TW492981B - Oligomer, uncured polymer or cured polymer, a process for forming an uncured polymer or a cured polymer, and an integrated circuit article - 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

B7 五、發明説明（1 ) 本發明係有關聚亞苯基募聚物及聚合物及其製備及 使用之方法。此等寡聚物可用於微電子製備中作為介電樹 脂。 本申請案為序號711，838號案之部份連續案，·該案係 於1996年9月l〇a申請，其在此被併入以供參考。 聚合物介電質可作為諸如積體電路、多晶片組件及 層合電路板之微電子裝置中各種電路與電路内之層狀物間 之絕緣層。微電子製造工業現轉移成其裝置内較小之幾何 ，使其動力較低且速率較快。因導體線變得較細且更密合 包裝’此導體間之介電質要件變得更嚴格。 雖然相較於諸如二氧化矽之無機介電質，聚合物介 電質通常提供較低介電常數，其通常存在製備期間處理聚 體性之挑戰。例如，為替代積體電路中作為介電質之二氧 化石夕’介電質需能抵抗方法中之金屬化與退火步驟期間之 處理溫度。較佳者，介電付料需具有大於處理溫度之玻璃 ' 4 . 轉移溫度。介電質亦需於裝置使用條件下保持所欲性質。 f 例如’介電質應不吸水，其會造成介電常數之增加及金屬 導體之潛在腐蝕。 經濟部中央標準局員工消費合作社印製 對於某些積體圖，當以諸如自旋塗覆之傳統塗覆技 術塗覆時：寡聚物較佳需平面化且間隙填充圖案表面。 現今’聚醯亞胺樹脂為於電子工業中作為薄膜介電 質之一類材料。但是聚醯亞胺樹脂可吸收水且水解，其會 造成電路腐钮◊金屬離子可移入介電聚醯亞胺層，其於金 屬線與聚酿亞胺介電質間需障壁層❶聚醯亞胺會展現較差 4 (請先閲讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) M規格（21Q>< 297公慶） 492981 經濟部中央標隼局員工消費合作社印製 A7 _B7_ 五、發明説明（2 ) 之平面化及間隙填充性質。非氟化聚醯亞胺會展現非所欲 之高介電常數。B7 V. Description of the invention (1) The present invention relates to polyphenylene polymer and polymer, and a method for preparing and using the same. These oligomers can be used as dielectric resins in the preparation of microelectronics. This application is part of the serial case No. 711,838. This application was filed on September 10, 1996, and is hereby incorporated by reference. Polymer dielectrics can be used as insulating layers between various circuits and layers within circuits in microelectronic devices such as integrated circuits, multi-chip components, and laminated circuit boards. The microelectronics manufacturing industry is now shifting to smaller geometries within its devices, making them less powerful and faster. As the conductor wires become thinner and more tightly packed, the dielectric requirements between the conductors become stricter. Although polymer dielectrics generally provide lower dielectric constants compared to inorganic dielectrics such as silicon dioxide, they often present the challenge of handling polymer properties during preparation. For example, in order to replace the bismuth oxide as the dielectric in the integrated circuit, the dielectric needs to be resistant to the processing temperature during the metallization and annealing steps in the method. Preferably, the dielectric material needs to have a glass' 4. The dielectric also needs to maintain the desired properties under the conditions of use of the device. f For example, 'dielectrics should not absorb water, which will cause an increase in dielectric constant and potential corrosion of metal conductors. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs For certain integrated drawings, when coated with traditional coating techniques such as spin coating: the oligomers preferably need to be planarized and the gap-filled pattern surface. Today's polyimide resins are one of the materials used as thin film dielectrics in the electronics industry. However, polyimide resin can absorb water and hydrolyze, which will cause the circuit rot button. Metal ions can move into the dielectric polyimide layer, which requires a barrier layer between the metal wire and the polyimide dielectric. Imine will show poor 4 (Please read the notes on the back before filling in this page) This paper size is applicable to Chinese National Standard (CNS) M specification (21Q > < 297 Public Holiday) 492981 Employees of the Central Bureau of Standards, Ministry of Economic Affairs Cooperative printed A7 _B7_ 5. Description of the invention (2) The planarization and gap filling properties. Non-fluorinated polyfluorene imine exhibits an undesirably high dielectric constant.

Kumar及Neenan於巨分子（Macromolecules，1995年，28) 一書第124〜130頁揭示數種由雙環戊二烯酮與鼕乙炔製得 之聚亞苯。其教示聚亞苯具有作為可光界定之有機介電質 之潛質。Wrasidlo斑Augl於J. Polym. Sci.，B部份（1969)， 2(7)，519〜523，揭示1,4-雙（苯乙烯基）苯與3,3’-(l，4-亞 苯基)-雙（2,4,5-三苯基戊二烯酮）之共聚物。其報告可溶性 黃色不熔聚合物可被獲得之。Kumar and Neenan in Macromolecules (1995, 28), pages 124-130, disclose several polyphenylenes made from dicyclopentadienone and asthene. It teaches that polyphenylene has the potential to be a photo-definable organic dielectric. Wrasidlo Spot Augl in J. Polym. Sci., Part B (1969), 2 (7), 519 ~ 523, reveals 1,4-bis (styryl) benzene and 3,3 '-(l, 4- Copolymer of phenylene) -bis (2,4,5-triphenylpentadione). It reports that a soluble yellow, non-melting polymer is available.

Kumar與Wrasidlo所述材料為可溶性，但可能不適於 作為某些使用（諸如，自旋塗覆來填充間隙），因為此材料 被聚合而耗盡環戊二烯酮部份，其提供相對高之分子量。 此分子量可能過高而無法藉由自旋塗覆於含有藉由介電質 填充之間隙之圖案表面上塗覆之。以所報告之玻璃轉移溫 度為基準，此等材料可能無法抵抗積體電路内之内層介電 質所欲之處理。 於美國專利第 5,334,668 ; 5,236,686 ; 5，169,929及5,338,823 號案中，Tour描述許多製備用於製備玻璃態碳素之可交聯 聚亞苯.组合物之方法。聚亞苯係藉由聚合1-溴-4-鋰苯形 成溴化聚萃苯，然後偶合取代性苯基乙炔（諸如，苯基乙 炔基苯基乙炔）至殘餘溴而製備之。聚亞苯於交聯前具有 約200°C之熔點。 期望提供聚合物介電質給微電子製造工業，其提供 可信賴之低介電常數，高熱穩定性及尚玻璃轉移溫度’且 本紙張尺度適用中國國家標李（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 492981 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（3 )其較佳者能藉由自旋塗覆來塗覆，而使圖案表面平面化及 填充間隙。 第一方面，本發明為募聚物、未固化聚合物或固化 聚合物，其包含一或多種含有二或多種環戊二烯酮·基之多 官能基化合物與至少一含有二或多種芳族乙炔基之多官能 基化合物之反應產物，其中至少一些多官能基化合物含有 三或多種反應性基團。 在此所用之反應基係定義為環戊二烯酮或乙炔基。 在此所用之寡聚物係定義成本發明之二或多個單體單元之 反應產物，其會間隙填充（即，填充1微米深微米寬 之矩形溝槽），而於固化時不會留下空隙。此處所用之未 固化聚合物係定義成本發明單髏之反應產物，其不再間隙 填充，但含有大量未反應環戊二烯酮或乙炔官能基。此處 所用之固化產物係定義成本發明單體之反應產物，其不含 有大量未反應環戊二烯酮或乙炔官能基。大量未反應環戊 二烯酮或乙炔官能基需要該部份為具反應性而能進一步促 進聚合反應。 本發明之一特徵為其含有一或多種含有二或多種環 戊二烯酮基之多官能基化合物與至少一含有二或多種芳族 乙炔基之多官能基化合物之反應產物，其中至少一些多官 能基化合物含有三或多種反應基。此反應產物之一優點為 其能間隙填充及使圖案表面平面化，且固化時具有高的熱 穩定性，高玻璃轉移溫度及低介電常數。 第二方面（較佳方面），本發明係一種募聚物、未固化 I----；---^ — II (請先閲讀背面之注意事項再填寫本頁) 訂 響 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 6 492981 A7 B7 五、發明説明（4 ) 聚合物或固化聚合物，其含有一或多種含有二或多種環戊 二烯酮基之多官能基化合物與一或多種含有二或多種芳族 乙炔基之多官能基化合物之反應產物，其中至少一些含有 芳族乙炔基之多官能基化合物含有三或更多之乙決基。 本發明第二方面之特徵係其含有至少一或更多含有 '一或更多種環戍一婦嗣之多官能基化合物與至少一含有二 或更多芳族乙炔基之多官能基化合物之反應產物，其中至 少一些含有芳族乙炔基之該多官能基化合物含有三或更多 之乙炔基。此一反應產物之一特徵為其可間隙填充及使圖 案表面平面化，且固化時具有高的熱穩定性、高玻璃轉移 溫度及低介電常數。 高的熱穩定性、高玻璃轉移溫度、低介電常數及能 夠間隙填充及使圖案表面平面化之能力使本發明之組合物 適合作今微電子製備中之聚合物介電質。特別是，低介電 常數、高的熱穩定性及高玻璃轉移溫度之結合能允許使用 本發明組合物作為積體電路中之内層介電質β 較佳者’本發明之募聚物及聚合物及相對應之起始 單體為： 經濟部中夬標準局員工消費合作社印製 I---\---—I (請先閲讀背面之注意事項再填寫本頁) I、通式如下之寡聚物及聚合物： [A]w [B]z [EG]V 其中A具有下述結構： 本紙張尺度適财國國家標準（CNS) Α4規格（21GX 297公慶） 492981 A7 ___B7 五、發明説明（5 )The materials described by Kumar and Wrasidlo are soluble, but may not be suitable for some 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 patterned surface 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 polyphenylene. Compositions for use in the preparation of glassy carbons. Polyphenylene is prepared by polymerizing 1-bromo-4-lithiumbenzene to form brominated polyphenylene benzene, and then coupling a substituted phenylacetylene (such as phenylethynylphenylacetylene) to 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 noble glass transition temperature ', and this paper size is applicable to China National Standard (CNS) A4 specification (210X 297mm) (%) (Please read the notes on the back before filling this page) Order 492981 A7 B7 Printed by the Consumer Cooperatives 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 coating To planarize the pattern surface and fill the gaps. In a first aspect, the present invention is a polymeric polymer, an uncured polymer, or a cured polymer, which comprises one or more polyfunctional compounds containing two or more cyclopentadienone groups and at least one containing two or more aromatic compounds. The reaction product of an ethynyl polyfunctional compound, wherein at least some of the polyfunctional compounds contain three or more reactive groups. The reactive group used herein is defined as cyclopentadienone or ethynyl. As used herein, an oligomer is defined as the reaction product of two or more monomer units of the present invention, which will be gap-filled (ie, 1 micron deep micron wide rectangular grooves) without leaving behind during curing Void. The uncured polymer as used herein is defined as the reaction product of the single crossbones of the present invention, which is no longer gap-filled, but contains a large amount of unreacted cyclopentadienone or acetylene functional groups. As used herein, the cured product is defined as the reaction product of the monomers of the present invention and does not contain a large amount of unreacted cyclopentadienone 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 pattern, and has high thermal stability during curing, high glass transition temperature, and low dielectric constant. In the second aspect (preferred aspect), the present invention is a polymer-raising, uncured I ----; --- ^ — II (please read the precautions on the back before filling this page) Chinese National Standard (CNS) A4 specification (210 × 297 mm) 6 492981 A7 B7 V. Description of the invention (4) Polymer or cured polymer containing one or more polyfunctional groups containing two or more cyclopentadienone groups The reaction product of a radical compound with one or more polyfunctional compounds containing two or more aromatic ethynyl groups, at least some of which contain an aromatic ethynyl polyfunctional compound containing three or more ethylidene groups. A feature of the second aspect of the present invention is the reaction of at least one or more polyfunctional compounds containing 'one or more cyclopentadienes and at least one polyfunctional compound containing two or more aromatic ethynyl groups. Products where at least some of the polyfunctional compounds containing an aromatic ethynyl group contain three or more ethynyl groups. One of the characteristics of this reaction product is that it can gap-fill and planarize the pattern surface, 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 the pattern surface make the composition of the present invention suitable for use as a polymer dielectric in today's microelectronics manufacturing. 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 β in an integrated circuit. Preferred is the polymer and polymerization of the present invention. The corresponding starting monomers are: I --- \ ---- I printed by the Consumer Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page) I. The general formula is as follows Oligomers and polymers: [A] w [B] z [EG] V where A has the following structure: The size of this paper is suitable for the national standard of the country (CNS) A4 specifications (21GX 297 public holidays) 492981 A7 ___B7 5 Description of the invention (5)

且B具有下述結構：And B has the following structure:

(請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製(Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

R2-^—Ar3— P2~= - 」y-1 R2-=——Ar2—— 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 492981 A7 ---——___Β7 ---—--- 五、發明說明（6 ) 其中R1及R2各別為Η或未被取代或被惰性取代之芳族 部份，且Ar1、Ar2及Ar3各別為未被取代之芳族部份或惰 性取代之芳族部份，Μ為一鍵，且y為3或更大之整數，p 為已知每單元内未反應乙炔基之數目，1為已知每單元内 少於反應乙炔基之數目者，且p+r^yq , z為1〇〇〇之整 數；w為0至1〇〇〇之整數，且v為2或更大之整數。 此募聚物及聚合物可藉由使雙環戊二烯铜、含有三 個或多個乙炔部份之芳族乙炔及選擇性之含有二芳族乙炔 部份之多官能基化合物反應而製備之。此一反應可以下述 化學式之化合物之反應表示之， (a)如下示化學式之雙環戊二烯酮··R2-^ — Ar3— P2 ~ =-"y-1 R2-= —— Ar2—— This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) 492981 A7 -------___ Β7- ------ 5. Description of the invention (6) where R1 and R2 are each Η or an unsubstituted or inertly substituted aromatic moiety, and Ar1, Ar2, and Ar3 are each unsubstituted aromatic moiety Or an inertly substituted aromatic moiety, where M is a bond and y is an integer of 3 or greater, p is the number of known unreacted ethynyl groups per unit, and 1 is known to be less than the reactive acetylene per unit The number of bases, and p + r ^ yq, z is an integer of 1,000; w is an integer of 0 to 1,000, and v is an integer of 2 or more. The agglomerates and polymers can be prepared by reacting copper dicyclopentadiene, an aromatic acetylene containing three or more acetylene moieties, and optionally a polyfunctional compound containing a diaromatic acetylene moiety. . This reaction can be expressed by a reaction of a compound of the following chemical formula, (a) The dicyclopentadienone of the chemical formula is shown below.

(b) 如下示化學式之多官能基乙炔： (c) 及，選擇性，如下化學式之雙乙炔： 一 Ar2 -ΙΞΞΞΞ-R2 其中R1、R2、Ai:1、Ar2、Ar3及y係如前所定義。 芳族部份之定義包含苯基、多芳族及熔合芳族部份 。h f生取代思指取代基為基本上對環戊二烯酮與乙炔聚合 -------I---V------ (請先閱讀背面之注意事項再填寫本頁) tr---------· Γ > 經濟部智慧財產局員工消費合作社印製(b) The polyfunctional acetylene of the chemical formula is as follows: (c) and, optionally, the diacetylene of the following chemical formula:-Ar2-IΞΞΞΞ-R2 where R1, R2, Ai: 1, Ar2, Ar3 and y are as previously described definition. Aromatic moieties are defined to include phenyl, polyaromatic and fused aromatic moieties. hf raw substitution means that the substituent is basically the polymerization of cyclopentadienone and acetylene ------- I --- V ------ (Please read the precautions on the back before filling this page) tr --------- · Γ > Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

492981 A7 B7 五、發明説明（7 ) 反應為惰性且於微電子裝置中使用固化聚合物之條件下不 易與環境物種（諸如，水）反應。此取代基包含，例如，F 、a、Br、-CF3、-OCH3、-OCF3、-O-Ph及 1 至 8個碳原子 之烷基、3至8個碳原子之環烷基。例如，可為未被取代或 惰性取代之芳族部份者包含：492981 A7 B7 V. 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, a, Br, -CF3, -OCH3, -OCF3, -O-Ph, and alkyl groups of 1 to 8 carbon atoms, and cycloalkyl groups of 3 to 8 carbon atoms. For example, those that may be unsubstituted or inertly substituted aromatic moieties include:

經濟部中央標準局員工消費合作社印製 10 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 492981 A7 B7 五、發明説明（8 )Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 10 (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 492981 A7 B7 V. Description of the invention ( 8 )

(請先閲讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)

或or

、1T 其中 Z可為：-0-、-S-、亞烷基、-cf2、-ch2-、-0-、-cf2-、全氟烷基、全氟烷氧基、 R3 -k- 〇II -P- R3I -P- cf3 CF3 蠓 cf3, 1T where Z can be: -0-, -S-, alkylene, -cf2, -ch2-, -0, -cf2-, perfluoroalkyl, perfluoroalkoxy, R3 -k-. II -P- R3I -P- cf3 CF3 蠓 cf3

經濟部中夬標準局員工消費合作社印製 CHiPrinted by Employee Consumer Cooperatives, Chungli Standards Bureau, Ministry of Economic Affairs, CHi

Ph CH, CH, 或 -CF, CH，Ph CH, CH, or -CF, CH,

PhPh

Ph, 其中每一R3各別為-H、-CH3、-CH2CH3、-(CH2)2CH3或Ph 。Ph為苯基。 11 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 492981 A7 B7 五、發明說明（9 II、通式如下之聚亞苯寡聚物及聚合物Ph, where each R3 is -H, -CH3, -CH2CH3,-(CH2) 2CH3 or Ph. Ph is phenyl. 11 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 492981 A7 B7 V. Description of the invention (9 II. Polyphenylene oligomers and polymers with the following general formula

X R I I I I I I--I--*llll· — — — T. I ^ -4-,0 (請先閱讀背面之注意事項再填寫本頁)、X R I I I I I--I-* llll · — — — T. I ^ -4-, 0 (Please read the notes on the back before filling this page),

-R 經濟部智慧財產局員工消費合作社印製 R- 其中Ri、R2、Ar1及Ar2係如前所定義；x為}至1〇〇〇之整數 。較佳者，X為1至50，更佳為1至1〇。此寡聚物及聚合物 可藉由雙環戊二烯酮與如下通式之二乙炔反應而製備之：-R Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy R- where Ri, R2, Ar1 and Ar2 are as defined above; x is an integer from} to 1000. Preferably, X is 1 to 50, and more preferably 1 to 10. The oligomers and polymers can be prepared by reacting dicyclopentadienone with diacetylene of the following formula:

本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 12 其中Ar4為芳族部份或惰性取代之芳族部份、Rl、R2及X係 如前所定義，可藉由環戊二烯酮官能基與如下通式之多官 能基化合物之乙炔官能基反應製備之， 經濟部中夬標準局員工消費合作社印製 A7 五、發明説明（1〇 其中R1、R2、Arl及Αγ2係如前所定義。 ΠΙ'以下示化學式表示之聚亞苯募聚物及聚合物 〇This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) 12 where Ar4 is an aromatic part or an inertly substituted aromatic part, R1, R2 and X are as defined above, which can be determined by The cyclopentadienone functional group is prepared by reacting the acetylene functional group of a polyfunctional compound with the following general formula, printed by the Consumer Cooperative of the China Standards Bureau of the Ministry of Economic Affairs, A7. 5. Description of the invention (1 of which R1, R2, Arl and Αγ2 is as defined above. II ′ is a polyphenylene polymer and a polymer represented by the chemical formula shown below.

〇〇

其中R1、R2及Ar4係如前所定義。 IV、如下化學式表示之聚亞苯募聚物與聚合物 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁)R1, R2 and Ar4 are as defined above. IV. Polyphenylene polymers and polymers represented by the following chemical formula: The paper size is applicable to China National Standard (CNS) A4 (210 × 297 mm) (Please read the precautions on the back before filling in this page)

A7A7

其中R1、R2、Ar4及χ係如前所定義，可藉由使如下通式之 (請先閱讀背面之注意事項再填寫本頁) i0. 訂 經濟部中央橾準局員工消費合作社印製 多官能基化合物之環戊二烯酮官能基與乙炔官能基反應而 製備之， 〇Among them, R1, R2, Ar4, and χ are as defined above. You can use the following formula (please read the precautions on the back before filling out this page). I0. The cyclopentadienone functional group of the functional compound is prepared by reacting with the acetylene functional group.

