TWI247757B - Polyfunctional compounds and oligomer, uncured polymer or cured polymer - Google Patents

Abstract

An oligomer, uncured polymer or cured polymer comprising the reaction product of one or more polyfunctional compounds containing two or more cyclopentadienone groups and at least one polyfunctional compound containing two or more aromatic acetylene groups wherein at least some of the polyfunctional compounds contain three or more reactive groups. Such oligomers and uncured polymers may be cured to form cured polymers which are useful as dielectrics in the microelectronics industry, especially for dielectrics in integrated circuits.

Description

Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs 1247757 A7 V. INSTRUCTIONS (1) The present invention relates to polyphenylene polymer and polymers and methods for their preparation and use. These polymeric polymers can be used as dielectric resins in microelectronic fabrication. This application is a continuation-in-part of Serial No. 711,838, filed on Sep. 10, 1996, which is incorporated herein by reference. The polymer dielectric can serve as an insulating layer between various circuits and layers in the circuit of a microelectronic device such as an integrated circuit, a multi-chip module, and a laminated circuit board. The microelectronics manufacturing industry is now shifting to a smaller geometry within its device, making it less powerful and faster. As the conductor wires become thinner and more closely packed, the dielectric requirements between the conductors become more stringent. While polymeric dielectrics generally provide a lower dielectric constant than inorganic dielectrics such as Dioxide Dreams, they often present the challenge of handling polymer properties during preparation. For example, to replace the ruthenium dioxide as a dielectric in an integrated circuit, the dielectric needs to be resistant to the processing temperatures during the metallization and annealing steps of the process. Preferably, the dielectric # material needs to have a glass transition temperature greater than the processing temperature. The dielectric also needs to retain its desired properties under the conditions of use of the device. For example, the dielectric should not absorb water, which can cause an increase in dielectric constant and potential corrosion of the metal conductor. For some complexes, when coated with conventional coating techniques such as spin coating, the polymer is preferably planarized and gap filled with the surface of the file. Today, polyimine resins are a class of materials used as thin film dielectrics in the electronics industry. However, polyimine resins absorb water and hydrolyze, which can cause circuit corrosion. The metal ions can be transferred into the dielectric polyimide layer, which requires a barrier layer between the metal wire and the polyimide film. Polyimine will show poor paper size applicable to China National Standard (CNS) A4 specification (210X297 public) -4. Pack - (Please read the back note to write this page) Order 1247757 Α7 Β7 V. Invention Description (2) The planarization and gap filling properties. Non-fluorinated polyimines exhibit undesirably high dielectric constants.

Kumar and Neenan, Macromolecules (Macromolecules, 1995, 28), pages 124-130, disclose several polyphenylenes produced from dicyclopentadienone and diacetylene. It teaches that polyphenylene has the potential to be a photodefinable organic dielectric. Wrasidlo舆Augl, J. Polym. Sci., Part B (1969), 2(7), 519~523, reveals 1,4-bis(styryl)benzene and 3,3'-(l,4- Copolymer of phenylene)-bis(2,4,5-triphenylpentadienone). It reports that soluble yellow infusible polymers can be obtained.

The materials described by Kumar and Wrasidlo are soluble, but may not be suitable for some applications (such as spin coating to fill the interstitial) because the material is polymerized to deplete the cyclopentadienone moiety, which provides relatively high The molecular weight. This molecular weight may be too high to be applied by spin coating on the surface of the substrate containing the gap filled by the dielectric. Based on the reported glass transition temperature, these materials may not be able to withstand the processing of the inner dielectric in the integrated circuit. In U.S. Patent Nos. 5,334,668; 5,236,686; 5,169,929 and 5,338,823, Tour describes a number of processes for preparing crosslinkable polyphenylene compositions for the preparation of glassy carbon. Polyphenylene is prepared by polymerizing 1-bromo-4-lithium benzene to form a brominated polyphenylene and then coupling a substituted phenylacetylene such as phenylethylidene acetylene to residual bromine. Polyphenylene has about 200 before crosslinking. (: melting point. It is expected to provide polymer dielectrics to the microelectronics manufacturing industry, which provides reliable low dielectric constant, high thermal stability and high glass transition temperature, and this paper scale is applicable to China National Standard (CNS) aI specifications. (210χ297公ϋ "5 - (Please read the note on the back first 丨II installation - write this page) Printed by the Central Bureau of Standards and Staff of the Ministry of Economic Affairs, the consumer cooperatives printed 1247757 A7 B7 Ministry of Economic Affairs Central Bureau of Standards Bureau of Peking Consumer Cooperatives Printed 5 DESCRIPTION OF THE INVENTION (3) Preferably, it can be coated by spin coating to planarize the surface of the pattern and fill the gap. In a first aspect, the present invention is a polymer, an uncured polymer or a cured polymer, a reaction product comprising one or more polyfunctional compounds containing two or more cyclopentadienyl groups and at least one polyfunctional compound containing two or more aromatic ethynyl groups, wherein at least some of the polyfunctional compounds contain three or A plurality of reactive bases. The reactive groups used herein are defined as cyclopentadienone or ethynyl. The polymer used herein defines two or more monomeric forms of the invention. The reaction product, which is filled with time (ie, filled with a rectangular groove of 1 micron deep and 1/2 micron wide), does not leave a void when cured. The uncured polymer used herein defines the cost. The reaction product of the inventive monomer, which is no longer filled, but contains a large amount of unreacted cyclopentadienone or acetylene functional groups. The cured product used herein defines the reaction product of the inventive monomer, which does not contain a large amount of Reacting a cyclopentadienone or acetylene functional group. A large amount of unreacted cyclopentadienone or acetylene functional group requires that the moiety be reactive to further promote the polymerization. One feature of the present invention is that it contains one or more a reaction product of a polyfunctional compound of two or more cyclopentadienone groups with at least one polyfunctional compound containing two or more aromatic ethynyl groups, wherein at least some of the polyfunctional compounds contain three or more reactive groups. One of the advantages of the product is that it can fill the gap and planarize the surface of the file, and has high thermal stability, high glass transition temperature and low dielectric constant when cured. Aspect), the present invention is a merging polymer, uncured paper scale applicable to China National Standard (CNS) Α 4 specifications (210X297 public) 6 - installed - (please read the back note on this page), -ιτ- 1247757 A7 B7 V. INSTRUCTION DESCRIPTION (4) A polymer or cured polymer containing one or more polyfunctional compounds containing two or more cyclopentadienone groups and one or more containing two or more aromatic ethynyl groups a reaction product of a polyfunctional compound, wherein at least some of the polyfunctional compounds containing an aromatic ethynyl group contain three or more ethynyl groups. The second aspect of the invention is characterized in that it contains at least one or more containing two or more a reaction product of a polyfunctional compound of cyclopentadienone and at least one polyfunctional compound containing two or more aromatic ethynyl groups, wherein at least some of the polyfunctional compounds containing an aromatic ethynyl group contain three or more More ethynyl groups. One of the products of this reaction is characterized by gap filling and planarization of the surface of the pattern, and has high thermal stability, high glass transition temperature and low dielectric constant upon curing. The high thermal stability, high glass transition temperature, low dielectric constant, and ability to gap fill and planarize the surface of the crucible make the compositions of the present invention suitable as polymeric dielectrics in microelectronic fabrication. In particular, the combination of a low dielectric constant, a high thermal stability, and a high glass transition temperature allows the use of the composition of the present invention as an inner dielectric in an integrated circuit. Preferably, the polymer and the polymer of the present invention and the corresponding starting monomers are: The Central Standards Bureau of the Ministry of Economic Affairs, the Consumers' Cooperative, printed by I, the following polymer and polymer: [A]w [B]2 [EG]v where A has the following structure: This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1247757 A7 B7 V. Invention description (5)

And B has the following structure:

Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs where EG is the end group with one or more of the following structures:

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1247757

5. Description of the invention (6 wherein R1 and R2 are each an aromatic moiety which is unsubstituted or substituted by inertia' and Ar1, Ar2 and Ar3 are each an unsubstituted aromatic moiety or an inertly substituted aromatic moiety a family moiety, Μ is a bond, and y is an integer of 3 or greater, p is the number of unreacted ethynyl groups per unit known, and Γ is known to be less than the number of reactive ethynyl groups per unit' p + r==y-1, Z is an integer from 1 to 1 〇(9); W is an integer from 〇 to 1000, and V is an integer of 2 or greater. The oligomer and polymer can be made by making dicyclopentane It is prepared by reacting a dienone, an aromatic acetylene having three or more acetylene moieties, and a polyfunctional compound containing a diarylethyl fast moiety. This reaction can be carried out by a compound of the following chemical formula: Indicative, (a) Dicyclopentadienone of the formula:

(b) Polyfunctional acetylene of the formula: [r2^^ (c) and, optionally, the diacetylene of the following chemical formula:

Ar2 r2 wherein R1, R2, Ar1, Ar2, Ar3 and y are as defined above. The definition of the aromatic moiety includes a phenyl group, a polyaromatic group, and a fused aromatic moiety. By inert substitution is meant that the substituent is substantially polymerized with cyclopentadienone and acetylene.

Jr- ------------·装.丨丨ί — (Please read the notes on the back and fill out this page) Order-丨——·------ Gift! Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperatives, printing -

1247757 A7 B7 V. INSTRUCTIONS (7) The reaction is inert and does not readily react with environmental species such as water under the conditions of using a cured polymer in a microelectronic device. The substituent includes, for example, F, cn, Br, -CF3, ??0: ?3, -OCF3, -O-Ph and an alkyl group of 1 to 8 carbon atoms, and a cycloalkyl group of 3 to 8 carbon atoms. For example, an aromatic part that can be unsubstituted or inertly substituted includes: ^〇〇r alone (please read the back note on this page first) - binding

This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 10 1247757 A7 B7 V. Description of invention (8)

Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs, where Z can be: -0, -S-, Orthotriene, -CF:, -CHj-, -0-, -CF:-, perfluoroalkyl, all Fluoroalkoxy,

CH3 Ph CH3 〒H3 ------ or --CF3 · CH3 Ph Ph3 Each of R3 is -H, -CH3, -CH2CH3, -(CH2)2CH3 or Ph. Ph is a phenyl group. This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 11 A7 B7 1247757 V. Description of invention (9) II. Polyphenylene oligomers and polymers of the following formula

U to 50 ‘more preferably 丨 to 1〇. The oligomer and the polymer diene are prepared by reacting with diacetylene of the following formula: , r1 + R2 = -Ar2 -s- R2 4 The paper is used by the Guanji Group (CNS) A4 Na (2^^^ -

ΎΖ 1247757 A7 B7 V. INSTRUCTION DESCRIPTION (10) wherein R1, R2, Ar1 and Ar2 are as defined above. III. Polyphenylene condensates and polymers represented by the following chemical formula: 0

(Please read the note on the back to write this page) Pack. Among them, Ar4 is an aromatic part or an inertly substituted aromatic part, R1, R2 and X are as defined above, and can be functionalized by cyclopentadienone. The base is prepared by reacting an acetylene functional group of a polyfunctional compound of the following formula,

I - Order Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs Ο

Wherein R1, R2 and Ar4 are as defined above. IV. Polyphenylene propylene polymer and polymer represented by the following chemical formula: 13 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1247757 A7 B7

Please read the precautions on the back! Write this page) where R1, R2, Ar4 and x are as defined above by using a cyclopentadienone functional group and an acetylene functional group of a polyfunctional compound of the formula Prepared by reaction, 〇

