1,4-dichlorobenzene and 2,5 dichlorobenzophenone show appreciable decrease i solubility with 10% unsubstituted units, and only low M material can be prepared at greater than about 50 unsubstituted units. The solubilizing organic groups whic are substituted on, attached to, or pendant to the monome units are organic molecules that have solubility in one o more organic solvent system(s) . In order that relativel small organic groups, that is, those of a molecular weight of less than about 300, are capable of providing appropriate solubility, other favorable backbone interactions, as described above, may be required. For instance, at least one 2,2'-disubstituted biphenylene fragment would be required in the backbone for each 200 monomer units, and preferably for each 20 monomer units, and more preferably for each four monomer units in a polyparaphenylene type polymer. In embodiments of the invention, where the rigid-rod polymer is a homopolymer, the same organic or pendant group(s) occur(s) on each monomer unit. The side chains are chosen to enhance solubility, especially in the polymerization solvent system. For example, polar groups, such as N,N- dimethylamido groups, will enhance solubility in polar solvents. In one embodiment of the invention, the polymer is a copolymer of two or more rigid monomer unit types, and the majority of monomer units are substituted with solubilizing organic groups. The polymer can be formed from two different monomer units or monomers, three different monomer units or monomers, four different monomer units or monomers, and so on. At least one out of every 100 (1%) , preferably 10% and more preferably 50% of the monomer units in the rigid-rod backbone has a solubilizing organic group attached to it. In another embodiment of the invention, the polymer is a copolymer having rigid-rod segments with segment length (S jj ) of at least about eight, and non-rigid segments of any length. In the case where rigid-rod segments are separated by only a single non-parallel linkage, the non- parallel linkages represent kinks in an otherwise straight polymer molecule, as for example would be introduced with isolated 4,4'-diphenyl ether monomer units. In this case the angle between the rigid-rod segments is fixed. If the non-rigid monomer units have more than one non-parallel linkage, or if the non-rigid segments have length greater _ ι5 _ than one, the angle between the rigid-rod segments is not fixed, and the copolymer as a whole has much greater flexibility. In the case of long non-rigid blocks the copolymer may be considered a single component molecular composite, where the rigid blocks reinforce the flexible blocks. Where rigid-rod polyphenylene segments are used in a block copolymer with non-rigid segments, the rigid segments will have a dramatic effect on the physical and mechanical properties of the copolymer for relatively small aspect ratio of the rigid segments. Brief Description of the Drawings These and other features, aspects and advantages of the present invention will be more fully understood when considered with respect to the following detailed description, appended claims, and a accompanying drawings, wherein: FIG. 1 is a semi-schematic perspective view of a multi- filament fiber provided in accordance with practice of the present invention; FIG. 2 is a semi-schematic perspective view of a roll of free-standing film provided in accordance with practice of the present invention; FIG. 3 is a semi-schematic cross-sectional view of a semi-permeable membrane provided in accordance with practice of the present invention; FIG. 4 is a semi-schematic perspective view of a radome provided in accordance with practice of the present invention mounted on the leadin <g edge of an aircraft wing; FIG. 5. is a schematic cross-sectional side view of a four-layer printed wiring board provided in accordance with practice of the present invention; FIG. 6 is a semi-schematic perspective view of a non- woven mat provided in accordance with practice of the present invention; FIG. 7 is a semi-schematic perspective view of a block of foam provided in accordance with practice of the present invention; [and] FIG. 8 is a semi-schematic fragmentary cross-sectional side view of a multi-chip module provided in accordance with practice of the present invention; FIG. 9a is a semi-schematic side view of a fiber containing composite comprising a polymer provided in accordance with the present invention; and FIG. 9b is an enlarged view of an edge portion of the fiber containing composite of FIG. 9a. SUBSTITUTESHEET Detailed Description of the Invention In a first preferred embodiment, the rigid-rod polyme provided in accordance with practice of the prese invention are linear polyphenylenes which incorpora parallel covalent bonds (1,4 linkages) between monom units. Such rigid-rod polymers will have at least 95% 1, linkages, and preferably at least 99% 1,4 linkages, i.e. the polymers will have high aspect ratios. The rigid-rod polymers of the present invention ha the following general structure: Structure I wherein each R l f R 2 , R 3 , and R 4 are independently chos solubilizing groups or hydrogen..The structure is meant represent polymers having mixtures of monomer units well as those having a single type of monomer unit. T structure does not imply any particular' orientatio order, stereochemistry, or regiochemistry of R group Thus, the polymer may have head-to-head, head-to-tai random, block or more complicated order. The particul order will depend on the method of preparation and t reactivity and type of monomers used. In another preferred embodiment of the pres invention, rigid polyphenylene segments are separated flexible monomer units or flexible segments or blocks give a segmented rigid-rod polymer. In this case flexible segments contribute to solubility processability as well as the solubilizing side groups the rigid polyphenylene segments. The rigid backbone the rigid segments provide the segmented rigid-rod poly with a high degree of stiffness and strength, and a modify other properties, such as creep resistan flammability, coefficient of thermal expansion, and the like, to a degree proportional to the relative amounts of rigid and flexible segments. In fact, such physical and mechanical properties can be precisely adjusted by adjusting the rigid fraction. - For example, the coefficient of thermal expansion of a segmented rigid-rod polymer may be adjusted to match a particular material by controlling the amount of rigid monomer relative to flexible monomer used in its preparation. Dihaloaromatic monomers of Structure II may be used in the preparation of segmented rigid-rod polymers. Structure II where R^-R β are independently chosen from solubilizing side groups and H wherein G is -0-, -S-, -CH 2 -, -CY 2 -, -OCH 2 -, -OAT-, -0(ArO) n -, -(CH 2 ) n -, "(CY 2 ) n -, -CO-, -C0 2 ~, -CONY-, -0(CH 2 CH 2 0) n -, -(CF 2 ) n -, -COArCO-, -CO(CH 2 ) n CO-, -C(CF 3 ) 2 -, -C(CF 3 ) (Y)-, -NY-, -P(=0)Y-, X is Cl, or Br, or I and Ar is an aromatic group, heteroaromatic group, or substituted aromatic group, and Y is independently selected from the group consisting of H, F, CF 3 , alkyl, aryl, heteroaryl, or aralkyl group, and n is 1 or greater. In order to provide significant improvement in physica and mechanical properties over flexible polymers th segmented rigid-rod polymers of the present inventio should have rigid segments with number average segmen length (SL n ) of at least about 8. One such exemplary embodiment of the structure of polymer comprising rigid-rod polyphenylene segment separated by flexible monomer units (the segmented rigid rod polymer of the present invention) is as follows: Structure III wherein: is a rigid-rod polymer segment, wherein each R l f R 2 , and R 4 on each monomer unit, independently, is H or solubilizing side group, and -[A] m - is a non-rig segment, for example as derived from non-rigid monomers Structure II; wherein the rigid-rod polyphenylene segmen have number average segment length SL n of at least abo 8, n is the average number of monomer units in the rig segment, m is the average number of monomer units in t flexible segment and is at least 1. In one exemplary embodiment, the segmented rigid-r polymer of the present invention has structure III where -A- is: wherein B'-'-B 4 are independently selected from the gr consisting of H, C χ to C 22 alkyl, C 6 to C 20 Ar, alkaryl, CF 3 , phenoxy, -COAr,. -COalkyl, -C0 2 Ar, -C0 2 alkyl, wherein Ar is aryl or heteroaryl. The flexible monomer units in this case may be derived from substituted 1,3- dichloroarenes. In another exemplary embodiment -A- is 1,3-phenylene and is derived from 1,3-dichlorobenzene. Other flexible monomers and monomer units may be used as are apparent to one skilled in the art. The segmented rigid-rod polymers may be used in the same ways as the rigid-rod polymers including compression and injection molding, extrusion, to prepare films and fibers, in blends, alloys and mixtures, as additives, as matrix resins, and in other ways apparent to those skille in the art. Other polymer systems have been described in the pas as rigid .r rod-like but must not be confused with tru rigid-rod polymers provided in accordance with this inven tion. For instance, long chain para-oriented aromati polyamides and polyesters often exhibit .ordering, due t various intermolecular forces, into rod-like assemblie and consequently demonstrate some of the advantages (e.g. , high strength) and disadvantages (poor solubility) of tru rigid-rod polymers. Such polymer systems are actuall only "pseudo-rigid" because ester and amide linkages ar not inherently rigid or parallel and only adopt paralle configurations under certain conditions. At lowe concentrations or higher temperature they may behave lik flexible polymers. It is known in the art that th theoretical stiffness of aromatic polyamide and polyeste backbones is lower than a polyphenylene backbone. Stiffe polymers will of course have greater reinforcin properties. The rigid-rod and segmented rigid-rod polymers of th present invention will have at least one monomer unit fo each 100 monomer units in the rigid-rod backbon substituted with a solubilizing organic group Preferably, the polymer will have at least about on monomer unit in ten substituted with solubilizing organi groups. More preferably, the polymer will have more tha one monomer unit per 10 monomer units substituted wit solubilizing organic groups. The solubilizing organi groups which are substituted-on, attached to, or pendan to, the monomer units are organic molecules that hav solubility in one or more organic solvent syste (s) Solubilizing organic groups which can be used include, bu are not limited to, alkyl, aryl, alkaryl, aralkyl, alky or aryl amide, alkyl or aryl thioether, alkyl or ary ketone, alkoxy, aryloxy, benzoyl, phenoxybenzoyl sulfones, esters, imides, imines, alcohols, amines, an aldehydes. Other organic groups providing solubility i particular solvents can also be used as solubilizin organic groups. In an exemplary embodiment, a polymer of Structure or III is provided where at least one of the R groups is wherein X is selected from the group consisting hydrogen, amino, methylamino, dimethylamino, methy phenyl, benzyl, benzoyl, hydroxy, methoxy, phenox -SC 6 H 5 , and -OCOCH 3# In another exemplary embodiment, a polymer of Structu I or III is provided where at least one of the R grou is: and wherein X is sel A ected from, the group consisting methyl, ethyl, phenyl, benzyl, F, and CF 3 , and n is 1, 2, 3 , 4, or 5. In another exemplary embodiment, a polymer of Structure I or III is provided wherein one of R x , R 2 , R 3 or R 4 is selected from the group consisting of -CR 5 R 6 Ar where Ar is aryl, R 5 and R 6 are H, methyl, F, Cl to C20 alkoxy, OH, and R 5 and R 6 taken together as bridging groups -OCH 2 CH 2 0- , -OCH 2 CH(CH 2 OH)0-, -OC 6 H 4 0- (catechol) , -OC 6 H 10 O- (1,2- cyclohexanediol) , and -OCH 2 CHR 7 0- where R 7 is alkyl, or aryl. In yet another exemplary embodiment, a polymer of Structure I or III is provided wherein R χ is -(CO)X where X is selected from the group consisting of 2-pyridyl, 3-pyridyl, 4-pyridyl, -CH 2 C 6 H 5 , -CH 2 CH 2 C 6 H 5 , 1-naphthyl and 2-naphthyl or other aromatic, fused ring aromatic or heteroaromatic group. In an additional exemplary embodiment, a polymer of Structure I or III is provided wherein at least one of th R groups is -S0 2 X and wherein X is selected from the grou consisting of phenyl, tolyl, 1-naphthyl, 2-naphthyl, methoxyphenyl, and phenoxyphenyl or other aromatic o substituted aromatic groups. In a further exemplary embodiment, a polymer o Structure I or III is provided wherein at least one of th R groups is -NR 5 R 6 and wherein R 5 and R 6 may be the sam or different and are independently chosen from the grou consisting of alkyl, aryl, alkaryl, hydrogen, methyl ethyl, phenyl, -C0CH 3 and R 5 and R 6 taken together a bridging groups -CH 2 CH 2 0CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 -, an -CH 2 CH 2 CH 2 CH 2 - and the like. In another exemplary embodiment, a polymer of Structur I or III is provided wherein at least one of the R group is -N=CR 5 R 6 and R 5 and R 6 may be the same or differen and are independently selected from the group consistin of alkyl, aryl, alkaryl, -H, -CH 3 , -CH 2 CH 3 , phenyl, tolyl methoxyphenyl, benzyl, aryl, Cl to C22 alkyl, and R 5 an R 6 taken together as bridging groups -CH 2 CH 2 OCH 2 CH 2 - -CH 2 CH 2 CH 2 CH 2 CH 2 -, and -CH 2 CH 2 CH 2 CH 2 - and the like. The rigid-rod and segmented rigid-rod polymers of th present invention are made in accordance with well-kno chemical polymerization and addition reactions or by nove processes described herein. Such processes fo preparation of the rigid-rod and segmented rigid-r polymers of the present invention employ chemical polyme ization addition reactions in solvent systems in which t rigid-rod and segmented rigid-rod polymers and the monom starting materials are both soluble. Of course, t monomer and polymer will not demonstrate comple solubility under all conditions. The polymer will like demonstrate solubility only up to a certain weig fraction, depending on the exact solvent-polymer pair a other factors, such as temperature. Obviously, it is n necessary for the monomer to be completely soluble in solvent for a chemical reaction to proceed. As is we known in the art, compounds demonstrating limit solubility in a chemical mixture will completely react give product due to the equilibrium between dissolved a undissolved monomer, that is, undissolved monomer wi slowly undergo dissolution as that fraction of dissolv monomer is continuously exhausted in the reaction. As discussed above, the monomer and polymer are consider "soluble" in a particular solvent system when a soluti can be prepared which contains at least about 0.5% weight monomer and at least about 