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WO1993018077A1 - Polymeres en tiges rigides - Google Patents

Polymeres en tiges rigides Download PDF

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Publication number
WO1993018077A1
WO1993018077A1 PCT/US1993/001733 US9301733W WO9318077A1 WO 1993018077 A1 WO1993018077 A1 WO 1993018077A1 US 9301733 W US9301733 W US 9301733W WO 9318077 A1 WO9318077 A1 WO 9318077A1
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WIPO (PCT)
Prior art keywords
polymer
rigid
rod
polymers
group
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English (en)
Inventor
Matthew L. Marrocco, Iii
Robert R. Gagne
Mark Steven Trimmer
Ying Wang
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Maxdem Inc
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Maxdem Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
    • H05K3/4676—Single layer compositions

Definitions

  • This invention relates to soluble rigid-rod polymers having rigid-rod backbones and pendant, solubilizing organic groups attached to the backbone, and to methods for preparing the polymers.
  • This invention also relates tc copolymers comprising rigid-rod segments, having solubilizing organic groups attached to the rigid-ro segments.
  • the rigid-rod polymers can, for example, b used as self-reinforced engineering plastics, can be use in combination with flexible coiled polymer binders fo the preparation of high tensile strength molecula composites and can be used as matrix resins for fiber containing composites.
  • High-performance fiber-polymer composites are rapidl achieving a prominent role in the design and constructio of military and commercial aircraft, sports andheft equipment, and automotive components. Composites fill th need for stiffness, strength, and low weight that canno be met by other materials.
  • the most widely utilized high performance fiber-polymer composites are composed o 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 l t about 100. Mechanical properties still improve but at slower rate for further increases in aspect ratio.
  • 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. Fabricatingfiber-containingcomposites, however, require significant manual labor and such composites cannot b recycled. Furthermore, defective 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.
  • 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 composite Molecular composites with the optimum mechanica properties will contain a large fraction, at least 3 percent, of rigid-rod polymers, with the balance bein polymeric binder. Molecular composites may contain eithe 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 bundling of the rigid-rod molecules.
  • the flexible polymer in a molec lar composite helps to distribute stress along the rigi rod molecules via elastic deformation of the flexibl polymer.
  • the second, or matrix-resin, polymer mus be sufficiently flexible to effectively surround t rigid-rod molecules while still being able to stretch up stress.
  • the flexible and rigid-rod polymers can al interact strongly via Van der aals, hydrogen bonding, ionic interactions. The advantages of molecular co posites can only be realized with the use of rigid-r polymers.
  • 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.
  • 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.
  • 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.
  • the resulting polymers are soluble only in strong acids, making further processing difficult.
  • rigid-rod polyphenylenes provided i accordance with the present invention are line polyphenylenes in which the polymer chain has at lea about 95% 1,4 linkages, and incorporates penda solubilizing side groups.
  • Rigid-rod polyphenylenes may homopolymers or copolymers having more than one type 1,4-phenylene monomer unit.
  • the number average degree polymerization (DP n ») is greater than about 25.
  • DP n is defined as follows:
  • 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-r polyphenylene segments have a number average segme length (SL n ) of greater than about eight.
  • each polymer chain typically contai many rigid segments. However, some may contain less th others, or only one rigid segment.
  • the number avera segment length may be approximated by:
  • the rigid-rod and segmented rigid-rod polymers of the present invention are unique in that they are soluble in one or more organic solvents.
  • the polymer and the monomers demonstrate a significant degree of solubility in a common solvent system so that the polymer will remain in a dissolved state in the polymerization solvent system.
  • the rigid-rod and segmented rigid-rod polymers of the present invention are made soluble by pendant solubilizing organic groups (side groups or side chains) which are attached to the backbone, that is, to the monomer units.
  • the pendant organic groups impart increased solubility and meltability to the polymer by disrupting interactions between the rigid chains, providing favorable interactions with organic solvents, increasing the entropy (disorder) of the chains, and causing steric interactions which twist the phenylene units out of planarity. Therefore, such polymers can be considered to be self-reinforced plastics or single-component molecular composites.
  • the rigid-rod and segmented rigid-rod polymers of the present invention have incorporated rod-like and coil-like com ⁇ ponents into a single molecular species.
  • the rigid-rod or segmented rigid-rod polymer can also be mixed with a coil ⁇ like matrix resin to form a blend, wherein the pendant organic groups act as compatibilizers to inhibit phase separation.
  • Rigid-rod polymers produced in the past are, in general, highly insoluble (except in the special case of polymers with basic groups which may be dissolved in strong acid) and are infusible. These properties make them difficult, and often impossible, to prepare and process.
  • 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 solven and can be processed with standard methods to give stable, single-component, molecular composite or se reinforced polymer useful for structural and oth applications requiring high strength and modulus.
  • the rigid-rod and segmented rigid-rod polymers of t present invention when used in a blend with a flexib polymer are the primary source of tensile strength a modulus of the resulting molecular composite.
  • Su molecular composites may be homogeneous single pha blends, blends having microphase structure, or multi-pha blends having macroscopic structure.
  • Pendant side grou can be chosen to increase compatibility between the rigi rod or segmented rigid-rod polymer and the flexib polymer. The more compatible system will have finer pha structure. The most compatible will be miscible a homogeneous single phase.
  • the rigid-rod and segment rigid-rod polymers of the present invention can be blend with thermoplastics, thermosets, liquid crystalli polymers (LCP's), rubbers, elastomers, or any natural synthetic polymeric material.
  • LCP's liquid crystalli polymers
  • 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.
  • 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. Helminiak, Journal of Macromolecular
  • the rigid-rod polymer of the present invention when employed as a self-reinforcing plastic, 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.
  • aspect ratios greater than 100 are desirable.
  • the rigid-rod polymer backbone can have an aspect ratio of 25 or more.
  • 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.
  • 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.
  • 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 diameter 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.
  • 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.
  • th rigid-rod polymers provided in accordance with practice o the present invention will have at least 95% 1,4 linkage and preferably, at least 99% 1,4 linkage. Any 1,2 or 1, linkage in the polymer chain will reduce the averag length of straight segments.