R2 其中R1、R2與Αι:4係如前所定義。 含有二或多個芳族環戊二烯酮部份之多官能基化合 物可藉由使用傳統方法使二苯乙二酮與苯甲基酮縮合反應 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 14 經濟部智慧財產局員工消費合作社印製 492981 A7 ____ B7 五、發明說明（u) 而製備之。例示方法係揭示於Kumar等人之巨分子 (Macromolecules)，1995,这，124-13〇; 〇gHarus〇等人之j 〇rgR2 wherein R1, R2 and Aι: 4 are as defined above. Polyfunctional compounds containing two or more aromatic cyclopentadienone moieties can be used to condense diphendione and phenylmethyl ketone by using traditional methods. This paper applies Chinese National Standard (CNS) A4 specifications. (210X 297 mm) 14 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 492981 A7 ____ B7 5. Prepared by the invention (u). Exemplary methods are disclosed in Macromolecules of Kumar et al., 1995, this, 124-13 〇; Harus 〇 et al. J 〇rg

Chem·，1965，拉，3354; Ogliaruso 等人之 J· 〇rg· Chem·， 1963,处，2725;及美國專利第4,400,540號案。 含有二或多個芳族乙炔部份之多官能基化合物可藉 由傳統方法製備之。芳族化合物可被鹵化，然後於芳基乙 炔基化之催化劑存在中與適當取代之乙炔反應，以便以取 代之乙快化合物代替齒素。 一旦多官能基化合物單體製成，其較佳係被純化之 。特別是，用於作為有機聚合物介電質之製備中，金屬及 離子物種被移除之。例如，含有芳族乙炔基之多官能基化 合物可與水洗 '脂族烴溶劑接觸，然後溶於芳族溶劑且經 純化矽石凝膠過濾。此處理可移除殘餘之乙炔基化之催化 劑。額外之再結晶可助於移除非所欲之雜質。 雖然不欲被理論所限制，深信聚亞苯募聚物及聚合 物係於溶液中之環戊二烯酮與乙炔之混合物加熱時，經由 環戍二烯酮與乙炔基之Diels Alder反應而形成之。此等寡 聚物可含有環戊二烯酮及/或乙炔端基及/或側基。當進 步加熱此/谷液或以此溶液塗覆之物件時，額外的鍵延伸 會經由殘餘環戊二烯_端基與殘餘乙炔基之Diels人^以反 應產生，造成分子量之增加。依所用溫度而定，乙炔基彼 此之反應亦會發生。 券5^物與t合物係以具有環戊二婦嗣及/或乙炔端 基及/或側基之結構顯示之。一般，端基係依反應所用之 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公愛） T5 ------"7----♦•丨•丨 I (請先閱讀背面之注意事項再填寫本頁) 訂---------線邊 492981 A7 B7 五、發明説明（l3 ) 環戊二烯酮對Diels Alder反應性乙炔官能基之相對濃度而 定，且化學計量過量之環戊二烯酮官能基產生更多環戊二 烯酮端基，化學計量過量之Diels Alder反應性乙炔官能基 產生較大比例之乙炔端基。 本發明較佳實施例之特徵為於所有環戊二烯酮部份 反應前停止進行聚合反應。然後，於進行聚合反應使其餘 之環戊二烯酮部份反應前，募聚物可被塗於表面。於此一 寡聚化狀態中，當被塗於圖案表面時，募聚物可平面化且 間隙填充之。較佳者，至少10%之環戊二烯酮部份未反應 。最佳者，至少20%之環戊二烯酮部份未反應。可藉由光 譜分析測定未反應環戊二烯酮部份之百分率。環戊二烯酮 部份於可見光譜中為高色度，其具有明顯之紅或紫色，其 於環戊二烯酮部份反應時褪色。 此處所用之平面化係指隔離之特徵可被平面化70%或 更多，較佳為80%或更多，最佳為90%或更多。平面化之 百分率或程度係由下列方程式計算之： 經濟部中央標準局員工消費合作社印製 平面化百分率=(l-ts/tm) X 100 當募聚物層被塗於隔離方形線時，2微米平.均厚度時為1微 米寬及1微米高，且ts為募聚物或聚合物平均高度上特徵 上之募聚物或聚合物高度，^為此特徵之高度（1微米）。 此定義之使用係例示於，例如，Proceedings of IEEE，Vol· 80, No· 12, 1992年 12月，第 1948頁。 雖然不欲被理論所限制，聚亞苯聚合物之製備一般 係以如下所述表示之： 16 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 492981 Μ Β7 五、發明説明（14)Chem., 1965, La, 3354; J. Org. Chem., Ogliaruso et al., 1963, Division, 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 halogenated and then reacted with an appropriately substituted acetylene in the presence of an arylacetylenated catalyst in order to replace the halides with acetyl compounds. 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 contacted with a water-washed 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 polymers and polymers are formed by the reaction of a mixture of cyclopentadienone and acetylene in a solution, which is formed by the reaction of Diels Alder of cyclopentadienone and acetylene Of it. These oligomers may contain cyclopentadienone and / or acetylene end groups and / or pendant groups. When this / valley solution or an object coated with this solution is further heated, additional bond extension may occur through the reaction of the residual cyclopentadienyl end group and the residual ethynyl group of Diels, resulting in an increase in molecular weight. Depending on the temperature used, the reaction of ethynyl groups with one another also occurs. The compound 5 and the compound t are shown in a structure having a cyclopentadiene and / or an acetylene end group and / or a side group. Generally, the end group is based on the size of the paper used for the reaction. It is applicable to China National Standard (CNS) A4 (21〇X 297). T5 ------ " 7 ---- ♦ • 丨 • 丨 I ( Please read the precautions on the back before filling in this page) Order --------- line edge 492981 A7 B7 V. Description of the invention (l3) Relative concentration of cyclopentadienone to Diels Alder reactive acetylene functional group Depending on the stoichiometric excess of cyclopentadienone functional groups, more cyclopentadienone end groups are generated, and the stoichiometric excess of Diels Alder reactive acetylene functional groups generates a larger proportion of acetylene end groups. The preferred embodiment of the present invention is characterized in that the polymerization reaction is stopped before all the cyclopentadione portions are reacted. The agglomerates can then be applied to the surface before polymerization proceeds to allow the remaining cyclopentadienone to partially react. In this state of oligomerization, when applied to a patterned surface, 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 cyclopentadione portion is highly chromatic in the visible spectrum, it has a distinct red or purple color, and it discolors when the cyclopentadione portion is reacted. As used herein, planarization means that the 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 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs = (l-ts / tm) X 100 When the polymer layer is coated on the isolated square line, 2 Micron flat. The average thickness is 1 micron wide and 1 micron high, and ts is the height of the polymer or polymer on the average height of the polymer or polymer, and ^ is the height of the feature (1 micron). An example of the use of this definition is, for example, Proceedings of IEEE, Vol. 80, No. 12, December 1992, p. 1948. Although it is not intended to be limited by theory, the preparation of polyphenylene polymers is generally expressed as follows: 16 (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) Α4 specifications (210 × 297 mm) 492981 Μ B7 V. Description of the invention (14)

(請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製(Please read the notes on the back before filling out this page) Order Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

