TW200948858A - Oligomeric adducts of bismaleimide, diamine, and dithiol - Google Patents
Oligomeric adducts of bismaleimide, diamine, and dithiol Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09D179/085—Unsaturated polyimide precursors
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200948858 九、發明說明: 【發明所屬之技術領域】 本發明一般有關一種寡聚物的化合物,发 胺化合物及二胺之加成物。寡聚物係經馬來:為醯亞 端且使用胺基鍵聯而延伸《此等化合物係有亞胺官能度封 產業中各種製造步驟之黏著劑、塗料、及用為半導體封裝 【先前技術】 ❹ 15 ❹ 20 雙馬來醯亞胺為一種已發現用於微電子 固性樹脂的代表。雙馬來輕胺能夠在自^裝工業之熱 與情況下進行同元聚合作用及能夠鱼盆它白土 f光引發劑參 一,、匕自由基固化單體 (如丙炸駿醋、曱基丙烯酸醋、苯乙稀系、乙稀鍵、旨、 烯丙基單體、烯烴等)進行聚合作用。彼等亦可在共聚用曰單 體參與情況下經由狄耳士一阿德爾(Diels_Alde〇 ^應、烯 烴(-ene)反應、及麥可(Michael)加成機制進行聚合化。 如本說明書及申請專利範圍所用,固化將意指聚合作用。 商業可得的馬來醯亞胺熱固性樹脂被注意到彼等的高 模數,及對熱降解之優異抗性。然而,此等熱固組成物亦易 脆,其造成彼等於固化後經震動破裂。較高的分子量馬來醯 亞胺有助於解決脆性問題,但對於許多組成物而言,額外分 子量須要較高水準的稀釋劑以達到可分配性。用較高水準的 稀釋劍,增加固化_剩之除氣,其增加經固化的馬來酿 亞胺中空隙之可能性。空隙導致自馬來醯亞胺製備的黏著劑 或封裝劑之潛在失敗及最終電子裝置之失敗。 固體馬來醯亞胺募聚物之另一種適合用途為下一代晶 5 200948858 片:之背側塗布(WBC)配方。WBC配方典型地為在晶片 切單(smgulate)成個別裸晶(die)前直接塗敷於矽半導體 晶片不活性面之黏著劑。此材料之要求包含更好開放印刷次 5 Ο 10 15200948858 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention generally relates to a compound of an oligomer, an adduct of a hair amine compound and a diamine. The oligomers are extended by Malay: 醯-end and using amine linkages. These compounds are adhesives, coatings, and semiconductor packages for various manufacturing steps in the industry. ❹ 15 ❹ 20 Bismaleimide is a representative that has been found to be used in microelectronic curable resins. Double maleic amine can carry out homopolymerization under the heat and conditions of the industry, and can be used as a white clay f photoinitiator, and a free radical curing monomer (such as C-explosive vinegar, sulfhydryl) Acrylic vinegar, styrene, ethylene bonds, allylic monomers, olefins, etc. are polymerized. They may also be polymerized via Diels-Alde®, ene reaction, and Michael addition mechanism with the participation of the oxime monomer. As described in this specification and As used in the scope of the patent application, curing will mean polymerization. Commercially available maleic imine thermosetting resins are noted for their high modulus and excellent resistance to thermal degradation. However, such thermosetting compositions It is also brittle, which causes it to be ruptured by vibration after curing. The higher molecular weight of maleimide helps to solve the brittle problem, but for many compositions, the extra molecular weight requires a higher level of diluent to achieve Dispensing. Use a higher level of dilution of the sword to increase the cure_remaining degassing, which increases the likelihood of voids in the cured maleimide. The voids result in an adhesive or encapsulant prepared from maleimide. Potential failures and failure of the final electronic device. Another suitable use for solid maleimide concentrating polymers is next-generation crystal 5 200948858: back side coating (WBC) formulation. WBC formulations are typically cut on wafers. (Smgulate) into individual die (Die) before the semiconductor wafer is directly applied to the silicon surface of the adhesive inactive. This requires better materials comprising a printed open times 5 Ο 10 15
20 數之經控制溶解度’允許較高切财度之較幼性,及經 改良的流。因此’有持續需求馬來輕胺化合物可致力於面 對微電子封裝產業之挑戰。 【發明内容】 本發明為藉由麥可加成反應製備的雙馬來酿亞胺及二 ^,雙馬3M!賴及二贿二硫醇之絲物加成物。馬來The controlled solubility of 20' allows for a higher degree of cut-off, and improved flow. Therefore, there is a continuing need for maleic amine compounds to address the challenges of the microelectronics packaging industry. SUMMARY OF THE INVENTION The present invention is a filamentary adduct of bismaleimide and di-, bisme 3M! and dibres-dithiol prepared by a Michael addition reaction. Malay
If月女係經二胺、或經二胺與二硫醇的結合而延伸。寡聚物 H用作為黏㈣、塗料、及封㈣’且在半導體封裝產 業範圍内具有特別用途。 在-項具體實例中,本發明為一種可固化組成物,其適 :將半導絲晶或轉體封料黏著於基底,錢合在切單 成^裸晶前塗布於半導體晶片之不活性側,已知為晶 =布^BC)/可固化組成物包括雙馬來酿亞胺及二胺、 ^ ^亞版及—胺與二硫醇之加成物;固化劑;視需要 的填料;及視需要的溶劑。 ,始馬來㈣贿胺、或與胺及硫醇之莫耳比可為任何 1 =效於未來末端用途的分子量、黏度、溶解度、及勤性 ,物。§亥比可為任何於1 : 1至99 : 1範圍内。胺與硫 任何選擇的比例呈現。在—項具體實例中,該比將於 轨圍内,在另項具體實例中,該比將於2 :工範圍内; 在又另一項具體實例中,該比將於5 : i範_。熟習技藝 6 200948858 者將瞭解隨著分子量增加,溶解度可降低,且黏度及韌性(由 模數測量)將增加。 在設計雙馬來醯亞胺及二胺、或雙馬來醯亞胺及二胺與 二硫醇之寡聚物加成物中,實踐者可於上述莫耳比範圍内使 用一或多種雙馬來醯亞胺與一或多種二胺及二硫醇。使用若 干雙馬來醯亞胺、二胺及二硫醇作為起始材料之能力擴張寡 聚物加成物的全部功能開放給實踐者,且允許設計具有關於 黏度、溶解度、及勃性的特定性能特性之產物。 •° ?-"Ν-Χ— 適合使用之雙馬來醯亞胺包含具有結構 0 0’之固 體芳香族雙馬來醯亞胺(ΒΜΙ)樹脂粉末,其中X為芳香族 基0 示範之芳香族基包含 各 ❹If the female is extended by a diamine or by a combination of a diamine and a dithiol. The oligomer H is used as a binder (4), a coating, and a seal (4) and has a special use in the semiconductor packaging industry. In a specific example, the present invention is a curable composition which is suitable for: adhering a semi-conductive filament crystal or a rotating sealing material to a substrate, and inactively coating the semiconductor wafer before the dicing is performed. Side, known as crystal = cloth ^ BC) / curable composition including bismaleimide and diamine, ^ ^ subtype and - amine and dithiol adduct; curing agent; ; and depending on the solvent required. , Malay (four) bribe amine, or with the amine and mercaptan molar ratio can be any 1 = molecular weight, viscosity, solubility, and diligence for future end uses. § Haibi can be anywhere from 1:1 to 99:1. The ratio of amine to sulfur is chosen in any ratio. In the specific example, the ratio will be within the rail circumference. In another specific example, the ratio will be within the range of 2: in another specific example, the ratio will be 5: i _ . Familiarity 6 200948858 It will be appreciated that as molecular weight increases, solubility decreases and viscosity and toughness (measured by modulus) increase. In the design of bismaleimide and diamine, or bismaleimide and oligomers of diamines and dithiols, practitioners may use one or more pairs in the above molar ratio. Maleimide with one or more diamines and dithiols. The ability to use several bismaleimides, diamines, and dithiols as starting materials to extend the full functionality of the oligomer adduct is open to the practitioner and allows design to have specific properties regarding viscosity, solubility, and bourn Product of performance characteristics. • ° ?-"Ν-Χ- Suitable bimaleimide contains a solid aromatic bismaleimide (ΒΜΙ) resin powder with structure 0 0', where X is an aromatic group. Aromatic group contains each
7 2009488587 200948858
具有此等x橋聯基之雙馬來醯亞胺樹脂為商業可得且 ίο 可從例如Sartomer (美國)及HOS-Technic GmbH (奥地利) 200948858 獲得。Bismaleimide resins having such x bridged groups are commercially available and are available, for example, from Sartomer (United States) and HOS-Technic GmbH (Austria) 200948858.