  • a polymer chain o length 1000 monomer units having 99% 1,4 linkage and wil contain, on average, 11 straight segments with a numbe average segment length ( ⁇ L 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 an strong and will be useful where high tensile and flexura strengths and moduli are required, as in aerospac applications.
  • Rigid-rod polymers having between about 95% and 99% parallel covalent bonds will be useful for les stringent applications, such as body panels, molded parts, electronic substrates, and myriad others.
  • non-rigid-rodmonome units may intentionally be introduced into the polymer, t promote solubility or to modify other properties such a T g or elongation to break.
  • the polymers provided in accordance with practice o the present invention can be homopolymers or can b copolymers of two or more different monomers.
  • Th polymers of the present invention comprise a rigid-ro backbone comprising at least about 25 phenylene units preferably at least about 100 phenylene units, wherein a least about 95%, and preferably 99%, of the monomer unit 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.
  • solubilizing group is attached to at least 1 out of 10 monomer units.
  • 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.
  • 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 syste . It is understood that various factors must b considered in choosing a solubilizing group for particular polymer and solvent, and that, all else bein the same, a larger or higher molecular weight solubilizin group will induce a higher degree of solubility.
  • rigid-rod monomer unit it is meant th basic, organic, structural units of the polymer rigid-ro backbone chain in which the covalent bonds connecting the to adjacent monomer units are parallel regardless o conformational changes within the rigid-rod monomer unit
  • rigid-rod monomer unit will be limited to 1,4-phenylene units, including an attached side chain, i.e., solubilizing groups.
  • the term "monomer unit” will always be used in th present invention to mean “rigid-rod monomer unit.” I the instances where a flexible or non-rigid-rod monome unit is discussed, it will be indicated as a “non-rigi monomer unit.” Most non-rigid monomer units cannot attai a conformation in which the bonds to the polymer chain ar parallel, for example, the 1,3-phenylene group or th
  • non-rigid monome units will admit a conformation in which the bonds to th polymer chain are parallel, such as the phenylene amid type non-rigid monomer units of a polymer provided b DuPont Company under the trademark KEVLAR (polyamide o
  • Polymer comprised of such non-rigid monomer units are "pseudo rigid" due to the possibility of bent or kinked conforma tions.
  • Rigid-rod polymers are, in general, stiffer tha pseudo-rigid polymers.
  • a monomer for the purposes of the presen invention, it is meant the immediate chemical precursor 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
  • 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.
  • organic substituent pendant organic group
  • polymer backbone polymer backbone
  • polymer configuration polymer configuration
  • solvent system solvent system
  • other environmental factors e.g., temperature, pressure
  • the rigid-rod and segmented rigid-rod polymers (homopolymers and copolymers) provided in accordance with the present invention will have at least one monomer unit 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.
  • a higher degree of substitutio is needed for good solubility.
  • 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.
  • 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.
  • polar groups such as N,N- dimethylamido groups, will enhance solubility in polar solvents.
  • 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.
  • the polymer is a copolymer having rigid-rod segments with segment length (S-L jj ) of at least about eight, and non-rigid segments of any length.
  • segment length S-L jj
  • the non- parallel linkages represent kinks in an otherwise straight polymer molecule, as for example would be introduced with isolated 4, ' -diphenyl ether monomer units. In this case the angle between the rigid-rod segments is fixed.
  • non-rigid monomer units have more than one non-paralle linkage, or if the non-rigid segments have length greater than one, the angle between the rigid-rod segments is no fixed, and the copolymer as a whole has much greate flexibility.
  • th copolymer may be considered a single component molecula composite, where the rigid blocks reinforce the flexibl blocks.
  • 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 leading 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.
  • 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. 9 is a semi-schematic side view, including an enlarged section, of a fiber containing composite comprising a polymer provided in accordance with the present invention.
  • the rigid-rod polym provided in accordance with practice of the pres invention are linear polyphenylenes which incorpor parallel covalent bonds (1,4 linkages) between mono units.
  • Such rigid-rod polymers will have at least 95% linkages, and preferably at least 99% 1,4 linkages, i. the polymers will have high aspect ratios.
  • the rigid-rod polymers of the present invention h the following general structure:
  • each R ⁇ , R 2 , R 3 , and R 4 are independently cho solubilizing groups or hydrogen.
  • the structure is mean represent polymers having mixtures of monomer units well as those having a single type of monomer unit. structure does not imply any particular orientati order, stereochemistry, or regiochemistry of R grou Thus, the polymer may have head-to-head, head-to-ta random, block or more complicated order. The partic order will depend on the method of preparation and reactivity and type of monomers used.
  • rigid polyphenylene segments are separate flexible monomer units or flexible segments or block give a segmented rigid-rod polymer.
  • flexible segments contribute to solubility processability as well as the solubilizing side group the rigid polyphenylene segments.
  • the rigid backbon the rigid segments provide the segmented rigid-rod pol with a high degree of stiffness and strength, and modify other properties, such as creep resista 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.
  • 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.
  • I and Ar is an aromatic group, heteroaromatic group, or substituted aromatic group
  • Y is independently selected from the group consisting of H, F, CF 3 , alkyl, aryl, heteroaryl, or aralkyl group, and n is l or greater.
  • segmented rigid-rod polymers of the present invention should have rigid segments with number average segment length (SL n ) of at least about 8.
  • segmented rigid- rod polymer of the present invention is as follows:
  • each R l R 2 , R 3 and R 4 on each monomer unit, independently, is H or a solubilizing side group, and -[A] m - is a non-rigid segment, for example as derived from non-rigid monomers of Structure II; wherein the rigid-rod polyphenylene segments have number average segment length SL n of at least about 8, n is the average number of monomer units in the rigi segment, m is the average number of monomer units in th flexible segment and m is at least 1.
  • the segmented rigid-ro polymer of the present invention has structure III wherei -A- is:
  • B 1 -B 4 are independently selected from the grou consisting of H, C ⁇ 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.
  • the flexible monomer units in this case may be derived from substituted 1,3- dichloroarenes.
  • -A- is 1,3-phenylene and is derived from 1,3-dichlorobenzene.
  • 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 skilled in the art.
