MXPA98001925A

MXPA98001925A - Aromatic compounds substituted by etinyl, synthesis, polymers and uses of the mis

Info

Publication number: MXPA98001925A
Application number: MXPA/A/1998/001925A
Authority: MX
Inventors: A Babb David; W Smith Dennis Jr; j martin Steven; P Godschalx James
Original assignee: The Dow Chemical Company
Priority date: 1995-09-12
Filing date: 1998-03-11
Publication date: 1998-11-12

Abstract

A compound having the structure (RC = C) nAr-L (Ar (c = Cr) mq where each Ar is an aromatic group or inertly substituted aromatic group, each R is independently hydrogen, an alkyl, aryl or alkyl or aryl group inertly substituted, L is a covalent bond or a group that binds an Ar or at least another Ar; n and me are integers of at least 2; and q is an integer number of at least

Description

AROMATIC COMPOUNDS SUBSTITUTED BY ETHYLIN, SYNTHESIS, POLYMERS AND USES THEREOF The present invention relates to aromatic compounds substituted by ethynyl, to polymers of aromatic compounds substituted by ethynyl and to methods for the preparation and use of the aromatic compounds substituted by ethynyl and polymers thereof. Polymeric materials that are relatively easy to process and are resistant to temperatures of 300 ° C to 450 ° C are of interest for preparing laminates, films, coatings, fibers, electronic components and mixed components. Depending on the specific end use application, the polymers should exhibit one or more of the following properties: mechanical integrity, low moisture absorption, ter-oxidative stability, thermal stability, solvent resistance, hydrolytic stability, resistance to highly acid solutions or basic, a low coefficient of thermal expansion and a low dielectric constant. For example, in electronic the material should exhibit a low dielectric constant equilibrium, good thermal stability and solvent resistance and a low moisture absorption thermal expansion coefficient. In addition, the processing capacity can also be important to achieve uniform and free films. defects. Poly-imide resins are a class of materials that are used as a method for preparing high-strength films, fibers, mixed materials and coatings, including insulating or protective coatings in the electronics industry. However, poly-imide resins tend to to absorb water and hydrolyze, which can lead to corrosion and migration of metal ions. In addition, poly-imides typically exhibit poor planarization and space filling properties. Undesirable polyimides undesirably exhibit high dielectric constants Poharlens are thermally stable polymers, but are often difficult to process due to the low solubility of common organic solvents. A number of different routes have been proposed for the preparation of molecular weight polyphenylenes. high soluble in an organic solvent. For example, US Patent 5,227,457, teaches the introduction of solubilization groups such as phenyls in the polymer chain. Unfortunately, these substituents may also become sensitive to the resulting polymers for processing solvents. In another approach, the Interlaxable pohphenylene compositions are prepared having initially a relatively low molecular weight, but which is entangled upon heating to form polymers exhibiting resistance to solvents (See for example U.S. Patents 5,334,668, 5,236,686, 5,169,929 and 5,338,823). They may not flow enough to fill the spaces, particularly submicron spaces and flat surfaces, a critical limitation in many applications, including electronics. Processable pohphenylenes have also been prepared by reacting a diacetylene with bicyclopentadienone. However, the resulting polymers are thermoplastic materials and sensitive to organic solvents used in the process. Other polymers that are useful in electrical applications include poly (naphthalenevinylene) which alternatively contains naphthalenevinylene ligatures (see for example, Antoun, S., Gagnon, DK, Darasz, FE, Lenz, RW, J. Polym, Sci. : Polym, Lett, 1986, 24, 503); poly (perylene) or poly (perinaphthalene) substituted (see, for example, Lehmann, G .., Synthetic Metals 1991, 41-43, 1615-1618; and monoaryl orthodiacetylenes such as phenyl-1,2-bis (phenylacetylene) and their reaction to form linear polynaphthalenes (see, for example, John, Jens A. and Tour, James, in J. Amer. Chem. Soc., 1994, (116) 5011-5012.) However, these polymers are soluble. in organic solvents and thermoplastic materials In view of the deficiencies in the prior art, it is convenient to provide a compound having the desirable balance of physical and processing properties, accordingly, in one aspect the present invention is an aromatic ethynyl compound, of the formula: (RC = O-nAr-LfC = CR or (I) wherein each Ar is an aromatic group or inertly substituted aromatic group; each R is independently hydrogen, an alkyl, aryl or unsubstituted alkyl or aryl group; L is a covalent ligature or a group linking an Ar to at least one other Ar; n and m are integers of at least; and q is an integer of at least 1. As such, the ethynyl aromatic compounds of the present invention have four or more ethynyl groups (for example, aromatic tetraethyl compounds) and are useful as monomers in the preparation of polymers including their oligomeric precursors. In another aspect the present invention is a polymer, including copolymers, comprising the units of: R R / fAr '} (M) R R where Ar 'is the residual of the product reaction of the portions of (C = C Ar or ArfC = C) m and y L are as defined above. In a particularly preferred embodiment, the copolymers of the present invention comprise units of: R R / fAr'l- R R I / (ll) fAr'3-. { -Ar'L / \ R R where Ar 'and R are as defined above. The aromatic ethynyl compounds of the present invention prior to substantial curing, for example, oligomers or oligomeric precursors of the final polymers, exhibit good melt processability and solution. The resulting thermofixed polymers are generally resistant to high temperatures and the solvents commonly used in their processing. In addition, when interlocked, the polymers exhibit an exceptional balance of solvent resistance and mechanical strength, without losing electrical properties such as low dielectric constants and dissipation factor. Polymer coatings on a variety of substrates can be prepared using conventional techniques such as the application of an oligomer of the solution monomers and then forming the polymer. The polymers can withstand high temperatures such as the temperatures required to anneal aluminum which can be as high as 450 ° C for cumulative time reaching two hours or more. Furthermore polymers can be prepared without forming volatile materials during polymerization and at temperatures of polymerization and entanglement at relatively low temperatures Due to their high dielectric strength, resistance to degradation by heat, oxygen and moisture and many chemicals, the polymers of the present invention are particularly useful as (films) dielectric capacitors; on screens such as flat panel screens, especially liquid crystal displays (CL); and as integrated circuit packages (Cl). As such, the polymers are useful for applications such as laminates, coatings or thin films to form integrated circuits, such as microprocessors, memory modules and multimicrocircuits, as well as mixed structures such as carbon matrixes, such as high performance matrix resins. useful in aerospace and aircraft industries, high temperature adhesives and mixed matrices, precursors for fibers and carbon glasses. In another aspect, the present invention is a substrate coated with the described polymer, for example, a computer microcircuit having a coating of the described polymers such as a computer microcircuit having the polymer as a dielectric insulation coating of intermediate layers. In still another aspect, the present invention is a laminate having at least two layers, at least one layer of which comprises a polymer of the present invention. Laminates of these polymers are particularly useful in electronics, building materials, matrix resins for aircraft and aerospace applications and for applications that require resistance to heat or weather. The invention is also a method for forming the monomers of Formula (I). The method comprises: (a) selectively halogenating a polyphenol to halogenate each phenolic ring with a halogen in one of the two available positions ortho to the phenolic -OH group; (b) converting the phenolic -OH in the resulting poly (orio-halophenol) to a leaving group which reacts with terminal ethinyl groups, for example, sulfonate ester; and (c) reacting the product of step (b) with an ethynyl-containing compound or an ethynyl synthon in the presence of an aryl ethynylation catalyst and an acid acceptor to replace the halogen and the leaving group (e.g., trifluoromethyl sulfonate) with a group containing ethynyl. Those ethynyl-containing groups which are substituted with protecting groups (such as trimethylsilyl or 2-hydroxy-2-propyl) can be optionally treated to remove the protecting groups in order to provide monomers of the present invention. Alternatively, the protecting groups can remain during the polymerization. In still another aspect, the present invention is a compound of the following formula (RO2So) X (n-1) -Ar-LfAr (OS02R) X <m.?] q (IV) wherein X is halo, preferably bromine, iodine or chlorine, more preferably bromine; m, n and q are as defined above, and R is any group so that RSO20 is a leaving group preferably perfluoroalkyl. The compounds of the present invention are ethyl aromatic monomers of the formula: (RC = C) -pAr-L ArfC = CR) m] q (I) wherein each Ar, L, R, n and q are as defined above the term "inertly substituted" means a group or portion having one or more substituent groups that are essentially inert (ie, non-reactive or, if reactive, will not significantly and detrimentally affect the properties of the compound or polymer made from of the same) and preferably is inert, to the subsequent polymerization of the compound as well as to any reagent or solvent used in subsequent processing. For example, the group R may be substituted inertly with an alkyl such as an alkyl having from one to twelve carbon atoms; a halogen such as fluorine or chlorine; an alkene or alkene conjugate; phosphorus, silicon, sulfur, nitrogen; or oxygen and combinations thereof. Similarly, each R group can be substituted with a halogen such as fluorine, chlorine and bromine; match; silicone; sulfur; nitrogen; -CF3, -OCH3, -OCF3, or -O-Ph. Substitution with fluorine is especially preferred to achieve a low dielectric constant in the resulting polymers. In the formation of polymers resistant to high temperatures, it is usually preferable to avoid the hydrogen atoms in a benzylic or allylic position or Ar groups or aromatic R groups substituted with straight chained or branched alkyl esters or ethers. The size of cf Ar and R is not particularly critical to the invention; however, the size of the group Ar and R, particularly the size of the group R, due to steric hydration, may undesirably interfere with subsequent polymerization of the compound and Ar and R are selected accordingly. In general, any R group which does not prevent the formation of an aromatic ring from the reaction of the ethynyl groups in the heat treatment can be used. In general, each Ar will have from 6 to 50, preferably from 6 to 40, more preferably from 6 to 30 carbon atoms and each R, when aromatic will have from 1 to 20, more preferably from 6 to 15, more preferably from 6. to 10 carbon atoms. Representative examples of Ar-L C = -R) - when R is aromatic include: and the representative L-Ar-L (-C = C-R) m groups being the aromatic Ar and R groups preferably being phenyl groups phenylene, naphthyl, naphthylene, biphenyl, biphenylene, 2,2-diphenylene-1,1,1,3,3-hexafluoropropane, 9,9-diphenylfluorene, diphenyl sulfide, diphenyl ether, trifluoromethylphenyl, trifluoromethoxyphenyl anthracene, phenanthrene, anthraquinone, triphenylphosphine, triphenyl phosphine oxide, or groups containing aromatic silicones. In addition to being aromatic, R may also be hydrogen or an alkyl or inertly substituted alkyl or cycloalkyl group. When greater reactivity is desired, R is preferably hydrogen an alkyl group having from 1 to 8 carbon atoms. Preferably, R is unsubstituted or inertly substituted phenyl, still more preferably phenyl substituted with one or more fluorine atoms or a fluoroalkyl group having from 1 to 6 carbon atoms. While L may be a covalent ligature or any group that joins Ar groups; L preferably is a ligation, an unsubstituted hydrocarbon group or an inertly substituted hydrocarbon group such as a halogen-substituted hydrocarbon (for example perfluoroalkyl); silicone or substituted silyl; oxygen, sulfur nitrogen or substituted amine; phosphorus or substituted phosphine. The group L may also be a polymer chain such polyarylene or polyaryl ether (eg, polyphenylene, polinaphthalene or polyphenylene oxide) of essentially any molecular weight depending on the desired properties of the substituted ethynyl aromatic polymer. The preferred L depends on the desired properties of the resulting polymer with; in general L being preferably a ligature, oxygen or an unsubstituted or inertly substituted alkyl group having from 1 to 13, more preferably from 3 to 6 carbon atoms (for example hexafluoropropane, or 9,9-fluorene). Representative examples of compounds of the structure of the Formula (I) include: wherein Ar-L-Ar is preferably bisphenyl such as biphenyl, 2-diphenylpropane, 9,9'-diphenyl fluorene, 2,2-d? phen? hexafluoro propane, diphenyl sulfide, oxydiphenylene, diphenyl ether, b ? s (fen? len) diphenylsilane, b? s (fen? len) phosphine oxide, b? s (fen? len) benzene b? s (phen? len) naphthalene, b? s (fen? len) anthracene, thiodiphenylene, 1,1-t-phenylenetene, 1, 3,5-tr? phen? lebenzene, 1, 3,5- (2-phen? len-2-prop? l) benzene, 1,1,1- Please rate me, 1,1,2,2-terafen? len-1,2-d? phen? letano b? s (1, 1-d? phen? lenet? l) benzene, 2,2'- d? phenol, 1,1,3,3-3-hexafluoropropane, 1,1-d? phen? len-1-phenoyl, naphthalene, anthracene ob? s (fen? len) naphthalene, more preferably bisphenylene, naphthylene p, p '(2,2-d? phen? len propane) [-C6H4-C (CH3) 2-C6H4-], p, p' - (2,2-d? phen? len-1,1) , 1,3,3,3 hexafluoropropane) and [-C6H4-C (CF3) 2-C6H4-] More preferably, Ar-L-Ar is biphenyl, 2,2-d? Phen? L propane, 99'-d ? fen? l fluorene, 2,2'd? phen? hexafluoro propane, diphenyl sulfide, diphenyl ether, b? s (fen? len) diphenylsilane, x gone from b? s (fen? len) phosphine bis (phenylene) benzene; bis (phenylene) naphthalene; bis (phenylene) anthracene; or bis (phenylene) naphthalene. The ethinyl groups in each Ar are on adjacent carbon atoms within the ring. It is thought that they are dimerized by applying heat to form an aromatic ring having a 1,4-diradix which serves to polymerize and / or entangle the compound. While not bound by theory, it is thought that this dimerization occurs via the Bergman cyclization as described by Warner et al., In Science, 268, 11 Aug. 1995, pp. 814-816. Ethynyl aromatic monomers are preferably bis (o-dithynyl) monomers (herein referred to as BODA monomers (bis (ortho-diacetylene), which means that at least two groups of adjacent ethynyl groups are in the monomer). say, at least one set of ethynyl groups in each group Ar. Preferably, the ethynyl aromatic compound contains from 2 to 4, even more preferably from 2 to 3, sets of diethynyl, even more preferably, except when additional entanglement is desired. , the sets (ie, four) of the ethynyl groups The monomers of the present invention will advantageously be prepared by: (a) selectively halogenating, preferably in a solvent, a polyphenol (preferably a bisphenol) to selectively halogenate, preferably bromate, each phenolic ring with a halogen in one of the two positions ortho to the phenolic -OH group. (b) converting the phenolic -OH to the resulting poly (ortho-halophenol), preferably in a solvent, to a leaving group such as a sulfonate ester (eg, a trifluoromethanesulfonate ester prepared from trifluoromethanesulfonyl halide or trifluoromethane acid anhydride) sulfonic) which is reactive with and replaced by terminal ethinyl compounds; and (c) reacting the reaction product of step (b) with an ethynyl-containing compound or an ethynyl synthon in the presence of an aryl ethynylation, preferably palladium, catalyst and an acid acceptor to simultaneously replace the halogen and the trifluoromethyl sulfonate with an ethynyl-containing group (for example acetylene, phenylacetylene, substituted phenylacetylene or substituted acetylene). In the halogenation step of step (a), the polyphenol corresponds to (HO) -Ar-L-Ar- (OH), where Ar and L are as described above. Preferred polyphenols include 4,4'-bisphenol; 9,9-bis (4'-hydroxyphenyl) fluorene; 4,4'-dihydroxydiphenyl ether; 4,4'-dihydroxy diphenyl thioether; 2, 2-bis (4 '-hydroxy fe nyl) hexafluoropropane; bis (4'-hydroxyphenyl); phenylphosphine oxide; trisphenols such as 1,1,1-tris (4'-hydroxyphenyl) ethane; 1,1,1-tris (4'-hydroxyphenyl) phosphine oxide; 2,6-naphthalenediol; and 2,7-naphthalenediol. The conditions at which the halogenation step (a) is conducted are not particularly critical; as long as the selective halogenation takes place and the most advantageously employed conditions will depend on a variety of factors including the specific polyphenol being halogenated and the halogenating agent. In general, the reaction is carried out in a solvent for the bisphenol and the halogenated product such as carbon tetrachloride or methylene chloride or a mixture of these solvents with glacial acetic acid. In the case where n and m in Formula (I) are each 2, the temperature, pressure (which is most commonly atmospheric) and bromine stoichiometry are controlled so that only one ortho-bromine atom is attached to each group of phenol. In general, temperatures of -20 ° C to 100 ° C are used, preferably 0 ° to 50 ° C are used with the reaction times being from 1 to 168 hours. The conditions at which the halogenated product is converted to the sulfonate ester are also not particularly critical, as long as the desired conversion is achieved. These more advantageously employed conditions depend on a variety of factors including the specific halogenated polyphenol and other reagents, the temperature and pressure (generally atmospheric) being maintained to react the halopolyphenol with a sulfonate esterification reagent such as trifluoromethanesulfonyl halide, preferably trifluoromethanesulfonyl chloride. or trifluoromethane sulfonic acid anhydride, to form the corresponding aryl of 2-halophenyl poly (trifluoromethanesulfonate) of the formula: (RO 2 SO) X (n.1) -Ar-L-Ar (OSO 2 R) X (m.1)) q preferably of the formula: (CF3O2SO) Br (n-1) -Ar-L [-Ar- (OSO2CF3) Br (m.1)] q The reaction is advantageously carried out in a solvent such as methylene chloride, as carbon tetrachloride, or chloroform at a reaction temperature of -20 ° to 100 ° C, preferably from 0 ° to 50 ° C, for a reaction time of 0.5 to 96 hours. The final step (c) is carried out at a temperature and pressure (generally atmospheric) sufficient to react the poly (2-halophenyl trifluoromethane) with an ethynyl-containing compound or an ethynyl synthon in the presence of an aryl ethynylation, preferably palladium, catalyst and an acid acceptor. Advantageously, a solvent is used for the acid acceptor and the reactants and reaction product and is generally a polar aprotic solvent. Representative solvents include tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, triethylamide, di-isopropylamine, other amine solvents and mixtures of amine solvents. The ethynyl-containing compounds that may be employed include those compounds reactive with the poly (2-bromophenyl trifluoromethane) sulfonate and preferably have the formula R-C = C-X, where R is as previously defined and X is hydrogen or a copper salt (I). These include phenylacetylene, pentafluorophenylacetylene, trifluoromethylphenylacetylene and 4-fluorophenylacetylene. The ethynyl synthons are compounds that form ethynyl groups in the final product and include such compounds as tpmethylsilylacetylene. The ethynyl group is optionally protected by such groups as acetals, ketones, ketals, hydroxymethyl, hydroxymethyl protected by tetrahydropyran, dimethylcarbinol, ethyl ester, tpmethylsilane, especially trimethylsilyl and dimethylcarbinol Acid acceptors that may be employed include acceptors of inorganic acids such as potassium carbonate, amines, such as tetylamine, tp-isopropylamine, pipepdine, di-isopropylamine, and pipdine, as well as mixtures of these amines and / or acceptors of inorganic acids More preferably, the acid acceptor is tethylamine The ethylation catalysts of aplo which may be used include copper and / or palladium, a source of phosphine preferably phosphine of triam (for example tpphenyl phosphine, tp-o-tolyl phosphine), as long as palladium is in the form of palladium metal or palladium complexed, either zero valent or precursors thereof (eg Pd "including, for example, palladium diacetate and palladium dichloride). Preferred catalysts include palladium acetate and chlorine with a phosphine source and copper as described by Ritter, Svnthesis. 1993, p. 749-750, Grissom and others J Orq Chem 1993, 58, 5422-5427 on p. 5423, Jones, et al., Polvmer. 36 (11 pp. 187-192, Chem et al., Tet Lett. 27 (101 pp. 1171-1174 (1986), Alami et al., Tet Lett. 34 (40) pp. 6403-6406 (1993), Nguyen, et al. Inorganic Chimics Acta 220. pp. 289-296 (1984), and Cacchi and others Svnthesis, 1986. pp. 320-322 In general, the ethynylation reaction is carried out at temperatures of 40 ° C to 180 ° C, preferably 60 ° C. ° C to 100 ° C, more preferably 70 ° C to 95 ° C, for a reaction time of 1 to 48 hours, preferably 1 to 24 hours, more preferably 2 to 6 hours. Monomers are more advantageously employed in the organic liquid reaction medium, when employed, they depend on a variety of factors including the specific monomers and organic liquid used in the polymer being prepared. In general, reagents are used to prepare a solution that contains from 1 to 70, preferably from 5 to 50 percent solids The preparation of bis (ortho-diacetylene) -6F, a more preferable monomer of the present invention, can be described as follows: After the preparation of the ethynyl (or monomer) aromatic compound, the product can be recovered by conventional methods or, if prepared in a solvent, used directly without recovery. The ethynyl aromatic monomers of Formula (I) are useful for preparing Polymers of any Formula (II) or (III) While it is not bound to theory it is thought that the ethinyl groups specifically those of ortho orientation, in the aromatic ring cyclize upon heating, forming a dehydro aromatic ring which reacts to form a polymer chain Monomers with more than two ethynyl ortho groups (ie, more than one group of ethynyl groups) are used to form thermosetting polymers and depending on the concentration of monomers having more than one set of ortho-ethynyl groups they can contain of almost none (i.e., a polymer having essentially repeating units of Formula (II) only) to substantially nceles of linear polymer chain structure (ie, a polymer of Formula (III)). Ethynyl aromatic monomers can be thermally polymerized. The polymerization can be detected by increasing the viscosity or reaction exotherm. The polymerization will generally be at a temperature of more than 150 ° C, but the polymerization temperatures are preferably at least 180 ° C, more preferably at least 210 ° C. The polymerization temperature preferably does not exceed that temperature which could result in undesirable degradation of the resulting polymer, which means that the polymerization is generally carried out at a temperature lower than 300 ° C for monomer having benzylic hydrogen atoms and, to monomers that do not have a benzyl hydrogen, less than 450 ° C, preferably less than 400 ° C, more preferably less than 350 ° C. The polymerization temperature will vary with Ar-L-Ar and R, with smaller R groups such as H that generally require lower temperatures than the larger R group and more conjugated Ar and R groups (when aromatic) requiring lower temperatures than the groups Ar and R less conjugated. For example, when R or Ar is an anthracene. the polymerization is carried out more advantageously at a lower temperature than when Ar or R is phenyl.