R2 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Printed R1, R2 and Ar4 are as previously defined. Polyfunctional compounds containing two or more aromatic cyclopentadienone moieties can be condensed by diphenylethylenedione with benzyl ketone using conventional methods. This paper scale applies to Chinese National Standard (CNS) A4 specifications. (21〇><297 public) -14 · 1247757 A7 B7 V. Preparation of the invention (12). Exemplary methods are disclosed in Kumar* et al., Macromolecules, 1995, this, 124-130; Ogliaruso et al., J. 〇rg. Chem., 1965, La, 3354; Ogliaruso et al., J. Org. Chem., 1963, 2725; and U.S. Patent No. 4,400,540. Polyfunctional compounds containing two or more aromatic acetylene moieties can be prepared by conventional methods. The aromatic compound can be self-catalyzed and then reacted with an appropriately substituted acetylene in the presence of an aryl acetylenication catalyst to replace the dentate with a substituted acetylene compound. Once the polyfunctional compound monomer is made, it is preferably purified. In particular, metal and ionic species are removed for use in the preparation of organic polymeric dielectrics. For example, a polyfunctional compound containing an aromatic ethynyl group can be contacted with a water wash, an aliphatic hydrocarbon solvent, then dissolved in an aromatic solvent and filtered through a purified vermiculite gel. This treatment removes residual acetylenated catalyst. Additional recrystallization can help remove unwanted impurities. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, although it is not intended to be limited by theory, it is believed that the polyphenylene propylene polymer and the polymer are heated in a mixture of cyclopentadienone and acetylene in solution via cyclopentadiene. The ketone is formed by reacting with Diels Alder of the ethynyl group. These oligomers may contain cyclopentadienone and/or acetylene end groups and/or pendant groups. When the solution or the article coated with the solution is further heated, additional chain extension results in an increase in molecular weight via the Reels Alder reaction of the residual ketone ketone end group with the residual ethynyl group. Depending on the temperature used, the reaction of ethynyl groups with each other also occurs. The oligomers and polymers are shown in a structure having cyclopentadienone and/or acetylene end groups and/or pendant groups. Generally, the end-based system is based on the Chinese National Standard (CNS) A4 specification (21〇X 297 public) according to the standard of the paper used for the reaction. 1247757 A7 B7 (13) ίι Λ Λ - ^ ene __Diels Alder reactive acetylene functional group relative concentration and 'stoichiometric excess of cyclopentadienone functional groups to produce more cyclopentane quinone end groups, stoichiometric excess of Diels Alder reactivity The acetylene functional group produces a greater proportion of acetylene end groups. A preferred embodiment of the invention is characterized in that the polymerization is stopped before all of the cyclopentadienone moiety & Then, the polymer can be applied to the surface before the polymerization reaction is carried out to partially react the remaining cyclopentadienyl oxime. In this cold polymerization state, when applied to the surface of the pattern, the polymer can be planarized and filled with gaps. Preferably, at least 10% of the cyclopentadienone moiety is unreacted, and at least 20% of the cyclopentadienone moiety is unreacted. The percentage of unreacted cyclopentadienone moiety can be determined by Shenguang spectrum analysis. The cyclopentadienone component is highly chroma in the visible spectrum and has a distinct red or purple color which fades when the cyclopentadienyl moiety reacts. Planarization as used herein means that the features of the isolation can be planarized by 70% or more, preferably 80% or more, and most preferably 90% or more. The π fraction or degree of planarization is calculated by the following equation: Percentage of planarization = (l-ts/tm) X 100 When the polymer layer is applied to the isolated square line, the thickness is 1 micron and the average thickness is 1 Micron width and 1 micron high, and ts is the height of the polymer or polymer on the average height of the polymer or polymer, and tm is the height of this feature (1 micron). The use of this definition is exemplified by, for example, Proceedings of IEEE, Vol. 80, N〇·12, December 1992, p. 1948. Although not intended to be limited by theory, the preparation of polypyramid polymers is generally expressed as follows: 16 This paper scale applies to China National Standard (CNS) Α4 specifications (21〇Χ297 mm) 1247757 A7 B7 V. Invention Description (14)

R1 + R-~=-Ar2-ss-R2

Please read the note on the back first.

Pi write next to I book Printed by the Central Bureau of Standards and Staff of the Ministry of Economic Affairs