額外示範之馬來醯亞胺包含具有一般結構 者,其為1至3且X1為脂族或芳香族基。示範之χι實 5An additional exemplary maleimide comprises a general structure which is from 1 to 3 and X1 is an aliphatic or aromatic group. Demonstration of χι 5
體包含聚(丁二烯)、聚(碳酸酯)、聚(胺甲酸醋)、聚(醚)、聚 (酯)、簡單烴、及含有官能度如羰基、羧基、酿胺、胺甲酸 酯、脲、或醚之簡單烴。此等類型之樹脂為商業可得且可從 例如 National Starch and Chemical Company 及 Dainippon Ink and Chemical, Inc 獲得。 特定較好的馬來醯亞胺包含 10The body comprises poly(butadiene), poly(carbonate), poly(carbamic acid vinegar), poly(ether), poly(ester), simple hydrocarbon, and contains functional groups such as carbonyl, carboxyl, lanthanum, uric acid A simple hydrocarbon of an ester, urea, or ether. Resins of this type are commercially available and are available, for example, from National Starch and Chemical Company and Dainippon Ink and Chemical, Inc. Particularly preferred maleic imine contains 10
其中C36表示36個石炭原子之 線型或分支鏈(具有或沒有環狀部分> .Wherein C36 represents a linear or branched chain of 36 asbestos atoms (with or without a cyclic moiety >).
;及 9 200948858; and 9 200948858
Ο 5 10Ο 5 10
15 適合的二胺為任何具有ΝΗ2—X~NH2結構者,其中χ 為脂族或芳香族烴。二胺之結構及分子量可為任何適合用於 所欲的最終組成物。廣泛多樣化的二胺為商業可得。在若干 具體實例中,二胺係選自由2,2-雙[4-(4-胺基苯氡基)苯基丙 ,]、二胺基二苯基-甲烷、及2,2-雙[4_(4_胺基苯氧基) 苯基甲烷]、4,4,-二胺基-3,3,-二曱基二苯基曱烷、4,4,_(1,3_ 伸苯基二氧基)-二苯胺、1,4-伸苯基二胺所組成之組群。 適合的二硫醇為任何具有SH—X-SH結構者,其中χ 為月曰知或芳香族烴。二硫醇之結構及分子量可為任何適合用 ^所欲的最終組成物。廣泛多樣化的二硫醇為商業可得Γ在 或來自Akcros Che祕als之Thi〇細G4所组成之組 為當由烯基甲醯胺化合物之可固化組成物用引發劑 勺田由熱(熱引發劑)或電磁輻射 ……鈉 造自由基或陽離子引發物種之化丨發劑)觸發時可製 _至10重量%用量呈現。〇物。引發劑將以總樹脂的 L 5的自由基熱引發劑包 過乳化物,如過氧化苄醯、 200948858 5 ❹ 10 15 ❹ 20 過氧化月桂醯、過氧化辛醯、過辛酸丁酯、過氧化二異丙苯、 過氧化乙醯、過氧化-對_氯苄醯及二鄰羧基過苯曱酸二_第三 丁酯;l,l-二-(第三戊基_過氧基)_環己烷;偶氮化合物,如 偶氮異丁腈、2,2’-偶氮雙丙烷、2,2,_偶氮雙(2-甲基丁腈)、 及m,m’-偶氮氧基苯乙烯。商業可得之偶氮引發劑為從Wak〇 Specialty Company 可得者,例如以商品名 va-044、VA-057、 VA-085、V-70、VF-096、V-65、V-6(H、V-59、V-40、VF-096、 V-30販售者’及從Akzo Nobel可得者,例如以商品名 Perkadox ACCN、Perkadox AIBN、Perkadox AMBN-GR 販售 者’及從Dupont可得者,例如以商品名Vazo-52、Vazo-64、 Vazo-67 及 Vazo-88 販售者。 示範之自由基光引發劑係揭示於及⑽CwWwg·: Science and Technology > 1992 » Plenum Press » New York ; S.P. Pappas,Ed·及 少c/ope出〇/ 尸«SWewce Engineerings 11» 187» 1988 > John Wiley and Sons > New York ; H.F. Mark,N.M. Bikales,C.G. Overberger,G· Menges,Eds。 亦可選擇固化目的用之自由基熱引發劑,示範之熱引發劑係 揭示於少,211,1991,John Wiley and Sons,New York ; G.G. Odian ’ Ed。 在若干具體實例中,光引發作用及熱引發作用兩者可為 令人嚮往。例如,固化含光引發劑之黏著劑可由UV照射開 始,在稍後加工步驟中’固化可由應用熱完成以達到自由基 固化。UV及熱引發劑兩者可因此添加於黏著劑組成物。 對某些應用而言,可將一或多種填料或隔離物(spacer) 11 200948858 5 10 15 ❹ 20 或雨者添加於可固化組成物且通常添加用以改良的流變性 質、應力降低、及膠層(bondline)控制。適合的非導電性 填料實例包含氧化鋁、氫氧化鋁、二氧化矽、經石、雲母、 矽灰石、碳酸鈣、氧化鈦(titania)、砂、玻璃、硫酸鋇、錐、 碳黑、有機填料、及有機聚合物(包含但不限於經齒化的1乙 烯聚合物,如四氟乙稀、三氟乙烯、偏氟乙烯、氟乙烯、偏 氯乙烯、及氣乙烯)。適合的導電性填料實彳彳自 墨、金、銀、銅、銘'把、錄、魅、碳切二石 及氧化鋁。顆粒可為範圍自奈米大小至數個毫米之任何適+ 尺寸’取決於其等是否制作為填料或隔離物(隔離物典二 為具有更多尺寸均勻性之更大尺寸齡)。針對任何特別末 端用途選擇如此尺寸係於熟f技藝者之專門技術範圍内。填 料可由實踐者決定以適合所選擇末端用途之任何量呈現。、 —裸晶黏接及WBC應用需要給予強度、韌性、及耐熱性 之寡聚物馬來醯亞胺,但其亦溶解於低沸點溶劑及展現優異 可加工性。本發明經二胺及二硫醇延伸之募聚物馬來醯亞胺 典型地為固體樹脂且適合於WBC組成物。經二胺及二硫醇 延伸之本發明寡聚物馬來醯亞胺的分子量及黏度可由適當 選擇用於麥可加成反應之馬來醯亞胺與二胺或二硫醇增添 劑及其等相對莫耳比而修改合適。 本發明馬來醯亞胺/二胺加成物係 以組成物總重量為 基之2重里百分比至約%重量百分比(重量%)呈現於組 成曰中在其匕具體實例中,一或多種共單體可以組成物總 重重為基之10重量%至約90重量%呈現於組成物中。該 12 200948858 等^單體包含例如丙騎S旨、甲基丙婦酸醋、馬來醯亞胺、 乙稀Si乙稀Sa、苯乙烯系化合物、烯丙基官能性化合物 等。 各組成物之時間與溫度固化曲線圖將多樣化,可設計不 同f成物喷供適合軸產業製造過程之固化曲線圖。一般 而言,此等組成物將於70°c至250°C範圍内固化,且固化將 於十秒至三小時範圍内實現。 ❹ 15 20 在若干具體實例中,黏著劑組成物可含有將額外撓性及 勃。f生借、”σ所得纟賴化黏著劑之化合物。該等化合物可為具有 5〇c或更小Tg之任何熱目性或熱塑性材料,且典型地將為 I。物材料’其特徵為自由旋轉化學鍵、存在⑽基、及缺乏 環、”《構_該等適合改質劑包含聚丙烯酸醋、聚(丁二婦)、聚 THF (㈣合四氫料,亦已知絲(μ 丁二醇))、㈣n (缓基終端之丁二稀_丙烯腈)橡膠、及聚丙二醇。當存在 時’勤性化合物可為本發明馬練亞胺^二胺加成物之高至 約15重量%用量。 自由基固化用抑·亦可添加於本文所述之黏著劑組 成故長3有本發明化合物的組成物之有用搁置壽命。此 等抑制劑之實例包含受㈣,例如2,6•二第三丁基冬甲基 二2f二:第三丁基I甲氧基酚、第三丁基氫醌、肆(亞甲 基-(,_一-弟二丁基-4-對羥笨丙酸酯))苯、 第;:基-對-甲盼)、及⑻-三甲基-2,仏參二^ 丁土㈣基)苯。其它有用給予氫之抗氧化劑包含對-伸笨 基二胺及二苯基胺之衍生^技藝中亦熟知給錢之抗氧化 13 200948858 劑可與醌、及金屬去活化劑增效組合以製造非常有效的抑制 劑套裝物。適合醌之實例包含苯醌、2-第三丁基_154_苯醒、 2-苯基-1,4-苯醌、萘醌、及2,5-二氯-l,4-苯醌。金屬去活化 劑之實例包含N,N’-雙(3,5_二-第三丁基_4_對羥苯丙醯基) 5 肼、草醯基雙(亞苄基醯肼)、及N-苯基-N,-(4-甲苯確醯基)_ 對-伸苯基二胺。硝醯自由基化合物如TEMPO (2,2,6,6-四甲 基-1-派咬氧基’自由基)亦有效作為在低濃度之抑制劑。抗 氧化劑加增效劑之總用量典型地落於100至2000ppm的範 〇 圍’以總原料樹脂之重量為基礎。亦可以技藝中已知的類型 ίο 及用量添加其它添加劑,如黏著促進劑。 【實施方式】 在所有下列實施例中,結構中「η」為多樣化的整數, 且各反應混合中’將有具不同「η」值之寡聚物。因此,針 對本文目的’ η為可變的整數。由於此混合,雖然各反應產 15 物之確切整數將為未定,但平均整數可根據起始材料之化學 &十量法及藉由產物之分子量決定,一般而言,η將於1至5 ❹ 範圍。 、 實施例1合成 14 20094885815 Suitable diamines are those having the structure of ΝΗ2-X~NH2 wherein χ is an aliphatic or aromatic hydrocarbon. The structure and molecular weight of the diamine can be any suitable final composition for use. A wide variety of diamines are commercially available. In several embodiments, the diamine is selected from the group consisting of 2,2-bis[4-(4-aminophenylhydrazino)phenylpropane,], diaminodiphenyl-methane, and 2,2-dual [ 4-(4-aminophenoxy)phenylmethane], 4,4,-diamino-3,3,-didecyldiphenylnonane, 4,4,_(1,3_phenylene) A group consisting of dioxy)-diphenylamine and 1,4-phenylenediamine. Suitable dithiols are those having the SH-X-SH structure, wherein χ is a known or aromatic hydrocarbon. The structure and molecular weight of the dithiol can be any suitable final composition. A widely diversified dithiol is commercially available or consists of a group of Thi 〇 fine G4 from Akcros Che als, when the curable composition of the curable composition of the alkenylcarbamide compound is heated by the scoop ( A thermal initiator) or electromagnetic radiation... a sodium-derived free radical or a cation-initiated species hair styling agent can be formulated to be used in an amount of up to 10% by weight. Booty. The initiator will be coated with an emulsion of L 5 free radical thermal initiator of the total resin, such as benzammonium peroxide, 200948858 5 ❹ 10 15 ❹ 20 peroxide laurel, octyl peroxide, butyl peroctoate, peroxidation Diisopropylbenzene, acetonitrile peroxide, peroxy-p-chlorobenzylhydrazine and di-tert-carboxyperoxybenzoic acid di-tert-butyl ester; l,l-di-(tripentyl-peroxy)_ Cyclohexane; azo compounds such as azoisobutyronitrile, 2,2'-azobispropane, 2,2,-azobis(2-methylbutyronitrile), and m,m'-azo Oxystyrene. Commercially available azo initiators are available from Wak(R) Specialty Company, for example under the tradenames va-044, VA-057, VA-085, V-70, VF-096, V-65, V-6 ( H, V-59, V-40, VF-096, V-30 venders' and those available from Akzo Nobel, for