TW202017899A - Polymers for use in electronic devices - Google Patents

Polymers for use in electronic devices Download PDF

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TW202017899A
TW202017899A TW108125283A TW108125283A TW202017899A TW 202017899 A TW202017899 A TW 202017899A TW 108125283 A TW108125283 A TW 108125283A TW 108125283 A TW108125283 A TW 108125283A TW 202017899 A TW202017899 A TW 202017899A
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維亞切斯拉夫 Ｖ 戴夫
二世 麥可 亨利 郝瓦德
东江 武
諾拉 莎賓那 拉杜
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美商杜邦股份有限公司
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Abstract

Disclosed is a diamine having Formula I
Figure 108125283-A0101-11-0001-1
. In Formula I: Qa is CRx , SiRx , GeRx , PRx , or N; Qb is CRy , SiRy , GeRy , PRy , or N; R1 , R2 , and R3 are the same or different at each occurrence and are F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, or siloxy, where adjacent R1 groups can be joined together to form a fused aromatic ring; Rx is H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, siloxy, or R6 ; Ry is H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, siloxy, or R7 ; R6 and R7 are the same or different and are NH2 , ArNH2 , or OArNH2 ; Ar is the same or different at each occurrence and is an unsubstituted or substituted C6-18 hydrocarbon aryl; m and n are the same or different and are an integer from 0-2, such that m + n ≤ 2; x is an integer from 0-4; y and z are the same or different and are an integer from 0 to the maximum available.

Description

用於電子裝置中之聚合物Polymers used in electronic devices

本揭露涉及新穎的聚合化合物。本揭露進一步涉及用於製備此類聚合化合物之方法以及具有至少一個包含該等材料的層的電子裝置。The present disclosure relates to novel polymeric compounds. The present disclosure further relates to methods for preparing such polymeric compounds and electronic devices having at least one layer containing such materials.

用於電子應用的材料通常在其結構特性、光學特性、熱特性、電子特性和其他特性方面具有嚴格要求。隨著商業電子應用的數量不斷增加，所需特性的廣度和特異性要求對具有新的和/或改進的特性的材料的創新。聚醯亞胺代表廣泛用於各種電子應用中的一類聚合化合物。它們可以充當電子顯示裝置中的玻璃的可撓性(flexible)替代物，前提係它們具有合適的特性。該等材料可用作液晶顯示器（「LCD」）的部件，其中它們的適度電功率消耗、重量輕和層平整度係實際效用的關鍵特性。優先設置此類參數的電子顯示裝置中的其他使用包括裝置基板、濾色片的基板、覆蓋膜、觸控式螢幕面板等。Materials used in electronic applications usually have strict requirements in terms of their structural properties, optical properties, thermal properties, electronic properties, and other properties. As the number of commercial electronic applications continues to increase, the breadth and specificity of the required characteristics require innovation in materials with new and/or improved characteristics. Polyimide represents a class of polymeric compounds widely used in various electronic applications. They can serve as flexible alternatives to glass in electronic display devices, provided they have suitable characteristics. These materials can be used as components of liquid crystal displays ("LCDs"), where their moderate electrical power consumption, light weight, and layer flatness are key characteristics of practical utility. Other uses in electronic display devices that preferentially set such parameters include device substrates, color filter substrates, cover films, touch screen panels, etc.

在具有有機發光二極體（「OLED」）的有機電子裝置的構建和操作中，許多該等部件也是重要的。由於高功率轉換效率和對廣泛範圍的最終用途的適用性，OLED對於許多顯示器應用都很有前景。它們越來越多地用於手機、平板裝置、掌上型/膝上型電腦以及其他商業產品中。除了低功率消耗外，該等應用還要求具有高資訊含量、全色和快速視頻速率響應時間的顯示器。Many of these components are also important in the construction and operation of organic electronic devices with organic light-emitting diodes ("OLEDs"). Due to high power conversion efficiency and applicability to a wide range of end uses, OLED is promising for many display applications. They are increasingly used in mobile phones, tablet devices, palmtop/laptop computers and other commercial products. In addition to low power consumption, these applications also require displays with high information content, full color, and fast video rate response time.

聚醯亞胺膜總體上具有充足的熱穩定性、高玻璃化轉變溫度、和機械韌性以便值得考慮此類用途。而且，當經受重複撓曲時，聚醯亞胺通常不會產生霧度，所以相對於其他透明基板像聚對苯二甲酸乙二醇酯（PET）和聚萘二甲酸乙二醇酯（PEN），在可撓性顯示器應用中它們經常是較佳的。Polyimide films generally have sufficient thermal stability, high glass transition temperature, and mechanical toughness to be worth considering for such applications. Moreover, when subjected to repeated deflection, polyimide usually does not produce haze, so compared to other transparent substrates like polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) ), they are often preferred in flexible display applications.

然而，由於優先考慮光學透明度，妨礙了傳統琥珀色的聚醯亞胺在一些顯示器應用如濾色片和觸控式螢幕面板中的使用。此外，聚醯亞胺通常是硬的、高度芳香族的材料；並且隨著形成膜/塗層，聚合物鏈趨向於在膜/塗層的平面內取向。這導致膜的平行方向與垂直方向的折射率差異（雙折射率），產生可能不利地影響顯示器性能的光延遲。如果在顯示器市場中尋找聚醯亞胺的附加用途，需要維持其希望特性而同時改善其光學透明度並降低琥珀色和導致光延遲的雙折射率的解決方案。However, due to the priority given to optical transparency, the use of traditional amber-colored polyimide has been hindered in some display applications such as color filters and touch screen panels. In addition, polyimide is generally a hard, highly aromatic material; and as the film/coating is formed, the polymer chains tend to be oriented in the plane of the film/coating. This results in a difference in refractive index (birefringence) between the parallel direction and the vertical direction of the film, creating optical retardation that may adversely affect the performance of the display. If you are looking for additional uses of polyimide in the display market, you need a solution that maintains its desired characteristics while improving its optical transparency and reducing amber and birefringence that causes light retardation.

因此對於適用於電子裝置的聚合物材料存在持續需求。Therefore, there is a continuing demand for polymer materials suitable for electronic devices.

提供了一種具有式I之二胺，

Figure 02_image003
其中： Qa 選自由CRx 、SiRx 、GeRx 、PRx 、以及N所組成的群組； Qb 選自由CRy 、SiRy 、GeRy 、PRy 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； Rx 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、矽烷氧基、以及R6 所組成的群組； Ry 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、矽烷氧基、以及R7 所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； m和n係相同或不同的，並且是從0~2的整數，使得m + n ≤ 2； x係從0~4的整數； y和z係相同或不同的，並且是從0至可用最大值的整數； 其前提係： (i) 如果m + n = 2，則Rx ≠ R6 且Ry ≠ R7 ； (ii) 如果m + n = 1，則Rx ≠ R6 ，Qb ≠ N，並且Ry = R7 ； (iii) 如果m + n = 0，則Qa ≠ N，Qb ≠ N，Rx = R6 ，並且Ry = R7 。Providing a diamine of formula I,
Figure 02_image003
Where Q a is selected from the group consisting of CR x , SiR x , GeR x , PR x , and N; Q b is selected from the group consisting of CR y , SiR y , GeR y , PR y , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R x is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted Aryloxy, silyl, silaneoxy, and R 6 ; R y is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or The group consisting of substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, silaneoxy, and R 7 ; R 6 and R 7 are the same or different , And is selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; m and n are The same or different, and an integer from 0~2, such that m + n ≤ 2; x is an integer from 0~4; y and z are the same or different, and are integers from 0 to the maximum value available; The premise is: (i) If m + n = 2, then R x ≠ R 6 and R y ≠ R 7 ; (ii) If m + n = 1, then R x ≠ R 6 , Q b ≠ N, and R y = R 7 ; (iii) If m + n = 0, then Q a ≠ N, Q b ≠ N, R x = R 6 , and R y = R 7 .