0.5% by weight polyme In order to assure solubility of the monomer a polymer in the solvent, the properties of the append organic groups must be matched to those of the desir solvent. Thus, if the rigid-rod and segmented rigid-r polymers are to be synthesized in polar solvents, t pendant solubilizing organic groups of the polymer and t monomer starting material will be groups that are solu in polar solvents. Similarly, if the rigid-rod segmented rigid-rod polymers are to be synthesized in n polar solvents, the pendant solubilizing organic group the rigid-rod and segmented rigid-rod polymer and the monomer starting material will be a group that is soluble in non-polar solvents. We have found that it is very important to match the dielectric constant and dipole moment of the solubilizing organic groups to that of the solvent to achieve solubilization. For instance, to achieve solubility in polar aprotic solvents such as NMP, the solubilizing organic groups should have dielectric constants greater than about 5 and dipole moments greater than about 1.5. In general, relatively long organic side chains, e.g. those with a molecular weight of greater than about 300, are preferred to enhance solubility of the rigid-rod polymers of the present invention. Surprisingly, however, we have found that rigid-rod polyphenylene type polymers, that is, rigid-rod polymers comprised of linear polyparaphenylene type monomer units having Structure I can be soiubilized with relatively short organic groups appended, e.g. , organic groups with molecular weights from about 15 to about 300. Solubility is typically achieved by a combination of favorable interactions acting together. For instance, solubility can be achieved in rigid-rod polyparaphenylenes substituted with the very small (i.e., low molecular weight) but very polar sid chains hydroxy (-OH) and amino (-NH ) . Planar aromatics tend to stack well, causing them ' to b very crystalline and, thus, have low solubility. Thi tendency to stack can be reduced by forcing adjacen aromatic rings, e.g., monomer units, to twist away fro planarity. This can be effected by the addition o substituents next to the covalent bonds linking th monomer units, leading to significant numbers o disubstituted 2,2'-biaryl type linkages. Such units hav been shown to increase solubility when incorporated int other types of polymer systems. Therefore, to achiev maximum solubility of short chain appended polyparaphenyl enes, either the nature of the monomer units or of th polymerization should be such that significant numbers o disubstituted 2,2'-biphenyl linkages are introduced in the polymer. For example, if every monomer unit has single non-hydrogen side group (R^H, R =R 3 =R =H) , then regular head-to-tail catenation will lead to no 2,2' disubstituted linkages, however, a regular head-to-he catenation will lead to 50% of the linkages having 2,2' disubstitution and 50% 2,2'-unsubstituted. A perfect random catenation will give 25% 2,2'-unsubstituted, 5 2,2'-monosubstituted and 25% 2,2'-disubstituted linkage We have found, in particular, that rigid-r polyphenylenes having benzoyl or substituted benzo solubilizing side groups are soluble in amide solvent for example N-methylpyrrolidinone (NMP) , and high rigid-rod polyphenylenes can be prepared in ami solvents. Poly-l,4-(benzoylphenylene) , 1, may be prepar from 2,5-dichlorobenzophenone by reductive coupling wi a nickel catalyst. The resulting polymer dopes have ve high viscosities and may be purified by precipitation in ethanol or other non-solvents. The dried polymer soluble in NMP, dimethylacetamide, phenylether, m-creso sulfuric acid, anisole, 5% NMP in ' chlorofor chlorobenzene, and similar solvents. Poly-l,4-(benzoylphenylene) , 1 The molecular weight of polymer 1 will depend on exact conditions of polymerization, including monomer catalyst ratio, purity of the reactants and solve dryness of solvent, oxygen concentration, and the li The method by which the zinc is activated grea influences the molecular weight. It appears that highest MW is obtained when the zinc is most active, t is when the reaction time is shortest. It is important that the zinc be free flowing powder which does not contain clumps which may form in the drying steps. The method of zinc activation given in the examples below is effective and convenient, however, other methods of activation are suitable including sonication, distillation, and treatment with other acids followed by rinsing and drying. It is also important that the zinc be well mixed during, and especially at the beginning of, the reaction. Molecular weight may be measured by many methods, most of which give only a relative molecular weight. Two of the most widely used methods are viscosity and gel permeation chromatography (GPC) . The intrinsic viscosity, [π], may be related to the molecular weight by the Mark- Houwink Equation: [TJ] = k-MW 01 For flexible polymers α is typically about 0.6, however, for rigid polymers α is usually greater than 1 and may be as high as 2. In order to determine absolute molecular weight, k and α must be obtained from other methods, or estimated using standards having structure similar to the polymer under study. Since there are no known rigid-rod polymers soluble in organic solvents there are no good standards for the polyphenylenes described here. We can make a crude estimate based on the expected relationship between viscosity and molecular weight for rigid-rods as has been "applied to polyparabenzobisthiazole and polyparabenzobisoxazole {J.F. Wolfe "Polybenzothiazoles and Oxazoles." in Encyclopedia of Polymer Science and Engineering,' John Wiley & Sons, Inc., New York, 1988; Vol. 11, pp. 601-635.>: [TJ] = 4.86xl0 20 (d h 0 - 2 /M £ ) (M- j /M j e) 1 - 8 where [η] is in dL/g, d h is the hydrodynamic diameter o a chain element in cm, and M t is the mass-per-unit lengt in g/cm. If d h is taken to be 10 ~7 cm (lnm) , the M t o trans-PBT is 2.15 x 10 9 cm _1 , the l χ of cis-PBO is 1.83 10 9 cm "1 , V. η = =1.3 then the weight-average molecular weight can be determined from th simple measurement of [rj], For polymer 1 we estimate d h « 1.5xl0 ~7 cm; IA & 4.19xl0 9 cm -1 = MW/£ = 180/4.3A; and [rj] = 2.4xl0 "8 -MW 1*8 Thus the polymer of Example 1 below has [ η = 7.2 dL/g a an estimated viscosity average MW of 51,000. Intrinsic viscosity is useful as a relative measure molecular weight even without Mark-Houwink constants. F comparison the highest reported viscosity for polyphenylene is 2.05 dL/g {M. Rehahn, A.-D. Schlύter, Wegner Makromol . Chem . 1990, 191 , 1991-2003}. Similarly, molecular weights as determined by G require a calibration standard, and no rigid-rod standar are available. The GPC data given in the examples bel are reported using a polystyrene standard and a therefore expected to be much higher than the actu weight average molecular weights. The soluble rigid-rod polymers of the present inventi can be made by any method which is highly selective f 1,4-phenylene regiochemistry. Non-limiting examples such reactions are: nickel catalyzed coupling 4-chloroaryl Grignard reagents, nickel or palladi catalyzed coupling of 1,4-arylhalides, palladium catalyz coupling of 4-chlorophenylboronic acids, Diels-Ald coupling of monosubstituted 2-pyrones (J.N.Braha T.Hodgins, T.Katto, R.T.Kohl, and J.K.Still Macromolecules. 11, 343-346, 1978.), anodic oxidation 1,4-dialkoxybenzene, and addition polymerization cyclohexadienediol derivatives. The polymer will be least 25 monomer units in length, preferably at least 1 monomer units in length, and, most preferably, longer th 100 monomer units. The polymer can be a homopolymer o single monomer or a copolymer of two or more differe monomers or monomer units. The segmented rigid- polymers of the present invention can be made using sa e methods as for the rigid-rod polymers, except that non-rigid-rod monomer is added to the rigid-rod monomer before or during polymerization. Processes for preparing unsubstituted or alkyl sub stituted polyphenylenes from aryl Grignard reagents ar described in T. Ya amoto et al, Bull. Chem. Soc. Jpn. 1978, 51, 2091 and M. Rehahn et al, Polymer, 1989, 30 1054. Paraphenylene polymers (made up of monomer units o Structure I) can be prepared by the coupling of Grignar reagents of paradihalobenzenes catalyzed by transitio metal complexes. Thus, a mixture of 4-bromo phenylmagnesium bromide (1 mole) and 4-bromo-3-alkyl phenylmagnesium bromide (1 mole) , the alkyl group havin an average chain length of about 24 carbon atoms, wil react in an ether solvent in the presence of a transitio metal complex to yield a polyparaphenylene rigid-ro polymer having about one out of two monomer units sub stituted with a long chain alkyl group. The transitio metal-catalyzed coupling reaction proceeds selectively an quantitatively under mild conditions. In another varian of the reaction, 1,4-dibromobenzene (0.5 mole) and a 1,4 dibromobenzene substituted with a long-chain alkoxy grou (1 mole) can be coupled in the presence of magnesium meta and a transition metal catalyst in an inert solvent, suc as ether, to produce a polyparaphenylene rigid-rod polym having on the average about two monomer units out of thr monomer,units substituted with a long-chain alkoxy grou A variety of dihalogenated benzenes (monomers of Formu IA) , biphenyls (monomers of Formula IB) , terpheny (monomers of Formula IC) , can be polymerized using the methods .( R ι~ R i 2 °f monomers IA, IB and IC a independently chosen from solubilizing groups and H) Dibromo-substituted compounds (X=Br) are the compounds choice for the reaction; however, in many instances, t dichloro compound (X=C1) can also be used, if the reacti can be initiated. We have found that the NiCl 2 (2,2 bipyridine) transitionmetal catalystworks satisfactori or this reaction. When the rigid-rod or segmented rigid-rod polymers a prepared under Grignard conditions, the following types organic groups may react with the Grignard reagent causing undesirable side reactions: alkyl halide amides, esters, ketones, and the like. Thus, such grou should be avoided as solubilizing side groups when t polymers of the present invention are prepared usi Grignard conditions. Coupling of the paradihaloarene monomers is preferab carried out with nickel or palladium catalysts with zi as the reducing agent. We have discovered that su polymerizations give soluble rigid-rod polyparaphenyle polymers with high molecular weights in virtually quant tative yields. This approach has distinct advantage since a wider variety of solvents can be employed, such N,N-dimethylformamide (DMF) , N-methylpyrrolidinone (NMP hexamethylphosphoric triamide (HMPA) , benzen tetrahydrofuran (THF) , and dimethoxyethane (DME) . Th coupling reaction can also be used with monomers havi specially reactive groups, such as nitrile and carbon groups. In addition, zinc- is less expensive and easier handle than magnesium. Similar reactions to prepa biphenyl derivatives and non-rigid polymer systems ha been demonstrated by Colon (I. Colon and D. Kelsey, Org. Chem.. 1986, 51, 2627; I. Colon and C. N. Merria U.S. Patent No. 4,486,576, . December 4, 1984 Unfortunately, this technique was demonstrated to b unsatisfactory to produce high molecular weight polymer from substituted dihalobenzene type monomers due t deactivation of the nickel catalyst by the substituents. It was, therefore, unexpected when we discovered tha certain mixtures of anhydrous nickel compounds, triaryl phosphine ligands, inorganic salt promoters, and zin metal were efficient for the preparation of high molecula weight polyparaphenylenes from the reductive coupling o paradihalobenzene monomer units substituted wit solubilizing organic groups in anhydrous polar aproti solvents. It is highly recommended to utilize highl purified (preferably greater than about 99% pure paradihalobenzene monomer from which any water or othe aprotic impurities have been removed. For instance, mixture of one equivalent of anhydrous nickel chloride three equivalents of sodium iodide, seven equivalents o triphenylphosphine, and 50 equivalents pf zinc metal i effective in the polymerization of about 30 equivalents o substituted paradichlorobenzene monomer. Th polymerization reaction is preferably carried out at abou 50°C but is effective from about 25°C to about 100°C. Th ratio of equivalents of monomer to equivalents of nicke catalyst can vary over the range from about 10 to abou 5000, and the ratio of equivalents of zinc to equivalen of monomer is at least 1.0. The ratio of equivalents phosphine ligands to equivalents of nickel catalyst vari from about 3.0 to about 10 or more. The concentration phosphine ligands should be about 2.5 M or more to preve the formation of highly unsaturated nickel zero complex which lead to undesired side reactions. Use of inorgan salt promoters is optional. When used, the inorganic sa promoter should be at a concentration of about 0.05 M 1 M, preferably about 0.1 M. Non-limiting examples inorganic salt promoters are alkali iodides, alka bromides, zinc halides and the like. These promote reduce or eliminate the induction period which is typic of nickel catalyzed couplings of aryl halides. When rigid rod or segmented rigid-rod polymers are prepared by nicke catalyzed coupling, the following types of side groups ma interfere with the reaction and should be avoided halides, acids, alcohols, primary and secondary amines nitro groups, and any protic groups. If side groups o these types are desired they should be introduced i protected form. When using the nickel-triarylphosphine cataly described above, one must be careful to sele sufficiently reactive monomers in order to obtain hi molecular weight polyparaphenylenes. If the reactivity too low, we believe that side reactions are more likely occur, which can limit molecular weight and/or deactiva the catalyst. Also, the two halide groups of t paradihaloarene monomers may have different reactivitie depending on the identity and location.of the substitue groups. Therefore, the orientation (e.g. head-to-hea head-to-tail, and tail-to-tail) of the monomer grou along the polymer backbone will be largely determined the relative reactivities of the halo groups of t monomer. Relative reactivities are also important consider when copolymers are being prepared. F instance, it is desirable to choose comonomers of simil reactivities when a completely random distribution of t different monomer groups is desired in the copolyme Conversely, it may be desirable to choose monomers wi significantly different reactivities in order to obta block-type copolymers, although molecular weight may limited if the reactivity of any of the monomers is t low. In general, it is desirable to have some knowledge the reactivity of monomers or comonomers in order to ma some predictions about the quality, structure, properties of the resulting polymers or copolymers. F instance, we have utilized a simple semi-quantitat procedure (see Example 29) for determining the relat coupling reactivities of various monohaloarene model compounds using nickel-triarylphosphine catalysts. The results of such experiments can then be used to estimate the relative reactivities of corresponding paradihaloarene monomers or comonomers. In general, we have found that to obtain the highest molecular weights, monomers must be chosen such that high conversions are achieved within about 4-6 hours when carried out under the preferred reaction conditions described above. For instance, if it is desired to prepare the corresponding polyparaphenylene from " the reductive coupling of 2,5-dichlorobenzoylmorpholine, one woul consider the relative reactivities of 3-chlorobenzoylmorpholine (fast) and o 2-chlorobenzoylmorpholine (slow) and would expect a head to-head and tail-to-tail orientation and that molecula weight might be somewhat limited. Similarly, if on wanted to prepare a- copolymer comprisin paradichlorobenzene and 2,5-dichlorobenzophenon comonomers, then the relative reactivities o chlorobenzene, 2-chlorobenzophenone, and 3 chlorobenzophenone should be considered (e.g. from Exampl 29, we see that the reactivities are similar, and fast, s a random copolymer with high molecular weight would b expected) . Aryl group coupling to afford polyphenylenes has als been effected by the palladium catalyzed condensation o haloaryl boronic acids as reported by Y. H. Kim et al Polymer Preprints. 