Wherein R1, R2, Ar1, Ar2 and X are as defined above. Furthermore, although the structure is not specifically shown, the carbonyl bridged species can be stored in the paper scale applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm). 17 The Central Bureau of Standards Bureau of the Ministry of Economic Affairs printed the 1246757 A7 B7. DESCRIPTION OF THE INVENTION (15) lies in the preparation of the polymer, depending on the particular monomer used and the reaction conditions. Upon further heating, the carbonyl bridge species are substantially completely converted to an aromatic ring system. When more than one acetylene containing monomer is used, the polymer and polymer formed are random, although the structure depicted may suggest that the block is formed. The Diels Alder reaction between the cyclopentadienone and the acetylene functional group occurs to form an attachment to the para or meta position on the phenyl ring. Any inert organic solvent which dissolves the monomer to an appropriate degree and is heated to a suitable polymerization temperature at atmospheric pressure, below atmospheric pressure or at atmospheric pressure can be used. Examples of suitable solvents include 1,3,5-trimethylbenzene, pyridine, triethylamine, N-methylpyrrolidone (NMP), methyl benzoate, ethyl benzoate, butyl benzoate , cyclopentene, cyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl pyrrolidone and ether or hexyloxy ether, such as diphenylmethyl ether, bis(2-methoxyethyl) ether, three (2· Methoxyethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, tripropylene glycol methyl ether , toluene, 1,3,5·trimethylbenzene, benzene, dipropylene glycol monomethyl ether acetate, diphenylbenzene, propylene carbonate, naphthalene, diphenyl ether, butyrolactone, dimercapto Acetamide, dimethyl decylamine and mixtures thereof. Preferred solvents are 1,3,5-trimethylbenzene, N-methylpyrrole ketone (NMP), r-butyrolactone, diphenyl ether and mixtures thereof. Alternatively, the monomer can be reacted in one or more elevated temperatures, and the resulting polymer solution can be cooled and formulated with one or more additional solvents to aid in processing. In another method, a single vessel can be reacted in one or more solvents at elevated temperatures to form a polymer, which can then be applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) by precipitating the paper. 18 (Please read the note on the back 3 write this page) - Install. • Order 1247757 A7 B7 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperative Printed 5, Invention Description (16) Removed in non-solvent or by other solvents The method is isolated to produce a substantially solvent free polymer. These isolated polymeric polymers can be redissolved in one or more different solvents and the resulting solution can be used in processing. The conditions most favorable for the polymerization are determined by various factors, including the particular reactants and solvent. Generally, the reaction is carried out under a non-oxidizing atmosphere such as a nitrogen or other inert gas blanket gas. The reaction can be carried out neatly (no solvent or other diluent). However, in order to ensure a homogeneous reaction mixture and a mild exothermic reaction at this temperature, it is generally desirable to use an inert organic solvent, such as the foregoing, and the time and temperature at which the ruthenium is most advantageously used in the reactants will depend on the particular monomer employed. In particular, its reactivity, the specific polymer or polymer and solvent it desires. The reaction of the general shaped polymer is carried out at a temperature of from 150 ° C to 250 ° C for from 60 minutes to 48 hours. At this point, the polymer can be separated from the reaction mixture or used to coat the surface. The additional chain extension (increase) can be carried out at a temperature of from TC to 475X: preferably from 200 ° C to 450 ° C for from 1 minute to 10 hours, more preferably from 1 minute to 1 hour. Uncured or The cured polymer can be used to coat the surface by casting from a solvent. Although this polymer may not be sufficiently gap filled or planarized, it can be used in a damascene process. The concentration of the monomers used in the reaction medium will depend on a variety of factors, including the particular monomer and all of the organic liquid and the polymer and polymer to be prepared. In general, the single system is a cyclopentadienone pair & The stoichiometric ratio of the monument is 1:1 to 1:3, preferably 1:1 to 1:2. The polymer or polymer can be directly cast in thin, coated with a coating or The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 19 (Please read the note on the back to write this page) -Installation 1247757 A7 X B7 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Print i, invention Description (17) Pour into a non-solvent to precipitate a polymer or polymer. Methanol, ethanol and other similar polar liquids are typical non-solvents which can be used to precipitate oligomers. Solid polymer or polymer can be dissolved and treated by a suitable solvent. When the version is obtained, it can be further processed using conventional compression molding techniques or melt spinning, casting or extrusion techniques, provided that the solid precursor requires a sufficiently low glass transition temperature. More generally, the polymer or The polymer is directly treated with an organic liquid reaction solution, and the advantages of the present invention are more fully understood in this example. Since the polymer or polymer is soluble in the organic liquid reaction medium, the organic solution of the polymer can be cast or The coating is applied and the solvent is evaporated. The molecular weight is increased (chain extension or promotion) and, in some instances, crosslinked to form the final polymer, which occurs after exposure to a sufficiently high temperature. As one or more insulating or dielectric layers in a single or multi-layer electronic connection construction for an integrated circuit, multi-wafer assembly or flat panel display. The polymer of the invention can be used as this Applied or combined with other organic polymers or inorganic dielectrics such as cerium oxide, cerium nitride or cerium oxynitride as the underlying dielectric. For example, the coating of the present invention and the coating of the polymer (for example, for electrically insulating coating for preparing a continuous structure on an electronic thin piece) by spin-casting a film-like polymer or polymer organic liquid solution or coating the substrate with the solution, and then The solvent is evaporated and the polymer or polymer is exposed to a temperature sufficient to cause the polymer or polymer to undergo a higher molecular weight, and in a preferred embodiment, a crosslinked polymer having a higher glass transition temperature. The polymer is especially useful as an integrated circuit (for example, applicable to Chinese National Standard (CNS) Α4 specifications (210Χ297 mm) on 矽 or this paper size 20 (please read the note on the back page first) - ν^ιτ 1247757 The low-dielectric constant insulating material in the successive structure of the A7 B7 5, invention description (18) gallium telluride producer) printed by the Central Standards Bureau of the Ministry of Economic Affairs. The integrated circuit typically has multiple layers of metal conductors separated by one or more insulating materials. The polymeric material of the present invention can serve as insulation between the individual metal conductors within the same layer and/or between the conductor layers of the bonded structure. The polymer of the present invention can also be used in combination with other materials such as SiO 2 *Si 3 N 4 in a miscellaneous bonded structure. For example, the present invention can be used to teach the preparation of the present invention as taught in U.S. Patent No. 5, 550, 405, U.S. Patent No. 5,591,677, and to the name of the s. A method of integrating a circuit device. The polymer and polymer of the present invention can be substituted for BCB or other resins disclosed in the disclosed methods. The polymer, uncured polymer or polymer of the present invention can be used as a dielectric in the above teaching method or the like to prepare an integrated circuit article comprising an activated substrate having a transistor and a patterned metal line ( Electrically connected structures of a small portion of which are separated by layers or regions of the present invention. The polymers of the present invention can also be used as planarization materials, such as germanium in semiconductors, to produce smaller (higher density) ) Circuit. To achieve the desired planarization, the polymer or polymer coating is applied from the solution to the flow by spin coating or spray coating to flatten any coarse chain surface on the surface of the substrate. Such methods are exemplified in "Microelectronic Applications of High Tech Polymers" by Bowden et al., American Chemical Society, 1987, pages 261-269. In the preparation of microelectronic devices, relatively thin no-missing film (usual thickness (please read the precautions on the back ^^ write. Ben buy) • Packing, book paper scale applicable to China National Standard (CNS) A4 specification (210X297 21 1247757 A7 B7 V. Invention (19) 0.01 to 20 μm, preferably 0.1 to 2 μm) can be deposited on the surface of a substrate, for example, ruthenium, ruthenium containing material, ruthenium dioxide, aluminum oxide, Copper, tantalum nitride, aluminum nitride, aluminum, quartz, and gallium arsenide. The coating is generally prepared by a polymerase solution having a molecular weight of, for example, 3000 Mn or less and 5200 Mw or less, which is in various organic solvents (such as xylene, 1,3,5-trimethylbenzene). In NMP, 7-butyrolactone and n-butyl acetate, the dissolved polymer or polymer can be cast onto the substrate by general spin and spray coating techniques. Controlled by changing the percent solids, molecular weight, solution viscosity and spin rate. The polyphenylene propylene polymer or polymer of the present invention can be applied by dipping coating, spray coating, extrusion coating. Preferably, it is coated by spin coating. In all cases, the environment around the substrate and the coating before curing can be controlled by the relevant temperature and humidity. In particular, NMP can be self-contained in the surrounding air. Water vaporizes oxygen to absorb water. When it is dissolved in NMP, it needs to protect the solution from moisture, gas and cast film in low humidity environment. When using NMP as solvent, the relative humidity should be controlled below 30. %, and the temperature is controlled at 27 ° C or more. The coating can be coated with one or more hot plates , furnace, or a mixture of these tools. The Central Bureau of Standards, the Bureau of Economics, the Consumer Cooperative, printed adhesion promoter (such as decane chemistry) can be coated with polyphenylene polymer or polymer solution. Coated on the substrate, or directly applied to the solution. The polymer and polymer of the present invention can be used in the "inlaid" metal inlaid negative umbrella layer pattern. The preparation of the integral t-connected structure. The tube is known in the industry. For example, see US Patent No. 5,262,354. 22 The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm). 1247757 The Central Bureau of Standards of the Ministry of Economic Affairs, the Beigong Consumer Cooperative, printed A7 B7. Description of the Invention (2〇) and 5,093,279. The pattern of the material can be used in a typical ion etching procedure using a compound containing oxygen, argon, nitrogen, helium, carbon dioxide, fluorine or a mixture of such gases and other gases, using a photoresist "soft cover" (such as epoxy novolac) or a photoresist mixed with an inorganic "hard cover" such as SiO 2 , Si 3 N 4 or metal. Oligomers and polymers can be physically Gas deposition, chemical vapor deposition, evaporation, electroplating, electroless deposition, and other deposition methods are used in conjunction with A-A1 alloy, Cu, Cu alloy, gold, silver, W, and other general metal conductive materials (as wires and plugs). Additional metal layers of basic metal conductors, such as groups, titanium, towns, roads, agglomerates, alloys thereof, or vapors thereof, can be used to fill holes, promote metal filling, promote adhesion, provide barriers, or improve metal reflections. Depending on the tissue to be prepared, the metal or dielectric material of the present invention can be removed or planarized using chemical-mechanical polishing techniques. For activated or passive substrates (such as tantalum, niobate glass, tantalum carbide, aluminum) The multi-wafer module on aluminum nitride or FR-4) can be constructed using the polyphenylene polymer of the present invention as a dielectric material. A flat panel on an active or passive substrate such as tantalum, niobate glass, tantalum carbide, aluminum, aluminum nitride or FR-4 exhibits the construction of the polyphenylene polymer of the present invention as a dielectric material It. The polymer and polymer of the present invention can be further protected as a protective coating on a circuit board to protect against alpha particles. When the alpha-particles released by the radiation trace contaminants in the package or other nearby materials strike the activated surface, the semiconductor device is susceptible to softening errors. The integrated circuit can be supplied with the present invention (please read the note on the back to write this page). * Packing · Ding Ben paper scale applicable to China National Standard (CNS) Α 4 specification (210X297 mm) 23 Central Bureau of Standards of the Ministry of Economic Affairs Employee Consumption Cooperative Printed 1247757 A7 B7 V. Invention Description (21) Protective coating. Typically, the integrated circuit wafer is placed on the substrate and held in place with proper adhesion. The polymer coating of the present invention provides an alpha-particle protective layer to the wafer activation surface. Alternatively, additional protection is provided by a package prepared, for example, by epoxide or ruthenium. The polymer of the present invention can also be used as a substrate (dielectric material) on a circuit board or a printed wiring board. Circuit boards composed of the polymers of the present invention have been placed on their surface defects for various electrical conductor circuits. In addition to the polymers of the present invention, the circuit board may contain various reinforcements such as woven non-conductive fibers such as glass cloth. This board can be single side and double or multiple sides. The polymers of the present invention can also be used in reinforcing complexes wherein the resin substrate polymer is strongly reinforced by one or more reinforcing materials such as reinforcing fibers or mats. Reinforced materials representing enamel include glass fibers (in particular, fiberglass mats (fabric or non-woven); graphite (especially, graphite mats (fabric or non-woven)); KevlarTM; NomexTM; and glass spheres The complex can be molded by a pre-formed, monomer or polymer-polymerized impregnation pad and resin transfer (the pad is placed in the mold, and the monomer or prepolymer is added and heated to produce a polymerization reaction). The polymer layer of the present invention can be patterned by wet etching, plasma etching, reactive ion etching (RIE), dry etching or light laser cutting, as exemplified in "polymers for electronic applications" ( Polymers for Electronic Applications), Lai, CRC Press (1989), pp. 42-47. Patterns can be accomplished by multi-layer techniques, during which / patterns are stenciled and applied to the polymer dielectric layer. The barrier layer is then etched into the underlying layer. A particularly useful technique involves masking the polymer or polymer that is not intended to be removed. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 24 (please first read Precautions for writing this page) - Packing · • Book 1247757 A7 B7 V. Inventive Note (22), remove the unmasked oligomer or polymer part, and then, for example, leave it with heat curing Oligomers or polymers. In addition, the polymer of the present invention can also be used to prepare shaped articles, films, fibers, and foams. In general, the industry is known for the technique of casting a polymer or polymer from a solution. Used to prepare this product. When preparing a shaped polyphenylene polymer or polymer article, additives such as fillers, colorants, carbon black, conductive metal particles, abrasives, and lubricious polymers can be used. The method is not critical and can be conveniently added to the polymer or polymer solution prior to the preparation of the shaped article. The liquid carrier composition containing the polymer or polymer alone or also containing the filler can be any general technique (scraper, shovel) , impregnation, brush, stimuli, self-green coating, extrusion coating or sputum coating) applied to a variety of different substrates. If polyphenylene oligomers or polymers are prepared in solid form, additives Can be made before the molded object Adding melts. The Central Standards Bureau of the Ministry of Economic Affairs, the employee consumption cooperative, printed the polymer and polymer of the present invention can be applied to various substrates by various methods, such as solution deposition, liquid phase phase extraction, shield printing, and melt spin. , impregnation coating, roll coating, powder coating, plasma deposition, dispersion spraying, solution casting, slurry spraying, dry powder spraying, fluidized bed technology, welding, including line explosion spraying method And explosive method of explosive bonding, thermocompression bonding, plasma polymerization, dispersing in a dispersion medium, then removing the dispersion medium, press bonding, pressure heating bonding, gas environment vulcanization, extrusion melt polymerization Materials, hot gas soldering, baking, coating and sintering. Single layer and multilayer films can also be deposited on substrates using air-water or other interfaces using Langmuir-Blodgett technology. 25 The paper size applies to the Chinese National Standard (CNS) A4 specification (210X29*7 mm) 1247757 A7 B7 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Printing V. Inventions (23) When the solution is coated with the present invention Or polymer, the most favorable polymerization conditions and other processing parameters are determined by various factors, especially the specific polymer or polymer to be deposited, coating conditions, coating amount and thickness and final use. The application, and the solvent chosen. Representative solvents that can be used are described above. The substrate to which the inventive polymer or polymer is coated may be any material having sufficient integrity to be coated with a monomer, a polymer or a polymer. Representative examples of substrates include wood, metals, ceramics, glass, other polymers, paper, cardboard, woven fibers, non-woven fabrics, synthetic fibers, KevlarTM, carbon fibers, gallium arsenide, antimony and others. Inorganic substrates and their oxides. The substrate used is selected on the basis of the intended application. Illustrated materials include fiberglass (woven, non-woven or strand), ceramic, gold shavings (such as Shao, Zhen, Titanium, Copper, Cord, Gold, Silver, Town, Stainless Steel, HastalloyTM, Carbon Steel, others) Metal alloys and their oxides) and thermosetting and thermoplastic polymers (such as epoxy resins, polyimine, perfluorocyclobutane polymers, benzofluorene cyclobutane polymers, polystyrene, polyamines, Polycarbonate, polyarylene ether and polyester). The substrate can be a cured version of the polymer of the invention. The substrate can be of any shape and the shape will depend on the final application. For example, the substrate may be in the form of a dish, a sheet, a wire, a tube, a plate, a sphere, a tube, a tube, a cylinder, a monument, a fiber, a woven or non-woven fiber, or a yarn (including a blend). Yarn), regular polymer; woven or non-woven mat. In each case, the substrate can be hollow or solid. In the case of a hollow article, the polymer layer is attached to the inside or outside of the substrate or both. The substrate may comprise a porous layer, such as a graphite mat or fabric, a glass mat or fabric, a scrim, and (please read the back sheet for notes on this page). Loading and binding paper scales for the Chinese National Standard (CNS) A4 Specifications (21〇X297 mm) 26 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Printed 1247757 Δ7 Α7 Β7 V. Invention Description (24) Granular materials. The present polymer or polymer is directly attached to many materials, such as compatible polymers, polymers with common solvents, metals (especially metallic materials), tantalum or cerium oxide (especially, etching) Shi Xi or Oxidized Stone Xi), glass, gasification dream, gasification copper, oxidation Ming, Shenhua married, quartz and ceramics. However, when it is desired to increase the adhesion, materials can be introduced to improve adhesion. A representative example of such an adhesion promoting material is decane, preferably an organic decane such as trimethoxyvinyl decane, triethoxyvinyl decane, hexamethyldioxane [(CH3)3-Si- NH-Si(CH3)3], or an amine-based oxime conjugate, such as 7-aminopropyl triethoxy carbamide, or a chelating agent such as aluminum monoethyl ethinyl acetate Propionate [((iso C3H70)2A1(0C0C2H5CHC0CH3))]. In some cases, the adhesion promoter is applied in a 0.01% to 5% by weight solution, the excess solution is removed, and then the polyphenylene is applied. In other cases, for example, a chelating agent of aluminum monoethyl acetoxyacetate diisopropyl ester can be spray coated on a substrate by spraying a toluene solution of a chelating agent and then baking at 350 ° C in oxygen. The substrate was coated for 30 minutes to form a very thin (e.g., 5 nm) aluminum oxide adhesion promoting layer on the surface and added to the substrate. Other methods of depositing the oxides are also suitable. Further, the adhesion promoter (in an amount of, for example, 5% to 5% by weight based on the weight of the monomer) may be blended with the monomer before the polymerization to eliminate the need to form an additional layer. Adhesion can also be facilitated by surface preparation, for example, by texturing (eg, scraping, etching, plasma treatment, or buffing) or cleaning (eg, this paper size applies to the Chinese National Standard (CNS) Α4 specification ( 210Χ297 mm) 27