進一步提供了一種二胺，其具有式IA、式IB、式IC、或式ID，

Figure 02_image004
Figure 02_image006
Figure 02_image008
Figure 02_image010
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q2 選自由CR5 、SiR5 、GeR5 、PR5 、以及N所組成的群組； Q3 選自由CR6 、SiR6 、GeR6 、以及PR6 所組成的群組； Q4 選自由CR7 、SiR7 、GeR7 、以及PR7 所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數； c係從0~2的整數； d和e係相同或不同的，並且是從0~3的整數；以及 f和g係相同或不同的，並且是從0~4的整數。Further provided is a diamine having Formula IA, Formula IB, Formula IC, or Formula ID,
Figure 02_image004
Figure 02_image006
Figure 02_image008
Figure 02_image010
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 2 is selected from the group consisting of CR 5 , SiR 5 , GeR 5 , PR 5 , and N; Q 3 is selected from the group consisting of CR 6 , SiR 6 , GeR 6 , and PR 6 ; Q 4 is selected from the group consisting of CR 7 , SiR 7 , GeR 7 , and PR 7 ; R 1 , R 2 , And R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, Fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy groups, where adjacent R 1 groups can be joined together to form a fused aromatic ring; R 4 and R 5 is the same or different, and is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, Unsubstituted or substituted aryloxy, silyl, and silaneoxy groups; R 6 and R 7 are the same or different and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl; a is an integer from 0 to 4; c is an integer from 0 to 2; d and e are The same or different, and an integer from 0 to 3; and f and g are the same or different, and are an integer from 0 to 4.

進一步提供了一種具有式II之重複單元的聚醯胺酸，

Figure 02_image012
其中： Ra 在每次出現時是相同或不同的，並且表示一個或多個四羧酸組分殘基；以及 Rb 在每次出現時是相同或不同的，並且表示一個或多個芳香族二胺殘基； 其中10~100 mol%的Rb 係來自一種或多種具有式I之二胺的二胺殘基。Further provided is a polyamide having a repeating unit of formula II,
Figure 02_image012
Where: R a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R b is the same or different at each occurrence and represents one or more aromatics Group diamine residues; where 10 to 100 mol% of R b is derived from one or more diamine residues having the diamine of formula I.

進一步提供了一種組成物，其包含 (a) 具有式II之重複單元的聚醯胺酸和 (b) 高沸點非質子溶劑。Further provided is a composition comprising (a) a polyamic acid having a repeating unit of formula II and (b) a high-boiling aprotic solvent.

進一步提供了一種聚醯亞胺，該聚醯亞胺的重複單元具有式III中的結構，

Figure 02_image014
其中Ra 和Rb 如式II中所定義。Further provided is a polyimide whose repeating unit has the structure in formula III,
Figure 02_image014
Where R a and R b are as defined in formula II.

進一步提供了一種聚醯亞胺膜，其包含式III的重複單元。A polyimide membrane is further provided, which comprises a repeating unit of formula III.

進一步提供了一種或多種用於製備聚醯亞胺膜的方法，其中該聚醯亞胺膜具有式III的重複單元。Further provided is one or more methods for preparing a polyimide film, wherein the polyimide film has a repeating unit of formula III.

進一步提供了一種電子裝置中的玻璃的可撓性替代物，其中該玻璃的可撓性替代物係具有式III的重複單元的聚醯亞胺膜。Further provided is a flexible substitute for glass in an electronic device, wherein the flexible substitute for glass is a polyimide film having a repeating unit of formula III.

進一步提供了一種具有至少一個層的電子裝置，該至少一個層包含具有式III的重複單元的聚醯亞胺膜。There is further provided an electronic device having at least one layer comprising a polyimide film having a repeating unit of formula III.

進一步提供了一種有機電子裝置，如OLED，其中該有機電子裝置含有如本文揭露的玻璃的可撓性替代物。There is further provided an organic electronic device, such as an OLED, wherein the organic electronic device contains a flexible alternative to glass as disclosed herein.

前述總體描述和下文詳細描述僅為示例性和說明性的，並不限制如所附申請專利範圍所限定的本發明。The foregoing general description and the following detailed description are merely exemplary and illustrative, and do not limit the invention as defined by the scope of the appended patent application.

提供了如以下詳細描述的一種具有式I之二胺。A diamine of formula I is provided as described in detail below.

進一步提供了如以下詳細描述的一種具有式II之重複單元的聚醯胺酸。Further provided is a polyamide having a repeating unit of formula II as described in detail below.

進一步提供了一種組成物，其包含 (a) 具有式II之重複單元的聚醯胺酸和 (b) 高沸點非質子溶劑。Further provided is a composition comprising (a) a polyamic acid having a repeating unit of formula II and (b) a high-boiling aprotic solvent.

進一步提供了如以下詳細描述的一種聚醯亞胺，該聚醯亞胺的重複單元具有式III中的結構。Further provided is a polyimide as described in detail below, the repeating unit of the polyimide having the structure in Formula III.

進一步提供了一種或多種用於製備聚醯亞胺膜的方法，其中該聚醯亞胺膜具有式III的重複單元。Further provided is one or more methods for preparing a polyimide film, wherein the polyimide film has a repeating unit of formula III.

進一步提供了一種電子裝置中的玻璃的可撓性替代物，其中該玻璃的可撓性替代物係具有式III的重複單元的聚醯亞胺膜。Further provided is a flexible substitute for glass in an electronic device, wherein the flexible substitute for glass is a polyimide film having a repeating unit of formula III.

進一步提供了一種具有至少一個層的電子裝置，該至少一個層包含具有式III的重複單元的聚醯亞胺膜。There is further provided an electronic device having at least one layer comprising a polyimide film having a repeating unit of formula III.

進一步提供了一種有機電子裝置，如OLED，其中該有機電子裝置含有如本文揭露的玻璃的可撓性替代物。There is further provided an organic electronic device, such as an OLED, wherein the organic electronic device contains a flexible alternative to glass as disclosed herein.

許多方面和實施例已在以上進行描述並且僅是示例性且非限制性的。在閱讀本說明書後，熟練的技術人員應理解在不背離本發明範圍的情況下其他方面和實施例係可能的。Many aspects and embodiments have been described above and are only exemplary and non-limiting. After reading this specification, skilled artisans should understand that other aspects and embodiments are possible without departing from the scope of the invention.

從以下詳細說明並且從申請專利範圍中，任何一個或多個實施例的其他特徵和益處將是明顯的。詳細說明首先提出術語的定義和闡明，隨後是具有式I之二胺、具有式II之重複單元結構的聚醯胺酸、具有式III的重複單元結構的聚醯亞胺、用於製備聚醯亞胺膜的方法、電子裝置、以及最後的實例。Other features and benefits of any one or more embodiments will be apparent from the detailed description below and from the scope of patent applications. Detailed description First of all, the definition and clarification of terms are proposed, followed by polyamines having a diamine of formula I, having a repeating unit structure of formula II, polyimides having a repeating unit structure of formula III, and used for the preparation of polyamides Imine film method, electronic device, and last example.

1.   術語的定義和闡明1. Definition and clarification of terms

在提出下述實施例的詳情之前，定義或闡明一些術語。Before presenting details of the following embodiments, some terms are defined or clarified.

如在「術語的定義和闡明」中所使用的，R、Ra 、Rb 、R’、R’’和任何其他變數係通用名稱，並且可以與式中定義的那些相同或不同。As in "Definitions and Clarification of Terms" used, R, R a, R b , R ', R'' and any other system variables common name, and may be defined as those of formula in the same or different.

術語「取向層」旨在係指液晶裝置（LCD）中的有機聚合物層，該層作為其在LCD製造過程期間在一個較佳的方向上摩擦到LCD玻璃上的結果而使分子最接近每個板對齊。The term "orientation layer" is intended to refer to the organic polymer layer in a liquid crystal device (LCD), which causes the molecules to be closest to each molecule as a result of their rubbing onto the LCD glass in a preferred direction during the LCD manufacturing process Boards aligned.