1988, 29, 310 and M. Rehahn et al Polymer. 1989, 30, 1060. The para-haloaryl boronic aci monomers required for formation of polyparaphenylenes ca be prepared by the monolithiation of the paradihalobenzen with butyl lithium at low temperature and subsequen trimethylborate quench and aqueous acid workup. Thes polymerizations are carried out in aromatic and etherea solvents in the presence of a base such as sodiu carbonate. Therefore, this type of reaction is suitabl for producing polyparaphenylenes substituted with organ groups such as alkyl, aryl, aralkyl, alkary polyfluoroalkyl, alkoxy, polyfluoroalkoxy, and the lik The choice of solvents for the various polymerizati or condensation reactions will be somewhat dependent the reaction type and the type of solubilizing organ groups appended to the monomers. For the condensation aryl monomers employing Grignard reagents with transiti metal catalysts, the solvents of choice are ethers, a the best solubilizing side chains are ethers, such phenoxyphenyl, and long-chain alkyls. Anodic polymer zation is done in acetonitrile-type solvents, and ethe and aromatic side chains, such as phenylether, and benz would be the favored side chains. The monomer units are known or can be prepared conventional chemical reactions from known starting mate ials. For example, the 1,4-dichlorobenzophen derivatives can be prepared from 2,5-dichlorobenzoic a via 2,5-dichlorobenzoyl chloride followed by Frie Crafts condensation with an aromatic compound, for exam benzene, toluene, diphenylether and the like. paradihalobenzene monomers substituted at the 2 posit with an alkoxy group can be prepared from corresponding 2,5-dihalophenol by allowing the phenol the presence of sodium hydroxide and benzylt ethylammonium chloride to react with the corresponding haloalkyl, such as benzyl bromide. Substitu dichlorobenzenes may also be prepared from the inexpens 2,5-dichloroaniline by diazotization of the amine gro to yield corresponding p-dichlorobenzenediazonium sa The diazonium salt is treated with nucleophiles in presence of copper salts to form the desired product. In addition to being soluble in organic solven surprisingly, the polymers of the present invention may thermally processed, for example, by compression mold or by injection molding. For example, injection mol specimens of poly-l,4-(4'-phenoxybenzoylphenylene) , have flexural moduli greater than 1 million pounds per square inch (MSI) . Poly-1,4-(4'-phenoxybenzoylphenylene) , 2 Some of the polymers of the present invention will melt t o f o rm fr e e f l owing l i qu i d s . Poly-l,4-(methoxyethoxyethoxyethoxycarbonylphenylene) ,3, is a freely flowing liquid at about 250°C if protected from air. It was totally unexpected that high MW rigid- rod polyphenylenes having side groups with molecular weights less than 300 could be compression molded. It was even more surprising that such polymers would melt without decomposing. Polymer 3 In addition to solubility, the side groups impart fusibility. That is the side groups lower the T g and melt viscosity to ranges suitable for thermoprocessing. Polyparaphenylene devoid of side groups is essentiall infusible. It can be sintered at high temperature an pressure but it cannot be injection or compression molde or thermoformed by conventional techniques. Likewis other known rigid-rod polymers such a poly(benzobisthiazole) and rigid-rod polyquinolines ar not thermoformable. The polymers of the present inventio are thermoformable. Rigid-rod polyphenylenes having long very flexible side groups will melt. For example, th triethylene glycol side groups of 3 imparts a low T g an T m . Even short side groups impart fusibility. Polymer has side groups with molecular weight 105 and exceptional flexibility. It was unexpected that polyme 1 and 2 could be compression molded. Surprisingly, ev relatively high molecular weight 1 ([n])6, MW W >500,000 GPC vs polystyrene standard) can be compression molded translucent to transparent panels. The polymers of the present invention have very hi tensile moduli. Isotropic cast films and compressi molded coupons have given moduli in the range of 1 milli pounds per square inch (MPSI) to 3 MPSI. For the sa polymer the modulus increases as the molecular weig increases. The high modulus is a clear indication of t rigid-rod nature of these polymers. Tensile moduli f polyphenylenes have not been reported, presumably becau known polyphenylenes have molecular weights too small give film flexible enough to be tested. It is well known that rigid-rod polymers form liqu crystalline solutions if their aspect ratio and hen molecular weight increase beyond a critical value. Ma pseudo-rigid-rod polymers are known to form liqu crystalline phases as they melt. It was therefo unexpected to find that the rigid-rod polymers 1, 2 and neither form liquid crystalline solutions nor thermotrop liquid crystalline phases, even at intrinsic viscosity over 7 and GPC molecular weights over 500,000. This is advantage in molding operations where liquid crystallini can lead to poor weld lines, poor transverse mechanic properties, poor compressive strength, and a fibrill morphology. Polymers 1 and 2, in contrast give near isotropic molded panels, show no evidence crystallinity, and do not have a fibrillar structure. low crystallinity of the polymers of the present invent is advantageous in many applications including moldi atrix resins, optical polymers, and blending. Because the polymers of the present invention are soluble and will melt they can be processed using a wide variety of techniques. Polymer solutions may be spun into fibers by wet spinning, wherein the polymer solution is forced through an orifice directly into a non-solvent. The polymer forms a continuous fiber as it precipitates and may be washed dried and further processed in one continuous operation. Spinnerets having multiple orifices may be used to form poly-filament yarn. The orifices may have shapes other than round. The polymers of the present invention may also be dry jet wet spun, wherein an air gap is maintained between the spinneret and the non-solvent. Fibers may also be spun from a gel state. Gels have significantly different visco-elastic properties than liquids, and spinning fiber or casting film from a gel will often give products with dramatically different physical properties than those processed from simple solutions. Fibers spun from gels will can have a high degree of molecular orientation resulting in stronger, stiffer fibers. Fibers may also be spun directly from the melt. This method is environmentally the cleanest since it does not require any solvents. The polymer is heated and forced through an orifice. Orientation may occur at the orifice as a result of expansive flow. Orientation may also be induced by controlling the tension on the fiber to cause stretching. Multifilament yarn may also be spun from the melt. Fibers spun by any method may be further treated to influence physical and chemical properties. Further stretching, heating, twisting, etc. may be used to improve mechanical properties. Chemical treatments such as surface oxidation, reduction, sizing, coating, etching, etc. may be used to alter the chemical properties such a interaction with adhesives, matrix resins, dyes, and th like, and may also alter physical properties, such a appearance, tensile strength, flexural strength resistance to light, heat and moisture, and the like. Referring to FIG. 1, there is shown a semi-schemati view of a multi-filament fiber 10 comprising a pluralit of mono-filaments 12, comprising a rigid-rod or segmente rigid-rod polymer provided in accordance with practice o the present invention. The polymers of the present invention may also b fabricated into film. As with fibers many differen methods may be used to form films. Since the rigid-ro and segmented rigid-rod polymers of this invention ar both soluble and meltable, all of the conventional fil forming techniques are applicable. Films may be cast fro solution onto a substrate and the solvent removed eithe by emersion into a non solvent or by oven drying, under vacuum or inert atmosphere if necessary. Eithe continuous or batch processes may be used. Films may als be extruded from the melt through a slit. Films may als be formed by blow extrusion. Films may also be furthe processed by stretching and/or annealing. Special film such as bilayers, laminates, porous films, textured film and the like may be produced by techniques known in th art. Films, like fibers, may be oriented by stretchin Stretching along one dimension will result in uniaxi orientation. Stretching in two dimensions will gi biaxial orientation. Stretching may be aided by heati near the glass transition temperature. Stretching m also be aided by plasticizers. More complex process such as applying alternating cycles of stretching a annealing may also be used with the polymers of t present invention. Referring to FIG. 2, there is shown a roll 20 of fre standing film 22, formed from a rigid-rod or segment rigid-rod polymer, prepared in accordance with practice the present invention. The polymers of the present invention may also fabricated into membranes useful for separations of mixed gases, liquids and solids. Membranes may be produced by the usual methods, for example asymmetric membranes by solvent casting. Filters may be prepared by weaving fibers prepared as described above, or forming non-woven mats from chopped fibers or fibrous material produced by precipitation of polymer solution with a non-solvent. Referring to FIG. 3, there is shown a cross-sectional side view of a semi-permeable membrane 30 comprised of a rigid-rod or segmented rigid-rod polymer provided in accordance with practice of the present invention. As a result of the casting technique, the upper surface 32 has very small pores and is denser than the lower surface 34, which has courser pores. Tlie asymmetric structure of the membrane provides for higher selectivity and faster flow rates. Coatings may also be formed by any of the established techniques, including but not limited to: coating from solution, spray coating of solution, spin coating, coating from a latex, powder coating, laminating preformed films, spray coating molten droplets, and coating from the melt. Various molding techniques may be used to form article from the polymers of the present invention. Powders, pellets, beads, flakes, reground material or other form of rigid-rod and segmented rigid-rod polyphenylenes may b molded, with or without liquid or other additives, premixed or fed separately. Rigid-rod and segmente rigid-rod polyphenylene may be compression molded, th pressure and temperatures needed being dependent on th particular side groups present. Exact conditions may b determined by trial and error molding of small samples Upper temperature limits may be estimated from therma analysis such as thermogravimetric analysis. Lowe temperature limits may be estimated from T g as measure for example by Dynamic Mechanical Thermal Analysis (DMTA) Some suitable conditions for particular side groups ar given in the examples below. Some of the polymers provided in accordance with th present invention may also be injection molded. determine if a particular polymer can be injection mold it is necessary to measure the melt viscosity under shea typically using a • capillary melt flow rheomete Typically polymers having melt viscosities of less th 10,000 poises at shear rates greater than 10 3 sec "1 can injection molded. To be suitable for injection moldin polymers must also remain fluid (ie. without gelling solidifying) at the molding temperature during the moldi operation. It is also desirable if the polymer can remelted several times without degradation, so th regrind from molding processes can be used. Particul examples of rigid-rod and segmented rigid-r polyphenylenes which meet these requirements are giv below. However, injection molding is not limited to t particular side groups shown, and the-utility of injecti molding for any of the polymers of the present inventi may readily be determined by one skilled in the art. Referring to FIG. 4, there is shown a schematic view a radome 42 molded from a rigid-rod or segmented rigid-r polymer provided in accordance with practice of t present invention. The radome 42 is shown mounted on t wing structure 44 of an aircraft. The radome essentially a radar transparent cover which structurally self-supporting. In addition to films and fibers, other forms of rigi rod and segmented rigid-rod polyphenylenes may be produc by extrusion. Non-limiting examples include: angl channel, hexagonal bar, hollow bar, I-beam, joining stri rectangular tube, rod, sheet, square bar, square tube, section, tubes, or other shapes as is required for particular application. Related to extrusion pultrusion, wherein a fiber reinforcement is continuou added to an extruded polymer. The polymers of the pres invention may be used as a thermoplastic matrix which pultruded with fibers, such as carbon fiber or gl fiber. Alternatively, the polymers of the present invention may be used as the fiber for pultrusion of a thermoplastic having a lower processing temperature. In the first case, composites with exceptional moduli and compressive strength will result. In the second case, lower cost thermoplastics having moderate moduli and strength can be formed into composites with high moduli and strength by the