  • the rigid-rod and segmented rigid-rod polymers of the present invention will have at least one monomer unit for each 100 monomer units in the rigid-rod backbone substituted with a solubilizing organic group.
  • the polymer will have at least about one monomer unit in ten substituted with solubilizing organic 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 system(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, ⁇ ulfones, esters, i ides, imines, alcohols, amines, an aldehydes.
  • Other organic groups providing solubility i particular solvents can also be used as solubilizin organic groups.
  • a polymer of Structure or III is provided where at least one of the R groups is
  • X is selected from the group consisting o hydrogen, amino, methyla ino, dimethylamino, methyl phenyl, benzyl, benzoyl, hydroxy, methoxy, phenoxy
  • X is selected from the group consisting o methyl, ethyl, phenyl, benzyl, F, and CF 3 , and n is 1, 2, 3, 4, or 5.
  • a polymer of Structure I or III wherein one of 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 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.
  • a polymer of Structure I or III wherein R ⁇ 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 , -naphthyl and 2-naphthyl or other aromatic, fused ring aromatic or heteroaromatic group.
  • a polymer of Structure I or III 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 or other aromatic or substituted aromatic groups.
  • a polymer of Structure I or III wherein at least one of the R groups is -NR 5 R S and wherein R 5 and R 6 may be the same or different and are independently chosen from the group consisting of alkyl, aryl, alkaryl, hydrogen, methyl, ethyl, phenyl, -COCH 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 -, an -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-know chemical polymerization and addition reactions or by nove processes described herein. Such processes fo preparation of the rigid-rod and segmented rigid-ro polymers of the present invention employ chemical polymer ization addition reactions in solvent systems in which th rigid-rod and segmented rigid-rod polymers and the monome starting materials are both soluble.
  • th monomer and polymer will not demonstrate complet solubility under all conditions.
  • the polymer will likel demonstrate solubility only up to a certain weigh fraction, depending on the exact solvent-polymer pair an other factors, such as temperature. Obviously, it is no necessary for the monomer to be completely soluble in solvent for a chemical reaction to proceed.
  • the properties of the appende organic groups must be matched to those of the desire solvent.
  • the rigid-rod and segmented rigid-ro polymers are to be synthesized in polar solvents, th pendant solubilizing organic groups of the polymer and t monomer starting material will be groups that are solubl in 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.
  • the solubilizing organic groups should have dielectric constants greater than about 5 and dipole moments greater than about 1.5.
  • rigid-rod polyphenylene type polymers that is, rigid-rod polymers comprised of linear polyparaphenylene type monomer units having Structure I can be solubilized 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 side chains hydroxy (-0H) and amino (-NH 2 ) .
  • Planar aromatics tend to stack well, causing them to be very crystalline and, thus, have low solubility.
  • This tendency to stack can be reduced by forcing adjacent aromatic rings , e.g., monomer units, to twist away from planarity.
  • This can be effected by the addition of substituents next to the covalent bonds linking the monomer units, leading to significant numbers of disubstituted 2,2'-biaryl type linkages.
  • Such units have been shown to increase solubility when incorporated into other types of polymer systems.
  • either the nature of the monomer units or of the polymerization should be such that significant numbers o disubstituted 2,2 '-biphenyl linkages are introduced int the polymer.
  • regular head-to-tail catenation will lead to no 2,2' disubstituted linkages
  • a regular head-to-hea catenation will lead to 50% of the linkages having 2,2' disubstitution and 50% 2,2'-unsubstituted.
  • a perfectl random catenation will give 25% 2,2 ⁇ -unsubstituted, 50 2,2'-monosubstituted and 25% 2 , 2'-disubstituted linkages
  • rigid-ro polyphenylenes having benzoyl or substituted benzoy solubilizing side groups are soluble in amide solvents for example N-methylpyrrolidinone (NMP)
  • NMP N-methylpyrrolidinone
  • high M rigid-rod polyphenylenes can be prepared in amid solvents.
  • Poly-1,4-(benzoylphenylene) , 1, may be prepare from 2,5-dichlorobenzophenone by reductive coupling wit a nickel catalyst.
  • the resulting polymer dopes have ver high viscosities and may be purified by precipitation int ethanol or other non-solvents.
  • the dried polymer i soluble in NMP, di ethylacetamide, phenylether, m-cresol sulfurie acid, anisole, 5% NMP in chloroform chlorobenzene, and similar solvents.
  • the molecular weight of polymer 1 will depend on t exact conditions of polymerization, including monomer catalyst ratio, purity of the reactants and solven dryness of solvent, oxygen concentration, and the lik
  • the method by which the zinc is activated great influences the molecular weight. It appears that t highest MW is obtained when the zinc is most active, th 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, [rj] may be related to the molecular weight by the Mark-
  • Intrinsic viscosity is useful as a relative measure o molecular weight even without Mark-Houwink constants. Fo comparison the highest reported viscosity for polyphenylene is 2.05 dL/g ⁇ M. Rehahn, A.-D. Schl ⁇ ter, G Wegner Makromol. Chem . 1990, 191 , 1991-2003 ⁇ .
  • molecular weights as determined by GP require a calibration standard, and no rigid-rod standard are available.
  • the GPC data given in the examples belo are reported using a polystyrene standard and ar therefore expected to be much higher than the actua weight average molecular weights.
  • the soluble rigid-rod polymers of the present inventio can be made by any method which is highly selective fo 1,4-phenylene regiochemistry.
  • Non-limiting examples o such reactions are: nickel catalyzed coupling o 4-chloroaryl Grignard reagents, nickel or palladiu catalyzed coupling of 1,4-arylhalides, palladium catalyze coupling of 4-chlorophenylboronic acids, Diels-Alde coupling of monosubstituted 2-pyrones (J.N.Braham T.Hodgins, T.Katto, R.T.Kohl, and J.K.Stille Macromolecules. 11. 343-346, 1978.), anodic oxidation o 1,4-dialkoxybenzene, and addition polymerization o cyclohexadienediol derivatives.
  • the polymer will be a least 25 monomer units in length, preferably at least 10 monomer units in length, and, most preferably, longer tha 100 monomer units.