如本文使用的，術語「烷基」包括支鏈和直鏈的飽和脂肪族烴基。除非另外指明，否則該術語還旨在包括環狀基團。烷基基團的實例包括甲基、乙基、丙基、異丙基、異丁基、二級丁基、三級丁基、戊基、異戊基、新戊基、環戊基、己基、環己基、異己基等。術語「烷基」進一步包括取代和未取代的烴基二者。在一些實施例中，烷基基團可以是單-、二-和三-取代的。取代的烷基基團的一個實例係三氟甲基。其他取代的烷基基團由本文所述的取代基中的一個或多個形成。在某些實施例中，烷基基團具有1至20個碳原子。在其他實施例中，該基團具有1至6個碳原子。該術語旨在包括雜烷基基團。雜烷基基團可以具有從1~20個碳原子。As used herein, the term "alkyl" includes branched and straight chain saturated aliphatic hydrocarbon groups. Unless otherwise indicated, the term is also intended to include cyclic groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl , Cyclohexyl, isohexyl, etc. The term "alkyl" further includes both substituted and unsubstituted hydrocarbon groups. In some embodiments, the alkyl group can be mono-, di-, and tri-substituted. An example of a substituted alkyl group is trifluoromethyl. Other substituted alkyl groups are formed from one or more of the substituents described herein. In certain embodiments, the alkyl group has 1 to 20 carbon atoms. In other embodiments, the group has 1 to 6 carbon atoms. The term is intended to include heteroalkyl groups. The heteroalkyl group may have from 1 to 20 carbon atoms.

術語「非質子」係指一類缺乏酸性氫原子且因此不能充當氫供體的溶劑。常見的非質子溶劑包括烷烴、四氯化碳（CCl4）、苯、二甲基甲醯胺（DMF）、N-甲基-2-吡咯啶酮（NMP）、二甲基乙醯胺（DMAc）等。The term "aprotic" refers to a class of solvents that lack acidic hydrogen atoms and therefore cannot serve as hydrogen donors. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc )Wait.

術語「芳香族化合物」旨在係指包含至少一個具有4n+2非定域π電子的不飽和環狀基團的有機化合物。該術語旨在涵蓋芳香族化合物和雜芳香族化合物兩者，該芳香族化合物僅具有碳和氫原子，該雜芳香族化合物中的環狀基團內的一個或多個碳原子已被另一個原子如氮、氧、硫等替換。The term "aromatic compound" is intended to mean an organic compound containing at least one unsaturated cyclic group having 4n+2 unlocalized π electrons. The term is intended to cover both aromatic compounds and heteroaromatic compounds. The aromatic compound has only carbon and hydrogen atoms. One or more carbon atoms in the cyclic group in the heteroaromatic compound have been replaced by another Replace atoms such as nitrogen, oxygen, and sulfur.

術語「芳基」或「芳基基團」係指藉由從芳香族化合物中去除一個或多個氫（「H」）或氘（「D」）所形成的部分。芳基基團可以是單個環（單環）或具有稠合在一起或共價連接的多個環（二環、或更多）。「烴芳基」在一個或多個芳環中僅具有碳原子。「雜芳基」在至少一個芳環中具有一個或多個雜原子。在一些實施例中，烴芳基基團具有6至60個環碳原子；在一些實施例中，6至30個環碳原子。在一些實施例中，雜芳基基團具有從4~50個環碳原子；在一些實施例中，4~30個環碳原子。The term "aryl" or "aryl group" refers to a portion formed by removing one or more hydrogen ("H") or deuterium ("D") from an aromatic compound. The aryl group may be a single ring (monocyclic) or have multiple rings (bicyclic, or more) fused together or covalently linked. The "hydrocarbon aryl group" has only carbon atoms in one or more aromatic rings. "Heteroaryl" has one or more heteroatoms in at least one aromatic ring. In some embodiments, the hydrocarbon aryl group has 6 to 60 ring carbon atoms; in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, the heteroaryl group has from 4 to 50 ring carbon atoms; in some embodiments, 4 to 30 ring carbon atoms.

術語「烷氧基」旨在係指基團-OR，其中R係烷基。The term "alkoxy" is intended to refer to the group -OR, where R is alkyl.

術語「芳氧基」旨在係指基團-OR，其中R係芳基。The term "aryloxy" is intended to refer to the group -OR, where R is aryl.

除非另外指明，所有基團可以是取代的或未取代的。視需要取代的基團，如但不限於烷基或芳基，可以被一個或多個可以是相同或不同的取代基取代。合適的取代基包括烷基、芳基、硝基、氰基、-N(R’)(R’’)、鹵素、羥基、羧基、烯基、炔基、環烷基、雜芳基、烷氧基、芳氧基、雜芳氧基、烷氧基羰基、全氟烷基、全氟烷氧基、芳基烷基、矽基、矽烷氧基、矽氧烷、硫代烷氧基、-S(O)2 -、-C(=O)-N(R’)(R’’)、(R’)(R’’)N-烷基、(R’)(R’’)N-烷氧基烷基、(R’)(R’’)N-烷基芳氧基烷基、-S(O)s -芳基（其中s = 0~2）、或-S(O)s -雜芳基（其中s = 0~2）。每個R’和R’’獨立地是視需要取代的烷基、環烷基或芳基基團。R’和R’’，與它們所結合的氮原子一起，在某些實施例中可以形成環系統。取代基還可以是交聯基團。Unless otherwise indicated, all groups may be substituted or unsubstituted. Optionally substituted groups, such as but not limited to alkyl or aryl groups, may be substituted with one or more substituents which may be the same or different. Suitable substituents include alkyl, aryl, nitro, cyano, -N(R')(R''), halogen, hydroxyl, carboxyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkyl Oxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, silaneoxy, siloxane, thioalkoxy, -S(O) 2 -, -C(=O)-N(R')(R''), (R')(R'')N-alkyl, (R')(R'')N -Alkoxyalkyl, (R')(R'')N-alkylaryloxyalkyl, -S(O) s -aryl (where s = 0~2), or -S(O) s -heteroaryl (where s = 0~2). Each R'and R'' is independently an optionally substituted alkyl, cycloalkyl, or aryl group. R'and R'', together with the nitrogen atom to which they are bound, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

術語「胺」旨在係指含有具有孤對電子的鹼性氮原子的化合物。術語「胺基」係指官能基-NH2 、-NHR或-NR2 ，其中R在每次出現時是相同或不同的並且可以是烷基基團或芳基基團。術語「二胺」旨在係指含有具有締合的孤對電子的兩個鹼性氮原子的化合物。術語「芳香族二胺」旨在係指具有兩個胺基的芳香族化合物。術語「彎曲二胺（bent diamine）」旨在係指這樣的二胺，其中兩個鹼性氮原子和締合的孤對電子圍繞相應化合物或官能基的對稱中心不對稱地安置，例如間苯二胺：

Figure 02_image016
。The term "amine" is intended to mean a compound containing a basic nitrogen atom with a lone pair of electrons. The term "amino" means a functional group -NH 2, -NHR or -NR 2, wherein R in each occurrence can be the same or different and is an alkyl group or an aryl group. The term "diamine" is intended to refer to a compound containing two basic nitrogen atoms with associated lone pairs. The term "aromatic diamine" is intended to refer to an aromatic compound having two amine groups. The term "bent diamine" is intended to refer to a diamine in which two basic nitrogen atoms and associated lone pairs of electrons are arranged asymmetrically around the center of symmetry of the corresponding compound or functional group, such as m-benzene Diamine:
Figure 02_image016
.

術語「芳香族二胺殘基」旨在係指與芳香族二胺中的兩個胺基鍵合的部分。術語「芳香族二異氰酸酯殘基」旨在係指與芳香族二異氰酸酯化合物中的兩個異氰酸酯基團鍵合的部分。這在下文進一步說明。

Figure 02_image018
The term "aromatic diamine residue" is intended to refer to a portion bonded to two amine groups in the aromatic diamine. The term "aromatic diisocyanate residue" is intended to refer to a portion bonded to two isocyanate groups in an aromatic diisocyanate compound. This is explained further below.
Figure 02_image018

術語「二胺殘基」和「二異氰酸酯殘基」旨在係指分別與兩個胺基或兩個異氰酸酯基鍵合的部分，其中該部分係脂肪族的或芳香族的。The terms "diamine residue" and "diisocyanate residue" are intended to refer to portions that are bonded to two amine groups or two isocyanate groups, respectively, where the portion is aliphatic or aromatic.