其中R1、R2、Ar1、Ar2及X係如前所定義，再者，雖然未特別顯示其結構，羰基橋鍵物種可存 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 17 492981 A7 B7 五、發明説明（15 ) 在於所製備之募聚物，其係依使用之特定單體與反應條件 而定。進一步加熱時，羰基橋鍵物種基本上會完全轉換成 芳族環系統。當使用多於一個之含乙炔單體時，形成之寡 聚物及聚合物為無規，雖然所畫結構可能暗示嵌段被形成 。環戊二烯酮與乙炔官能基間之Diels Alder反應會發生而 形成苯環上之對位或間位之附接。 任何可溶解單體至適當程度且於大氣壓、低於大氣 * 壓或超過大氣壓時被加熱至適當聚合反應溫度之惰性有機 溶劑可被使用之β適當溶劑之例子包含1，3,5-三甲苯、处 啶、三乙基胺、Ν-甲基吡咯烷酮（ΝΜΡ)、曱基苯甲酸酯、 乙基苯曱酸酯、丁基苯曱酸酯、環戎酮、環己酮、環庚酮 、環辛酮、環己基咣咯烷酮及醚或己氧基醚，諸如，二苯 甲基醚、雙（2-甲氧乙）醚、三（2-甲氧乙）醚、二乙二醇乙 基醚、二乙二醇曱基醚、二丙二醇甲基醚、二丙二醇二甲 基醚、丙二醇苯基醚、丙二醇甲基醚、三丙二醇曱基醚、 曱苯、1，3,5-三甲苯二甲苯、苯、二丙二醇單曱基醚乙酸 酯、二氣苯、亞丙基碳酸酯、萘、二苯基醚、丁内酯、二 曱基乙醯胺、二甲.基甲醯胺及其混合物。較佳溶劑為1，3,5- 經濟部中央標準局員工消費合作社印製 三曱苯、Ν-甲基吡咯燒酮（ΝΜΡ)、τ-丁内酯、二苯基醚 ，、 * 及其混合物。 另外，單體可於,升高溫度之一或多種溶劑中反應， 所形成之募聚物溶液可被冷卻且與一或多種額外溶劑配製 ，而有助於加工處理。於另一方法中，單體可於升高溫度 之一種或多種溶劑中反應而形成募聚物，然後可藉由沈澱 18 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 492981 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明（16 ) 於非溶劑内或藉由其它溶劑移除方法隔離，產生基本上無 溶劑之募聚物。此等被隔離之募聚物可再溶於一或多種不 同溶劑中，所形成之溶液可用於加工處理。 聚合反應最有利進行之條件係依不同因素而定，包 括特定反應物與溶劑。一般，反應係於非氧化氛圍（諸如 ，氮氣或其它惰性氣體覆蓋氣體）下進行之。反應可簡潔 地進行（無溶劑或其它稀釋劑）。但是，為確保均勻反應混 合物及於此溫度為溫和放熱反應，其通常欲使用惰性有機 溶劑，諸如前述者，用於反應物中。 最有利使用之時間及溫度會依所用特定單體而定， 特別是其反應性、所欲特定募聚物或聚合物及溶劑。一般 ，形丰寡聚物之反應係於150°C至25(TC之溫度進行60分鐘 至48小時。於此時，募聚物可自反應混合物分離或用於塗 覆表面。額外之鏈延伸（增加）可於100。(：至475。(：之溫度進 行，較佳為200°C至450°C，進行1分鐘至10小時，更佳為1 分鐘至1小時。未固化或固化之聚合物可被用於藉由從溶 劑鑄製來塗覆表面 '雖然此一聚合物可能無法充分間隙填 充或平面化，但仍可用於金屬鑲嵌方法中。 可最有利於有機液體反應介質中使用之單體之濃度 係依各種因素而定，包括特定單體及所有之有機液體及被 製備之寡聚物及聚合物。一般，單體係以環戊二烯酮對g _之化學計量比例為1:1至1:3，較佳為1:1至1:2之比例使 用之β 募聚物或聚合物可直接以薄鑄製，以塗覆物塗覆或 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 19 I------；:—蝥II i (請先閲讀背面之注意事項再填寫本頁) 訂 492981 A7 B7 五、發明説明（Π) 倒入非溶劑内以便沈殺募聚物或聚合物。水、甲醇、乙醇 及其它相似極性液體為典型上非溶劑，其可被用於沈澱募 聚物。固體募聚物或聚合物可由適當溶劑溶解及處理之。 若募聚物或聚合物係以固體型式獲得時，其可進一步使用 傳統壓縮模製技術或熔融自旋、鑄製或壓出技術處理之， 其條件為固體先質需具有足夠低之玻璃轉移溫度。 更普遍者，募聚物或聚合物直接由有機液體反應溶 液處理，且本發明之優點為於該實例中更完全瞭解。因募 聚物或聚合物可溶於有機液體反應介質，寡聚物之有機溶 液可被鑄製或塗覆且溶劑被蒸發。分子量增加（鏈延伸或 增進），且於某些例子中交聯而形成最終聚合物，其係發 生於其後曝需於足夠高之溫度時。 本發明聚合物可作為用於積體電路、多晶片組件或 平喪板展示器之單一或多層電子連接建構中之一或多個絕 緣或介電層。本發明聚合物可作為此等應用或與其它有機 聚合物或無機介電質（諸如，二氧化矽、氮化矽或氧氮化 矽）結合中作為底介電質。 經濟部中央標準局員工消費合作社印裝 I ’ ^ — ! (請先閲讀背面之注意事項再填寫本頁) 、1Τ 例如，本發明之寡聚物及聚合物之塗覆（諸如，用於 電子薄件上製備接連結構之電絕緣塗覆）可藉由自旋鑄製 一拜膜狀之寡聚物或聚合物之有機液體溶液或以此溶液塗 覆基材’然後蒸發溶劑，且使募聚物或聚合物曝露於足以 使寡聚物或聚合物進行較高分子量之溫度，且於最佳例中 ，成具較高玻璃轉移溫度之交聯聚合物。 本發明之聚合物特別可作為積體電路（諸如，以矽或 8 9 2 9 4 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（18 ) 鎵之砷化物製備者）之接連結構中之低介電常數絕緣材料 。積體電路典型上具有多層以一或多種絕緣材料分離之金 屬導體。本發明之聚合物材料可作為相同層内之各別金屬 導體間及/或連接結構之導體層間之絕緣。本發明之聚合 物亦可與其它材料（諸如，3丨02或3丨31^4)結合使用於錯合接 連結構。例如，本發明寡聚物及聚合物可用於教示於美國 專利第5,550,405 ;美國專利第5,591，677及Hayashi等人之 1996 Symposium on VLSI Technology Digest of Technical Papers，89-89頁，中所教示之製備積體電路裝置之方法。 本發明之寡聚物及聚合物可取代BCB或其它揭示方法中所 揭示之樹脂。 本發明之寡聚物、未固化聚合物或聚合物可作為上 述教示方法或相似方法中之介電質，以製備積體電路物件 ，該物件含有具有晶體管之活化基材及具有圖案金屬線（ 其少部份藉由本發明組合物層或區域分離）之電接連結構 〇 本發明之聚合物亦可作為平面化材料，諸如，用於 半導體中之矽晶元，以製備較小（較高密度）電路。為達成 所欲之平面化，募聚物或聚合物之塗覆物藉由自旋塗覆或 喷灑塗覆自溶液塗覆至流動物，以使基材表面上之任何粗 链面平坦。此等方法係例示於諸如Bowden等人之“高科 技聚合物之微電子應用”，美國化學協會，1987年，261 〜269頁。 於製備微電子裝置中，相對薄之無缺失膜（通常厚度 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 21 (請先閲讀背面之注意事項再填寫本頁) " ♦ ♦ 492981 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（19 ) 為〇·〇1至20微米，較佳為01至2微米）可沈積於基材表面， 例如，矽、含矽材料、二氧化矽、氧化鋁、銅、氮化矽、 氮化鋁、鋁、石英及砷化鎵。塗覆物一般係具有分子量為 ，例如，3000 Μη*更少及52〇〇 或更少，之募聚物溶 液製備’其係於各種有機溶劑（諸如，二甲苯、1，3,5-三甲 苯、NMP、7 •丁内酯及正丁基乙酸醋中。溶解之募聚物 或聚合物可藉由一般自旋及噴灑塗覆技術鑄製於基材上。 塗覆物之厚度可藉由改變固體百分率、分子量、溶液黏度 及自旋速率來控制。 本發明中之聚亞苯募聚物或聚合物可藉由浸潰塗覆 、喷灑塗覆、壓出塗覆來塗覆之，更佳係以自旋塗覆為之 。所有情況中，基材週爵之環境及固化前之塗覆物可藉由 相關之溫度及濕度來控制。特別是，NMP可自週圍空氣 中之水蒸氧吸收水。當溶於NMP時，需保碟溶液免於潮 濕空，氣，且於低濕度環境中鑄膜。當使ffiNMp作為溶鄙 時，較佳者，相對濕度需控制於低於3〇%，且溫度係控制 在2fC或更大。塗覆物可於塗覆後以一或多個熱板、爐、 或此等工具之混合固化之。 黏著促進劑（諸如，以矽烷化學為基準者）可於聚亞苯 募聚物或聚合物溶液塗覆前塗覆於基材上，或直接塗於溶 液。 本發明之募聚物及聚合物可以“鑲嵌式，，金屬鑲嵌負 式傘層圖案使用於積體笮路接連結構之製備。製備鑲嵌式 線及管為業界已知β例如’可參看美國專利第5,262,354 表紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 22 (請先閲讀背面之注意事項再填寫本頁} 、1Τ 492981 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（20 ) 及 5,093,279 號案。 材料之圖案可以典型離子蝕刻程序使用含氧、氬、 氮、氦、二氧化碳、氟之化合物或此等氣體與其它氣體之 混合物，使用光阻“軟罩”（諸如，環氧線型酚醛)或與無 機“硬罩”（諸如，Si02、Si3N4或金屬）混合之光阻為之。 募聚物及聚合物可藉由物理蒸氣沈積、化學蒸氣沈 積、蒸發、電鍍、無電沈積及其它沈積方式，與A卜A1合 金、Cu、Cu合金、金、銀、W及其它一般金屬導電材料（ 作為導線及插頭）接合使用之。基本金屬導電物之額外金 屬層，諸如，組、鈦、鎢、鉻、始、其合金、或其氮化物 ，可被用以填充孔洞、促進金屬填充、促進黏著、提供障 壁，或改良金屬反射性。 依製備組織而定，本發明之金屬或介電材料可使用 化學-機械拋光技術移除或平面化。 於活化或鈍態基材（諸如，矽、矽酸鹽玻璃、碳化矽 、鋁、氮化鋁或FR-4)上之多晶片模組可以本發明之聚亞 苯聚合物作為介電材料構建之β 於活性或鈍態基材（諸如，矽、矽酸鹽玻璃、碳化矽 、鋁、氮化鋁或FR-4)上之平嵌板展現可以本發明之聚亞 苯聚合物作為介電材料構建之。 本發明之募聚物及聚合物可進一步作為積電路晶片 上之保護塗覆，以保護對抗α -粒子《當由包裝或其它附 近材料内之輻射微量污染物釋出之α-粒子撞擊活化表面 時，半導體裝置易軟化失誤。積體電路可被供以本發明之 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 23 (請先閱讀背面之注意事項再填寫本頁)% 492981 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（21 ) 保護塗覆。典型上，積體電路晶片被置於基材上且保持於 具適當黏著性之位置。本發明聚合物塗覆對晶片活化表面 提供α-粒子保護層。選擇性地，額外之保護藉由以，例 如，環氧化物或矽酮製備之封裝提供之。 本發明聚合物亦可被作為電路板或印刷線路板上之 基材（介電材料由本發明聚合物組成之電路板已置於用 於各種電導體電路之其表面圖案上。除本發明聚合物外， 電路板可含有各種強化物，諸如，織狀非導電纖維（諸如 ，玻璃布）。此電路板可為單一側及雙側或多側。 本發明聚合物亦可用於強化錯合物中，其中，樹脂 基材聚合物以一或多種強化材料（諸如，強化纖維或墊）強 化之。代、表佚之強化材料包含玻璃纖維（特別是，玻璃纖 維墊（織物狀或非織物狀）；石墨（特別是，石墨垫（織物狀 或非織物狀））；Kevlar™ ; Nomex™ ;及玻璃球。此錯合 物可由預成型、單體或募聚物之浸潰墊及樹脂轉移模製（ 其間墊被置於模内，且單體或預聚物被添加並加熱而產生 聚合反應）而形成之。 本發明聚合物層可藉由濕式蝕刻，電漿蝕刻、反應 性離子蝕刻（RIE)、乾式蝕刻或光雷射切除枣成，圖案，如 例示於“電子應用之聚合物”（Polymers for Electronic Applications)，Lai，CRC Press (1989)，第 42〜47 頁。圖案 可藉由多層次技術完成之，其間I圖案係石板印刷式地界 定於塗覆於聚合物介電層上之阻層，然後辞刻於底層内。 特別有用之技術包含掩蔽不欲被移除之募聚物或聚合物部 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 24 • · · ^ (請先閲讀背面之注意事項再填寫本頁) A7 ^___B7__ 五、發明説明（22 ) 份，移除未掩蔽之募聚物或聚合物部份，然後，例如，以 熱固化留下之寡聚物或聚合物。 此外，本發明之募聚物亦可用於製備成型物件、膜 、纖維及發泡體。一般，業界用以由溶液鑄製寡聚物或聚 合物之已知技術可被用以製備此產物。 製備成型聚亞苯募聚物或聚合物物件時，可使用添 加劑，諸如，填料、色料、碳黑、導電金屬粒子、磨料及 潤滑性聚合物。加入此添加劑之方法並不重要，可於製備 成型物件前方便性地添加至募聚物或聚合物溶液。單獨含 有募聚物或聚合物或亦含有填料之液體組合物可以任何一 般技術（刮刀、軋式、浸潰、刷式、喷灑、自綠塗覆、壓 出塗覆或彎液面塗覆）塗覆於各種不同基材上。若聚亞苯 寡聚物或聚合物以固態製備，添加劑可於製成成型物件前 被加入溶融物。 經濟、邓中央標準局員工消費合作社印製 本發明之募聚物及聚合物可以各種方法塗於各種基 材，諸如，溶液沈積、液相取相附生、屏蔽印刷、溶融自 旋、浸潰塗覆、軋式塗覆、粉末塗覆、電漿沈積、分散液 喷灑、溶液鑄製、漿料喷灑、乾粉喷灑、流體化床技術、 焊接、包含線爆喷灑方法及***鍵結之***方法、以熱壓 縮鍵結、電漿聚合、於分散介質内分散其後再移除分散介 質、加壓鍵結、加壓加熱鍵結、氣體環境硫化、壓出熔融 聚合物、熱氣焊接、烘焙、塗覆及燒結。單一層及多層膜 亦可使用Langmuir-Blodgett技術於空氣-水或其它界面沈 積於基材上。 25 (請先閱讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) Μ規格（210X297公釐） 492981 A7 B7 五、發明説明（23 ) 當由溶液塗覆本發明寡聚物或聚合物時，所用之最 有利聚合反應特定條件及其它處理參數係依各種不同因素 ‘而定，特別是被沈積之特定募聚物或聚合物，塗覆條件、 塗覆量及厚度及最終使用之應用，及所選用之溶劑。可被 使用之代表性溶劑係描述於前。 可以本發明募聚物或聚合物塗覆之基材可為任何具 有與以單體、募聚物或聚合物塗覆之足夠整體性之材料。 基材之代表性例子包含木材、金屬、陶瓷、玻璃、其它聚 合物、紙、紙板布、織狀纖維、非織狀纖維墊、合成纖維 、Kevlar™、碳纖維、砷化鎵、矽及其它無機基材及其氧 化物β所用基材係以所欲應用為基準選擇之。例示之材料 包含玻璃纖維（織狀、非織狀或線股）、陶瓷、金屬（諸如 ，銘、鎮、鈦、銅、鉻、金、銀、鎢、不鎮鋼、Hastalloy™ 、碳鋼、其它金屬合金及其氧化物）及熱固性及熱塑性聚 合物（諸如，環氧樹脂、聚醯亞胺、全氟環丁烷聚合物、 苯曱基環丁烷聚合物、聚苯乙烯、聚醯胺、聚碳酸酯、聚 亞芳基醚及聚酯）。基材可為固化型式之本發明聚合物。 經濟部中央標準局員工消費合作社印製 基材可為任何形狀，且形狀係依最終應用而定。例 如，基材可為碟狀、片狀、線狀、管狀、板狀、球狀、桿 狀、管線狀、圓柱狀、碑形、纖維狀、織物或非織物纖維 、紗線狀（包含摻合紗線）、規則聚合物；織物或非織物墊 。每一情況中，基材可為中空或實心。於中空物件情況中 ，聚合物層係於基材之内側或外側或二者。基材可包含多 孔層，諸如，石墨墊或織物、玻璃墊或織物、稀鬆布、及 26 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 492981 A7 B7 五、發明説明（24 ) 顆粒材料。 本發明寡聚物或聚合物直接附接於許多材料，諸如 ，可相容聚合物、具有普通溶劑之聚合物、金屬（特別是 具質地之金屬）、矽或二氧化矽（特別是，蝕刻之石夕或氧化 矽）、玻璃、氮化矽、氮化銅、氧化鋁、砷化鎵、石英及 陶瓷。但是，當期望增加黏著性時，材料可被引入以改良 黏著性。 經濟部中央標準局員工消費合作社印製 此促進黏著性材料之代表性例子為矽烷，較佳為有 機矽烷，諸如，三甲氧基乙烯基矽烷、三乙氧基乙烯基矽 烷、六甲基二矽氨烷[(CH3)3-Si-NH-Si(CH3)3]，或胺基矽 烷偶合物，諸如，7-胺基丙基三乙氧基矽烷，或螯合劑 ，諸如，鋁單乙基乙醯基乙酸酯二異丙酸酯I；((異 C3H7〇)2Al(OCOC2H5CHCOCH3))]。某些情況中，黏著促 進劑係以0.01重量％至5重量％溶液施用之，過量溶液被移 除，然後施用聚亞苯。其它情況中，例如，鋁單乙基乙醯 基乙酸酯二異丙酸酯之螯合劑可藉由將螯合劑之甲苯溶液 喷灑於基材上，然後於氧氣中35(TC時烘焙塗覆基材30分 鐘，形成非常薄（例如，5 nm)之鋁氧化物黏著促進層於表 面上，而加入基材上。其它沈積鋁氧化物之方法亦適合。 另外t，黏著促進劑（其量為，例如，以單體重量為基準為〇.〇5 重量％至5重量°/。)在聚合反應前可與單體摻合，取消形成 額外層之需求。 黏者性亦可藉由表面製備促進之，例如，使具質地 化（例如，刮、蝕刻、電漿處理或、磨光）或清理（例如， 27 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公羞） 492981 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（25) 脫脂或音波清理），其它處理（例如，電漿、溶劑、so3、 電漿成長放電、電暈放電、鈉、濕式蝕刻、或臭氧處理） 或吹砂處理基材表面或使用電子束（諸如，6 MeV氟離子） ;50至2000 V強度之電子；0.2至500 ev至1 MeV之氫質子 ;200 KeV至1 MeV之氦質子；0.5 MeV之氟或氣離子；280 KeV之氖；富氧火焰處理；或加速氬離子處理。 為塗覆3,3’-(氧二-1，4-亞苯基）雙（2,4,5-三苯基環戊二 烯酮）與1，3,5-三（苯乙炔基）苯反應之寡聚化產物（本發明較 佳實施例），矽烷為基準之黏著促進劑（其含有溶於甲氧基 丙醇内之3-胺基丙基矽烷，可由杜邦之VM-652或陶氏化 學公司之AP8000得之）先被塗於晶元表面；緩慢旋轉以便 喷灑整個表面；靜置2秒鐘；於3000 rpm作最後旋轉乾燥10 秒鐘。當晶元以750 rpm旋轉，以高精確泵/過濾系統 (Millipore Gen-2)將寡聚物溶液分散（200 mm晶元為4 mL) 於晶元表面上。於分散聚合物溶液後立即將晶元旋轉加速 至2000 rpm，且保持該旋轉速率20秒。1，3,5-三甲苯之連 續流於分散募聚物溶液期間被塗於晶元背側5秒鐘。於自 旋塗覆後，膜於7〇°C之熱板上乾燥20秒。於乾烘步驟後， 2 mm至5 mm之塗覆端緣小珠以連續之1，3，5 -三甲苯流移除 ，且以由背側塗覆或直接由接近端緣之頂部直接塗覆使晶 元以2000 rpm旋轉。移除端緣小珠後，於氮氣罩下寡聚物 於325°C之熱板上進一步聚合90秒。膜於氮氣下之450°C熱 板上交聯2分鐘或於450°C之氮汽提爐中交聯6分鐘。 本發明之寡聚物或聚合物可結合其它添加劑來應用 -~2S~: (請先閱讀背面之注意事項再填寫本頁) T ϋ Mmmmw i·— n n - a ϋ" I an i_l in 1_ϋ < 線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 492981Among them, R1, R2, Ar1, Ar2, and X are as defined above. Furthermore, although the structure is not specifically shown, the carbonyl bridge species can be stored. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 17 492981 A7 B7 V. The description of the invention (15) lies in the prepared polymer, which depends on the specific monomers used and the reaction conditions. Upon further heating, the carbonyl bridged species is essentially completely converted into 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. Diels Alder reaction between cyclopentadienone and acetylene functional group will occur to form para or meta attachment on the benzene ring. Any inert organic solvent that can dissolve monomers to an appropriate level and is heated to the appropriate polymerization temperature at atmospheric pressure, below atmospheric * or above atmospheric pressure. Examples of β suitable solvents that can be used include 1,3,5-trimethylbenzene Trimethoprim, triethylamine, N-methylpyrrolidone (NMP), fluorenyl benzoate, ethyl benzoate, butyl benzoate, cyclobutanone, cyclohexanone, cycloheptanone , Cyclooctanone, cyclohexylpyrrolidone, and ethers or hexyloxy ethers, such as benzhydryl ether, bis (2-methoxyethyl) ether, tris (2-methoxyethyl) ether, diethylene glycol Alcohol ethyl ether, diethylene glycol ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, tripropylene glycol ethyl ether, toluene, 1, 3, 5 -Xylene, benzene, dipropylene glycol monofluorenyl ether acetate, digas benzene, propylene carbonate, naphthalene, diphenyl ether, butyrolactone, difluorenylacetamide, dimethyl. Formamidine and mixtures thereof. Preferred solvents are 1,3,5-trimethylbenzene, N-methylpyrrolidone (NMP), τ-butyrolactone, diphenyl ether, * and mixture. In addition, the monomers can be reacted in one or more solvents at elevated temperatures, and the resulting polymer solution can be cooled and formulated with one or more additional solvents to facilitate processing. In another method, the monomers can react in one or more solvents at elevated temperatures to form agglomerates, which can then be precipitated by precipitation 18 (please read the precautions on the back before filling this page) This paper is for China National Standard (CNS) A4 specification (210X297 mm) 492981 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (16) Isolation in a non-solvent or by other solvent removal methods, resulting in essentially no Polymerization of solvents. These sequestered polymers can be redissolved in one or more different solvents and the resulting solution can be used for processing. The conditions under which the polymerization proceeds most favorably depend on various factors, including specific reactants and solvents. Generally, the reaction is performed under a non-oxidizing atmosphere (such as nitrogen, or other inert gas blanket gas). The reaction can be carried out concisely (without solvents or other diluents). However, to ensure a homogeneous reaction mixture and a mild exothermic reaction at this temperature, it is generally desired to use an inert organic solvent, such as the foregoing, for the reactants. The most advantageous time and temperature will depend on the particular monomer used, especially its reactivity, the particular polymer or polymer and solvent desired. Generally, the reaction of the Xingfeng oligomer is performed at a temperature of 150 ° C to 25 ° C for 60 minutes to 48 hours. At this time, the polymer can be separated from the reaction mixture or used to coat the surface. Additional chain extension (Increase) can be carried out at a temperature of 100. (: to 475. (:, preferably 200 ° C to 450 ° C, 1 minute to 10 hours, more preferably 1 minute to 1 hour. 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 damascene methods. It is most beneficial for use in organic liquid reaction media The concentration of the monomers depends on various factors, including the specific monomers and all organic liquids and the oligomers and polymers prepared. Generally, the single system uses the stoichiometric ratio of cyclopentadione to g _ The β-aggregate or polymer used in a ratio of 1: 1 to 1: 3, preferably 1: 1 to 1: 2, can be directly thinly cast, coated with a coating or this paper is applicable to China Standard (CNS) A4 specification (210X 297 mm) 19 I ------ ;:-蝥 II i (Please read the Note: Please fill in this page again.) Order 492981 A7 B7 V. Description of the invention (Π) Pour into the non-solvent to kill the polymer or polymer. Water, methanol, ethanol and other similar polar liquids are typically non-solvent. Can be used to precipitate agglomerates. Solid agglomerates or polymers can be dissolved and processed with a suitable solvent. If the agglomerates or polymers are obtained in a solid form, they can be further processed using conventional compression molding techniques or melted from It is processed by spinning, casting or extrusion technology, provided that the solid precursor needs to have a sufficiently low glass transition temperature. More generally, the polymer or polymer is directly treated by the organic liquid reaction solution, and the advantage of the present invention is that Learn more fully in this example. Because the polymer or polymer is soluble in the organic liquid reaction medium, the organic solution of the oligomer can be cast or coated and the solvent is evaporated. The molecular weight increases (chain extension or enhancement), And in some examples, the cross-linking to form the final polymer occurs when the subsequent exposure to a sufficiently high temperature. The polymer of the present invention can be used for integrated circuits, multi-chip components One or more insulating or dielectric layers in a single or multi-layer electronic connection construction of a flat panel display. The polymers of the present invention can be used for these applications or with other organic polymers or inorganic dielectrics such as silicon dioxide , Silicon nitride or silicon oxynitride) as the bottom dielectric. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs I ^ ^! (Please read the precautions on the back before filling this page), 1T For example, The coating of the oligomers and polymers of the present invention (such as, for example, electrical insulation coatings for making successive structures on electronic thin parts) can be made by spin casting a film-like organic oligomer or polymer. A liquid solution or a substrate coated with this solution, and then the solvent is evaporated, and the polymer or polymer is exposed to a temperature sufficient to allow the oligomer or polymer to undergo a higher molecular weight, and in the best case, a Cross-linked polymer with high glass transition temperature. The polymer of the present invention is particularly useful as a continuum of integrated circuits (such as printed on silicon or 8 9 2 9 4 printed by A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (18) Preparation of gallium arsenide). Low dielectric constant insulating material in the structure. 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 in the same layer. The polymer of the present invention can also be used in combination with other materials such as 3 丨 02 or 3 丨 31 ^ 4 in a staggered continuous structure. For example, the oligomers 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, Method of integrated circuit device. The oligomers and polymers of the present invention can replace the resins disclosed in BCB or other disclosure methods. 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 that includes an activated substrate with a transistor and a patterned metal wire ( A small part of it is electrically connected 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 make smaller (higher density) ) Circuit. To achieve the desired planarization, the polymer or polymer coating is applied from the solution to the flow by spin coating or spray coating to flatten any rough chain surfaces on the substrate surface. Such methods are exemplified in "Microelectronic Applications of High-Tech Polymers", such as Bowden et al., American Chemical Society, 1987, pages 261-269. In the preparation of microelectronic devices, relatively thin non-missing film (usually the thickness of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 21 (Please read the precautions on the back before filling out this page) " ♦ ♦ 492981 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The description of the invention (19) is 0.001 to 20 microns, preferably 01 to 2 microns) can be deposited on the surface of substrates, for example, silicon, Silicon-containing materials, silicon dioxide, aluminum oxide, copper, silicon nitride, aluminum nitride, aluminum, quartz, and gallium arsenide. The coatings are generally prepared with a molecular weight of, for example, 3000 Mn * less and 5200 or less, which are prepared from various organic solvents such as xylene, 1, 3, 5-three Toluene, NMP, 7-butyrolactone and n-butyl acetate. The dissolved polymer or polymer can be cast on the substrate by ordinary spin and spray coating techniques. The thickness of the coating can be borrowed 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 more preferably spin-coated. In all cases, the environment of the substrate Chou and the coating before curing can be controlled by the relevant temperature and humidity. In particular, NMP can be obtained from the ambient air. Water vaporizes oxygen to absorb water. When dissolving in NMP, it is necessary to protect the dish solution from moisture, air, and casting in a low humidity environment. When ffiNMp is used as a solvent, it is better to control the relative humidity to be low 30%, and the temperature is controlled at 2fC or more. The coating can be applied in one or more after coating. Plate, furnace, or a mixture of these tools. Adhesion promoters (such as those based on silane chemistry) can be applied to the substrate before the polyphenylene polymer or polymer solution is applied, or directly Coated in solution. The polymer and polymer of the present invention can be "embedded," and the metal-embedded negative umbrella layer pattern is used for the preparation of integrated road structures. The preparation of inlaid wires and tubes is known in the industry, such as' Please refer to US Patent No. 5,262,354. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 22 (Please read the precautions on the back before filling this page} 、 1T 492981 Printed by the Consumers' Cooperative 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 a compound containing oxygen, argon, nitrogen, helium, carbon dioxide, fluorine or a mixture of these gases with other gases, using photoresist "Soft cover" (such as epoxy novolac) or mixed with inorganic "hard cover" (such as SiO2, Si3N4 or metal) for photoresist. Polymers and polymers can be Use physical vapor deposition, chemical vapor deposition, evaporation, electroplating, electroless deposition and other deposition methods to join with A1 A1 alloy, Cu, Cu alloy, gold, silver, W and other general metal conductive materials (as wires and plugs) The additional metal layer of the base metal conductor, such as group, titanium, tungsten, chromium, alloy, or its nitride, can be used to fill holes, promote metal filling, promote adhesion, provide barriers, or improve Metal Reflectivity. Depending on the structure of the preparation, the metal or dielectric material of the present invention can be removed or planarized using chemical-mechanical polishing techniques. For activated or passive substrates (such as 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 on β active or passive substrates (such as silicon, silicate glass, Flat panel on silicon carbide, aluminum, aluminum nitride or FR-4) exhibits that the polyphenylene polymer of the present invention can be constructed as a dielectric material. The polymer and polymer of the present invention can be further used as a protective coating on a circuit chip to protect against α-particles. When the α-particles released by radiation trace pollutants in packaging or other nearby materials hit the activated surface As a result, semiconductor devices are prone to soften mistakes. 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 (Please read the precautions on the back before filling this page)% 492981 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperative A7 B7 V. Description of Invention (21) 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 an alpha-particle protective layer to the activated surface of the wafer. Optionally, additional protection is provided by packaging made of, for example, epoxide or silicone. The polymer of the present invention can also be used as a substrate for a circuit board or a printed wiring board (a circuit board whose dielectric material is composed of the polymer of the present invention has been placed on its surface pattern for various electrical conductor circuits. Except for the polymer of the present invention In addition, the circuit board can contain various reinforcements, such as woven non-conductive fibers (such as glass cloth). The circuit board can be single-sided and double-sided or multi-sided. The polymer of the present invention can also be used to strengthen the complex. Wherein, the resin base polymer is reinforced with one or more reinforcing materials (such as reinforcing fibers or pads). On the other hand, the reinforcing materials for the surface include glass fibers (especially, glass fiber mats (woven or non-woven) Graphite (especially, graphite mats (fabric or non-woven)); Kevlar ™; Nomex ™; and glass spheres. This complex can be pre-formed, monomer or polymer impregnated pads and resin transfer molds (The mat is placed in the mold, and the monomer or prepolymer is added and heated to generate a polymerization reaction.) The polymer layer of the present invention can be formed by wet etching, plasma etching, reactive ion etching (RIE), dry etching or light laser ablation, patterns, as exemplified in "Polymers for Electronic Applications" (Lai, CRC Press (1989), pages 42 ~ 47. Patterns can be borrowed This is accomplished by multi-level technology, during which the I-pattern is lithographically defined on a resistive layer coated on a polymer dielectric layer, and then etched into the bottom layer. Particularly useful techniques include masking of funds that are not to be removed. Polymer or polymer department This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 24 • · ^ (Please read the precautions on the back before filling out this page) A7 ^ ___ B7__ 5. Description of the invention ( 22), remove the unmasked polymer or polymer portion, and then, for example, leave the oligomer or polymer cured by heat. 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 solutions can be used to make this product. When forming shaped polyphenylene polymers or polymer objects, Use additives such as Fillers, colorants, carbon black, conductive metal particles, abrasives, and lubricating polymers. The method of adding this additive is not important, and can be conveniently added to the polymer or polymer solution before preparing the molded object. Polymers or polymers or liquid compositions that also contain fillers can be applied by any general technique (squeegee, roll, dip, brush, spray, self-green coating, extrusion coating, or meniscus coating) On various substrates. If the polyphenylene oligomer or polymer is prepared in a solid state, the additive can be added to the melt before it is made into a molded article. Materials and polymers can be applied to a variety of substrates in a variety of ways, such as solution deposition, liquid phase phasing, mask printing, melt spin, dip coating, roll coating, powder coating, plasma deposition, Dispersion spraying, solution casting, slurry spraying, dry powder spraying, fluidized bed technology, welding, explosion method including line explosion spraying method and explosive bonding, thermal compression bonding, plasma polymerization, dispersion Dispersion in the medium is followed by removal of the dispersion medium, pressurized bonding, pressurized heating bonding, vulcanization in a gaseous environment, extrusion of 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. 25 (Please read the precautions on the back before filling this page) The paper size is applicable to the Chinese National Standard (CNS) M specification (210X297 mm) 492981 A7 B7 V. Description of the invention (23) When the present invention is coated with a solution Polymer or polymer, the most favorable polymerization conditions and other processing parameters used depend on a variety of factors, especially the particular polymer or polymer being deposited, coating conditions, coating amount and thickness And end-use applications, and the solvents selected. 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, paperboard, woven fibers, non-woven fiber mats, synthetic fibers, Kevlar ™, carbon fibers, gallium arsenide, silicon, and other inorganic materials The substrate and its oxide β are selected based on the intended application. Exemplary materials include glass fibers (woven, non-woven or strand), ceramics, metals (such as Ming, Zhen, Titanium, Copper, Chrome, Gold, Silver, Tungsten, Stainless Steel, Hastaloy ™, Carbon Steel, Other metal alloys and their oxides) and thermosetting and thermoplastic polymers (such as epoxy resins, polyimide, perfluorocyclobutane polymers, phenylfluorenyl cyclobutane polymers, polystyrene, polyamidoamine , Polycarbonate, polyarylene ether and polyester). The substrate may be a polymer of the present invention in a cured form. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economics The substrate can be of any shape, and the shape depends on the final application. For example, the substrate may be dish-like, sheet-like, wire-like, tubular, plate-like, spherical, rod-like, pipe-like, cylindrical, stele-like, fibrous, woven or non-woven fiber, yarn-like (including blended Yarn), regular polymers; woven or non-woven mats. In each case, the substrate can 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 26 (Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) Α4 specifications ( 210X297 mm) 492981 A7 B7 V. Description of the invention (24) Particulate material. The oligomers or polymers of the present invention are directly attached to many materials, such as compatible polymers, polymers with common solvents, metals (particularly textured metals), silicon or silicon dioxide (particularly, etching Stone eve or silicon oxide), glass, silicon nitride, copper nitride, aluminum oxide, gallium arsenide, quartz and ceramics. However, when it is desired to increase adhesion, materials may be introduced to improve adhesion. A representative example of this adhesion-promoting material printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs is silane, preferably organic silanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazine Aminoalkane [(CH3) 3-Si-NH-Si (CH3) 3], or an aminosilane conjugate such as 7-aminopropyltriethoxysilane, or a chelating agent such as aluminum monoethyl Acetyl acetate diisopropylate I; ((isoC3H7O) 2Al (OCOC2H5CHCOCH3))]. 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 in oxygen at 35 ° C (TC). Cover the substrate for 30 minutes to form a very thin (for example, 5 nm) aluminum oxide adhesion promotion layer on the surface and add it to the substrate. Other methods of depositing aluminum oxide are also suitable. In addition, an adhesion promoter (which The amount is, for example, 0.05% by weight to 5% by weight based on the weight of the monomer.) It can be blended with the monomer before the polymerization reaction, eliminating the need to form additional layers. Adhesiveness can also be achieved by Surface preparation facilitates, for example, texturing (eg, scraping, etching, plasma treatment, or polishing) or cleaning (eg, 27 (please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X29 * 7 public shame) 492981 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (25) Degreasing or sonic cleaning), other treatments (for example, plasma, solvents, so3, Plasma growth discharge, corona Electricity, sodium, wet etching, or ozone treatment) or sandblasting the substrate surface or using an electron beam (such as 6 MeV fluoride ion); electrons with an intensity of 50 to 2000 V; hydrogen protons from 0.2 to 500 ev to 1 MeV ; Helium protons of 200 KeV to 1 MeV; fluorine or gas ions of 0.5 MeV; neon of 280 KeV; oxygen-enriched flame treatment; or accelerated argon ion treatment. For coating 3,3 '-(oxydi-1,4- Oligomerization product of the reaction between phenylene) bis (2,4,5-triphenylcyclopentadienone) and 1,3,5-tris (phenylethynyl) benzene (the preferred embodiment of the present invention), Silane-based adhesion promoter (which contains 3-aminopropylsilane dissolved in methoxypropanol, which can be obtained from DuPont VM-652 or Dow Chemical Company AP8000) is first coated on the surface of the wafer Rotate slowly to spray the entire surface; let stand for 2 seconds; spin dry at 3000 rpm for 10 seconds. When the wafer is rotated at 750 rpm, oligomerize with a high precision pump / filtration system (Millipore Gen-2) The polymer solution was dispersed (200 mL wafers with 4 mL) on the wafer surface. Immediately after the polymer solution was dispersed, the wafer rotation was accelerated to 2000 rpm, and the rotation was maintained. The rate is 20 seconds. The continuous flow of 1,3,5-trimethylbenzene is applied to the back of the wafer for 5 seconds during the dispersion of the polymer solution. After spin coating, the film is placed on a hot plate at 70 ° C. Dry for 20 seconds. After the dry-baking step, coated end-edge beads from 2 mm to 5 mm are removed with a continuous stream of 1,3,5-trimethylbenzene, and either coated from the back side or directly near the end edge The top was directly coated to rotate the wafer at 2000 rpm. After removing the edge beads, the oligomer was polymerized on a hot plate at 325 ° C for 90 seconds under a nitrogen blanket. The membrane was crosslinked for 2 minutes on a 450 ° C hot plate under nitrogen or 6 minutes in a nitrogen stripper at 450 ° C. The oligomer or polymer of the present invention can be applied in combination with other additives- ~ 2S ~: (Please read the precautions on the back before filling this page) T ϋ Mmmmw i · — nn-a ϋ " I an i_l in 1_ϋ < Line · This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 492981