While not bound by theory, the representative units of Formula (II) are thought to have the following structural formulas: The polymerization is conveniently carried out at atmospheric pressure, but pressures higher than atmospheric pressure can be employed. The polymerization can be carried out in the presence of agents to control (accelerate) the cyclization reaction such as free radical initiators, or the chlorides described by Warner et al. In Science 269, p. 814-816 (1995) can be used in the polymerization reaction. While not bound by theory it is thought that the polymerization of the most preferred bis (ortho-d-acetylene) -6F can be described as follows While the specific polymerization conditions depend on a variety of factors including the specific ethynyl aromatic monomers being polymerized and the desired properties of the resulting polymer, in general, the polymerization conditions are dictated or determined by the specified end-use application of the polymer . The polymerization can be carried out pure or in a solvent and a solvent is used or not depends on the specific monomers used, polymer formed, processing conditions and application of end use. For example, when the resulting polymer is to be used as a powder coating, or in resin transfer molding or injection molding, the polymerization is often advantageously carried out pure or in bulk. Alternatively, a solvent may be used in the polymerization. In general, a solvent is employed for applications wherein the polymer or an oligomeric precursor of the polymer will be applied to the solution such as a spin coating of solution. These applications as well as others, the monomers are heated until the oligomers are formed (i.e., a mixture of unspecified amount of unreacted monomers in combination with the reaction products of monomers having a molecular weight greater than the monomer but less than its gel point, generally a number average molecular weight of less than 100,000, often less than 25,000, still more frequently less than 15,000 and one Mp / Mn ranging from 1 to 100, preferably from 1 to 50 and even more preferably from 1 to 25, as determined by size exclusion chromatography using the normal polystyrene calibration). Preferably, the oligomer solution is a liquid solution having a convenient viscosity for the coating. In general, said solution will comprise from 1 to 70, preferably from 10 to 60 percent solids by weight. Subsequently, the oligomers are applied in or from a solution and subsequently heated to remove solvent and cure or crosslink the oligomers to the final thermosetting polymer. In general, the solvent most advantageously employed will be a solvent for both the monomer and the resulting oligomer. such as dusopropylbenzene, 1, 3,5-tr? soprop? l-benzene, 1-met? l-2-pyrrolidone; mesitylene, gamma-butyrolactone, cyclohexanone, cyclopentanone, diphenyl ether, and 1,3-di-t-butylbenzene The time and temperature most advantageously employed to form the oligomers will vary depending on the specific monomers employed, particularly their reactivity, the specific monomers and ohgomeros and the organic liquid In general the oligomers are formed at temperatures of 150 ° C to 250 ° C and for a time of 1 to 48 hours and the extension of additional chain (advance) and entanglements conducted at a higher temperature of 200 ° C to 450 ° C, preferably 225 ° C to 400 ° C and for a time of 05 to 10 hours, more preferably 05 to 2 hours The extension of chains and curing temperature will normally cause evaporation of the solvent Depending on the the desired properties of the polymerized producer, two or more different ethynyl aromatic monomers can be copolymected having two or more pairs of ethynyl groups, or one or more monomers aromatic ethynyl rings having two or more pairs of ethynyl groups can be copolymeated with a monomer having only two (i.e., one pair) polyepable ethynyl groups to form polymers having linear segments The comonomer employed will affect the stiffness, glass transition temperature , adhesion, solution viscosity, processability and flexibility in the final polymer. When the compounds of the invention are copolymerized with monomers that can be used to prepare linear polynaphthalene polymers, the resulting thermosetting copolymer will often exhibit improved mechanical properties such as increased stiffness (as measured by the Klc and Glc values in accordance with ASTM methods numbered D5045). The polymers and copolymers of the present invention are useful for applications such as coatings or thin films to form electronic and computer microcircuits especially in microprocessors and also in memory microcircuits and in EPROMS (erasable programmable read only memory), as well as structures mixed high performance matrix resins useful in aerospace and aircraft industries; high temperature adhesives and mixed matrices; ceramic precursors for fibers or carbon glasses useful in automotive, autoelectronic or aerospace industries and medical implants; electro / optical polymers; conducting polymers; non-linear optics; photoelectric luminescence apparatus such as light-emitting diodes (LED); and thermochromic indicators that have similar properties to simiconductors when oxidized and / or reduced useful in LED. The matrix applications are similar to those explained in Hergenrother, Encyclopedia Polvmer Science and Enaineerina. vol. 1, 2d. John Wiley & Sons, NY (1995) p. 61-86. The polymers or oligomers of the oligomeric polymer precursor can be applied by a number of methods such as vapor deposition (chemical or physical), splashing, solution deposit, liquid phase epitaxy, screen printing, fusion rotation, submersion coating , roll coating, rotating, brushing (eg varnish), spray coating, powder coating, plasma deposition, spraying by disposal, solution casting, vacuum storage, slurry spraying, dry powder spraying, bedding techniques fluidized, welding, blasting methods including the method of explosion of cables explosion and union with explosion, connection to pressure with heat; plasma polymerization; dispersion in a dispersion medium with subsequent removal of dispersion mean; pressure union; bonding by heat with pressure; vulcanization of gaseous environment; extrusion of molten polymer; hot gas welding; coating by baking and concresionado. Mono and multilayer films may also be deposited on a substrate using a Langmuir-Blodgett technique in an air-water or other interface. The oligomer can be cast directly as a film, apply as a coating or pour into a non-solvent to precipitate the oligomer. Water, methanol, acetone and other similar polar liquids are normal non-solvents that can be used to precipitate the oligomer. If the oligomer is obtained in solid form, it can also be processed using conventional compression molding techniques or spinning techniques with melting, casting or extrusion as long as the solid precursor has a sufficiently low glass transition temperature. For example, polymers can be used as powder coatings in the electronics industry for coatings of electron components, such as networks of resistors, capacitors and hybrids and apply , for example, by automatic fluidized beds, submersion equipment and electrostatic spraying When used as a powder coating, the polymer preferably has a melting temperature below the melting point of tin-lead solder, more preferably below 150 ° C, even more preferably e Low 130 ° C Alternatively, monomers having a melting point below 200 ° C can be applied as a powder and heated to effect polymerization. Optionally other components of a desired coating can be mixed with the monomers before Polymerization so that the components remain in the final polimetre coating Most commonly the oligomers are processed directly from the organic liquid reaction solution The organic solution of the ohgomero can be squeezed or applied and the solvent evaporated and the molecular weight increased (extension or progress chain) to form the final polymer upon exposure to a sufficiently high temperature When the monomer, prepolymer or oligomeric polymer of the solution is applied, the specific polymerization conditions of other processing parameters more advantageously employed depend on a variety of factors, particularly the monomer, specific oligomer or polymer being deposited, the coating conditions, the quality and thickness of the coating and the end-use application, the solvent being selected accordingly Representative solvents that may be employed include hydrocarbons such as o-, m- or p-xylene , mesitylene, toluene and trnsopropylbenzenebenzene, chlorinated hydrocarbons such as chlorobenzene and dichloromethane, ketones such as methyl ethyl ketone isoferone, acetone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, esters such as isoamyl acetate, n-butyl acetate, ethyl acetate , cellosolve acetate, methyl cellosolve acetate and gamma-butyrolactone, esters such as diglyme and tetrahydrofuran, amides such as N, Nd? met? lformam? da, and other polar solvents such as nitrometran, or 1-met? l-2 -p? rrol? d? nona The substrates that can be coated can be any material that has enough integrity to be coated with the monomer, oligome Examples of substrates include wood, metal, ceramic, glass, other polymers, paper, paperboard fabric, woven fibers, non-woven fiber esters, synthetic fibers, Kevlar ™, carbon fibers, silicone and other substrates inorganic and their oxides. The substrates that are used are selected based on the desired application. Preferred materials include glass, including glass fibers (woven as non-woven or braided); ceramics, metals such as aluminum, magnesium, titanium, copper, chromium, gold, silver, tungsten, stainless steel, Hatalloy ™, carbon steel, other metal alloys and their oxides; and thermosetting and thermoplastic polymers such as epoxy resins, polyimides, perfluorocyclobutane polymers, benzocyclobutane polymers, polystyrene, polyamides, polycarbonates, and polyesters. The substrate can be of any form and the form depends on the application of the final use. For example, the substrates can have the shape of disc, silver, cable, tubes, board, sphere, rod pipe, cylinder, brick, fiber, woven or non-woven fabric, spinning (including joined yarns), ordered polymers and woven mats or nonwoven In any case, the substrate may be hollow or solid. In the case of hollow objects, the polymer layer (s) is (are) on either or both of the inner side or outer side of the substrate. The substrate may comprise a porous layer such as mat or graphite cloth, mat or glass cloth, a canvas and particulate material. The polymers adhere directly to many materials such as compatible polymers, polymers having a common solvent, metals, particularly textured metals, silicon or silicon dioxide, especially silicon or etched silicon oxides, glasses, silicon nitride, aluminum nitride, alumina, gallium arsenide, quartz and ceramics. However, when increased adhesion is desired, a material can be introduced to improve adhesion. Representative examples of said adhesion promoter materials are silanes, preferably organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilasano [(CH3) 3-Si-NH-Si (CH3) 3], or aminosilane coupler such as? -aminopropyltriethoxy silane, or as a chelate such as aluminum monoethylacetoacetatediisopropylate [((isoC3H70) 2AI (OCOC2H5CHCOCH3))]. In a preferred method, a solution of toluene is diffused from the chelate onto a substrate and after baking at 350 ° C for 30 minutes in oxygen to form a very thin (for example 5 nanometers) adhesion promoter layer of aluminum oxide on the surface. Other means for depositing aluminum oxide are also suitable. Alternatively, the adhesion promoter, preferably in an amount of 0.05 weight percent to 5 weight percent based on the weight of the monomer, may be mixed with the monomer prior to polymerization, negating the need for additional layer formation . Adhesion promoters useful in the practice of the invention include specialized elastomeric Chemloc ™ adhesives, fluoroepoxides; vinyl tri-tert-butyl silane peroxide; neoalkoxytitanates, neoalkoxyzirconates, iminoxyl radical compounds, polyaplene sulfide resins, aromatic polyether sulfone resins, aromatic polyether ketone resins, alkoxy-containing silicone compounds, organotitanates, organohydrogenphosphine compounds, m-aminophenol (optionally in a mixture with a phenoplast), chromic acid, phosphoric acid, pohalkyl silicate containing a finely divided metal such as zinc, chromium complex III of acid compounds such as fumpas, curable epoxy resins, ammonium chromium phosphate scavenge, chrome blends / chromium oxide, carboxyl-containing alpha-olefin polymers, fluorinated acids and organic complex alcohols of group 2B or 8 metals, fluoropolymer particles, fluorinated rubber, optionally containing extenders such as urethane, epoxy or acrylic resins, hydrocarbon polymers with agents allogenants, tpalyl cyanurate, tpalyl isocyanurate, agent silicone tackifier, perfluoroalkoxyl resin with resin containing imide ligatures, polysulphide silane compounds, epoxy adhesive, alkali metal and / or alkaline earth silicate glass, bis-chloroalkyl vinyl phosphonate, polyurethane mastic, film bases polyester, acid salt of polyamide, metal oxides, fluoro resin promoters optionally containing oxidants and / or inorganic acids, copolymers of methyl methacrylate, zinc phosphate, zinc dispersion, water hardening cements, organic peroxy compounds, fluorine resin contains asbestos paper, lithium polysilicate, acid powder and alkali-resistant inorganic substance (such as silica, graphite, molybdenum sulfate or chromium oxide); aluminum borophosphate; alkyl silicates; alkali metal silicates; polyamine-imides; polyvinyl cinnamic acid (optionally exposed to ultraviolet light), and deposited carbon layers. Adhesion can be increased by surface preparation such as texturizing (e.g., scraping, etching, plasma treating or polishing) or cleaning (e.g. degreasing or sonic cleaning); treating in some other way (for example, treatments by plasma, solvent, SO3, plasma brightness discharge, corona discharge, sodium, wet etching or ozone) or sand destruction of the substrate surface or using beam techniques electronic, such as 6 MeV fluorine ions; electrons at intensities of 50 to 2000V; hydrogen cations at 0.2 to 500 ev at 1MeV; helium cations from 200 KeV to 1 MeV; fluorine or chlorine at 0.5 MeV; neon at 280 KeV; treatment by flame enriched with oxygen; or a treatment with the accelerated argon ion. Fillers including glass; copper oxide and other metal oxides; colloidal silica; glass fibers; water-hardening cements; mineral fibrils such as potassium titanate, titanate dioxide or boehmite fibrils; or boehmite in another form, they can also be used to improve adhesion. The fillers may optionally be coated or treated, for example, with surface active agent or adhesion promoter to improve adhesion to the polymer. The processes involving the grafting of said monomers as acrylic ethers and / or other vinyl compounds to the polymer (for example using catalysts or radiation), and optionally treating the grafted molecules (eg saponification), polymer adhesion can also be increased. The polymer can be applied in combination with other additives to improve the performance. Representative of said additives are metal-containing compounds such as magnetic particles, for example, barium ferpta, iron oxide, optionally in a mixture with cobalt, or other metal-containing particles for use in magnetic media, optical media or other etching media, conductive particles such as metal or carbon to be used as conductive sealants , conductive adhesives conductive coatings, electromagnetic interference protective coating (EMI) / radio frequency (I FR), static dissipation and electrical contacts When these additives are used, the polymer can act as a binder The polymers of the present invention are also useful s in seals and gaskets, preferably as a layer of a seal or packaging, for example around a canvas and also only in addition, the polymer is useful in coatings against incrustations on said objects such as parts of cans, electrical conductor boxes, tubs bath and shower coatings, in mold-resistant coatings, or to impart an article flame resistance, such as weather resistance or moisture resistance Due to the temperature resistance scale of polymers, polymers can be coated on cryogenic containers, autoclaves, and ovens, as well as heat exchangers and other heated or cooled surfaces and on items exposed to microwave radiation. The polymers can also be used as protection against the environment (i.e., protection against at least one substance or force in an object environment, including manufacturing, storage and use conditions) such as coatings for imparting surface passivation to metals, semiconductors , capacitors, inductors, conductors, solar cells, glass and glass fibers, quartz and quartz fibers Polymers are particularly useful in electronic packaging such as multimicrocircuit modules, multilayer microcircuits, microwave circuits, coating layers, optical interconnection, boards and circuits, and cable insulation. The polymers are also useful as environmentally protective layers, impact absorbing layers for micromachines. When treated, the polymers are useful as conductive layers for such applications as LED and non-linear optics (ONL). In addition, the polymers of the present invention can be applied to gallium arsenide and its homologs, which are frequently used in semiconductor devices such as high-speed transistors, high-speed integrated circuits, light-emitting diodes and laser diodes; silicon dioxide, which is often formed on silicone (preferably surface treated such as with silicon nitride or phosphorus treatment to increase adhesion) which is commonly used as an insulator in semiconductor devices; silicon dioxide treated with phosphorus; chrome, which is useful as an opaque layer in optical masks; copper and copper sheet. In such cases, the surface on which a polymer film is applied preferably is clean and free of dust particles to avoid adhesion problems and / or defects in the film. The cleaning of the silicone wafer surface, for example, may involve: (1) boiling it in a solvent, for example trichlorethylene, for example, for 5 minutes, (2) washing it in another solvent, for example acetone (room temperature), for a similar time followed by (3) boiling in an acid, for example concentrated nitric acid, for example, for 15 minutes. Other substrate treatments include, for example, etched silicon dioxide, with hydrofluoric acid (AF); treatment with hexamethyl disilane (DSHM) of polysilicon, silicon dioxide, silicon dioxide treated with phosphorus or silicon nitride. The aromatic ethynyl compound or oligomer thereof is applied to obtain a preferably continuous and / or uniform coating followed by an initial heating to remove solvents for example from 100 ° to 200 ° C, and then curing from 190 ° to 350 ° C. In a particularly preferred embodiment of that invention one or more layers of the polymer are applied onto optical fibers, for example glass fibers, usually by applying an oligomeric solution, preferably of sufficient viscosity for even spraying to form a uniform coating; stirring the solvent to form a fiber coated without glue preferably by rapid heating, for example in a plasma (electronic UV beam) or infrared (IR) furnace; optionally followed by additional heat cure to achieve a polymer that is preferably at least 50, more preferably at least 80, even more preferably at least 99 weight percent cured. In the manufacture of microelectronic devices, the relatively thin defect free films, generally from 1 to 200, preferably from 1 to 20, μm in thickness, can be deposited on an inorganic support substrate (preferably clean) eg silicone; or silicone-containing materials such as silicon dioxide, alumina, copper, silicon nitride; aluminum nitride; aluminum, quartz and gallium arsenide. The coatings are conveniently prepared from solutions of an oligomer having a molecular weight of, for example, 2,000 Mn, 15,000 Mp. 25,000 Mz (high average), in any of a variety of organic solvents such as xylene, mesitylene, and n-butyl acetate. The dissolved oligomer (or prepolymer) can be cast into a substrate by common rotary spray coating techniques. The viscosity of these solutions is important to control the coating thickness by any deposit technique.

