TWI243182B - Polyfunctional compound of cyclopentadienone group and polyfunctional compound of aromatic acetylene group - 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

1243182 'A7 Printed invention description printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (This invention relates to polyphenylene polymers and polymers and methods for their preparation and use. These oligomers can be used in the preparation of microelectronics as Dielectric Resin. This application is part of a serial case No. 711,838, which was filed on September 10, 1996 and is hereby incorporated by reference. Polymer dielectrics can be used as Insulation layers between various circuits and layers in circuits in microelectronic devices of integrated circuits, multi-chip components and laminated circuit boards. The microelectronics manufacturing industry is now shifting to smaller geometries in its devices, making it more dynamic Low and faster speeds. As conductor wires become thinner and more tightly packed, the dielectric requirements between this conductor become stricter. Although polymer dielectrics are compared to inorganic dielectrics such as silicon dioxide The dielectric usually provides a lower dielectric constant, which often presents the challenge of handling polymer properties during preparation. For example, to replace silicon dioxide as a dielectric in integrated circuits, the dielectric needs to be resistant to metallization and Annealing step Intermediate processing temperature. Preferably, the dielectric material needs to have a glass transition temperature greater than the processing temperature. The dielectric also needs to maintain the desired properties under the conditions of use of the device. For example, the dielectric should not absorb water, which will cause Increased dielectric constant and potential corrosion of metal conductors. For some compacts, when coated by traditional coating techniques such as spin coating, the oligomers preferably need to be planarized and gap-filled on the surface. Today, polyimide resins are one of the materials used as thin film dielectrics in the electronics industry. However, polyimide resins can absorb water and hydrolyze, which can cause circuit corrosion. Metal ions can migrate into the dielectric polyimide layer It requires a barrier layer between the metal wire and the polyimide dielectric. Polyimide will exhibit poor performance. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297).

4 1243182

Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2) The planarization and gap filling properties. Non-fluorinated polyfluorene imines will exhibit high dielectric constants.

Kumar and Neenan in Macromolecules (1995, 28), pages 124-130, disclose several polyphenylenes made from dicyclopentadienone and diacetylene. It teaches that polyphenylene has the potential to be a photo-definable organic dielectric. Wrasidlo Spot Augl in J. Polym. ScL, Part B (1969), 2 (7), 519 ~ 523, revealing 1,4-bis (styryl) benzene and 3,3 '-(1,4-sub Copolymer of phenyl) -bis (2,4,5-triphenylpentadione). It reports that a soluble yellow, non-melting polymer is available.

The materials described by Kumar and Wrasidlo are soluble, but may not be suitable for certain uses (such as spin coating to fill gaps) because this material is polymerized to deplete the cyclopentadienone moiety, which provides a relatively high Molecular weight: This molecular weight may be too high to be applied by spin coating on a surface of a project containing gaps filled with a dielectric. Based on the reported glass transition temperature, these materials may not be able to resist the desired processing of the inner dielectric within 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 methods for preparing crosslinkable polyarylene compositions for the production of glassy carbon. Polyphenylene is prepared by polymerizing 1 · bromo-4-chain benzene to form brominated polybenzen, and then coupling a substituted phenylacetylene (such as phenylethynylphenylacetylene) to the residual bromine. Polyphenylene has a melting point of about 200 ° C before crosslinking. It is expected to provide polymer dielectrics to the microelectronics manufacturing industry, which can provide reliable low dielectric constant, high thermal stability and high glass transition temperature, and this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) )-^ _ {Please pay attention to the notes on the back of K1 # before filling in this page. Order 12323182 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) The better one can be coated by spin To apply, while planarizing the pattern surface and filling the gaps. In a first aspect, the present invention is an oligomer, an uncured polymer or a cured polymer, which comprises one or more polyfunctional compounds containing two or more cyclopentadienyl groups and at least one containing two or more aromatics. The reaction product of an ethynyl polyfunctional compound, at least some of the polyfunctional compounds contain three or more reactive groups. The reactive group used herein is defined as cyclopentadienone or ethynyl. The polymer used herein is defined as the reaction product of two or more monomer units of the present invention, which will be gap-filled (ie, rectangular grooves of 1 micron depth and 1/2 micron width), and upon curing, Will not leave empty. The uncured polymer as used herein is defined as the reaction product of the monomer of the invention, which is no longer aging and filled, but contains a large amount of unreacted cyclopentanone or ethyl functional group. The reaction product of the monomer of the invention does not contain a large amount of unreacted cyclopentadione or acetylene functional groups. Large amounts of unreacted cyclopentadienone or acetylene functional groups require that the moiety be reactive to further promote polymerization. One feature of the present invention is 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 ethynyl groups, at least some of which are The functional compound contains three or more reactive groups. One of the advantages of this reaction product is that it can gap-fill and planarize the surface of the die, and has high thermal stability, high glass transition temperature, and low dielectric constant during curing. In the second aspect (preferred aspect), the present invention is an agglomerate, uncured!丨 (Please read the precautions on the back before filling in this page) Ding

This paper size applies to China National Standard (CNS) A4 specification (210X297 public love) 6 1243182

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) A polymer or cured polymer containing one or more polyfunctional compounds containing two or more cyclopentadienone groups and one or more Reaction products of polyfunctional compounds containing two or more aromatic ethynyl groups, at least some of which contain polyacetyl compounds containing aromatic ethynyl groups containing three or more ethylidene groups. A feature of the second aspect of the present invention is the reaction of at least one polyfunctional compound containing two or more cyclopentadienone with at least one polyfunctional compound containing two or more aromatic ethynyl Products, at least some of which contain an aromatic ethynyl group. The multifunctional compound contains three or more ethyl block groups. One of the characteristics of this reaction product is that it can gap-fill and planarize the surface of the solution, and has high thermal stability, high glass transition temperature, and low dielectric constant during curing. The high thermal stability, high glass transition temperature, low dielectric constant, and ability to fill gaps and planarize surfaces make the composition of the present invention suitable for use as a polymer dielectric in microelectronics preparation. In particular, the combination of low dielectric constant, high thermal stability, and high glass transition temperature allows the use of the composition of the present invention as an interlayer dielectric in integrated circuits. The preferred ones are the polymer and polymer of the present invention and the corresponding starting monomers: I 'An oligomer and a polymer having the general formula: [A] w [B] z [EG] V where A It has the following structure: This paper standard is suitable for financial standards (CNS) Α4 specification (2lQx297 public broadcasting) --------- ^ ------ 1T ------ 0 (please first Μ Read the notes on the back and fill out this page again) 1243182 ', A7, B7 V. Description of the invention (

• R ”and B has the following structure: 1 J ^ 丨 卜 — h-ip! (Please read the precautions on the back before filling this page)

R 』

R 丨 Ar R1 R Order Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs where EG is an end group with one or more of the following structures: EG =

This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 1243182 Λ: Β7

Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs JP System 5. Description of the invention (6 where R and R2 are each Η or unsubstituted or inertly substituted aromatic parts, and Ar1, At * 2 and Ar3 are each unfinished A substituted aromatic moiety or an inertly substituted aromatic moiety, where M is a bond and y is an integer of 3 or greater, ρ is the number of unreacted ethynyl groups in the known parent unit, and 1 * is known Less than the number of reaction groups in each unit, and p + r = yl, Z is an integer from 1 to 1,000; w is an integer from 0 to 1000, and V is an integer from 2 or more. Polymers and polymers can be prepared by reacting dicyclopentadienone, an aromatic acetylene containing three or more acetylene moieties, and optionally a polyfunctional compound containing a diaromatic ethyl moiety. This reaction can be expressed by the reaction of compounds of the following chemical formula, (a) The dicyclopentadienone of the chemical formula is shown below:

R1 (b) is the polyfunctional acetylene R2 ~ s =: j ^ Ar3 (c) and the selectivity is the diacetylene of the following formula: R2-rz =-Ar2-^ ξξ: R2 where R1, R2 Ar1, Aγ2, Ar3 and y are as defined above. Aromatic moieties are defined to include phenyl, multi-j, and fused aromatic moieties. Inert substitution means taking 彳 Gorky as the basic size of cyclopentyl ketone and ethyl methacrylate paper. Chinese national standard (CNS) A4 specification (210 X 297 mm) is applied. — ^ ----- ----- ^ --------- (back of ir-c ^ ti; fill in this page for χφί matters) 1243182

AT ___ —__ B7 ____ 5. Description of the Invention (7) The reaction is inert and it is not easy to react with environmental species (such as water) under the conditions that the cured polymer is used in the microelectronic device. This substituent includes, for example, F, Ch Γ, -CF3, -0CH3, -OCF3, -0-Ph, and 1 to 8 carbon atoms, and 3 to 8 cyclohindering groups. ·, Which can not be replaced by the inert aromatic part include: c Xu Xianwen 许 Note on the back then fill in {if 第 j

'm m,., 1T.n I— m printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

1243182 A7 B7 V. Description of the invention (8)

Or where Z may be: -0-, -S-, alkylene, -CF2, -CH2-, -0, -CFr, perfluoroalkyl, perfluoroalkoxy,

R3 -k- 1 〇II -P- -La CF3 CF3-丨 1 ------ 1T ------ ^ (Please read the precautions on the back before filling in the page) cf3 Central Standards of the Ministry of Economic Affairs Bureau employee consumer cooperative printed CH,

Ph CH, CH, CH,

Ph

Ph, or * CF, where each R3 is -H, -CH3, _CH2CH3,-(CJi2) 2CH3 or Ph. Ph is phenyl. '' This paper size applies to China National Standards (CNS) A4 specification (210X297 mm) 11 1243182 Λ7 B7 V. Description of the invention (9) II. Polyarylene oligomers and polymers of the following general formula

R-

-R (Baked before visiting the back of the page before filling out this page) β

Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs where R1, R2, Ar1 and Ar2 are as defined above; X is an integer from 1 to 1000. Preferably, X is 1 to 50, and more preferably 1 to 10. This oligomer and polymer can be prepared by the reaction of dicyclopentadienone with diacetylene of the following general formula.