example under the trade names Perkadox ACCN, Perkadox AIBN, Perkadox AMBN-GR venders' and from Dupont Available, for example, under the trade names Vazo-52, Vazo-64, Vazo-67 and Vazo-88. Exemplary free radical photoinitiators are disclosed in (10) CwWwg:: Science and Technology > 1992 » Plenum Press » New York ; SP Pappas, Ed·and less c/ope out / corpse «SWewce Engineerings 11» 187» 1988 > John Wiley and Sons > New York ; HF Mark, NM Bikales, CG Overberger, G· Menges, Eds may also choose a free radical thermal initiator for curing purposes. The exemplary thermal initiators are disclosed in Shao, 211, 1991, John Wiley and Sons, New York; GG Odian ' Ed. In several specific examples, light-induced Both action and thermal initiation can be desirable. For example, curing an adhesive containing a photoinitiator can UV irradiation begins, and in a later processing step 'curing can be done by applying heat to achieve free radical curing. Both UV and thermal initiators can thus be added to the adhesive composition. For some applications, one or more can be used Fillers or spacers 11 200948858 5 10 15 ❹ 20 or rain is added to the curable composition and is usually added for improved rheological properties, stress reduction, and bondline control. Suitable non-conductivity Examples of fillers include alumina, aluminum hydroxide, cerium oxide, feldspar, mica, apatite, calcium carbonate, titania, sand, glass, barium sulfate, cone, carbon black, organic fillers, and organic polymerization. (including but not limited to a toothed 1 ethylene polymer such as tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene chloride, and ethylene). Suitable conductive fillers are Ink, gold, silver, copper, Ming 'put, record, charm, carbon cut two stones and alumina. Particles can range from nanometer size to several millimeters of any suitable size> depending on whether it is made into a filler Or spacer (isolated Code two having more uniform size of the larger size of age). The selection of such dimensions for any particular end use is within the skill of those skilled in the art. The filler can be presented by the practitioner in any amount suitable for the end use selected. — Bare bonding and WBC applications require the addition of strength, toughness, and heat resistance to the oligo-maleimide, but it also dissolves in low-boiling solvents and exhibits excellent processability. The polymerized maleimide of the present invention extended by diamine and dithiol is typically a solid resin and is suitable for the WBC composition. The molecular weight and viscosity of the oligomer of the invention, which is extended by diamine and dithiol, can be appropriately selected from the maleimide and diamine or dithiol addition agent for the wheat addition reaction and Modify the appropriate relative to the molar ratio. The maleidanilide/diamine addition product of the present invention is present in the composition enthalpy in the range of 2% by weight to about % by weight (% by weight) based on the total weight of the composition, in one or more specific examples, one or more The monomer may be present in the composition from 10% by weight to about 90% by weight based on the total weight of the composition. The monomer of the present invention includes, for example, propylene, methyl acetoacetate, maleic imide, ethylene thialate, styrene compound, allyl functional compound, and the like. The time and temperature curing profiles of the various compositions will be diversified, and different f-products can be designed to be applied to the curing curve suitable for the manufacturing process of the shaft industry. In general, such compositions will cure from 70 ° C to 250 ° C and curing will be achieved in the range of ten seconds to three hours. ❹ 15 20 In several embodiments, the adhesive composition may contain additional flexibility and bob. a compound obtained by sigma, which may be any thermal or thermoplastic material having a Tg of 5 〇c or less, and will typically be I. The material is characterized by Freely rotating chemical bonds, the presence of (10) groups, and the absence of rings," "Construction_ such suitable modifiers include polyacrylic acid vinegar, poly (butting), polyTHF ((tetra) tetrahydrogen, also known as silk (μ Glycol)), (iv) n (successive terminal dibutyl acrylonitrile) rubber, and polypropylene glycol. When present, the <RTIgt; </ RTI> compound can be used in an amount up to about 15% by weight of the maleimine diamine adduct of the present invention. The free-radical curing may also be added to the adhesive composition described herein. The useful shelf life of the composition of the compound of the present invention. Examples of such inhibitors include (iv), for example, 2,6•di-tert-butyl-m-methyl-m- 2f-di: tert-butyl-l-methoxyphenol, tert-butylhydroquinone, hydrazine (methylene- (, _-di-dibutyl-4-p-hydroxybenzopropionate)) benzene, s::yl-p-methyl phenyl), and (8)-trimethyl-2, ginseng 2 butyl (4) )benzene. Other useful antioxidants for the administration of hydrogen include the derivatization of p-diphenyldiamine and diphenylamine. The antioxidants are also known to be useful in combination with antimony and metal deactivators. An effective inhibitor package. Examples of suitable oximes include benzoquinone, 2-tert-butyl-154-benzene, 2-phenyl-1,4-benzoquinone, naphthoquinone, and 2,5-dichloro-l,4-benzoquinone. Examples of metal deactivators include N,N'-bis(3,5-di-t-butyl-4-[p-hydroxyphenylpropanyl) 5 oxime, oxalyl bis(benzylidene fluorene), and N-phenyl-N,-(4-toluene)-p-phenylene diamine. Nitroxide free radical compounds such as TEMPO (2,2,6,6-tetramethyl-1-pyraloxy-radical) are also effective as inhibitors at low concentrations. The total amount of antioxidant plus synergist typically falls within the range of from 100 to 2000 ppm by weight based on the weight of the total raw material resin. Other additives, such as adhesion promoters, may also be added in the type known in the art. [Embodiment] In all of the following examples, "η" in the structure is a diversified integer, and each reaction mixture will have an oligomer having a different "η" value. Therefore, 'η is a variable integer for the purposes of this document. Due to this mixing, although the exact integer of each reaction will be undetermined, the average integer can be determined according to the chemical & tens method of the starting material and by the molecular weight of the product. In general, η will be 1 to 5 ❹ Scope. Synthesis of Example 1 14 200948858