The polymer layer (s) can be molded (s) such as by photoresistors and by such means as wet etching, plasma etching, reactive ion etching (GIR), dry etching, or wear with photolaser, as illustrated by Polymers for Electronic Applications, Lai, CRC Press (1989) p. 42-47. The molding can be achieved by multilevel techniques in which the pattern is lithographically defined in a resist layer coated on the polymeric dielectric layer and then etched in the lower layer. A particularly useful technique involves masking the portions of the polymer (or prepolymer) that will not be removed, removing the unmasked portions of the polymer, then curing the remaining polymer, for example, thermally. The polymers of the present invention are particularly useful for planarizing materials such as silicone wafers useful in semiconductors to allow the production of smaller circuitry (higher density). To achieve the desired planarity, a coating of the oligomer or polymeric precursor of the solution such as spin coating or spray coating is applied to flow so as to level any roughness on the surface of the substrate. These methods are illustrated by such references as Jenekhe, S.A., Polymer Process to Thin Films for Microelectronic Applications in Poymers for High Technology, Bowden et al., Ed. American Chemical Society 1987, pgs. 161-269.

When used for planarization, a solution, preferably of prepolymers, is sprayed onto the substrate, rotated at a constant rotary speed which is advantageously maintained for a time advantageously to allow to precede a uniform thickness, for example for 30 to 60 seconds . The resulting solution film, thinned by centrifugal force, is dried to form a solid film. In the case of silicone wafers, the polymers can be effectively applied and allowed to adhere during thermal cyclization to reduce the deviation in the optical plane often caused by deposition of the oxide layer. After a polymeric film is formed, for example by the rotary coating process, the film is conveniently baked. Baking evaporates the solvent remaining in the film and generally more fully polymerizes the monomer and / or oligomer. The baking temperatures are preferably 180 ° C to 350 ° C, more preferably 250 ° C to 350 ° C. The planarization layer of the polymer can optionally be smoothed by polishing. A planarization layer is preferably 0.1 μm to 5 μm thick, more preferably 0.1 μm to 2 μm.