incorporation of rigid-rod or segmented rigid-rod polyphenylene fibers. Such a composite is unique in that the reinforcing fibers are themselves thermoplastic and further processing at temperatures above the fiber T g will result in novel structures as the fibers physically and/or chemically mix with the matrix. Many of the forms of rigid-rod and segmented rigid-rod polyphenylenes alluded to above, i.e., fiber, film, sheet, rod, etc. , may be further processed and combined with other material to yield articles of higher value. Sheet stock may be cut, stamped, welded, or thermally formed. For example, printed wiring boards may be fabricated from sheet or thick films by a process wherein copper is deposited on to one or both sides, patterned by standard photolithographic methods, etched, then holes are drilled, and several such sheets laminated together to form a finished board. Such boards are novel in that they do not contain any fiber reinforcement. Such reinforcement is not necessary because of the unusually high modulus of the instant polymers. Such boards are also unique in that they may be bent into non-planar structures, by application of heat and pressure, to better fit limited volume enclosures, such as laptop computers. Sheet and film may also be thermoformed into any variety of housings, cabinets, containers, covers, chassis, plates, panels, fenders, hoods, and the like. Referring to FIG. 5, there is shown a semi-schematic cross-sectional side view of a four-layer wiring board 50. The board is comprised of rigid-rod or segmented rigid-rod polymer dielectric 52. Copper lines 54 are embedded i the dielectric 52 to form the inner two circuit planes Copper lines 56 on the surface of the board form the tw outer circuit planes. A via 58 is used to connec conducting lines in different planes. The via 58 connect conducting lines in the two outer planes with the line i one of the inner planes. The dielectric 52 can be a pur rigid-rod polymer, a segmented rigid-rod polymer, a blend a laminate or fiber-containing composite. Referring to FIG. 6, there is shown a non-woven mat 6 which consists of chopped fibers 62 comprised of a rigid rod or segmented rigid-rod polymer provided in accordanc with practice of the present invention. Such non-wove mats may be used as filters or the like. Referring to FIG. 7, there is shown a block of foam 7 comprising a rigid-rod or segmented rigid-rod polyme provided in accordance with practice of the presen invention. Rigid-rod and segmented rigid-rod polyphenylenes ma also form the dielectric layers of multichip modules Multichip modules (MCM) are similar to printed wirin boards except that integrated circuits are mounte directly on the MCM without prior packaging. T integrated circuits may be more closely packed, savi total system volume, reducing propagation delays, a increasing maximum operating frequency, among oth benefits. The basic structure of a multichip module shown in Fig 8. There are alternating layers dielectric and current carrying conducting lines. Mea for electrically and physically attaching integrat circuits is provided, as well as interconnection to t next highest level of packaging. Such MCM structures m be fabricated by many diverse processes. Because t rigid-rod and segmented rigid-rod polyphenylenes of t present invention both melt and dissolve in comm solvents any of the currently practiced methods of M fabrication may be applied. Referring to FIG. 8, a semi-schematic cross-sectional side view of an MCM, provided in accordance with practice of the present invention is shown. The MCM is typically (but not necessarily) fabricated using photolithographic techniques similar to those used in integrated circuit fabrication. As a non-limiting example an MCM may b constructed by spin coating a .layer 82 of rigid-rod o segmented rigid-rod polyphenylene onto a silicon substrat 84, having a plurality of resistors 86 on its surface, t thereby form a dielectric layer. The polyphenylene laye 82 may be further cured thermally or chemically i necessary. A layer of copper 88 is deposited onto th polyphenylene layer, and a layer of photoresist (no shown) is deposited, exposed, developed and the underlyin copper etched through the developed pattern in the resist. A second layer 90 of rigid-rod or segmented rigid-ro polyphenylene is spin coated and cured. Vias (not shown to the underlying copper lines are -cut, for example b laser drilling. Additional layers of copper 92 an dielectric 94 are added and patterned. Completed MCM' may have six or more alternating layers depending on th circuit complexity. The dielectric for MCM's may also b fabricated by laminating films, by spray coating or b other methods known in the art. The rigid-rod o segmented rigid-rod polyphenylene layer itself may b photosensitive, allowing additional methods of processing Photosensitivity of the rigid-rod or segmented rigid-ro polyphenylene will depend on the side group and additio of catalysts and sensitizers. The polymers of the present invention may also b combined with a variety of other polymers, additives fillers, and the like, collectively called additives before processing by any of the above or other methods For example, the polymers of the present invention may blended with some amount of a more flexible polymer improve the extension-to-break of the blend. Thu finished products formed from such a blend, e.g., fil sheet, rod or complex molded articles will be relatively tougher. Rubbers may be added to toughen the finished product. A liquid crystalline polymer may be added to reduce melt viscosity. Many other combinations will be apparent to those skilled in the art. The particular amounts of each additive will depend on the application but may cover the range from none (pure rigid-rod or segmented rigid-rod polyphenylene) to large amounts. As the amount of additives becomes much larger than the amount of rigid- rod polyphenylene the rigid-rod polyphenylene itself may be considered an additive. Polymers comprising the rigid-rod and segmented rigid- rods of the present invention can also be used in structural applications. Because of their high intrinsic stiffness, parts fabricated with rigid-rod or segmented rigid-rod polymers will have mechanical properties approaching or equal to fiber containing composites. In many applications where fibers are necessary for structural reasons they cause other undesirable effects. For example, radomes for airborne radar are typically constructed of glass fiber reinforced composites, but the glass fibers lead to signal loss and degredation of radar performance. Fiberless radomes comprised of rigid-rod or segmented rigid-rod polymers would improve radar performance over composite radomes. Fiberless radomes would also be easier to fabricate than composite radomes. Fiberless radomes comprising rigid-rod or segmented rigid-rod polymers provided in accordance with the present invention could be injection or compression molded or stamped from sheet, or machined from stock. Rigid-rod and segmented rigid-rod polymers can also be used to advantage in fiber containing composites as the matrix resin. As is known in the art the compressive strength of composites is related to the modulus of the matrix resin. Referring to FIGs. 9a and 9b, a composite 100 comprising reinforcing fibers 102 and 104 in the plane of the composite surface is shown. The fibers 102 run in a direction perpendicular to the fibers 104. Resins with high moduli will give composites with high compressive strength. The polymers of the present invention can be used to form composites by any of the established techniques, such as solution or powder impregnating (prepregging) fiber tows, yarns, tapes and fabrics, followed by lay-up of the .prepregs to the desired shape with a mold or form, and consolidating the composite by application of heat and pressure. Additives may be used as is known in the art including mold releases, anti- oxidants, curing agents, particulates, tougheners and the like. Non limiting examples of additives which may be used with rigid-rod or segmented rigid-rod polyphenylenes are: adhesion promoters, antioxidants, carbon black, carbon fibers, compatibilizers, curing agents, dyes, fire retardants, glass fibers, lubricants, metal particles, mold release agents, pigments, plasticizers, rubbers, silica, smoke retardants, tougheners, UV absorbers, and the like. The rigid-rod and segmented rigid-rod polymers of the present invention may be used as additives to modify the properties of other polymers and compositions. Relatively small amounts of the polymers of the present invention will significantly increase the mechanical properties of flexible polymers. Addition of about 5% of the polymer 1 to a blend of polystyrene and polyphenylene oxide increases the tensile modulus by about 50%. The polyphenylenes of the present invention may be added t any other polymer. The degree of improvement o mechanical properties will depend on the properties of th other polymer without the added polyphenylene, on th amount of polyphenylene used, on the degree to which th polyphenylene is soluble in the other polymer, and on th amounts and types of additives or compatibilizers. In general, polymers of differing types do not mix There are many-exceptions to this rule and many pairs o completely iscible polymers are known. For most of thes miscible polymers specific interactions result in negative heat of mixing, for example, hydrogen bonding, o ionic interactions. Polymer pairs which are not miscibl can often be made miscible by addition of a third polymer typically a low MW copolymer having segments similar t the polymers to be blended. Use of these and other type of compatibilizers are known in the art. These technique may be applied to the rigid-rod and segmented rigid-ro polyphenylenes of the present invention to enhance thei utility as additives. Thus a copolymer having segment which interact strongly with a rigid-rod polyphenylene a well as segments which interact strongly with a secon polymer will act as a compatibilizer for the two. Smalle molecules such as NMP, triphenylphosphate, an diphenylether will also aid compatibility by solvating th polyphenylenes of the present invention. It will also apparent to one skilled in the art that the particul side group on the rigid-rod or segmented rigid-r polyphenylene will strongly influence its ability blend. In general the side group should be chosen so th there is a negative heat of mixing between the side gro and the polymer in which it must mix. It should also apparent that complete miscibility is not always require Blending often results in mixing on a microscopic, but n molecular, level. Such blends ' will have properti different than the pure polymers and are often desirabl Even blends with macroscopic phases may have utility a may be considered another form of composite. Rigid-rod and segmented rigid-rod polyphenylenes wi be particularly useful as additives for flame retardant smoke retardants, tougheners, or to control or enhan creep resistance, coefficient of thermal expansio viscosity, modulus, tensile strength, hardness, moistu resistance, gas permeability, and abrasion resistance. GENERAL PROCEDURES 1. 2.5 - dichlorobenzoyl-containing compounds A wide variety -of 2,5-dichlorobenzoyl-containing compounds (e.g. 2,5-dichlorobenzophenones and 2,5- dichlorobenzamides) can be readily prepared from 2,5- dichlorobenzoylchloride. Pure2,5-dichlorobenzoylchloride is obtained by vacuum distillation of the mixture obtained from the reaction of commercially available 2,5- dichlorobenzoic acid with a slight excess of thionyl chloride in refluxing toluene. 2,5-dichlorobenzophenones (e.g. 2,5-dichlorobenzophenone, 2,5-dichloro-4'- methylbenzophenone, 2,5-dichloro-4'-methoxybenzophenone, and 2,5-dichloro-4'-phenoxybenzophenone) are prepared by the Friedel-Crafts benzoylations of an excess of benzene or substituted benzenes (e.g. toluene, anisole, or diphenyl ether, respectively) with 2,5-dichlorobenzoylchloride at 0-5°C using 2-3 mole equivalents of aluminum chloride as a catalyst. The solid products obtained upon quenching with water are purified by recrystallization from toluene/hexanes. 2,5-dichlorobenzoylmorpholine and 2,5-dichloro- benzoylpiperidine are prepared from the reaction of 2,5-dichloro-benzoylchloride and either morpholine or piperidine, respectively, in toluene with pyridine adde to trap the hydrogen chloride that is evolved. Afte washing away the pyridinium salt and any excess a ine, th product is crystallized from the toluene solution. 2. Activated Zinc Powder Activated zinc powder is obtained after 2-3 washings o commercially available 325 mesh zinc dust with 1 mola hydrogen chloride in diethyi ether (anhydrous) and dryin in vacuo or under inert atmosphere for several hours a about 100-120°C. The resulting powder should be sifte (e.g. a 150 mesh sieve seems to be satisfactory) , t remove the larger clumps that sometimes form, to assur high activity. This material should be used immediate or stored under an inert atmosphere away from oxygen a moisture. The following specific examples are illustrative of t present invention, but are not considered limiting there in any way. Example 1 Poly-1,4-(benzoylphenylene) Anhydrous bis(triphenylphosphine) nickel(II) chlori (34.7 g; 53 mraole) , triphenylphosphine (166.6 g; 7 mmole) , sodium iodide (34.6 g, 231 mmole), and 325 me activated zinc powder (181.8 g, 2.8 mole) were weigh into a bottle under an inert atmosphere and added to oven dried 12-liter flask, containing 1.6 liters anhydrous N-methylpyrrolidinone (NMP) , against a vigoro nitrogen counterflow. This mixture was stirred for abo 15 minutes, leading to a deep-red coloration. Sol 2,5-dichlorobenzophenone and another 0.8 liters anhydrous NMP were then added to the flask. After initial slight endotherm (due to dissolution of monomer the temperature of the vigorously stirred reaction mixtu warmed to about 60°C over 30 minutes and was held th (60-65°C) by use of a cooling bath. After stirring for additional 10-15 minutes, the viscosity of the react mixture increased drastically and stirring was stopp After heating this mixture for several days at 65°C, resulting viscous solution was poured into 10 L of 1 mo hydrochloric acid in ethanol to dissolve the excess z metal and to precipitate the macromonomer. T suspension was filtered and the precipitate tritura with acetone and dried to afford 283 g (85% yield) o fine pale-yellow powder. The sample was found to have an intrinsic viscosity 7.2 dL/g in 0.05 molar lithium bromide in NMP at 40 GPC analysis indicated a weight average molecular weig relative to narrow polydispersity polystyrene standar Of 550,000-600,000. Exa ple 2 Polv-1,4- ( '-phenoxybenzoylphenylene) 2,5-Dichloro-4'-phenoxybenzophenone To a 22L open-mouth round bottom flask fitted with a three-necked flange head, a mechanical stirrer, a nitroge inlet