This paper size is in accordance with China National Standard (CNS) A4 (210 x 297 mm) 1243182 A7 B7 V. Description of the invention (10 III, where R1, R2, ΑΓ1 and Αγ2 are as defined previously. The chemical formula shown below Polymers and polymers

Where Ar4 is an aromatic moiety or an inertly substituted aromatic moiety, Ri, R2, and X are as defined above. The cyclopentadienone functional group and the acetylene functional group of a polyfunctional compound of the following formula can be used. Reaction prepared,

R Ar Production by the Central Bureau of Standards

R wherein R1, R2 and Ar4 are as defined above. IV. Polyphenylene oligomers and polymers represented by the following chemical formulas 13 This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 1243182 Α7 Β7 5. Description of the invention (11)

Where EG is represented by any of the following chemical formulas: 0

Or or

Where Ri, R2, eight] * 4 and χ are as defined above, which can be prepared by reacting a cyclopentadienone functional group of a polyfunctional compound of the following formula with an acetylene functional group, 1 is called -bu — J9!-(Please fill in this page before the notice on the back of KTt) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

R 〇

R1, R2 and Ar4 are as defined above. The polyfunctional compound I containing two or more aromatic cyclopentadienone moieties can be used to condense the reaction of diphendione and benzophenone by using traditional methods. CNS) A4 size (210X297 mm) 14

1243182 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (12). Exemplary methods are disclosed in Macromolecules of Kumar et al., 1995, 28 ^, 124-130; Ogliaruso et al. J. Org. Chem., 1965, 30 ^, 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. Aromatic compounds can be iated and then reacted with a suitably substituted acetylene in the presence of a catalyst for arylethynylation in order to replace the acetylene with a substituted acetylene compound. Once the polyfunctional compound monomer is made, it is preferably purified. In particular, metal and ionic species are removed in the preparation of dielectrics for organic polymers. For example, a polyfunctional compound containing an aromatic ethynyl group can be washed with water, an aliphatic hydrocarbon solvent, then dissolved in an aromatic solvent and filtered through a purified silica gel. This treatment removes residual acetylenated catalyst. Additional recrystallization can help remove unwanted impurities. Although not intending to be limited by theory, it is believed that polyphenylene oligomers and polymers are formed by the reaction of a mixture of cyclopentadienone and acetylene in a solution when heated by the reaction of Diels Alder of cyclopentadione and ethynyl. Of it. These oligomers may contain cyclopentadione and / or acetylene end groups and / or pendant groups. When this solution or an object coated with this solution is further heated, additional bond extension will occur via the Diels Alder reaction of the residual cyclopentadienyl end group and the residual ethynyl group, resulting in an increase in molecular weight. Depending on the temperature used, the reaction of ethynyl groups with one another also occurs. The oligomers and polymers are characterized by a structure having cyclopentadienone and / or acetylene end groups and / or side groups. In general, the end group is based on the size of the paper used for the reaction. It is applicable to China National Standard (CNS) A4 (210 X 297 mm) T5 ------- Γ --- ^ --------- (ί, νΓ-^ 'ίτ Note on the back of this page, please fill out this page again) 1243182 Printed by A7 _B7___, Consumer Co-operation, Central Standards Bureau, Ministry of Economic Affairs The relative concentration of acetylene functional groups depends on the stoichiometric excess of cyclopentadienone functional groups to generate more cyclopentadienyl end groups, and the stoichiometric excess of Diels Alder reactive acetylene functional groups produces a larger proportion of acetylene. End group. The preferred embodiment of the present invention is characterized in that the polymerization reaction is stopped before all the cyclopentadione portions are reacted. The oligomer can then be applied to the surface before polymerization is carried out to allow the remaining cyclopentadienone to partially react. In this state of oligomerization, when applied to the surface of the case, the agglomerates can be planarized and gap-filled. Preferably, at least 10% of the cyclopentadienone portion is unreacted. At best, at least 20% of the cyclopentadienone portion is unreacted. The percentage of unreacted cyclopentadienone fraction can be determined by spectroscopic analysis. The cyclopentadienone moiety is highly chromatic in the visible spectrum, it has a distinct red or purple color, and it changes color when the cyclopentadienyl's moieties react. As used herein, planarization means that isolated features can be planarized by 70% or more, preferably 80% or more, and most preferably 90% or more. The percentage or degree of planarization is calculated by the following equation ... The percentage of planarization = (l-ts / tm) X 100 When the polymer layer is coated on the isolated square line, the average thickness of 2 microns is 1 micron and 1 micron 'and ts is the height of the polymer or polymer on the average height of the polymer or polymer, and U is the height of the feature (1 micron). An example of the use of this definition is, for example, Proceedings of EEEE, Vol. 80, No. 12, December 1992, p. 1948. Although it is not intended to be limited by mold theory, the preparation of polyphenylene polymers is generally expressed as follows: Standard (CNS) A4 specification (210x297 mm)-·-{Please read the notes of K first * (Fill in this page again) ΑΨ Order

1243182 A7 B7 V. Description of the invention (14)

Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

R1, R2, Ar1, Ar2 and χ are as defined above. Furthermore, although the structure is not specifically shown, the carbonyl bridge species can be stored on this paper. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) 17 1243182 A7 ______ 5. The invention description (15) lies in the prepared The agglomerates depend on the specific monomers used and the reaction conditions. Upon further heating, the carbonyl bridged species is essentially completely converted to an aromatic ring system. When more than one acetylene-containing monomer is used, the oligomers and polymers formed are random, although the structure drawn may suggest that blocks are formed. A Diels Alder reaction between cyclopentadienone and an acetylene functional group will occur to form a para or meta attachment on the benzene ring. Printed by Shelley Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs An inert organic solvent at the reaction temperature may be used. Examples of suitable solvents include 1,3,5 · xylene, pyridine, triethylamine, N · methylpyrrolidone (NMP), methylbenzoate, ethyl Parabens, butylbenzoates, cycloalanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclohexylpyrrolidone and ethers or hexamethylene ethers, such as diphenylfluorenyl ether, bis (2 -Methoxyethyl) ether, tris (2-oxoethyl) 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-xylene xylene, benzene, dipropylene glycol monomethyl ether acetate, dichlorobenzene, propylene carbonate, naphthalene, Benzyl ether, butyrolactone, diamidinoacetamide, dimethylamidamine and mixtures thereof. The preferred solvent is 1, 3,5-Trimethylbenzene, N-methylpyrrole, NMP, τ-butyrolactone, diphenyl ether and mixtures thereof. In addition, a single vessel can be reacted in one or more solvents at elevated temperatures, The resulting oligomer solution can be cooled and formulated with one or more additional solvents to facilitate processing. In another method, the monomers can be reacted in one or more solvents at elevated temperatures to form Polymer, which can then be deposited on the paper by applying the Chinese National Standard (CNS) A4 specification (210X 297mm) " I 一 7Z— ^

Consumers' cooperation with the Central Standards Bureau of the Ministry of Economic Affairs, Du Duan made 1243182, Invention Description (Isolated in a non-solvent or by other solvent removal methods, resulting in a substantially solvent-free agglomerate. These isolated agglomerates It can be re-dissolved in one or more different solvents, and the resulting solution can be used for processing. The conditions under which the polysigma reaction proceeds most favorably depend on different factors, including special reactants and solvents. Generally, the reaction is based on non-oxidation. It is carried out under an atmosphere (such as' nitrogen or other inert gas covering gas). The reaction can be carried out concisely (without solvents or other diluents). However, in order to ensure a homogeneous reaction mixture and a mild exothermic reaction at this temperature, it is usually used Inert organic solvents 'such as those mentioned above, the most advantageous time and temperature for the use of β in the reactant will depend on the particular monomer used, especially its reactivity, the particular oligomer or polymer and solvent desired. Generally' The reaction of the agglomerates is between 15 ° C and 250 ° C. The temperature is between 60 minutes and 48 hours. At this time, the agglomerates can be separated from the reaction mixture or used for Cover the surface. Additional chain extension (increase) can be performed at 100. (: to 475. (: at a temperature, preferably 200X: to 450t, for 1 minute to 10 hours, more preferably 1 minute to 1 Hours. Uncured or cured polymers can be used to coat surfaces by casting from solvents. Although this polymer may not be adequately gap-filled or planarized, it can still be used in metal mounting methods. Can be most advantageous The concentration of the monomers used in the organic liquid reaction medium depends on various factors, including the specific monomers and all organic liquids and the polymers and polymers being prepared. Generally, cyclopentadienone is used in single systems. The stoichiometric ratio to q 垮 is from 1: 1 to 1: 3, preferably from 1: 1 to 1: 2. The polymer or polymer can be directly cast in thin and coated with the coating. Cover or this paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 19 --------- ¾ ------ 1T ------ line (please read the back first (Notes on this page, please fill in this page) 1243182 A7 ____B7_ V. Description of the Invention (I7) 'Pour into non-solvent to precipitate oligomer or polymer. Water, Alcohols, ethanol, and other similarly polar liquids are typically non-solvents that can be used to precipitate oligomers. Solid oligomers or polymers can be dissolved and treated with a suitable solvent. If the polymer or polymer is fixed When the type is obtained, it can be further processed using traditional compression molding technology or melt spin, casting or extrusion technology, provided that the solid precursor needs to have a sufficiently low glass transition temperature. More generally, the polymer or The polymer is directly treated by the organic liquid reaction solution, and the invasion point of the present invention is 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 coating and the solvent is evaporated. The molecular weight increases (chain extension or enhancement), and in some cases cross-links to form the final polymer, which occurs when it is subsequently exposed to a sufficiently high temperature. The polymers of the present invention can be used as one or more insulation or dielectric layers in a single or multilayer electrical connection construction for integrated circuits, multi-chip assemblies or flat panel displays. The polymers of the present invention can be used as such or in combination with other organic polymers or inorganic dielectrics such as silicon dioxide, silicon nitride or silicon oxynitride as the underlying dielectric. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) For example, the polymer of the present invention and the coating of the polymer (such as used to prepare continuous structures on electronic thin parts) Electrical insulation coating) can be made by spin casting a film-like organic polymer solution of polymer or polymer or coating the substrate with this solution, then the solvent is evaporated and the oligomer or polymer is exposed At a temperature sufficient to allow the oligomer or polymer to undergo a higher molecular weight, and in the best case, a crosslinked polymer with a higher glass transition temperature is formed. The polymer β of the present invention is particularly useful as an integrated circuit (such as silicon or this paper standard applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) "20--1243182