  • the polymer can be a homopolymer of single monomer or a copolymer of two or more differe monomers or monomer units.
  • the segmented rigid-r polymers of the present invention can be made using t same methods as for the rigid-rod polymers, except that a non-rigid-rod monomer is added to the rigid-rod monomers before or during polymerization.
  • 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 polyme having on the average about two monomer units out of thre monomer units substituted with a long-chain alkoxy group.
  • a variety of dihalogenated benzenes can be polymerized using thes methods ( ⁇ Ri 2 of monomers IA, IB and IC ar independently chosen from solubilizing groups and H)
  • the rigid-rod or segmented rigid-rod polymers ar prepared under Grignard conditions, the following types o organic groups may react with the Grignard reagents causing undesirable side reactions: alkyl halides amides, esters, ketones, and the like. Thus, such group should be avoided as solubilizing side groups when th polymers of the present invention are prepared usin Grignard conditions.
  • Coupling of the paradihaloarene monomers is preferabl carried out with nickel or palladium catalysts with zin as the reducing agent.
  • suc polymerizations give soluble rigid-rod polyparaphenylen polymers with high molecular weights in virtually quanti tative yields.
  • This approach has distinct advantages since a wider variety of solvents can be employed, such a N,N-dimethylformamide (DMF) , N-methylpyrrolidinone (NMP) hexamethylphosphoric triamide (HMPA) , benzene tetrahydrofuran (THF) , and dimethoxyethane (DME) .
  • DMF N,N-dimethylformamide
  • NMP N-methylpyrrolidinone
  • HMPA hexamethylphosphoric triamide
  • THF benzene tetrahydrofuran
  • DME dimethoxyethane
  • Thi coupling reaction can also be used with monomers havin specially reactive groups, such as nitrile and carbony groups.
  • zinc is less expensive and easier t handle than magnesium.
  • Similar reactions to prepar biphenyl derivatives and non-rigid polymer systems ha been demonstrated by Colon (I. Colon and D. Kelsey, J Org. Chem.. 1986, 51, 2627; I. Colon and C. N. Merria U.S. Patent No. 4,486,576, December 4, 1984) Unfortun tely, this technique was demonstrated to be unsatisfactory to produce high molecular weight polymers from substituted dihalobenzene type monomers due to deactivation of the nickel catalyst by the substituents.
  • a mixture of one equivalent of anhydrous nickel chloride, three equivalents of sodium iodide, seven equivalents of triphenylphosphine, and 50 equivalents of zinc metal is effective in the polymerization of about 30 equivalents of substituted paradichlorobenzene monomer.
  • the polymerization reaction is preferably carried out at about 50°C but is effective from about 25°C to about 100°C.
  • the ratio of equivalents of monomer to equivalents of nickel catalyst can vary over the range from about 10 to about 5000, and the ratio of equivalents of zinc to equivalents of monomer is at least 1.0.
  • the ratio of equivalents of phosphine ligands to equivalents of nickel catalyst varies from about 3.0 to about 10 or more.
  • the concentration of phosphine ligands should be about 2.5 M or more to prevent the formation of highly unsaturated nickel zero complexes which lead to undesired side reactions.
  • Use of inorganic salt promoters is optional. When used, the inorganic salt promoter should be at a concentration of about 0.05 M to 1 M, preferably about 0.1 M.
  • Non-limiting examples of inorganic salt promoters are alkali iodides, alkali bromides, zinc halides and the like. These promoters reduce or eliminate the induction period which is typical of nickel catalyzed couplings of aryl halides.
  • the nickel-triarylphosphine catalys described above When using the nickel-triarylphosphine catalys described above, one must be careful to selec sufficiently reactive monomers in order to obtain hig molecular weight polyparaphenylenes. If the reactivity i too low, we believe that side reactions are more likely t occur, which can limit molecular weight and/or deactivat the catalyst. Also, the two halide groups of th paradihaloarene monomers may have different reactivities depending on the identity and location of the substituen groups. Therefore, the orientation (e.g. head-to-head head-to-tail, and tail-to-tail) of the monomer group along the polymer backbone will be largely determined b the relative reactivities of the halo groups of th monomer.
  • Relative reactivities are also important t consider when copolymers are being prepared. Fo instance, it is desirable to choose comonomers of simila reactivities when a completely random distribution of th different monomer groups is desired in the copolymer Conversely, it may be desirable to choose monomers wit significantly different reactivities in order to obtai block-type copolymers, although molecular weight may b limited if the reactivity of any of the monomers is to low.
  • Aryl group coupling to afford polyphenylenes has also been effected by the palladium catalyzed condensation of 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 acid monomers required for formation of polyparaphenylenes can be prepared by the monolithiation of the paradihalobenzene with butyl lithium at low temperature and subsequent trimethylborate quench and aqueous acid workup. These polymerizations are carried out in aromatic and ethereal solvents in the presence of a base such as sodiu carbonate.
  • this type of reaction is suitabl for producing polyparaphenylenes substituted with organi groups such as alkyl, aryl, aralkyl, alkaryl polyfluoroalkyl, alkoxy, polyfluoroalkoxy, and the like
  • organi groups such as alkyl, aryl, aralkyl, alkaryl polyfluoroalkyl, alkoxy, polyfluoroalkoxy, and the like
  • solvents of choice are ethers
  • an the best solubilizing side chains are ethers, such a phenoxyphenyl, and long-chain alkyls.
  • Anodic polymeri zation is done in acetonitrile-type solvents, and ether and aromatic side chains, such as phenylether, and benzy would be the favored side chains.
  • the monomer units are known or can be prepared b conventional chemical reactions from known starting mater ials.
  • the 1,4-dichlorobenzopheno derivatives can be prepared from 2,5-dichlorobenzoic ac via 2,5-dichlorobenzoyl chloride followed by Fried Crafts condensation with an aromatic compound, for examp benzene, toluene, diphenylether and the like.
  • T paradihalobenzene monomers substituted at the 2 positi with an alkoxy group can be prepared from t corresponding 2,5-dihalophenol by allowing the phenol the presence of sodium hydroxide and benzyltr ethylammoniu chloride to react with the corresponding haloalkyl, such as benzyl bromide.