The polymers of the present invention are also useful in reinforced composite materials in which a resin matrix polymer is reinforced with one or more reinforcing materials such as a reinforcing fiber or mat. Representative reinforcing materials include glass fiber, particularly glass fiber mats (woven or non-woven); graphite, particularly graphite mat (woven or non-woven); Kevlar ™; Nomex ™; glass spheres Mixed materials can be made from preforms, immersing mats in monomer or oligomer, and resin molding and transfer (where the mat is placed in the mold and the monomer or prepolymer is added and heated to polymerize). While polymers are particularly useful as outer layers and dielectric layers, they are also useful as reinforcement layers or other inner layers, such as tire reinforcements and seat belts. The following examples are presented to illustrate the present invention and should not be construed as limiting its scope. The ratios, parts and percentages are by weight unless stated otherwise. Example 1 Preparation of 2,2-bis (3 ', 4'-di (phenyletinyl) -phenyl) -1.1.1.3,3.3. -hexafluoropropane 2.2 - ((3,3'-D¡bromo-4.4'-dihydroxy) phenyl) -1,1.1.3.3,3-hexafluoropropane A 250 milliliter round bottom flask (ml) (equipped with a gas vent connected to an acid gas scrubber) containing 50 ml of carbon tetrachloride (CCI4) and 10 ml of glacial acetic acid (HOAc) kept at room temperature At room temperature, 16 grams (g) (0.048 moles) of 2,2-bis (4'-h-hydroxyphenyl) -1,1,1,3,3-hexaluoropropane were added with stirring. Iron powder (1.5 g) was added to the mixture and then 9.71 g of fuming liquid bromide (0.972 mol) were added dropwise to the mixture for 6 hours. The resulting solution was heated to 35 ° C with continuous stirring, the reaction mixture was kept at 35 ° C for 48 hours. At that time, the entire amount of bisphenol was converted to 2-b? S (3,3'-d). ? bromo-4,4, -d? hydroxyphen? l) -1 > 1,1,3,3,3-propane The reaction mixture was transferred to a separatory funnel where it was washed once with saturated aqueous sodium bicarbonate solution and twice with deionized water. The CCI 4 solution was then dried over Anhydrous magnesium sulfate (MgSO4) is filtered and the solvent is evaporated to provide 232 g of a yellow powder This corresponds to 0047 molar or a yield of 9795 percent, 934 percent pure by GC analysis having the IR properties (cm -1) 3506 7 (-OH), 16053, 15782, 14997 (Ar), 1256, 1208 9, 1175 3, 11367 (CF, 1046 (CO) Mass spectrum, m / e (%) 423 (454), 424 (572), 425 (88 9), 426 (655), 427 (52 0), 428 (332), 492 (45 1), 494 (1000), 496 (375) This product was isolated and used for the following reaction without further purification 2,2-B? s (3-bromo-4-tr? fluoromethanesulfonatofen? l) -1,1,1-3,3,3-hexafluoropropane Dibrominated bisphenol (232g, 047 moles) was dissolved ) in 150 ml of dichloromethane (CH2Cl2) and 15 ml (0108 mol) of Dry tetylamine To this mixture maintained at 8 ° C to 12 ° C was added 182 g of t-fluoro-methanesulfonyl chloride (0 108 moles) dissolved in 30 ml of CH2Cl2 for 30 minutes while the solution was kept from 8 ° C to 10 ° C, the reaction mixture was stirred for two hours, then transferred to a separatory funnel and washed successively with two portions of 5 percent aqueous HCl solution (each 100ml), two portions of sodium bicarbonate solution, saturated aqueous sodium (75 ml each), then once with deionized water. The CH2Cl2 solution was then dried over MgSO, anhydride was filtered to remove the drying agent and evaporated to give 28.7 g of 2,2-bis (3-bromo-4-trifluoromethanesulfonatophenyl) -1, 1, -3. , 3, 3-hexaf luoropropane as a light yellow solid (0.348 moles, 80.8 percent yield) having the following characteristics. IR (cm-1): 1479.0, 882.5, 737.3 (Ar), 1429.3, (S03), 1137.2, 1213.5 (C-F). 1 H NMR (400 MHz, CDC13): d 7.4 (4H, br, m), 7.74 (2H, s), 13 C NMR (100 MHz, CDCl 3): d 63.64 (hept, C (CF 3) 2, J = 30 Hz ), 116.57, 116.98, 122.97, 130.94, 133.71, 135.81, 147.83. 19 F NMR (376 MHz, CDC13): d -64.27 (6F, s), -73.86 (6F, s). DEP / MS m / e (%): 758 (5), 624 (4), 207 (5), 69 (100). 2.2-Bis (3,4-di (phenylethynyl) phenyl) -1.1.1.3,3.3-hexafluoropropane To a 250 ml steel autoclave with glass insert equipped with a mechanical stirrer, thermocouple and monometer and kept under a dry and inert atmosphere were added 10.0 g (0.013 mol) of 2, 2-bis ((3-b rom or -4-trif-uomethanesulfonat) f-ethyl) -1,1,1,3,3,3-hexafluoropropane, followed in order, by 1.85 g (2.64 mmol, 0.05 equivalents) of bis (triphenylphosphine) chloride of palladium (II), 0.40 g (2.11 mmol, 0.04 equivalents) of copper iodide (I), 18.69 g (0.185 mol, 3.5 equivalents) of amine of diisopropyl, 18.86 g (0.85 moles, 3.5 equivalents of acetylene of phenyl and finally 60 ml of tetrahydrofuran.) The autoclave was sealed and purged with nitrogen for 5 minutes, then stirred for one hour at 26 ° C. installed a heating mantle and the reactor was heated from 65 ° C to 70 ° C for 20 hours and then at 105 ° C for 13 hours with rapid and constant stirring e) When cooled to room temperature, the dark mixture was added to 100ml of CH2CI2 and 200ml of distilled water. The aqueous layer was separated and washed three times with 75 ml of CH2Cl2. The organic layers were combined and washed several times with 100 ml of saturated aqueous ammonium chloride, then twice with distilled water, filtered by gravity, dried over anhydrous MgSO 4, filtered and reduced to dryness by rotary evaporation. This crude product mixture was stirred in hot hexane and the insoluble portion was predominantly a mixture of phenylacetylene addition products together with other polyunsaturated oligomers. The hexane mixture was deposited on neutral alumina and separated by column chromatography, first eluting extensively with hexane, followed by elution with a mixture of six parts of hexane and four parts of CH2Cl2 to remove the alumina product. The solvent was removed and the oil in the product was suspended in twice the volume of hexane. With gentle rolling, the product was crystallized and washed with hexane to remove any introduced material. The isolated product was a light yellow crystalline solid with a melting point (m.p.) of 152 ° C to 164 ° C. It was isolated in an optimum yield of 54 percent It has the following characteristics 1 H NMR (400 MHz, CDC13) * d 7.30-740 (13H, br, m), 7.52-7.62 (13H, br, m) 13C NMR (100 MHz , CDC13) d 640 (hept, C (CF3) 2, J = 30 Hz), 8723, 8748, 9454, 9538 (-CCPh) 12277, 12616, 126.93, 128.36, 12840, 128.71, 128.78, 1294, 13163, 13172, 13251, 13311 19F NMR (376 MHz, CDC13) d -6384 (s) FTIR (crn-1) 3059, 2998 (w ArH), 2216 (w, alkyne), 1599, 1495 (st), 1437, 1262 (br, st, CF), 1209 (br, st, CF), 1178 (br, st), 1100 (sh), 963, 827, 756, 691 cm-1 DEP / MS m / z (%) 704 (100), the other fragments < 4% Example 2 Preparation of 3,3 ', 4,4'-Tetra (phen? Let? N? L) b? Phenol (Method 1) of 3,3'-D? Bromo-4,4'- d? h? drox? b? phenomenon In a 3-liter Morton 5-necked flask equipped with a mechanical stirrer, a thermocouple on the glass thermocouple and a drip addition funnel were placed 20083 g of 4 , 4-biphenol (1 07 moles), 25 liters of CH2CI2, 40 ml of HOAC and 1 37 g of iron powder (00245 moles) The reaction mixture was cooled to ° C, and 370.86 g of liquid bromine (2 32 moles) were added for two days. The temperature in the flask varies from 10 ° C to 18 ° C during the course of the reaction. The crude reaction mixture is filtered to stir solids and the filtrate was placed on a rotary evaporator to evaporate the CH2CI2. The residue was washed with saturated aqueous sodium bicarbonate, then in deionized water. The solid residue was dried on a rotary evaporator, then added to one liter of CCI4 and heated to 60 ° C to dissolve the solids. The resulting solution was cooled and the reaction product was collected as a crystalline solid. The solid product was washed with two 250 ml portions of hot hexane to remove its colored products, giving 230 g of 3,3'-dibromo-4,4'-dihydroxybiphenyl as a white crystalline solid (81 percent pure, 61.5 percent of performance). The main byproducts of the reaction were almost an equal mixture of monobrominated and tribrominated biphenols. (Method 2) 3,3'-Dibromo-4,4'-dihydroxybiphenyl In an alternative method, 20.0 g of 4,4'-biphenol (0.1075 moles) was added to a mixture of 4: 1 of CCI4 / HOAC and 36 g of bromine were added dropwise for 3 hours. The mixture was allowed to stir for 72 hours and the reaction was found to be 89 percent complete with the remainder being unreacted starting material. The mixture was washed twice with deionized water, forming an emulsion layer that separated slowly. The remaining CCI4 layer was removed by evaporation and the residue was dissolved in hot CH2CI2. The insoluble portion was filtered and washed CH2Cl2 with deionized water. The solution was dried over MgSO, filtered and evaporated to give 28.6 g of 3,3'-dibromo-4,4'-dihydroxybiphenyl (0.83 mol, 77.2 percent yield) as a light pink solid, with m.p. from 118 ° C to 121 ° C and having the following characteristics: FTIR (cm'1): 676.6 (0.19), 733.8 (0.20), 809.4 (.054), 823.0 (0.61), 865.7 (0.27), 964.9 (0.12), 1040.4 (0.50), 1061.0 (0.16), 1137.0 ( 0.50), 1206.5 (0.91), 1245.3 (0.53), 1275.3 (0.87), 1341.1 (0.65), 1370.4 (0.47), 1427.7 (1.00), 1490.2 (0.82), 1571.4 (0.18), 1603.5 (0.27), 3315.6 ( 0.056). Spec. Mass, m / e (%): 53 (20.4), 62 (15.6), 63 (18.4), 74 (20.5), 75 (16.6), 77 (12.8), 124 (12.4), 125 (16.5), 126 (24.7), 152 (12.2), 153 (18.0), 154 (17.3) 155 (46.9), 156 (14.1), 342 (9.14), 343 (14.9), 344 (100), 345 (15.6), 346 ( 47.7), 347 (6.1). (Method 1) 3,3'-Dibromo-4,4'-ditrifluoromethanesulfonate) biphenyl A 5-liter Morton 5-neck flask adapted with a mechanical stirrer, a thermocouple well, a drip addition funnel and nitrogen pad Dry at 150 ° C for 4 hours with a nitrogen sweep. To the reactor was added 229 g (0.67 moles) of 3,3'-dibromo-4,4'-dihydroxybiphenyl and 1 liter of CH 2 Cl 2. The solution was cooled to 10 ° C. 185 g (1.37 mol) of triethylamine was slowly added to the cooled mixture to maintain the reaction mixture at a temperature between 10 ° C and 15 ° C. Then, trifluoromethanesulfonic acid anhydride (378.0 g, 1.34 moles) was added dropwise from a dropping funnel over 2 hours and 10 minutes. During this addition, the temperature of the addition mixture varied from 5 ° C to 14 ° C. After the addition, the reaction mixture was raised at 22 ° C for 16 