術語「b*」旨在係指CIELab顏色空間中代表黃色/藍色對立顏色的b*軸線。黃色由正b*值表示，並且藍色由負b*值表示。測量的b*值可能受溶劑影響，特別是因為溶劑選擇可以影響在暴露於高溫加工條件的材料上測量的顏色。這可以作為溶劑的固有特性和/或與各種溶劑中含有的低水平雜質相關的特性的結果而出現。通常預先選擇特定溶劑以實現特定應用所希望的b*值。The term "b*" is intended to refer to the b* axis representing the opposite color of yellow/blue in the CIELab color space. Yellow is represented by positive b* values, and blue is represented by negative b* values. The measured b* value may be affected by the solvent, especially because the choice of solvent can affect the color measured on materials exposed to high temperature processing conditions. This can occur as a result of the inherent characteristics of the solvent and/or characteristics related to low levels of impurities contained in various solvents. Usually a specific solvent is pre-selected to achieve the desired b* value for a specific application.

術語「雙折射率」旨在係指聚合物膜或塗層中在不同方向上的折射率的差異。該術語通常是指x軸或y軸（平面內）與z軸（平面外）折射率之間的差異。The term "birefringence" is intended to refer to the difference in refractive index in different directions in a polymer film or coating. The term usually refers to the difference between the x-axis or y-axis (in-plane) and the z-axis (out-of-plane) refractive index.

當涉及層、材料、構件、或結構時，術語「電荷傳輸」旨在係指此類層、材料、構件、或結構促進此類電荷以相對效率和小的電荷損失穿過此類層、材料、構件、或結構的厚度的遷移。電洞傳輸材料有利於正電荷；電子傳輸材料有利於負電荷。雖然發光材料也可以具有一些電荷傳輸特性，但是術語「電荷傳輸層、材料、構件、或結構」不旨在包括其主要功能係發光的層、材料、構件、或結構。When referring to a layer, material, component, or structure, the term "charge transport" is intended to mean that such layer, material, component, or structure promotes such charge to pass through such layer, material with relative efficiency and small charge loss , Thickness of components, or structures. Hole transport materials are conducive to positive charges; electron transport materials are conducive to negative charges. Although the luminescent material may also have some charge transport characteristics, the term "charge transport layer, material, member, or structure" is not intended to include a layer, material, member, or structure whose main function is to emit light.

術語「化合物」旨在係指由分子組成的不帶電物質，該分子進一步包括原子，其中原子不能藉由不破壞化學鍵的物理手段與其對應的分子分離。該術語旨在包括低聚物和聚合物。The term "compound" is intended to refer to an uncharged substance composed of molecules that further include atoms, where atoms cannot be separated from their corresponding molecules by physical means that do not break chemical bonds. The term is intended to include oligomers and polymers.

術語「線性熱膨脹係數（CTE或α）」旨在係指定義材料隨溫度膨脹或收縮的量的參數。它被表示為每攝氏度的長度變化，並且通常以µm/m/ºC或ppm/ºC的單位表示。 α = (ΔL/L0 )/ΔTThe term "linear thermal expansion coefficient (CTE or α)" is intended to refer to a parameter that defines the amount by which a material expands or contracts with temperature. It is expressed as a change in length per degree Celsius and is usually expressed in units of µm/m/ºC or ppm/ºC. α = (ΔL/L 0 )/ΔT

本文揭露的測量的CTE值係在第一次或第二次加熱掃描期間經由已知方法產生的。對材料的相對膨脹/收縮特徵的理解可以是電子裝置的製造和/或可靠性的重要考慮因素。The measured CTE values disclosed herein are generated during the first or second heating scan via known methods. Understanding the relative expansion/contraction characteristics of the material can be an important consideration in the manufacture and/or reliability of electronic devices.

術語「摻雜劑」旨在係指包括主體材料的層內的材料，與在沒有這種材料的情況下該層的輻射發射、接收、或過濾的一種或多種電子特性或一個或多個波長相比，該材料改變該層的輻射發射、接收、或過濾的一種或多種電子特性或一個或多個目標波長。The term "dopant" is intended to refer to the material within the layer that includes the host material, and one or more electronic properties or one or more wavelengths of the layer's radiation emission, reception, or filtering in the absence of such material In contrast, the material changes one or more electronic properties or one or more target wavelengths of the layer's radiation emission, reception, or filtering.

當涉及層或材料時，術語「電活性(electroactive)」旨在表示電子地促進裝置的運行的層或材料。電活性材料的實例包括但不限於傳導、注入、傳輸或阻斷電荷的材料，其中電荷可為電子或電洞，或者在接收輻射時發射輻射或表現出電子-電洞對濃度變化的材料。非活性材料的實例包括但不限於平面化材料、絕緣材料和環境阻擋材料。When referring to a layer or material, the term "electroactive" is intended to mean a layer or material that electronically facilitates the operation of the device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charges, where the charges can be electrons or holes, or materials that emit radiation or exhibit electron-hole pair concentration changes when receiving radiation. Examples of inactive materials include but are not limited to planarizing materials, insulating materials, and environmental barrier materials.

術語「拉伸伸長率」或「拉伸應變」旨在係指材料在施加的拉伸應力下斷裂之前在材料中發生的長度的百分比增加。它可以藉由例如ASTM方法D882進行測量。The term "tensile elongation" or "tensile strain" is intended to refer to the percentage increase in the length of a material that occurs in the material before it breaks under the applied tensile stress. It can be measured by, for example, ASTM method D882.

前綴「氟」旨在表示基團中的一個或多個氫已經被氟替換。The prefix "fluorine" is intended to indicate that one or more hydrogens in the group have been replaced by fluorine.

術語「玻璃化轉變溫度（或Tg ）」旨在係指在無定形聚合物中或半結晶聚合物的非晶區域中發生可逆變化時的溫度，其中材料突然從硬、玻璃質或脆性狀態變成可撓性或彈性的狀態。在顯微鏡下，當正常捲繞的靜止聚合物鏈變得自由旋轉並可以相互移過時發生玻璃化轉變。可以使用差示掃描量熱法（DSC）、熱機械分析（TMA）或動態機械分析（DMA）或其他方法來測量Tg 。The term "glass transition temperature (or Tg )" is intended to refer to the temperature at which a reversible change occurs in an amorphous polymer or in an amorphous region of a semi-crystalline polymer, where the material suddenly changes from a hard, glassy or brittle state It becomes flexible or elastic. Under the microscope, a glass transition occurs when the normally wound static polymer chains become freely rotating and can move through each other. You can use differential scanning calorimetry (DSC), thermal mechanical analysis (TMA) and dynamic mechanical analysis (DMA) or other methods for measuring T g.

前綴「雜」表示一個或多個碳原子已經被不同的原子替換。在一些實施例中，雜原子為O、N、S、或它們的組合。The prefix "hetero" indicates that one or more carbon atoms have been replaced by different atoms. In some embodiments, the heteroatom is O, N, S, or a combination thereof.

術語「高沸點」旨在表示高於130ºC的沸點。The term "high boiling point" is intended to mean a boiling point above 130ºC.

術語「主體材料」旨在係指向其中添加摻雜劑的材料。主體材料可以或可以不具有發射、接收、或過濾輻射的一種或多種電子特性或能力。在一些實施例中，主體材料以較高的濃度存在。The term "host material" is intended to refer to a material to which a dopant is added. The host material may or may not have one or more electronic properties or capabilities to emit, receive, or filter radiation. In some embodiments, the host material is present at a higher concentration.