ΟΟ
上述馬來醯亞胺/二胺加成物係由具有結構 •° Λ 〇 Q 5 f之馬來醯亞胺,其中C36表示 36個碳原子之線型或分支鏈(具有或沒有環狀部分),下文 稱BMI-1,及4,4’-二胺基-二苯基曱烷根據下列程序製備。 將 BMI-1 ( lOO.Og,0.1087mol)、4,4,-二胺基-二苯基 〇 曱烷(10.77g,0.05435mol)及甲苯(100mL)裝填於裝備 有溫度計、機械混合器、及冷凝器之500mL四頸圓底反應 燒瓶。反應燒瓶以氮淨化,而在預熱至90 °C之油浴中以 ίο 400rpms混合。當反應溫度達到65°C時,所有固體溶解形成 清澈金色溶液。然後添加五滴醋酸。在溫度80°C下,反應時 間開始,持續加熱及混合48小時。此時期間,反應從清澈 金色溶液改變為深紅橙色溶液。冷卻至室溫後,將反應溶液 從燒瓶側上的次要凝膠傾析,在旋轉蒸發器上自溶液萃提溶 15 200948858 劑。結果為121g黏稠深琥騎液體。將此產物有力地混合 於乙醇(300mL) 30分鐘,然後靜置澄清6〇分鐘。將不透 明黃色乙剩層從__色底独析並丟棄1覆另外三 次此混合/澄清/傾析循環。根據τιχ (▼苯/thf W 體積)顯示乙醇洗_移除殘餘二胺。在魏旋轉蒸發器及 60°CKUgelr〇hr上自產物萃提溶劑。獲得6〇g深紅褐色油狀 產物。結構由1H NMR確認。 實施例2 合成The above maleimide/diamine adduct is derived from the maleimine having the structure •° Λ 5Q 5 f, wherein C36 represents a linear or branched chain of 36 carbon atoms (with or without a cyclic moiety) BMI-1, and 4,4'-diamino-diphenyldecane are hereinafter prepared according to the following procedure. BMI-1 (100.Og, 0.1087 mol), 4,4,-diamino-diphenylnonane (10.77 g, 0.05435 mol) and toluene (100 mL) were charged with a thermometer, a mechanical mixer, And a 500 mL four-neck round bottom reaction flask with a condenser. The reaction flask was purged with nitrogen and mixed at ίο 400 rpms in an oil bath preheated to 90 °C. When the reaction temperature reached 65 ° C, all solids dissolved to form a clear golden solution. Then add five drops of acetic acid. At a temperature of 80 ° C, the reaction time was started, and heating and mixing were continued for 48 hours. During this time, the reaction changed from a clear golden solution to a deep reddish orange solution. After cooling to room temperature, the reaction solution was decanted from the secondary gel on the side of the flask, and the solution was extracted from the solution on a rotary evaporator. The result was 121 g of viscous deep aerated liquid. This product was vigorously mixed in ethanol (300 mL) for 30 minutes and then allowed to stand for 6 minutes. The opaque yellow residual layer was separated from the __ colour base and discarded 1 additional three times of this mixing/clarification/decanting cycle. The ethanol wash was removed according to τιχ (▼ benzene / thf W volume) to remove residual diamine. The solvent was extracted from the product on a Wei rotary evaporator and 60 °C KUgelr〇hr. A 6 〇g dark reddish brown oily product was obtained. The structure was confirmed by 1H NMR. Example 2 Synthesis
ΒΜΙ-2)製備。 將麗-2 (5〇.〇g,0.0991m〇1)、4,4,二胺基二苯基甲 15烧(9.81g ’ 〇·〇495ΠΚ>1)及甲苯(5_0裝填於裝備有溫度 16 200948858 計、機械混合器、及& * 令為是器之_ 9 S Π r 反應燒瓶以氮淨化, 〇〇m:L四頸圓底反應燒瓶。 混合。當反應溫度軸至听之油浴中 以 200ipms 液。然後添加五滴醋酸。在况产固體溶解形成濃金色溶 續加熱及混合46小時。此:;^ 時間開始,持 變為稀薄非常深紅色溶液。然後將反色溶液改 的黑色凝膠傾析。藉由,C旋轉篆發J瓦:上形成ΒΜΙ-2) Preparation. Li-2 (5〇.〇g, 0.0991m〇1), 4,4, diaminodiphenylmethyl 15 (9.81g '〇·〇495ΠΚ>1) and toluene (5_0 are loaded with temperature 16 200948858 Meter, mechanical mixer, and & * Order as a device _ 9 S Π r Reaction flask with nitrogen purge, 〇〇m: L four-neck round bottom reaction flask. Mix. When reaction temperature axis to the oil Add 200 drops of acetic acid in the bath. Then add five drops of acetic acid. Dissolve in solid state to form concentrated gold and heat and mix for 46 hours. This:; ^ time starts, hold into a thin very dark red solution. Then change the reverse color solution Black gel decantation. By, C rotates bursts of J watts: formed on
1010
15 =1*3小時自紅色溶液萃提溶劑,果為 混合於乙醇(15一 =0 4。將不透明黃色6醇職從黏贿褐色底層傾析 :’ 。重覆另外三次此混合/靜置/傾析循環。使用40 C知:轉蒸發器及8(rCKugelrohr自產物萃提溶劑。獲得6〇g 產物。結構由1H NMR罐認。 實施例3合成15 =1*3 hours extraction solvent from the red solution, the fruit is mixed with ethanol (15-=0 4. The opaque yellow 6 alcohol is decanted from the brown bottom of the sticky bribe: '. Repeat this three times for further mixing/resting / decantation cycle. Using 40 C known: rotary evaporator and 8 (rCKugelrohr from the product extraction solvent to obtain 6 〇g product. The structure was recognized by 1H NMR tank. Example 3 synthesis
17 20094885817 200948858
之馬來.醯亞胺(下 文稱BMI-3 )及4,4’-二胺基二苯基曱烧根據下列程序製備。 將 BMI-3 (70.0g,0.1203mol)及 4,4’-二胺基二苯基甲 烷(11.9g,0.0602mol)裝填於裝備有溫度計、機械混合器、 5 及冷凝器之四頸圓底反應燒瓶。反應燒瓶以氮淨化, ® 而在預熱至ll〇°C之油浴中以300rpms混合。當反應溫度達 到83°C時’所有固體溶解形成清澈紅色溶液。然後添加五滴 醋酸。在溫度so c下’反應時間開始,持續加熱及混合η 小時。此時期間,反應從稀薄紅色溶液改變為濃厚紅撥色溶 ίο 液。冷卻至室溫後,將反應溶液溶解於二氯甲烧(6〇〇mL)。 此撥色溶液以10% (重量)鹽酸洗條兩次以移除殘餘二胺。 使用鹽水破壞由洗滌形成之乳液。使有機餾分於硫酸鎮 (50g )上乾燥並過濾。藉由4(TC旋轉蒸發器及6〇°C 〇 Kugelrohr自清澈銅色濾液萃提溶劑,得到濃厚琥珀色液體 15 產物。結構由1HNMR確認。 實施例4 合成Malay yttrium (hereinafter referred to as BMI-3) and 4,4'-diaminodiphenyl oxime were prepared according to the following procedure. BMI-3 (70.0 g, 0.1203 mol) and 4,4'-diaminodiphenylmethane (11.9 g, 0.0602 mol) were charged in a four-necked round bottom equipped with a thermometer, mechanical mixer, 5 and condenser. Reaction flask. The reaction flask was purged with nitrogen, and mixed at 300 rpms in an oil bath preheated to ll 〇 °C. When the reaction temperature reached 83 ° C, all solids dissolved to form a clear red solution. Then add five drops of acetic acid. Start at the temperature so c 'reaction time, continue heating and mixing for η hours. During this time, the reaction changed from a thin red solution to a thick red-dish solution. After cooling to room temperature, the reaction solution was dissolved in dichloromethane (6 mL). This dialle solution was washed twice with 10% by weight hydrochloric acid to remove residual diamine. The emulsion formed by the washing was destroyed using saline. The organic fraction was dried over sulphuric acid (50 g) and filtered. The solvent was extracted from the clear copper filtrate by 4 (TC rotary evaporator and 6 〇 ° C 〇 Kugelrohr to give a thick amber liquid 15 product. The structure was confirmed by 1H NMR.