五、發明說明（26) 經濟部智慧財產局員工消費合作社印製 以獲得特殊結果。料添加劑之代表料含金属化合物（ 諸如，磁性粒子，例如，銷鐵、氧化⑹，㈣㈣㈣ 钻混合’或其它用於磁性介f、光學介質或其它記錄性介 質之含金屬粒子；導電粒子(諸如，用作導電密封劑之金 屬或碳)、導電黏著劑、導電塗覆、電磁界面⑽I)/A線 電頻率界面_)屏蔽塗覆、靜電消散及電接觸。當使用 此等添加劑時，本發明之寡聚物或聚合物可作為結合劑。 本發明之寡聚物或聚合物亦可作為對抗環境之保護 層（即，保護對抗物件環境中至少_物質或力量，包括製 備、儲存及使用之條件），諸如，使表面對金屬、半導體 、電容、感應器、導電器、太陽能電池、玻璃及玻璃纖維 、石央及石英纖維不具活性。 下列範例係用以例示本發明，而非用以限制其範圍 。於範例中，所有份數及百分率，除非有其它指示，皆係 以重量計。 &M1_复_備環戊二烯酮化合物盥i块化合物 數種環戊二稀酮化合物及乙炔化合物如下所述製備 之。此等化合物之結構係顯示於第I表中， Α· 本棊乙炔基1表基）_2,3,5-三笨某碌戍二嫌酮（化合 物A) ㈤製備4-溴笨基乙醯基氯化物 4-溴苯基乙酸（1〇〇克，0.465莫耳）、亞硫醯二氣（3 〇〇 毫升）及DMF(約2毫升）被注入裝備有迴流冷凝器及機械攪 拌器之1公升圓底3頸燒瓶。反應混合物於氮氣下加熱2小 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） * »—------—tr---------% (請先閱讀背面之注意事項再填寫本頁) 492981 A7V. Description of the invention (26) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to obtain special results. Representatives of additives include metal compounds (such as magnetic particles, for example, iron pin, hafnium oxide, hafnium, diamond, or other metal-containing particles used in magnetic media, optical media or other recording media; conductive particles such as , Metal or carbon used as conductive sealant), conductive adhesive, conductive coating, electromagnetic interface ⑽I) / A line electrical frequency interface _) shielding coating, 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 be used as a protective layer against the environment (that is, to protect at least _ substances or forces in the environment of the object, including conditions for preparation, storage and use), such as making the surface against metals, semiconductors, Capacitors, inductors, conductors, solar cells, glass and glass fibers, stone central 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. & M1_complex_preparation of cyclopentadienone compound. Block compounds. Several cyclopentadione compounds and acetylene compounds were prepared as described below. The structures of these compounds are shown in Table I, Α · benzyl ethynyl 1 epitope) _2,3,5-tribenzyldioxanone (compound A) ㈤ Preparation of 4-bromobenzylacetone 4-bromophenylacetic acid (100 g, 0.465 mol), dithionine (300 ml) and DMF (about 2 ml) were injected into a reactor equipped with a reflux condenser and a mechanical stirrer 1 liter round bottom 3-necked flask. The reaction mixture is heated under nitrogen. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm). * »—------— tr ---------% (Please (Please read the notes on the back before filling out this page) 492981 A7

五、發明說明（27) 經濟部智慧財產局員工消費合作社印制农 時，使用用於氣體逃脫之木炭滌氣器。亞硫醯二氣被蒸發 ’且產物（4-溴苯基乙醯基氣化物）被置入具苯（3〇毫升）之 添加漏斗内。 ⑻製備4·-漠脫氣安息香 苯（200毫升）與氣化鋁（74克，0.558毫升）被混入燒瓶 内，步驟（a)之4-溴苯基乙醯基氣化物與苯被一滴滴加入 使反應而蒸發HC1。反應混合物於室溫攪拌1至1 ·5小時且 被倒入冰水中。乙酸乙酯（1公升）被添加以溶解沈殿固體 。層狀物被分離且有機層連續以1M HC1水溶液、飽和 NaHC〇3水溶液、鹽水清洗，然後以Na2s〇2乾燥。然後蒸 發溶劑產生固體物質，將其由乙基乙酸酯/己烷再結晶， 以產生84%產率之黃色固體之標題化合物。 (c)製備4-溴二笑 乙二嗣 全氣酸（2 50毫升）、水（250毫升）、乙二醇二甲基驗（2-甲氧乙謎）（500毫升）、銘（πΐ)硝酸鹽三水合物（222.0克，0.5 莫耳）及4_溴脫氧安息香（68.75克，0·25莫耳）被注入2公升 之圓底3頸燒瓶（其配置有迴流冷凝器及機械式擾拌器）。 反應混合物於氮氣下加熱迴流6小時。冷卻至週圍溫度時 ’一氣曱烷（500亳升）被添加之。所形成之雙層物被倒出 形成之沈澱Τ1(Ι)鹽。層狀物被分離，且有機層以水、飽和 NaHC〇3水溶液及鹽水清洗，其後由孓丙醇再結晶所形成 之固體’產生標題化合物。 (d)复逸^(笨某乙炔D二茉乙二酮 臭二笨乙二酮（1〇·〇克，0·0346莫耳）、笨基乙炔（3.88 (請先閱讀背面之注意事項再填寫本頁) 裝 訂--------- %| 本紙張尺度適用中關家標準（CNS)A4規格⑽χ挪公爱） -- 492981 A7V. Description of the invention (27) When the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints agricultural products, it uses charcoal scrubbers for gas escape. The thionite gas was evaporated and the product (4-bromophenylethylfluorenyl gaseous) was placed in an addition funnel with benzene (30 ml). ⑻ Preparation of 4 · -degassed benzoin (200 ml) and vaporized aluminum (74 g, 0.558 ml) were mixed into the flask, and the 4-bromophenylethylfluorenyl vapor of step (a) was dropped with benzene. The reaction was added to 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 Shen Dian solids. The layers were separated and the organic layer was successively washed with a 1M aqueous HC1 solution, a saturated aqueous NaHC03 solution, brine, and then dried over Na2s02. 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 of 4-bromodistilbene oxalic acid (2 50 ml), water (250 ml), ethylene glycol dimethyl test (2-methoxyethane puzzle) (500 ml), Ming (π 铭) Nitrate trihydrate (222.0 g, 0.5 mol) and 4-bromodeoxybenzoin (68.75 g, 0.25 mol) were injected into a 2-liter round-bottom 3-neck flask (equipped with a reflux condenser and mechanical Stirrer). The reaction mixture was heated at reflux under nitrogen for 6 hours. When cooled to ambient temperature, ‘gas gas (500 liters) 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, a saturated NaHC03 aqueous solution, and brine, and then a solid 'formed from recrystallisation of propylpropanol yielded the title compound. (d) Fuyi ^ (Stupid Acetylene D Dimoethylene Ethyl Ketone Odor Diethylene Glycol (10.0 g, 0.0346 Molar), Stupid Acetylene (3.88 (Please read the precautions on the back before (Fill in this page) Binding ---------% | This paper size is applicable to Zhongguanjia Standard (CNS) A4 (⑽χ 挪 公 爱)-492981 A7

經濟部智慧財產局員工消費合作社印製 五、發明說明（28 ) 克 ’ 0.0380 莫耳）及（pph3)2PdCl2(0.121 克，0.0002 莫耳）， 其存在於二乙胺内（95毫升），於週圍溫度攪拌72小時，其 後濃縮至乾燥。殘質被接納於二氣甲烷内。標準之水溶液 其後由2-丙醇再結晶產生標題化合物。 0)製備化合物a 4-(苯基乙炔基）二苯乙二酮（2〇克，0·0644莫耳）、ι，3-二苯基乙酸酯（14.2克，0.0677莫耳）及乙醇（150毫升）被加 熱至75°C。溶於乙醇（15毫升）之氫氧化鉀（K〇H)(1 8克， 0.0322莫耳）於15分鐘期間被一滴滴添加。反應混合物被 加熱迴流30分鐘，然後冷卻至4〇°c，過濾沈澱產物，以冷 的乙醇清洗並乾燥之。由2-丙醇再結晶產生標題產物。 Β·ϋ!-(1，4-亞苯基）螯（2·4·5-三笨基環戊二烯酮（化合物b) 1，3-二苯基乙酸酯（123克，〇〇〇584莫耳）、}，‘雙（苯 基乙二駿基）苯（可由Ken Seika公司之Bis-PGB購得，1.000 克’ 0.00292莫耳）及乙醇（5〇毫升）被添加至1〇〇毫升之3頸 圓底燒瓶（其配置有迴流冷凝器/氮氣入口）。反應混合物 被加熱迴流，且存在於水（2.25毫升）中之KOH水溶液（0.112 克’ 0.002莫耳）被添加之。額外iK〇H被添加至溶液變暗 且保持暗色為止。混合物被迴流45分鐘，然後使其冷卻。 沈殿之深色固體以過濾收集之，且以ιΗ-ΝΜΚ、i3C-nMR 、HPLC及FT-IR分析。所有資料與化合物b之形成一致。 C·生雙（4_(苯基乙炔基）笨氣基）-2,2，,3,3，，5,5，，6,6，-八氟 雙苯基（化合物ΓΛ ㈤製備4_峨化苯基乙酸醋 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） :~J1 ~= ------；-------------„----訂---------線 , - 产 ♦ (請先閱讀背面之注意事項再填寫本頁) 492981Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (28) g '0.0380 mol) and (pph3) 2PdCl2 (0.121 g, 0.0002 mol), which are present in diethylamine (95 ml). The ambient temperature was stirred 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. 0) Preparation of compound a 4- (phenylethynyl) diphenylenedione (20 g, 0.064 mol), ι, 3-diphenylacetate (14.2 g, 0.0677 mol) and ethanol (150 ml) was heated to 75 ° C. Potassium hydroxide (KOOH) (18 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 and then cooled to 40 ° C. The precipitated product was filtered, washed with cold ethanol and dried. Recrystallization from 2-propanol gave the title product. Beta-ϋ!-(1,4-phenylene) chelate (2.4.5-tritylcyclopentadienone (compound b) 1,3-diphenylacetate (123 g, 0.000) 〇584mol),}, 'bis (phenylethylene glycol) benzene (commercially available from Bis-PGB of Ken Seika Company, 1.000 g' 0.00292 mole) and ethanol (50 ml) were added to 10 A 0 ml 3-neck round bottom flask (equipped with a reflux condenser / nitrogen inlet). The reaction mixture was heated to reflux, and an aqueous KOH solution (0.112 g '0.002 mole) in water (2.25 ml) was added. Additional iKO was added until the solution became dark 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 filtered with ιΗ-NMK, i3C-nMR, HPLC, and FT- IR analysis. All data are consistent with the formation of compound b. C. bis (4- (phenylethynyl) benzyl) -2,2,3,3,5,5,6,6, -eight Fluorobisphenyl (Compound ΓΛ ㈤ Preparation of 4_Ehua Phenyl Acetate) This paper is sized for Chinese National Standard (CNS) A4 (210 X 297 public love): ~ J1 ~ = ------;- ----------- „ ---- Order --------- Line,-Product ♦ (Please read the precautions on the back before filling this page) 492981

五、發明說明（29) 經濟部智慧財產局員工消費合作社印製 4-碘代酚（25.00克，〇·114莫耳）及二氣甲烷（1〇〇毫升） 被添口至250毫升之圓底燒瓶（其配置有冷凝器/氮氣入口 、熱偶及滴液漏斗）。漿料被攪拌且吡啶（1〇11毫升，〇.125 宅升）經由注射器添加。反應混合物使用冰浴冷卻至1 〇 ，乙醯基氣化物（8·89毫升，0.125莫耳）被一滴滴添加。混 合物於10°C攪拌1小時，使其加溫至室溫並攪拌2小時。反 應混合物被過濾，且濾液以水清洗4次。有機層被乾燥 (MgS〇4)，溶劑於真空乾燥而產生273克之桔色油。nmr 分析與所欲產物之結構一致。 (b) 製備4-(苯基乙炔某）苯基乙醅酷 4-碘代苯基乙酸酯（5〇·〇〇克，〇·19ι莫耳）、苯基乙炔 (23.40克’ 0.229莫耳）及三乙基胺（54亳升）被加至25毫升 之圓底燒瓶（其配置有冷凝器/氮氣入口、熱偶及止流器）。PdCl2(PPh3)2(0.200克，〇·286毫莫耳）及（PPh3(1.50克，5.73 毫莫耳）被添加且混合物被加熱迴流。當反應混合物達4〇 C時’添加Cul(0.054克，0.286亳莫耳）。2小時後，反應 被冷卻。混合物以二氯甲烷稀釋且倒入水（5〇〇毫升）中。 水性層以二氣甲烷（1〇0毫升）萃取。混合之有機層以三部 份300毫升之水清洗，乾燥（MgS〇4)並過濾。溶劑於真空 中移除產生49克黃色固體。物質由己烷再結晶產生黃色結 晶，mp 104.5°C 至 105.5°C。 (c) 製備4-(苯基乙快基）盼 4-(苯基乙炔基）苯基乙酸酯（60.6克，〇·256莫耳）、20% 氫氧化鈉水溶液（400毫升）及四氫決喃（4〇〇毫升）被加入2_ 公升之Erlenmeyer燒瓶，並於室溫攪拌5小時。混合物以 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 37 (請先閱讀背面之注意事項再填寫本頁) ----------訂------ 線丨· 492981 A7V. Description of the invention (29) 4-iodophenol (25.00 g, 0.1114 mol) and digas methane (100 ml) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs were added to the 250 ml circle Bottom flask (equipped with condenser / nitrogen inlet, thermocouple, and dropping funnel). The slurry was stirred and pyridine (1011 ml, 0.125 liters) was added via a syringe. The reaction mixture was cooled to 10 using an ice bath, and acetofluoride (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 was filtered, and the filtrate was washed 4 times with water. The organic layer was dried (MgS04) and the solvent was dried under vacuum to produce 273 grams of orange oil. The nmr analysis is consistent with the structure of the desired product. (b) Preparation of 4- (phenylacetylene) phenylacetamidine 4-iodophenylacetate (5.0 g, 0.19 mol), phenylacetylene (23.40 g '0.229 mol) Ear) and triethylamine (54 liters) were added to a 25 ml round bottom flask (equipped with a condenser / nitrogen inlet, a thermocouple and a stopper). PdCl2 (PPh3) 2 (0.200 g, 0.286 mmol) and (PPh3 (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) was added , 0.286 mol). After 2 hours, the reaction was cooled. The mixture was diluted with dichloromethane and poured into water (500 ml). The aqueous layer was extracted with methane (100 ml). Mixed organic The layer was washed with three portions of 300 ml of water, dried (MgS04) and filtered. The solvent was removed in vacuo to yield 49 g of a yellow solid. The material was recrystallized from hexane to produce yellow crystals, mp 104.5 ° C to 105.5 ° C. (c) Preparation of 4- (phenylethynyl) pan 4- (phenylethynyl) phenylacetate (60.6 g, 0.256 mol), 20% aqueous sodium hydroxide solution (400 ml) and Hydroxan (400 ml) was added to a 2-liter Erlenmeyer flask and stirred at room temperature for 5 hours. The mixture is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 37 (please first (Read the notes on the back and fill in this page) ---------- Order ------ Line 丨 492981 A7

五、發明說明（30) (請先閱讀背面之注意事項再填寫本頁) 冰乙酸（120毫升i酸化至pH值達7為止。水性層被移除且以 四氫呋喃萃取。有機層被混合且於旋轉濃縮機上濃縮產生 褐色固體。固體與蒸氣浴上之己烷加熱且熱溶液由固體緩 慢倒出。以第二體積之己烷（700毫升）重複此步驟。冷卻 時由己烧溶液結晶白色固體，且以過濾隔離並於真空乾燥 產生18克白色固體，126°C至127。(：。NMR分析與所 欲材料之結構一致。V. Description of the invention (30) (Please read the precautions on the back before filling this page) Glacial acetic acid (120ml i acidified to pH 7). The aqueous layer was removed and extracted with tetrahydrofuran. The organic layer was mixed and Concentrate on a rotary concentrator to produce a brown solid. The solid is heated with hexane on a steam bath and the hot solution is slowly decanted from the solid. Repeat this step with a second volume of hexane (700 ml). When cooling, a white solid crystallizes from the hexane solution. , And isolated by filtration and dried under vacuum to produce 18 grams of white solid, 126 ° C to 127. (:. NMR analysis is consistent with the structure of the desired material.