1247757 Degreasing or sonic cleaning) 'Other treatments (eg, plasma, solvent, S〇3, plasma growth discharge, corona discharge, sodium, wet etching, or ozone treatment) or sandblasting the substrate surface or using electrons a beam (such as 6 MeV fluoride ion), an electron of 50 to 2000 V intensity; a hydrogen proton of 2 to 500 ev to 1 MeV, a proton of 200 KeV to 1 MeV; a fluorine or a gas ion of 〇·5 Mev; 28〇KeV; oxygen-enriched flame treatment; or accelerated argon ion treatment. For coating 3,3'-(oxybis-1,4-phenylene)bis(2,4,5-triphenylcyclopentadienone) with 1,3,5·tris(phenylethynyl) Oligomerization product of benzene reaction (better embodiment of the present invention) 'crush-based adhesion promoter (which contains 3-aminopropyl decane dissolved in methoxypropanol, which can be used by DuPont vm -652 or Dow Chemical Company's AP8000) was first applied to the surface of the wafer; slowly rotated to spray the entire surface; allowed to stand for 2 seconds; final spin drying at 3000 rpm for 1 second. When the wafer was rotated at 750 rpm, the oligomer solution was dispersed (4 mL of 2 〇〇 mm wafer) on the surface of the wafer with a high precision pump/filter system (Millipore Gen-2). Immediately after dispersing the polymer solution, the wafer rotation was accelerated to 2000 rpm, and the rotation rate was maintained for 20 seconds. The continuous flow of 1,3,5-trimethylbenzene was applied to the back side of the wafer for 5 seconds during the dispersion of the oligomer solution. After spin coating, the film was dried on a hot plate at 70 ° C for 20 seconds. After the dry bake step, the coated edge beads of 2 mm to 5 mm are removed in a continuous flow of 1,3,5-trimethylbenzene and coated either directly from the back side or directly from the top of the near end edge. The wafer was rotated at 2000 rpm. After the edge beads were removed, the oligomer was further polymerized on a hot plate at 325 ° C for 90 seconds under a nitrogen blanket. The membrane was crosslinked for 2 minutes on a 450 ° C hot plate under nitrogen or 6 minutes in a nitrogen stripping oven at 450 °C. The oligomer or polymer of the present invention can be combined with other additives to apply the paper scale to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------^---^-- ----Line (please read the notes on the back and then fill out this page) Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives -Zo - Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives - 1247757 V. Inventions (26) For special results. These added deuterated phases are metal-containing compounds (such as magnetic particles, such as lock iron, iron oxide), may be mixed with cobalt, or other metals used in magnetic media, optical media, or other recording media. Particles; conductive particles (such as metals or carbon used as conductive sealants), conductive adhesives, conductive coatings, electromagnetic interface (emi) / radio frequency interface (RFI) shield coating, static dissipation, and electrical contact. When such additives are used, the oligomer or polymer of the present invention can be used as a binder. The oligomer or polymer of the present invention may also act as a protective layer against the environment (ie, protect against at least one substance or force in the environment of the article, including conditions for preparation, storage, and use), such as surface-to-metal, semiconductor, Electric valleys, inductors, conductors, solar cells, glass and fiberglass, quartz and quartz fibers are not active. The following examples are intended to illustrate the invention and not to limit its scope. In the examples, all parts and percentages are by weight, unless otherwise indicated.

Hi_gas cyclopentadienone compound cantharidin. Several cyclopentadienone compounds and acetylene compounds are prepared as described below. The structure of these compounds is shown in Table I, Α·i bis('p-styl ethynyl)phenyl)-2,3,5-triazine to dienone (Compound A) (gl 4 - Bromo-ethyl acetophenone vapor 4-bromophenylacetic acid (100 g, 0.465 mol), sulfoxide dichloride (300 ml) and DMF (about 2 ml) were injected with a reflux condenser and mechanical stirring 1 liter round bottom 3-neck flask. The reaction mixture is heated under nitrogen for 2 small papers. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable.

«装---------tr-.------Line- (Please read the notes on the back and fill out this page) 1247757 A: -------B7____ V. Invention Description (27) Use a charcoal scrubber for gas escape. The sulphur dioxide gas was evaporated and the product (4-bromophenylethenyl chloride) was placed in an addition funnel with benzene (3 mL). (b) Preparation of 4-bromo degassed benzoin (200 ml) and vaporized aluminum (74 g, 〇 · 558 ml) were mixed into the flask, step (a) 4-bromophenylethyl sulfonate and benzene The reaction was carried out by evaporation of HC1 by a drop. The reaction mixture was stirred at room temperature for 1 to 1.5 hours and poured into ice water. Ethyl acetate (1 liter) was added to dissolve the solid. The layer was separated and the organic layer was washed successively with 1 Μ aqueous HCl solution, saturated aqueous NaHCI 3 and brine, and then dried over Na.sub.2. The solvent was then evaporated to give a solid material which was crystallised from ethyl acetate (hexane) (c) Preparation of 4-bromodiphenylethylenedione total acid (250 ml), water (250 ml), ethylene glycol dimethyl ether (2-methoxyethyl ether) (500 ml), hydrazine (nitric acid) nitric acid Salt trihydrate (222 g, 〇5 mol) and 4-bromodeoxybenzoin (68.75 g, 0.25 m) were injected into a 2 liter round bottom 3-neck flask equipped with a reflux condenser and mechanical mixing Device). The reaction mixture was heated to reflux under a gas atmosphere for 6 hours. Dimethyl methane (500 ml) was added while cooling to ambient temperature. The formed bilayer was poured out to form a precipitated T1(I) salt. The layer was separated and the organic layer was washed with water, saturated aqueous NaHCI3 and brine, and then recrystallised from 2-propanol to give the title compound. (d) Preparation of 4-(p-phenylethynyl)dimosyldione 4-bromodiphenylethylenedione (1〇·〇克, 0.0346 mol), phenylacetylene (3 88 paper scales applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm) (Please read the note on the back and fill out this page) | Install-----Γ---订---J-Line Economics Department Intellectual Property Bureau employee consumption cooperative printing -

5, 1247757 Description of the invention (28 g, 0.0380 mol) and (PPh3) 2 PdCl2 ((U21 g, 0·0002 mol), which is present in diethylamine (95 ml), stirred at ambient temperature for 72 hours, After concentration to dryness, the residue is taken up in di-methane. The standard aqueous solution is then recrystallized from 2-propanol to give the title compound.

(6) Preparation of Compound A 4_(stupylethynyl)diphenylethylenedione (2 gram, 0.0644 mole), ι, 3·1 phenyl acetate (14.2 g, 0.0677 mol) and ethanol (150 liters) ) is heated to 75C. Potassium hydroxide (K〇H) (18 g, 0.0322 mol) dissolved in ethanol (15 liters) was added dropwise over 15 minutes. The reaction mixture was heated to reflux for 30 minutes, then cooled to 4 {rc, and the precipitated product was filtered, washed with cold ethanol and dried. Recrystallization from 2-propanol gave the title product. Β·h3 -(丨,4·phenylene) bis(2,4,5·triphenylcyclopentadienone (compound β) 1,3-diphenylacetic acid vinegar (ι·23 g, 0.00584 mo Ear), 1,4-bis(phenyl oxalyl) benzene (available from Bis-PGB of Ken Seika, 1.000 g '0.00292 mol) and ethanol (50 ml) were added to 1 ml A 3-neck round bottom flask equipped with a reflux condenser/nitrogen inlet. The reaction mixture was heated to reflux, and aqueous KOH (0.112 g, 0.002 mol) in water (2.25 mL) was added. 〇11 was added until the solution became dark and remained dark. The mixture was refluxed for 45 minutes and then allowed to cool. The precipitated dark solid was collected by hydrazine and purified by lH-NMR, NMR, HPLC and FT-IR. Analysis. All data are consistent with the formation of compound b. C·^^14 bis(phenylethynyl)mosynyl)-2,2,,3,3,.5.5,",-octaqiodiphenyl (compound) C丨(8) Preparation of 4-Iodide Cage 篡 醅 A § This paper scale applies to China National Standard (CNS) A4 specification (2) 0 X 297 mm) ------------· -I (please read the back first) Notes on filling out this page) book - · -----

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumption Cooperative, Printing I

IT 1247757 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 ^------------_ _ 5, invention description (29) 4-iodophenol (25.00 g, 0.114 m) and two Methyl chloride (1 mL) was added to a 250 mL round bottom flask equipped with a condenser/nitrogen inlet, a thermocouple and a dropping funnel. The slurry was stirred and pyridine (io. n mL, 〇 125 mL) was added via syringe. The reaction mixture was cooled to 1 (rc, acetonitrile chloride (8·89 liters, 0.125 moles) using an ice bath and added dropwise. The mixture was stirred at 10 ° C for 1 hour, allowed to warm to room temperature and stirred. 2 hours. The reaction mixture was filtered, and the filtrate was washed 4 times with water. The organic layer was dried (MgSO.sub.4), and the solvent was dried in vacuo to yield 27.3 g of an orange oil. The NMR analysis was consistent with the structure of the desired product. Preparation of phenyl acetylene a) ethyl 4-iodophenyl acetate (50.00 g, 0.191 mol), phenyl acetylene (23.40 g '0.229 mol) and triethylamine (54 liters) It was added to a 25 liter round bottom flask equipped with a condenser/nitrogen inlet, thermocouple and flow stop. PdCl2(PPh3)2 (0.200 g, 0.286 mmol) and (PPh3 (1.5 g, 5.73 mmol) were added and the mixture was heated to reflux. When the reaction mixture reached 4 ° C, Cixl (0.054 g) was added. After 2 hours, the reaction was cooled. The mixture was diluted with methylene chloride and poured into water (5 mL). The aqueous layer was extracted with dichloromethane (100 mL). Three portions of 300 ml of water were washed, dried (MgS 〇 4) and filtered. The solvent was removed in vacuo to yield 49 g of a yellow solid. The material was recrystallised from hexane to yield yellow crystals, mp l s s s s s s s. (g) Preparation of 4-(jammaacetylene) phenol 4-(benyl hexyl) phenylacetic acid g (60.6 g, 0.256 mol), 20% aqueous sodium hydroxide solution (400 ml) and tetrahydrofuran (400) ML) was added to a 2 liter Erlenmeyer flask and stirred at room temperature for 5 hours. The mixture was applied to the Chinese National Standard (CNS) A4 specification (2) 0x297 mm on the paper scale.