自芳香族鍵聯之馬來醯亞胺經胺—2,2-雙[4-(4-胺基苯氧基) 苯基丙烷]延伸。 20 將雙馬來醯亞胺(來自Huntsman Advanced Materials 18 200948858The maleimine from the aromatic linkage is extended by the amine-2,2-bis[4-(4-aminophenoxy)phenylpropane]. 20 will be Bismaleimide (from Huntsman Advanced Materials 18 200948858
10 1510 15
Americas Inc·獲得之 Matrimid 5292A,CAS# 13676-54-5,下 文稱8]\115292人)(26.02,0.0726111〇1)、2,2-雙[4-(4-胺基 苯氧基)苯基丙烷](14.0g,0.0341mol)、及2-曱氧基乙醇 (2〇g)裝填於裝備有溫度計、機械混合器、及冷凝器之 100mL三頸圓底反應燒瓶。燒瓶固定於預熱至i3〇〇c之油浴 中’内容物以300rpms混合。逐漸地’反應於i〇5°C從黃色 糊狀物改變為深褐色溶液。持續加熱2.5小時,而保持反應 溫度介於100與ll〇°C間。使濃厚深紅色反應產物於燒瓶中 冷卻至室溫。將燒瓶於乾冰中急冷,造成產物凍結及碎裂。 此允許自燒瓶易於收集冷產物作為堅硬玻璃材料。產物置放 於1L單頸燒瓶中,在70°CKugelr〇hr上萃提溶劑3小時。將 產物收集,粉碎為精細金色粉末,且在至8〇°c真空下乾 燥總共16小時。因而自此反應收集超過35g精細金色粉末。 軟化點為135至140。(:。結構由iHNMR確認》 實施例5 合成Matrimid 5292A, CAS# 13676-54-5, hereinafter referred to as 8]\115292 people) (26.02, 0.0726111〇1), 2,2-bis[4-(4-aminophenoxy)benzene Propane] (14.0 g, 0.0341 mol) and 2-decyloxyethanol (2 〇g) were charged in a 100 mL 3-neck round bottom reaction flask equipped with a thermometer, a mechanical mixer, and a condenser. The flask was fixed in an oil bath preheated to i3〇〇c. The contents were mixed at 300 rpms. The reaction was gradually changed from a yellow paste to a dark brown solution at i 〇 5 °C. Heating was continued for 2.5 hours while maintaining the reaction temperature between 100 and ll 〇 °C. The thick dark red reaction product was allowed to cool to room temperature in a flask. The flask was quenched in dry ice causing the product to freeze and fragment. This allows the cold product to be easily collected from the flask as a hard glass material. The product was placed in a 1 L single-necked flask, and the solvent was extracted on a 70° Clugelr hr for 3 hours. The product was collected, pulverized into a fine gold powder, and dried under vacuum to 8 ° C for a total of 16 hours. Thus more than 35 g of fine gold powder was collected from this reaction. The softening point is 135 to 140. (: Structure confirmed by iHNMR) Example 5 Synthesis
自芳香族鍵聯之馬來醯亞胺經胺—2,2-雙[4-(4-胺基苯氧基) 苯基丙烷]延伸 將雙馬來醯亞胺(來自 National Starch and Chemical Co. 獲得之 SR525, CAS#3006-93-7,下文稱 BMI525)(26.0g, 0.0969mol)、2,2-雙[4-(4-胺基苯氧基)苯基丙烷](i4.〇g, 0.0341mol)、及2-曱氧基乙醇(20g)裝填於裝備有溫度計、 19 20 200948858 機械混合器、及冷凝器之100mL三頸圓底反應燒瓶。燒瓶 固疋於預熱至125 C之油浴中’内容物以300rpms混合。逐 漸地,反應於l〇5°C從黃色漿體改變為加深的橙色漿體。持 續加熱6.0小時,而保持反應溫度介於105與丨^它間。使 5 反應產物—濃厚深橙紅色糖漿一於燒瓶中冷卻至室溫。產物 溶液轉移至250mL單頸燒瓶中’在6(TCKiigelrohr上萃提溶 劑1小時。在短暫將泡沫化插曲後,將產物收集為深橙色固 體’粉碎且在60至80°C真空下乾燥總共16小時。自此反應 獲得超過35g精細金色粉末。觀測軟化點為115至125。(:。 ίο 結構由hNMR確認。 實施例6 合成Extension of a maleic amine from an aromatic linkage to an amine- 2,2-bis[4-(4-aminophenoxy)phenylpropane] (from National Starch and Chemical Co) Obtained SR525, CAS#3006-93-7, hereinafter referred to as BMI525) (26.0g, 0.0969mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (i4.〇 g, 0.0341 mol), and 2-methoxyethanol (20 g) were charged in a 100 mL three-neck round bottom reaction flask equipped with a thermometer, 19 20 200948858 mechanical mixer, and a condenser. The flask was solidified in an oil bath preheated to 125 C. The contents were mixed at 300 rpms. Gradually, the reaction was changed from a yellow slurry to a deepened orange slurry at 10 °C. Heating was continued for 6.0 hours while maintaining the reaction temperature between 105 and 丨^. The 5 reaction product, a thick dark orange-red syrup, was cooled to room temperature in a flask. The product solution was transferred to a 250 mL one-necked flask. The solvent was extracted at 6 (TCKiigelrohr for 1 hour. After a brief burst of foaming, the product was collected as a dark orange solid' pulverized and dried under vacuum at 60 to 80 ° C for a total of 16 Hour. More than 35 g of fine gold powder was obtained from this reaction. The observed softening point was 115 to 125. (: ίο The structure was confirmed by hNMR. Example 6 Synthesis
自芳香族鍵聯之馬來醯亞胺經胺一2,2-雙[4-(4-胺基苯氧基) 苯基丙烧]延伸。 15 將雙馬來醯亞胺(來自Daiwakasei Industry Co. Ltd·獲 得之 5100,CAS# 105391-33-1,下文稱 BMI 5100) (26.0g, 0.0588111〇1)、2,2-雙[4-(4-胺基苯氧基)苯基丙烷](14.(^, 0·0341πιο1)、及2-曱氧基乙醇(20g)裝填於裝備有溫度計、 機械混合器、及冷凝器之lOOmL三頸圓底反應燒瓶。燒瓶 2〇 固定於預熱至125°C之油浴中,内容物以200rpms混合。逐 漸地,反應於l〇5°C從褐黃色漿體改變為清澈深紅色溶液。 持續加熱75.0小時,而保持反應溫度介於105與120°C間。 20 200948858 當胺耗盡時,反應產物為濃厚深紅色液體。為了協助回收, 將反應燒瓶於乾冰中急冷。以此方式,使黏稠液體凍結、碎 裂且易於自反應燒瓶獲得固體塊。固體然後轉移至置放於 Kugelrohr上之lOOOmL單頸燒瓶中。固體熔化回液體,在 80°C下萃提殘餘溶劑。萃提後,將產物收集為褐色粉末,且 在60至80°C真空下乾燥。自此反應獲得超過35g具軟化點 為180至185°C之產物。結構由1HNMR確認。 實施例7 合成The maleimine from the aromatic linkage is extended by the amine-2,2-bis[4-(4-aminophenoxy)phenylpropanone]. 15 Bismaleimide (from 5100, CAS# 105391-33-1 from Daiwakasei Industry Co. Ltd., hereinafter referred to as BMI 5100) (26.0g, 0.0588111〇1), 2,2-double [4- (4-Aminophenoxy)phenylpropane] (14. (^, 0·0341πιο1), and 2-decyloxyethanol (20 g) were charged in 100 mL of a thermometer equipped with a thermometer, a mechanical mixer, and a condenser. The flask was shaken in a flask. The flask was fixed in an oil bath preheated to 125 ° C, and the contents were mixed at 200 rpm. Gradually, the reaction was changed from a brownish yellow slurry to a clear dark red solution at 10 °C. Heating was continued for 75.0 hours while maintaining the reaction temperature between 105 and 120 ° C. 20 200948858 When the amine was consumed, the reaction product was a thick dark red liquid. To aid recovery, the reaction flask was quenched in dry ice. The viscous liquid was frozen, chipped and readily obtained from the reaction flask. The solid was then transferred to a 1000 mL single-necked flask placed on Kugelrohr. The solid was melted back to the liquid and the residual solvent was extracted at 80 ° C. The product was collected as a brown powder and dried under vacuum at 60 to 80 ° C. The reaction is obtained having a softening point of more than 35g of 180 to 185 ° C of the product. Structure confirmed by 1H-NMR is. Example 7 Synthesis of