(d)製備化合物C 十氟雙苯基（5.00克，14.96毫莫耳）、4-(苯基乙炔基） 酚（5.81克，29.93毫莫耳）、碳酸鈉（16.54克，0.1197莫耳） 及二甲基乙醯胺（150毫升）被加至250毫升圓底燒瓶（其配 有冷凝器/氮氣入口、熱偶及止流器）。混合物被攪拌加 熱至70°C持續16·5小時。反應混合物被過濾移除固體。濾 液被添加至水（500毫升）且以二氣甲烷萃取。添加鹽水破 壞乳化液，有機層被分離且以水清洗兩次，經由矽石凝膠 栓過濾。溶劑於真空中移除留下油。添加甲醇，形成白色 固體，其藉由過濾隔離且於真空中乾燥。NMR光譜與標 題化合物之結構一致。 經濟部智慧財產局員工消費合作社印製 D· 4-(4-(乙炔某1某）-2,3,5-三笨基環戊二烯酮（化合物D) 依範例1Α使用三甲基甲矽烷基乙炔替代苯基乙炔製 備化合物D，其後使用稀釋鹼移除三甲基甲矽烷基保護基 〇 E. 3,4-雙彳4-(蓋基乙炔基）茉某V2,5-二茉基環戊二烯酮 合物Ε) 33 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 492981 A7 __ B7 五、發明說明（31) (a) 製備4，4 ’ -二 >臭安息香 存在於乙醇（125毫升）内之4-溴苯醛（25.0克，0.135莫 耳）、3-乙基-5-(2-羥基乙基）-4-甲基噻唑溴化物（1·70克， 0.0068莫耳）及三乙基胺（4.10克，0.0405莫耳）於室溫攪拌60 小時。反應混合物被濃縮乾燥，倒入CH2C12(150毫升）， 以1M HC1及飽和NaHC03水溶液清洗，並乾燥（Na2S04)， 然後濃縮、產生25.2克（100%)之黏性黃色油，其於室溫靜 置時固化。1H NMR (CDC13) 5 7.73 (d，J=8.5 Hz，2H)，（5 7.52 (d, J=8.5 Hz, 2H), 7.44 (d, J=8.2 Hz, 2H), 7.17 (d, J=8.2 Hz, 2H); 13C NMR (CDC13) δ 197.33, 137.56, 132.33, 132.13, 131.90, 130.43, 129.46, 129.31，122.93, 75.68。 (b) 製備4,4’-二溴安覓香 於80%乙酸水溶液（200毫升）中之4,4，-二溴安息香 (20·2克，0.055莫耳）、硝酸銨（4.6克，0.0575莫耳）及乙酸 銅（11)(0.100克，0.0005莫耳）被加熱迴流3小時。反應混合 物被冷卻至室溫，且結晶產物被過濾，以乙醇清洗並乾燥 ，產生13.0克（64%)之淡黃色固體之產物，mp為226°C至 228〇C。4 NMR (CDC13) 5 7.83 (d，J=8.5 Hz，4H)，7·66 (d， J=8.5 Hz, 4H); 13C NMR (CDC13) 5 192.25, 132.44, 13 1.45, 131.22, 130.7。 (c) 製備4,4、雙（笨基乙炔某）二茉乙二酮 存於二乙基胺（150毫升）中之4,4’-二溴二苯乙二酮 (15.8克，0.431莫耳）、苯基乙炔（5.06克，0.0495莫耳）、 (PPh3)2PdCl2(0.151 克，0.0002 莫耳）及 Cul(0.820 克，0.0043 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------110 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製(d) Preparation of compound C decafluorobisphenyl (5.00 g, 14.96 mmol), 4- (phenylethynyl) phenol (5.81 g, 29.93 mmol), sodium carbonate (16.54 g, 0.1197 mole) And dimethylacetamide (150 ml) were added to a 250 ml round bottom flask (equipped with a condenser / nitrogen inlet, a thermocouple, and a 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 was broken by adding brine, the organic layer was separated and washed twice with water, and filtered through a silica gel 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 title compound. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, D · 4- (4- (acetylene, 1 and 2) -2,3,5-tritylcyclopentadienone (Compound D) Trimethyl methyl is used according to Example 1Α Silyl acetylene was substituted for phenyl acetylene to prepare compound D, and then the dimethylsilyl protecting group was removed using a dilute base. E. 3,4-bisfluorene 4- (capryl ethynyl) molybdenum V2,5-di Mosylcyclopentadienone compound E) 33 This paper size applies to Chinese National Standard (CNS) A4 (210 x 297 mm) 492981 A7 __ B7 V. Description of the invention (31) (a) Preparation 4, 4 ' -Di > 4-bromobenzaldehyde (25.0 g, 0.135 mol), 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazole bromide present in ethanol (125 ml) The compound (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, which was allowed to stand at room temperature. Cure when set. 1H NMR (CDC13) 5 7.73 (d, J = 8.5 Hz, 2H), (5 7.52 (d, J = 8.5 Hz, 2H), 7.44 (d, J = 8.2 Hz, 2H), 7.17 (d, J = 8.2 Hz, 2H); 13C NMR (CDC13) δ 197.33, 137.56, 132.33, 132.13, 131.90, 130.43, 129.46, 129.31, 122.93, 75.68. (B) Preparation of 4,4'-dibromoamphetamine in 80% acetic acid 4,4, -dibromobenzoin (20 · 2 g, 0.055 mol), ammonium nitrate (4.6 g, 0.0575 mol) and copper acetate (11) (0.100 g, 0.0005 mol) in an aqueous solution (200 ml) It was heated to reflux for 3 hours. The reaction mixture was cooled to room temperature and the crystalline product was filtered, washed with ethanol and dried, yielding 13.0 g (64%) of the product as a pale yellow solid with an mp of 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) 5 192.25, 132.44, 13 1.45, 131.22, 130.7. ( c) Preparation of 4,4'-dibromodiphenyldione (15.8 g, 0.431 moles) in 4,4, bis (benzyl acetylene) dimothione in diethylamine (150 ml) ), Phenylacetylene (5.06 g, 0.0495 mol), (PPh3) 2PdCl2 (0.151 g, 0.0002 mol), and Cul (0. 820 g, 0.0043 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------- 110 (Please read the notes on the back before filling this page) Employees of the Bureau of Intellectual Property, Ministry of Economic Affairs Printed by Consumer Cooperatives

492981 A7 _ B7 五、發明說明（32) 莫耳）被迴流加熱隔夜。反應混合物被濃縮乾燥，倒入 CH2C12(150毫升）内，以 1M HC1、10%之Na2C03/H20、鹽 水清洗並乾燥（NaJO4)，然後濃縮之。由2-丙醇結晶產生 7.92 克（45%)淡褐色固體，mp 為 168°C 至 170°C。β NMR (CDC13) δ 7.97 (d, J=8.2 Hz, 4H), 7.64 (d, J=8.2 Hz, 4H), 7.55 (m5 4H), 7.37 (m, 6H); 13C NMR (CDC13) δ 193.03, 132.46，132.03，131.82，130.21，129.84，129·06，128.47,492981 A7 _ B7 V. Description of the Invention (32) Moore) was heated under reflux overnight. The reaction mixture was concentrated and dried, poured into CH2C12 (150 ml), washed with 1M HC1, 10% Na2C03 / H20, brine, dried (NaJO4), and concentrated. Crystals from 2-propanol yielded 7.92 g (45%) of a light brown solid with an mp of 168 ° C to 170 ° C. β NMR (CDC13) δ 7.97 (d, J = 8.2 Hz, 4H), 7.64 (d, J = 8.2 Hz, 4H), 7.55 (m5 4H), 7.37 (m, 6H); 13C NMR (CDC13) δ 193.03 , 132.46, 132.03, 131.82, 130.21, 129.84, 120.6, 128.47,

122.37, 94.28, 88.55 〇 (d)製備化合物E 存在於乙醇（5毫升）内之ΚΟΗ(0·34克，0.0061莫耳）溶 液被滴入存在於75°C乙醇（75毫升）内之4,4，-雙（苯基乙炔 基）二苯乙二酮（5.0克，0.0122莫耳）與1，3-二苯基丙酮（2.69 克，0 · 012 8莫耳）溶液。所形成溶液被迴流加熱1小時，冷 卻至室溫且沈澱物被過濾出並乾燥之。由沸騰乙醇提浸出 產物產生5.26克產物（74%)，為碑紅色固體：m.p. 222°C (DSC); 'H NMR (CDC13) δ 7.5 (bd5 J=3 Hz, 4H), 7.34 (m, 5H)，7.25 (bs，5H)，6.93 (d，J=8.0 Hz，4H); 13C NMR (CDC13) 5 199.02，152.72，132.31，131.14，130.83，129.93，129.67, 128.99，128.04，127.93，127.71，127.28，125.31，123.12, 122.46, 90.60, 88.71; MS (El) 585 (28)，584 (M+，56)，556 (19)，378 (36)，278 (100) 〇 F· 雙-(3-(苯基乙炔基）笨基V2.5·二笨基環戊二烯酮（化 合物F) (a)製備3,3’-二溴妥泉岙 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁}122.37, 94.28, 88.55 (d) Preparation of a solution of Compound KO (0.44 g, 0.0061 mol) in ethanol (5 ml) was dripped into 4,4 in ethanol (75 ml) at 75 ° C. A solution of 4, -bis (phenylethynyl) diphendione (5.0 g, 0.0122 mol) and 1,3-diphenylacetone (2.69 g, 0.012 8 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); 'H NMR (CDC13) δ 7.5 (bd5 J = 3 Hz, 4H), 7.34 (m, 5H), 7.25 (bs, 5H), 6.93 (d, J = 8.0 Hz, 4H); 13C NMR (CDC13) 5 199.02, 152.72, 132.31, 131.14, 130.83, 129.93, 129.67, 128.99, 128.04, 127.93, 127.71, 127.28, 125.31, 123.12, 122.46, 90.60, 88.71; MS (El) 585 (28), 584 (M +, 56), 556 (19), 378 (36), 278 (100) 〇F · Double- (3- (Phenylethynyl) benzyl V2.5 · dibenzylcyclopentadienone (compound F) (a) Preparation of 3,3'-dibromotoquan This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page}

T . -n n mmmamw « ^ · mmMe nfl II I— mmMmw ί I 經濟部智慧財產局員工消費合作社印製 492981 A7 B7 五、發明說明（33) 如範例lE(a)所述製備之，但其係由存在於乙醇（125 毫升）中之3-溴苯甲醛（25.0克，0.135莫耳）、3-乙基-5-(2-羥基乙基）-4-甲基噻唑溴化物（ι·7〇克，0.0068莫耳）及三乙 基胺（4· 10克，0.0405莫耳），產生24·8克（99%)之黏性黃色 油。1H NMR (CDC13) 5 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)，5·87 (s，1H); 13C NMR (CDC13) 5 196.96, 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) 製備3,3’-二溴二策乙二酮 如範例lE(b)般製備，但係由80%乙酸水溶液（200毫升） 中之3,3、二溴安息香（24.8克，0.067莫耳）、硝酸銨（5.63克 ，〇·〇7〇莫耳）及乙酸銅（11)(0.12克）製備，產生17·〇克（69%) 產物，為淡黃色固體。1H NMR (CDC13) 5 8.12 (s，2Η)，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) 製備3,3’-雙（笨基乙快基）二笨乙二_ 3,3’-二溴二苯乙二酮（5·〇克，〇·136莫耳）及苯基乙炔 (3.47克’ 0.0340莫耳）之三乙基胺（30亳升）溶液藉由使氮 氣泡通過此溶液ίο分鐘來除氣。然後添加（pph3)2pdci2 (0·067克’ 0.0001莫耳），反應混合物被迴流加熱隔夜。混 合物被濃縮乾燥，倒入CH2C12(100毫升），依序以iM HC1 、飽和之NaHC〇3清洗，並乾燥之（Na2S04),然後濃縮之 本紙張尺度適用令國國家標準（CNS)A4規格（210 X 297公H —-36一"" --------^---,--- (請先閱讀背面之注音？事項再填寫本頁；> 訂---------· I 一 經濟部智慧財產局員工消費合作社印製 492981 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（34) ’產生3.67克（66%)產物，為白色固體：m.p· 144°C至145°C ; !H NMR (CDC13) δ 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); 13C NMR (CDCI3) 5 192.83, 137.40, 132.82, 131.52, 129.04, 128.58, 128.25，124.50，122.37, 91.11，87.62。T. -nn mmmamw «^ · mmMe nfl II I— mmMmw ί I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 492981 A7 B7 V. Description of the invention (33) Prepared as described in Example lE (a), but it is 3-Bromobenzaldehyde (25.0 g, 0.135 moles), 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazole bromide (ι · 7 0 grams, 0.0068 moles) and triethylamine (4.10 grams, 0.0405 moles), yielding 24.8 grams (99%) of a viscous yellow oil. 1H NMR (CDC13) 5 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), 5.87 (s, 1H); 13C NMR (CDC13) 5 196.96, 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 3,3'-dibromodicerdione is prepared as in Example 1E (b), but it is made from 3,3, dibromobenzoin (24.8 g, 0.067 mole) in 80% aqueous acetic acid (200 ml), Preparation of ammonium nitrate (5.63 g, 0.0007 mol) and copper acetate (11) (0.12 g) yielded 17.0 g (69%) of the product as a pale yellow solid. 1H NMR (CDC13) 5 8.12 (s, 2Η), 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'-bis (benzylethenyl) dibenzylethylene-3,3'-dibromodiphenyldione (5.0 g, 0.136 mole) and phenylacetylene (3.47 g '0.0340 mol) of triethylamine (30 liters) was degassed by passing nitrogen bubbles through the solution for 1 minute. (Pph3) 2pdci2 (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 CH2C12 (100 ml), washed sequentially with iM HC1, saturated NaHC03, and dried (Na2S04). Then the paper was concentrated to the national standard (CNS) A4 specification ( 210 X 297 male H —-36 a " " -------- ^ ---, --- (Please read the note on the back? Matters before filling out this page; > Order ---- ----- · I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 492981 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (34) 'Produces 3.67 grams (66%) of the product, which is white Solid: mp · 144 ° C to 145 ° C;! H NMR (CDC13) δ 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); 13C NMR (CDCI3) 5 192.83, 137.40, 132.82, 131.52, 129.04, 128.58, 128.25, 124.50, 122.37, 91.11, 87.62.

(d)製備化合物F K〇H(0.25克，0.0045莫耳）之乙醇（5毫升）溶液被一滴 滴加入75°C乙醇之3,3，-雙（苯基乙炔基）二苯乙二酮（3.67克 ，0.0089莫耳）及1，3-二苯基丙酮（2.07克，0.0098莫耳）之 乙醇（100毫升）。形成之溶液被迴流加熱！小時，然後冷卻 至室溫。形成之沈澱物被過濾並乾燥之。產物由沸騰之乙 醇浸提產生2.0克（38%)之暗紅色固體產物：m.p. 208 °C (DSC). lU NMR (CDCI3) (5 7.45 (bm, 6H), 7.31-7.21 (bm5 20H), 6.9 (d, J=7.9 Hz, 2H); l3C NMR (CDC13) δ 199.38, 152.83，132.87，131.48，131.25，131.12，129.80，129.60, 128.53，127.99，127.92，127.84，127.70，127.29，125.03, 122.96, 122.47, 90.60, 88.71。 G· 1,3,5-三（笨基乙炔基）苯（化合物G) 三乙基胺（375克）、三苯基膦（4.7865克）、乙酸鈀（1.0205 克）及N，N-二曱基甲醯胺（2000毫升）被注入5公升之3頸圓 底燒瓶（其裝置有熱偶、位於上方之機械式攪拌器、冷凝 器、添加漏斗及具有溫度控制器之加熱罩）。混合物被擾 拌5分鐘以溶解催化劑。然後添加二乙基羥基（5克）、：ι，3,5-三溴苯（190克）及苯基乙炔（67.67克）。反應器以氮氣汽提15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） · -37 —: "" ------^----1 -----^----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 492981(d) A solution of the compound FKOH (0.25 g, 0.0045 mole) in ethanol (5 ml) was added dropwise to 75 ° C ethanol 3,3, -bis (phenylethynyl) diphenylethylene dione ( 3.67 g, 0.0089 mol) and 1,3-diphenylacetone (2.07 g, 0.0098 mol) in ethanol (100 ml). The resulting solution was heated at reflux! Hours, 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 ° C (DSC). LU NMR (CDCI3) (5 7.45 (bm, 6H), 7.31-7.21 (bm5 20H), 6.9 (d, J = 7.9 Hz, 2H); l3C NMR (CDC13) δ 199.38, 152.83, 132.87, 131.48, 131.25, 131.12, 129.80, 129.60, 128.53, 127.99, 127.92, 127.84, 127.70, 127.29, 125.03, 122.96, 122.47, 90.60, 88.71. G · 1,3,5-tris (benzylethynyl) benzene (compound G) triethylamine (375 g), triphenylphosphine (4.7865 g), palladium acetate (1.0205 g) And N, N-dimethylformamide (2000 ml) were injected into a 5-liter 3-necked round bottom flask (equipped with a thermocouple, a mechanical stirrer located above, a condenser, an addition funnel and a temperature controller (Heating hood). The mixture was stirred for 5 minutes to dissolve the catalyst. Then diethylhydroxyl (5 g), ι, 3,5-tribromobenzene (190 g) and phenylacetylene (67.67 g) were added. Reaction The device is stripped with nitrogen by 15 pages. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). · -37 —: " " ------ ^ ---- 1 ---- -^ ---- Order --------- Line (Please read the precautions on the back before filling this page) 492981

經濟部智慧財產局員工消費合作社印製 五、發明說明（35) 分鐘，然後加熱至70°C ,且保持氮氣氛圍。於7(rc加熱3〇 为姜里後，於約1小時期間一滴滴緩慢加入苯基乙炔（丨3 5 3 3 克）’溫度增至80°C。加熱持續額外之9小時。反應冷卻至 室溫，並添加水（1公升），其沈澱粗製產物。產物被過濾 ’以500毫升之水清洗三次，然後以5〇〇毫升環己烷清洗一 次。結晶於75°C真空乾燥隔夜，產生226·4〇克（99.1%產率） ，其以氣體色谱分析為97.25面積％純度。結晶溶於甲苯 (1800毫升），經由矽石凝膠再次過濾，且於旋轉蒸發器上 移除溶劑，產生214.2克（94.2%產率），其以氣體色譜分析 為99.19面積％純度。殘質由甲苯（375毫升）與孓丙醇（696 毫升）所成混合物再結晶。白色結晶被過濾，以甲苯（丨〇〇 毫升）及2-丙醇（400毫升）之混合物潤濕，且於75。^真空乾 燥隔夜’產生1，3,5-三（苯基乙炔基）苯（190.0克，83.91產 率）’其以氣體色譜分析為99.83面積％純度。由甲苯/異 丙醇之額外再結晶產生可接受之有機及離子純度之材料。 Η· 4,4，-雙（笨基乙快基）二笨基鱗（化合物Η) 於1公升之3頸圓底燒瓶（其具有熱偶、機械式攪拌器、冷 凝器及具有溫度控制器之加熱罩），注入三乙基胺（11 i .5克） 、三苯基膦（1.158克）、乙酸鈀（〇·2487克）、二乙基羥基胺 (1.24克）、4,4’-二溴二苯基謎（68·8克）、苯基乙炔（67.74克） 、Ν，Ν-二曱基甲醯胺（136毫升）及72毫升之水。反應器以 氮汽提15分鐘，然後加熱至90°C，同時保持氮氣氛圍19小 時。反應被冷卻至室溫’並添加水（8 0毫升）。粗製產物被 過濾，並且固體以120毫升之曱苯潤濕一次並以16〇毫升之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -- --I---------I L----訂--------- • · 命 ％ (請先閱讀背面之注意事項再填寫本頁) A7 A7Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (35) minutes, then heated to 70 ° C, and maintain a nitrogen atmosphere. After heating 30 ° C to 7 ° C in rc, slowly add phenylacetylene (315 5 3 g) dropwise over about 1 hour. The temperature is increased to 80 ° C. Heating is continued for an additional 9 hours. The reaction is cooled to At room temperature, and water (1 liter) was added, the crude product was precipitated. The product was filtered 'washed three times with 500 ml of water and then once with 500 ml of cyclohexane. The crystals were dried overnight at 75 ° C under vacuum to produce 226.40 g (99.1% yield), which was 97.25 area% purity by gas chromatography analysis. The crystals were dissolved in toluene (1800 ml), filtered again through a silica gel, and the solvent was removed on a rotary evaporator. 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 methylpropanol (696 mL). White crystals were filtered, and toluene was used. (丨 00mL) and 2-propanol (400mL) were wetted and dried at 75 ° C under vacuum overnight to produce 1,3,5-tris (phenylethynyl) benzene (190.0g, 83.91) Ratio) 'which was 99.83 area% purity by gas chromatography analysis. Additional recrystallization of toluene / isopropanol produces materials of acceptable organic and ionic purity. Η · 4,4, -bis (benzylethoxy) dibenzyl scale (compound Η) at a diameter of 3 necks Bottom flask (with thermocouple, mechanical stirrer, condenser, and heating mantle with temperature controller), filled with triethylamine (11 i.5 g), triphenylphosphine (1.158 g), palladium acetate ( 0.2487 g), diethylhydroxylamine (1.24 g), 4,4'-dibromodiphenyl mystery (68. 8 g), phenylacetylene (67.74 g), Ν, Ν-dimethylaminomethyl Amidine (136 ml) and 72 ml of water. The reactor was stripped with nitrogen for 15 minutes and then heated to 90 ° 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 is filtered, and the solid is moistened once with 120 ml of toluene and applied to the national paper standard (CNS) A4 (210 X 297 mm) at a paper size of 160 ml---I --- ------ I L ---- Order --------- • · Life% (Please read the notes on the back before filling this page) A7 A7

五、發明說明（36) 水潤濕四次，於真空下乾燥隔夜，產生66·37克（85.6%產 率）之白色針狀之4,4，-雙（苯基乙炔基）二苯基醚，以氣相 色譜分析為99.64面積％純度。 I· -雙（本基乙快基鄰-三聯笨（化合物I) 二溴-鄰-三聯苯 鄰-三聯苯（1〇〇克）、Fe(5克）、及CHC13(475毫升）被注 入1公升之3頸燒瓶（其配置有機械式攪拌器、連接至HBr 捕捉器之冷凝器及添加漏斗）。混合物被授拌且溫度以水 浴保持。存在於CHC13(150毫升）中之Βγ2(47·5毫升）於2·5小 時期間被一滴滴加入。混合物於室溫攪拌額外之二小時。 GC顯示5%之單溴-鄰-三聯苯、81%之二溴_鄰_三聯苯及9〇/〇 之二〉臭鄰-三聯苯。 冰及2Ν之NaOH溶液被添加至上溶液至其呈鹼性為止 。上層被倒出，且CHC13溶液以更多水清洗。硫酸鈉被加 至CHCh溶液，然後經由填充塞里特之Buchne^^斗過濾 。移除氣仿。於白色固體添加750毫升之冰醋酸，且漿料 以水浴加熱至95°C。約一半固體溶解。熱溶液被倒入100 亳升之燒瓶。殘餘固體為71克，其包含1.4%之單溴-鄰-三 聯苯、93%之4,4，，-二溴-鄰-三聯苯及6%之4,4，，4，，-三溴-鄰-三聯苯。乙酸溶液被冷卻至室溫。收集白色結晶。GC顯 示1%之單溴-鄰-三聯苯、83%之4,4，，_二溴_鄰-三聯苯及13〇/〇 之4,4’，4”-三溴-鄰-三聯苯。此材料被用於製備4,4”-雙（苯 基乙炔基）-鄰-三聯笨。V. Description of the invention (36) Wetted four times with water and dried overnight under vacuum, yielding 66.37 g (85.6% yield) of white needle-like 4,4, -bis (phenylethynyl) diphenyl Ether was 99.64 area% purity by gas chromatography. I · -bis (benzylethenyl-o-tribenzyl (Compound I) dibromo-o-terphenyl-o-terphenyl (100 g), Fe (5 g), and CHC13 (475 ml) were injected 1 liter 3-necked 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 in CHC13 (150 ml)) (5 ml) was added dropwise over 2.5 hours. The mixture was stirred at room temperature for an additional two hours. GC showed 5% monobromo-o-terphenyl, 81% dibromo-o-terphenyl and 9 〇 / 〇bis> Stinky 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 CHCh solution. , And then filtered through a Buchne bucket filled with Serritt. 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 solid is dissolved. The hot solution is poured 100-liter flask. Residual solids are 71 g, which contains 1.4% monobromo-o-terphenyl, 93% 4,4 ,,-dibromo -O-terphenyl and 6% 4,4,4,4, -tribromo-o-terphenyl. The acetic acid solution was cooled to room temperature. White crystals were collected. GC showed 1% monobromo-o-terphenyl 83% of 4,4 ,, _ dibromo-o-terphenyl and 13 / 4,4 ', 4 "-tribromo-o-terphenyl. This material is used to prepare 4,4"- Bis (phenylethynyl) -o-triple.