hours to complete the reaction. The crude mixture was then washed with 500 ml of water followed by 500 ml of saturated sodium bicarbonate and then again by 500 ml of deionized water. The CH2Cl2 and the residue was dissolved in hot hexane saturated with acetonitrile. The solution was cooled and the separated acetonitrile phase contained the black impurities in the product mixture. The hexane phase was isolated, heated to 60 ° C and cooled to crystallize the desired product. The product was then isolated (110 g, 95.5 pure percent, 33 percent yield) as a white crystalline solid with a m.p. from 69 ° C to 70.5 ° C. It was suggested that the low yield of this preparation may be due to the substantial solubility of 3,3'-dibromo-4,4'-di (trifluoromethanesulfonate) biphenyl in the wash water and certainly in the acetonitrile phase used to collect the impurities. (Method 2) 3,3'-dibromobiphenyl-4,4'-ditriphate In a second procedure, 28.56 g of 3,3'-dibromo-4,4'-biphenol (0.083 mol) were dissolved / suspended in 160 ml of CH2CI2, in 1 1-liter necked flask. When adding 25 ml of tritylamine, the solution was briefly rinsed, then accentuated in a thick paste. The solution of dibromobiphenol was cooled to 10 ° C with constant stirring and 28 grams of trifluoromethanesulfonyl chloride (0.166 moles) dissolved in 40 ml of CH 2 Cl 2 was created by dripping for 30 minutes. The thick solution became less viscous, but the solids did not completely dissolve. After the addition was complete, the solution was heated to 22 ° C and stirred overnight. The crude reaction mixture was washed twice with 5 percent HCl (100 ml each), saturated aqueous NaHCO3 (75 ml) and deionized water (100 ml). The washing of deionized water caused an emulsion to break slowly. The CH 2 Cl 2 solution was separated and dried over anhydrous MgSO 4, after it had entered and evaporated to provide 92 g of trifluoromethanesulfonate ester (9,969 moles) as a light brown solid. The yield was 83.2 percent and the product was 95 percent pure with the following characteristics: FTIR (crtT1): 723.4 (0.12), 747.0 (0.17), 839 (0.23), 886.0 (0.50). 1036.4 (0.23), 1135.4 (0.58), 1180.0 (0.38), 1206.4 (1.00), 1248.8 (0.37), 1433.1 (0.88), 1469.0 (0.38). Spec. of Mass, m / e (%): 69 (22.3), 126 (44.6), 127 (10.4), 381 (8.0), 383 (17.3), 385 (7.8), 473 (39.3), 473 (39.3), 474 (23.0), 475 (100), 476 (22.7), 477 (47.3), 478 (10.0), 606 (5.6), 608 (10.6), 610 (5.5). 3, 3 ', 4. 4'-Tetra (phenylethynyl) biphenyl. Oven-dried 3,3'-dibromo-4,4'-di (trifluoromethanesulfonate) biphenyl (60.85 g, 0.10 mole) was added to a 5 neck flask. one liter with DMF (270 ml) and triethylamine (270 ml). The solution was continuously purged with nitrogen. After sweeping the reactor contents with nitrogen for 20 minutes, a dichlorobis (trifenephosphine) palladium II catalyst was added and the reaction mixture was heated to 60 ° C. Then 16.5 g of phenylacetylene were added, causing an exotherm that increases the temperature to 80 ° C. The mixture was cooled to 70 ° C and the temperature was maintained at 70 ° to 80 ° C, while an additional 33.5 g of phenylacetylene was added dropwise. The reaction temperature was maintained after 75 ° C for 3 hours. Raw reaction mixture by CL at this point indicated a significant amount of unreacted agitating material and intermediate conversion products an additional 10 g of phenylacetylene and one gram of the catalyst and the reaction mixture was heated at 85 ° C for one hour. time, the CL indicated that the conversion was complete The cooled reaction mixture was diluted with 500 ml of CH2CI2 washed with three one-liter portions of 10 percent HCl The CH2CI2 solution was isolated and evaporated to provide a solid product crude that was suspended in hexane The solid was collected by filtration and purified by over washing with hot CCI4 This wash moved the discoloration and many of the by-products, but was not effective enough to remove the residual Pd (II) catalyst from the monomer. The monomer was further purified by chromatography on neutral alumina using tetrahydrofuran as an eluent. The resulting monomer was isolated (320 g 58 percent yield) as a solid. light yellow with a mp of 172 ° C to 174 ° C with properties 13 NMR (400 MHz, CDC13) d 730-740 (12H, br, m), 752-762 (12H, br, m), 782 (2H) 13 C NMR (100 MHz, CDC13) d 8823 (-CCPh, 4C) 9394 (-CCPh, 2C) 9466 (-CCPh, 2C), 1235 (4C), 12526 (2C), 12649 (4C), 1285 (m 12C ), 13016 (2C), 131 76 (8C), 13238 (2C), 13919 (2C) FTIR (en -) "1): 485.9 (0.17), 503.8 (0.15), 527.9 (0.23), 623.7 (0.05) , 687.7 (0.70), 752.8 (1.00), 822.7 (0.38), 886.1 (0.11), 911.5 (0.12), 1022.6 (0.08), 1067.0 (0.12), 1273.9 (0.04), 1384.9 (0.10), 1439.9 (0.18) , 1492.44 (0.49), 1534.2 (0.06), 1592.0 (0.19), 2967.2 (0.04), 3028.9 (0.07), 3050.2 (0.08). Mass spec, m / e (%): 80 (4), 183 ( 3.5), 236 (6.2), 237 (9.1), 238 (3.4), 261 (6.8), 262 (8.0), 268 (6.2), 269 (6.0), 274 (22.1), 275 (21.2), 276 (20.0), 277 (21.0), 472 (3.6), 474 (8.8), 476 (47), 554 (100), 555 (46.5), 556 (10.6). Failure to remove the catalyst resulted in a product of the monomer that was subjected to premature and excessively rapid polymerization upon heating to the melting point. Example 3 3,3-, 4,4'-Tetra (phenylethynyl) diphenyl ether 3-Ether , 3'-Dibromo-4,4-Dihydroxydiphenyl To a 3-neck 5-neck Morton flask adapted with a mechanical stirrer, thermocouple and dropping funnel was added one liter of CH2Cl2, 20 ml of HOAc, 100g of 4,4-dihydroxydiphenyl ether and 0.74 g of iron powder This mixture was stirred and cooled to 10 ° C under a nitrogen atmosphere. 170 g of liquid bromine was added slowly to the reaction mixture over a period of 2 hours and 15 minutes with vigorous stirring of the mixture. The temperature of the reaction mixture was maintained between 7 ° C and 10 ° C during this addition, when it was completed, the temperature was raised to 18 ° C and maintained at that temperature with stirring for 18 hours. The resulting mixture was washed with 2 liters of water followed by 500 ml of saturated sodium bicarbonate solution. The remaining organic solution was filtered to remove the suspended solids and the filtrate was evaporated to remove the solvent. The residue was washed with water to remove residual HOAc and dried under vacuum and then washed with hexane to remove colored by-products. The solid residue was dried under vacuum to provide 157g of a white crystalline solid product (86.3 percent yield) having, as indicated by GC, a purity of 97.1 percent with a melting point of 101 ° C to 102.5 ° C. . The product had these characteristics: GC / MS, m / e (%): 51 (16.0), 53 (27.0, 63 (30.0), 79 (16.5), 144 (7.4), 199 (7.3), 200 (13.0) , 359 (42.2), 360 (100), 362 (46.9), FTIR (cm-1): 799 (0.29), 859 (0.30), 880 (0.09), 922 (0.37), 1031 (0.13), 1184 ( 0.81), 1259 (0.40), 1331 (0.35), 1475 (1.00), 1577 (0.10), 1600 (0.13), 3395 (0.35), 3421 (0.38), 3,3'Dibromo-4,4 'ether bis (trifluoromethanesulfonate) diphenyl A 1 liter of CH 2 Cl 2 and 155 g of ether from a 2-neck Morton 5-liter flask equipped with a mechanical stirrer, a thermocouple, a dropping funnel with a connected nitrogen pad were added. 3,3'-dibromo-4,4'-dihydroxydiphenyl The solution was cooled to 10 ° C. Triethylamine (97.75 g) was added dropwise from a dropping funnel over a period of 30 minutes with the reactor temperature maintained. At 10 ° C. during the addition, the dropping funnel was cleaned and dried.Tpfluoromethanesulfonic acid anhydride (2408 g) was added at a low temperature. and maintained a reaction temperature of between 10 ° C to 20 ° C. By complete addition, the reaction mixture was stirred at 15 ° C for 3 hours and then washed with two 500 ml portions of water followed by a 250 ml portion. ml of saturated sodium bicarbonate solution The CH2Cl2 was evaporated and the residue was dissolved in acetonitop to form a 50 percent solution This solution of the crude reaction mixture was extracted 5 times with 250 ml portions of hexane The extracts were combined and the solvent was reduced to crystallize the product, which was then filtered and diluted as a white crystalline powder (165 grams, 986 percent pure, 65 percent yield) with a melting point of 46 ° C to 47 ° C GC / MS, m / e ( %) 63 (41 0), 69 (59 1), 142 (6 8), 144 (55) 198 (6 3) 356 (104), 357 (76), 490 (11 0), 491 (355), 492 (100), 493 (466), 494 (7 1), 621 (1 5), 623 (2 7), 625 (1 5) FTIR (cm-1) 823 (0 12), 878 (075), 1036 (0 12), 1137 (0 68), 1162 (072), 1212 (1 00), 1296 (0 17), 1426 (081), 1474 (082), 583 (021) Ether of 3.3'.4.4 ' -Tetra (fen? Let? N? L) d? Fen? Lo A solution of 50 g of ether 3, 3'-d? Bromo-4,4'-b? S (tr? Fluormetan sulfonate) d? Fen? The (0 08 molar) between (180 ml) and DMF (180) in a one-liter round five-necked flask was deoxygenated with nitrogen for 30 minutes. To the deoxygenated solution was added 30 g of dichloro b? s. (tr? phen? lfosf? na) palladium (II) The temperature of the flask was raised to 75 ° C. A dropping funnel was placed in the flask and 49 g of phenylacetylene, deoxygenated for 15 minutes, was added at a rate to maintain a reaction temperature of 80 ° C to 95 ° C. When the addition of phenylacetylene was complete, the reaction mixture was maintained at a temperature of 90 ° C to 91 ° C for two hours with a continuous nitrogen purge. Then an additional 2.5 g of phenylacetylene was added to the reaction mixture and the mixture was heated from 90 ° C to 91 ° C for an additional 45 minutes. After cooling the mixture to room temperature, 350 ml of CH 2 Cl 2 was added and the mixture was washed with three 500 ml portions of 10 percent HCl solution. For a 500 ml wash with deionized water. The organic solution was evaporated to remove the solvent and the residue was purified using liquid chromatography with silica gel as a stationary phase and CCI as a mobile phase. A total of 45g (0.0789 moles) of monomer was isolated by this method with a 98% redemption. The analysis of this monomer by CI / MS indicated a purity of more than 98.5 percent. This monomer had a p.f. from 107 ° C to 108 ° C and the following characteristics: 1C NMR (100 MHz, CDC13): d 6.96-6.98 (2H, dd), 7.17 (2H, d), 7.30 (12H, m), 7.51-7.53 ( 8H, m). 13 C NMR (100 MHz, CDC13): d 87.63 (1C, -CC-), 87.74 (1C, -CC-), 93.23 (1C, -CC-), 94.41 (1C, -CC-) 119.23 (1C), 121.44 (1C), 121.77 (1C), 122.90 (1C), 123.28 (1C), 127.59 (1C), 128.37 (4C), 128.64 (1C), 131.57 (2C), 131.72 (2C), 133.50 (1C), 156.11 (1C).