自芳香族鍵聯之馬來醯亞胺經胺一4,4,-二胺基二苯基曱烷 延伸。 將 BMI5292A(30.00g,〇.〇838mol)、4,4,-二胺基二苯 基曱烷(8.3g,0.0419mol)、及2-甲氧基乙醇(19g)裝填 於裝備有溫度計、機械混合器、及冷凝器之l〇〇mL三頸圓 底反應燒瓶。反應燒瓶之内容物在預熱至125°C之油浴中以 300rPms混合。當反應溫度達到丨的^時,混合物形成稀薄 深紅色溶液。在該溫度下,反應時間開始,持續加熱及混合。 使用薄層層析法(曱苯/四氳呋喃,1/1體積)以監控反應。 7小時後,所有胺耗盡,反應從黃色糊狀物改變為黏稠深紅 色液體。反應藉由冷卻凝固且為黏土樣的固體轉移至丨頸 500mL反應燒瓶中。使用旋轉蒸發器2小時及接著Kugelr〇hr 1.5小時(兩者皆於6〇°C )自燒瓶萃提殘餘溶劑。然後粉碎 21 200948858 所得金褐色固體’使用加熱至8(TC之真空烘箱移除殘餘溶 劑。獲得幾近35g具軟化點為180至19(TC之淡褐色粉末。 結構由bNMR確認。 實施例8 合成The maleimide from the aromatic linkage is extended by the amine-4,4,-diaminodiphenylnonane. BMI5292A (30.00 g, 〇. 〇 838 mol), 4,4,-diaminodiphenyl decane (8.3 g, 0.0419 mol), and 2-methoxyethanol (19 g) were charged with a thermometer and a machine. A 10 mL round neck reaction flask with a mixer and a condenser. The contents of the reaction flask were mixed at 300 rPms in an oil bath preheated to 125 °C. When the reaction temperature reached 丨, the mixture formed a dilute deep red solution. At this temperature, the reaction time begins, heating and mixing are continued. Thin layer chromatography (nonyl/tetrafurfuran, 1/1 volume) was used to monitor the reaction. After 7 hours, all amines were consumed and the reaction changed from a yellow paste to a viscous dark red liquid. The reaction was transferred to a 500 mL reaction flask by cooling solidified and clay-like solids. The residual solvent was extracted from the flask using a rotary evaporator for 2 hours followed by Kugelr hr 1.5 hours (both at 6 ° C). Then, the gold brown solid obtained by pulverizing 21 200948858 'removed the residual solvent using a vacuum oven of 8 (TC) to obtain almost 35 g of a pale brown powder having a softening point of 180 to 19 (TC. The structure was confirmed by b NMR. Example 8 Synthesis
於50%固體溶液中’自芳香族鍵聯之馬來醯亞胺經胺—4,4,_ ® 二胺基二苯基曱烷延伸。 將81^1 5292八(30.00§’〇.〇838111〇1)、4,4’-二胺基二苯 基曱烷(8.3g,0.0419mol)、及碳酸丙烯酯(38 3g)裝填 10 於裝備有溫度計、機械混合器、及冷凝器之500mL四頸圓 底反應燒瓶。反應燒瓶之内容物在預熱至125°C之油浴中以 200rpms混合。當反應溫度達到^的它時,混合物形成稀薄 深紅橙色溶液。在該溫度下,反應時間開始,持續加熱及混 合。使用薄層層析法(曱苯/四氫呋喃,1/1體積)以監控 ||15 反應。9小時後’所有胺耗盡,反應從最初黃色漿體改變為 黏稠深紅色液體。當熱時,黏稠產物轉移至HDPE瓶中。獲 得幾近65g產物於碳酸丙烯酯中之5〇%溶液。BMI/胺加成 物之溶液被期待提供更大效率於製備、加工及配製。結構由 iNMR確認。 20 實施例9 合成 22 200948858The maleimide from the aromatic linkage is extended from the amine-4,4,-diaminodiphenylnonane in a 50% solids solution. 81^1 5292 八(30.00§'〇.〇838111〇1), 4,4'-diaminodiphenyl decane (8.3g, 0.0419mol), and propylene carbonate (38 3g) were packed in 10 A 500 mL four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The contents of the reaction flask were mixed at 200 rpms in an oil bath preheated to 125 °C. When the reaction temperature reached it, the mixture formed a thin, deep reddish orange solution. At this temperature, the reaction time begins and heating and mixing are continued. Thin layer chromatography (nonylbenzene/tetrahydrofuran, 1/1 volume) was used to monitor the ||15 reaction. After 9 hours, all amines were depleted and the reaction changed from the initial yellow slurry to a viscous dark red liquid. When hot, the viscous product is transferred to the HDPE bottle. Nearly 65 g of the product was obtained as a 5 % solution in propylene carbonate. Solutions of BMI/amine adducts are expected to provide greater efficiency in preparation, processing and formulation. The structure was confirmed by iNMR. 20 Example 9 Synthesis 22 200948858
ΟΟ
自兩種不同芳香族鍵聯之馬來醯亞胺(ΒΜΙ 5292Α、ΒΜΙ 5100)經胺-2,2-雙[4-(4-胺基苯氧基)苯基丙烷]延伸 將 BMI 5292A( 15.〇g,〇.〇4i9mol)、BMI 5100( 18.5g, M419mol)、2,2-雙[4-(4-胺基苯氧基)苯基丙烷](17 2g, 0.0419mol)、及2-曱氧基乙醇(26g)裝填於裝備有溫度計、 機械混合器、及冷凝器之250mL·三頸圓底反應燒瓶。燒瓶 固定於預熱至125C之油浴中,内容物以3〇〇rpms混合。逐 漸地,反應於105 C從黃色混合物改變為淡橙色漿體。持續 加熱約9小時,而保持反應溫度介於1〇5與115。〇間。使反 應產物-濃厚深紅色㈣—轉移至25GmL單賴瓶中。使 用2-甲氧基乙賴洗。纟贼使雜轉紐器自反應萃提 溶劑。將產物收集為深橙色粉末,且在6〇至8〇。〔真空下乾 燥總共16小時。自此反應獲得超過4〇g具軟化點為15〇至 160°C之粉末。結構由iHNMR確認。 實施例10 合成 23 15 200948858BMI 5292A is extended from two different aromatic linkages of maleimine (ΒΜΙ 5292Α, ΒΜΙ 5100) via amine-2,2-bis[4-(4-aminophenoxy)phenylpropane] 15. 〇g, 〇.〇4i9mol), BMI 5100 ( 18.5g, M419mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (17 2g, 0.0419mol), and 2-methoxyethanol (26 g) was charged in a 250 mL three-necked round bottom reaction flask equipped with a thermometer, a mechanical mixer, and a condenser. The flask was fixed in an oil bath preheated to 125 C and the contents were mixed at 3 rpm. Gradually, the reaction was changed from a yellow mixture to a pale orange slurry at 105 C. Heating was continued for about 9 hours while maintaining the reaction temperature between 1 and 5 and 115. In the daytime. The reaction product - thick dark red (four) - was transferred to a 25 GmL single-bottle. It was washed with 2-methoxyacetone. The thief will make the solvent from the reaction. The product was collected as a dark orange powder and was between 6 Torr and 8 Torr. [Drying under vacuum for a total of 16 hours. From this reaction, more than 4 g of a powder having a softening point of 15 to 160 ° C was obtained. The structure was confirmed by iH NMR. Example 10 Synthesis 23 15 200948858
❹ 於50%固體溶液中,自兩種芳香族鍵聯之馬來醯亞胺(BMI 5292A及BMI 5100)經胺一2,2-雙[4-(4-胺基苯氧基)苯基丙 烧]延伸。 5 將 BMI 5292A( 15.0g,〇.〇419mol)、BMI5100( 18.5g, 0.0419mol)、2,2-雙[4-(4-胺基苯氧基)苯基丙烷](17.2g, 0.0419mol)、及碳酸丙烯酯(5〇.7g)裝填於裝備有溫度計、 機械混合器、及冷凝器之500mL四頸圓底反應燒瓶。反應 燒瓶之内容物在預熱至125°C之油浴中以200rpms混合。當 ❹ίο 反應溫度達到105°C時,混合物形成稀薄深紅橙色溶液。在 該溫度下’反應時間開始,持續加熱及混合。使用薄層層析 法(甲苯/四氫呋喃,1/1體積)以監控反應。31.5小時後, 所有胺耗盡。反應從金黃色漿體改變為黏稠深紅色糖漿。當 熱時’黏稠產物轉移至HDPE塑膠瓶中。結構由1HNMR確 15 認。獲得幾近95g產物之50%溶液。BMI/胺加成物之溶液 被期待提供更大效率於製備、加工及配製。 實施例11 合成 200948858马 In a 50% solids solution, two aromatic linked maleimides (BMI 5292A and BMI 5100) are amine- 2,2-bis[4-(4-aminophenoxy)phenyl Propylene] extended. 5 BMI 5292A (15.0 g, 〇. 〇 419 mol), BMI 5100 ( 18.5 g, 0.0419 mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (17.2 g, 0.0419 mol) And propylene carbonate (5 〇.7g) were packed in a 500 mL four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The contents of the reaction flask were mixed at 200 rpm in an oil bath preheated to 125 °C. When the reaction temperature reached 105 ° C, the mixture formed a thin dark red orange solution. At this temperature, the reaction time begins and heating and mixing are continued. Thin layer chromatography (toluene/tetrahydrofuran, 1/1 volume) was used to monitor the reaction. After 31.5 hours, all amines were consumed. The reaction changed from a golden yellow syrup to a viscous dark red syrup. When hot, the viscous product is transferred to a HDPE plastic bottle. The structure was confirmed by 1H NMR. A nearly 50 g solution of nearly 95 g of product was obtained. Solutions of BMI/amine adducts are expected to provide greater efficiency in preparation, processing and formulation. Example 11 Synthesis 200948858