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (18) The low dielectric constant insulation material in the continuous structure of the gallium arsenide producer. Integrated circuits typically have multiple layers of metal conductors separated by one or more insulating materials. The polymer material of the present invention can be used as insulation between individual metal conductors and / or between conductor layers of a connection structure within the same layer. The polymer of the present invention can also be used in combination with other materials, such as SiO2 or Si3N4, in a staggered continuous structure. For example, the polymers and polymers of the present invention can be used in the preparations taught in U.S. Patent No. 5,550,405; U.S. Patent No. 5,591,677 and Hayashi et al. 1996 Symposium on VLSI Technology Digest of Technical Papers, pages 89-89, Integrated circuit device method. The polymers and polymers of the present invention can replace the resins disclosed in BCB or other methods of disclosure. The oligomer, uncured polymer or polymer of the present invention can be used as a dielectric in the above-mentioned teaching method or a similar method to prepare an integrated circuit object, the object comprising an activated substrate with a transistor and a metal wire with a denial. The electrical connection structure (a small part of which is separated by the layer or region of the composition of the present invention). The polymer of the present invention can also be used as a planarization material, such as silicon wafers used in semiconductors to prepare 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 make any rough surface on the substrate surface flat. Such methods are exemplified in "Microelectronic Applications of High-Tech Polymers" such as Bowden et al., American Chemical Society, 1987, pp. 261-269. In the preparation of microelectronic devices, relatively thin non-missing films (usually the thickness of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 21 .- ^ ------ 1T ----- -Line (please read the precautions on the back before filling this page) 1243182 A7 B7 V. Description of the invention (19) '0.01 to 20 microns, preferably 0.1 to 2 microns) can be deposited on the surface of the substrate, for example , Silicon, silicon-containing materials, silicon dioxide, aluminum oxide, copper, silicon nitride, aluminum nitride, aluminum, quartz, and gallium arsenide. Coatings are generally prepared from oligomer solutions having molecular weights of, for example, 3000 Mn or less and 5200 Mw or less, which are based on various organic solvents such as xylene, 1,3,5-trimethylbenzene Polymers or polymers that dissolve dysprosium in N, NMP, τ · butyrolactone, and n-butyl acetate can be cast on the substrate by ordinary spin and spray coating techniques. The thickness of the coating can be It is controlled by changing the solid percentage, molecular weight, solution viscosity, and spin rate. The polyphenylene polymer or polymer in the present invention can be coated by dip coating, spray coating, and extrusion coating. It is better to use 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 removed from the surrounding air. Water vapor absorbs water. When dissolving in NMP, it is necessary to protect the solution from moisture, air, and cast film in a low humidity environment. When using NMP as a solvent, it is better to control the relative humidity below 30%. And the temperature is controlled at 27 ° C or more. The coating can be heated by one or more heat after coating. , Furnace, or a mixture of these tools. Adhesion promoters printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (such as those based on Shiyaki chemistry) can be applied to polyphenylene polymers or polymer solutions. Before coating, it can be coated on the substrate, or directly applied to the solution. The polymer and polymer of the present invention can be used for the "inlay" metal-inlaid negative-layer layering scheme for the preparation of continuous structures of integrated roads. The type wire and tube are known in the industry. For example, please refer to US Patent No. 5,262,354 22 (Please read the precautions of Kg before reading this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297) ) 1243182 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (20) and Case No. 5,093,279. The pattern of the material can be a typical ion etching process using compounds containing oxygen, argon 'nitrogen, helium, carbon dioxide, and fluorine Or a mixture of these gases with other gases, using a photoresist "soft cover" (such as epoxy novolac) or an inorganic "hard cover" (such as SiO2, Si3N4 or metal) The photoresist is for this purpose. Polymers and polymers can be deposited with Al, A1 alloy, Cu, Cix alloy, gold, silver, W by physical vapor deposition, chemical vapor deposition, evaporation, electroplating, electroless deposition and other deposition methods Other general metal conductive materials (as wires and plugs) are used for bonding. Additional metal layers of basic metal conductive materials, such as tantalum, titanium, tungsten, road, cobalt, its alloys, or its nitrides, can be used for Fill holes, promote metal filling, promote adhesion, provide barriers, or improve metal reflectivity. Depending on the preparation structure, the metal or dielectric material of the present invention can be removed or planarized using chemical and mechanical polishing techniques. Activated or blunt Multi-chip modules on a solid substrate (such as silicon, silicate glass, silicon carbide, aluminum, aluminum nitride, or FR-4) can be constructed using the polyphenylene polymer of the present invention as a dielectric material. Flat panels on active or passive substrates (such as silicon, silicate glass, silicon carbide, aluminum, aluminum nitride, or FR-4) can be constructed using the polyphenylene polymer of the present invention as a dielectric material Of it. The polymer and polymer of the present invention can be further used as a protective coating on an integrated circuit wafer to protect against Jiang particles. Semiconductor devices are prone to softening errors when alpha particles released from radiating trace contaminants in packaging or other nearby materials hit the activation surface. The integrated circuit can be supplied with the paper size of the present invention which is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 23-^ ------ 1T ------ ^ (please first Read the notes on the back and fill out this page) 1243182 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2l) Protective coating. Typically, the integrated circuit wafer is placed on a substrate and held in a position with proper adhesion. The polymer coating of the present invention provides a protective layer of alpha particles to the activated surface of the wafer. Optionally, additional protection is provided by packaging made of, for example, epoxide or silicone. The polymers of the present invention can also be used as substrates (dielectric materials) on circuit boards or printed wiring boards. A circuit board composed of the polymer of the present invention has been placed on its surface pattern for various electric conductor circuits. In addition to the polymers of the present invention, the circuit board may contain various reinforcements, such as woven non-conductive fabrics (such as glass cloth). This circuit board can be single-sided and double-sided or multi-sided. The polymers of the present invention can also be used to reinforce complexes, where the resin substrate polymer is reinforced with one or more reinforcing materials, such as reinforcing fibers or mats. Representative, reinforced materials include glass weave (especially, glass fiber mats (woven or non-woven); graphite (especially, graphite mats (woven or non-woven)); Kevlar ™; Nomex ™; and Glass ball. This complex can be molded by pre-forming, impregnated pads of monomers or oligomers, and resin transfer molding (with the pads placed in the mold, and the monomers or prepolymers are added and heated to produce a polymerization reaction. ). The polymer layer of the present invention can be formed by wet cooking, plasma etching, reactive ion cooking (RIE), dry etching or light laser ablation, as exemplified in "Electronic Applications "Polymers for Electronic Applications", Lai, CRC Press (1989), pages 42 ~ 47. Round cases can be completed by multi-level technology, in which, the / case system is slate-printed and defined by coating on Resistive layer on the polymer dielectric layer, and then engraved into the bottom layer. Particularly useful techniques include masking oligomers or polymer parts that are not to be removed (# 先 ΚRead the notes on the back before filling out this page) Φ Order

This paper size applies to China National Standards (CNS) A4 specifications (210X 297 mm) 24 1243182

Printed by A7 B7, Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the invention (22) “Remove the unmasked polymer or polymer part, and then, for example, leave the polymer or polymer left by heat curing” Thing. In addition, the polymer of the present invention can also be used to prepare molded articles, films, fibers, and foams. Generally, known techniques used in the industry to cast oligomers or polymers from solution can be used to make this product. Additives such as fillers, pigments, carbon black, conductive metal particles, abrasives, and lubricating polymers can be used in the preparation of shaped polyphenylene polymers or polymer objects. The method of adding this additive is not important and can be conveniently added to the polymer or polymer solution before preparing the shaped article. Liquid compositions containing oligomers or polymers alone or fillers can be applied by any general technique (squeegee, roll, dip, brush, spray, self-green coating, extrusion coating, or other surface coating ) Coated on a variety of different substrates. If the polyphenylene oligomer or polymer is prepared in a solid state, the additive may be added to the melt before it is made into a molded article. The oligomers and polymers of the present invention can be applied to a variety of substrates by various methods, such as solution deposition, liquid phase phasing, mask printing, melt spin, dip coating, roll coating, and powder coating. , Plasma deposition, dispersion spraying, solution casting, slurry spraying, dry powder spraying, fluidized bed technology, welding, explosion methods including line burst spraying methods and explosive bonding, thermal compression bonding, Plasma polymerization, dispersing in a dispersion medium and then removing the dispersion medium, pressure bonding, pressure heating bonding, vulcanization in a gaseous environment, extruding molten polymer, hot gas welding, baking, coating and sintering. Single-layer and multi-layer films can also be deposited on the substrate using Langmuir-Blodgett technology at air-water or other interfaces. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 25 --------- i clothing ------ 1T ------ ^ (Please read the back of K first Note: Please fill in this page again) 1243182 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A B7 V. Description of the invention (23) When the polymer or polymer of the present invention is coated with a solution, the most favorable polymerization reaction is used The specific conditions and other processing parameters depend on various factors, especially the particular polymer or polymer being deposited, the coating conditions, the amount and thickness of the coating, the end-use application, and the solvent used. Representative solvents that can be used are described above. The substrate that can be coated with the polymer or polymer of the present invention can be any material that has sufficient integrity with the monomer, polymer or polymer. Representative examples of substrates include wood, metal, ceramics, glass, other polymers, paper, cardboard cloth, woven fibers, non-woven fiber mats, synthetic fibers, Kevlar ™, carbon weave, gallium arsenide, silicon, and Other inorganic substrates and their oxides. The substrate used is selected based on the intended application. Exemplary materials include glass fibers (woven, non-woven or strand), ceramics, metals (such as aluminum, magnesium, titanium, copper, chromium, gold, silver, tungsten, stainless steel, Hastaloy ™, barrier steel, other metals Alloys and their oxides) and thermosetting and thermoplastic polymers (such as epoxy resins, polyimide, perfluorocyclobutane polymers, benzylcyclobutane polymers, polystyrene, polyamide, polyimide Carbonate, polyarylene puzzle and polyester). The base may be a polymer of the present invention in a cured form. The substrate can be any shape, and the shape depends on the end application. For example, the substrate can be dish-shaped, sheet-shaped, linear, tubular, plate-shaped, spherical, rod-shaped, pipeline-shaped, cylindrical, brick-shaped, fibrous, woven or non-woven fiber, yarn-like (including blended Yarns), regular polymers; woven or non-woven mats. The 'substrate' in each case may be hollow or solid. In the case of hollow objects, the 'polymer layer is inside or outside the substrate or both. The substrate can include porous layers, such as graphite, mats or fabrics, glass mats or fabrics, scrims, and this paper is compliant with China National Standards (CNS) A4 specifications (21〇χ297297) 26 (Please (Read the notes on the back before filling out this page)

1243182 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (24) Particulate materials. The polymer or polymer of the present invention is directly attached to many materials, such as' compatible polymers, polymers with common solvents, metals (particularly textured metals), silicon or silicon dioxide (particularly, etching Silicon or silicon oxide), glass, silicon nitride, copper nitride, aluminum oxide, thallium arsenide, quartz and ceramics. However, when it is desired to increase adhesion, materials may be introduced to improve adhesion. Representative examples of this adhesion-promoting material are silanes, preferably organic silanes, such as trimethoxyvinylsilane, triethoxyvinylsiloxane, hexamethyldisilazane [(CH3) 3_Si-NH -Si (CH3) 3], or an aminosilane conjugate such as aminopropyltriethoxysilane, or a chelating agent such as aluminum monoethylacetamidoacetate diisopropylate [( (IsoC3H70) 2A1 (0C0C2H5CHC0CH3))]. In some cases, the adhesion promoter is applied as a 0.01% to 5% solution, the excess solution is removed, and then polyphenylene is applied. In other cases, for example, the chelating agent of aluminum monoethylacetamidate diisopropylate can be sprayed on the substrate with a toluene solution of the chelating agent, and then baked and coated at 350 ° C in oxygen. The substrate was formed for 30 minutes, and a very thin (for example, 5 nm) aluminum oxide adhesion promoting layer was formed on the surface and added to the substrate. Other methods of depositing aluminum oxide are also suitable. In addition, an adhesion promoter (in an amount of, for example, 0.05% to 5% by weight based on the weight of the monomer) may be blended with the monomer before the polymerization reaction, eliminating the need to form an additional layer. Adhesion can also be promoted by surface preparation, such as texturing (for example, scraping, etching, plasma treatment, or polishing) or cleaning (for example, this paper size applies Chinese National Standard (CNS) A4 specifications) (2i〇x297 mm) 27 --------- install ------ II ------ line (read the notes on the back first and then fill out this page) Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives <-1243182 Λ: * ------- V. Description of the invention (25) Degreasing or sonic cleaning), other processing (for example, plasma, solvent, s〇 ;, electropolymerization growth Discharge, corona discharge, sodium, wet shoe engraving, or ozone treatment) or sandblasting the substrate surface or using an electron beam (such as 6 MeV fluoride ion), 50 to 2000 V electrons; 0.2 to 5 〇〇 ... to] MeV hydrogen protons, 200 KeV to 1 MeV helium protons; 0.5 MeV fluorine or gas ions; 28 KeV neon; oxygen-enriched flame treatment; or accelerated argon ion treatment. For coating 3, Oligomerization of 3 '-(oxydi-l, 4-phenylene) bis (2,4,5-triphenylcyclopentadienone) with 1,3,5-tri (benzylethynyl) Chemical product Good only; Jc example) 'Shiyaki-yaki-based adhesion promoter (which contains 3-aminopropyl Shiyaki-yaki dissolved in methoxypropanol, can be obtained from DuPont's vm-652 or Dow Chemical Company's AP8000 It is) coated on the surface of the wafer first; slowly rotated to spray the entire surface; left to stand for 2 seconds; and finally spin-dried at 3000 rpm for 10 seconds. When the wafer is rotated at 750 rpm, a high-precision pump / Filtration system (Millipore Gen-2) disperse the oligomer solution (200 mm wafers as 4 mL) on the wafer surface. Immediately after dispersing the polymer solution, accelerate the wafer rotation to 2000 rpm and keep the Spin rate is 20 seconds. Continuous flow of 1,3,5-trimethylbenzene is applied to the backside of the wafer for 5 seconds during the dispersion of the oligomer solution. After spin coating, the film is placed on a 70 ° C hot plate Dry for 20 seconds. After the dry-baking step, coated end-edge beads of 2 mm to 5 mm are removed with a continuous stream of 1,3,5-trimethylbenzene 'and coated from the back side or directly from the end edge. The top was directly coated to rotate the wafer at 2000 i * pm. After removing the edge beads, the oligomer was polymerized on a hot plate at 325 ° C for 90 seconds under a nitrogen blanket. Cross-linking for 2 minutes on a hot plate at 450 ° C under nitrogen or 6 minutes in a nitrogen stripping furnace at 450 ° C. The oligomer or polymer of the present invention can be combined with other additives to apply this paper. Chinese National Standard (CNS) A4 specification (2Ι〇χ 297 mm)