  • Substitut dichlorobenzenes may also be prepared from the inexpensi 2,5-dichloroaniline by diazotization of the amine grou to yield corresponding p-dichlorobenzenediazonium sal
  • the diazonium salt is treated with nucleophiles in t presence of copper salts to form the desired product.
  • the polymers of the present invention may thermally processed, for example, by compression moldi or by injection molding.
  • injection mold specimens of poly-l,4-(4'-phenoxybenzoylphenylene) have flexural moduli greater than 1 million pounds pe: square inch (MSI) .
  • polymers of the present invention will melt t o f o r m f r e e f l o w i n g l i q u 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 impar fusibility. That is the side groups lower the T g and mel 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 lon very flexible side groups will melt. For example, t triethylene glycol side groups of 3 imparts a low T g a 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.
  • 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 as interaction with adhesives, matrix resins, dyes, and the like, and may also alter physical properties, such as appearance, tensile strength, flexural strength, resistance to light, heat and moisture, and the like.
  • 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 may be oriented by stretching Stretching along one dimension will result in uniaxia orientation. Stretching in two dimensions will giv biaxial orientation. Stretching may be aided by heatin near the glass transition temperature. Stretching ma also be aided by plasticizers. More complex processe such as applying alternating cycles of stretching an annealing may also be used with the polymers of th present invention.
  • the polymers of the present invention may also b 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.
  • 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.
  • the upper surface 32 has very small pores and is denser than the lower surface 34, which has courser pores.
  • the 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.
  • Powders, pellets, beads, flakes, reground material or other forms 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) .
  • DMTA Dynamic Mechanical Thermal Analysis
  • 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. T determine if a particular polymer can be injection molde it is necessary to measure the melt viscosity under shear typically using a capillary melt flow rheometer
  • polymers having melt viscosities of less tha 10,000 poises at shear rates greater than 10 3 sec -1 can b injection molded.
  • polymers must also remain fluid (ie. without gelling o solidifying) at the molding temperature during the moldin operation. It is also desirable if the polymer can b remelted several times without degradation, so tha regrind from molding processes can be used.
  • tha regrind from molding processes Particula examples of rigid-rod and segmented rigid-ro polyphenylenes which meet these requirements are give below.
  • injection molding is not limited to th particular side groups shown, and the utility of injectio molding for any of the polymers of the present inventio may readily be determined by one skilled in the art. Referring to FIG.
  • FIG. 4 there is shown a schematic view o a radome 42 molded from a rigid-rod or segmented rigid-ro polymer provided in accordance with practice of th present invention.
  • the radome 42 is shown mounted on th wing structure 44 of an aircraft.
  • the radome i essentially a radar transparent cover which i structurally self-supporting.
  • rigid rod and segmented rigid-rod polyphenylenes may be produce by extrusion.
  • Non-limiting examples include: angle channel, hexagonal bar, hollow bar, I-beam, joining strip rectangular tube, rod, sheet, square bar, square tube, section, tubes, or other shapes as is required for particular application.
  • a fiber reinforcement is continuous added to an extruded polymer.
  • the polymers of the prese invention may be used as a thermoplastic matrix which pultruded with fibers, such as carbon fiber or gla fiber.
  • the polymers of the present invention may be used as the fiber for pultrusion of a thermoplastic having a lower processing temperature.
  • 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.
  • printed wiring boards may be fabricated fro sheet or thick films by a process wherein copper is deposited on to one or both sides, patterned by standar photolithographic methods, etched, then holes are drilled, and several such sheets laminated together to form finished board.
  • Such boards are novel in that they do no contain any fiber reinforcement. Such reinforcement i not necessary because of the unusually high modulus of th instant polymers.
  • Such boards are also unique in tha they may be bent into non-planar structures, b application of heat and pressure, to better fit restrictive volume enclosures, such as laptop computers.
  • Sheet an film may also be thermoformed into any variety o housings, cabinets, containers, covers, chassis, plates, panels, fenders, hoods, and the like.
  • FIG. 5 there is shown a semi-schemati cross-sectional side view of a four-layer wiring board 50
  • the board is comprised of rigid-rod or segmented rigid-ro 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.
  • 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.
  • 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 are similar to printed wiri boards except that integrated circuits are mount 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.
  • an MCM is typically (but not necessarily) fabricated using photolithographic techniques similar to those used in integrated circuit fabrication.
  • an MCM may be constructed by spin coating a layer 82 of rigid-rod or segmented rigid-rod polyphenylene onto a silicon substrate 84, having a plurality of resistors 86 on its surface, to thereby form a dielectric layer.
  • the polyphenylene layer is typically (but not necessarily) fabricated using photolithographic techniques similar to those used in integrated circuit fabrication.
  • an MCM may be constructed by spin coating a layer 82 of rigid-rod or segmented rigid-rod polyphenylene onto a silicon substrate 84, having a plurality of resistors 86 on its surface, to thereby form a dielectric layer.
  • the polyphenylene layer is typically (but not necessarily) fabricated using photolithographic techniques similar to those used in integrated circuit fabrication.
  • an MCM may be constructed by spin coating a layer 82 of rigid-rod or segmented rigid-rod polyphenylene onto a silicon substrate 84
  • a layer of copper 88 is deposited onto the polyphenylene layer, and a layer of photoresist (not shown) is deposited, exposed, developed and the underlying copper etched through the developed pattern in the resist.
  • a second layer 90 of rigid-rod or segmented rigid-rod polyphenylene is spin coated and cured. Vias (not shown) to the underlying copper lines are cut, for example by laser drilling. Additional layers of copper 92 and dielectric 94 are added and patterned. Completed MCM's may have six or more alternating layers depending on the circuit complexity. The dielectric for MCM's may also be fabricated by laminating films, by spray coating or by other methods known in the art.
  • the rigid-rod or segmented rigid-rod polyphenylene layer itself may be photosensitive, allowing additionalmethods 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.
  • the polymers of the present invention may b blended with some amount of a more flexible polymer t improve the extension-to-break of the blend.
  • finished products formed from such a blend e.g. , film, sheet, rod or complex molded articles will be relativel tougher. Rubbers may be added to toughen the finishe product.