自兩種不同芳香族鍵聯之馬來醯亞胺(BMI 5292A、BMI © 5100)經胺_4,4’-二胺基二苯基甲烷延伸。 將 BMI5292A(15.0g’ 0.0419mol)、BMI5100(18,5g, 5 0.0419m〇l)、4,4,-二胺基二苯基曱烷(8.3g,0.0419mol)、 及2-曱氧基乙酵(50g)裝填於裝備有溫度計、機械混合器、 及冷凝器之500mL四頸圓底反應燒瓶。燒瓶固定於預熱至 125 C之油浴中,内容物以200rpms混合。逐漸地,反應於 105 C從黃橙色混合物改變為稀薄清澈紅橙色溶液。持續加 10 熱7.5小時’而保持反應溫度介於105與115°C間。使反應 ❹ 產物—濃厚深紅色液體一轉移至500mL單頸燒瓶中。使用 2_曱氡基乙醇潤洗。在60至70。〇使用旋轉蒸發器自反應萃 提溶劑。將產物收集為深琥珀色粉末,且在75它真空下乾 燥。自此反應獲得超過35g具軟化點為130至14〇。(:之粉末。 15 結構由hNMR確認。 實施例12 合成 25 200948858Maleimide (BMI 5292A, BMI © 5100) from two different aromatic linkages was extended via amine-4,4'-diaminodiphenylmethane. BMI5292A (15.0g' 0.0419mol), BMI5100 (18,5g, 5 0.0419m〇l), 4,4,-diaminodiphenylnonane (8.3 g, 0.0419 mol), and 2-decyloxy Ethanol (50 g) was loaded in a 500 mL four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The flask was fixed in an oil bath preheated to 125 C, and the contents were mixed at 200 rpms. Gradually, the reaction was changed from a yellow-orange mixture to a thin, clear red-orange solution at 105 C. Continue to add 10 heat for 7.5 hours' while maintaining the reaction temperature between 105 and 115 °C. The reaction ❹ product, a thick dark red liquid, was transferred to a 500 mL one-necked flask. Rinse with 2_mercaptoethanol. At 60 to 70.自 Extract the solvent from the reaction using a rotary evaporator. The product was collected as a dark amber powder and dried under vacuum at 75. From this reaction, more than 35 g was obtained with a softening point of 130 to 14 Å. (: Powder. 15 Structure confirmed by hNMR. Example 12 Synthesis 25 200948858
❹ 於50%固體溶液t,自兩種芳香族鍵聯之馬來驢亞胺(BMI 5292A及BMI5100)經胺一4,4,-二胺基二苯基曱烷延伸。 將 BMI 5292A ( 15.0g,〇.〇419mol)、BMI 5100 ( 18.5g, 5 〇.〇419mol)、4,4’-二胺基二苯基曱烷(8.3g,0.0419mol)、 及碳酸丙烯酯(41.8g)裝填於裝備有溫度計、機械混合器、 及冷凝器之500mL四頸圓底反應燒瓶。反應燒瓶之内容物 在預熱至125°C之油浴中以200rpms混合。當反應溫度達到 105°C時,混合物形成稀薄紅橙色溶液。在該溫度下,反應 ❹1〇 時間開始,持續加熱及混合。使用薄層層析法(曱苯/四氫 呋喃’ 1/1體積)以監控反應。12小時後,所有胺耗盡, 反應從金黃色漿體改變為黏稠深紅色糖漿。當熱時,黏稠產 物轉移至高密度聚乙烯瓶中。結構由1H NMR確認。因而獲 得幾近80g於碳酸丙烯酯中之50%溶液。ΒΜΙ/胺加成物之 15 溶液被期待提供更大效率於製備、加工及配製。 實施例13 合成 26 200948858马 50% solid solution t, from two aromatic linked maleimide (BMI 5292A and BMI5100) extended by amine-4,4,-diaminodiphenyl decane. BMI 5292A (15.0 g, 〇. 〇 419 mol), BMI 5100 ( 18.5 g, 5 〇. 〇 419 mol), 4,4'-diaminodiphenyl decane (8.3 g, 0.0419 mol), and propylene carbonate The ester (41.8 g) was packed in a 500 mL four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The contents of the reaction flask were mixed at 200 rpms in an oil bath preheated to 125 °C. When the reaction temperature reached 105 ° C, the mixture formed a thin reddish orange solution. At this temperature, the reaction is started for a period of time, and heating and mixing are continued. Thin layer chromatography (nonylbenzene/tetrahydrofuran '1/1 volume) was used to monitor the reaction. After 12 hours, all amines were consumed and the reaction changed from a golden yellow slurry to a viscous dark red syrup. When hot, the viscous product is transferred to a high density polyethylene bottle. The structure was confirmed by 1H NMR. Thus, nearly 80 g of a 50% solution in propylene carbonate was obtained. The hydrazine/amine adduct 15 solution is expected to provide greater efficiency in the preparation, processing and formulation. Example 13 Synthesis 26 200948858
自芳香族鍵聯之馬來醯亞胺(BMI 5292A)經兩種不同胺一 2,2-雙[4-(4-胺基苯氧基)苯基丙烷]及4,4,_二胺基二苯基曱烷 延伸。 5 將 BMI5292A (40.0g,〇.lll7mol)、2,2-雙[4-(4-胺基 苯氧基)苯基丙烷](11.5g,〇.〇279mol)、4,4,-二胺基二苯基 曱烧(5.5g ’ 〇.〇279mol)、及2-曱氧基乙醇(30g)裝填於 裝備有溫度計、機械混合器、及冷凝器之250mL三頸圓底 反應燒瓶。燒瓶固定於預熱至125°C之油浴中,内容物以 10 200rPms混合。逐漸地,反應於1〇5。(:從淡黃色漿體改變為 深紅色溶液。在保持介於105與115。(:間之反應溫度下持續 加熱及混合2小時。使反應產物—深紅橙色液體一轉移至 ❹ 500mL單頸燒瓶中。使用2_曱氧基乙醇潤洗。在6〇〇c使用 旋轉蒸發器萃提溶劑4小時。將產物收集,粉碎為金橙色粉 15 末’且進—步在75。(:真空下乾燥。自此反應獲得超過40g 粉末。結構由1H NMR確認。 實施例14 合成 27 200948858Maleimide-bonded maleimide (BMI 5292A) via two different amines, 2,2-bis[4-(4-aminophenoxy)phenylpropane] and 4,4,-diamine Diphenyl decane is extended. 5 BMI5292A (40.0g, 〇.lll7mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (11.5g, 〇.〇 279mol), 4,4,-diamine Diphenylpyrene (5.5 g '〇.〇 279 mol) and 2-methoxyethanol (30 g) were charged in a 250 mL three-neck round bottom reaction flask equipped with a thermometer, a mechanical mixer, and a condenser. The flask was fixed in an oil bath preheated to 125 ° C and the contents were mixed at 10 200 rPms. Gradually, the reaction is at 1〇5. (: Change from pale yellow paste to dark red solution. Continue to heat and mix for 2 hours while maintaining the reaction temperature between 105 and 115. Transfer the reaction product - dark red orange liquid to ❹ 500 mL single-necked flask The solution was rinsed with 2_methoxyethanol. The solvent was extracted using a rotary evaporator for 4 hours at 6 ° C. The product was collected and pulverized to a golden orange powder 15 and then stepped at 75. (: vacuum Drying. More than 40 g of powder were obtained from this reaction. The structure was confirmed by 1H NMR. Example 14 Synthesis 27 200948858
自芳香族鍵聯之馬來醯亞胺經兩種不同胺—2,2-雙[4-(4-胺 基苯氧基)苯基丙烧]及4,4,-二胺基二苯基曱烧延伸 ❹ 將 BMI 5100 (49.4g,〇.iii7mol)、2,2-雙[4-(4-胺基苯 5 氧基)苯基丙烷](U.5g ’ 0.0279mol)、4,4,-二胺基二苯基曱 娱·(5.5g,〇.〇279mol)、及2_甲氧基乙醇(3〇g)裝填於裝 備有溫度計、機械混合器、及冷凝器之25〇mL三頸圓底反 應燒瓶。燒瓶固定於預熱至125。〇之油浴中,内容物以 200rpms混合。隨著加熱,反應於i〇5t>c從淡黃色漿體改變 1〇 為清澈撥紅色溶液。在保持介於105與115°C間之反應溫度 下持續加熱及混合28小時。使反應產物—深紅色黏稠液體 。轉移至5GGmL單頸燒瓶中。使用2-曱氧基乙醇潤洗。在 6GC使用旋轉蒸發$萃提溶劑4小時。將產物收集,粉碎為 金撥色粉末,且進―步在75至贼真空下乾燥。自此反應 15獲付超過4〇g具軟化點為145至155。(:之粉末。結構由1Η NMR確認。 實施例15 合成Maleic amines from aromatic linkages via two different amines - 2,2-bis[4-(4-aminophenoxy)phenylpropane] and 4,4,-diaminodiphenyl Base 曱 ❹ ❹ ❹ BMI 5100 (49.4g, 〇.iii7mol), 2,2-bis[4-(4-aminophenylbenzeneoxy)phenylpropane] (U.5g '0.0279mol), 4, 4,-Diaminodiphenyl oxime (5.5g, 〇.〇 279mol), and 2-methoxyethanol (3〇g) are packed in a thermometer equipped with a thermometer, mechanical mixer, and condenser. mL three-neck round bottom reaction flask. The flask was fixed to preheat to 125. In the oil bath of 〇, the contents were mixed at 200 rpms. With heating, the reaction was changed from light yellow slurry to i〇5t>c to a clear red solution. Heating and mixing were continued for 28 hours while maintaining a reaction temperature between 105 and 115 °C. The reaction product - dark red viscous liquid. Transfer to a 5 GG mL single neck flask. Rinse with 2-methoxyethanol. The solvent was extracted by rotary evaporation at 6GC for 4 hours. The product was collected, pulverized into a gold-colored powder, and further dried at 75 to a thief vacuum. Since then, reaction 15 has been paid in excess of 4 〇g with a softening point of 145 to 155. (: powder) The structure was confirmed by 1 NMR. Example 15 Synthesis