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1247757 V. INSTRUCTIONS (30) Glacial acetic acid (120 ml) is acidified to a pH of up to 7. The aqueous layer was removed and extracted with tetrahydromanate. The organic layer was mixed and concentrated on a rotary concentrator to give a brown solid. The solid and steam baths are heated and the hot solution is slowly poured from the solids. This step was repeated in a second volume of hexane (700 mL). Upon cooling, a white solid was crystallized from hexanes, and filtered and dried in vacuo to yield 18 g of white solid, mp. The NMR analysis was consistent with the structure of the desired material. (d) Preparation of compound Γ Decafluorobisphenyl (5.00 g, 14.96 mmol), 4-(phenylethynyl)phenol (5.81 g, 29.93 mmol), sodium carbonate (16.54 g, 0.1197 mol) And dimethylacetamide (150 ml) was added to a 250 ml round bottom flask equipped with a condenser/nitrogen inlet, thermocouple and flow stop. The mixture was stirred and heated to 70 ° C for 16.5 hours. The reaction mixture was filtered to remove solids. The filtrate was added to water (500 mL) and extracted with di-methane. The brine was broken and the emulsion was removed. The organic layer was separated and washed twice with water and filtered through a vermiculite gel plug. The solvent was removed in vacuo to leave the oil. Methanol was added to form a white solid which was isolated by filtration and dried in vacuo. The NMR spectrum is consistent with the structure of the title compound. D· 4-(4-(ethynylphenyl-5-trisylcyclopentaphenone (Compound D)) Compound D was prepared by substituting trimethylstilbestylacetylene for phenylacetylene according to Example 1A, followed by dilute base Removal of trimethylmethanyl protecting group bis-(4-(mythylethynyl)methyl)-2,5-diphenylcyclopentadienone (Compound E) This paper size applies to China Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back and fill out this page)

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Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed I 33 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative 4 System 1247757 a7 B7 V. Description of Invention (31) Preparation of 4,4'-dibromobenzoin in ethanol (125 ml) 4-bromobenzaldehyde (25.0 g, 0.135 mol), 3-ethyl-5-(2-hydroxyethyl)-4-mercaptothiazolium bromide (1.70 g, 0.0068 mol) and triethylamine ( 4·10 g, 0.0405 mol) was stirred at room temperature for 60 hours. The reaction mixture was concentrated to dryness EtOAc mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj It solidifies when it is allowed to stand at room temperature. 1H NMR (CDC13) 5 7.73 (d, J = 8.5 Hz, 2H), 5 7.52 (d, J = 8.5 Hz, 2H), 7.44 (d, J = 8.2 Hz, 2H), 7.17 (d, J = 8.2 Hz, 2H); 13C NMR (CDC13) δ 197.33, 137.56, 132.33, 132.13, 131.90, 130.43, 129.46, 129.31, 122.93, 75.68. (b) Preparation of 4,4'-dibromobenzoin (20.2 g, 0.055 mol), ammonium nitrate (4.6 g, 0.0575 Mo) in 4,4'-dibromoanthine in 80% aqueous acetic acid (200 ml) The ear) and copper acetate (11) (0.100 g, 0.0005 mol) were heated to reflux for 3 hours. The reaction mixture was cooled to room temperature and the crystalline product was filtered, washed with ethanol and dried to give <RTI ID=0.0>> NMR (CDC13) 5 7.83 (d, J = 8.5 Hz, 4H), 7.66 (d, J = 8.5 Hz, 4H); 13C NMR (CDC13) δ 192.25, 132.44, 131.45, 131.22, 130.7 〇 (£) Preparation 4 4,4-bis(phenylethynyl)diphenylethylenedicarboxylate 4,4,-dibromodiphenylethylenedione (15·8 g, 0.431 mol) in diethylamine (150 ml) Phenylacetylene (5·〇6 g, 0.0495 mol), (PPh3)2PdCl2 (0.151 g, 0.0002 mol) and Cul (0.820 g, 0.0043) This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 34 Pack----------Book---.------ (Please read the notes on the back and fill out this page) A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1247757 i, description of the invention (32) Moh) was heated under reflux overnight. The reaction mixture was concentrated to dryness, poured into CH.sub.2 C.sub.2 (150 mL), washed with <RTIgt;</RTI> Crystallized from 2-propanol

7.92 g (45%) of light brown solid, mp 168 ° C to 170 ° C. A NMR (CDC13) δ 7.97 (d, J = 8.2 Hz, 4H), 7.64 (d, J = 8.2 Hz, 4H), 7.55 (m, 4H), 7.37 (m, 6H); 13C NMR (CDC13) δ 193.03, 132.46, 132.03, 131.82, 130.21, 129.84, 129.06, 128.47, 122.37, 94.28, 88.55 〇

(d) Preparation of compound E A solution of hydrazine (0.33 g, 0.0061 mol) in ethanol (5 ml) was added dropwise to 4,4'·bis (benzene) in ethanol (75 ml) at 75 °C. A solution of ethynyl)diphenylethylenedione (5.0 g, 0.0122 mol) and 1,3-diphenylacetone (2.69 g, 0.0128 mol). The resulting solution was heated under reflux for 1 hour, cooled to room temperature and the precipitate was filtered and dried. The product was extracted from boiling ethanol to give 5.26 g of product (74%) as a brick red solid: 111 卞.222 ° 〇 (DSC); H NMR (CDCI3) δ 7.5 (bd, J = 3 Hz, 4H), 7.34 (m, 5H), 7.25 (bs, 5H), 6.93 (d, J=8.0 Hz, 4H); 13C NMR (CDC13) 5 199.02, 152.72, 132.31, 131.14, 130.83, 129.93, 129.67, 128.99, 128.04, 127.93 , 127.71, 127.28, 125.31, 123.12, 122.46, 90.60, 88.71; MS (El) 585 (28), 584 (M+, 56), 556 (19), 378 (36), 278 (100). F. 3,4-bis-(3-(p-styl acetylene) methyl)-2,5-di-cyclohexadienone (formation compound F) (g) preparation of 3,3, dibromo The standard of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page)

1247757 A7 B7 1. Description of the invention (33) Prepared as described in Example 1E(a) but consisting of 3-bromobenzaldehyde (25.0 g, 0.135 mol) present in ethanol (125 liters), 3 -ethyl-5-(2-hydroxyethyl)-4-methylthiazole bromide (1·70 g, 0.0068 mol) and triethylamine (4.10 g, 0.0405 mol), yielding 24.8 g (99 %) viscous yellow oil. 1H NMR (CDC13) (5 8.04 (s, 1 Η), 7.75 (d, J = 7.8 Ηζ, 1 Η), 7.61 (d, J = 8.0 Hz, 1H), 7.47 (s, 1H), 7·26·7 · 15 (m, 4H), 5·87 (s, 1H); 13C NMR (CDC13) δ 196.96, 140.48, 136.86, 134.94, 131.93, 131.86, 130.69, 130.63, 130.26, 127.57, 126.33, 123.19, 75.76 〇( b) Preparation of 3,3'-dibromodiphenylethylenedione Prepared as in Example 1E(b) but from 3,3'-dibromobenzoin (24.8 g, 0.067) in 80% aqueous acetic acid (200 mL) Prepared by a solution of ammonium nitrate (5.63 g, 0.070 mol) and copper acetate (11) (0.12 g), yielding 17 g (69 〇 / 〇) product as pale yellow solid. 1H NMR (CDC13) 5 8.12 (s, 2H), 7.88 (d, J = 7.8 Hz, 2H), 7.79 (d, J = 7.9 Hz, 2H), 7·40 (dd, J = 8.0, 8.0 Hz, 2H); 13C NMR (CDC13 5 191.58, 137.87, 134.27, 132.53, 130.60, 128.59, 123.39. (clIL 3,3'-double (stupidyl ethynyl) dimethylene glycol

Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed I 3,3'-dibromodiethylidene (5 gram, 〇136 m) and phenyl acetylene (3.47 g, 0.0340 m) of triethylamine (3 mM) solution was degassed by passing nitrogen bubbles through the solution for 10 minutes. Then (pph3) 2pdcl2 (0·067 g 'o.oooi Mo) was added and the reaction mixture was heated under reflux overnight. The mixture was concentrated to dryness, poured into Ch2C12 (100 ml), washed sequentially with W1M HC1, saturated NaHC〇3, and dried (Na2S04). The concentrated paper size was then applied to the Chinese National Standard (CNS) A4 specification (210 X). 297 mm) 1247757 A7 B7 V. INSTRUCTIONS (34) 'Generate 3.67 g (66%) of product as a white solid: mp·i 44 ° C to 145. (:; !H NMR (CDC13) 5 8.12 (s, 2H)? 7.96 (d, J=7.9 Hz, 2H), 7.81 (d5 J=7.7 Hz, 2H), 7.52 (m, 6H) 7.36 (m, 6H); 13C NMR (CDC13) 5 192.83, 137.40, 132.82, 131.52, 129.04, 128.58, 128.25, 124.50, 122.37, 91.11, 87.62.

(d) Preparation of a solution of compound F 0 (0·25 g, 0.0045 mol) in ethanol (5 ml) was added dropwise to 3,3,-bis(>phenylethynyl)diphenylacetate at 75 °C ethanol. Diketone (3.67 g of ' 0.0089 mol) and 1,3-diphenylacetone (2.07 g, 0.0098 mol) of ethanol (100 ml). The resulting solution was heated under reflux for 1 hour and then cooled to room temperature. The formed precipitate is filtered and dried. The product was extracted from boiling ethanol to yield 2.0 g (38%) of dark red solid product: mp 208 ° C (DSC). !H NMR (CDCI3) 5 7.45 (bm, 6H), 7.31-7.21 (bm, 2 〇H), 6.9 (d, J=7.9 Hz, 2H); 13C NMR (CDC13) δ 199.38, 152.83, 132.87, 131.48, 131.25, 131.12, 129.80, 129.60, 128.53, 127.99, 127.92, 127.84, 127.70, 127.29, 125.03, 122.96, 122.47, 90.60, 88.71. G·!^3 (stupyl ethynyl) jasmine (compound m triethylamine (375 g), triphenylphosphine (4.7865 g), palladium acetate (1.0205 g) and N,N-dimercaptocarboxamide (2 〇〇〇 ml) was injected into a 5 liter 3-neck round bottom flask (with thermocouple, mechanical stirrer above, condenser, addition funnel and heating mantle with temperature controller). The mixture was stirred 5 minutes to dissolve the catalyst. Then add diethyl hydroxy (5 grams), H5-tribromo stupid (190 grams) and phenyl acetylene (67.67 grams). The reactor is stripped with nitrogen 15 paper scale applicable to Chinese national standards ( CNS)A4 specification (210 X 297 mm) (Please read the note on the back and fill out this page) -Install-----^----Book---^------Line g Economy Ministry of Intellectual Property Bureau employee consumption cooperative printed 37 1247757 A7