術語「等溫失重」旨在係指與其熱穩定性直接相關的材料特性。它通常經由熱重分析（TGA）在恒定的目標溫度下進行測量。具有高熱穩定性的材料通常在所要求的使用或加工溫度下在所希望的時間段內表現出非常低的等溫失重百分比，並且因此可以用於在該等溫度下的應用而無顯著強度損失、脫氣和/或結構變化。The term "isothermal weightlessness" is intended to refer to the material properties directly related to its thermal stability. It is usually measured by thermogravimetric analysis (TGA) at a constant target temperature. Materials with high thermal stability typically exhibit very low isothermal weight loss percentages in the desired time period at the required use or processing temperature, and therefore can be used for applications at these temperatures without significant strength loss , Degassing and/or structural changes.

術語「雷射粒子計數器測試」係指用於評估聚醯胺酸和其他聚合物溶液的顆粒含量的方法，由此將測試溶液的代表性樣品旋塗到5’’矽晶圓上並進行軟烘/乾燥。藉由任何數量的標準測量技術評價由此製備的膜的顆粒含量。此類技術包括雷射粒子檢測和本領域中已知的其他技術。The term "laser particle counter test" refers to the method used to assess the particle content of polyamide and other polymer solutions, whereby a representative sample of the test solution is spin coated onto a 5" silicon wafer and soft Bake/dry. The particle content of the film thus prepared is evaluated by any number of standard measurement techniques. Such techniques include laser particle detection and other techniques known in the art.

術語「液體組成物」旨在係指材料溶解在其中以形成溶液的液體介質、材料分散在其中以形成分散體的液體介質、或材料懸浮在其中以形成懸浮液或乳液的液體介質。The term "liquid composition" is intended to refer to a liquid medium in which the material is dissolved to form a solution, a liquid medium in which the material is dispersed to form a dispersion, or a liquid medium in which the material is suspended to form a suspension or emulsion.

術語「基體」旨在係指在例如電子裝置的形成中一個或多個層沈積在其上的基礎。非限制性實例包括玻璃、矽等。The term "substrate" is intended to refer to the foundation on which one or more layers are deposited, for example, in the formation of electronic devices. Non-limiting examples include glass, silicon, and the like.

術語「1% TGA失重」旨在係指1%的原始聚合物重量由於分解而損失（不包括吸收的水）時的溫度。The term "1% TGA weight loss" is intended to refer to the temperature at which 1% of the original polymer weight is lost due to decomposition (not including absorbed water).

術語「光延遲（或RTH ）」旨在係指平均平面內折射率與平面外折射率之間的差值（即，雙折射率），然後將此差值乘以膜或塗層的厚度。典型地對於給定頻率的光測量光延遲，並且以奈米報告單位。The term "optical retardation (or R TH )" is intended to mean the difference between the average in-plane refractive index and the out-of-plane refractive index (ie, birefringence), and then multiply this difference by the thickness of the film or coating . The light delay is typically measured for light of a given frequency, and the units are reported in nanometers.

術語「有機電子裝置」或有時「電子裝置」在本文中旨在係指包括一個或多個有機半導體層或一種或多種材料的裝置。The term "organic electronic device" or sometimes "electronic device" is intended herein to refer to a device that includes one or more organic semiconductor layers or one or more materials.

術語「顆粒含量」旨在係指存在於溶液中的不溶性顆粒的數量或計數。顆粒含量的測量可以在溶液本身上或在由那些膜製備的成品材料（片、膜等）上進行。可以使用各種光學方法來評估這種特性。The term "particle content" is intended to refer to the number or count of insoluble particles present in the solution. The measurement of the particle content can be carried out on the solution itself or on the finished materials (sheets, films, etc.) prepared from those films. Various optical methods can be used to evaluate this characteristic.

術語「光主動(photoactive)」係指當藉由所施加的電壓激活時發射光（如在發光二極體或化學電池中）、在吸收光子之後發射光（如在下變頻磷光體裝置中）、或者響應於輻射能並且在或不在所施加的偏壓下生成訊號（如在光電偵測器或光伏電池中）的材料或層。The term "photoactive" refers to emitting light when activated by an applied voltage (as in a light emitting diode or chemical battery), emitting light after absorbing photons (as in a down-converter phosphor device), Or a material or layer that generates a signal (such as in a photodetector or photovoltaic cell) in response to radiant energy and with or without an applied bias.

術語「聚醯胺酸溶液」係指含有具有分子內環化能力以形成醯亞胺基團的醯胺酸單元的聚合物的溶液。The term "polyamide solution" refers to a solution of a polymer containing an amide acid unit that has an intramolecular cyclization ability to form an imidate group.

術語「聚醯亞胺」係指由一種或多種雙官能羧酸組分與一種或多種一級二胺或二異氰酸酯反應得到的縮聚物。它們沿著聚合物骨架的主鏈含有醯亞胺結構-CO-NR-CO-作為線性或雜環單元。The term "polyimide" refers to a polycondensate obtained by reacting one or more bifunctional carboxylic acid components with one or more primary diamines or diisocyanates. They contain amide imide structure-CO-NR-CO- as linear or heterocyclic units along the main chain of the polymer backbone.

當關於材料特性或特徵時，術語「令人滿意的」旨在係指該特性或特徵滿足使用中材料的所有要求/需求。例如，在本文揭露的聚醯亞胺膜的背景下，在氮氣中在350ºC下3小時小於1%的等溫失重可視為「令人滿意」的特性的非限制性實例。When referring to a material characteristic or characteristic, the term "satisfactory" is intended to mean that the characteristic or characteristic satisfies all requirements/requirements of the material in use. For example, in the context of the polyimide film disclosed herein, an isothermal weight loss of less than 1% in nitrogen at 350ºC for 3 hours can be considered as a non-limiting example of "satisfactory" characteristics.

術語「軟烘」旨在係指在電子製造中通常使用的製程，其中塗覆的材料被加熱以驅除溶劑並固化膜。軟烘通常在90ºC與110ºC之間的溫度下在熱板上或在排氣烘箱中進行，以作為隨後對塗覆的層或膜進行熱處理的製備步驟。The term "soft bake" is intended to refer to a process commonly used in electronic manufacturing, where the coated material is heated to drive off the solvent and cure the film. Soft baking is usually carried out on a hot plate or in an exhaust oven at a temperature between 90ºC and 110ºC as a preparation step for subsequent heat treatment of the coated layer or film.

術語「基板」係指可以是硬性(rigid)或可撓性並且可以包括一種或多種材料的一個或多個層的基底材料，該等材料可以包括但不限於玻璃、聚合物、金屬或陶瓷材料或其組合。該基板可以或可以不包括電子部件、電路或導電構件。The term "substrate" refers to a base material that can be rigid or flexible and can include one or more layers of one or more materials, which can include, but are not limited to, glass, polymers, metals, or ceramic materials Or a combination thereof. The substrate may or may not include electronic components, circuits, or conductive members.

術語「矽氧烷」係指基團R3 SiOR2 Si-，其中R在每次出現時是相同或不同的並且是H、C1-20 烷基、氟烷基、或芳基。在一些實施例中，R烷基基團中的一個或多個碳被Si替換。The term "siloxane" refers to the group R 3 SiOR 2 Si-, where R is the same or different at each occurrence and is H, C 1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

術語「矽烷氧基」係指基團R3 SiO-，其中R在每次出現時是相同或不同的並且是H、C1-20 烷基、氟烷基、或芳基。The term "siloxy" refers to the group R 3 SiO-, where R is the same or different at each occurrence and is H, C 1-20 alkyl, fluoroalkyl, or aryl.

術語「矽基」係指基團R3 Si-，其中R在每次出現時是相同或不同的並且是H、C1-20 烷基、氟烷基、或芳基。在一些實施例中，R烷基基團中的一個或多個碳被Si替換。The term "silyl" refers to the group R 3 Si-, where R is the same or different at each occurrence and is H, C 1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

術語「旋塗」旨在係指用於將均勻薄膜沈積到平坦基板上的製程。一般來說，將少量塗覆材料施用在基板的中心上，該基板以低速旋轉或者根本不旋轉。該基板然後以規定速度旋轉，以便藉由離心力均勻地鋪展塗覆材料。The term "spin coating" is intended to refer to a process for depositing a uniform thin film onto a flat substrate. Generally, a small amount of coating material is applied to the center of the substrate, which rotates at a low speed or does not rotate at all. The substrate is then rotated at a prescribed speed to spread the coating material uniformly by centrifugal force.