28 200948858 於50%固體溶液甲,自芳香族鍵聯之馬來醯亞胺經胺一 2,2-雙[4-(4-胺基苯氧基)苯基丙烷]延伸。 5 ❹ 10 將 BMI 5292A (360.0g,l.〇〇56mol)、2,2-雙[4-(4-胺 基苯氧基)笨基丙烷](206.4g,〇.5028mol)、及碳酸丙烯酯 (566.4g)裝填於裝備有溫度計、機械混合器、及冷凝器之 2L四頸圓底反應燒瓶。反應燒瓶之内容物在預熱至i25°C之 油浴中以200rpms混合。當反應溫度達到i〇5°C時,混合物 形成稀薄深紅橙色溶液。在該溫度下,反應時間開始,持續 加熱及混合。(註:内容物溫度逐漸地增加至約122t)。 藉由來自每小時抽取的樣品測量溶液於5〇°c黏度以監控反 應。21.5小時後’溶液於50°C黏度測量為4580mPa.s(cPs), 反應終止。當熱時,易於排放深紅色黏稠產物。獲得幾近900g 產物之50%溶液,且使樣品特徵化。結構由ijjNMR確認。 由GPC決定Mw為20,646及MWD為7.3。 實施例16 合成28 200948858 In a 50% solid solution, a maleimine from an aromatic linkage is extended with an amine 2,2-bis[4-(4-aminophenoxy)phenylpropane]. 5 ❹ 10 BMI 5292A (360.0g, l. 〇〇 56mol), 2,2-bis[4-(4-aminophenoxy)phenylpropane] (206.4g, 〇.5028mol), and propylene carbonate The ester (566.4 g) was loaded into a 2 L four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser. The contents of the reaction flask were mixed at 200 rpms in an oil bath preheated to i25 °C. When the reaction temperature reached i 〇 5 ° C, the mixture formed a thin dark red orange solution. At this temperature, the reaction time begins and heating and mixing are continued. (Note: The temperature of the contents gradually increased to about 122t). The reaction was monitored by measuring the viscosity of the solution at 5 ° C from samples taken every hour. After 21.5 hours, the viscosity of the solution at 50 ° C was measured to be 4580 mPa·s (cPs), and the reaction was terminated. When hot, it is easy to discharge dark red sticky products. A nearly 50 g solution of nearly 90 g of product was obtained and the sample was characterized. The structure was confirmed by ijj NMR. The Mw is determined by GPC to be 20,646 and the MWD is 7.3. Example 16 Synthesis
15 ❹ 於50%固體溶液中,自芳香族鍵聯之馬來醯亞胺(bmi 5292A)經胺一2,2-雙[4-(4-胺基苯氧基)苯基丙烷]延伸 將 BMI 5292A (360.0g,1.0056mol)、2,2-雙[4-(4-胺 基苯氧基)苯基丙烧](206.4g,0.5〇28mol)、及碳酸丙婦醋 (566.4g)裝填於裝備有溫度計、機械混合器、及冷凝器之 2L四頸圓底反應燒瓶。反應燒瓶之内容物在預熱至之 油浴中以200rpms混合。當反應溫度達到l〇5°C時,混合物 29 20 200948858 5 Ο 形成稀薄深紅橙色溶液。在該溫度下,反應時間開始,持續 加熱及混合。(註:内容物溫度逐漸地增加,且在多數反應 期間’溫度範圍介於130與132°C間)。藉由來自每小時抽 取的樣品測量溶液於50°C黏度以監控反應。幾近7小時後, 溶液於50°C黏度測量為4915mPa . s (cPs),反應終止。當 熱時’易於排放深紅色黏稠產物。獲得幾近9〇〇g產物之5〇 %溶液’且使樣品特徵化。結構由NMR確認。由GPC 決定產物之Mw為28,161及MWD為10.19。 實施例17 合成15 ❹ In a 50% solids solution, the aromatic-linked maleimide (bmi 5292A) is extended by the amine-2,2-bis[4-(4-aminophenoxy)phenylpropane] BMI 5292A (360.0 g, 1.056 mol), 2,2-bis[4-(4-aminophenoxy)phenylpropanone] (206.4 g, 0.5 〇 28 mol), and propylene carbonate (566.4 g) A 2 L four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser was charged. The contents of the reaction flask were mixed in an oil bath preheated to 200 rpms. When the reaction temperature reached l 〇 5 ° C, the mixture 29 20 200948858 5 形成 formed a thin dark red orange solution. At this temperature, the reaction time begins and heating and mixing are continued. (Note: The temperature of the contents gradually increases, and during most reactions, the temperature range is between 130 and 132 ° C). The reaction was monitored by measuring the viscosity of the solution at 50 ° C from samples taken every hour. After almost 7 hours, the viscosity of the solution at 50 ° C was measured to be 4915 mPa·s (cPs) and the reaction was terminated. When hot, it is easy to discharge dark red sticky products. Approximately 5 〇〇g of product was obtained as a solution of 5 〇 % solution and the sample was characterized. The structure was confirmed by NMR. The Mw of the product determined by GPC was 28,161 and the MWD was 10.19. Example 17 Synthesis
10 於50%固體溶液中,自芳香族鍵聯之馬來醯亞胺經胺一2,2_ 雙[4-(4-胺基苯氧基)苯基丙烷]延伸 ’ 將 BMI 5292A (360.0g ’ l.〇〇56mol)、2,2-雙[4-(4-胺 15 ❹ 基本氧基)本基丙烧](206.4g ’ 〇.5028mol)、及碳酸丙稀g旨 (566.4g)裝填於裝備有溫度計、機械混合器、及冷凝器之 2L四頸圓底反應燒瓶。反應燒瓶之内容物在預熱至之 油浴中以200i*Pms混合。當反應溫度達到丨仍它時,混合物 形成稀薄深紅橙色溶液。在該溫度下,反應時間開始,持續 加熱及混合。(註:内容物溫度逐漸地增加,且在多數反廯 期間,溫度範圍介於123與125。(:間)。藉由來自每小時二 取的樣品測量溶液於5(TC黏度以監控反應。1〇小時15分鐘 後,溶液於50°C黏度測量為4536mPa. s(cPs),反應終1。 30 20 200948858 當熱時’易於排放深紅色黏稠產物。因而獲得幾近900g實 施例24之50%溶液,且使樣品特徵化。結構由NMR確 認。由GPC決定實施例24之Mw為19,975及MWD為7.44。 實用性10 in a 50% solids solution, from the aromatic linkage of maleimine by amine-2,2-bis[4-(4-aminophenoxy)phenylpropane] extension BMI 5292A (360.0g ' l. 〇〇 56 mol), 2,2-bis[4-(4-amine 15 ❹ basic oxy) ketone propyl] (206.4 g ' 〇.5028 mol), and propylene carbonate (566.4 g) A 2 L four-neck round bottom reaction flask equipped with a thermometer, mechanical mixer, and condenser was charged. The contents of the reaction flask were mixed in an oil bath preheated to 200i*Pms. When the reaction temperature reached 丨 still, the mixture formed a dilute deep reddish orange solution. At this temperature, the reaction time begins and heating and mixing are continued. (Note: The temperature of the contents gradually increases, and during most ruminations, the temperature range is between 123 and 125. (:). The solution is measured at 5 (TC viscosity) by monitoring the reaction from a sample taken every two hours. After 1 hour and 15 minutes, the viscosity of the solution at 50 ° C was measured to be 4536 mPa·s (cPs), and the final reaction was 1. 30 20 200948858 When it was hot, it was easy to discharge the deep red viscous product. Thus, nearly 900 g of Example 24 was obtained. % solution, and the sample was characterized. The structure was confirmed by NMR. The Mw of Example 24 was determined by GPC to be 19,975 and the MWD was 7.44.
10 在一項具體實例中,本發明為具有活性面與不活性面之 半導體矽晶片,不活性面係以包括一或多種本發明雙馬來醯 亞胺及一胺、或雙馬來醯亞胺及二胺與二硫醇之寡聚物加成 物的組成物塗布。塗布可由用來添加材料於矽晶片背侧之任 何彼等技術而實施’且包含刻板印刷、噴敷、 墨印刷等。 雖然本發明已敘述有關此等特定實施例,但應清楚在未 背離本發明精髓下,將有可能其它修改及變化。In one embodiment, the invention is a semiconductor germanium wafer having an active face and an inactive face, the inactive face to include one or more of the present inventions of bismaleimide and monoamine, or double malayan The amine and the composition of the diamine and the oligomer addition product of the dithiol are coated. Coating can be carried out by any of the techniques used to add material to the backside of the wafer, and includes stencil printing, spray coating, ink printing, and the like. Although the present invention has been described with respect to the specific embodiments, it will be apparent that other modifications and changes may be made without departing from the spirit of the invention.
3131
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US11999817B1 (en) | 2020-09-25 | 2024-06-04 | Hrl Laboratories, Llc | Bismaleimide-thiol-epoxy polymer compositions, and methods of making and using the same |
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