  • a liquid crystalline polymer may be added t reduce melt viscosity. Many other combinations will b apparent to those skilled in the art.
  • each additive will depend on the applicatio but may cover the range from none (pure rigid-rod o segmented rigid-rod polyphenylene) to large amounts. A the amount of additives becomes much larger than th amount of rigid-rod polyphenylene the rigid-ro polyphenylene itself may be considered an additive.
  • Polymers comprising the rigid-rod and segmented rigid rods of the present invention can also be used i structural applications. Because of their high intrinsi stiffness, parts fabricated with rigid-rod or segmente rigid-rod polymers will have mechanical propertie approaching or equal to fiber containing composites. I many applications where fibers are necessary fo structural reasons they cause other undesirable effects For example, rado es for airborne radar are typicall constructed of glass fiber reinforced composites, but th glass fibers lead to signal loss and degradation of rada performance. Fiberless radomes comprised of rigid-rod o segmented rigid-rod polymers would improve rada performance over composite radomes. Fiberless radome would also be easier to fabricate than composite radomes Fiberless radomes comprising rigid-rod or segmented rigid rod polymers provided in accordance with the presen invention could be injection or compression molded o stamped from sheet, or machined from stock.
  • Rigid-rod and segmented rigid-rod polymers can also b used to advantage in fiber containing composites as th matrix resin.
  • the compressiv strength of composites is related to the modulus of th matrix resin.
  • a composite 10 comprising reinforcing fibers 102 and 104 in the plane o the composite surface is shown.
  • the fibers 102 run in 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 to any other polymer.
  • the degree of improvement of 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.
  • polymers of differing types do not mix. There are many exceptions to this rule and many pairs o completely miscible polymers are known. For most of these miscible polymers specific interactions result in a negative heat of mixing, for example, hydrogen bonding, or ionic interactions. Polymer pairs which are not miscible can often be made miscible by addition of a third polymer, typically a low MW copolymer having segments similar to the polymers to be blended. Use of these and other types of compatibilizers are known in the art. These techniques may be applied to the rigid-rod and segmented rigid-rod polyphenylenes of the present invention to enhance their utility as additives.
  • a copolymer having segments which interact strongly with a rigid-rod polyphenylene as 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.
  • the particula side group on the rigid-rod or segmented rigid-ro polyphenylene will strongly influence its ability t blend.
  • the side group should be chosen so tha there is a negative heat of mixing between the side grou and the polymer in which it must mix. It should also b apparent that complete miscibility is not always required.
  • Blending often results in mixing on a microscopic, but no molecular, level. Such blends will have propertie different than the pure polymers and are often desirable Even blends with macroscopic phases may have utility an may be considered another form of composite.
  • Rigid-rod and segmented rigid-rod polyphenylenes wil be particularly useful as additives for flame retardants smoke retardants, tougheners, or to control or enhanc creep resistance, coefficient of thermal expansion viscosity, modulus, tensile strength, hardness, moistur resistance, gas permeability, and abrasion resistance.
  • 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 added to trap the hydrogen chloride that is evolved. After washing away the pyridinium salt and any excess amine, the product is crystallized from the toluene solution.
  • Activated zinc powder is obtained after 2-3 washings of commercially available 325 mesh zinc dust with 1 molar hydrogen chloride in diethyl ether (anhydrous) and drying in vacuo or under inert atmosphere for several hours a about 100-120°C.
  • the resulting powder should be sifted
  • This material should be used immediatel or stored under an inert atmosphere away from oxygen an moisture.
  • Example 1 Poly-1,4-(benzoylphenylene) Anhydrous bis(triphenylphosphine) nickel(II) chlorid (34.7 g; 53 mmole) , triphenylphosphine (166.6 g; 74 mole) , sodium iodide (34.6 g, 231 mmole), and 325 mes activated zinc powder (181.8 g, 2.8 mole) were weighe into a bottle under an inert atmosphere and added to a oven dried 12-liter flask, containing 1.6 liters o anhydrous N-methylpyrrolidinone (NMP) , against a vigorou nitrogen counterflow.
  • NMP N-methylpyrrolidinone
  • 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 weigh relative to narrow polydispersity polystyrene standard Of 550,000-600,000.
  • Example 2 Polv-1,4-f4'-phenoxybenzoylphenylene) 2,5-Dichloro-4'-phenoxybenzophenone
  • NMP N-methylpyrrolidinone (3400ml) .
  • the solution wa stirred and heated with a hot air gun to 40°C.
  • Th monomer 2,5-dichloro-4 '-phenoxybenzophenone (935g, 2725mmol) was added.
  • the temperature dropped to 36.3°C and then climbed to about 65°C when an ice water bath was 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 zin metal.
  • the polymer was collected by filtration, washe with water and acetone and dissolved in 16L of methylen chloride.
  • the solution was filtered through 10 u polypropylene membrane with the aid of celite, coagulate in the same volume of acetone, filtered, extracted wit acetone for three days and dried to 3afford 700g pal yellow polymer (94%) .
  • GPC analysis showed a weigh average molecular weight of 653,000 with th polydispersity being 1.97, relative to polystyren standard.
  • Monomethylated triethyleneglycol 2,5- dichlorobenzoate (2.8 g, 7.95 mmol) was added as a neat 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 obtained after stirring. It became a clear and almost colorless solution when 10 ml of 36% hydrochloric acid was added. The solution then was neutralized with diluted aqueous sodium hydroxide. The resulting suspension containing gel-like polymer was extracted with methylene chloride.
  • the organic layer was filtered and concentrated.
  • the polymer was precipitated with ethanol, separated by using a centrifuge and dried under vacuum. A white, gum-like solid was obtained (1.48 g, 67%).
  • the weight average molecular weight, relative to polystyrene standard, was
  • 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.
  • Poly -l,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.
  • the extruder 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.
  • the extruder 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
  • the stretched film is annealed and cooled on a further roller train and collected as a continuous roll.
  • the extruder 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 multifila ents allowed to air cool before being collected on a windup bobbin.
  • the extruder In a fourth extrusion run, the extruder is fitted with a die having 200 spinnerets, each 400 in diameter microns at the exit. The extruded filaments are pulled away from the exit at high velocity resulting in a draw ratio of about 12. The oriented fiber is collected on a windup bobbin.