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing I 5, invention instructions (35) minutes, then heated to 7〇t, and maintain a nitrogen atmosphere. After heating at 7 (rc for 3 min, phenylacetylene (135 33 g) was slowly added dropwise over a period of about 1 hour, and the temperature was increased to 80 ° C. Heating was continued for an additional 9 hours. The reaction was cooled to room temperature and added. Water (1 liter), which precipitated the crude product. The product was filtered, washed three times with 500 ml of water, and then washed once with 5 liters of cyclohexane. The crystals were dried overnight at 75 ° C under vacuum to give 2:26. 4 g (99.1% yield), which was 97.25 area% purity by gas chromatography. The crystal was dissolved in methyl stupid (1800 ml), filtered again through a vermiculite gel, and the solvent was removed on a rotary evaporator. 214.2 g (94.2% yield) of 99.19 area% purity by gas chromatography. Residues were recrystallized from a mixture of toluene (375 ml) and 2-propanol (696 ml). White crystals were filtered toluene A mixture of (1 ml) and 2-propanol (400 ml) was wetted and dried under vacuum at 75 ° C overnight to yield 1,3,5-tris(phenylethynyl)benzene (19.0 g, 83.91 yield), which was analyzed by gas chromatography to be 99.83 area% purity. Additional recrystallization of /isopropanol yields acceptable organic and ionic purity materials. Η·ϋ'-bis(styl ethynyl) bis-methyl ether (compound η) in a 1 liter 3-neck round bottom flask (its With thermocouple, mechanical stirrer, condensation and temperature control | § heating cover) 'injected triethylamine (111.5 grams), triphenylphosphine (1.158 grams), acetic acid (0.2487 grams), two Hydroxylamine (1.24 g), 4,4'-dibromodiphenyl ether (68.8 g), phenylacetylene (67.74 g), hydrazine, hydrazine-dimercaptocaramine (136 ml) and 72 ml Water. The reactor was stripped with nitrogen for 15 minutes and then heated to 90 ° C while maintaining a nitrogen atmosphere for 19 hours. The reaction was cooled to room temperature 'and water (80 mL) was added. The crude product was filtered and solid The milliliter of toluene is wetted once and applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) on a 16-inch paper scale.---------Book---^---- -- Line (please read the notes on the back and fill out this page) 1247757 A7 B7 V. INSTRUCTIONS (36) Water wetting four times, drying under vacuum 66.37 g (85.6% yield) of white needle-like 4,4'. bis(phenylethynyl)diphenyl ether was analyzed by gas chromatography to be 99.64 area% purity. I·4,4"- Bis(Methyl ethynyl)-o-trismidine (Compound D (a) is prepared 4,4"-dibromo-o-tripleto-terphenyl (100 g), Fe (5 g), and CHC13 (475 Milliliter) was injected into a 1 liter 3-neck flask equipped with a mechanical stirrer, a condenser connected to the HBr trap, and an addition funnel. The mixture was stirred and the temperature was maintained in a water bath. Br2 (47.5 ml) in CHC13 (150 ml) was added dropwise over a period of 2.5 hours. The mixture was mixed for an additional two hours at room temperature. GC showed 5% monobromo-o-terphenyl, 81% dibromo-o-terphenyl and 9% tribromo-o-terphenyl. Ice and 2N NaOH solution were added to the upper solution until it was tested. The upper layer was poured out and the CHC13 solution was washed with more water. Sodium sulfate was added to the CHCI3 solution and then filtered through a Buchner funnel filled with Celite. Remove the air imitation. 750 ml of glacial acetic acid was added to the white solid, and the slurry was heated to 95 ° C in a water bath. About half of the solids are dissolved. The hot solution was poured into a 1 ml flask. The residual solid is 71 grams, which contains 1.4% monobromo-o-triplet, 93% 4,4''-dibromo-o-terphenyl, and 6% 4,4,4,,-tribromo - o-terphenyl. The acetic acid solution was cooled to room temperature. White crystals were collected. GC showed 1% mono-o-terphenyl, 83% 4,4,-dibromo-o-terphenyl and 13% 4,4',4',-tribromo-o-terphenyl. This material was used to prepare 4,4, bis(phenylethynyl)-o-terphenyl.

Also) Preparation of Compound I This paper scale is applicable to China National Standard (CNS) A4 specification (21〇X 297 mm) (please read the notes on the back and fill out this page) ---------- ---^------ line

Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative I 39

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing I 1247757 A7 ---------21___ V. Description of Invention (37 ) 4,4''-Second-O-Diphenyl (4 gram, 〇〇 1 〇 3 mol), phenyl acetylene (5 〇 ml), triethylamine (500 ml) and. The pyridine (300 ml) was injected into a 1 liter 4-neck flask equipped with a mechanical stirrer, condenser, n2 inlet and thermocouple. Air is used to strip the system for 2 minutes. After dissolving the solid, 2.783 g of Pd(PPh3)2Cl2, 2.538 g of 匸111 and 5.54 g were added. ? 113. Nitrogen was bubbled through the solution and stirred for 3 minutes. The heating was turned on to reflux the mixture. The reflux is kept overnight. A white solid formed during the reaction. The solution was poured into a 2 liter ice-containing flask. The flask was wetted several times with water and poured into the flask. The solid formed was filtered through a Buchner funnel and then washed several times with water. Toluene was used to dissolve the solids in a 2 liter flask. The upper layer was poured into a 1 liter flask. The lower layer containing the undissolved material was wetted with toluene, and the toluene solution was mixed by pouring out the upper layer to form a dark brown solution. The dark brown solution was decolorized with charcoal. The solution is heated in a water bath and stirred. Na2S04 was added. The solution was filtered through a sintered glass filter and the solvent was concentrated by spin. The solid was dissolved in 2 ml of hot toluene in 350 ml of hot toluene. Once dissolved, 1300 ml of isopropanol was added to crystallize the solid. A 2 liter flask was placed in the refrigerator overnight, and the crystals were collected and washed with isopropyl alcohol. The yellow solid weighed 25 grams. The 'yellow solid was then washed with acetone and then crystallized twice in ethyl acetone. The yield of white chips is 12 grams. J. 4,4'-Diethynyl diphenyl ether (compound j) 4,4,-dibromodiphenyl ether (9.8 g, 0.030 mol) in triethylamine (40 ml), Pd(OAc)2 (0.05g, 0.0002m), copper iodide paper size applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -4D -

^ r---订·--K-line L (please read the notes on the back first ^: write this page) 1247757 A7 B7 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Printed 5, Invention Description (38) (1) (0.15 g, 0.0008 mol) and triphenylphosphine (1.0 g, 0.0038 mol) The slurry was stripped with nitrogen for 30 minutes while slowly heating to reflux 2-methyl•3 Butyl-2-ol (7.6 g, 0.090 mol), which was stripped with nitrogen for 30 minutes and quickly added to the refluxing solution over 5 minutes. The resulting reaction mixture was heated under reflux for 14 hours, cooled to ambient temperature and concentrated to dryness. The residue was poured into CH2C12, washed with water and brine, and then concentrated. The residue was poured into toluene (200 ml and sodium hydride (0.10 g, 0.20 mol) was added. The reaction mixture was heated to reflux and evaporated to yield a solvent of about 100 ml. The solution was cooled and then concentrated. Into CH2C12, washed with IN HC1, water, saturated NaHC03 and brine, then dried (Na2S04) and concentrated to give a dark oil. The residue is filtered through a silica gel pad, eluted with CH2C12 and concentrated to give a viscous oil. Slowly solidified upon standing. 1H NMR (CDC13) 5 7.45 (d, J = 8.6 Hz, 4H), 6.93 (d, J = 8.7 Hz, 4H), 3.04 (s, 2H); l3C NMR (CDC13) 5 157.02 , 133.93, 119.20, 118.94, 117.16, 83.16 The 〇 reaction is as follows:

NaH

-OH

Pd(OAc) PPh3 Cul Et3N 2 K. 3,3'·(gas di-M-yamyl) bis(2,4,5-trimosylcyclopentadienone (Compound K) 41 This paper size applies China National Standard (CNS) A4 Specification (210X297 mm) 1247757 A7 B7 V. INSTRUCTIONS (39) Dichloromethane of diammonium bromide in dichloromethane (200 ml) at 0 ° C Alumina (97.9 g, 0.734 mol) slurry, diphenyl ether (50·0 g, 〇294 mol) and benzene present in dichloromethane (5 ml) were added dropwise over 3 min. a solution of hydrazino chloride (102 g, 661·661 mol). When the addition was complete, the reaction mixture was warmed to ambient temperature and stirred overnight. The reaction mixture was carefully stirred and poured into 1.5 kg. Ice/water. Add dichloromethane (1500 ml) as a solution solid, and separate the layers. The organic layer was filtered over Celite, then concentrated and dried. Recrystallized from toluene to give 11 () g (92%) The title compound of light brown ribbed shape. Double (Mam 乙 趑 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The solution (97 ml of 48% by weight solution) was added to 4,4, diphenylethenyl diphenyl ether (5 g, 0·123 mol) slurry in DMSO (400 ml). And the resulting mixture was heated to i〇〇r for 2 hours, then cooled to ambient temperature. The reaction mixture was separated between toluene (500 mL) and water (750 mL). The organic layer was washed with water (3×250 mL). It was then washed with brine and concentrated to give a viscous bright yellow oil which solidified upon standing ambient temperature. Recrystallization from ethanol yielded 35. 9 g (67 〇 / 〇) of the title compound as a bright yellow cube. Preparation of compound κ in a 5 liter Morton flask with nitrogen stripping (configured with a thermocouple, reflux condenser with nitrogen inlet, mechanical stirrer and addition funnel), adding 195.4 grams (0.4498 moles, lo eq) of 4 , 4, _ bis (phenylglyoxal) diphenyl ether, 193.9 grams of diphenyl propyl net (〇 922 〇 Mo Er, 2 〇 5 )) and 2 5 liters 42 paper size for China TCNS )A4 specification (210X297 mm) Printed by the Central Bureau of Standards and Staff of the Ministry of Economic Affairs, 1247757 A7 B7 V. Deoxyethanol of the invention (4〇). The mixture was heated to reflux, at which point a homogeneous solution was reached, and the solution was diffused with nitrogen for 30 minutes. Adding 25.2 g of KOH (0.4498 mol, 1.0 eq) in the addition funnel, A solution of 200 ml of ethanol and 25 ml of water. The temperature was lowered to 74 ° C, and the KOH solution was quickly added during 5 minutes. The exothermic reaction quickly established, and the reflux was maintained until 3/4 of the solution was added, after which the temperature began to decrease. A deep purple color was observed immediately upon addition of the base, and a solid was observed before the addition was completed. After the addition was complete, the heterogeneous solution was heated under reflux for 15 minutes with more solids formed. The mixture was cooled to 251, 29.7 g of glacial acetic acid (0.4948 mol, l.leq) was added and stirred for 30 min. The crude product was isolated by filtration and washed with 1 liter of water, 3 liters of ethanol, 2 liters of methanol in a filter funnel, and dried under vacuum at 60 ° C to 9 (TC for 12 hours, yielding 323 g (92%) of crude DPO. -CPD, which was found to be 94% pure by 1^. The crude material was dissolved in HPLC grade di-methane (10% by weight) and transferred to a 5 liter Morton flask equipped with a bottom flush valve and a mechanical stirrer to the same volume. The low-ion water was washed vigorously 2 to 7 times for 10 to 90 minutes each time. The CH2C12 solution was then rinsed through a 5 cm tube containing 75 grams of vermiculite gel in CH2C12. The column was washed with an additional 1 liter of CH2C12. At this point the filtrate was essentially clear. The solution was evaporated to dryness and redissolved in THF and evaporated again to remove the entire residual di-methane. The powder was transferred to a 5 liter flask equipped with an addition funnel and a Friedrichs reflux condenser. And dissolved in refluxed deoxygenation HPLC (0.07 to 0.12 g / ml). Then add 1 liter of THF, nitrogen diffusion tube was inserted into the solution. The solution was diffused with nitrogen for 3 hours, and THF at 45 ° C to 50 ° C is concentrated while the residual digas methane is distilled Connect the distillation head and remove 700 ml to 1 liter of THF. Then the solution is slowly applied to the Chinese National Standard (CNS) A4 size (210X297 mm) 43 (Please read the back note 8 first) ) - Install ·, order A7 B7 1247757 $, invention description (41) Cool for several hours to room temperature, then cool to less than 10 ° C in an ice bath, during which crystallization occurs. In 4-Lilliliter Millipore clip-sinter suction filter flask The crystallization was isolated using a 5//m PTFE filter, then washed with 1 liter of methanol and dried overnight at 80 ° C to 90 ° C under vacuum to yield a 70 to 85% yield of DPO-CPD with 99% LC purity, mp 270. (: L. 2,4,4'-tris(p-phenylethynyl) bis-methyl ether (compound l) (a) Preparation of 2,4,4'-tribromodiethyl ether Bromine (57.3 g, 0.358 mol) was slowly added dropwise to a neatly stirred diphenyl ether (20.0 g, 0.118 mol) at 40 ° C. During the addition, the temperature was slowly raised to 60 ° C and the reaction was maintained at this temperature for 2 hours. The mixture was heated to 701: 30 minutes and then cooled to ambient temperature. The mixture was poured into CH2C12 (100 mL) with 10% Na2CO3 water. The solution was washed, then dried (Na 2 SO 4 ) and concentrated to give 44.8 g (100%) of product as a viscous oil which slowly solidified upon standing ambient.