Consumers' Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs-Print 1243182 5. Description of Invention (π) to obtain special results. Representative examples of such additives are gold-containing compounds, such as magnetic particles, such as barium-iron, iron oxide, which can be selectively mixed with the starting material, or used for other magnetic, optical, or other recording properties. Metal-containing particles of the medium; conductive particles (such as metals or carbon used as conductive sealants), conductive adhesives, conductive coatings, electromagnetic interface (EMI) / radio frequency interface (RFI) shielding coatings, static dissipation, and electrical contact. When these additives are used, the oligomer or polymer of the present invention can be used as a binding agent. The oligomer or polymer of the present invention can also serve as a protective layer against the environment (that is, protect against at least one substance or force in the environment of the object, including conditions for preparation, storage and use), such as making the surface against metal, Semiconductor valley sensors, electrical conductors, solar cells, glass and glass fibers, ballast 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. Example 1 Congratulations to a ketadienone compound and an acetylene hafnium compound. Several cyclopentadione compounds and acetylene compounds were prepared as described below. The structures of these compounds are shown in Table I. A · Ethynyl) phenylcyclopentadiene_f, sulfide A) hydrazone to prepare 4-bromomosylethenyl gaseous 4-bromobenzyl Acetic acid (100 g, 0.465 mol), dithionine (300 ml), and DMF (about 2 ml) were injected into a 1-liter round-bottomed 3'-neck flask equipped with a reflux condenser and a mechanical stirrer. The reaction mixture was heated under nitrogen for 3 small paper sizes. Applicable to China National Standard (CNS) A4 (210x 297 mm) — I · ^ ----- r --- ^ --------- Line (¾before the back; 1 meeting; matters, please fill out this page) 1243182 A7 B7 V. Description of the invention (27) (Please read the back of the cockroach; 1 matters before filling out this page) When 'use for gas escape Charcoal scrubber. Thiophosphine gas was evaporated and the product (4-bromobenzylacetamido gaseous) was placed in an addition funnel (30 ml). (b) Prepare 4-bromo degassing Anquan Xiangben (200 ml) and vaporized aluminum (74 g, 0.558 ml) into the flask. The 4-bromophenylacetamido gaseous substance of step (a) is mixed with Benzene was added dropwise to make the reaction evaporate HC1. 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 precipitated solids. The layers were decanted and the organic layer was washed successively with a 1M aqueous HC1 solution 'saturated aqueous NaHC03 solution, brine, and then dried over Na2SO2. The solvent was then evaporated to give a solid material which was recrystallized from ethyl acetate / hexane to give the title compound as a yellow solid in 84% yield. (c) _ Preparation 4-> Stinky Dibendi Class II: Bed / household! Consumer Cooperatives of the Ministry of Intellectual Property Bureau • Printed full gas acid (250 ml), water (250 ml), ethylene glycol dimethyl ether (2-methoxyethyl ether) (500 ml), thallium (III) nitrate Trihydrate (222 gram, 0.5 mol) and 4-bromodeoxybenzoin (68.75 g, 0.25 mol) were injected into a 2-liter round-bottom 3-necked flask (equipped with a reflux condenser and mechanical mixing) Device). The reaction mixture was heated at reflux under nitrogen for 6 hours. When cooled to ambient temperature, digas methane (500 ml) was added. The bilayer formed is decanted to form a precipitated T1 (I) salt. The layers were separated, and the organic layer was washed with water, saturated aqueous NaHC03 solution and brine, and then a solid formed by recrystallization from 2-propanol to give the title compound. (d) Preparation of 4- (jasmine ethynyl) dimosamethylenedione 4-bromodibenzyl diamine (10.0 g, 0.0346 mol), and benzyl acetylene (3.88) This paper size applies Chinese National Standard (CNS) A4 specifications (2) 0 X 297 mm 1243182 Λ7 B7 V.

Description of the invention (28) g, 0.0380 mol) and (PPh3) 2PdCl2 (0.121 g, 0.0002 mol) are present in diethylamine (95 ml), stirred at ambient temperature for 72 hours, and then concentrated to dryness. The residue is taken up in digas methane. A standard aqueous solution was subsequently recrystallized from 2-propanol to give the title compound. (e) Preparation of compound A 4- (benzylethyl) -dibenzidine (20 g, 0.0644 mol), 13 · dibenzyl acetate (14.2 g, 0.0677 mol) And ethanol (150 ml) was heated to 75 ° C. Potassium hydroxide (K0Η) (1.8 g, 0.0322 mol) dissolved in ethanol (15 ml) was added dropwise over a period of 15 minutes. The reaction mixture was heated to reflux for 30 minutes, then cooled to 40 ° C, the Shen Dian product was filtered, washed with cold ethanol and dried. Recrystallization from 2-propanol gave the title product. Β · Ambentyl) bis (2,4,5-tritylcyclopentadione)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1,3-Dibenzylacetate (1.23 g, 0.00584 mol), 1,4 · bis (phenylglyoxal) benzyl (available from Bis of Ken Seika Company) -PGB was purchased, 1.000 g, 0.00292 mol) and ethanol (50 ml) was added to a 100 ml 3-necked round bottom flask (equipped with a reflux condenser / nitrogen inlet). The reaction mixture was heated to reflux and an aqueous KOH solution (0.21 g, 0.002 mole) in water (2.25 ml) was added thereto. Additional KOH was added until the solution darkened and remained dark. The mixture was refluxed for 45 minutes and then allowed to cool. The dark solid of Shen Dian was collected by filtration and analyzed by iH-NMR, 13C-NMR, HPLC and FT-IR. All information is consistent with the formation of compound B. C. ^, bis (4- (phenylethynyl) phenoxy) -2,2, .373,, 5,5,6,6, -octade | Dibenzyl Mil compound C) (a ) Preparation of 4-Iodized Silly Tomb Acetate This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) ΤΓ --------- ^ ------— II (Please read the precautions on the back before filling this page) 1243182 A: B: V. Description of the invention (29 Iodophenol (25.00 g, 0.4 mol) and digas methane (100 mTorr) Fill a 250-ml round-bottomed flask (equipped with condenser / nitrogen inlet, thermocouple, and dropping funnel). The slurry is stirred and tons of bite (HU ml, 0 ″. Ml) are added via syringe. Reaction mixture Use an ice bath to cool to 〇. [, Ethyl acetate (8.89 ml, 0.125 mol) was added dropwise. The mixture was stirred at 10 C for 1 hour, allowed to warm to room temperature and stirred for 2 hours. The reaction mixture It was filtered, and the filtrate was washed 4 times with water. The organic layer was dried (MgS04). The solvent was dried under vacuum to yield 273 grams of orange oil. The nmr analysis was consistent with the structure of the desired product. Preparation 4 · ( Phenylethynyl Benzoyl 4-Methylbenzyl Acetate (5.0 g, 191 mol), Phenyl Acetyl (23.40 g '0.229 mol) and Triethylamine (54 ml) Add to a 25 ml round bottom flask (equipped with condenser / nitrogen inlet, thermocouple, and stopper). The Consumer Cooperative JP M, Employees' Bureau of the Ministry of Intellectual Property, Ministry of Economic Affairs. PdCl2 (PPh3) 2 (0.200 g, 0.286 mmol) and (PP1ΐ3 (1.50 g, 5 73 mmol) were added and the mixture was heated to reflux. When the reaction mixture reached 40 ° C, Cul ( 0.054 g, 0.286 mmol). After 2 hours, the reaction was cooled. The mixture was diluted with Diqiangyuan and poured into water (500 mL). The aqueous layer was extracted with Diqiangyuan (100 mL). The mixed organic layer was washed with three portions of 300 ml of water, dried (MgS04) and filtered. The solvent was removed in vacuo to produce 49 g of a yellow solid. The substance was recrystallized from hexane to produce yellow crystals, mp 104.5 ° C to 105.5 ° C. (C) Preparation of 4- (benzylethynyl) phenol 4- (phenylethynyl) phenyl acetate (60 · 6 g, 0.256 mol), 20% aqueous sodium hydroxide solution (400 ml) And tetrahydrofuran (400 ml) were added to a 2-liter Erlenmeyer flask and stirred at room temperature for 5 hours. The mixture was mixed with ^

3Z (ίτ first ^^ irir face; ± matter, please fill out this page)

This paper size applies Chinese National Standard (CNS) A4 specifications (2) 0 X 297 male: g) 1243182 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (3) Glacial acetic acid (120 ml) Acidify to pH 迳 7. The aqueous layer was removed and extracted with tetrahydrofuran. The organic layers were mixed and concentrated on a rotary concentrator to give a brown solid. The solids were heated by sintering on the steam bath and the hot solution was decanted from the solids. Repeat this step with a second volume of hexane (700 mL). Upon cooling, a white solid crystallized from the Kelvin solution, isolated with a vacuum, and dried under vacuum to produce 18 g of a white solid, mp i26oc to 127 «c. The nmR analysis is consistent with the structure of all 4 materials. [D] Preparation of compound c decafluorobisphenyl (5.00 g, 14.96 mmol), 4- (phenylethynyl) (5.81 g, 29.93 mmol), sodium carbonate (16.54 g, 0.1197 mmol) Ear) and dimethylacetamide (150 ml) were added to a 250 ml round bottom flask (equipped with condenser / nitrogen inlet, thermocouple, and stop). The mixture was heated with stirring 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 methane gas. The emulsion 'organic layer was broken by the addition of brine, and the organic layer was separated and washed twice with water, and transited through Shi Xishi Ningsheng plug. The solvent was removed in vacuo leaving an 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 target compound. D · fluorenylbenzyl) -2,3,5-tribenzylcyclopanadienone (彳. N. N. According to Example 1A, a trifluorenylsulfanylacetylene was used in place of phenylacetylene to prepare compound D, Then dilute alkali was used to remove the tris (fluorenyl) silyl protecting group OE · (phenylacetylene), dimethyl dimolybdenum / ¾dienone (compound E), ... This paper size applies Chinese national standards (CNS) A4 specifications (210 X 297 issued)