FTRI (cm-1): 689 (0.77), 784 (0.59), 824 (0.39), 878 (0.34), 913 (0.27), 970 (0.42), 1025 (0.25), 1071 (0.28), 1084 (0.28) ), 1139 (0.33), 1214 (1.00), 1252 (0.52), 1323 (0.47), 1378 (0.17), 1415 (0.41), 1443 (0.38), 1471 (0.64), 1495 (0.82), 1553 (0.40) ), 1588 (0.65), 2210 (0.16), 3058 (0.27). Spec. of mass m / e (%): 263 (10.1), 265 (10.7), 274 (6.9), 275 (5.65), 276 (2.33), 463 (5.71), 464 (4.33), 539 (4.17), 570 (100), 571 (36.3), 572 (9.51). Example 4 9.9-Bis ((3,3 ', 4,4'-tetraphenylethynylphenyl) fluorene 9,9-Bis ((3,3'-dibromo-4,4'-dihydroxy) phenyl) fluorene To a 5-ounce Morton flask. necks of 2 I, essentially the same as that used in Example 3, were added 700 ml of CH2CI2, 50 ml of HOAc, 104 g of 9,9-bis (4-hydroxyphenyl) fluorene and 1.0 g of iron powder This mixture was stirred and cooled to 10 ° C under a nitrogen atmosphere.While the reaction mixture was vigorously stirred, 99 g of liquid bromine was added to the reaction mixture from the dropping funnel over a period of 1 hour. The reaction temperature was maintained between 8 ° C and 10 ° C during the addition of bromine.After completing the addition, the reaction temperature rises to 22 ° C and is maintained at that temperature with stirring for 18 hours. The resulting mixture is then washed with 1.5 l of water followed by 500 ml of saturated sodium bicarbonate solution.The remaining organic solution is evaporated to remove the solvent e) The solid residue was dissolved in hot hexane which has been saturated with acetonitrile. Upon cooling, a second liquid phase is separated to the bottom of the container. This second phase contained most of the colored impurities from this reaction and was removed as a means to purify the product. The solvent was removed under vacuum to give 115 g of a white crystalline solid product corresponding to a 77 percent yield. This product has a p.f. from 119 ° C to 120 ° C and the following characteristics: GC / MS, m / e (%): 63 (16.9), 226 (17.8), 335 (13.7), 427 (9.6), 428 (27.8), 429 (22.3), 430 (15.4), 507 (6.6), 508 (33.3), 509 (100), 510 (36.8), 511 (8.2). FTIR (cm-1): 743 (0.36), 782 (0.30), 844 (0.21), 932 (0.78), 1017 (0.20), 1096 (0.79), 1129 (0.76), 1167 (0.77), 1199 (1.00) ), 1272 (0.11), 1326 (0.52), 1447 (0.17), 1503 (0.49), 3065 (0.06). 9,9-Bis ((3,3'-dibromo-4-4-di (trifluoromethanesulfonate)) phenylfluorene In a 5-necked Morton 5-necked flask. As used above, 500 ml of CH 2 Cl 2 and 111.75 g of 9 9-bis ((3,3'-dibromo-4-4-dihydroxy) phenyl) fluorene The solution was cooled to 10 ° C. Triethylamine (97.75 g) was added, using the dropping funnel, over a period of 30 minutes while the reactor temperature was maintained at 10 ° C. Using a clean drip funnel, 250.8 g of trifluoromethanesulfonic acid anhydride was added at a rate that maintained a reaction temperature of 10 ° C to 20 ° C. addition of trifluoromethanesulfonic anhydride, the reaction mixture was stirred at 15 ° C for 3 hours The reaction solution was then washed with 500 ml portions of water followed by a 250 ml portion of saturated sodium bicarbonate solution. The CH2Cl2 was evaporated and the residue was dissolved in acetonitrile to form a 50 percent solution. The crude reaction mixture was extracted with 250 ml portions of hexane. The extracts were combined and the solvent was reduced to crystallize a white powder product. When it was filtered, it weighed 165 g and was 98.6 percent pure. This corresponds to a yield of 65 percent. The product has a p.f. from 46 ° C to 47 ° C and the following characteristics: FTIR (cm-1): 738 (0.39), 786 (0.16), 826 (0.15), 880 (0.50), 1037 (0.29), 1137 (0.68), 1214 (1.00), 1428 (0.74), 1479 (0.42), 1579 (0.10), 3039 (0.07), 3068 (0.09). CL / MS, m / e (%): 143 (13.2), 145 (9.8), 224 (12.5), 226 (64.4), 227 (21.0), 263 (23.5), 276 (12.0), 277 (7.9) , 287 (25.6), 288 (11.1), 289 (86.5), 290 (39.0), 291 (7.9), 317 (16.5), 318 (41.1), 334 (11.4), 345 (14.3), 346 (27.0), 347 (7.07), 369 (11.2), 397 (45.1), 398 (10.5), 399 (37.1), 400 (10.3), 424 (11.20), 425 (46.2), 426 (21.1) , 427 (50.1), 428 (10.6), 637 (43.8), 639 (100), 641 (40.4), 770 (25.8), 772 (52.8), 774 (26.0). 9.9-Bis (3,3'-4,4'-tetraphenylethynyl) phenyl) fluorene Fifty g of 9,9-Bis ((3,3'-dibromo-4,4'-di (trifluoromethanesulfonate)) phenyl) fluorene were placed in a 5-neck, 5-neck, round-bottomed flask equipped with a mechanical stirrer, a dropping funnel, a gas dispersion tube and a thermocouple. To the flask was added 150 g of triethylamine and 180 ml of N, N-dimethylformamide. This mixture was stirred and heated to 45 ° C while introducing nitrogen gas under the level of liquids in the flask through the tube. of dispersion of gases To the deoxygenated solution was added 30 g of dichloro bis (triphenylphosphine) palladium (II) The reaction mixture was heated to 70 ° C and 330 g of deoxygenated phenylacetylene were added to the flask for 30 minutes This addition of phenylacetylene went to a controlled regime to maintain the temperature of the reaction mixture at 90 ° C After the addition was complete, the reaction mixture was maintained at 90 ° C for 2 hours and 45 minutes at which time an additional 4 7 g was added. phenylacetylene as a single tile and the reaction was maintained at 90 ° C for an additional 45 minutes. The solution was then cooled and diluted with 400 ml of CH 2 Cl 2 and washed with 2 l of a 10 percent HCl solution after evaporation. n, the residue was dissolved in CCI and purified by column chromatography on silica gel using CCI4 CH2Cl2 as an eluent to provide 32.5 g (696 percent yield) of monomer with 985 percent purity having the characteristics 1H NMR (400 MHz, CDCl 3) d 775-781 (4H, dd) 7 52-754 (12H, m) 738-744 (12H, m), 727-730 (12H, m), 7 13-7 16 (4H, dd) 13 C NMR (100 MHz, CDCl 3) d 6490 (1C, spiro), 88 08 (1VC, -CC-), 8836 (1C, -CC), 93 72 (1C, -CC-), 9388 (1C, -CC-), 120.45, 12307, 12324, 124 57, 12589, 126 04, 12789, 128 04, 128 11, 12828 128 31, 128 37, 12842, 131 01, 131 60, 131 65, 131 87, 140 16, 14553, 14952 FTIR (cm-1): 662 (0.12), 688 (0.63), 737 (0.63), 754 (1.00), 823 (0.24), 913 (0.09), 1027 (0.11), 1067 ( 0.11) 1090 (0.09), 1140 (9.07), 1160 (0.08), 1213 (0.07), 1278 (0.07), 1401 (0.13), 1443 (0.35), 1495 (0.61), 1593 (0.22), 2210 (0.07) ), 3031 (0.14), 3055 (0.16). CL / MS, m / e (%): 305 (8.2), 311 (8.3), 312 (9.7), 318 (8.3), 319 (12.1), 363 (16.3), 437 (13.4), 439 (11.1) , 441 (20.7), 638 (8.2), 639 (14.8), 640 (12.9), 641 (13.6), 718 (100), 719 (22.4), 720 (12.5). Example 5 Oligomerization solution, cast by rotation and duration of thin films of 2,2-bis (3,4-di (phenylethynyl) phenyl) -1,1, 1,3,3,3-hexafluoropropane on silicone substrates To a 25 ml Schlenk tube equipped with nitrogen purge and magnetic stirrer were added 1.0 g (1.42 millimoles) of 2,2-bis (3,4-di (phenylethynyl) phenyl) -1, 1, 1, 3,3,3-hexafluoropropane made in Example 1 and 1.0 g of 1, 3,5-tri-isopropylbenzene. The flask was thoroughly purged with dry nitrogen and heated in an oil bath at 210 ° C for 12 hours while continuously stirring the solution. The resulting oligomeric product exhibited a relative PCB Mp of 1000, an Mp / Mn of 1.5 and Mz of 2300 (against a normal of polystyrene in THF) and remained completely soluble at 50 weight percent in tri-isopropylbenzene at room temperature. The experiment was repeated using the same monomer, but using the solvents and conditions set forth in Table I to give oligomeric products having the properties shown in the same Table I.