(b) Preparation of compound L 2,4,4,-tribromodiphenyl ether (44.3 g, 0.116 mol), Pd(OAc) 2 (0.182 g, 0.00081) in triethylamine (300 ml) Moer), copper iodide (1) (574 g, 0.00302 mol) and triphenylphosphine (3.95 g, 0.0151 mol of slurry) were diffused with nitrogen for 30 minutes while slowly heating to reflux and diffused with nitrogen. A 30 minute phenylacetylene (41.4 g, 0.406 mol) was added to the refluxing solution over a period of 5 minutes. The resulting reaction mixture was heated under reflux for 14 hours. The solution was cooled to ambient temperature and concentrated. CH2C12, with 1N of HC1, water, saturated NaHC〇3 aqueous solution and this paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) --II I--^---Γ---- ( Please read the notes on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives_Printed Μ 1247757 B7 V. INSTRUCTIONS (42) Wash with salt water and concentrate to a volume of 100 ml. This solution is condensed by gangue. The pad was filtered, extracted with di-methane and concentrated to form a filtrate. The residue was crystallized from EtOAc / EtOAc to yield EtOAc (EtOAc: EtOAc: EtOAc , 14H), 7.34-7.26 (m, 20H), 6.98 (dd, J = 8.0, 8.0, 2H); 13C NMR (CDC13) 5156.81, 156.00, 136.49, 132.93, 132.57, 131.31, 131.22, 128.23, 128.10, 128.06 , 127.99, 127.87, 123.04, 122.74, 122.51, 119.63, 119.09, 118.67, 117.84, 116·30, 95.05, 89.47, 88.72, 87.79, 83·87. Μ. 3,3'-(1,4-Astyl ) bis(2,5-di-(4-fluorophenyl)V4-phenylindolediene ketone (compound oxime) 1,3-bis(4-fluorophenyl)-2-propanone (1.476 g, 0.006 Mo) Ear) and 1,4· bis(phenyl oxalyl) benzene (acquired by Ken Seika's Bis-PGB, 1.020 g, 0.003 mol) is dissolved in 90 ml of 1 propanol and added with benzyl Trimethylammonium hydroxide (0.32 g, 40% in methanol). The solution was immediately purple and refluxed for 2 hours. The mixture was cooled to room temperature and then to 〇 °C. The solid was collected and washed with cold methanol. The yield was 1.92 g. The solid has a metallic sparkle color and melts at 316 ° C as measured by DSC. Bis(4-phenylphenyl)-2-propionamidine is prepared by the procedure described in E. Elce, A. S. Hay, J. Poly. Sci.: Part A: Polymer Chemistry, 33, 1143-1151. N·么斗'^”-二心笨基乙快基卜邻-三联笨”匕合]]^) (a) Preparation of 4,4”-tribromo-o-tri-m-o-terphenyl (39.6 g) ), Fe (3.3g) and CHC13 (450ml) are applied to the paper size of China National Standard (CNS) A4 specifications (2) 0 X 297 mm) (Please read the back of the note? ) I-----r---订·---J------ Line Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 45 1247757

V. Description of the invention (43

The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed a 1-liter 3-neck flask equipped with a mechanical stirrer, a condenser connected to the ηΒγ trap, and an addition funnel. The mixture was stirred and the temperature was maintained in a water bath. Br (26.5 liters) of Br present in CHC13 (1 mL) was added dropwise over 1.5 hours. The mixture was stirred at room temperature for 2 hours and then at 65 {> (: stirred for 2 hours. GC showed 14% of dibromo-o-terphenyl, 85% of tribromo-o-di- and bi-bromo and 0.7% of tetrabromo _ o-terphenyl. Ice and 2 NaOH solution was added to the solution until it was alkaline. The upper layer was poured out and the CHCI3 solution was washed with more water. Sodium sulfate was added to the CHCl3 solution and then passed through the Celite The Buchner funnel was filtered. The gas was removed. The white solid was mixed with 750 ml of glacial acetic acid and the slurry was heated in a water bath at 95 ° C. The solid yield after removal of all acetic acid was 44.5, which contained 11% of 4, 4', · dibromo-o- triplet, 88% of 4,4,,4,,-tribromo-o-terphenyl and 0.6% tetrabromo-o-terphenyl. Solids were used for preparation 4, 4,, 4,, · bis(local ethynyl)-o-terphenyl. The acetic acid solution contains 56% of 4,4''-dibromo-o-terphenyl, 36% of 4,4,,4, ,-Tribromo-o-terphenyl and 1.8% tetrabromo-o-tetraphenyl. (b) Preparation of compound Ν 4,4',4''-tribromo-o-terphenyl (24.7 g, 0.053 Mo Ear), phenyl acetylene (22 ml), triethylamine (280 ml) And acridine (180 ml) was poured into a 1000 ml 4-neck flask equipped with a mechanical stirrer, condenser and N2 inlet and thermocouple. Nitrogen was used in the stripping system for 20 minutes. Pd(PPh3)2Cl2 (1.113 g), Cul (1.005 g) and PPh3 (2.218 g) were added. Nitrogen was bubbled through the solution and stirred for 30 minutes. Heating was turned on and the mixture was refluxed overnight. A white solid formed during the reaction. China National Standard (CNS) A4 Specification (210 X 297 mm) 46 — Pack-----„----订·!------. (Please read the notes on the back and fill out this page. ) 1247757

V. INSTRUCTIONS (44) The solution was placed in a 2 liter flask containing ice. The flask was wetted several times with water and poured into the flask. The resulting viscous solid was passed through a Buchner funnel and then washed several times with water. Toluene was used to dissolve the solids in a 2 liter flask. The upper layer was poured into a 1 liter flask. The lower layer containing the undissolved material was mixed with toluene toluene' toluene solution to form a dark brown solution. It is then decolorized with charcoal. The solution was heated and stirred in a water bath. Then add Na2S〇4. The solution was filtered through a sintered glass filter and the solvent was rotary evaporated. The viscous solid was dissolved in a 2 liter flask with 6 liters of hot acetone. The crystals were then collected and washed with acetone. The pale yellow solid weighed 11 grams. The solid was crystallized twice from ethyl acetate. The white powder yield was 8 grams. 〇·double (stupyl acetylene) 芏 (compound 〇) stupid acetylene (8·0 g '78.3 mmol), ι,3-dibromobenzene (6.24 g '26.6 mmol), bis (triphenyl) Phosphine) palladium (π) vapor 〇 gram, 4.23 millimolar), copper iodide (1) (〇·5〇3 g, 2.64 mmol), mouth ratio (73 ml, 〇.93 Mo) Ear), triethylamine (11 〇 ml, Ministry of Economic Affairs, Intellectual Property Bureau Consumer Cooperative - printed 0 · 7 8 3 moles) was mixed and stirred under nitrogen for 3 minutes, then the mixture was refluxed overnight. The solution was poured into a water/ice bath. The formed solids are collected and washed with water. The solid was dissolved in toluene and the insoluble material was filtered. The solution of the stupid solution is decolorized with charcoal. Isopropanol was added to form a yellow crystal. The crystals were isolated by filtration and weighed 4 · gram (1 3 · 1 mmol) 50% yield. The melting point is (DSC). The nmR and mass spectrometric analysis was consistent with the structure of 1,3_bis(p-acetylethynyl)benzene. Τι This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1247757 A7 " ---------Mi______ V. Invention description (45) Ρ·1^: Double (stupid base) Acetylene tomb) Moss (Compound p) The compound is prepared in the same manner as the compound, but 1,3 -dibromobenzene is used in place of 1,3 -dioxabenzene. Q·1^,4-three (stupidyl ethynyl) stupid (compound 〇) 1,2,4-tribromobenzene (20.0 g, 〇·〇635 mol) present in triethylamine (250 ml) The slurry was degassed by diffusion at ν 2 for 30 minutes. Add triphenylphosphine (2.2 g, 0.00836 mol) followed by Pd(〇Ac) 2 (0.1 g, 0.000445 mol) and Cui (0.3 i5 g, 0·00165 mol) to form a mixture Heat to reflux. Phenylacetylene (20.1 g, 〇.197 mol), which was diffused with Ν2 for 30 minutes, was added dropwise over 10 minutes. The reaction mixture was heated to reflux overnight. The reaction mixture was cooled to ambient temperature and concentrated to dryness. The residue was poured into acetone (200 ml) and water (3 ο mM) was slowly added and stirred. The precipitate was taken out and washed with methyl alcohol (500 ml) and then with water (2 ml). The product was washed, dried, to give a pale brown solid which was further recrystallised from EtOAc/MeOH to yield a white solid, yield 60% NMR analysis consistent with the desired material. The reaction diagram is as follows: Pack----------Book-----I--- (Please read the notes on the back and fill out this page)

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumption Cooperative, Printing I

Br

Br

Br

PhCCH

Pd(OAc) PPh3 Cul Et3N .Ph Ph' ~Ph -48 - This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1247757 A7 --------B7_______ V. Description of invention (46) Example 2 Mixed gold compound (M) (316 mg, FW=762, 0.415 mmol) of worm gold and 1.3-糁ί笑 acetylene oxime phenyl ethynyl) jasmine (Compound G) ), compound (0) (72 mg, FW = 278, 〇 · 259 mmol) and compound ((}) (44 g, 0.1163⁄4 mol) in ι,3-diisopropylbenzene (4 ml) The mixture was refluxed for 42 hours. The dark solution turned red and became viscous. The solution was spin coated on the wafer and cured at 400 ° C for 1 hour to form a film. The reaction was as follows: i 1 ----- ----I ! (Please read the notes on the back and then fill out this page) Order rll·-----Line of Economics Department Intellectual Property Bureau Staff Consumer Cooperatives PCT 97 2 X 10 2 /IV Grid A4 S) N (C Pre-standard country country with moderate scale Zhang Zhangyi paper 1247757 A7 B7 V. Invention description (47)

F

Ph

(Please read the notes on the back and fill out this page.) Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs.