3J · I --- ^ ---- ^ · I I ---- II (fr ^ J4lr face; it is necessary to fill out this page again) 1243182 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-A7 B7 V. Description of the invention (31) Preparation of 4-bromobenzaldehyde (25.0 g, 0.135 mol), 3-ethyl-5- ( 2-Hydroxyethyl) -4-methylthiazole bromide (1.70 g, 0.0068 mole) and triethylamine (4.10 g, 0.0405 mole) were stirred at room temperature for 60 hours. The reaction mixture was concentrated and dried, poured into CH2C12 (150 ml), washed with 1M HC1 and saturated NaHC03 aqueous solution, and dried (Na2S04), and then concentrated to produce 25.2 g (100%) of a viscous yellow oil in a chamber. Cure when left at rest. 1H NMR (CDC13) 5 7.73 (d, J = 8.5 Ηζ, 2Η), 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. Preparation of 4,4'-dibromoamphetamine A in 4,4, -dibromobenzoin (20.2 g, 0.055 mol), 80% aqueous acetic acid (200 ml), ammonium nitrate (4.6 g, 0.0575 mol) And copper (II) acetate (0.100 g, 0.0005 mol) was heated under 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 13.0 g (64%) of a light yellow solid product, mp was 226 ° C to 228 ° C. 4 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. (g) Preparation of 4,4, -dibromodiphenylethylene dione (15.8 g, 0.44'-bis (benzylethynyl) dimothione in diethylamine (150 ml)). · 431 moles), phenylacetylene (5.06 grams, 0.0495 moles), (PPh3) 2PdCl2 (0.151 grams, 0.0002 moles), and Cul (0.820 grams, 0.0043) This paper size applies the Chinese National Standard (CNS) A4 specifications ( 210 X 297 public love) 34 called the first note on the back ^ please fill in this page)

I243182 Λ: Five,

Jing, • Printed by the Consumer Affairs Bureau of Ma Ma Zhihui Property Co., Ltd. ______ Β7 ____ Invention Description (32 mol) was heated under reflux overnight. The reaction mixture was concentrated and dried, poured into CH2C12 (150 ml), washed with 1M HC1, 10% Na2C03 / H: 0, saline and dried (Na2S04), and then concentrated. Crystallization from 2-propanol gave 7.92 g (45%) of a light brown solid with an mp of 168 ° C to 170 ° C. W NMR (CDC13) 0 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) 5 193.03, 132.46, 132.03, 131.82, 130.21, 129.84, 129.06, 128.47, 122.37, 94.28, 88.55. (d) Preparation of a solution of compound K0Η (0.34 g, 0.0061 mole) in ethanol (5 ml) was dripped into 4,4'-bis (phenylacetylene) in 75 t ethanol (75 ml) Solution) of diphenyldioxane (5.0 g, 0.0122 mol) and 1,3-diphenylacetone (2.69 g, 0.0128 mol). The resulting solution was heated at reflux for 1 hour, cooled to room temperature and the precipitate was filtered off and dried. Extraction of the product from boiling ethanol yielded 5.26 g of product (74%) as a monumental red solid: mp 222 ° C (DSC); lH NMR (CDCI3) (5 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) 0 199.02, 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) 〇F. 3 , 4-Bis- (3- (benzylacetylene) fluorenyl) -2,5-dimozine is converted to dienone (compound F) (a) Preparation of 3,3'-dibromobenzoin paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (2) 〇χ 297 mm 35 -----: ---- Order --------- line (first read the tabs on the back; jLt Please re-fill the page on this page} Printed by the Consumer Consumption Cooperative of the Ministry of Economic Affairs and Intellectual Property of the Ministry of Justice 123182 A: B7 V. Description of the invention (33) Prepared as described in Example 1E (a) / but it is made from ethanol (125 ml ) Of 3-bromobenzaldehyde (25.0 g, 0.135 moles), 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%) of a viscous yellow oil. 1H NMR (CDC13) δ 8.04 (s, 1Η), 7.75 (d, J = 7.8 Ηζ, 1Η), 7.61 (d, J = 8.0 Hz, 1H), 7.47 (s, 1H), 7.26-7.15 (m, 4H), 5.S7 (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'-dibromobismoethylenedione as in Example 1 E (b) It is prepared from 3,3, -dibromobenzoin (24.8 g, 0.067 mol) in 80% aqueous acetic acid (200 ml), ammonium nitrate (5.63 g, 0.070 mol), and copper acetate (π) (〇 • 2 g), yielding 17.0 g (69%) of the product as a 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. (c) Preparation of 3,3'-chelate (jasmine acetylene) dibenzyl dione 3,3'-dibromodiphenylethylene dione (5.0 g, 0.136 mol) and phenylacetylene (3.47 g, 0.0340 Moore) triethylamine (30 ml) solution was degassed by passing nitrogen bubbles through the solution for 10 minutes. (Pph3) 2pdcl2 (0.067 g '0.0001 mole) was then added and the reaction mixture was heated at reflux overnight. The mixture was concentrated and dried, poured into CH2Cl2 (109 ml), washed sequentially with 1M HC1, saturated NaHC03, and dried l [Na2S04), and then the concentrated paper was applied to Chinese national standards (CNS) A4 size (2) 0 X 297 mm

1243182 Λ7 B7

V. Description of the invention (34), yielding 67 g (66%) of the product as a white solid. · Mp · 144 to 145; · H NMR (CDC13) 5 8.12 (s, 2H), 7.96 (d, J = 7.9 Hz? 2H), 7.81 (d, J = 7.7 Hz, 2H), 7.52 (m, 6H) 7.36 (m, 6H);% NMR (CDC13) 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 KOH (0.25 g, 0.0045 moles) in ethanol (5 ml) was added dropwise to 75 C ethanol of 3,3 bis (, benzylethynyl) dibenzyl ethylene difluoride (3 67 g '0.0089 moles) and ι, 3-diphenylacetone (2.07 g, 0.0098 moles) in ethanol (100 ml). The resulting solution was heated at reflux for 1 hour and then cooled to room temperature. The formed precipitate was filtered and dried. The product was extracted by boiling ethanol to produce 2.0 g (38%) of a dark red solid product. Mp 208 t: (DSC).] H NMR (CDCI3) 5 7.45 (bm, 6H), 7.31-7.21 (bm, 20H ), 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. Packing --- ^ first, ^^ on the back; please fill in this page for the items you want); printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-G · 1,3,5-tri (benzylethynyl) (Compound G) Triethylamine (375 g), triphenylphosphine (4.7865 g), palladium acetate (1.0205 g) and N, N-dimethylphosphonium amine (2000 ml) were injected into three necks of 5 liters Round-bottomed flask (the device includes a thermocouple, a mechanical stirrer located above, a condenser, an addition funnel, and a heating mantle with a temperature controller). The mixture was stirred for 5 minutes to dissolve the catalyst. Then add diethylhydroxyl (5 g), 1,3,5 · tribromobenzyl (1 ^ 0 g) and benzyl, acetylene (67.67 g). The reactor was stripped with nitrogen 15 This paper is in Chinese standard (CNS) A4 size (2) 0 X 297 mm T7 1243182 A7 B: Economic and Intellectual Property Bureau Staff Consumption Cooperative System V. Invention Description (35) Minutes, then heated to 70 ° C. while maintaining a nitrogen atmosphere g. At 7 ° C after 30 minutes of heating, 'Bentylacetylene (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 water was added (1 liter), which precipitated the crude product. The product was filtered, washed three times with 500 ml of water, and then once with 500 ml of cyclohexane. The crystals were dried under vacuum at 75 ° C overnight to yield 226 4 g (99 1% yield), which was 97.25 area% purity by gas chromatography. The crystals were dissolved in methylbenzyl (1800 ml), filtered again through a silica gel, and the solvent was removed on a rotary evaporator to yield 214.2 g (94.2 % Yield), which was 99.19 area% purity by gas chromatography analysis. The residue was recrystallized from a mixture of toluene (375 ml) and 2.propanol (696 ml). The white crystals were filtered and the mixture was filtered with toluene (丨 〇〇 Ml) and a mixture of 2-propanol (400 ml) was moistened and vacuum-dried at 75 ° C to produce 1,3,5-tris (benzylethynyl) benzene (1 900 g, 83.91 yield) , Which is 99.83 area% purity by gas chromatography. Additional recrystallization of / isopropanol produces materials of acceptable organic and ionic purity. Η. Bis (benzylethynyl) dimosome ether (Compound Η, 3-neck round bottom flask with 1 liter (which has a thermocouple) , Mechanical mixer, condenser and heating hood with temperature controller), inject triethylamine (HU g), dibenzyl scale (1.158 g), acetic acid handle (0.2487 g), diethyl via base Amine (1.24 g), 4,4'-dibromodibenzyl ether (68.8 g), benzylacetylene (67.74 g), N, N-dimethylformamide (136 ml) and 72 ml of water. The reactor was stripped with nitrogen for 15 minutes and then heated to 9 ° C while maintaining the nitrogen atmosphere for 19 hours. The reaction was cooled to room temperature and water (80 mL) was added. The crude product was v * must be filtered, and The solid is moistened once with Ϊ20 ml of toluene and then benefits with 160 ml (i is called the back; jL sound? Please fill in this page again) nn ϋ l · n I n I: «J · n I l I ϋ II ·