Table I Each of the resulting oligomeric products was spin-tumbled from the solution by pouring the solution directly onto a silicone substrate and rotating at a rate of 700 to 1000 rpm sufficient to give a continuous coating of 1 μm or at 400 rpm to give a continuous coating of 4 μm after curing. Coated silicone substrates are cured by heating from 30 ° C to 125 ° C at 30 ° C / minute and maintaining isothermally for 60 minutes, then heating at 30 ° C / minute at 250 ° C and maintaining isothermally for 60 minutes and finally heating to 30 ° C / min at 350 ° C and maintaining isothermally for 60 minutes. The coated substrates were allowed to cool slowly to room temperature for 14 hours. To varying degrees, each of the resulting coatings adhered to the silica and remained uniform without delamination or cracking. Example 6 Bulk Oligomerization of bis (ortho-diacetylene) monomers Each of the bis (ortho-diacetylene) monomers prepared in Examples 1-4 was purified to more than 99 percent purity by LC by flash chromatography on gel of silica using CCI / cyclohexane (70/30). The monomer was dried overnight at 80 ° C to 100 ° C under vacuum and stored under nitrogen at room temperature. To a clean, dry, nitrogen-filled 25 ml Schlenck flask equipped with a syringe, pass-through stopcock, nitrogen inlet side arm and mechanical stirrer was added 1.5 g of purified bis (ortho-diacetylene) monomer prepared in Example 1. The flask was placed in a stirred oil bath which was preheated to 210 ° C and a nitrogen purge decreased to a slightly positive pressure. Within 60 seconds, the light yellow transparent melt turned dark yellow, then orange and eventually dark red to essentially black within 1 hour. During the polymerization, the ability of the oligomeric product to form a coating was determined using a mesitylene solution of 30 percent of the oligomer and applied the solution on a silicon wafer or glass plate and excess solvent removed by centrifugal force to form a movie. The experiment was repeated under the variety of conditions described in Table II using the different monomers and reaction times and temperatures specified in the table. The molecular weights resulting from each of these tests were reported in Table II. Table II After the desired molecular weight was obtained, each of the mixtures set forth in Table II was allowed to cool to room temperature under nitrogen and then dissolved to form a filtered organic liquid solution, spin-coated on a silicone substrate. a thickness of 1 μl and finally thermally cured under nitrogen giving films free of defects or substantially free of defects Example 7 Formulation v Application of Oligomeopic Solutions Each of the bimetallic monomers (ortho-acetylene) prepared in Examples 1 -4 were purified using the techniques of Example 6 A sample of each purified monomer was oligomep- ated at the molecular weights taught in Table III using the techniques employed in Example 5 or 6 The oligomeric products were then formed as a coating on a wafer of silicone by applying a solution of the oligomer (the solvent and concentration being recorded in Table III) in a silicon wafer and removing excess solvent by centrifugal force, followed by exposure to an elevated temperature of 100 ° C to form a film. The resulting coating is then cured. This procedure was repeated using the different monomers and solvent systems specified in Table III Table III Each of the oligomeric materials was easily applied as a coating of the solution and when cured it adhered to the silicone substrate as a defect-free or substantially defect-free film. Example 8 Polymerization of 2,2-bis (3'-4'-bis (phenyletininphenyl) -1.1.1.3.3.-hexafluoropropane (1) A sample of 28 g of 2, 2-bis (3'-4'-bis (phenylethynyl) phenyl) -1,1,1,3,3-hexafluoropropane was heated on an aluminum tray under an inert atmosphere at a temperature of 200 ° C to 250 ° C for 8 hours giving a black film, glazed, hard in an essentially quantitative yield. The film was intractable and insoluble in common organic solvents and had the following properties of PTIR: PTIR (transmission diamond cell) cm-1: 3059, 3026 (ArH), 1598 (Ar), 1493 (Ar), 1443 (w), 1253 (st, CF), 1206 (st, CF), 1135 (w, SH), 965 (w), 755 (w) cm -1. A differential scanning calorimetry (DSC) analysis at 10 ° C / minute) of the pure monomer (6.73 mg) gave a peak melting endotherm at 163 ° C (DH = -62 J / g), an onset of polymerization exotherm at 200 ° C, peak exotherm at 314 ° C and end of exotherm at 380 ° C, respectively with an? H of 583 Joules per gram. Subsequent DSC scans resulted in undetectable thermal transitions. In situ polymerization and evaluation of thermal stability by TGA were carried out by heating the pure monomer from room temperature to 200 ° C to 200 ° C / minutes, equilibrating at 200 ° C for 5 to 10 minutes and then heating to 20 ° C. / minutes at 300 ° C, followed by an isothermal soaking at 300 ° C for 3 hours. During this healing program, there was no detectable weight loss. The thermal stability was then calculated by increasing the temperature from 300 ° C to 450 ° C at 10 ° C / min and maintaining isothermally at 450 ° C for 10 hours. The thermal stability was calculated by measuring the weight loss regime for at least 9 hours which gave a weight loss of 0.60 percent per hour. The polymer samples were then heated at 900 ° C to 10 ° C / min and held for 4 hours to evaluate the ash yield calculated by the weight loss after baking at 450 ° C for 10 hours until the baking was completed of 4 hours at 900 ° C. Example 9 Thermal polymerization of bis (ortho-diacetylepo) monomers and thermal stability of the resulting polymers The monomers of Examples 1-4 were thermally polymerized in a DSC tray according to the procedure set forth in Example 8. The results of each of these DSC analyzes appear in Table VI: Table VI The resulting polymers demonstrated the following thermal stabilities measured by TGA according to the method described in Example 8. The results are tabulated in Table V. Table V The thermal degradation regime was measured by the loss of weight or the percentage weight loss per hour at 450 ° C; each of the polymers exhibiting much better thermal stability, with the monomer of Example 2 being the most superior. The yield of organic ash was a measure of the performance of the polymer at ultra high temperature (900 ° C), the percentages being higher.