㈤製備化合物I 本紙張尺度適用中國國家標準（CNS)A4規格（21Q x 297公爱） -39二 -------Φ---J1-------«----訂---------線 ·,*V (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 Α7 •--^___ Β7 五、發明說明（37 ) 4,4”-二溴-鄰-三聯苯（40克，0.0103莫耳）、苯基乙炔（50 亳升）、三乙基胺（500毫升）及吡啶（300毫升）被注入1〇〇〇毫 升之4頸燒瓶（其配置有機械式攪拌器、冷凝器、Ν2入口及 熱偶）。氮氣被用以汽提此系統20分鐘。 溶解固體後，添加2.783克之Pd(PPh3)2Cl2、2.538克之 Cul及5.54克之PPh3。氮氣經溶液起泡並攪拌30分鐘。打 開加熱使混合物迴流。迴流保持隔夜。反應期間形成白色 固體。 溶液被倒入2公升之含有冰之燒瓶。燒瓶以水潤濕數 次且被倒入燒瓶内。形成之固體以Buchner漏斗過濾、，然 後以水清洗數次。甲苯被用於溶解2公升燒瓶内之固體。 上層被倒入1公升燒瓶。含有未溶解材料之較低層以甲苯 潤濕，且甲苯溶液以倒出之上層混合，形成深棕色溶液。 深棕色溶液以木炭脫色。溶液於水浴中加熱且被擾拌之。 Na2S04被添加之。 溶液以燒結玻璃過濾、器過遽，且溶劑被旋轉濃縮掉 。固體以350毫升熱甲苯溶於2公升燒瓶，一旦溶解時，添 加1300毫升之異丙醇以結晶固體。2公升燒瓶被置入冰箱 内隔夜’收集結晶，並以異丙醇清洗。黃色固體重25克。 然後，黃色固體以丙酮清洗，然後於乙基丙酮中結晶兩次 。白色碎片之產量為12克。 J · 4,4 -二乙块基二笨基鱗（化合物j) 存在於三乙基胺（40毫升）内之4,4、二溴二苯基醚（9.8 克 ’ 0.030莫耳）、Pd(〇Ac)2(〇.〇5克，〇·〇0〇2莫耳）、碘化銅 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) |_裝㈤Preparation of compound I The paper size is applicable to Chinese National Standard (CNS) A4 (21Q x 297 public love) -39 二 ------- Φ --- J1 ------- «---- Order --------- line ·, * V (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 •-^ ___ Β7 V. Description of the invention ( 37) 4,4 "-dibromo-o-terphenyl (40 g, 0.0103 mole), phenylacetylene (50 liters), triethylamine (500 ml) and pyridine (300 ml) were injected into the product. 〇mL 4-necked flask (equipped with mechanical stirrer, condenser, N2 inlet and thermocouple). Nitrogen was used to strip the system for 20 minutes. After dissolving the solid, add 2.783g of Pd (PPh3) 2Cl2 2.538 grams of Cul and 5.54 grams of PPh3. Nitrogen was bubbled through the solution and stirred for 30 minutes. The mixture was heated to reflux. The reflux was kept overnight. A white solid formed during the reaction. The solution was poured into a 2 liter flask containing ice. The flask was hydrated Wet several times and poured into a flask. The formed solid was filtered through a Buchner funnel, and then washed several times with water. Toluene was used to dissolve 2 liters The solids in the flask. The upper layer was poured into a 1 liter flask. The lower layer containing undissolved material was wetted with toluene, and the toluene solution was mixed by pouring the upper layer to form a dark brown solution. The dark brown solution was decolorized with charcoal. The solution was Heat and stir in a water bath. Na2S04 is added. The solution is filtered through sintered glass, filtered, and the solvent is concentrated by rotation. The solid is dissolved in a 2 liter flask with 350 ml of hot toluene. Once dissolved, add 1300 ml Isopropanol is a crystalline solid. The 2 liter flask was placed in the refrigerator overnight to collect the crystals and washed with isopropanol. The yellow solid weighed 25 grams. Then, the yellow solid was washed with acetone and then crystallized in ethyl acetone for two times. The yield of white fragments is 12 g. J. 4,4-Diethyl block dibenzyl scale (compound j) 4,4, dibromodiphenyl ether present in triethylamine (40 ml) (9.8 g '0.030 mole), Pd (〇Ac) 2 (0.05 g, 0.002 mole), copper iodide This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling P) | _ loaded

-ϋ ·1 .^1 一-口t 讎 1··^ I Μ· I 經濟部智慧財產局員工消費合作社印製 492981 A7 B7 五、發明説明（38 ) (1)(0.15克，0.0008莫耳）及三苯基膦（1·0克，0.0038莫耳） 而成之漿料以氮氣汽提30分鐘，同時缓慢加熱迴流2-甲基 -3-丁基-2-醇（7.6克，0.090莫耳），其以氮氣汽提30分鐘， 於5分鐘期間快速添加至迴流溶液。所形成之反應混合物 迴流加熱14小時，冷卻至週圍溫度，並濃縮乾燥之。殘質 被倒入CH2C12，以水及鹽水清洗，然後濃縮之。殘質被倒 入甲苯（200毫升且添加氫化鈉（0.10克，0.20莫耳）。反應 混合物被加熱迴流，且蒸餾出約100毫升之溶劑。溶液被 冷卻，然後濃縮之。殘質被倒入CH2C12，以IN HC1、水 、飽和NaHC03及鹽水清洗，然後乾燥(Na2S04)及濃縮， 產生暗色油。殘質經由矽石凝膠墊過濾，以CH2C12洗提並 濃縮，產生黏性油，其於靜置時緩慢固化。1HNMR(CDC13) 5 7.45 (d, J=8.6 Hz, 4H), 6.93 (d, J=8.7 Hz, 4H), 3.04 (s, 2H); 13C NMR (CDC13) (5 157.02, 133.93, 119.20, 118.94, 117.16, 83.16 〇 反應係如下所示： (請先閱讀背面之注意事項再填寫本頁) 一βγ 經濟部中央標隼局員工消費合作社印製-ϋ · 1. ^ 1 一-口 t 雠 1 ·· ^ I Μ · I Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economy 492981 A7 B7 V. Description of the invention (38) (1) (0.15 g, 0.0008 mol ) And triphenylphosphine (1.0 g, 0.0038 mole) and stripped with nitrogen for 30 minutes, while slowly heating and refluxing 2-methyl-3-butyl-2-ol (7.6 g, 0.090 Mol), which was stripped with nitrogen for 30 minutes and quickly added to the refluxing solution 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 into CH2C12, washed with IN HC1, water, saturated NaHC03 and brine, then dried (Na2S04) and concentrated 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 is Slow curing when standing. 1HNMR (CDC13) 5 7.45 (d, J = 8.6 Hz, 4H), 6.93 (d, J = 8.7 Hz, 4H), 3.04 (s, 2H); 13C NMR (CDC13) (5 157.02 , 133.93, 119.20, 118.94, 117.16, 83.16 〇 The response is as follows: (Please read the precautions on the back before filling out this page)-Printed by the Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs

NaHNaH

-OH-OH

Pd(OAc) PPh3 Cul Et3N 2 K. 3,3’-(氣二-1，4-亞笨基）雙（2,4,5-三茉基環戊二嬌酮（化合 物K) 41 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 492981 A7 B7 五、發明説明（39 ) 二苯基乙醯基二芏某醚 於存在於〇°C之二氣甲烷（200毫升）中之氯化鋁（97·9克， 0.734莫耳）之漿料，於3〇分鐘期間一滴滴添加存在於二氣 甲烧（50毫升）之二苯基醚（50·〇克，0.294莫界）與苯基乙醯 基氣化物（1〇2克，0.661莫耳）所成之溶液。當添加完成時 ’反應藏合物被加溫至週圍溫度且攪拌隔夜。反應混合物 被小心攪拌倒入丨.5公斤之冰/水内。添加二氣曱烷（1500 毫升）以溶液固體，並分離層狀物。有機層經赛里特過濾 ’然後濃縮乾燥之。由甲苯再結晶產生110克（92%)之淡褐 色稜狀之標題化合物。 經濟部中央標準局員工消費合作社印製 雙（茉某乙二醛基）二芏暮馘 HBr水溶液（97毫升之48重量％溶液）被加至於DMSO (400毫升）中所成之4,4，-二苯基乙酿基二苯基醚（50.0克， 0.123莫耳）漿料，且所成混合物被加熱至1〇〇«c持續2小時 ，然後冷卻至週圍溫度。反應混合物於甲苯（5〇〇毫升）與 水（750毫升）間分開。有機層以水（3 X250毫升）清洗，然後 以鹽水清洗，且濃縮產生黏性鮮黃色油，其於週圍溫度靜 置時固化。由乙醇再結晶產生35·9克（67%)之標題化合物 ，其為鮮黃色立方體。 ㈦製備化合物Κ 於氮氣汽提之5公升Morton燒瓶（其配置有熱偶、具氣 氣入口之迴流冷凝器、機械授样is及添加漏斗），添加195.4 克（0.4498莫耳，1·〇 eq)之4,4’-雙（笨基乙二醛基）二苯基醚 、193.9克之二苯基丙酮（0.9220莫耳，2·〇5 eq)及2.5公升 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公慶） 42 492981 經濟部中夬標準局員工消費合作社印製 A7 B7 五、發明説明（4〇) 之去氧乙醇。混合物被加熱迴流，此時達成均勻溶液，溶 液以氮氣擴散30分鐘。於添加漏斗添加含有25.2克κ：〇Η (0.4498莫耳，l.Oeq)、200毫升乙醇及25毫升水之溶液。 溫度被降至74°C，且於5分鐘期間快速添加KOH溶液。玫 熱反應快速成立，且保持迴流至3/4溶液被添加，其後溫 度開始下降。於添加鹼時立即觀察到深紫色，且於添加完 成前觀察到固鱧。完成添加後，異相溶液強力迴流加熱15 分鐘，更多固體形成。混合物被冷卻至25°C，29·7克之冰 醋酸（0.4948莫耳，l.leq)被添加且攪拌30分鐘。粗製產物 被過濾隔離，且以1公升水、3公升乙醇、2公升曱醇於過 濾漏斗中清洗，且於真空下在60°C至9(TC乾燥12小時，產 生323克（92%)粗製DPO-CPD，以1^測得其為94%純度。 粗製材料溶於HPLC等級之二氣甲烷（10重量％)，轉移至配 置有底沖洗閥及機械授拌器之5公升Morton燒瓶，以等體 積之低離子水劇烈清洗2至7次，每次10至90分鐘。然後 CHei2溶液經含有於CHei2中之75克矽石凝膠之5公分管 沖清。管柱以額外之1公升Ct^Cl2清洗，此時過濾物基本 上為清淅。溶液被蒸發乾燥，且再溶於THF並且再次蒸發 移除整體之殘餘二氣甲烷。粉末被轉移至5公升燒瓶（其配 置有添加漏斗及Friedrichs迴流冷凝器）且溶於迴流之去氧 HPLC(0.07至0.12克/毫升）。然後添加1公升之THF，氮 氣擴散管被***該溶液内。溶液以氮氣擴散3小時，且THF 於45°C至50°C濃縮，同時殘餘之二氣甲烷以蒸餾移除之。 接上蒸餾頭且移除700毫升至1公升THF。然後溶液被緩慢 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X 297公釐） -43 - (請先閲讀背面之注意事項再填寫本頁，> · ' ♦ 492981 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（4υ 冷卻數小時至室溫，然後以冰浴冷卻至低於1〇。(3，期間產 生結晶。於4-公升Millip0re夾一燒結吸引過濾燒瓶内使用 5 /z m PTFE過濾器隔離結晶。然後以1公升甲醇清洗，於 真空下在80°C至90°C乾燥隔夜，產生70至85%產率之 DPO-CPD，其具有 99%之LC純度，mp 270〇C。 L. 2,4,4’-三（笨基乙炔基）二策基驗（化合物l) (a) 製備2,4,4’-三溴二苯某醚 >臭（57·3克’ 0.3 58莫耳）被緩慢滴人4〇°c之純淨攪拌之 二苯基醚（20.0克，0.118莫耳）。添加期間，溫度緩慢升至 6 0 C ’反應於此度保持2小時。混合物被加熱至7 0。〇 3 0 分鐘，然後冷卻至週圍溫度。混合物被倒入CH2C12(100毫 升），以10%Na2C〇3水溶液清洗，然後乾燥（Na2S〇4)並濃 縮之，產生44_8克（100%)產物，其為黏性油，於週圍溫度 靜置時緩慢固化。Pd (OAc) PPh3 Cul Et3N 2 K. 3,3 '-(Gasd-1,4-benzylidene) bis (2,4,5-trimosylcyclopentadione (Compound K) 41 sheets The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 492981 A7 B7 V. Description of the invention (39) Diphenyl ethyl fluorenyl disulfonium ether in digas methane (200 ml) present at 0 ° C A slurry of aluminum chloride (97 · 9 g, 0.734 moles) was added dropwise over a period of 30 minutes to diphenyl ether (50 · g, 0.294 moles) present in digasmethane (50 ml). ) And phenylacetamyl gaseous solution (102 g, 0.661 mole). When the addition is complete, the 'reaction Tibetan compound is warmed to ambient temperature and stirred overnight. The reaction mixture is carefully poured into丨. In 5 kg of ice / water. Dioxane (1500 ml) was added to solution the solids, and the layers were separated. The organic layer was filtered through Celite and concentrated to dryness. Recrystallization from toluene yielded 110 g ( 92%) of the title compound in the form of light brown prisms. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. The solution (97 ml of a 48% by weight solution) was added to a slurry of 4,4, -diphenylethyl diphenyl ether (50.0 g, 0.123 moles) in DMSO (400 ml), and The resulting mixture was heated to 100 ° C for 2 hours and then cooled to ambient temperature. The reaction mixture was separated between toluene (500 ml) and water (750 ml). The organic layer was washed with water (3 x 250 ml), It was then washed with brine and concentrated to give a viscous bright yellow oil, which solidified when left at ambient temperature. Recrystallization from ethanol yielded 35.9 g (67%) of the title compound as a bright yellow cube. ㈦ Preparation of compound K In a 5 liter Morton flask stripped with nitrogen (which is equipped with a thermocouple, a reflux condenser with a gas inlet, a mechanical sampler, and an addition funnel), add 195.4 g (0.4498 moles, 1.0 eq) of 4, 4'-bis (benzylglyoxal) diphenyl ether, 193.9 g of diphenylacetone (0.9220 mol, 2.05 eq) and 2.5 liters This paper is in accordance with China National Standard (CNS) A4 specifications ( 210x297 Public Holiday) 42 492981 Consumers' Cooperatives of Zhongli Standards Bureau, Ministry of Economic Affairs Print A7 B7 V. Description of the invention (40) of deoxyethanol. The mixture is heated to reflux and a homogeneous solution is reached at this time. The solution is diffused with nitrogen for 30 minutes. Add 25.2 grams of κ: 〇 克 (0.4498 mol) to the addition funnel. , L. Oeq), 200 ml of ethanol and 25 ml of water. The temperature was reduced to 74 ° C, and the KOH solution was quickly added during 5 minutes. The rose heat reaction was quickly established, and kept at reflux until 3/4 of the solution was added. After that, the temperature started to drop. A dark purple color was immediately observed when the alkali was added, and a solids was observed before the addition was complete. After the addition was complete, the heterogeneous solution was heated under vigorous 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 9 (TC for 12 hours, yielding 323 g (92%) of crude DPO-CPD, 94% purity measured at 1 ^ The crude material was dissolved in HPLC-grade digas methane (10% by weight), transferred to a 5 liter Morton flask equipped with a bottom flush valve and a mechanical stirrer, and Wash the same volume of low ion water vigorously 2 to 7 times for 10 to 90 minutes each time. Then the CHei2 solution is washed through a 5 cm tube containing 75 g of silica gel in CHei2. The column is filled with an extra 1 liter of Ct ^ Cl2 wash, the filter is basically clear at this time. The solution is evaporated to dryness, and redissolved in THF and evaporated again to remove the remaining residual digas methane. The powder is transferred to a 5 liter flask (equipped with an addition funnel and 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 with nitrogen for 3 hours and the THF was at 45 ° Concentrated at 50 to 50 ° C, while the remaining methane is removed by distillation Connect the distillation head and remove 700 ml to 1 liter of THF. Then the solution is slowly. The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -43-(Please read the precautions on the back first Fill out this page again, > · ♦ 492981 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (4υ Cool for several hours to room temperature, then cool to below 10 with an ice bath. (3, Crystals were generated during this time. A sintered suction filtration flask with a 4-liter Millip0re was used to isolate the crystals using a 5 / zm PTFE filter. The crystals were 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, which has an LC purity of 99%, mp 270 ° C. L. 2,4,4'-tris (benzylethynyl) detyl test (Compound 1) (a) Preparation 2,4,4'-tribromodiphenyl ether > Odor (57 · 3 g '0.3 58 mol) was slowly dripped into a pure stirred diphenyl ether (20.0 g, 0.118 mol) at 40 ° C ). During the addition, the temperature slowly rises to 60 ° C. The reaction is held for 2 hours at this time. The mixture is heated to 70. 30 minutes, then To ambient temperature. The mixture was poured into CH2C12 (100 ml), washed with 10% Na2CO3 aqueous solution, then dried (Na2SO4) and concentrated to give 44-8 g (100%) of the product as a viscous oil. Slowly cure when left at ambient temperature.