This paper scale applies to Chinese national standards (CNS>A4 specification (210X297 mm) -50 - 1247757 A7 B7 V. Description of invention (48) Example 3 From compound Μ and 4,4'- 别 (Momo ethynyl group V- A compound of a compound (Μ) (316 mg, 0.415 mmol), a compound (a compound of bismuth) and 4,4',4"-tris(m-ethynyl-o-triphenyl) 1) (107 mg, FW = 430, 0.249 mmol) and compound (N) (88 mg, FW = 530 '0.116 mmol) in 5 ml of 1,3-diisopropylbenzene for 48 hours. The yellow viscous solution was cooled to room temperature and spin coated on the wafer. The polymer was cured at 400 ° C for 1 hour to form a film. The reaction system is as follows: ----------- Installation -------- Order --------- (Please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative - Print this paper scale for Chinese national standards (CNS) A4 specification (210 X 297 mm) ΤΓ 1247757 A7 B7 V. Description of invention (49) Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs (I)

This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 52 1247757 A7 B7 V. Description of invention (5G: Example 4 insect ^3,-(oxygen double (2.4·5-; Two thin sounds!) (Compound Κ) retanning, - bis (V. sylvestris) bis-methyl ether (compound oxime) to prepare polymerized τ 3,3'-(oxydi-1,4-phenylene) Bis(2,4,5-triphenylcyclopentadienone) (15.0000 g, 0.019158 mol), 4,4,-bis(phenylethynyl)diphenyl ether (7.0974 g '0.019158 mol) And hydrazine-methylpyrrolidinedione (51.60 g) was added to a 250 ml round bottom flask. The flask was attached to a nitrogen inlet and the magnetically mixed solution was heated to 200 ° C in an oil bath. 200 ° C 19.5 hours Thereafter, gel permeation chromatography showed Mn of 1551 and 2, which was relative to polystyrene standards. The solution was cooled and bottled. A portion of the solution was poured into a syringe and passed through a 1.0 micron syringe filter. It was filtered on a 4" germanium wafer. The wafer was spin coated at 2000 rpm for 60 seconds under a heat lamp for heating the wafer. The coated wafer was placed on a hot plate set at 90 ° C for several minutes. Yuan is placed Nitrogen stripping furnace, which was gas-solidified at room temperature for 45 minutes, then heated to 400 ° C at 10 ° C / min, held at 400 ° C for 1 hour, and then allowed to cool to room temperature. The material is coated with polyphenylene polymer. When the solution is applied to the gap filling structure of the submicron gap and solidified, the solution is found to completely fill the gap. Example 5 3,3'-(oxydi-1,4-a stupid) Bis(2·4·5-trisylcyclopentadienone) (compound 1〇, 4,4′-bis(methylethynyl)diphenyl ether (compound), and 1,3, 5-tris(phenylidene acetylene) stupid (compound G) Prepare a polymer in a 100 ml 3-neck round bottom flask with 3,3'-(oxydi-1,4-phenylene) bis (2,4) , 5-triphenylcyclopentadienone) (10.0000 g, 0.01277 mol) This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) • f. > Pack----- ---Book---.------. (Please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Officer X Consumer Cooperation Du-Print 1247757 ΚΙ

5. Description of the invention (51), 4,4'-bis(phenylethynyl)diphenyl ether (2·366 g, 0〇〇6386 mol), 1,3,5-tris(phenylacetylene) Base) benzene (2.4170 g, 0.006386 mol) and hydrazine-methyl hydrazine diketone (34.5 liters). The flask was attached to a nitrogen inlet and the magnetically stirred solution was heated to 2 ° C in an oil bath. After 11 hours at 200 ° C, the solution was cooled and bottled. A portion of the solution was poured into a syringe and transitioned to a 4 inch stone solar cell via a 1 micron left shot filter. The wafer was spin coated at 2 rpm for 60 seconds. The coated wafer was placed at a setting of 9 Torr. 2 minutes on the hot plate. The wafer was placed in a nitrogen stripping furnace, solidified by stripping at room temperature for 45 minutes, then heated to 400 ° C at 10 ° C / min, kept at 400 ° C for 1 hour, and then allowed to cool to room temperature. The formed wafer is coated with a polyphenylene polymer. When the solution was applied to a gap-filled structure with submicron gaps and solidified, the solution was found to completely fill the gap. The cured polymer is insoluble in methylpyrrolidinedione. Example 6 Fish 3,3'-(oxydi-M-yamyl)bis(2·4·5-tris-pyl-cyclopentanone) (compound Κ), 1,3'-bis (stupyl acetylene)芏η厶铷 and 1,3,5-tris(phenylethynyl) stupid (compound (7) prepared in a 25 ml Schlenk tube, adding 3,3'-(oxydi-1,4-phenylene) Bis(2,4,5-triphenylcyclopentadienone) (2.0000 g, 0.002554 mol), 1,3,. bis(phenylethynyl)benzene (0.4740 g, 0.001703 mol), 1, 3,5-tris(phenylethynyl)benzene (0.4834 g, 0.001277 mol) and N-decylpyrrolidinone (6.9 ml). The tube was attached to a nitrogen inlet and the solution was mechanically stirred in an oil bath. Heated to 200 ° C. After 20 hours at 200 ° C, gel permeation chromatography indicated] \ ^ = 1463 and 1 ^, 2660, which is equivalent to polystyrene standards. The size of the paper is applicable to the Chinese National Standard (CNS) A4 size (210 X 297 mm) (Please read the note on the back and fill out this page) One-------------------: Ministry of Economic Affairs Intellectual Property Office staff Consumer Cooperatives Printed 1247757 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed - A7 B7 V. INSTRUCTIONS (52) The liquid is cooled to room temperature and bottled. A portion of the solution is poured into a syringe and filtered through a 1·〇 micron syringe filter onto a 4” germanium wafer. Heating by a heated crystal cell Under the lamp, the wafer was spin coated at 2000 rpm for 60 seconds. The coated wafer was then placed on a hot plate set at 90 ° C for 2 minutes. The wafer was placed on a nitrogen stripping furnace. It was cured in 20 minutes, then heated to 400 ° C at 10 ° C / min, held at 400 ° C for 1 hour, and then cooled to room temperature. The formed wafer was coated with polyphenylene polymer. _3,3'-(gas di-1,4-yamyl) bis(2,4,5-triphenyl hydrazide) (compound K) and 1,3,5-three (stupid) Acetylene) Molybdenum (Compound Q) Preparation of a ruthenium solution in a Pyrex® 1 liter three-necked round bottom flask that has been wetted with deionized water and HPLC grade acetone, adding low ions 3,3, _ (oxygen) Diq,4_phenylene)bis(2,4,5-triphenylcyclopentadienone) (100.0 g, 0.128 mol) low-ion 1,3,5-tris(phenylethynyl)benzene 48.3 grams, 0.128 moles) and electronic grade N-曱 base Diketone (346 g). The flask was attached to a nitrogen/vacuum inlet. The magnetically agitated solution was degassed by vacuum and refilling with nitrogen five times. Then, nitrogen flowed through the head space of the flask and flowed through the inorganic oil foamer. The solution was heated to an internal temperature of 200. (: After heating the solution for 8.5 hours, it was cooled and transferred to a bottle made of tetrafluoroethylene. The final product was analyzed by gel permeation chromatography to show 1\411 = 1498 and <RTI ID=0.0>> The final solution was analyzed by reverse phase chromatography to show that the residual 3,3'-(oxybis-1,4.phenylene)bis(2,4,5-triphenylcyclopentadiene) content was 1 · 8 by weight. %. The final solution showed a sodium content of 52 ppb, a potassium content of 190 ppb, a palladium content of 90 ppb, and a bromine content of 2.4 ppm. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Please read the notes on the back and fill out this page} tr..—i---- 1247757 The Ministry of Economic Affairs, Central Bureau of Standards, Staff Consumer Cooperatives, Printed A7 B7 V, Invention Description (53), Moth Content 0.6 ppm, Gas Content 2.4 ppm. Example 8 Example 7 Coating and Curing the Plug Polymer Solution Decane as the basic adhesive accelerator (AP8000 available from The Dow Chemical Company) was first coated (200 mL of a 300 mm wafer) The surface of the wafer; slowly rotated to disperse it over the entire surface; allowed to stand for 2 seconds; finally spin-dried at 3000 rpm for 10 seconds. The polyphenylene condensate solution prepared in Example 7 was prepared by a high precision pump/filter system Millipore Gen_2 coating (4 ml of 200 mm wafer) on the surface of the wafer coated with the adhesion promoter, at which time the wafer was rotated at 750 rpm. Immediately after coating the polymer solution, the wafer rotation was accelerated to 2000 rpm and keep this spin rate for 20 seconds During the application of the polymerase solution, a continuous stream of 1,3,5-trimethylbenzene is applied to the back side of the wafer. After spin coating the wafer with the polymer solution solution, the crucible is dried on a hot plate at 70 ° C. 20 seconds. After the dry baking step, 2 ml to 5 ml of the edge beads of the coating are removed in a continuous stream of 1,3,5-trimethylbenzene while the wafer is rotated at 2000 rpm, either by the back side or The coating was applied directly from the top of the edge. After removing the edge beads, the polymer was further polymerized on a hot plate at 325 ° C for 90 seconds under a nitrogen blanket. Then, the film was hot-filled at 45 ° C under nitrogen. The mixture was crosslinked for 6 minutes in a 2 minute or at a 450 ° C nitrogen stripping furnace. The film had a glass transition temperature greater than 450 ° C as measured by dynamic mechanical analysis. > (Please read the back of the precautions on this page - this page) The standard paper size is applicable to China National Standard (CNS) A4 specification (21〇X297 mm) 56 1247757 A7 B7 V. Invention description (54) The first table of the Ministry of Economic Affairs, Central Bureau of Standards, employee consumption cooperative printing

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(Please read the note on the back first to write this page) 1113⁄4 Loading · •, the standard paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -57 - 1247757 A7 B7 V. Invention description (55) I Form (read) Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs

κ (Please read the note on the back to write this page) Pack * - Book paper size applies to China National Standard (CNS) A4 size (210X297 mm) -58 - 1247757 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Print A 7 B7 V. Description of invention (56) Table I (read)

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This paper scale applies to Chinese National Standard (CNS) A4 specification (21 OX 297 mm) -59 · 1247757 A7 B7 V. Description of invention (57) Because the above compound preparation procedure is carried out using standard chemistry, and it is known that slightly different reactants may be used. Requires slightly different reaction parameters from other reactions. It can be understood that the reaction parameters are slightly parameterized (such as using an excess of reactants, using a catalyst, using a temperature slightly above or below room temperature, for example, and/or high). Rate mixing and other conventional variations are within the scope of the invention. Printed by the Consumer Standards Agency of the Central Bureau of Standards of the Ministry of Economic Affairs 60 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm)

Claims (1)

The first special shot (four) applied for a patent _ amendment this 94 years ... 曰 1. - a polyfunctional compound of the following formula: 0 (Please read the note on the back and then fill out this page) « Installed by the Ministry of Economic Affairs, the Intellectual Property Office, the Consumer Cooperative, which prints the aromatic part in which R and R2 are either unsubstituted or inert, and Ar4 is not An aromatic moiety that is replaced or inertly substituted. An oligomer, an uncured polymer or a cured polymer containing the reaction product of the polyfunctional compound of claim 1 of the patent. 3. A polymeric, uncured or curable polymer comprising at least one reaction product comprising at least one cyclopentadienone moiety and at least one acetylene moiety. 4. The oligomer, uncured polymer or cured polymer of claim 3, which is based on 4-(4-phenylethynyl)phenyl)-2,3,5-triphenyl The reaction of cyclopentadienone or 4-(4-ethynylphenyl)-2,3,5-triphenylcyclopentadiene is formed. 5. A polyfunctional compound of the following formula: The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ··61- 1247757 0^888 ABCD VI. Patent application scope Each of them is anthracene or unsubstituted or inertly substituted, and each of Ar is an aromatic moiety which is not substituted or an aromatic moiety which is inertly substituted. 6. A polymeric, uncured or cured polymer which is formed by reacting a compound of claim 5 of the scope of the patent application. 7. A polymerized, uncured or cured polymer as claimed in claim 6 which is based on 3,4-bis(4-phenylethynyl)phenyl)-2,5-diphenyl. The cyclopentadienone or 3,4-bis(3-phenylethynyl)phenyl)-2,5-diphenylcyclopentadienone is reacted to form. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 62- This paper scale + _ group (CNS) A4 specifications (210 χ 297 public Chu)