術語「螺基團」係指具有二環有機部分的基團，其中這兩個環具有一個共用的原子。該等環可以在性質上係不同的或者相同的，並且可以形成其他環系統的部分。共用的原子在每個環中具有兩個鍵，並且被稱作螺原子。在一些實施例中，螺原子選自由C和Si組成的組。The term "spiro group" refers to a group having a bicyclic organic moiety, where the two rings have a common atom. The rings may be different or identical in nature, and may form part of other ring systems. A common atom has two bonds in each ring, and is called a spiro atom. In some embodiments, the spiro atom is selected from the group consisting of C and Si.

術語「拉伸模量」旨在係指固體材料的剛度的量度，其定義材料如膜中的應力（單位面積的力）與應變（比例變形）之間的初始關係。通常使用的單位係吉帕斯卡（GPa）。The term "tensile modulus" is intended to refer to a measure of the rigidity of a solid material, which defines the initial relationship between stress (force per unit area) and strain (proportional deformation) in materials such as membranes. The commonly used unit is Gigapascal (GPa).

術語「四羧酸組分」旨在係指以下中的任一種或多種：四羧酸、四羧酸單酐、四羧酸二酐、四羧酸單酯、和四羧酸二酯。The term "tetracarboxylic acid component" is intended to mean any one or more of the following: tetracarboxylic acid, tetracarboxylic acid monoanhydride, tetracarboxylic acid dianhydride, tetracarboxylic acid monoester, and tetracarboxylic acid diester.

術語「四羧酸組分殘基」旨在係指與四羧酸組分中的四個羧基鍵合的部分。這在下文進一步說明。

Figure 02_image020
The term "tetracarboxylic acid component residue" is intended to refer to the portion bonded to the four carboxyl groups in the tetracarboxylic acid component. This is explained further below.
Figure 02_image020

術語「透射率」係指撞擊在膜上的穿過膜以便在另一側上可檢測的給定波長的光的百分比。在可見光區（380 nm至800 nm）中的光透射率測量對於表徵對於理解本文揭露的聚醯亞胺膜的使用中特性最重要的膜顏色特徵特別有用。The term "transmittance" refers to the percentage of light of a given wavelength that impinges on the film through the film so as to be detectable on the other side. The measurement of light transmittance in the visible region (380 nm to 800 nm) is particularly useful for characterizing the film color characteristics that are most important for understanding the characteristics of the polyimide film disclosed in this article in use.

術語「黃度指數（或YI）」係指相對於標準物的黃度的量級。YI的正值表示黃色的存在和量級。具有負YI的材料看起來係帶藍色的。特別是對於在高溫下運行的聚合和/或固化過程，還應指出，YI可以是溶劑依賴性的。例如，使用DMAC作為溶劑引入的顏色的量級可能不同於使用NMP作為溶劑引入的顏色的量級。這可以作為溶劑的固有特性和/或與各種溶劑中含有的低水平雜質相關的特性的結果而出現。通常預先選擇特定溶劑以實現特定應用所希望的YI值。The term "yellowness index (or YI)" refers to the magnitude of the yellowness relative to the standard. A positive value of YI indicates the presence and magnitude of yellow. The material with negative YI looks blue. Especially for polymerization and/or curing processes operating at high temperatures, it should also be noted that YI can be solvent dependent. For example, the magnitude of the color introduced using DMAC as the solvent may be different from the magnitude of the color introduced using NMP as the solvent. This can occur as a result of the inherent characteristics of the solvent and/or characteristics related to low levels of impurities contained in various solvents. Usually a specific solvent is pre-selected to achieve the desired YI value for a specific application.

在其中如下所示取代基鍵穿過一個或多個環的結構中，

Figure 02_image022
這意味著取代基R可在一個或多個環上的任何可用位置處鍵合。In the structure where the substituent bond passes through one or more rings as shown below,
Figure 02_image022
This means that the substituent R can be bonded at any available position on one or more rings.

當用來指裝置中的層時，短語「鄰近的」不一定係指一層緊鄰著另一層。另一方面，短語「相鄰的R基團」用來指化學式中彼此緊鄰的R基團（即，藉由鍵結合的原子上的R基團）。以下示出示例性相鄰的R基團：

Figure 02_image024
When used to refer to a layer in a device, the phrase "adjacent" does not necessarily mean that one layer is next to another. On the other hand, the phrase "adjacent R groups" is used to refer to R groups immediately adjacent to each other in the chemical formula (ie, R groups on atoms bonded by bonds). Exemplary adjacent R groups are shown below:
Figure 02_image024

在本說明書中，除非由使用上下文另外明確指明或相反指示，否則其中在本發明主題的實施例被陳述或描述為包含（comprising）、包括（including）、含有（containing）、具有某些特徵或要素、由某些特徵或要素組成或由某些特徵或要素構成時，除了明確陳述或描述的那些之外的一個或多個特徵或要素也可存在於該實施例中。所揭露的本發明主題的替代實施例被描述為主要由某些特徵或要素組成，其中將實質性改變操作原理或實施例的區別特徵的實施例特徵或要素在此不存在。所描述的本發明主題的另一個替代實施例被描述為由某些特徵或要素組成，在該實施例中或在其非本質變型中，僅存在所具體陳述或描述的特徵或要素。In this specification, unless explicitly indicated otherwise by the context of use or otherwise indicated, embodiments in which the subject matter of the present invention is stated or described as comprising, including, containing, having certain features or When an element, consists of, or consists of certain features or elements, one or more features or elements other than those expressly stated or described may also be present in this embodiment. The disclosed alternative embodiments of the inventive subject matter are described as consisting essentially of certain features or elements, wherein embodiment features or elements that would substantially change the operating principle or distinguishing features of the embodiments do not exist here. Another alternative embodiment of the described subject matter of the invention is described as consisting of certain features or elements, and in this embodiment or in its non-essential variants, only the features or elements specifically stated or described are present.

此外，除非有相反的明確說明，否則「或」係指包含性的「或」，而不是指排他性的「或」。例如，條件A或者B藉由以下中的任一個滿足：A為真（或存在）且B為假（或不存在），A為假（或不存在）且B為真（或存在），以及A和B均為真（或存在）。In addition, unless expressly stated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, condition A or B is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and Both A and B are true (or exist).

而且，使用「一個/種（「a/an」）」來描述本文所述的要素和組分。這樣做只是為了方便並給出本發明範圍的一般意義。此描述應被解讀為包括一個/種或至少一個/種，並且單數形式也包括複數形式，除非其明顯地另有所指。Also, use "a/an" to describe the elements and components described herein. This is done for convenience only and to give a general meaning of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it clearly indicates otherwise.

對應於元素週期表內的列的族編號使用如在CRC Handbook of Chemistry and Physics [CRC化學與物理手冊]，第81版（2000-2001）中所見的「New Notation [新命名法]」慣例。The family number corresponding to the column in the periodic table of elements uses the convention of "New Notation" as seen in CRC Handbook of Chemistry and Physics , 81st Edition (2000-2001).

除非另有定義，否則本文所使用的所有技術和科學術語均具有與本發明所屬領域普通技術人員所通常理解的相同含義。儘管與本文所述的那些類似或等同的方法和材料可用於本發明實施例的實踐或測試中，但在下面描述了合適的方法和材料。除非引用具體段落，否則本文提及的全部出版物、專利申請、專利以及其他參考文獻均藉由援引以其全文併入本文。在衝突的情況下，則以本說明書，包括定義為准。此外，材料、方法和實例僅為說明性的並且不旨在係限制性的。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. Unless specific paragraphs are cited, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting.