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -38-1243182 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Λ7 B: 5. Description of the invention (36) Water wetting four times, Drying under vacuum overnight yielded 66.37 g (85.6% yield) of white needle-like 4,4, -bis (phenylethynyl) dibenzyl ether, which was 99.64 area% purity by gas chromatography. L (benzyl acetylene, V, o-terpene (compound I) dibromo-o-terpene-o-terpene (100 g), Fe (5 g), and CHC13 (475 ml) were injected into three necks of 1 liter Flask (equipped with mechanical stirrer, condenser connected to HBr trap and addition funnel). The mixture was stirred and the temperature was maintained in a water bath. Βγ2 (47 · 5 ml) in CHC13 (150 ml) at 2.5 It was added dropwise during the hour. The mixture was stirred at room temperature for an additional two hours. GC showed 5% monobromo-o-tribenzyl, 81% dibromo-o-tribenzyl and 9/0 tribromo -O-Terphenyl. Ice and 2N NaOH solution was added to the upper solution until it became alkaline. The upper layer was decanted and the CHC13 solution was washed with more water. Sodium sulfate was added to the CHCI3 solution and then passed through the filling plug. Special Bucher funnel filtration |. Remove the gas imitation. Add 750 ml of glacial acetic acid to the white solid and heat the slurry to 95 ° C in a water bath. About half of the solids are dissolved. The hot solution is poured into a 100 ml flask. Residual solids 71 grams, which contains 1.4% monobromo-o-tribenzyl, 93% 4,4 ,,-dibromo-o-o- Biben and 6% of 4,4,4,4, -tribromo-o-tribenzene. The acetic acid solution was cooled to room temperature. White crystals were collected. GC showed 1% monobromo-o-terphenyl, 83% 4,4 "-dibromo-o-terphenyl and i3〇 / 0 4,4 ', 4" -tribromo-o-terphenyl. This material is used to prepare 4,4,, · bis (benzene (Ethynyl) -o-terphenyl. (^) Preparation of compound f. This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm). 39 ------------- ^ -----: ---- ^ --------- (ίτ ^^ ίτΐ face; it matters to fill out this page again) 1243182 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs% Cooperative A: B: V. Description of the Invention (37) 4,4 "-Di-mo-o-tribenzyl (40 g, 0.0103 mole), benzyl acetylene (50 ml), triethylamine (500 ml) and pyridine (500 ml) 300 ml) was injected into a 1000 ml 4-neck flask (equipped with a mechanical stirrer, condenser, ν2 inlet and thermocouple). Nitrogen was used to strip the system for 20 minutes. After dissolving the solids, add 2.783 g of Pd ( PPh3) 2Cl2, 2.538 grams of Cul and 5.54 grams of PPI13. Nitrogen was bubbled through the solution and mixed 30 minutes. The mixture was heated to reflux. The reflux was maintained overnight. A white solid formed during the reaction. The solution was poured into a 2 liter flask containing ice. The flask was moistened with water several times and poured into the flask. The solid formed was The Buchner funnel was rinsed with radon and washed several times with water. Toluene was used to dissolve the solids in the 2-liter flask. The upper layer was poured into a 1 liter flask. The lower layer containing undissolved material was wetted with methylbenzyl, and the methylbenzyl 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 was heated in a water bath and searched. Na2S04 was added. The solution was filtered through a fritted glass and the solvent was concentrated by rotation. The solid was dissolved in a 2 liter flask with 350 ml of hot toluene. Once dissolved, 1300 ml of isopropanol was added to crystallize the solid. The 2-liter flask was placed in the refrigerator overnight, and the crystals were collected and washed with isopropanol. The yellow solid weighed 25 grams. The 'yellow solid was then washed with acetone and then crystallized twice from ethylacetone. The yield of white shards was 12 grams. J. Hepta 4'-diethynyl bis-molybdenum ether (compound J) 4,4, dibromodiphenyl ether (9.8 g, 0.030 moles), P present in 4 triethylamine (40 ml), P , D (〇Ac) 2 (0.05 g, 0 · 0002 mol), copper iodide, first note on the Tt side, then fill in this page) • Μ Μ. .Μ J5J · I ϋ nn ϋ I · I I-

η This paper size applies to China National Standard (CNS) A4 (210 x 297 public love) 1243182 A: B "

V. Description of the invention (38) (1) (0.15 g, 0.0008 mol) and triphenylphosphine (1.0 g, 0.0038 mol) The slurry formed by stripping with nitrogen for 30 minutes, while slowly heating and refluxing 2-methyl 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 during 5 minutes. The resulting reaction mixture was heated at reflux for 14 hours, cooled to ambient temperature, and concentrated to dryness. The residue was poured into CH2C12, washed with water and brine, and concentrated. The residue was poured into toluene (200 ml and sodium hydride (0.10 g, 0.20 mole) was added. The reaction mixture was heated to reflux and about 100 ml of the solvent was distilled off. The solution was cooled and then concentrated. The residue was poured Enter CH2C12, wash with IN HC water, saturated NaHC03 and brine, then dry (Na2S04) and concentrate to produce a dark oil. The residue is filtered through a silica gel pad, extracted with CH2C12 and concentrated to produce a viscous oil, which Cure slowly when standing. 1hnmr (cdci3) 5 7.45 (d, J = 8.6 Hz, 4H), 6.93 (d, J = 8.7 Hz, 4H), 3.04 (s, 2H); 13C NMR (CDC13) δ 157.02 , 133.93, 119.20, 118.94, 117.16, 83.16. The reaction system is as follows: ^ ------ 1T ------ line (please read the precautions on the back before filling this page) Central Standards of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives βγ ^ 〇 ^ -〇- < 〇) -βγ

NaH

-OH

Pd (OAc) PPh3 Cul Et3N K. 3,3 '-(Gasid-1,4-molylidene) bis (2,4,5-trimosylcyclopentadienone (Compound K)) This paper is applicable to the standard China National Standard (CNS) A4 specification (210X297 mm) 41 1243182 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (39) (a) Preparation of 4,4 ', -di'benzylacetamidine A charge of ammonium ether in aluminum chloride (97.9 g, 0.734 moles) in dioxane (200 ml) at 0 ° C was added dropwise over a period of 30 minutes. A solution of methylene chloride (50 ml) of dibenzyl ether (500 g, 0.294 mol) and benzyl ethyl chloride (102 g, 0.61 mol). When the addition is complete The reaction mixture was warmed to ambient temperature and stirred overnight. The reaction mixture was carefully stirred and poured into 1.5 kg of ice / water. Dichloromethane (1500 ml) was added to solution the solid and the layers were separated. Organic The layer was filtered through Cyrit 'and then concentrated and dried. The β was recrystallized from methylbenzyl to give gram (92%) of the title compound in the form of light brown prisms. Aqueous solution of IΒΓ (97 ml of 48% by weight solution) was added to 4,4, -dibenzylacetamidinyl diphenyl ether (5.0 g, 0 ··) in DMSO (400 ml). 123 moles), and the resulting mixture was heated to 100. (: 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 water ( (3 × 250 ml), then washed with brine, and concentrated to produce a viscous bright yellow oil, which solidifies when left at ambient temperature. Recrystallization from ethanol yields 35.9 g (67%) of the title compound 'It is fresh Yellow cubic boat. (C) A 5 liter Morton flask (which is equipped with a thermocouple, a reflux condenser with a nitrogen inlet, a mechanical stirrer, and an addition funnel) must be stripped of nitrogen, and 195 4 g (0 · 4498 mol 'w eq) of 4'4' · bis (benzylethylene diethylene) diphenyl ether, 193.9 g of diphenylmethyl acetone (0922 mol, called by 2005) and 25 liters— This paper size is applicable to Chinese countries ^ ΪΤ ^ Τ ^ ϋ210χ))-(Please read the precautions of VG before filling this page)

1243182

M * printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of invention (40) Deoxyethanol. The mixture was heated to reflux, at which point a homogeneous solution was reached, and the solution was diffused with nitrogen for 30 minutes. In the addition funnel, a solution containing 25.2 g of KOH (0.4498 moles, 1.0 eq), 200 ml of ethanol, and 25 ml of water was added. The temperature was reduced to 74 ° C and the KOH solution was added quickly over a period of 5 minutes. The exothermic reaction quickly established and kept refluxing until 3/4 of the solution was added, after which the temperature began to drop. A dark purple color was immediately observed upon addition of the base, and a solid was observed before the addition was complete. After the addition was complete, the heterogeneous solution was heated vigorously under reflux for 15 minutes, and more solids formed. The mixture was cooled to 25 ° C, 29.7 grams of glacial acetic acid (0.4948 moles, l.leq) was added and stirred for 30 minutes. The crude product was isolated by filtration and washed in a filter funnel with 1 liter of water, 3 liters of ethanol, and 2 liters of methanol, and dried under vacuum at 60 ° C to 90 ° C for 12 hours, yielding 323 g (92%) of crude DPO -CPD, 94% purity by LC. The crude material was dissolved in HPLC grade dichloromethane (10% by weight), transferred to a 5 liter Morton flask equipped with a bottom flush valve and a mechanical stirrer, and washed vigorously 2 to 7 times with an equal volume of low ion water, each time 10 To 90 minutes. The CH2C12 solution was then rinsed through a 5 cm tube containing 75 g of silica gel in CH2C12. The column was cleaned with an additional 1 liter of CH2C12. At this time, the filter was basically clear. The solution was evaporated to dryness, and redissolved in THF and evaporated again to remove the whole residual dichloromethane. The powder was transferred to a 5 liter flask (equipped with an addition funnel and a Friedrichs reflux condenser) and dissolved in refluxing deoxygenated HPLC (0.07 to 0.12 g / ml). Then 1 liter of THF was added, and a nitrogen diffusion tube was inserted into the solution. The solution was diffused under nitrogen for 3 hours, and THF was concentrated at 45 ° C to 50 ° C, while the remaining dioxane was removed by distillation. Attach the distillation head and remove 700 ml to 1 liter of THF. Then the solution is slowly applied. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -43-^ ------_ 11 ------ 0 (Please note before the K7 * back (This page) 1243182 A7 B: Printed by the Consumers' Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs. “Printing 5. Description of the invention (41) Cool for a few hours to room temperature, and then use an ice bath to cool below lot. Crystals will be produced during this period. A sintered suction filtration flask with a 4-liter Millipore was used to isolate the crystals using a 5 # m PTFE filter. It is then washed with 1 liter of methanol and dried overnight at 80 ° C to 90 ° C under vacuum, yielding 70 to 85. /. Yield of DPO-CPD with 99% LC purity, mp 270 ° C 0 1 ^ .2,4,4'-tris (benzylethynyl) dibenzyl ether (Compound 1 ^ (a) Preparation 2 , 4, 4, Tribromodibenzyl ether bromide (57.3 g, 0.358 mol) was slowly dropped into a purely stirred diphenyl mystery (20.0 g '0.118 mol) at 40 ° C. During the addition, the temperature The temperature was slowly raised to 60 ° C, and the reaction was held at this temperature for 2 hours. The mixture was heated to 70 ° C for 30 minutes, and then cooled to ambient temperature. The mixture was poured into CH2C12 (100 ml), washed with 10% Na2CO3 aqueous solution, and then dried. (Na2S04) and concentrated to produce 44.8 g (100%) of the product, which is a viscous oil that slowly solidifies when left to stand at ambient temperature.