and an outlet connected to a HCl scrubbing tower wa added 2,5-dichlorobenzoic chloride (4500g, 21.5mol) an phenyl ether (5489g, 32.3mol) . The solution was cooled i ice to 5°C under stirring and aluminum chloride (3700g, 27.8mol) was added slowly. After about 300g aluminu chloride was added, the solution started to foa violently. The rest was added carefully over about 1 min. On several occasions, the stirring had to be stoppe to control the foaming. The temperature of the reactio mixture was about 35°C after the addition. The mixtur was then stirred for about 30 min. and poured into abou 20 gallon of ice water. The large reddish mass wa dissolved by adding about 12L of methylene chloride an stirring. The organic layer * was separated and the aqueou layer was extracted with some methylene chloride. Afte methylene chloride was removed from the combined organi layer by distillation, the residue was recrystallize twice from cyclohexane (2xlOL) , washed with cooled hexane air dried and then vacuum dried to afford 5387g monome (73%) . The mother liquor was kept for later recovery o remaining product. Polv-1.4- ( ■ -phenoxybenzoylphenylene) To a 12L open-mouth round bottom flask equipped with flange head, an air driven stirrer, a thermowell with thermocouple, and a nitrogen purge line, was added unde nitrogen bis(triphenylphosphine)nickel(II) chlori (58.2g, 88.9mmol), sodium iodide (54.7g, 365mmol) triphenylphosphine (279.3g, 1065mmol) , 325mesh activat zinc dust (239.5g, 3663mmol) and anhydro N-methylpyrrolidinone (NMP) (3400ml) . The solution w stirred and heated with a hot air gun to 40°C. T monomer 2,5-dichloro-4'-phenoxybenzophenone (935g 2725mmol) was added. The temperature dropped to 36.3° and then climbed to 'about 65°C when an ice water bath wa used to control the temperature below 86°C. After abou 15 min. the mixture became viscous. After 17 min. th solution became very thick and the stirring was stopped The reaction mixture was allowed to come to roo temperature and was left to stand overnight. The nex morning the reaction mixture was coagulated into a acetone bath and ground up in a blender. The crud polymer was then stirred for several days in 1 mola hydrochloric acid in ethanol to remove the excess zi metal. The polymer was collected by filtration, wash with water and acetone and dissolved in 16L of methyle chloride. The solution was filtered through 10 polypropylene membrane with the aid of celite, coagulat in the same volume of acetone, filtered, extracted wi acetone for three days and dried to 3afford 700g pa yellow polymer (94%) . GPC analysis showed a weig average molecular weight of 653,000 with t polydispersity being 1.97, relative to polystyre standard. Example 3 Polv-l,4-(2-r2-(2-methoxyethoxy)ethoxy1ethox carbonyl)phenylene 2-T2-(2-Methoxyethoxy)ethoxy1ethv1 2.5-dichlor benzoate (Triethyleneglvcol 2.5-dichlorobenzoate) To a round bottom flask fitted with a Dean-Steak wat separation apparatus, a magnetic stirrer and a condens were added 2,5-dichlorobenzoic acid (20g, O.llmol triethylene glycol monomethylether (30ml, 0.17mol concentrated sulfuric acid (0.4ml) and benzene (100ml The mixture was refluxed for 3 days and about 1.8ml water was collected. The solution was cooled to ro temperature and the solvent was removed on a rota evaporator. The residue was diluted with ether and was with diluted aqueo s sodium bicarbonate, washed with brine, and dried with magnesium sulfate. The liquid obtained after the " removal of solvent was purified by filtration through about 5g of basic alumina, with methylene chloride as the eluent. The fraction, after distillation of solvent, was dried under vacuum overnight with stirring to afford 30.8g of pure ester (88%). Polv-1.4-(2-T2-(2-methoxyethoxy) ethoxy1ethoxycar- bonyl) henylene Into a 100 ml round bottom flask containing NMP (7.5 ml) were weighted in a glove box anhydrous nickel(II) chloride (30 mg, 0.23 mmol), sodium iodide (125 mg, 0.83 mmol), triphenylphosphine (0.5g, 1.91 mmol), activated zinc dust (0.65 g, 10.16 mmol). This mixture was stirred with a magnetic stirrer for 40 min. at 50°C, leading to a deep red solution. Monomethylated triethyleneglycol 2,5- dichlorobenzoate (2.8 g, 7.95 mmol) was added as a nea liquid with a syringe. The mixture was stirred at this temperature for 3 days, resulting a viscous solution. Ethanol (100 ml) was added. A suspension was obtaine after stirring. It became a clear and almost colorles solution when 10 ml of 36% hydrochloric acid was added. The solution then was neutralized with diluted aqueou sodium hydroxide. The resulting suspension containin gel-like polymer was extracted with methylene chloride The organic layer was filtered and concentrated. Th polymer was precipitated with ethanol, separated by usin a centrifuge and dried under vacuum. A white, gum-lik solid was obtained (1.48 g, 67%). The weight averag molecular weight, relative to polystyrene standard, wa 116,000 according to GPC analysis. Exam le 4 Polv-i,4-(3'-methylbenzoylphenylene) 2,5-Dichloro-3'-methylbenzophenone A mixture of m-toluoyl chloride (22g, 0.17mol) and 1,4 dichlorobenzene (120g, 0.82mol) was heated to lOOoC in flask. Aluminum chloride (60g, 0.45mol) was added in on portion. Hydrogen chloride started to evolve from th solution. The mixture was heated to 170°C in 30 min. an stirred at this temperature for 3 hours. The resultin brownish solution was cooled to about 80°C and poured on ice. Ether (50ml) was added. The organic layer wa separated and distilled under vacuum after the removal ether. The residue from distillation was recrystalliz twice from hexane to give 20g of white crystals (53%) . Polv-1.4-(3'-methylbenzoy1)phenylene Anhydrous nickel(II) chloride (60mg, 0.47mmol), sodi iodide (175mg, 1.17mmol), triphenylphosphine (0.75 2.86mmol), activated zinc dust (2.3g, 35.9mmol) we weighed in a glove box into a 100ml round bottom fla containing NMP (8ml) . This mixture was stirred with magnetic stirrer for 30min. at 50°C, leading to a deep r solution. A solution of 2,5-dichloro-3 methylbenzophenone (2.6g, 9.85mmol) in NMP (7ml) w added. A viscous solution was obtained after stirring f 40 minutes. The mixture was kept at this temperature f another 10 hours and then at 65°C for another 3 day Ethanol was added to the reaction mixture. The solid w moved into a blender, ground into small pieces and th stirred with 50ml of 1 molar hydrochloric acid in ethan for 2 hours. The off-white solid was filtered and stirr with acetone overnight. Filtration and vacuum drying ga 1.62g off-white powder (85%). The weight avera molecular weight, relative to polystyrene standard, w 139,000 according to GPC analysis. EXAMPLE 5 Melt extrusion of Polv -1.4-(4'-phenoxybenzoylphenyle Poly -1,4-(4'-phenoxybenzoylpheneylene) provided accordance with Example 2 is dried to constant weight in a vacuum oven at 170 °C. The dry polymer is loaded into the hopper of a twin screw extruder with inlet and barrel temperature set to 270 °C. In a first extrusion run, the extruder is fitted with a heated die having a 50 cm by 2 mm slit-. The extruded sheet is air cooled and cut into 50 cm lengths. The sheet stock is thermoformed by pressing between shaped platens of a steel mold at 250 °C and 500 psi. In a second extrusion run, the extruder is fitted with a heated die having -a 10 cm by 0.2 mm slit. The extruded film is passed through a train of heated rollers and then abruptly accelerated between two rollers of different speeds to stretch the film by about 500%. Addition heat may be applied to keep the-film above its T g (about 160 °C) by radiant heating. The stretched film is annealed and cooled on a further roller train and collected as a continuous roll. In a third extrusion run, the extruder is fitted with a die having 500 spinnerets, each 200 microns in diameter at the exit. The polymer is extruded through the die and the multifilaments allowed to air cool before being collected on a windup bobbin. In a fourth extrusion run, the extruder is fitted wit a die having 200 spinnerets, each 400 in diameter micron at the exit. The extruded filaments are pulled away fro the exit at high velocity resulting in a draw ratio o about 12. The oriented fiber is collected on a windu bobbin. In a fifth extrusion run, the extruder is fitted wit a die suitable for extrusion of 1/2 inch pipe having 1/1 inch wall thickness. The pipe is cut into 4 foot lengths Example 6 Production of Angle Stock of polv-1.4-f4'-phenoxybenzoylphenylene) A blend of poly-l,4-(4'-phenoxybenzoylphenylene provided in accordance with Example 2, 200 g, polystyrene, 1000 g, and triphenylphosphate, 100 g is loaded into the hopper of a single screw extruder. The blend is extruded through a die having an L shaped slit 1 inch by 1 inch by 3/16 inch to produce angle stock. Example 7 Production of Fibers of polv-1,4- (4'-phenoxybenzoylphenylene) 50 g of poly-1,4-(4'-phenoxybenzoylphenylene) provide in accordance with Example 2 is dissolved in a mixture o NMP, 25 ml, and methylene chloride, 425 ml by stirring fo 48 hours. The viscous solution is pumped through a 0.2 m orifice. In the first run, the orifice is submerged at one en of a one meter trough containing 95% ethanol. The solutio coagulates as it is injected into the ethanol. Th coagulated polymer is manually pulled through the troug to the end opposite the orifice where it is threade through rollers and attached to a take up spool. The spee of the take up spool is regulated to provide a constan tension to the fiber. In the second run, the orifice is held one centimete from the surface at one end of a trough containing 95 ethanol. The solution is forced through the orifice as fine jet directed downward. The solution coagulates as i impinges on the ethanol. The coagulating fiber is fe around a roller and across the trough to the opposite en where it is collected on a constant tension take up roll Example 8 Coating a Silicon Wafer with polv-l,4-(4'-phenoxybenzoylphenylene) 50 g is of poly-1,4-(4'-phenoxybenzoylphenylen dissolved in a mixture of NMP, 25 ml, and methyle chloride 425 ml by stirring for 48.hours. A 4" silic wafer is coated with a thin film of poly-l,4-(4' phenoxybenzoylphenylene) by spin coating the solution 300 rpm for 15 sec followed by 1500 rpm for 60 sec. The coated wafer is further dried in a 100°C vacuum oven for 6 hrs. Example 9 Melt Spray Coating with polv-1,4-(4'-phenoxybenzoylphenylene) A blend of poly-1, -(4'-phenoxybenzoylphenylene) 50 g, and polystyrene, 400 g are loaded into the heated reservoir of a spray gun. The molten blend is forced by compressed nitrogen through the gun nozzle to form a coarse spray. The spray is directed such that a metal part is uniformly covered with polymer. The coated part may be heated further in an oven to level the polymer coating. Example 10 Powder Prepregging with polv-1,4-( '-phenoxybenzoylphenylene) Poly-1,4-(4'-phenoxybenzoylphenylene) provided in accordance with Example 2 'is prepared as a powder havin average particle size of about 10 microns. The powder is placed at the bottom of a closed chamber having a means to stir the powder. Carbon fiber tow is drawn through th chamber whereupon the stirred powder forms a dust clou which adheres to the carbon fibers. On leaving the powde chamber the coated carbon fibers then pass through a 150° oven to fix the polymer powder. The resulting prepreg ma be used to form composites by further forming an processing under heat and pressure. Example 11 Composite Fabrication with Prepreg from polv-1.4-f4'-phenoxybenzoylphenylene) The prepreg of Example 10 is wound onto a cylindrica tool. Heat and pressure are applied as the prepreg to contacts the cylinder surface so as to consolidate th polymer powder. The cylinder is completely wound with si layers of prepreg. During this operation the new layer are bonded to the underlying layers with local applicatio of heat and pressure. This on-line consolidation allow large parts to be fabricated without the use of a autoclave. Example 12 Comingled Filament Winding with polv-1.4-(4'-phenoxybenzoylphenylene) Fibers The fiber tow of the fourth extrusion run of Example is co-mingled with carbon fiber tow having 500 filament and wound on a bobbin. The resulting tow is used t filament wind a nosecone. The nosecone and tool ar placed in a 200°C oven for 1 hour to consolidate th polymer filaments. Example 13 Pultrusion with Rigid-Rod Polyphenylene Fibers The fiber tow of the fourth extrusion run of Example is continuously pulled through a polyetheretherketone mel and co-extruded through a die to form ribbed panels. Example 14 Blow Molding of a polycarbonate polv-1.4-(4'-phenoxybenzoylphenylene) Blend A 90:10 blend of polycarbonate and poly-l,4-(4' phenoxybenzoylphenylene) provided in accordance wi Example 2 is used in an injection blow molding machine produce 1 liter bottles. In the process a parison formed by an injection molding operation, the parison then moved to a mold and inflated to fill the mold. Aft cooling the finished bottle is removed from the mold. Example 15 Polv-1.4-(4'-phenoxybenzoylphenylene) Anhydrous bis(triphenylphosphine) nickel(II) chlori zinc powder (420 g, 6.42 mole) were weighed into a bottle under an inert atmosphere and added to an oven dried 22- liter flask, containing 4 liters of anhydrous NMP, against a vigorous nitrogen counterflow. This mixture was stirred for about 15 minutes, leading to a deep-red coloration. Solid 2,5-dichloro-4 '-phenoxy-benzophenone and another 2 liters of anhydrous NMP were then added to the flask. After an initial slight endotherm (due to dissolution of monomer) , the temperature of the vigorously stirred reaction mixture warmed to about 85°C over 15-20 minutes and was held there by use of a cooling bath. After stirring for an additional 10-15 minutes, the viscosity of the reaction mixture increased drastically and stirring was stopped. After cooling the reaction mixture to room temperature overnight, the resulting viscous solution was coagulated into 25 L of 1 molar hydrochloric acid i ethanol to dissolve the excess zinc metal and t precipitate the polymer. This suspension was filtered, and the precipitate was continuously extracted wit ethanol and then with acetone and dried. To achieve high purity, the crude polymer was dissolve in about 35 liters of NMP, pressure filtered through 1. micron (nominal) polypropylene fiber filters, coagulate into about 70 liters of acetone, continuously extracte with acetone, and dried to afford 1,186 g (91% yield) o a fine pale-yellow powder. The sample was found to have an intrinsic viscosity o 5.0 dL/g in 0.05 molar lithium bromide in NMP at 40°C GPC analysis indicated a weight average molecular weight relative to narrow polydispersity polystyrene standards Of 450,000-500,000. EXAMPLE 16 Copolv- -f 1 , 4- (benzoylphenylene) T- - -C 1 . 