  • the extruder 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 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.
  • the orifice In the second run, the orifice is held one centimet 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 impinges on the ethanol.
  • the coagulating fiber is f around a roller and across the trough to the opposite e where it is collected on a constant tension take up rol Example 8
  • 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.
  • a blend of poly-1,4-(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.
  • Poly-1,4-(4'-phenoxybenzoylphenylene) provided in accordance with Example 2 is prepared as a powder having 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 the chamber whereupon the stirred powder forms a dust cloud which adheres to the carbon fibers.
  • the coated carbon fibers then pass through a 150°C oven to fix the polymer powder.
  • the resulting prepreg may be used to form composites by further forming and processing under heat and pressure.
  • 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.
  • 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 t polymer filaments.
  • the fiber tow of the fourth extrusion run of Example is continuously pulled through a polyetheretherketone me 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.
  • triphenylphosphine 408 g; 1.56 mole sodium iodide (96 g, 0.64 mole)
  • 325 mesh activat zinc powder 420 g, 6.42 mole
  • the crude polymer was dissolved in about 35 liters of NMP, pressure filtered through 1.2 micron (nominal) polypropylene fiber filters, coagulated into about 70 liters of acetone, continuously extracted with acetone, and dried to afford 1,186 g (91% yield) of 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.
  • 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.
  • Anhydrous bis(triphenylphosphine) nickel(II) chlori (3.75 g; 5.7 mmole), triphenylphosphine (18 g; 68 mmole) , 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.
  • 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 transitio temperature of 167°C.
  • 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
  • DMAc dimethylacetamide
  • NMP N-methylpyrrolidinone
  • 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.
  • a second method for preparing free-standing film involves casting from a solvent mixture of chloroform an NMP (generally containing about 1-10 volume percent NMP preferably about 1-2 volume percent) . Polyme concentrations typically range from about 1-15 weigh percent, preferably about 3-7 weight percent. Afte casting the film, the chloroform quickly evaporates leaving a highly NMP swollen (plasticized) but generall tack-free film. The remaining NMP can be easily remove by heating in an oven to form the final dry film, whic tends to be quite optically transparent and colorless Like those prepared from a single solvent, the completel dried films tend to be brittle but strong.
  • the following film samples were prepared from batche of rigid-rod polyparaphenylenes in Examples 1 and 15 wit the specified intrinsic viscosities (related to molecula weight) according to the general procedures specifie above and the conditions listed:
  • the mechanical (tensile) properties of the resulti films (A-F) were measured in accordance with ASTM-D-8 standards. Standard test samples were prepared by carefully cutting the films to the desired size (approximately 6"x 0.5"x 0.001"). The films prepared by method (b) were more easily cut (i.e. without microcracking along the edge of the test strip) in their plasticized state. The average test results are presented below:
  • Example 18 E The film of Example 18 E is dried until it is approximately 5% by weight NMP.
  • the NMP plasticized film is drawn through a set of rollers to give a draw ratio of 5 to 1.
  • the oriented film may be further dried in vacuo at 100 °c.
  • Coupons of the polymers provided in accordance with the procedures of Examples 1 and 2 can be compression molded at relatively moderate temperatures (200-400°C) and pressures (200-5,000 psi). Sometimes samples of the polymers of Examples l or 2 undergo darkening upon molding at these temperatures, but the properties do not seem to be adversely affected.
  • the mold cavity is filled with about 8.0 g of resin and placed into a hydraulic press preheated to the specified temperature.
  • th sample After holding the sample at the molding temperature an molding pressure for the specified molding time, th sample is cooled below at least about 100°C during th cooling time while retaining the molding pressure. Upo cooling to ambient temperature and removal from the mold, the following panels were obtained according to th specified conditions:
  • 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 test samples were prepared by carefully cutting the coupons to the desired size (40 mm x 6 mm x 2.5 mm) .
  • the polymer blends were prepared in a small (50 g)
  • the poly-l,4-(4'- phenoxybenzoylphenylene) or a mixture of poly-l,4-(4'- phenoxybenzoylphenylene) and triphenylphosphate (TPP; used as a plasticizer to lower the melt viscosity of the polyparaphenylene) was then added. If the blend was not uniform after about 5 minutes of mixing, the temperature was increased to about 280-300°C for 5 minutes. The mixer was then cooled to 165°C, and the blend was removed and allowed to cool to room temperature. The following blends were prepared in this manner:
  • Polystyrene HCC9100 from Hunter Chemical Co .
  • Poly (phenylene oxide) Noryl 731 from GE Plastics
  • Nylon-6 (poly-e-caprolactam) DYLARK 232 from ARCO Chemical .
  • Compression molded panels of the above blends were prepared for mechanical (tensile) testing according to ASTM-D-638 standards by molding at the temperature specif ied below at about 700 psi for 2 minutes and then cooling to room temperature .
  • the glass transition temperatures (T ⁇ ) were determined for the blends by dynamic mechanical thermal analysis (DMTA) of the compression molded parts .
  • DMTA dynamic mechanical thermal analysis
  • Specimens appropriate for DMTA 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 mixer was preheated to the temperature indicated below for the specified polymer to be blended with poly-1,4-(benzoylphenylene) , and the resin was added slowly and allowed to achieve uniform melt consistence over about 5 minutes.
  • the poly-1, -(benzoylphenylene) or a mixture of poly-1,4-(benzoylphenylene) and triphenylphosphate (TPP; used as a plasticizer to lower the melt viscosity of the polyparaphenylene) was then added. If the blend was not uniform after about 5 minutes of mixing, the temperature was increased to about 280- 300°C for 5 minutes. The mixer was then cooled to 165°C, and the blend was removed and allowed to cool to room
  • Compression molded panels of the above blends were 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 g ) 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-sa and/or a router. The following data was obtained:
  • the polymer blends were prepared by mixing solutions of each polymer in chloroform or a solvent mixture comprised of 90 % (vol/vol) chloroform and 10 % (vol/vol) NMP in proper proportion to achieve the compositions specified below.
  • the polystyrene was obtained from Hunter Chemical Co. (HCC9100) .