在本文未描述的範圍內，有關特定材料、加工行為和電路的許多細節均係常規的並且可以在有機發光二極體顯示器、光電偵測器、光伏和半導體構件領域的教科書和其他來源中找到。To the extent not described here, many details about specific materials, processing behaviors, and circuits are conventional and can be found in textbooks and other sources in the fields of organic light-emitting diode displays, photodetectors, photovoltaics, and semiconductor components .

2.   具有式I之二胺2. Diamine with formula I

本文所述的二胺具有式I，

Figure 02_image003
其中： Qa 選自由CRx 、SiRx 、GeRx 、PRx 、以及N所組成的群組； Qb 選自由CRy 、SiRy 、GeRy 、PRy 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； Rx 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、矽烷氧基、以及R6 所組成的群組； Ry 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、矽烷氧基、以及R7 所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； m和n係相同或不同的，並且是從0~2的整數，使得m + n ≤ 2； x係從0~4的整數； y和z係相同或不同的，並且是從0至可用最大值的整數； 其前提係： (i) 如果m + n = 2，則Rx ≠ R6 且Ry ≠ R7 ； (ii) 如果m + n = 1，則Rx ≠ R6 ，Qb ≠ N，並且Ry = R7 ； (iii) 如果m + n = 0，則Qa ≠ N，Qb ≠ N，Rx = R6 ，並且Ry = R7 。The diamines described herein have the formula I,
Figure 02_image003
Where Q a is selected from the group consisting of CR x , SiR x , GeR x , PR x , and N; Q b is selected from the group consisting of CR y , SiR y , GeR y , PR y , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R x is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted Aryloxy, silyl, silaneoxy, and R 6 ; R y is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or The group consisting of substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, silaneoxy, and R 7 ; R 6 and R 7 are the same or different , And is selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; m and n are The same or different, and an integer from 0~2, such that m + n ≤ 2; x is an integer from 0~4; y and z are the same or different, and are integers from 0 to the maximum value available; The premise is: (i) If m + n = 2, then R x ≠ R 6 and R y ≠ R 7 ; (ii) If m + n = 1, then R x ≠ R 6 , Q b ≠ N, and R y = R 7 ; (iii) If m + n = 0, then Q a ≠ N, Q b ≠ N, R x = R 6 , and R y = R 7 .

在式I之一些實施例中，m = n = 1，並且y和z為0~3。In some embodiments of Formula I, m = n = 1, and y and z are 0~3.

在式I之一些實施例中，m = 1，n = 0，y = 0~3，並且z = 0~4。In some embodiments of Formula I, m=1, n=0, y=0-3, and z=0-4.

在式I之一些實施例中，m = 0，n = 1，y = 0~4，並且z = 0~3。In some embodiments of Formula I, m = 0, n = 1, y = 0~4, and z = 0~3.

在式I之一些實施例中，m = n = 0，並且y和z為0~4。In some embodiments of Formula I, m = n = 0, and y and z are 0~4.

在式I之一些實施例中，Qa = Qb 。In some embodiments of Formula I, Q a = Q b .

在式I之一些實施例中，Qa ≠ Qb 。In some embodiments of formula I, Q a ≠ Q b .

在式I之一些實施例中，Qa = CRx 。In some embodiments of Formula I, Q a = CR x .

在式I之一些實施例中，Qa = SiRx 。In some embodiments of Formula I, Q a = SiR x .

在式I之一些實施例中，Qa = GeRx 。In some embodiments of Formula I, Q a = GeR x .

在式I之一些實施例中，Qa = PRx 。In some embodiments of Formula I, Q a = PR x .

在式I之一些實施例中，Qa = N。In some embodiments of Formula I, Q a =N.

在式I之一些實施例中，Qb = CRy 。In some embodiments of Formula I, Q b = CR y .

在式I之一些實施例中，Qb = SiRy 。In some embodiments of Formula I, Q b = SiR y .

在式I之一些實施例中，Qb = GeRy 。In some embodiments of Formula I, Q b = GeR y .

在式I之一些實施例中，Qb = PRy 。In some embodiments of Formula I, Q b = PR y .

在式I之一些實施例中，Qb = N。In some embodiments of Formula I, Q b =N.

在式I之一些實施例中，x = 0。In some embodiments of Formula I, x=0.

在式I之一些實施例中，x = 1。In some embodiments of Formula I, x=1.

在式I之一些實施例中，x = 2。In some embodiments of Formula I, x=2.

在式I之一些實施例中，x = 3。In some embodiments of Formula I, x=3.

在式I之一些實施例中，x = 4。In some embodiments of Formula I, x=4.

在式I之一些實施例中，x > 0。In some embodiments of Formula I, x>0.

在式I之一些實施例中，x > 0且至少一個R1 係F。In some embodiments of Formula I, x> 0 and at least one R 1 is F.

在式I之一些實施例中，x > 0且至少一個R1 係CN。In some embodiments of Formula I, x> 0 and at least one R 1 is CN.

在式I之一些實施例中，x > 0且至少一個R1 係C1-20 烷基；在一些實施例中係C1-10 烷基。In some embodiments of Formula I, x> 0 and at least one R 1 is C 1-20 alkyl; in some embodiments it is C 1-10 alkyl.

在式I之一些實施例中，x > 0且至少一個R1 係C1-20 氟烷基；在一些實施例中係C1-10 氟烷基。In some embodiments of Formula I, x>0 and at least one R 1 is C 1-20 fluoroalkyl; in some embodiments it is C 1-10 fluoroalkyl.

在式I之一些實施例中，x > 0且至少一個R1 係C1-20 全氟烷基；在一些實施例中係C1-10 全氟烷基。In some embodiments of Formula I, x> 0 and at least one R 1 is C 1-20 perfluoroalkyl; in some embodiments it is C 1-10 perfluoroalkyl.

在式I之一些實施例中，x > 0且至少一個R1 係C1-20 烷氧基；在一些實施例中係C1-10 烷氧基。In some embodiments of Formula I, x> 0 and at least one R 1 is C 1-20 alkoxy; in some embodiments it is C 1-10 alkoxy.

在式I之一些實施例中，x > 0且至少一個R1 係C1-20 氟烷氧基；在一些實施例中係C1-10 氟烷氧基。In some embodiments of Formula I, x> 0 and at least one R 1 is C 1-20 fluoroalkoxy; in some embodiments it is C 1-10 fluoroalkoxy.

在式I之一些實施例中，x > 0且至少一個R1 係C1-20 全氟烷氧基；在一些實施例中係C1-10 全氟烷氧基。In some embodiments of Formula I, x> 0 and at least one R 1 is C 1-20 perfluoroalkoxy; in some embodiments it is C 1-10 perfluoroalkoxy.

在式I之一些實施例中，x > 0且至少一個R1 係SiH3 。In some embodiments of Formula I, x> 0 and at least one R 1 is SiH 3 .

在式I之一些實施例中，x > 0且至少一個R1 係C1-12 矽基；在一些實施例中係C3-6 矽基。In some embodiments of Formula I, x> 0 and at least one R 1 is C 1-12 silicon-based; in some embodiments it is C 3-6 silicon-based.

在式I之一些實施例中，x > 0且至少一個R1 係C1-12 矽烷氧基；在一些實施例中係C3-6 矽烷氧基。In some embodiments of Formula I, x> 0 and at least one R 1 is C 1-12 silaneoxy; in some embodiments it is C 3-6 silaneoxy.

在式I之一些實施例中，x > 0且至少一個R1 係未取代或取代的C6-30 烴芳基；在一些實施例中係未取代或取代的C6-18 烴芳基；在一些實施例中係未取代的。In some embodiments of Formula I, x>0 and at least one R 1 is an unsubstituted or substituted C 6-30 hydrocarbon aryl group; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; In some embodiments it is unsubstituted.

在式I之一些實施例中，x > 0且至少一個R1 係未取代或取代的C3‑30 雜芳基；在一些實施例中係未取代或取代的C3‑18 雜芳基；在一些實施例中係未取代的。In some embodiments of Formula I, x> 0 and at least one R 1 is unsubstituted or substituted C 3-30 heteroaryl; in some embodiments, it is unsubstituted or substituted C 3-18 heteroaryl; In some embodiments it is unsubstituted.