Claims

CLAIMS 1 A compound having the structure (RC = C) -pAr-L ArfC = CR) m +] q where each Ar is an aromatic group or inertly substituted aromatic group, each R is independently hydrogen, an alkyl group, aplo or alkyl or inertly substituted aplo, L is a covalent bond or a group joining an Ar or at least one other Ar, n and m are integers of at least 2, and q is an integer of at least 1 2 The compound of the claim 1, wherein at least two of the ethynyl groups in one of the aromatic rings are ortho to one another. The compound of claim 2, wherein each Ar independently has from 6 to 50 carbon atoms. claim 3, wherein each R is independently hydrogen or an alkyl, aplo or inertly substituted alkyl or apho group having from 1 to 20 carbon atoms The compound of claim 3, wherein each Ar is independently a phenyl, phenylene , naft ilo, naphthalene, biphenylene biphenylene, diphenyl, diphenylene, 9,9-d? fluorene, dif-ether in 11-diphenyl sulfide, anthracene, phenanthrene, anthraquinone-tp-phenyl-phosphine, tp-phenyl-phosphine oxide group or an inertly substituted phenyl , phenylene, naphthyl, naphthalene, biphenyl, biphenylene diphenyl diphenylene, 9,9-d? phen? lluorene, diphenylether, diphenyl sulfide, anthracene, phenanthrene, anthraquinone, triphenyl phosphine, or triphenylphosphine oxide group. The compound of claim 3, wherein each R is independently phenyl or phenylene, naphthyl or naphthalene, biphenyl or biphenylene, diphenyl or diphenylene, 9,9-diphenyl fluorene, diphenyl ether, diphenyl sulfide, anthracene, phenanthrene, anthraquinone, triphenylphosphine or triphenyl phosphine oxide groups. The compound of claim 3, wherein at least one Ar is an aromatic group substituted with an alkyl, halogen, perfluorocarbon or combination thereof and at least one R group is an alkyl or aryl group substituted with an aryl , halogen, perfluorocarbon or a combination thereof. 8. The compound of claim 3, wherein at least one Ar is an aromatic group substituted with fluorine, chlorine or bromine or at least one group R is substituted with fluorine, chlorine or bromine. 9. The compound of claim 2, wherein L is a covalent bond, an alkyl, aryl or aralkyl group or alkyl, aryl or aralkyl inertly substituted, sulfur, phosphorus or oxygen. The compound of claim 9, wherein L is a covalent bond, 2,2-isopropylidene, sulfur, oxygen, phosphorus, or 1,1,1,3,3,3-hexafluoro-2,2-isopropylidene. The compound of claim 9, wherein L is an unsubstituted or inertly substituted alkyl group of 1 to 20 carbon atoms. 12. The compound of claim 11, wherein L has from 3 to 6 carbon atoms. The compound of claim 11, wherein L is selected from bisphenyl, phenyl or naphthyl. The compound of claim 2, wherein each R is independently hydrogen or is unsubstituted or inertly substituted phenyl. 15. The compound of claim 14, wherein each R is independently phenyl substituted with one or more fluorine atoms or fluoroalkyl group of 1 to 6 carbon atoms. 16. A method for polymerizing a compound of claim 1, which comprises exposing the compound at a temperature sufficient to increase the molecular weight. 17. The method of claim 16, wherein the temperature is at least 140 ° C. 18. The method of claim 17, wherein the temperature is 150 ° to 400 ° C. 19. The process of claim 16, wherein at least a portion of the polymerization is carried out in a solvent to form an oligomer of the eitinyl aromatic and then exposing the oligomeric solution to a temperature that causes the solvent to Evaporate and the oligomer polymerizes more. The method of claim 19, wherein the reaction to form the oligomer is conducted at a temperature of 150 ° C to 250 ° C and the additional chain extension and / or interlacing is carried out at a temperature higher than 200. ° C to 400 ° C. 21. A polymer that has the units: R R \ / fAr '] - I (II) tAr'} / \ R R where Ar 'is the residual of the product reaction of the portions of (C = C) -nAr or ArfC = C) m; each R is independently hydrogen, an alkyl, aplo or alkyl or aryl inertly substituted group; each L is a covalent bond or a group joining an Ar to at least one other Ar '; n and m are integers of at least 2, and Ar is an aromatic group or inertly substituted aromatic group. 22. A polymer that has the units: R R \ / fAr'3-I (II) f-Ar '} / \ R R wherein each R is independently hydrogen an alkyl, aryl or alkyl or aryl inertly substituted group, the Ar -L-Ar each time it is presented is. The polymer of claim 22, wherein the polymer is an oligomer having a number average molecular weight of less than 100,000 and a weight average molecular weight at a number average molecular weight of from 1 to 100. A copolymer having units of RR \ / Ar RI \ / (II) fAr '} fAr '} / \ R R where Ar 'is the residual of the product reaction of the portions of (C = C) -nAr or Ar C = C) m, an aromatic ring and the ethynyl groups attached to the aromatic ring, each R is independently hydrogen, a alkyl, aplo or alkyl or substituted alkyl group; each L is a covalent bond or a group joining an Ar 'to at least one other Ar'; n and m are integers of at least 2; and Ar is an aromatic group or inertly substituted aromatic group. The copolymer of claim 24, wherein the polymer is an oligomer having a number average molecular weight of less than 100,000 and a weight average molecular weight at number average molecular weight of 1 to 100. 26. A copolymer which has the units: RR \ / t-Ar'3- RR \ / (ll) fAr 'fAr'j- / \ RR wherein each R is independently hydrogen, an alkyl, aryl, or alkyl or aryl group inertly substituted; and Ar'-L-Ar ', each time it is presented is: 27. A method for preparing the compounds of claim 1, which comprises: (a) selectively halogenating a polyphenol to selectively halogenate each phenolic ring with a halogen in one of the two available ortho positions respectively; (b) converting the phenolic -OH to the leaving group which reacts with terminal ethinyl groups, (c) reacting the product of step (b) with an ethynyl-containing compound such as phenylacetylene or an inertly substituted phenylacetyle, or a ethynyl such as a tri-methyl silyl acetylene in the presence of an aryl ethynylation catalyst and an acid acceptor to replace the halogen and trifluoromethyl sulfonate with an ethynyl-containing group. The method of claim 27, wherein the product (b) is a poly (2-halophenyl trifluoromethane sulfonate) and the ethynyl-containing compound reacts with the poly (2-halophenyl trifluoromethane sulfonate). 29. The method of claim 28, wherein the ethynyl-containing compound is R-CfC-X wherein X is hydrogen or a copper salt. 30. The method of claim 29, wherein the ethynyl-containing compound is phenylacetylene, pentafluorophenylacetylene, trifluoromethylphenylacetylene, 4-fluorophenylacetylene and combinations thereof. 31. The method of claim 30, wherein the acid acceptor is trimethylamine, triethylamine, tri-isopropylamine, di-isopropylamine, piperidine, pyridine, potassium carbonate and mixtures thereof. 32. The method of claim 31, wherein the aryl ethynylation catalyst is a palladium salt, a palladium complex. [0] with solubilizing ligands such as triphenylphosphine, copper metal or a compound containing palladium or copper. 33. The method of claim 32, wherein the palladium compound also includes a phosphine and copper. 34. A substrate coated with the polymer of I claim 21. 35. A substrate coated with the polymer of claim 21, wherein the coated substrate is a computer microcircuit.