  • the blended resins were rapidly precipitated by pouring the co-solutions into methanol (3 volumes relative to the volume of polymer co-solution) . The precipitate was filtered, washed with additional methanol, and dried under vacuum for 24 hours at 70°C. Compression molded panels of these blends were prepared for mechanical (tensile) testing according to ASTM-D-638 standards by molding at 175°C at about 700 psi for 2 minutes and then cooling to room temperature. The glass transition temperatures (T g ) were determined for the blends by dynamic mechanical thermal analysis (DMTA) of the compression molded parts. Specimens appropriate for DMTA 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 by mixing solutions of each polymer in chloroform in proper proportion to achieve the compositions specified below.
  • the polycarbonate was obtained from Mitsubishi Kasei Corporation (NOVAREX polycarbonate) .
  • the blended solutions were then cast onto a glass plate and dried rapidly to afford transparent free-standing thin film samples. The following mechanical
  • EXAMPLE 28 Solutions containing 1.5 to 3 wt.% of poly-1,4- (benzoylphenylene) provided in accordance with Example 1 in Epo ik R140 (Mitsui) were prepared by stirring the polymer and the epoxy resin at 100-140°C. The resulting solutions were almost colorless. Both 1.5 and 3 wt% solutions were very viscous at room temperature, however, the viscosity of the solution dropped sharply with warming. To about lg of solution of the polymer of Example 1 in Epomik R140 was added 6-12 drops of ethylenediamine (EDA) . The resulting solution was mixed with a spatula until a homogeneous solution was obtained. The mixture was left to sit at room temperature to cure.
  • EDA ethylenediamine
  • Curing took from a few hours to two days depending on the amount of EDA. In all cases, a hard transparent mass was obtained. If the polymer mixture with EDA was heated to about 70°C a very exothermic reaction occurred. The resulting cured polymer blend in this case was slightly turbid. Curing was also successful when a small amount of NMP was used as plasticizer.
  • Triarylphosphine Catalysts A mixture of 50 mg (0.39 mmole) of anhydrous nickel chloride, 175 mg (1.17 mmole) of sodium iodide, 750 mg (2.86 mmole) of triphenylphosphine, 1.0 g (15.30 mmole) of activated zinc powder, 500 mg (2.17 mmole) of ortho- terphenyl (used as an internal standard for chromatographic analysis) , and 7 ml of NMP was placed into a flask under an inert atmosphere and heated at 50°C for 10-15 minutes until the mixture achieved a deep red coloration, indicative of an activated catalyst solution.
  • 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 according to GPC analysis was 70,000.
  • 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.

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  • Health & Medical Sciences (AREA)
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Abstract

L'invention se rapporte à des polymères en tiges rigides et à des polymères segmentés en tiges rigides, à des procédés pour leur préparation et à des articles utiles comprenant lesdits polymères. Ceux-ci comprennent des squelettes en tiges rigides, des groupes stabilisants libres y étant rattachés pour les rendre solubles.
PCT/US1993/001733 1992-03-06 1993-02-24 Polymeres en tiges rigides Ceased WO1993018077A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0773249A1 (fr) * 1995-11-09 1997-05-14 Maxdem Incorporated Copolymères de polyphénylène
US5886130A (en) * 1995-11-02 1999-03-23 Maxdem Incorporated Polyphenylene co-polymers
EP2970652A4 (fr) * 2013-03-11 2017-01-18 Aonix Advanced Materials Corp. Matériau composite thermoplastique comprenant un constituant de renforcement et un polymère de poly(phénylène) et procédé pour fabriquer ledit matériau composite thermoplastique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1129418A (fr) * 1979-09-11 1982-08-10 Ismael Colon Combinaison de polyhalogenures d'aryle et d'heteroaryle
US4486576A (en) * 1982-04-22 1984-12-04 Union Carbide Corporation High-temperature, aromatic coating materials from aryl polyhalides
WO1989007617A1 (fr) * 1988-02-17 1989-08-24 Maxdem Incorporated Polymeres a tiges rigides
DE3821567A1 (de) * 1988-06-25 1989-12-28 Bayer Ag Loesliche polyaromaten
WO1991002764A1 (fr) * 1989-08-23 1991-03-07 Maxdem Incorporated Polymeres a tige rigide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1129418A (fr) * 1979-09-11 1982-08-10 Ismael Colon Combinaison de polyhalogenures d'aryle et d'heteroaryle
US4486576A (en) * 1982-04-22 1984-12-04 Union Carbide Corporation High-temperature, aromatic coating materials from aryl polyhalides
WO1989007617A1 (fr) * 1988-02-17 1989-08-24 Maxdem Incorporated Polymeres a tiges rigides
DE3821567A1 (de) * 1988-06-25 1989-12-28 Bayer Ag Loesliche polyaromaten
WO1991002764A1 (fr) * 1989-08-23 1991-03-07 Maxdem Incorporated Polymeres a tige rigide

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF ORGANIC CHEMISTRY, Vol. 51, 1986, (COLON et al.), "Coupling of Aryl Chlorides by Nickel and Reducing Metals", pages 2627-2637. *
MACROMOLECULES, Vol. 11, No. 2, March/April 1978, (BRAHAM et al.), "Polyphenylenes Via Bis(2-Pyrons) and Diethynylbenzenes. The Effect of M- and P- Phenylene Units in the Chain", page 2091. *
POLYMER, June 1989, Vol. 30, (REHAHN et al.), "Soluble Poly(Para-Phenylene)s. 1. Extension of the Yamamoto Synthesis to Dibromobenzenes Substituted with Flexible Side Chains", pages 1054-1059. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5886130A (en) * 1995-11-02 1999-03-23 Maxdem Incorporated Polyphenylene co-polymers
EP0773249A1 (fr) * 1995-11-09 1997-05-14 Maxdem Incorporated Copolymères de polyphénylène
EP2970652A4 (fr) * 2013-03-11 2017-01-18 Aonix Advanced Materials Corp. Matériau composite thermoplastique comprenant un constituant de renforcement et un polymère de poly(phénylène) et procédé pour fabriquer ledit matériau composite thermoplastique

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