(b) Preparation of compound L 2,4,4, · tribromodibenzyl ether (44.3 g, 0.116 mol), Pd (OAc) 2 (0.182 g, 0.00081) in triethylamine (300 ml) Mol), copper (I) iodide (574 g, 0.00302 mol) and tribenzylphosphine (3.95 g, 0.0151 mol) slurry diffused with nitrogen for 30 minutes, while slowly heating under reflux 0 diffused with nitrogen 30 minutes of phenylacetylene (41.4 g, 0.406 mole) was quickly added to the reflux solution over a period of 5 minutes. The resulting reaction mixture was heated at reflux for 14 hours. The solution was cooled to ambient temperature and concentrated. The residue was poured into CH2C12, 1N HCM, water, saturated NaHC03 aqueous solution and paper size are applicable to China National Standard (CNS) A4 (2) 0 X 297 mm) )

1243182

Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A: B: 5. Description of the invention (42) Washing with brine’ and then concentrating to a volume of 100 ml. This solution was filtered through a silica gel pad, extracted with digas methane, and the resulting filtrate was concentrated. The residue was crystallized from EtOAc / hexane to give 39.0 g (73%) of a light brown solid, mp 123 ° C to 126 ° C. Its NMR (CDC13) 5 7.77 (bs, 1H), 7.53-7.44 (m, 14H), 7.34-7.26 (m, 20H), 6.98 (dd, J = 8.0, 8.0, 2H); 13C NMR (CDC13) (5 156.81, 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.-M · 3,3 '-(1,4-phenylene) bis (2,5-di- (4-fluorenyl) -4-benzylcyclopentadiene Ketones (Compound M) 1,3-bis (4-fluorophenyl) -2-acetone (1.476 g, 0.006 mole) and 1,4-bis (phenylglyoxal) benzene (available from Ken Seika) Bis-PGB (1.020 g, 0.003 mole) was dissolved in 90 ml of 1 propanol, and benzyltrimethylammonium hydroxide (0.32 g, 40% in methanol) was added. The solution immediately became purple. The reflux was continued for 2 hours. The mixture was cooled to room temperature and then to 0 ° C. The solid was collected and washed with cold methanol. The yield was 1.92 g. The solid had a metallic sparkling color and was melted at 31 6 ° C as measured by DSC. 1,3-bis (4-fluorophenyl) -2-acetone with E. Elce, AS Hay J. Poly. Sci .: Part A: Polymer Chemistry, 33, 1143-1151. N. 4,4 ', 4 "-tri (benzylethynyl V-tri-benzyl (Compound N ) (a) Preparation of 4,4 "-tribromo-o-tris-mo-o-terphenyl (39.6 g), Fe (3.3 g) and CHC13 (450 ml) were injected ----- Γ --- ^- --- — — — — — (^ • H ”^ i? T face; t sound) Matters should be filled out on this page) η This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (2) 〇χ 297 公(Centimeter) 45 1243182 Λ7

V. Description of the Invention (43) Qiu Zhi, Employee Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, introduced a 1-liter 3-neck flask (equipped with a mechanical stirrer, a condenser connected to a 1 & capacitor, and an addition funnel). The mixture was stirred and the temperature was maintained in a water bath. Br (26.5 ml) in HCl (100 ml) was added dropwise over a period of 1.5 hours. The mixture was stirred at room temperature for 2 hours and then at 65 ° C. [Stir for 2 hours. GC showed 14% dibromo-o-terphenyl, 85% tribromo-o-terphenyl, and 0.7% tetrabromo-o-terphenyl. Ice and 2N NaOH solution were added to the solution until it became alkaline. The upper layer was decanted 'and the CHC13 solution was washed with more water. Sodium sulfate was added to the CHC13 solution ' and then filtered through a Buchner funnel with a Cerrit. Remove chloroform. Mix a white solid with 750 ml of glacial acetic acid and heat the slurry in a 95 ° C water bath. The solid yield after the removal of all acetic acid was 42.5, which contained 11% of 4,4 "-dibromo-o-terphenyl, 88% of 4,4,4,4, -tribromo-o-terphenyl Benzene and 0.6% tetrabromo-o-tribenzene. Solids were used to prepare 4,4,4,4, ... bis (benzylethynyl) -o-tribenzyl. Acetic acid solution contained 56% of 4,4, , -Di-mo-o-terphenyl, 36% of 4,4,4,4, -tribromo-o-terphenyl and 1.8% of tetrabromo-o-terphenyl. (B) Preparation of compound N 4, 4 ', 4' '-tribromo-o-terphenyl (24.7 g, 0.053 mole), benzyl acetylene (22 ml), triethylamine (280 ml), and pyrimidine (180 ml) were injected into 1000 ml 4-necked flask (equipped with mechanical stirrer, condenser, n2 inlet and thermocouple). Nitrogen was used to strip the system for 20 minutes. After the solid was dissolved, Pd (PPh3) 2Cl2 (1.113 g), Cul (1.005 g) and PPh3 (2.218 g). Nitrogen was foamed through the solution and stirred for 30 minutes. Turn on the heat and reflux the mixture overnight. A white solid formed during the reaction. 〇χ 297mm) {^ | \ ° ^ Notes to fill out the back of this page)

46 Ϊ243182

V. Description of Invention (44)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The solution was placed in a 2 liter flask containing ice. The flask was moistened with water several times and poured into the flask. The formed viscous solid was filtered through a Buchner funnel, and then washed several times with water. Clam is used to dissolve solids in a 2-liter flask. The upper layer was poured into a 1 liter flask. The lower layer containing undissolved material was wet with toluene, and the toluene solution was mixed to form a dark brown solution. It was subsequently decolorized with charcoal. The solution was heated in a water bath and mixed. Then Na2S04 was added. The solution was filtered through a sintered glass filter and the solvent was evaporated by rotary evaporation. The viscous solid was dissolved in a 2 liter flask with 600 ml of hot acetone. The crystals were then collected and washed with acetone. A pale yellow solid weighed 11 grams. The solid was crystallized twice from ethyl acetate. The white powder yield was 8 grams. 〇 · bis (benzylethynyl) stilbene η, phenyl acetylene (8.0 g, 78.3 mmol), 1,3-dibromobenzyl (6.24 g '26.6 mmol), double (three Phenylphosphine) Palladium (π) gaseous (1 η g '4.23 mmol), copper iodide 0) (0.503 g, 2.64 mmol), pyridine (73 ml, 0.93 Mol) Triethylamine (110 ml, 0.783 mol) was mixed and stirred under nitrogen for 30 minutes. The mixture was then refluxed overnight. The solution was poured into a water / ice bath. The formed solid was collected and washed with water. The solid was dissolved in toluene and the insoluble matter was filtered. The stupid solution was decolorized with charcoal. Isopropyl alcohol was added to form yellow crystals. The crystals were isolated by filtration and weighed 4.0 g (13. 1 mmol, 50% yield). Melting point was 109.匸 (DSC). NMR and mass spectrometric analysis were consistent with the structure of 1,3 · bis (benzylethynyl) benzyl. This paper size applies to China National Standard (CNS) A4 (210 X 297 public love)） ί l · — ---------- ^ --------- ^ (^^ Please fill out this page again) 1243182 A:

V. Description of the invention (45) P · 1 ^ _- bis (benzylethynyl) strategy (compound p, compound P is prepared as compound 0, but 丨, 4 • dibromobenzyl is used instead of 1, 3-dimo Q_U, 4-Di (benzylethenyl) benzyl (compound 0) 1,2,4-tribromobenzyl (20.0 g, 0.0635 mole) present in diethylamine (250 ml) The slurry was degassed by diffusion with n 2 for 30 minutes. Tribenzylphosphine (2.2 g, 0.00836 mol) was added, followed by Pd (〇Ac) 2 (0.10 g, 0.000445 mol) and Cul (0.315 g, 0.00165 mole), the resulting mixture was heated to reflux. Benthylacetylene (201 g, 0197 mole) diffused with A for 30 minutes was added dropwise over a period of 10 minutes. The reaction mixture was heated at reflux overnight. Reaction The mixture was cooled to ambient temperature and concentrated to dryness. The residue was poured into acetone (200 ml) and water (300 ml) was slowly added and stirred. The precipitate was filtered off, washed with fluorenyl alcohol (500 ml), and then Washed with water (200 mL) and dried to give a light brown solid which was further recrystallized from acetone / methanol to give a white solid The yield is 60%. The NMR analysis is consistent with the structure of the desired substance. The reaction diagram is as follows: f irx ^ ir on the back; please fill in this page for it) β 0 I nn —Γ ϋ I · 1 1: OJ · I n · 1 ϋ n ϋ n-

Br

Consumption Cooperative, Co., Ltd.- · The printed paper size is applicable to the Zhongguanjia Standard (CNS) A4 specification (210x297 public love) ": ^ ~ Γ 1243182 A7 B7 V. Description of the invention (46) Example 2 Compounds M and 1 Polymer compound (M) (316 mg, FW = 762) prepared from a mixture of 1,3-bis (benzylethynyl) (Compound 0) and 1,3,5-tri (benzylethynyl) benzyl (Compound G) 0.415 mmol), compound (0) (72 mg, FW = 278, 0.259 mmol) and compound (G) (44 mg, 0.116 mmol) in 1,3-diisopropylbenzene ( 4 ml) under reflux for 42 hours. The dark solution turned red and thickened. The solution was spin-coated on the wafer and cured at 400 ° C for 1 hour to form a film. The reaction system is as follows:

Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-However, the paper size of this paper applies to China National Standard (CNS) A4 (210 X 297 mm) -------- ^ -------- I (Please (Please read the Jiang Yi matters on the back of ti before filling out this page) 1243182

AT B7 V. Description of Invention (47)

F

Ph

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs v

(Please note the matters on the back of KTt before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 50 1243182 A7 B? V. Description of the invention (48) Example 3 Compound M and 4,4'-bis (benzyl acetylene ortho-triple Benzo (metallic compound I) and 4 · 4 ′, 4 ″ -tri (benzylethoxy ortho-tripleben (compound N) to prepare polymer compound (M) (3 16 mg, 0.415 mmol) Compound (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 Reflux for 48 hours. The yellow viscous solution is cooled to room temperature and spin-coated on the wafer. The polymer is cured at 400 ° C for 1 hour to form a film. The reaction system is as follows:; (Please fill in this page first »Notes on the back)

Qiu System, Consumer Cooperative of Employees of Intellectual Property Bureau of the Ministry of Economic Affairs •. Line This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ~-1243182 A " B 'V. Description of Invention (49)

◎ 9 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

(Please read the precautions on the back before filling out this page) .----- I I -1 i I! 1 · * 1— I Hi y · .....— Taiyi.