3-phenylene Anhydrous bis (triphenylphosphine) nickel (II) chlorid (10 g; 15 mmole) , triphenylphosphine (50 g; 0.19 mole) sodium iodide (12 g, 80 mmole) , and 325 mesh activate zinc powder (60 g, 0.92 mole) were weighed into a bottl under an inert atmosphere and added to an oven dried 2 liter flask, containing 800 milliliters of anhydrous NMP against a vigorous nitrogen counterflow. This mixture wa stirred for about 15 minutes, leading to a deep-re coloration. A mixture of 2,5-dichlorobenzophenone (127 g 0.51 mole) and 1,3-dichlorobenzene (11 ml; 96 mmole) wa then added to the flask. After an initial sligh endotherm (due to dissolution of monomer) , ' the temperatur of the vigorously stirred reaction mixture warmed to abou 80-85°C over 30 minutes. After stirring for an additiona 10-15 minutes, the viscosity of the reaction mixtu increased drastically and stirring was stopped. Aft cooling the reaction mixture to room temperatu overnight, the resulting viscous solution was poured in 6 L of 1 molar hydrochloric acid in ethanol to dissol the excess zinc metal and to precipitate the polyme This suspension was filtered and the precipitate w continuously extracted with ethanol and then with aceto and dried to afford 93 g (94% yield) of crude white resi To achieve high purity, the crude polymer was dissolv in about 600 L of methylene chloride, pressure filter through 1.2 micron (nominal) polypropylene fiber filter coagulated into about 2 liters of acetone, continuous extracted with acetone, and dried to afford 92 g (9 yield) of a fine white powder. The sample was found to have an intrinsic viscosity 1.75 dL/g in 0.05 molar lithium bromide in NMP at 40° GPC analysis indicated a weight average molecular weigh relative to narrow polydispersity polystyrene standard of 150,000-200,000. DSC analysis indicated a gla transition temperature of 167°C. EXAMPLE 17 Copolv--f1.4-(benzoylphenylene) >-{!.4-phenylene1 m ole) , sodium chloride (2.0 g, 34.2 mmole), 325 mesh activated zinc powder (19.5 g, 298 mmole), and 250 L of anhydrous NMP were weighed into an oven dried 1-liter flask under an inert atmosphere. This mixture was stirred for about 15 minutes, leading to a deep-red coloration. A mixture of 2,5-dichlorobenzophenone (45 g; 179 mmole) and 1,4-dichloro-benzene (2.95 g; 20 mmole) was then added to the flask. The temperature of the vigorously stirred reaction mixture was held at 60-70°C until the mixture thickened (about 30 minutes) . After cooling the reaction mixture to room temperature overnight, the resulting viscous solution was poured into 1.2 L of 1 molar hydrochloric acid in ethanol to dissolve the excess zinc metal and to precipitate the polymer. This suspension was filtered and the precipitate was washed with acetone and dried to afford crude resin. To achieve high purity, the crude polymer was dissolved in about 1.5 L of NMP and coagulated into about 4 L of acetone, continuously extracted with acetone, and dried to afford 30 g (89% yield) of an off-white powder. The sample was found to have an intrinsic viscosity of 4.9 dL/g in 0.05 molar lithium bromide in NMP at 40°C. GPC analysis indicated a weight average molecular weight, relative to narrow polydispersity polystyrene standards, of 346,000. DSC analysis indicated a glass transition temperature of 167°C. EXAMPLE 18 Preparation of Solvent Cast Thin Films of Rigid-Rod Polyparaphenylenes of Examples 1 and 2. Two methods are preferred for the preparation of good quality solvent cast films of the polymers provided in accordance with Examples 1 and 2. All films are cast i a particle free, low humidity environment, preferably fro filtered polymer solutions. (a) The first method involves casting from solution (about 1-15 weight percent, preferably about 3-7 weigh percent) in chloroform, anisole, dimethylacetamide (DMAc) N-methylpyrrolidinone (NMP) , or other suitable solvents The solvent is evaporated, if low boiling, or removed i a vacuum or convection oven, if high boiling. The films especially those thinner than about 1 mil, tend to b brittle but quite strong. (b) A second method for preparing free-standing fil involves casting from a solvent mixture of chloroform a NMP (generally containing about 1-10 volume percent NM preferably about 1-2 volume percent) . Polym concentrations typically range from about 1-15 weig percent, preferably about 3-7 weight percent. Aft casting the film, the chloroform quickly evaporate leaving a highly NMP swollen (plasticized) but general tack-free film. The remaining NMP can be easily remov by heating in an oven to form the final dry film, whi tends to be quite optically transparent and colorles Like those prepared from a single solvent, the complete dried films tend to be brittle but strong. The following film samples were prepared from batch of rigid-rod polyparaphenylenes in Examples 1 and 15 wi the specified intrinsic viscosities (related to molecul weight) according to the general procedures specifi above and the conditions listed: The mechanical (tensile) properties of the result films (A-F) were measured in accordance with ASTM-D- standards. Standard test samples were prepared b carefully cutting the films to the desired siz (approximately 6"x 0.5"x 0.001"). The films prepared b method (b) were more easily cut (i.e. withou microcracking along the edge of the test strip) in thei plasticized state. The average test results are presente below: The film of Example 18 E is dried until it approximately 5% by weight NMP. The NMP plasticized fi is drawn through a set of rollers to give a draw ratio 5 to 1. The oriented film may be further dried in vacuo 100 °C. EXAMPLE 20 Compression Molding of Rigid-Rod Polv-l,4-(benzoy phenylene) , Example 1 Material, and Polv-l,4-f4 phenoxybenzoylphenylene) , Example 2 Material. Coupons of the polymers provided in accordance with t procedures of Examples 1 and 2 can be compression mold at relatively moderate temperatures (200-400°C) a pressures (200-5,000 psi). Sometimes samples of t polymers of Examples 1 or 2 undergo darkening upon moldi at these temperatures, but the properties do not seem be adversely affected. To obtain 2"x 2"x 0.1" panels a batch of the polymer of Example 1 (with an intrin viscosity of 4.0 dL/g) or the polymer of Example 2 (w an intrinsic viscosity of 5.0 dL/g), the mold cavity filled with about 8.0 g of resin and placed into hydraulic press preheated to the specified temperatu After holding the sample at the molding temperature molding pressure for the specified molding time, sample is cooled below at least about 100°C during cooling time while retaining the molding pressure. U cooling to ambient temperature and removal from the mo the following panels were obtained according to specified conditions: The mechanical (flexural) properties of the resul panels (G-J) were measured in accordance with ASTM-D standards. Standard test samples were prepared carefully cutting the panels to the desired size (40 6 mm x 2.6 mm). The test results are presented belo A free-standing film, K, sample of copoly-{l,4- benzoylphenylene) }-{l,3-phenylene} ([TJ] = 1.75 dL/g) was prepared by conventional casting techniques from a 5.0 % (wt/wt) solution in chloroform. After drying, the mechanical (tensile) properties of the film were measured according to ASTM-D-882 specifications. A molded coupon (2"x 2"x 0.1") , L, of copoly-{l,4-benzoylphenylene) }-{l,3- phenylene} was prepared by compression molding about 8.0 g of resin at 300°C and 1,250 psi pressure for 30 minutes and then cooling slowly (about 3 hours) to ambient temperature while maintaining pressure. The mechanical (flexural) properties of the coupons were measured according to ASTM-D-790 specifications; standard tes samples were prepared by carefully cutting the coupons t the desired size (40 mm x 6 mm x 2.5 mm) . The followin data was obtained for samples K and L: Sample identi¬ Sample Measurement Strength Modulus Strai fication type Type (psi) (psi) % EXAMPLE 22 Injection Molding of Rigid-Rod Polv-1.4-(4 / phenoxybenzoyl-phenylene) Complex parts of the polymer provided in accordance wit the process of Example 2 were injection molded by standar techniques at moderate temperatures (280°C) . Mechanic (flexural) properties were measured according to ASTM- 790 specifications and melt viscosity was measured 280°C with a melt rheo eter with a capillary geometry 10 mm length and 1 mm diameter at a shear rate 1,000/sec. The following data was obtained for injecti molded strips of dimension 40 mm length x 6 mm width x mm thickness (MD, machine direction, refers to specime molded in the long direction (40 mm) to induce so orientation and TD, transverse direction, refers specimens molded in the short direction (6 mm) to minimi any orientation) : Sample Intrinsic Melt Flexural Flexural Flexura Identi- Viscosity Viscosity Strength Modulus Strain fication (dL/g) (poise) (psi) (psi) % Preparation of Blends of Polv-l,4-(4 -phenoxybenzoy phenylene) with Polvbutylene Terephthalate (PBT) by Me Extrusion/Injection Molding. Blendsofpoly-l,4-(4 -phenoxy-benzoylphenylene) ([ = 5.5 dL/g in 0.05 M LiBr/NMP at 40°C) and polybutyle terephthalate (e . g. NOVADUR PBT from Mitsubishi Kas Corporation; [77] = 1.1 dL/g in 1/1 1,1,2, tetrachloroethane/phenol) were prepared by conventional melt extrusion and test samples (40 mm length x 6 mm width x 1 mm thickness) were obtained by injection molding at 280°C. Relative to samples prepared from pure polybutylene terephthalate, the blend samples typically demonstrated better flexural strength andmodulus (ASTM-D- 790) and shown below (MD, machine direction, refers to specimens molded in the long direction (40 mm) to induce some orientation and TD, transverse direction, refers to specimens molded in the short direction (6 mm) to minimize any orientation) : The polymer blends were prepared in a small (50 g) Brabender mixer (C.W. Brabender, Inc. ; Hackensack, NJ) . The particular batch of poly-1 , 4 - (4 ' phenoxybenzoylphenylene) used for these experiment possessed the following properties: [η] = 3.5 dL/g (0.05 LiBr/NMP at 40°C) ; M„ GPC = 275,000; T g (DSC) = 143°C; an melt viscosity (at 300°C and 1,000/sec shear rate) = 4,10 poise. The mixer was preheated to the temperatur indicated below for the specified polymer to be blended with poly-1,4-(4'-phenoxybenzoylphenylene) , and the resin was added slowly and allowed to achieve uniform melt consistence over about 5 minutes. The poly-l,4-(4'- phenoxybenzoylphenylene) or a mixture of poly-l,4-(4 - phenoxybenzoylphenylene) andtriphenylphosphate (TPP; use as a plasticizer to lower the melt viscosity of th polyparaphenylene) was then added. If the blend was no uniform after about 5 minutes of mixing, the temperatur was increased to about 280-300°C for 5 minutes. The mixe was then cooled to 165°C, and the blend was removed an allowed to cool to room temperature. The following blend were prepared in this manner: Polystyrene = HCC9100 from Hunter Chemical Co.; Poly(phenylene oxide = Noryl 731 from GE Plastics; Nylon-6 (poly-e-caprolactam) = DYLAR 232 from ARCO Chemical. Compression molded panels of the above blends wer prepared for mechanical (tensile) testing according t ASTM-D-638 standards by molding at the temperatur specified below at about 700 psi for 2 minutes and the cooling to room temperature. The glass transitio temperatures (T ) were determined for the blends b dynamic mechanical thermal analysis (DMTA) of th compression molded parts. Specimens appropriate for DMT and mechanical testing (size approximately 6"x 0.5"x 0.1" were prepared from the molded panels by using a band-saw and/or a router. The following data was obtained: The polymer blends were prepared in a small (50 g) Brabender mixer (C.W. Brabender, Inc.; Hackensack, NJ) . The particular batch of poly-l,4-(benzoylphenylene) used for these experiments possessed the following properties: [17] = 3.5 dL/g (0.05M LiBr/NMP at 40°C) ; M„ GPC = 300,000; and melt viscosity (at 300°C and 100/sec shear rate) = 27,000 poise. The mixer was preheated to the temperature indicated below for the specified polymer to be blende with poly-l,4-(benzoylphenylene) , and the resin was adde slowly and allowed to achieve uniform melt consistenc over about 5 minutes. The poly-l,4-(benzoylphenylene) o a mixture of poly-l,4-(benzoylphenylene) an triphenylphosphate (TPP; used as a plasticizer to lowe the melt viscosity of the polyparaphenylene) was the added. If the blend was not uniform after about 5 minute of mixing, the temperature was increased to about 28Q 300°C for 5 minutes. The mixer was then cooled to 165°C and the blend was removed and allowed to cool to roo temperature. The following blends were prepared in manner: Polystyrene = HCC9100 from Hunter Chemical Co.; Poly(phenylene o = Noryl 731 from GE Plastics ; Polypropylene = Profax 6523 Himont; Polyethylene (high density) = # 8640 from Chevron. Compression molded panels of the above blends prepared for mechanical (tensile) testing accordin ASTM-D-638 standards by molding at the tempera specified below at about 700 psi for 2 minutes and cooling to room temperature. The glass transi temperatures (T ) were determined for the blend dynamic mechanical thermal analysis (DMTA) of compression molded parts. Specimens appropriate for and mechanical testing (size approximately 6"x 0.5"x 0 were prepared from the molded panels by using a ban and/or a router. The following data was obtained: The polymer blends were prepared by mixing solutions each polymer in chloroform or a solvent mixture compri of 90 % (vol/vol) chloroform and 10 % (vol/vol) NMP proper proportion to achieve the compositions specif below. The particular batch of poly-1 (benzoylphenylene) used for these experiments posses the following properties: [η] = 3.5 dL/g (0.05M LiBr/ at 40°C) ; M„ GPC = 300,000; and melt viscosity (at 30 and 100/sec shear rate) = 27,000 poise. The polysty was obtained from Hunter Chemical Co. (HCC9100) . blended resins were rapidly precipitated by pouring co-solutions into methanol (3 volumes relative to volume of polymer co-solution) . The precipitate filtered, washed.with additional methanol, and dried u vacuum for 24 hours at 70°C. Compression molded panel these blends were prepared for mechanical (tens testing according to ASTM-D-638 standards by molding 175°C at about 700 psi for 2 minutes and then cooling room temperature. The glass transition temperatures ( were determined for the blends by dynamic mechanic thermal analysis (DMTA) of the compression molded par Specimens appropriate for DMTA and mechanical test (size approximately 6"x 0.5"x 0.1") were prepared from molded panels by using a band-saw and/or a router. following data was obtained: Preparation of Blends of Poly-1.4-(4 '-phenoxybenzo phenylene) with Polycarbonate by Solution Mixing. The polymer blends were prepared by mixing solutions each polymer in chloroform in proper proportion to achi the compositions specified below. The particular batch poly-l,4-(benzoylphenylene) used for these experime possessed the following properties: [η] = 5.2 dL/g (0. LiBr/NMP at 40°C) and M W GPC = 450,000. The polycarbon was obtained from Mitsubishi Kasei Corporation (NOVA polycarbonate) . The blended solutions were then cast o a glass plate and dried rapidly to afford transpar free-standing thin film samples. The following mechani (tensile) properties were measured according to ASTM-D- specifications: Sample Polypara- Tensile Tensile Identi- phenylene Strength Modulus Elongation fication (wt %) (psi) (psi) (%) Solutions containing 1.5 to 3 wt.