(b) 製備化合物L 存在於三乙基胺（300毫升）中之2,4,4、三溴二苯基醚 (44·3克 ’ 0.116莫耳）、Pd(OAc)2(0.182克，0.00081 莫耳）， 埃化銅（1)(574克，0.00302莫耳）及三苯基膦（3·95克，〇〇151 莫耳而成之漿料以氮氣擴散30分鐘，同時緩慢加熱迴流之 〇 以氮氣擴散30分鐘之苯基乙炔（41.4克，0.406莫耳）被 快速於5分鐘期間加入迴流溶液。所形成之反應混合物被 迴流加熱14小時。溶液被冷卻至週圍溫度並濃縮之。殘質 被倒入CHKi2，以in之Hen、水、飽和NaHC〇3水溶液及 ^紙張尺度$用中國國家標準（CNS)A4規格（21〇 >c 297公釐 (請先閱讀背面之注意事項再填寫本頁) t 線. 492981 A7 B7 五、發明說明（42) 鹽水清洗，然後濃縮至100毫升之體積。此溶液經由矽石 凝膠塾過遽’以二氣甲烧沖提，並濃縮形成之過遽液。殘 質由EtOAc/己烷結晶而產生39.0克（73%)之淡褐色固體 ，mp 123°C 至 126°C。β 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) (J 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 〇 M. 3,3’-(l，4-亞笨基）雙（2,5-二-(4-氟笨基）-4-茉基瑗成二榆 酮（化合物M) 1,3-雙（4-氟苯基）-2-丙酮（1.476克，0.006莫耳）及1,4-雙（苯基乙二醛基）苯（可由Ken Seika公司之Bis-PGB得之， 1.020克，0.003莫耳）被溶於90毫升之1丙醇，並添加笨甲 基三甲基錄氫氧化物（〇·32克，40%，甲醇中）。溶液立即 呈紫色。持續迴流2小時。混合物被冷卻至室溫，然後至〇 °C。收集固體並以冷的甲醇清洗。產量為1.92克。固體具 有金屬閃耀顏色，且以DSC測量於316°C熔融。 1，3-雙（4-氟苯基）-2-丙酮以 E· Elce，A· S· Hay, J. Poly. Sci· : A部份：聚合物化學，33，1143-1151中所述程序製 備。 N. 4,4’，4”-三（袈某乙炔基）-鄰-三聯笨（化合物州 (a)製備4,4'三溴-鄰-三聯笨 鄰-三聯苯（39.6克）、Fe(3.3克）及CHC13(450毫升）被注 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)(b) Preparation of compound L 2,4,4, tribromodiphenyl ether (44.3 g '0.116 mol), Pd (OAc) 2 (0.182 g, 0.00081 mol), copper sulfide (1) (574 g, 0.00302 mol) and triphenylphosphine (3.95 g, 0.00151 mol) slurry diffused under nitrogen for 30 minutes while slowly heating to reflux Phenylacetylene (41.4 g, 0.406 mole) diffused with nitrogen for 30 minutes 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. Residue is poured into CHKi2, in Hen, water, saturated NaHC03 aqueous solution, and ^ paper size $ Chinese National Standard (CNS) A4 specification (21〇> c 297 mm (Please read the precautions on the back first) (Fill in this page again) Line t. 492981 A7 B7 V. Description of the invention (42) Rinse with brine, then concentrate to a volume of 100 ml. This solution was passed through a silica gel, washed with dichloromethane, and concentrated. Peroxide formed. The residue was crystallized from EtOAc / hexane to give 39.0 g (73%) of a light brown solid, mp 123 ° C To 126 ° C. Β 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) (J 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, 05.05. 89.47, 88.72, 87.79, 83.87 〇M. 3,3 '-(l, 4-benzylidene) bis (2,5-bis- (4-fluorobenzyl) -4-mosyl hydrazone into bisamulone ( Compound M) 1,3-bis (4-fluorophenyl) -2-acetone (1.476 g, 0.006 mole) and 1,4-bis (phenylglyoxal) benzene (available from Bis- Obtained from PGB, 1.020 g, 0.003 moles) was dissolved in 90 ml of 1 propanol, and benzyltrimethyl hydroxide was added (0.32 g, 40% in methanol). 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 316 ° C as measured by DSC. 1,3-bis (4-fluorophenyl) -2-acetone as described in E · Elce, A · S · Hay, J. Poly. Sci ·: Part A: Polymer Chemistry, 33, 1143-1151 Procedure preparation. N. 4,4 ', 4 "-tris (a certain ethynyl) -ortho-terphenyl (Compound State (a) Preparation of 4,4'tribromo-ortho-terphenyl-tero-terphenyl (39.6 g), Fe (3.3g) and CHC13 (450ml) are annotated. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

· ϋ αϋ ϋ Ki n ϋ 一 -口、 i^i «1— ϋ— ϋ ϋ i^i I 經濟部智慧財產局員工消費合作社印製 45 492981 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（43) 入1公升之3頸燒瓶（其配置有機械攪拌器、連接至^价捕 捉器之冷凝器及添加漏斗）。混合物被攪拌且溫度以水浴 保持。於1.5小時期間滴入存在於chC13(100毫升）内之Br 之（26·5毫升）。混合物於室溫攪拌2小時，然後於65 °C攪 拌2小時。GC顯示14%之二溴-鄰-三聯苯、85%之三溴-鄰-三聯苯及0.7%之四溴-鄰-三聯苯。 冰及2N之NaOH溶液被添加至溶液至呈鹼性為止。上 層被倒出’且CHC13溶液以更多水清洗。硫酸納被加入 CHC13溶液’然後經由具塞里特之Buchner漏斗過爐、。移 除氣仿。於白色固體與750毫升冰醋酸混合且漿料以95°C 之水浴加熱。於移除所有醋酸後之固體產量為42.5 ,其含 有11%之4,4”-二溴-鄰-三聯苯，88%之4,4，，4”-三溴-鄰-三 聯苯及0.6%之四溴_鄰_三聯苯。固體被用於製備4,4，，4，，-三（苯基乙炔基）-鄰-三聯苯。乙酸溶液含有56%之4,4”-二 溴-鄰-三聯苯、36%之4,4，，4，，-三溴-鄰-三聯苯及1.8%之四 溴-鄰-四聯苯。· Ϋ αϋ ϋ Ki n ϋ I-mouth, i ^ i «1— ϋ— ϋ ^ i ^ i I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 45 492981 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5 Description of the invention (43) A 1-liter 3-necked flask (equipped with a mechanical stirrer, a condenser connected to a trivalent trap, and an addition funnel). The mixture was stirred and the temperature was maintained in a water bath. Br (26.5 ml) of Br present in chC13 (100 ml) was dripped over a period of 1.5 hours. The mixture was stirred at room temperature for 2 hours and then at 65 ° C 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 passed through a Buchner funnel with a Cerrit. Remove gas imitation. 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 removing all acetic acid is 42.5, which contains 11% of 4,4 "-dibromo-o-terphenyl, 88% of 4,4,, 4" -tribromo-o-terphenyl and 0.6 % Of tetrabromo_o-terphenyl. The solid was used to prepare 4,4,4 ,,-tris (phenylethynyl) -o-terphenyl. Acetic acid solution contains 56% 4,4 "-dibromo-o-terphenyl, 36% 4,4,4,4, -tribromo-o-terphenyl and 1.8% tetrabromo-o-terphenyl .

(b)製備化合物N 4,4’，4”-三溴-鄰-三聯苯（24.7克，0.053莫耳）、苯基乙 炔（22毫升）、三乙基胺（280毫升）及响啶（180毫升）被注入 1000毫升之4頸燒瓶（其配置有機械式攪拌器、冷凝器及n2 入口及熱偶）。氮氣被用以汽提系統20分鐘。 於固體溶解後，添加 Pd(PPh3)2Cl2(1.113 克）、CuI(l.〇〇5 克）及PPh3(2.218克）。氮氣經溶液產生泡沫並攪拌30分鐘 。打開加熱且將混合物迴流隔夜。反應期間形成白色固體 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------；----*--------Γ---訂---------線 • I . * *'«» (請先閱讀背面之注意事項再填寫本頁) 492981 A7 --—------2L五、發明說明（44) 經濟部智慧財產局員工消費合作社印製 溶液被置入含有冰之2公升燒瓶。燒瓶以水潤濕數次 且倒入燒瓶内。形成之黏性固體以Buchnen^斗過濾，然 後以水清洗數次。甲苯被用於溶解2公升燒瓶内之固體。 上層被倒入1公升燒瓶。含有未溶解材料之下層以甲苯潤 濕’甲苯溶液被混合，形成深棕色溶液。其後財炭脫色 。溶液於水浴中加熱並攪拌之。然後添加Na2s〇4。溶液 以燒結玻璃過濾器過濾，溶劑被旋轉蒸發掉。黏性固體以 600毫升之熱丙酿j溶於2公升燒瓶。然後收集結晶並以丙酮 清洗。淡黃色固體重11克。固體由乙酸乙酯結晶兩次。白 色粉末產量為8克。 〇· 雙（苯基乙炔某、苯r化合物〇) 苯基乙炔（8.0克，78.3毫莫耳）、1，3-二溴苯（6.24 克’ 26.6毫莫耳）、雙（三苯基膦）鈀（11)氣化物（lu 克，4.23毫莫耳）、碘化銅（i)(〇.503克，2.64毫莫耳） 、吡啶（73毫升，〇·93莫耳）、三乙基胺（110毫升， 0·783莫耳）被混合並於氮氣下攪拌30分鐘。然後混 合物被迴流隔夜。溶液被倒入水/冰浴内。形成之 固體被收集並以水清洗。固體溶於甲苯且過濾不溶 解之物質。甲苯溶液以木炭脫色。添加異丙醇，形 成黃色結晶。結晶以過濾隔離且重4 · 0克（1 3 · 1毫莫 耳，50%產率）。熔點為1()9°C (DSC)。NMR及質譜 分析與1，3-雙（苯基乙炔基）苯之結構一致。 (請先閱讀背面之注意事項再填寫本頁) 訂---------線_ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）(b) Preparation of compound N 4,4 ', 4 "-tribromo-o-terphenyl (24.7 g, 0.053 moles), phenylacetylene (22 ml), triethylamine (280 ml), and pyridine ( 180 ml) was injected into a 1000 ml 4-necked flask (equipped with a mechanical stirrer, condenser, n2 inlet and thermocouple). Nitrogen was used to strip the system for 20 minutes. After the solids were dissolved, Pd (PPh3) was added 2Cl2 (1.113 g), CuI (1.05 g) and PPh3 (2.218 g). Nitrogen was foamed through the solution and stirred for 30 minutes. The heat was turned on and the mixture was refluxed overnight. A white solid formed during the reaction. National Standard (CNS) A4 Specification (210 X 297 mm) ------; ---- * -------- Γ --- Order --------- line • I. * * '«» (Please read the precautions on the back before filling out this page) 492981 A7 ------------ 2L V. Invention Description (44) Solution printed by employees of the Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Cooperatives It was placed in a 2 liter flask containing ice. The flask was moistened with water several times and poured into the flask. The formed sticky solid was filtered with a Buchnen bucket and then washed several times with water. Toluene was used to dissolve 2 The solids in the 1-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. The charcoal was then discolored. The solution was heated and stirred in a water bath. Then Na2s〇4 was added. The solution was filtered through a sintered glass filter, and the solvent was rotary evaporated. The viscous solid was dissolved in a 2 liter flask with 600 ml of hot acrylic j. The crystals were then collected and washed with acetone. The pale yellow solid weighed 11 G. The solid was crystallized twice from ethyl acetate. The yield of white powder was 8 g. Bis (phenylacetylene, benzener compound 0) phenylacetylene (8.0g, 78.3mmol), 1,3-bis Bromobenzene (6.24 g '26.6 mmol), bis (triphenylphosphine) palladium (11) gaseous (lu g, 4.23 mmol), copper (i) iodide (0.503 g, 2.64 mmol) Ear), pyridine (73 ml, 0.93 mole), triethylamine (110 ml, 0.783 mole) were mixed and stirred under nitrogen for 30 minutes. The mixture was then refluxed overnight. The solution was poured into water / In an ice bath. The solids formed are collected and washed with water. The solids are dissolved Benzene was filtered and the insoluble matter was filtered. The toluene solution was decolorized with charcoal. Isopropyl alcohol was added to form yellow crystals. The crystals were isolated by filtration and weighed 4.0 g (1 3 · 1 mmol, 50% yield). Melting point was 1 () 9 ° C (DSC). The structure of NMR and mass spectrometry is the same as that of 1,3-bis (phenylethynyl) benzene. (Please read the precautions on the back before filling this page) Order ----- ---- Line_ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

TT 492981 A7 B7 五、發明說明（45 ) 雙（笨基△炔基）茉（化合物P) 化合物Ρ以化合物〇般製備之，但使用L4-二溴苯替代 1，3 ·二漠苯。 <^1^，4-三（笨基乙炔基）茉（化合物〇、 存在於三乙基胺（250毫升）内之1，2,4-三溴苯（2〇·〇克， 0.0635莫耳）漿料藉由以A擴散30分鐘來脫氣。添加三苯 基膦（2·2克，0.00836莫耳），其後添加Pd(〇Ac)2(0.1〇〇克， 0.000445莫耳）及Cul(0.315克，0.00165莫耳），形成之混合 物加熱迴流。以N2擴散30分鐘之苯基乙炔（20.1克，0.197 莫耳）於10分鐘期間滴入。反應混合物被迴流加熱隔夜。 反應混合物被冷卻至週圍溫度，濃縮乾燥。殘質倒入丙酮 (200毫升）且水（300毫升）被緩慢添加並攪拌之。沈澱物被 濾出，以曱基醇（500毫升）清洗，再以水（200毫升）清洗， 乾燥之’產生淡褐色固體，其進一步由丙酮/甲醇再結晶 ，產生白色固體，產率60%。NMR分析與所欲物質之結構 一致。反應圖示係如下所示： (請先閱讀背面之注意事項再填寫本頁) ▼裝-----^----訂--------- 經濟部智慧財產局員工消費合作社印製TT 492981 A7 B7 V. Description of the invention (45) Bis (benzyl △ alkynyl) jasmine (compound P) Compound P is prepared as compound 0, but L4-dibromobenzene is used instead of 1,3. < ^ 1 ^, 4-tris (benzylethynyl) jasmine (compound 0, 1,2,4-tribromobenzene (2.0 g, 0.0635 mo) present in triethylamine (250 ml) Ear) The slurry was degassed by diffusion with A for 30 minutes. Triphenylphosphine (2.2 g, 0.00836 mol) was added, followed by Pd (〇Ac) 2 (0.100 g, 0.000445 mol). And Cul (0.315 g, 0.00165 mol), the resulting mixture was heated under reflux. Phenylacetylene (20.1 g, 0.197 mol) diffused with N2 for 30 minutes was dropped in over 10 minutes. The reaction mixture was heated at reflux overnight. Reaction mixture It was cooled to ambient temperature, concentrated and dried. The residue was poured into acetone (200 ml) and water (300 ml) was slowly added and stirred. The precipitate was filtered off, washed with ethyl alcohol (500 ml), and then water (200 ml) was washed and dried to give a light brown solid, which was further recrystallized from acetone / methanol to yield a white solid with a yield of 60%. The NMR analysis was consistent with the structure of the desired substance. The reaction diagram is shown below: (Please read the precautions on the back before filling this page) ▼ 装 ----- ^ ---- Order --------- Warp Intellectual Property Office employees consumer cooperatives printed

BrBr

PhCCH "Pd(OAc) /PhCCH " Pd (OAc) /

PPh3 Cul Et3NPPh3 Cul Et3N

本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） 492981 A7 B7 五、發明說明（46) 範例2 由化_舍物Μ及1，3-雙（笨基△炔基化合物〇)及 1，3，..5二乓（苯基乙炔皋）苯（化合物m之混合物製備 聚合物 化合物（M)(3 16毫克，FW=762，0.415毫莫耳）、化合 物（0)(72毫克，FW=278，0.259毫莫耳）及化合物（G)(44毫 克’ 0.116毫莫耳）於1，3 - 一異丙基苯（4¾升）中迴流42小時 。暗色溶液變成紅色且變黏稠狀。溶液被自旋塗覆於晶元 上，於400 C固化1小時’形成膜。反應係如下所示： (請先閱讀背面之注意事項再填寫本頁) 訂-------！線 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 492981 A7 B7 五、發明説明（47 )This paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 492981 A7 B7 V. Description of the invention (46) Example 2 Youhua_Shewu M and 1,3-bis (benzyl △ alkynyl) Compound 0) and 1,3, .. 5 dip (phenylacetylenehydrazone) benzene (mixture of compound m to prepare polymer compound (M) (3 16 mg, FW = 762, 0.415 mmol), compound (0 ) (72 mg, FW = 278, 0.259 mmol) and compound (G) (44 mg '0.116 mmol) were refluxed in 1,3-isopropylbenzene (4¾ liters) for 42 hours. The dark solution became Red and viscous. The solution was spin-coated on the wafer and cured at 400 C for 1 hour to form a film. The reaction is as follows: (Please read the precautions on the back before filling this page) Order --- ----! Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 492981 A7 B7 V. Description of Invention (47)

FF

(請先閱請背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製(Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 50 492981 A7 -----J7____ 五、發明說明（48) 範例3 由化合物Μ及4,4、俸Γ装某乙炔某:l·鄰二三聯笑Mh 合物I)及4,4’,4”-三Γ赛篡乙炔篡V鄰-三聯策Hh厶 物N)製備聚合物 化合物（M)(3 16毫克，0.415毫莫耳）、化合物⑴（107 毫克，FW=430,0.249毫莫耳）及化合物（N)(88毫克，FW=530 ，0.116毫莫耳）於5毫升之1，3-二異丙基苯中迴流48小時。 黃色黏性溶液被冷卻至室溫且自旋塗覆於晶元上。聚合物 於400°C固化1小時，形成膜。反應係如下所示： ------^---^---裝·-- ♦ (請先閱讀背面之注意事項再填寫本頁) .. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 492981 A7 B7 五、發明説明（49 ) 經濟部中央標隼局員工消費合作社印製This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 50 492981 A7 ----- J7____ V. Description of the invention (48) Example 3 A compound M, 4, 4, and 装 Γ are packed in an acetylene : l. o-di-triple Mh complex I) and 4,4 ', 4 "-tri-Saisai acetylene t-V o-triple Hh 厶 厶 N) Preparation of polymer compound (M) (3 16 mg, 0.415 mmol), compound VII (107 mg, FW = 430, 0.249 mmol) and compound (N) (88 mg, FW = 530, 0.116 mmol) in 1 ml of 1,3-diisopropyl Reflux in basic benzene for 48 hours. The yellow viscous solution was cooled to room temperature and spin-coated on the wafer. The polymer was cured at 400 ° C for 1 hour to form a film. The reaction system is as follows: ----- -^ --- ^ --- installation --- ♦ (Please read the precautions on the back before filling out this page): The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to Chinese national standards (CNS) A4 Specifications (210 X 297 mm) 492981 A7 B7 V. Description of the invention (49) Printed by the Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs

(請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 52 492981 Α7 Β7 五、發明說明（50) 範例4 ϋ3’·（氧二-M-亞笨基）雙（2,4,5-三笨基環戊二 (請先閱讀背面之注意事項再填寫本頁) 烯酮）（化合物Κ)奧4,4、蝥f笑基乙炔基）二茉基醚 (化合物H)盤備聚合铷 3,3’-(氧二-1，4-亞苯基）雙（2,4,5-三苯基環戊二烯酮） (15.0000克，0.019158莫耳）、4,4，_雙（苯基乙炔基）二苯基 醚（7.0974克，0.019158莫耳）及N-甲基吡咯烷二酮（51.60克） 被添加至250毫升圓底燒瓶。燒瓶被附接至氮氣入口，磁 性攪拌溶液於油浴中加熱至200°C。200°C19.5小時後，凝 膠滲透色譜法顯示“„為1551且]^〜為2383，其係相對於聚 苯乙烯標準物。溶液被冷卻裝瓶。一部份溶液被倒入注射 器，且經由1.0微米之注射濾器過濾於4”矽晶元上。於用 以加溫晶元之熱燈下以2000 rpm自旋塗覆晶元60秒。塗覆 晶元被置於設定為90°C之熱盤上數分鐘。晶元被置於氮氣 氣·^爐’將其於室溫以氣提固化4 5分鐘，然後以1 〇 °c /分 加熱至400 C ’於400°C保持1小時，然後使其冷卻至室溫 。形成之晶元以聚亞苯聚合物塗覆之。當溶液塗於亞微米 間隙之間隙填充結構並固化時，溶液被發現完全填充間隙 〇 經濟部智慧財產局員工消費合作社印製 範例5 由3,3’-(氧二-1，4-亞苯基）雙（2·4·5-三茉某澤木二 烯酮）（化合物K)、4,4，-雙（苯某乙炔基）二苯某_( 化合物H)、及1，3,5-三（笨基乙炔基）笨（化合物m 製備聚合物 於100毫升之3頸圓底燒瓶，添加3,3，-(氧二-ΐ，4·亞苯 基）雙（2,4,5-三苯基環戊二烯酮）（ΐ〇·〇〇〇0克，0·01277莫耳） 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ~'33 -二-- 492981 A7 B7 五、發明說明（51) 、4,4’-雙（苯基乙炔基）二苯基醚（2 366〇克，〇 〇〇6386莫耳） 、1，3,5-三（苯基乙炔基）苯（2.4170克，0.006386莫耳）及N- 甲基处洛烧二酮（34.5毫升）。燒瓶被附接至氮氣入口，且 磁力攪拌溶液於油浴中加熱至2〇〇°c。於200。(： 11小時後， 溶液被冷卻裝瓶。一部份溶液被倒入注射器且經由丨微米 注射濾器過濾於4英吋矽晶元上。晶元於2〇〇〇 rpm自旋塗 覆60秒。塗覆晶元被置於設定9(rc之熱盤上2分鐘。晶元 被置於鼠氣氣爐’於至溫藉由氣提45分鐘而固化，然後 以10°C/分加熱至400°C，保持於400°C1小時，然後使其 冷卻至室溫。形成之晶元以聚亞苯聚合物塗覆之。當溶液 被塗於具亞微米間隙之間隙填充結構並且固化時，溶液被 發現完全填充間隙。固化之聚合物不溶於N-甲基σ比咯烧 二酮。 範例6 鱼13’-(氧二-Μ-亞茉某）雙（2·4·5-二—苯某璜成二 歷__)(化合盤Κ)、I，3，-雙（笨基乙炔某彳苯^彳卜厶铷 及1，3,5-三（苯基乙炔基）笨（化合物Gk備聚合 物 於25毫升Schlenk管，添加3,3’-(氧二-ΐ，4-亞苯基）雙 (2,4,5-三苯基環戊二烯酮）(2.〇〇〇〇克，0·002554莫耳）、^3、 雙（本基乙快基）本（0.4740克’ 0.001703莫耳）、1 3 5-5 (苯 基乙炔基）苯（0.4834克，0.001277莫耳）及Ν-甲基吡洛烧二 酮（6.9¾升）。管被附接至氣氣入口，且機械搜拌溶液於 油浴中加熱至200°C。於200°C20小時後，凝膠滲透色譜法 指示Mn=1463&Mw=2660，其相當於聚苯乙晞標準物。溶 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------^---0---裝--- * (請先閱讀背面之注意事項再填寫本頁) · 經濟部智慧財產局員工消費合作社印製 492981 A7 B7 五、發明說明（52) J.--------裝—— ** (請先閱讀背面之注意事項再填寫本頁) 液被冷卻至室溫並裝瓶。一部份溶液被倒入注射器，且經 由1 ·〇微米注射濾器過濾於4”矽晶元上。於能加溫晶元之 加熱燈下，晶元以2000 rpm自旋塗覆60秒。然後塗覆晶元 被置於設定9〇°C之熱盤上2分鐘。晶元被置於氮氣氣提爐 上’於室溫以氣提20分鐘固化之，然後以i〇°c/分鐘加熱 至400 C ’於400°C保持1小時，然後冷卻至室溫。所形成 日日元以^亞苯聚合物塗覆之0 範例7 M3 (氧二-1，4·亞苯基）雙（2,4,5-三笑基璦成二 Hgl)(化合物K)及1·3,5-三（笨基乙炔某）笑厶物 gl製備寡聚物溶液 經濟部智慧財產局員工消費合作社印製 於已經以去離子水及HPLC等級丙酮潤濕並乾燥之 Pyrex(S>1公升之三頸圓底燒瓶，添加低離子3,3，-(氧二-1，4-亞苯基）雙（2,4,5-三苯基環戊二烯酮）（ΐ〇〇·〇克，〇·128莫耳） 低離子1，3,5-三（苯基乙炔基）苯（48.3克，0.128莫耳）及電子 等級之Ν-甲基处咯烷二酮（346克）。燒瓶被附接於氮氣/ 真空入口。磁性攪拌溶液以真空及再填充氮氣重複五次來 脫氣。然後，氮氣經燒瓶頭部空間流過且經無機油泡沫器 流出。溶液被加熱至内部溫度為200°C。加熱溶液8.5小時 後’將其冷卻並轉移至由四氟乙烯作成之瓶子内。以凝膠 滲透色譜法分析最後產物顯示Mn=1498&Mw=2746，其係 相對於聚本乙稀標準物。以逆相色譜法分析最終溶液顯示 殘留3,3’-(氧二-1，4-亞苯基）雙（2,4,5-三苯基環戊二烯酮）含 量為1·8重量％。以氮氣活化分析最終溶液顯示鈉含量為52 ppb、鉀含量為190 ppb、鈀含量為90 ppb、溴含量為2 4 ppm 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） - 492981 A7 B7 五、發明説明（53 ) 、蛾含量為0.6 ppm、氣含量為2.4 ppm。 範例8 由範例7塗覆並固化寡聚物溶液 經濟部中央標準局員工消費合作社印製 矽烷為基本之黏著劑促進劑（可由陶氏化學公司獲得 之AP8000)先被塗覆（200毫米之晶元為3毫升）於晶元表面 :缓慢旋轉使其分散於整個表面；使其靜置2秒；最後以 3000 rpm自旋乾燥10秒。範例7製備之聚亞苯募聚物溶液 藉由高精準泵/過濾系統Millipore Gen-2塗覆（200毫米晶 元為4毫升）於以黏著劑促進劑塗覆之晶元表面上，此時晶 元係以750 rpm旋轉。塗覆募聚物溶液後立即將晶元旋轉 加速至2000 rpm，且保持此自旋速率20秒。於塗覆募聚物 溶液期間，1，3,5-三甲苯連續流被塗覆於晶元背面。在以 募聚物溶液自旋塗覆晶元後，膜於70°C熱盤上乾燥20秒。 乾燥烘焙步驟後，塗覆物之2毫升至5毫升之端緣珠以1，3,5-三甲苯連續流移除，同時晶元以2000 rpm旋轉，而藉由自 背側或直接自接近端緣之頂部塗覆。移除端緣珠後，寡聚 物進一步於氮氣罩下於325°C熱盤上聚合90秒。然後，膜 於氮氣下之450 °C熱盤交聯2分鐘或於450 °C氮氣氣提爐交 聯6分鐘。以動力機械分析測得膜具有大於450°C之玻璃轉 移溫度。 56 (請先閱讀$面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 492981 A7 B7 五、發明説明（54 ) 第I表 經濟部中央標準局員工消費合作社印製(Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 52 492981 Α7 Β7 V. Description of the invention (50) Example 4 ϋ3 '· (Oxygen -M-Asianyl) bis (2,4,5-tribenzylcyclopentane (please read the precautions on the back before filling out this page) ketene) (compound K) ao 4,4, 笑 f Ethynyl) bis-molyl ether (Compound H) Polymerization of 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentadienone) ( 15.0000 g, 0.0119158 moles), 4,4, -bis (phenylethynyl) diphenyl ether (7.0974 g, 0.019158 moles) and N-methylpyrrolidinedione (51.60 g) were added to 250 ml Round-bottomed flask. The flask was attached to a nitrogen inlet, and the magnetically stirred solution was heated to 200 ° C in an oil bath. After 19.5 hours at 200 ° C, gel permeation chromatography showed that "" is 1551 and 2 ^ ~ 2383, which is relative to the polystyrene standard. The solution was cooled 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 used to heat the wafer. The wafer was coated It was placed on a hot plate set at 90 ° C for several minutes. The wafer was placed in a nitrogen gas furnace to cure it by stripping at room temperature for 4 5 minutes, and then heated to 400 ° C / min to 400 ° C. C 'was held at 400 ° C for 1 hour, and then allowed to cool to room temperature. The formed crystals were coated with polyphenylene polymer. When the solution was applied to the gap-filled structure of the submicron gap and cured, the solution was found Fill the gap completely. Example 5 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5 By 3,3 '-(oxydi-1,4-phenylene) bis (2 · 4 · 5-trimosome sapwood dienone) (Compound K), 4,4, -Bis (phenylethynyl) diphenyl_ (Compound H), and 1,3,5-tris (benzylethynyl) benzyl (compound m) Preparation of polymer in 100 ml In a 3-necked round bottom flask, 3,3,-(oxydi-fluorene, 4 · phenylene) bis (2,4,5-triphenylcyclopentadienone) (ΐ0.0000) was added. G, 0,01277 mole) Zhang scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ~ '33-2-492981 A7 B7 5. Description of the invention (51), 4,4'-bis (phenylethynyl) diphenyl Ether (2,366 g, 0006386 moles), 1,3,5-tris (phenylethynyl) benzene (2.4170 g, 0.006386 moles), and N-methyl-pyrrolidone (34.5 Ml). The flask was attached to a nitrogen inlet, and the magnetically stirred solution was heated to 200 ° C in an oil bath. At 200. (: After 11 hours, the solution was cooled and bottled. A portion of the solution was poured into a syringe And filtered through a 4-micron syringe filter on a 4-inch silicon wafer. The wafer was spin-coated at 2000 rpm for 60 seconds. The coated wafer was placed on a hot plate set at 9 (rc for 2 minutes. Crystal) The element was placed in a rat gas furnace to solidify by stripping for 45 minutes at room temperature, then heated to 400 ° C at 10 ° C / min, kept at 400 ° C for 1 hour, and then allowed to cool to room temperature. The wafers are coated with polyphenylene polymer. When the solution is applied to a gap-filling structure with sub-micron gaps and cured, the solution is found to completely fill the gaps. Cured polymerization Insoluble in N-methyl sigma biketone diketone. Example 6 Fish 13 '-(oxydi-M-jamomonium) bis (2 · 4 · 5-di-benzene hydrazine into two calendar __) (combination Disk K), I, 3, -bis (benzylacetylene, benzene, benzene), and 1,3,5-tris (phenylethynyl) benzyl (Compound Gk prepared polymer in a 25 ml Schlenk tube, add 3,3 '-(oxydi-fluorene, 4-phenylene) bis (2,4,5-triphenylcyclopentadienone) (2,000 g, 0.0052 mol), ^ 3, bis (benzylethenyl) benzyl (0.4740 g '0.001703 moles), 1 3 5-5 (phenylethynyl) benzene (0.4834 g, 0.001277 moles) and N-methylpyrrolidine Ketone (6.9¾ liters). The tube was attached to the gas inlet, and the mechanical search solution was heated to 200 ° C in an oil bath. After 20 hours at 200 ° C, gel permeation chromatography indicated Mn = 1463 & Mw = 2660, which is equivalent to a polyphenylenesulfonium standard. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------ ^ --- 0 --- install --- * (Please read the precautions on the back before filling in this Page) · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 492981 A7 B7 V. Description of Invention (52) J .-------- Installation—— ** (Please read the precautions on the back before filling this page ) The liquid is 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 heating lamp capable of warming the wafer. Then coated The wafers were placed on a hot plate set at 90 ° C for 2 minutes. The wafers were placed on a nitrogen stripping furnace to be cured by stripping at room temperature for 20 minutes, and then heated to 400 ° C / min. C 'is held at 400 ° C for 1 hour, and then cooled to room temperature. The formed Japanese yen is coated with ^ phenylene polymer. 0 Example 7 M3 (oxydi-1,4 · phenylene) bis (2, Preparation of 4,5-trisyl group into di-Hgl) (compound K) and 1,3,5-tris (benzyl acetylene) stilbyl compound gl Preparation of oligomer solution Printed on the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs A Pyrex (S > 1 liter three-necked round bottom flask that has been moistened and dried with deionized water and HPLC grade acetone, and low ion 3,3,-(oxydi-1,4-phenylene) bis (2 , 4,5-triphenylcyclopentadienone) (100,000 g, 0.128 mol) Low ion 1,3,5-tris (phenylethynyl) benzene (48.3 g, 0.128 mol Ear) and electronic grade N-methyl chloropyrrolidine (346 g). The flask was attached to a nitrogen / vacuum inlet. The magnetic stirring solution was degassed by repeating the vacuum and refilling nitrogen five times. Then, the nitrogen flowed through the head space of the flask and flowed out through the inorganic oil foamer. The solution It was heated to an internal temperature of 200 ° C. After heating the solution for 8.5 hours, 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 Relative to polyethylene standard. Analysis of the final solution by reversed phase chromatography revealed residual 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentane) Dienone) content was 1.8% by weight. The final solution analyzed by nitrogen activation showed a sodium content of 52 ppb, a potassium content of 190 ppb, a palladium content of 90 ppb, and a bromine content of 2 4 ppm. This paper applies Chinese national standards. (CNS) A4 specification (210 X 297 mm)-492981 A7 B7 V. Description of the invention (53), moth content is 0.6 ppm, gas content is 2.4 ppm. Example 8 Coating and curing oligomer solution from Example 7 is economical Printing of Silane by Consumer Cooperatives of the Ministry of Standards An adhesion promoter (AP8000 available from The Dow Chemical Company) is first coated (200 millimeters of crystals is 3 ml) on the surface of the crystals: slowly rotate to disperse the entire surface; let it stand for 2 seconds; finally Spin-dry at 3000 rpm for 10 seconds. The polyphenylene polymer solution prepared in Example 7 was coated with a high-precision pump / filtration system Millipore Gen-2 (200 millimeters of wafers was 4 milliliters) and coated with an adhesive accelerator. On the surface of the overlying wafer, the wafer was 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 polymer solution, a continuous stream of 1,3,5-trimethylbenzene was applied to the back of the wafer. After the wafers were spin-coated with the polymer solution, the film was dried on a 70 ° C 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 in a continuous flow of 1,3,5-trimethylbenzene while the wafer is rotating at 2000 rpm, and can be accessed from the back side or directly The top edge is coated. After removing the end beads, the oligomers were polymerized on a hot plate at 325 ° C for 90 seconds under a nitrogen blanket. The membrane was then crosslinked for 2 minutes at 450 ° C on a hot plate under nitrogen or 6 minutes for nitrogen stripping furnace at 450 ° C. The membrane has a glass transition temperature greater than 450 ° C as measured by a mechanical analysis. 56 (Please read the notes on the $ face before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 492981 A7 B7 V. Description of the invention (54) Table I Central Ministry of Economy Printed by Standards Bureau's Consumer Cooperative

(請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 57 492981 A7 B7 五、發明説明（55 ) 第I表（讀）(Please read the precautions on the back before filling out this page) The paper size applies to the Chinese National Standard (CNS) A4 (210X 297 mm) 57 492981 A7 B7 V. Description of the invention (55) Table I (read)

本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 58 492981This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 58 492981

本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -59 - 492981 A7 B7五、發明説明（57 ) 因上述化合物製備程序使用標準化學實施，且已知 些微不同反應物可能需要與其它反應些微不同之反應參數 ，能瞭解的是所示反應參數些微參數（諸如，使用過量之 反應物，使用催化劑、使用稍微高於或低於室溫之溫度， 例如，及/或高速率混合及其它傳統變化）係位於本發明 範圍内^ (請先閱讀背面之注意事項再填寫本頁) t -裝- 訂 經濟部中央標隼局員工消費合作社印製 60 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ；Ζ97公釐）This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -59-492981 A7 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 be required Slightly different reaction parameters from other reactions, it can be understood that some of the shown reaction parameters (such as using excess reactants, using catalysts, using temperatures slightly above or below room temperature, for example, and / or high rates Mixing and other traditional changes) are within the scope of the present invention ^ (Please read the notes on the back before filling out this page) t-Binding-Ordering Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 60 This paper size applies to Chinese national standards (CNS) Α4 specification (210 ×; Z97 mm)

Claims (1)

1. 申請專利範谭 第86113G27號專财請案巾請專利範圍健正本 修正日期：91年02月 -種寡聚物、未固化聚合物或固化聚合物，其含有一 或多個含有二個環戊二烯酮基之多官能基化合物與至 少-含有三或多個芳族乙炔基之多官能基化合物之反 應產物，*中至少-部份之該等多官能基化合物含有 三或多個反應性基團，其中該反應產物為： (a)下示化學式之雙環戊二烯酮：1. Apply for patent Fan Tan No. 86113G27, please apply for the patent, please apply for the patent scope, the original amendment date: February, 91-an oligomer, uncured polymer or cured polymer, which contains one or more containing two The reaction product of a cyclopentadienone-based polyfunctional compound with at least-polyfunctional compounds containing three or more aromatic ethynyl groups. At least-part of the polyfunctional compounds in * contain three or more A reactive group, wherein the reaction product is: (a) a dicyclopentadienone of the formula: R1 (b)下式化學式之多官能性乙炔： -ArJ (c)選擇性地’如下所示化學式之雙乙快： R2-gzg- Ar2 R2 其中R及R2各別為H或不被取代或惰性取代之芳族 部份，且Ar1、Ar2及Ar3各自為未被取代之芳族部份或 惰性取代芳族部份，且y為3或更多之整數。 2. —種具有下述化學式之寡聚物或未固化聚合物： [A]w [B]z [EG]V 61 - 本紙張尺度適用中國國家標準（CNs) A4規格（210X297公楚）R1 (b) a polyfunctional acetylene of the formula: -ArJ (c) optionally 'diacetyl fast' of the formula: R2-gzg- Ar2 R2 where R and R2 are each H or unsubstituted or An inertly substituted aromatic moiety, and Ar1, Ar2, and Ar3 are each an unsubstituted aromatic moiety or an inertly substituted aromatic moiety, and y is an integer of 3 or more. 2. — An oligomer or uncured polymer with the following chemical formula: [A] w [B] z [EG] V 61-This paper size applies to Chinese National Standards (CNs) A4 (210X297) 、? (請先閲讀背面之注意事項再填寫本頁) 492981 A8 B8 C8 D8 六、申請專利範圍 其中A具有下示結構：、? (Please read the notes on the back before filling this page) 492981 A8 B8 C8 D8 VI. Application for patent scope Where A has the structure shown below: 且B具有下示結構：And B has the structure shown below: (請先閲讀背面之注意事項再填寫本頁) 端基EG係各別以下列化學式之任一者表之： -62- 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） A8 B8 C8 ~~—---~ /、、申清專利範圍(Please read the notes on the back before filling this page.) End group EG is listed in any one of the following chemical formulas: -62- This paper size applies to China National Standard (CNS) A4 (210X297 mm) A8 B8 C8 ~~ ----- ~ / ,, apply for patent scope 其中R1及R2各別為H或未被取代或被惰性取代之〜 族部份，且Ar1、Ar2及Ar3各別為未被取代之芳族部份 或惰性取代之芳族部份，Μ為一鍵，且y為3或更大之 整數，p為已知每單元内未反應乙炔基之數目，r為已 知每單元内少於反應乙炔基之數目者，且p+r=y-1，z 為1至1000之整數；w為0至1000之整數，且v為2或更 大之整數。 3·如申請專利範圍第1項之寡聚物、未固化聚合物或固化 聚合物，其係由下示反應形成： (a)化合物K及G ; 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)Where R1 and R2 are each H or unsubstituted or inertly substituted ~ group portion, and Ar1, Ar2 and Ar3 are each unsubstituted aromatic portion or inertly substituted aromatic portion, M is One bond, and y is an integer of 3 or greater, p is the number of known unreacted ethynyl groups per unit, r is the number of known less than the number of reactive ethynyl groups per unit, and p + r = y- 1, z is an integer from 1 to 1000; w is an integer from 0 to 1000, and v is an integer from 2 or more. 3. If the oligomer, uncured polymer or cured polymer in item 1 of the scope of the patent application, it is formed by the reaction shown below: (a) Compounds K and G; This paper size applies Chinese National Standard (CNS) A4 Specifications (210X297mm) (Please read the notes on the back before filling this page) -63- _ ______ 492981 六、申請專利範圍 (b) 化合物Κ、Η及G ; (c) 化合物Κ、Η及L ; (d) 化合物Κ、Η及Q ; (e) 化合物Κ及Ν ; (f) 化合物K、0及G ; (g) 化合物Κ、P及G ; (h) 化合物Κ、Ο及L ; (i) 化合物Κ、P及L ; ⑴化合物K、0及Q ; (k) 化合物Κ、P及Q ; (l) 化合物K及L ;或 (m) 化合物K及Q ; 其中化合物G為1，3,5-三（苯基乙炔基）苯；化合物11為 4,4 -雙（笨基乙炔基）二苯基醚；化合物〖為3,3，_(氧三 1，4-亞苯基）雙（2,4,5_三苯基環戊二烯酮）；化合物〔為 2,4,4’-三（苯基乙炔基）二苯基醚；化合物1^為4,4，，4' = (苯基乙炔基）-鄰-三聯苯；化合物〇為1，3，_雙（苯基乙炔 基）苯；化合物P為1,4-雙（苯基乙炔基）苯且化合物9為 1，2,4-三（苯基乙炔基）苯。 4· 一種未固化或固化聚合物，其係於能使中至少一部份 之側及終端之乙炔基反應產生凝膠之溫度及時間，使 申请專利範圍第1 ·，2或3項之寡聚物或未固化聚合物加 熱形成之。 5.如申請專利範圍第1項之寡聚物、未固化聚合物或固化-63- _ ______ 492981 VI. Patent Application Range (b) Compounds K, Η, and G; (c) Compounds K, Η, and L; (d) Compounds K, Η, and Q; (e) Compounds K and N; ( f) Compounds K, 0, and G; (g) Compounds K, P, and G; (h) Compounds K, 0, and L; (i) Compounds K, P, and L; ⑴ Compounds K, 0, and Q; (k) Compounds K, P and Q; (l) compounds K and L; or (m) compounds K and Q; wherein compound G is 1,3,5-tris (phenylethynyl) benzene; compound 11 is 4,4- Bis (benzylethynyl) diphenyl ether; compound [is 3,3, _ (oxytri 1,4-phenylene) bis (2,4,5_triphenylcyclopentadienone); compound [Is 2,4,4'-tris (phenylethynyl) diphenyl ether; Compound 1 is 4,4,, 4 '= (phenylethynyl) -o-terphenyl; Compound 0 is 1, 3, _bis (phenylethynyl) benzene; compound P is 1,4-bis (phenylethynyl) benzene and compound 9 is 1,2,4-tris (phenylethynyl) benzene. 4. An uncured or cured polymer, which is at a temperature and time that can react at least part of the side and terminal acetylene groups to produce a gel, making the oligomers in the scope of patent applications No. 1, 2, or 3 Polymers or uncured polymers are formed by heating. 5. If the oligomer, uncured polymer or cured 492981 A8 B8 C8 __D8 六、申請專利範園 (請先閲讀背面之注意事項再填寫本頁) 聚合物，其係由使3,3,兴氧二]，4_亞苯基）雙（2,4,5_三 苯基環戊二烯酮）、1，3,5-三（苯基乙炔基）苯及4,4，-雙( 苯基乙炔基）二苯基鱗反應形成之。 6·如申請專利範圍第1項之寡聚物、未固化聚合物或固化 聚合物，其係由3,3’-(氧二-1，4-亞苯基）雙（2,4,5-三苯 基環戊二烯酮）及1，3,5 -三（苯基乙快基）苯反應形成之。 7. —種用於形成一未固化聚合物或固化聚合物的方法， 其包含使申請專利範圍第1 ’ 2或6項之寡聚物或未固化 聚合物塗覆於表面，且加熱使額外環戊二烯酮或乙炔 部份反應形成未固化聚合物或固化聚合物。 8. —種積體電路物件，其包含活化基材，該基材含有晶 體管及電連接結構，其含有至少部份以含有申請專利 範圍第1，2或6項之募聚物、未固化聚合物或固化聚合 物之介電材料之層或區域分離之圖案金屬線。 -65- 本紙張尺度適用中國國家標準（CNS) A4规格（210X297公釐）492981 A8 B8 C8 __D8 VI. Apply for patent Fanyuan (please read the precautions on the back before filling this page) Polymer, which is made of 3,3, oxobi], 4_phenylene) bis (2, 4,5-triphenylcyclopentadienone), 1,3,5-tris (phenylethynyl) benzene and 4,4, -bis (phenylethynyl) diphenyl scale are formed by reaction. 6. The oligomer, uncured polymer or cured polymer according to item 1 of the scope of patent application, which is composed of 3,3 '-(oxydi-1,4-phenylene) bis (2,4,5 -Triphenylcyclopentadienone) and 1,3,5-tris (phenylethoxy) benzene. 7. A method for forming an uncured polymer or a cured polymer, comprising applying an oligomer or uncured polymer in the scope of claims 1 '2 or 6 on the surface, and heating to cause additional The cyclopentadienone or acetylene partially reacts to form an uncured polymer or a cured polymer. 8. —A kind of integrated circuit object, which comprises an activated substrate, the substrate contains a transistor and an electrical connection structure, and it contains at least a part of an agglomerate and uncured polymer containing the patent application scope item 1, 2 or 6. Pattern or metal wire that separates layers or regions of dielectric material or cured polymer. -65- This paper size applies to China National Standard (CNS) A4 (210X297mm)