, 1T

This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) 52 1243182

Employees' Cooperatives of the Ministry of Economic Affairs and Intellectual Property of the Ministry of Education-Printed A7 B7 V. Description of the Invention (5G) Example 4 From Oxygen], 4-Asian Molybdenum) 铄 (2.4.5-Tri-benzylcyclopentane) (Compound K ) And 4,4,-# Γ ^: ylethynyl) dibenzyl ether (compound preparation of poly (3,3 '-(oxydi · 1,4 · benzylidene)) bis (2,4,5 -Tritylcyclopentadienone) (15.0000 g, 0.0119158 moles), 4,4, -bis (phenylethynyl) dibenzyl ether (7.0974 g, 0.019158 moles) and N · methylpyrrolidine Dione (5 1.60 g) was added to a 250 ml round bottom flask. The flask was attached to a nitrogen inlet, and the magnetic stirring solution was heated to 200 ° C in an oil bath. 20 (TC 19.5 hours later, gel permeation chromatography showed Μπ is 1551 & MW is 2383, which is relative to the polyethylene standard. The solution is cooled and bottled. A part of the solution is poured into a syringe and filtered through a 1.0 micron syringe filter on a 4 "silicon wafer. Spin-coated wafers at 2000 rpm for 60 seconds under a heat lamp used to heat the wafers. The coated wafers were placed on a hot plate set at 90 ° C for several minutes. The wafers were placed in a nitrogen stripping furnace , It was solidified by stripping 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 formed crystals were polymerized with polyphenylene When the solution is applied to the gap-filling structure of the sub-micron gap and cured, the solution is found to completely fill the gap. Example 5 By 3,3 '-(oxydi-1,4-suberyl) bis (2 · 4,5-tribenzylcyclohexadienone (compound K), 4,4'-bis (benzylacetylene) dimozine compound Η), and 1,3,5 · tri (benzylacetylene) A) Mo (chemical compound Γτ), a polymer was prepared in a 100 ml 3-neck round bottom flask, and 3,3,-(oxydi-1,4-benzylidene) bis (2,4,5-triphenyl) was added Base, cyclopentadienone) (10.00 000 g, 0 W277 mole) The paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 3? ---- * I --IIII ^ · 1111111 · (Please read the notes on the back before filling in this I> 1243182 A7 B7 V. Invention Description (51 Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs-Qiu System, 4,4'-Bis (phenyl Ethynyl) dibenzyl ether 2.3660 g, 0.006386 mole), 1,3,5-tris (benzylethynyl) benzyl (2.4170 g, 0.006386 mole) and N-fluorenylpyrrolidinedione (34.5 ml). The flask was attached to Nitrogen inlet and magnetically stir the solution in an oil bath to 200 ° C. After 11 hours at 200 ° C, the solution was cooled and bottled. A portion of the solution was poured into a syringe and filtered through a 1 micron syringe filter onto a 4 inch silicon wafer. The wafer was spin-coated at 2000 rpm for 60 seconds. The coated wafers were placed on a hot plate set at 90 ° C for 2 minutes. The wafer was placed in a nitrogen stripping furnace, solidified by stripping at room temperature for 45 minutes, and then heated to 400 ° c at 10 ° C / min, held at 4CKTC for 1 hour, and then allowed to cool to room temperature. The resulting crystals are coated with a polyarylene polymer. When the solution was applied to a gap-filled structure with sub-micron gaps and cured, the solution was found to completely fill the gaps. The cured polymer is insoluble in N-methylpyrrolidine dione. Example 6: Emperor 3,3 '-(oxydi-1,4-molylidene) 噔 (2 · 4 · 5-tribenzyl ring 戍 erpo__) (compound K), 1,3'- 蝥 ( Preparation of molybdenyl ethynyl) molybdenum (combined fluorene and 1,3,5-tris (benzylethenyl) benzyl (compound G)) Polymerization was applied to a 25 ml Schlenk tube and 3,3,-(oxydi-1, 4-benzylidene) bis (2,4,5-tribenzylcyclopentadienone) (2,000 g, 0.002554 moles), 1,3, -bis (phenylethynyl) benzene (0.4740 g, 0.001703 moles), 1,3,5-tris (benzylethynyl) benzyl (0.4834 g, 0.001277 moles), and N-fluorenyl 0-pyrrolidinedione (6.9 ml). The tube was attached It was connected to a nitrogen inlet, and the mechanically stirred solution was heated in an oil bath to 200 ° C. After 200 t: 20 hours, gel permeation chromatography indicated%, 1463, and ^ = 2660, which is equivalent to a polyethylene standard. (Please read the precautions on the back before filling this page)

Order ---------

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Consumers' Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs-Printing 1243182 A7 —-____ B7__ 5. Description of the invention (52) The liquid was cooled to room temperature and bottled. A portion of the solution was poured into a syringe and filtered on a 4 "silicon wafer through a 1.0 micron syringe filter. The wafer was spin-coated at 2000 rpm for 60 seconds under a heat lamp that could heat the wafer. The wafer was then coated It was placed on a hot plate set at 90 ° C for 2 minutes. The wafer was placed on a nitrogen stripping furnace to be cured by stripping at room temperature for 20 minutes, and then heated to 400 ° C at 10 ° / minute, Hold at 400 ° C for 1 hour, and then cool to room temperature. The crystals formed are coated with polyphenylene polymer. Example 7 Fish 3,3 '-(oxybis-1,4- · molylidene) bis (2,4,5-tribenzylcyclohexa + enone) (compound K) and 1,3,5-tris (benzylethynyl) benzyl (Chemical G) The oligomers have been dissolved in Deionized water and HPLC-grade acetone wetted and dried Pyrex @ l three-necked round bottom flask with low ion 3,3, · (oxydibenzylidene) bis (2,4,5-triphenyl ring) Pentadienone) (ΐ0.000 g, ΐ28 mole) Low ion 1,3,5 · tris (phenylethynyl) benzyl (48.3 g, 0.128 mole) and electronic grade N-formaldehyde Glycolin diketone (346 g). Flask was attached under nitrogen / True Inlet. The magnetic stirring solution was degassed by repeating five times with vacuum and refilling with nitrogen. Then, nitrogen flowed through the head space of the flask and flowed out through the inorganic oil bubbler. The solution was heated to an internal temperature of 2001. The solution was heated for 8.5 hours Then, it was cooled and transferred to a bottle made of tetrafluoroethylene. Analysis of the final product by gel permeation chromatography showed * Mn = 1498 & Mw = 2746, which is relative to the polystyrene standard. Reverse phase chromatography Analysis of the final solution showed that the residual 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-tritylcyclopentadienone) content was 1.8% by weight. The analysis was activated with nitrogen 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 p ^ m. This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) 35- ------- ^ --------- line — I ί Please read the notes on the back before filling out this page) 1243182 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (53), the Angstrom content is 0.6 ppm, and the gas content is 2.4 ppm. Example 8 Coating and curing from Example 7 Polymeric silane as the basic adhesive accelerator (AP8000 available from The Dow Chemical Company) is first coated (200 millimeters of crystals is 3 milliliters) on the surface of the crystals: slowly rotate them to disperse the entire surface; Allow it to stand for 2 seconds; finally spin-dry at 3000 irpm for 10 seconds. The polymer solution prepared in Example 7 was coated with a high-precision pump / transition system Millipore Gen-2 (200 millimeter wafers were 4 milliliters) ) On the surface of the wafer coated with an adhesive accelerator, the wafer is rotated at 750 rpm. Immediately after applying the polymer solution, the wafers were spun up to 2000 rpm, and this spin rate was maintained for 20 seconds. During the application of the recovery polymer solution, a continuous stream of 1,3,5 · xylene was applied to the back of the wafer. After the wafers were spin-coated with the polymer solution, the film was dried on a 70eC hot plate for 20 seconds. After the drying and baking step, the end beads of 2 ml to 5 ml of the coating are removed by a continuous flow of 1,3,5-triphenylbenzene, and the wafer is rotated at 2000 rpm, either by the back side or directly from Coat the top near the edge. After the end beads were removed, the oligomers were further polymerized on a hot plate at 325 ° C for 90 seconds under a nitrogen blanket. Then, the film was crosslinked under nitrogen at 45 ° C for 2 minutes on a hot plate or 6 minutes at 45 ° C under a nitrogen stripping furnace. The film had a glass transition temperature greater than 450 ° Ct measured by power mechanical analysis. Applicable to China National Standard (CNS) M specifications (210X297 public love) (讦 Please note the back of Klt before filling this page)

1243182 A7 B7 V. Description of Invention (54) Table I

This paper size applies to Chinese National Standard (CNS) A4 (210 乂 29 * 7mm) 57 Binding Line (please note the details on the back of Ktf before filling out this page) 1243182 A7 V. Description of Invention (55 Form I ( Performance

Ph

Ph

Qi G

Η ◎

Ph -Η

J Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs

Ph (Please read the precautions on the back before filling in this page)

This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 58 1243182 AT B7 V. Description of the invention (56) Table I (read)

This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) -59-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _ 1243182

AT B7 V. Description of the invention (57) Because the above compound preparation procedure is implemented using standard chemistry, and it is known that slightly different reactants may require slightly different reaction parameters from other reactions, it can be understood that the shown reaction parameters are slightly different (such as, The use of excess reactants, the use of catalysts, the use of temperatures slightly above or below room temperature, for example, and / or high rate mixing and other traditional variations) are within the scope of this invention. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 60 (Please read the precautions on the back before filling this page)

Claims (1)

n 1243182 A8 B8 C8 D8, patent application scope 1. A 4 ^ 4 phenylethynyl) phenyl) -2,3,5-triphenylcyclopentadienone It has the following chemical formula. 2. A species of 4-('ethynylphenyl) _2,3,5-triphenylcyclopentadienone, which has the following chemical formula. 3 · —3,4-bis (4- (phenylethynyl) phenyl) -2,5-diphenylcyclopentadienone or 3,4-bis- (3- (phenylethynyl) Phenyl) -2,5-diphenylcyclopentadienone, which has the following chemical formula. 4. A 4,4 ''-bis (benzylethynyl-o-triplebenzyl or 2,4,4 ,, _ tri (phenyl paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) (Please (Read the notes on the back before filling in this page) -61-1243182 A8 B8 C8 D8 6. Scope of patent application: ethynyl) diphenyl ether or 4,4, ', 4 "-tris (phenylethynyl) -o-terphenyl, which has the following chemical formula. ◎ ◎ 5. -Species 3,3 '-(1,4-phenylene) bis (2,5-bis- (4-fluorophenyl) -4-phenylcyclopentadienone has the following chemical formula. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ---------------------- • packing --------- --------- 、 may -----------------. Line (please read the notes on the back before filling this page) -62- Category A4 C4 1243182 The above blocks are to be filled in by this Bureau) The Ministry of Economic Affairs ’Smart Blanket 2: 4_ ^: Job Contract-!: 7 Printed by Cooperative Cooperative --- ^ --__ ^ Patent Specification ------------ _____ ___ Invention A I. Name of Chinese Cyclopentadione-based polyfunctional compound and aromatic acetylene-based multifunctional compound wSSL English POLYFUNCIIONAL COMPOUND OF CTG ^ OPENTADIENONE GROUP AND POLYFUNCTIONAL COMPOUND OF AROMATIC ACETYT .F | < rF Π ^ ΠΤ TP Name (1) James P. Goldscox ⑹Gary R. Busker (2) Duane R * Romao⑺PaulΗ. Townsend III Ⅲ Yingying. 莜 ⑻Dennis W. Smith ( 4) Nonan Lysenker Stephen J. Martin ⑶ Michael E. Mills (10) Robert A. Deveres Invented, Nationality 1.2. -10 United States 3. Canada J: A, M I Γ Live, Residence (1) Midland, Michigan, USA 2205 Mars Street (2) 4025 Lowell Street, Midland, MI, USA (3) 1524 Denoway Avenue, Midland, MI, USA (4) Mid, MI, USA 214 Westbrook Brook, Midland (5) 1604 Yavalon Street, Midland, MI, USA (6) 613 Siofang Lane, Midland, MI, USA (7) United States 1102 Wilder Street, Midland, MI (8) 4607 Fresno Present Trail, Texas (9) 3019 Scabarov Lane, Midland, MI, USA No. 1 (10) Midland, Michigan, USA • Greenthorn Thorns 3408 " Name (Name) American Business · Dow Global Technology Co., Ltd. Nationality US III. Applicant's Residence, Residence (Office) Name of Representative, 1790 Washington Street, Midland, Michigan, USA Noreen D. Warwick This paper size is applicable to Zhongjia County (CNS) M specification (21QX 297 mm)