% of poly-1, (benzoylphenylene) provided in accordance with Example in Epomik R140 (Mitsui) were prepared by stirring t polymer and the epoxy resin at 100-140°C. The resulti solutions were almost colorless. Both 1.5 and 3 w solutions were very viscous at room temperature, howeve the viscosity of the solution dropped sharply wi warming. To about lg of solution of the polymer Example l in Epomik R140 was added 6-12 drops ethylenediamine (EDA) . The resulting solution was mi with a spatula until a homogeneous solution was obtain The mixture was left to sit at room temperature to cu Curing took from a few hours to two days depending on amount of EDA. In all cases, a hard transparent mass obtained. If the polymer mixture with EDA was heated about 70°c a very exothermic reaction occurred. resulting cured polymer blend in this case was sligh turbid. Curing was also successful when a small amount NMP was used as plasticizer. Example 29 Determination of the Relative Coupling Reactivities Monohaloarene Model Compounds Using Nick Triarylphosphine Catalysts. A mixture of 50 mg (0.39 mmole) of anhydrous nick chloride, 175 mg (1.17 mmole) of sodium iodide, 750 (2.86 mmole) of triphenylphosphine, 1.0 g (15.30 mmole) activated zinc powder, 500 mg (2.17 mmole) of orth terphenyl (used as an internal standard f chro atographic analysis) , and 7 ml of NMP was placed in a flask under an inert atmosphere and heated at 50°C f 10-15 minutes until the mixture achieved a deep r coloration, indicative of an activated catalyst solutio Then approximately 19.3 mmole (50 mole equivalents v anhydrous nickel chloride) of the desired monohaloare model compound was added to the flask. The course of t reaction was then followed by monitoring the disappearan of the monohaloarene model compound by standa quantitative gas chromatographic (GC) or high pressu liquid chromatographic (HPLC) techniques. Two simp approaches were utilized to quantify the reactivities the model compounds: (1) extent of reaction (conversio of the model compound after two hours and * (2) the amou of time required to achieve at least 90% conversion. T first technique requires fewer measurements but can strongly affected if there is any initiation period. T following data was obtained by the above technique for t specified monohaloarene model compounds: trifluoride 3-chlorobenzo- > 95 < 1 hr trifluoride 2-chlorobenzoyl- 5-10 > 40 hrs morpholine 1.5-2.0 hrs N/A 30 min 30 min 2 hrs 2.5-3.0 hrs > 24 hrs > 24 hrs Example 30 Poly-1,4-(2 '-methylbenzoylphenylene) 2,5-DichIoro-2 '-methylbenzophenone A mixture of o-toluoyl chloride (22g, 0.17mol) an 1,4-dichlorobenzene (120g, j 0.82mol) was heated to 100°C i a flask. Aluminum chloride (60g, 0.45mol) was added i one portion. The mixture was heated to 170°C in 30 mi and stirred at this temperature for 3 hours. Th resulting brownish solution was cooled to about 80°C an poured onto ice. Ether (50ml) was added. The organi layer was separated and distilled under vacuum after th removal of ether. The residue from distillation wa recrystallized twice from hexane to give 16g of whit crystals (36%) . Polv-l.4-(2 '-methylbenzoylphenylene) Anhydrous nickel(II) chloride (60mg, 0.47mmol) sodium iodide (175mg, 1.17mmol), triphenylphosphin (0.75g, 2.86mmol), activated zinc dust (2.3g, 35.9mmol were weighted in a glove box into a 100ml round botto flask containing NMP (8ml) . This mixture was stirred wit a magnetic stirrer for 30 min at 50°C, leading to a dee red solution. A solution of 2,5-Dichloro-2 ' methylbenzophenone (lO mol) in NMP (7ml) was added Stirring was continued for about 40 minutes until viscous solution was obtained. The mixture was kept 65°C for another 2-3 days. Ethanol was added to t reaction mixture. The solid was moved into a blende ground into small pieces and then stirred with 50ml of molar hydrochloric acid in ethanol for 2 hours. The of white solid was filtered and stirred with aceto overnight. Filtration and vacuum drying gave off-white pale yellow powder. The weight average molecular weig relative to polystyrene standard according to GPC analys was 70,000. Example 31 Poly-1,4-(2 ' ,5 -dimethylbenzoylphenylene) 2,5-Dichloro-2 .5'-di ethylbenzophenone To p-xylene (120ml, 0.98mol) was added alumin chloride (32g, 0.24mol) at room temperature. To th mixture 2,5-dichlorobenzoyl chloride (30g, 0.14mol) w added slowly. The reaction was exothermic and hydrog chloride evolved from the reddish solution. After t addition, the mixture was stirred for lOmin and th hydrolysed by slow addition of water. The aqueous lay was extracted with ether. The organic layer was combi with ethereal extract and washed with water, satura sodium bicarbonate, brine, respectively, and then dr with magnesium sulfate. After the removal of solvent, residue was recrystallized from methanol twice and t from hexane to give 36.8g (92%) crystals (mp 58-61°C) . Polv-1,4-(2 ,5'-dimethylbenzoylphenylene) Anhydrous nickel(II) chloride (60mg, 0.47mmo sodium iodide (175mg, 1.17mmol), triphenylphosph (0.75g, 2.86mmol), activated zinc dust (2.3g, 35.9mm were weighted in a glove box into a 100ml round bot flask containing NMP (8ml) . This mixture was stirred w a magnetic stirrer for 30 min at 50°C, leading to a d red solution. A solution of 2,5-Dichloro-2 ' . dimethylbenzophenone (lO mol) in NMP (7ml) was add Stirring was continued for about 40 minutes until viscous solution was obtained. The mixture was kept at 65°C for another 2-3 days. Ethanol was added to the reaction mixture. The solid was moved into a blender, ground into small pieces and then stirred with 50ml of 1 molar hydrochloric acid in ethanol for 2 hours. The off- white solid was filtered and stirred with acetone overnight. Filtration and vacuum drying gave off-white or pale yellow powder. The weight average molecular weight relative to polystyrene standard was 50,000 according to GPC analysis. Example 32 Poly-1,4-(2-(2-pyrrolidinon-l-yl)ethoxycarbonylphenylene) 2-f2-Pyrrolidinon-l-yl)ethyl 2,5-dichlorobenzoate Amixture of 2,5-dichlorobenzoic acid (20g, O.llmol) , l-(2-hydroxyethyl-2-pyrrolidinone (27g, 0.22mol) in benzene (100ml) was refluxed in the presence of 1ml of concentrate sulfuric acid for 24 hours. About 2.2ml of water was collected. The mixture was cooled and washe with aqueous sodium bicarbonate and water, respectivel and evaporated. The residue was purified b recrystallization from hexane and ethyl acetate to giv the esters as white crystals (lOg, 32%) . Polv-l,4-f2-f2-pyrrolidinon-l-yl)ethoxycarbonyl phenylene) Anhydrous nickel(II) chloride (60mg, 0.47mmol), sodium iodide (175mg, 1.17mmol), triphenylphosphin (0.75g, -2.86mmol) , activated zinc dust (2.3g, 35.9mmol) were weighted in a glove box into a 100ml round botto flask containing NMP (8ml) . This mixture was stirred wit a magnetic stirrer for 30 min at 50°C, leading to a dee red solution. A solution of 2-(2-Pyrrolidinon-l-yl)ethy 2,5-dichlorobenzoate (lOmmol) in NMP (7ml) was added Stirring was continued for about one week and a viscou solution was obtained. The mixture was kept at 65°C fo another 2-3 days. Ethanol was added to the reactio mixture. The solid was moved into a blender, ground int small pieces and then stirred with 50ml of 1 mola hydrochloric acid in ethanol for 2 hours. The off-whi solid was filtered and stirred with acetone overnigh Filtration and vacuum drying gave off-white or pale yell powder. The polymer has structure I with R^= -C0 2 CH 2 CH 2 NCOCH 2 CH 2 CH 2 , and R 2 ~R 4 =H The weig average molecular weight, relative to polystyrene standa according to GPC analysis was 72,000. Example 33 Poly-1,4-(4'-(2-phenoxyethoxy)benzoylphenylene) 2,5-Dichloro-4 / -(2-phenoxyethoxy)benzophenone To a suspension of 1,2-diphenoxyethane (25 O.llmol), aluminum chloride (14g, O.llmol) chlorobenzene (400ml) was added slowly 2,5-dichlorobenzo chloride (9.8g, 0.05mol) at OoC. After the addition, t mixture was stirred for another 20 minutes and worked as usual. After the removal of solvent, the residue w purified by chromatography on silica gel a recrystallization from cyclohexane to give 9g pure keto (50%) . Polv-1,4-(4'-(2-phenoxyethoxy)benzoylphenylene) Anhydrous nickel(II) chloride (60mg, 0.47mmol sodium iodide (175mg, 1.17mmol), triphenylphosphi (0.75g, 2.86mmol), activated zinc dust (2.3g, 35.9mmo were weighted in a glove box into a 100ml round bot flask containing NMP (8ml) . This mixture was stirred w a magnetic stirrer for 30 min at 50°C, leading to a d red solution. A solution of 2.5-Dichloro-4 / -( phenoxyethoxy)-benzophenone (lOmmol) in NMP (7ml) added. Stirring was continued until a viscous solut was obtained, about 3 hours. The mixture was kept at 6 for another 2-3 days. Ethanol was added to the react mixture. The solid was moved into a blender, ground i small pieces and then stirred with 50ml of 1 mo hydrochloric acid in ethanol for 2 hours. The off-wh solid was filtered and stirred with acetone overnig Filtration and vacuum drying gave off-white or pale yellow powder. The weight average molecular weight relative to polystyrene standard was 218,000 by GPC analysis. The above descriptions of exemplary embodiments of processes for producing rigid-rod and segmented rigid-ro polymers, and the rigid-rod and segmented rigid-ro polymers produced by the processes, are for illustrativ purposes. Because of variations which will be apparent t those skilled in the art, the present invention is no intended to be limited to the particular embodiment described above. The scope of the invention is defined i the following claims.

Claims: What is claimed is: 1. A rigid-rod polymer of the formula: wherein each R 1# R 2 , R 3 and R 4 on each monomer unit, independently, is H or a solubilizing side group, where at least one out of one hundred of the monomer units incorporate a solubilizing side group and wherein the polymer has number average degree of polymerization of at least about 25. 2. The polymer of claim 1 wherein at least about 30% of the monomer units incorporate a solubilizing side group. 3. The polymer of claim 1 wherein at least one of the R groups is: wherein X is selected from the group consisting of hydrogen, amino, methylamino, dimethylamino, methyl, phenyl, benzyl, benzoyl, hydroxy, methoxy, phenoxy, -SC 6 H 5 , and -OCOCH 3# 4. The polymer of claim 1 wherein at least one of the R groups is: SUBSTITUTE SHEET and wherein X is selected from the group consisting of methyl, ethyl, phenyl, benzyl, F, and CF 3 , and n is 1, 2, 3, 4, or 5. 5. The polymer of claim 1 wherein one of R lf R 2 , R 3 or R 4 is selected from the group consisting of -CR 5 R 6 Ar where Ar is aryl, R 5 and R 6 are H, methyl, F, Cl to C20 alkoxy, OH, and R 5 and R 6 taken together as bridging groups -OCH 2 CH 2 0- , -OCH 2 CH_(CH 2 OH)0-, -OC g H 4 0- (catechol) , -OC 6 H 10 O- (1,2- cyclohexanediol) , and -0CH 2 CHR 7 0- where R 7 is alkyl, or aryl. 6. The polymer of claim 1 wherein at least one of the R groups is -(CO)X and X is selected from the group consisting of 2-pyridyl, 3-pyridyl, 4-pyridyl, -CH 2 C 6 H 5 , -CH 2 CH 2 C 6 H 5 , l-naphthyl and 2-naphthyl. 7. The polymer of claim 1 where at least one of the R groups is -S0 2 X and wherein X is selected from the group consisting of phenyl, tolyl, l-naphthyl, 2-naphthyl, methoxyphenyl, and phenoxyphenyl. 8. The polymer of claim 1 wherein at least one of the R groups is -NR 5 R 6 and wherein R 5 and R 6 may be the same or different and are independently chosen from the group consisting of hydrogen, methyl, ethyl, phenyl, -C0CH 3 and R 5 and R 6 taken together as bridging groups -CH 2 CH 2 0CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 -, and -CH 2 CH 2 CH 2 CH 2 -. 9. The polymer of claim 1 where at least one of the R groups is -N=CR 5 R 6 and R 5 and R 6 may be the same or different and are independently selected from the group consisting of -H, -CH 3 , -CH 2 CH 3 , phenyl, tolyl, methoxyphenyl, benzyl, aryl, Cl to C22 alkyl, and R 5 and R 6 taken together as bridging groups -CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 -, and -CH 2 CH 2 CH 2 CH 2 -. 10. The polymer of claim 1 where the intrinsic viscosity of said polymer is greater than about 1 deciliter/gram. 11. The polymer of claim 1 where the intrinsic viscosity of said polymer is greater than about 3 deciliters/gram. 12. The polymer of claim 1 where the intrinsic viscosity of said polymer is greater than about 5 deciliters/gram. 13. The polymer of claim 1 where the weight average molecular weight of said polymer as measured by gel permeation chromatography against polystyrene standards is greater than about 100,000. 14. The polymer of claim 1 where the weight average molecular weight of said polymer as measured by gel permeation chromatography against polystyrene standards is greater than about 250,000. 15. The polymer of claim 1 where the weight average molecular weight of said polymer as measured by gel permeation chromatography against polystyrene standards is greater than about 500,000. 16. The polymer of claim 1 wherein the tensile modulus of unoriented 25 micron film of said polymer is greater than about 0.75 million pounds per square inch. 17. The polymer of claim 1 where the tensile modulus of unoriented 25 micron film of said polymer is greater than about 1.5 million pounds per square inch. 18. A process for the preparation of the polymer of claim 1- wherein R 1 is benzoyl and R 2 -R 4 are H, comprising reductive coupling polymerization of 2,5-dichlorobenzophenone with Zn in an anhydrous amide solvent in the presence of 1) a nickel catalyst 2) a promoter selected from the group consisting of nil, alkali metal chlorides, alkali metal bromides, alkali metal iodides, and zinc chloride, and 3) a phosphine ligand. 19. A process for the preparation of the polymer of claim 3 comprising reductive coupling polymerization of an aroyl-2,5-dichlorobenzene with Zn in an anhydrous amide solvent in the presence of 1) a nickel catalyst 2) a promoter selected from the group consisting of nil, alkali metal chlorides, alkali metal bromides, alkali metal iodides, and zinc chloride, and 3) a phosphine ligand. 20. A process for fabricating free standing films of the polymer of claim 1 comprising melting said polymer and extruding the melt into a slit. 21. A process for fabricating a film of the polymer of claim 1 comprising casting a solution of said polymer onto a support surface, followed by removal of the solvent. 22. A process for fabricating film of the polymer of claim 1 comprising casting a solution of said polymer onto a support surface, followed by immersion into a non-solvent for said polymer. 23. A process for preparing fibers of the polymer of claim 1 comprising melt spinning compositions containing at least about 50% by weight of said polymer. 24. A process for preparing fibers of the polymer of claim 1 comprising wet spinning solutions wherein the dissolved solids comprise at least about 50% by weight of said polymer . 25. A process for preparing fibers of the polymer of claim 1 comprising dry jet wet spinning solutions of said polymer wherein the dissolved solids comprise at least about 50% by weight of said polymer. 29. A process for orienting film or fibers of the polymer of claim 1 comprising drawing or stretching film or fiber comprising said polymer which has been plasticized with between 0.1% and 10% solvent, wherein the solvent is removed either subsequent to or during the drawing process. 30. A process for coating solid articles with the polymer of claim 1 comprising application of a solution comprising said polymer, wherein the dissolved solids comprise at least about 50% by weight of said polymer, followed by removal of solvent. 31. A process for coating solid articles with polymer compositions containing at least about 50% by weight of the polymer of claim 1 comprising spraying the article with molten droplets of said polymer composition. 32. A process for coating solid articles with polymer compositions containing at least about 50% by weight of the polymer of claim 1 comprising powder coating the article with said polymer composition. 33. A process for fabricating solid articles by compression molding a composition comprising a polymer of claim 1. 34. A process for fabricating solid articles, by compression molding a composition comprising a polymer of claim 3. 35. A process for fabricating solid articles by rolling or calendering a composition comprising a polymer of claim 1. 36. A process for fabricating solid articles by blow molding a composition comprising a polymer of claim 1. 37. A process for fabricating solid articles by extruding a composition comprising a polymer of claim 1 through an orifice. 38. A process for fabricating fiber containing composites by the steps of: co-mingling fibers comprising the polymer of claim 1 with fibers of a second material; shaping the co-mingled fibers into a suitable shape; and heating to cause the fibers comprising the polymer of claim 1 to fuse. 39. A process for fabricating a solid article by 1) preparing sheet stock comprising the polymer of claim 1 and 2) thermoforming said sheet stock by application of heat and pressure into a final shape. 40. A process for fabricating a composite article by pultrusion of fibers comprising the polymer of claim 1 with a lower melting thermoplastic. 41. A process for fabricating a composite article by pultrusion of a thermoplastic composition comprising the polymer of claim 1 with fibers which will not melt under the pultrusion conditions. 42. A process for fabricating a solid article by injection molding a composition comprising the polymer of claim 1. 43. A process for fabricating a solid article by injection molding a compdsition comprising the polymer of claim 3. 44. A process for orienting the polymer molecules of an article comprising the polymer of claim l by heating and stretching the article. 45. The process of claim 44 where the article is a fiber and the stretching is carried out at a temperature above the glass transition temperature of the polymer of claim 1. 46. The process of claim 44 where the article is a film. 47. The process of claim 44 where the article is comprised of the polymer of claim 1 and from 0.01% to 10% of a plasticizer. 48. The process of claim 47 where the plastici-zer is selected from the group consisting of N- methylpyrrolidinone, N-cyclohexylpyrrolidinone, N,N- dimethylformamide, N , N-.dimethylacetamide , dioctylphthalate , diphenylether , anisole, triphenylphosphite, triphenylphosphate, and cresol. 49. Free-standing film comprising a polymer of claim 1. 50. Fibers comprising a polymer of claim 1. 51. Foams comprising a polymer of claim 1. 52. Non-woven fibrous mats comprising a polymer of claim 1. 53. Molded articles comprising a polymer of claim 1. 54. Fiber containing composites wherein the matrix resin comprises a polymer of claim 1. 55. Printed wiring boards wherein the dielectric comprises a polymer of claim 1. 56. Coatings compositions comprising a polymer of claim 1. 57. A multichip module comprising a plurality of dielectric layers comprising of a polymer of claim 1. 58. A semipermeable membrane formed by wet casting a solution of the polymer of claim 1. 59. A process for lowering the flammability of polymer compositions comprising introducing an additive comprising a polymer of claim 1 into said polymer composition. 60. A process for reducing creep in polymer compositions comprising blending or otherwise mixing and additive comprising a polymer of claim 1 with said polymer composition. 61. A process for lowering the coefficient of thermal expansion of polymeric compositions comprising blending or otherwise mixing an additive comprising a polymer of claim 1 with said polymer composition. 62. A polymeric composition comprising: (a) a polymer base; mixed together with (b) an additive comprising a polymer of claim 1 for lowering the coefficient of thermal expansion of said polymer base. 63. A process for increasing the modulus of a polymer composition consisting of blending or otherwise mixing an additive comprising a polymer of claim 1 with said polymer co position. 64. The process of claim 63, further comprising mixing one or more compatibilizers selected from the group consisting of NMP, DMAC, DMF, diphenylether, styrene-maleic anhydride copolymer, and copolymers wherein one component of said compatibilizer is similar to the said polymer composition to . be stiffened and another component of said compatibilizer is a polymer which will form a solid solution with said polymer of claim 1. 65. A process for increasing the toughness of polymer compositions comprising blending or otherwise mixing an additive comprising a polymer of claim 1 with said polymer composition. 66. A process for increasing the abrasion resistance of a polymer composition comprising blending or otherwise mixing an additive comprising a polymer of claim 1 with said polymer composition. 67. A composition comprising the polymer of claim 1 and a second polymer. 68. The composition of claim 67 wherein said second polymer is polycarbonate. 69. The composition of claim 67 wherein said second polymer is chosen from the group consisting of polya ides, polyimides, polyesters, polyolefins, polyacrylates, polystyrenes, polyarylates , polyarylethers , polyarylsulfides, polysiloxanes, polyacetals, polyurethanes, polycyanates, epoxy resins, phenolics, cellulosics, other natural polymers, gums, lacquers, rubbers and latexes, and copolymers, mixtures, blends and alloys of these polymers. 70. The composition of claim 67 wherein said second polymer is chosen from the group consisting of poly(hexamethyleneadipamide) , poly (bisphenol A carbonate) , poly (bisphenol A terephthalate), poly (bisphenol A isophthalate) , poly (aery lonitrile) , polystyrene, poly (methylmethacrylate) , poly (vinylchloride) , poly (vinylidenechloride) , poly (vinylalcohol) , poly(vinylacetate) , poly(acryla ide) , poly(ethyleneoxide) , poly (propy leneoxide) , poly (pheny leneoxide) , poly(phenylenesulf ide) , poly(acetal) , poly (ethylene) , poly ( isoprene) , poly (cyclopentadiene) , poly(chlorobutadiene, poly (tetrafluoroethylene) , and poly(vinylidenefluoride) . 71. The composition of claim 67 where said second polymer is a thermoset. 72. The composition of claim 67 where said second polymer is a thermoplastic. 73. The composition of claim 67 where said second polymer is a liquid crystalline polymer. 74. A segmented rigid-rod polymer having the formula wherein SUBSTITUTE SHEET is a rigid-rod polyphenylene segment and wherein each R l7 R 2 , R 3 and R 4 on each monomer unit, independently, is H or a solubilizing side group, where at least one out of one hundred of the monomer units in the rigid-rod segments incorporate a solubilizing side group, and are non-rigid segments, wherein the rigid-rod polyphenylene segments have a number average segment length (SL n ) at least about 8, and m is 1 or greater. 75. The polymer of claim 74 wherein the non-rigid-rod segments are derived from dihaloaromatic monomers of the structure: Structure II where ^- a are independently chosen from solubilizing side groups and H wherein G is -0-, -S-, -CH 2 -, -CY 2 -, -OCH 2 -, -OAr-., -0(ArO) n -, -1,3-phenylene-, -1,2-phenylene-, -(CH 2 ) n -, -(CY 2 ) n -, -CO-, -C0 2 -, -CONY-, -0(CH 2 CH 2 0) n -, "(CF 2 ) n -, -COArCO-, -CO(CH 2 ) n CO-, -C(CF 3 ) 2 ~, -C(CF 3 )Y-, -NY-, -P(=0)Y-, X is Cl, or Br, or I and Ar is an aromatic group, heteroaromatic group, or substituted aromatic group, and Y is independently selected from the group consisting of H, F, CF 3 , alkyl, aryl, heteroaryl, and aralkyl, and n is 1 or greater. 76. The polymer of claim 74 wherein -A- is wherein B 1 -B 4 are independently selected from the group consisting of H, C x to C 22 alkyl, C 6 to C 20 Ar, alkaryl, F, CF 3 , phenoxy, -COAr, -COalkyl, -C0 2 Ar, -C0 2 alkyl, wherein Ar is aryl or heteroaryl. 77. The polymer of claim 74 wherein -A- is 1,3-phenylene. 78. The polymer of claim 74 wherein at least about 30% of the monomer units incorporate a solubilizing side group. 79. The polymer of claim 74 wherein at least one of the R Groups is: and wherein X is selected from the group consisting of hydrogen,- amino, methylamino, dimethylamino, methyl, phenyl, benzyl, benzoyl, hydroxy, methoxy, phenoxy, -SC 6 H 5 , -0C0CH 3> 80. The polymer of claim 74 wherein at least one of th R groups is: wherein X is selected from the group consisting of methyl, ethyl, phenyl, benzyl, F, and CF 3 , and n is 1, 2, 3, 4, or 5. 81. The polymer of claim 74 wherein R x is chosen from the group consisting of -CR 5 R 6 Ar where Ar is aryl, R 5 and R 6 are H, methyl, F, λ to C 2 0 alkoxy, OH, and R s and R 6 taken together as bridging groups -0CH 2 CH 3 0-, OCH 2 CH(CH 2 OH)0-, -0C g H 4 0- (catechol) , -OC 6 H 10 O- (1,2- cyclohexanediol) , and -OCH 2 CHR 7 0 where R 7 is alkyl, or aryl. 82. The polymer of claim 74 wherein at least one of the R. groups is -(CO)X and wherein X is selected from the group consisting of 2-pyridyl, 3-pyridyl, 4-pyridyl, - CH 2 C 6 H 5 , -CH 2 CH 2 C 6 H 5 , l-naphthyl and 2-naphthyl. 83. The polymer of claim 74 wherein at least one of the R groups is -S0 2 X and wherein X is selected from the group consisting of phenyl, tolyl, l-naphthyl, 2-naphthyl, methoxyphenyl, and phenoxyphenyl. 84. The polymer of claim 74 wherein at least one of the R groups is -NR 5 R 6 and wherein R 5 and R 5 may be the same or different and are independently chosen from the group consisting of hydrogen, methyl, ethyl, phenyl, -C0CH 3 and R 5 and R 6 taken together as bridging groups -CH 2 CH 2 OCH 2 CH 2 - , -CH 2 CH 2 CH 2 CH 2 CH 2 -, and -CH 2 CH 2 CH 2 CH 2 -. 85. The polymer of claim 74 wherein at least one of the R groups is -N-CR 5 R 6 and wherein R5 and R6 may be the same or different and are independently selected from the group consisting of -H, -CH3, -CH2CH3, phenyl, tolyl, methoxyphenyl, benzyl, aryl, Cl to C22 alkyl, and R5 and R6 taken together as bridging groups -CH 2 CH 2 OCH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 -. 86. The polymer of claim 74. wherein the intrinsic viscosity of said polymer is greater than about 1 deciliter/gram. 87. The polymer of claim 74 wherein the weight average molecular weight of said polymer as measured by gel permeation chromatography against polystyrene standards is greater than about 100,000. 88. The polymer according to claim 74 wherein the tensile modulus of unoriented 25 micron film of said polymer is greater than about 0.75 million pounds per square inch. 89. A process for the preparation of the polymer of claim 74 comprising reductive coupling polymerization of an aroyl-2,5-dichlorobenzene and a non-rigid dichloroarene with Zn in a anhydrous amide solvent in the presence of 1) a nickel catalyst 2) a promoter selected from the group consisting of nil, alkali metal chlorides, alkali metal bromides, alkali metal iodides, and zinc chloride, and 3) a phosphine ligand. 90. A free-standing film comprising a polymer of claim 74. 91. Fibers comprising a polymer of claim 74. 92. Foams comprising a polymer of claim 74. 93. Non-woven fibrous mats comprising a polymer of claim 94. Molded articles comprising a polymer of claim 74. 95. Fiber containing composites wherein the matrix resin comprises a polymer of claim 74. 96. Printed wiring boards wherein the dielectric comprises a polymer. of claim 74. 97. Coatings compositions comprising a polymer of claim 74. 98. A process for fabricating films and fibers of the polymer of claim 74 comprising melting said polymer and extruding the melt through an orifice. 99. A process for fabricating solid articles by compression molding a composition comprising a polymer of claim 74. 100. A process for fabricating solid articles by extruding a composition comprising a polymer of claim 1 through an orifice. 101. A process for fabricating a solid article by 1) preparing sheet stock comprising the polymer of claim 74 and 2) thermoforming said sheet stock by application of heat and pressure into a final shape. 102. A process for fabricating a solid article by injection molding a composition comprising the polymer of claim 74. 103. A process for orienting the polymer molecules of an article comprising the polymer of claim 74 by heating and stretching the article. 104. A multichip module comprising a plurality of dielectric layers comprising of a polymer of claim 74. 105. A semipermeable membrane comprised of the polymer of claim 74. 106. A process for reducing creep in polymer compositions comprising blending or otherwise mixing and additive comprising a polymer of claim 74 with said polymer composition. 107. A process for lowering the coefficient of thermal expansion of polymeric compositions comprising blending or otherwise mixing an additive comprising a polymer of claim 74 with said polymer composition. 108. A process for increasing the modulus of a polymer composition consisting of blending or otherwise mixing an additive comprising a polymer of claim 74 with said polymer composition. 109. A composition comprising the polymer of claim 74 and a second polymer. SUBSTITUTESHEET

Inventors: GAGNE ROBERT R, MARROCCO MATTHEW L III, TRIMMER MARK STEVEN, GAGNE, ROBERT, R., MARROCCO, MATTHEW, L., III, TRIMMER, MARK, STEVEN
Applicants: MAXDEM INC, MAXDEM INCORPORATED
Application year: 1993
Main classification: C08G2
IPC codes: C08G61, C08L23, C08L25, C08L27, C08L65, C08L67, C08L69, C08L71, C08L101, H05K1