在式I之一些實施例中，x > 0且至少一個R1 係未取代或取代的C6-30 烴芳氧基；在一些實施例中係未取代或取代的C6-18 烴芳氧基；在一些實施例中係未取代的。In some embodiments of Formula I, x> 0 and at least one R 1 is an unsubstituted or substituted C 6-30 hydrocarbon aryloxy; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryloxy Radical; in some embodiments it is unsubstituted.

在一些實施例中，以上烴芳基、雜芳基、以及芳氧基基團中的任一個進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

在式I之一些實施例中，x ≥ 2。In some embodiments of Formula I, x ≥ 2.

在式I之一些實施例中，x ≥ 2並且兩個相鄰的R1 基團連接在一起以形成稠合的烴芳環。在一些實施例中，稠環進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments of Formula I, x ≥ 2 and two adjacent R 1 groups are joined together to form a fused hydrocarbon aromatic ring. In some embodiments, the fused ring is further substituted with one or more substituents selected from the group consisting of F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy , Silicon-based, and silane alkoxy.

在式I之一些實施例中，y = 0。In some embodiments of Formula I, y=0.

在式I之一些實施例中，y = 1。In some embodiments of Formula I, y=1.

在式I之一些實施例中，y = 2。In some embodiments of Formula I, y=2.

在式I之一些實施例中，y = 3。In some embodiments of Formula I, y=3.

在式I之一些實施例中，y = 4。In some embodiments of Formula I, y=4.

在式I之一些實施例中，y > 0。In some embodiments of Formula I, y>0.

在式I之一些實施例中，y > 0且至少一個R2 係F。In some embodiments of Formula I, y>0 and at least one R 2 is F.

在式I之一些實施例中，y > 0且至少一個R2 係CN。In some embodiments of Formula I, y>0 and at least one R 2 is CN.

在式I之一些實施例中，y > 0且至少一個R2 係C1-20 烷基；在一些實施例中係C1-10 烷基。In some embodiments of Formula I, y>0 and at least one R 2 is C 1-20 alkyl; in some embodiments, it is C 1-10 alkyl.

在式I之一些實施例中，y > 0且至少一個R2 係C1-20 氟烷基；在一些實施例中係C1-10 氟烷基。In some embodiments of Formula I, y>0 and at least one R 2 is C 1-20 fluoroalkyl; in some embodiments, it is C 1-10 fluoroalkyl.

在式I之一些實施例中，y > 0且至少一個R2 係C1-20 全氟烷基；在一些實施例中係C1-10 全氟烷基。In some embodiments of Formula I, y>0 and at least one R 2 is C 1-20 perfluoroalkyl; in some embodiments, it is C 1-10 perfluoroalkyl.

在式I之一些實施例中，y > 0且至少一個R2 係C1-20 烷氧基；在一些實施例中係C1-10 烷氧基。In some embodiments of Formula I, y>0 and at least one R 2 is C 1-20 alkoxy; in some embodiments it is C 1-10 alkoxy.

在式I之一些實施例中，y > 0且至少一個R2 係C1-20 氟烷氧基；在一些實施例中係C1-10 氟烷氧基。In some embodiments of Formula I, y>0 and at least one R 2 is C 1-20 fluoroalkoxy; in some embodiments it is C 1-10 fluoroalkoxy.

在式I之一些實施例中，y > 0且至少一個R2 係C1-20 全氟烷氧基；在一些實施例中係C1-10 全氟烷氧基。In some embodiments of Formula I, y>0 and at least one R 2 is C 1-20 perfluoroalkoxy; in some embodiments, it is C 1-10 perfluoroalkoxy.

在式I之一些實施例中，y > 0且至少一個R2 係SiH3 。In some embodiments of Formula I, y>0 and at least one R 2 is SiH 3 .

在式I之一些實施例中，y > 0且至少一個R2 係C1-12 矽基；在一些實施例中係C3-6 矽基。In some embodiments of Formula I, y>0 and at least one R 2 is C 1-12 silicon-based; in some embodiments it is C 3-6 silicon-based.

在式I之一些實施例中，y > 0且至少一個R2 係C1-12 矽烷氧基；在一些實施例中係C3-6 矽烷氧基。In some embodiments of Formula I, y>0 and at least one R 2 is a C 1-12 silaneoxy group; in some embodiments, it is a C 3-6 silaneoxy group.

在式I之一些實施例中，y > 0且至少一個R2 係未取代或取代的C6-30 烴芳基；在一些實施例中係未取代或取代的C6-18 烴芳基；在一些實施例中係未取代的。In some embodiments of Formula I, y>0 and at least one R 2 is an unsubstituted or substituted C 6-30 hydrocarbon aryl group; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; In some embodiments it is unsubstituted.

在式I之一些實施例中，y > 0且至少一個R2 係未取代或取代的C3‑30 雜芳基；在一些實施例中係未取代或取代的C3‑18 雜芳基；在一些實施例中係未取代的。In some embodiments of Formula I, y> 0 and at least one R 2 is unsubstituted or substituted C 3-30 heteroaryl; in some embodiments, it is unsubstituted or substituted C 3-18 heteroaryl; In some embodiments it is unsubstituted.

在式I之一些實施例中，y > 0且至少一個R2 係未取代或取代的C6-30 烴芳氧基；在一些實施例中係未取代或取代的C6-18 烴芳氧基；在一些實施例中係未取代的。In some embodiments of Formula I, y>0 and at least one R 2 is an unsubstituted or substituted C 6-30 hydrocarbon aryloxy; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryloxy Radical; in some embodiments it is unsubstituted.

在一些實施例中，以上烴芳基、雜芳基、以及芳氧基基團中的任一個進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

在式I之一些實施例中，z = 0。In some embodiments of Formula I, z=0.

在式I之一些實施例中，z = 1。In some embodiments of Formula I, z=1.

在式I之一些實施例中，z = 2。In some embodiments of Formula I, z=2.

在式I之一些實施例中，z = 3。In some embodiments of Formula I, z=3.

在式I之一些實施例中，z = 4。In some embodiments of Formula I, z=4.

在式I之一些實施例中，z > 0。In some embodiments of Formula I, z>0.

在式I之一些實施例中，z > 0且至少一個R3 係F。In some embodiments of Formula I, z> 0 and at least one R 3 is F.

在式I之一些實施例中，z > 0且至少一個R3 係CN。In some embodiments of Formula I, z> 0 and at least one R 3 is CN.

在式I之一些實施例中，z > 0且至少一個R3 係C1-20 烷基；在一些實施例中係C1-10 烷基。In some embodiments of Formula I, z> 0 and at least one R 3 is C 1-20 alkyl; in some embodiments it is C 1-10 alkyl.

在式I之一些實施例中，z > 0且至少一個R3 係C1-20 氟烷基；在一些實施例中係C1-10 氟烷基。In some embodiments of Formula I, z> 0 and at least one R 3 is C 1-20 fluoroalkyl; in some embodiments it is C 1-10 fluoroalkyl.

在式I之一些實施例中，z > 0且至少一個R3 係C1-20 全氟烷基；在一些實施例中係C1-10 全氟烷基。In some embodiments of Formula I, z> 0 and at least one R 3 is C 1-20 perfluoroalkyl; in some embodiments, it is C 1-10 perfluoroalkyl.

在式I之一些實施例中，z > 0且至少一個R3 係C1-20 烷氧基；在一些實施例中係C1-10 烷氧基。In some embodiments of Formula I, z> 0 and at least one R 3 is C 1-20 alkoxy; in some embodiments it is C 1-10 alkoxy.

在式I之一些實施例中，z > 0且至少一個R3 係C1-20 氟烷氧基；在一些實施例中係C1-10 氟烷氧基。In some embodiments of Formula I, z> 0 and at least one R 3 is C 1-20 fluoroalkoxy; in some embodiments it is C 1-10 fluoroalkoxy.

在式I之一些實施例中，z > 0且至少一個R3 係C1-20 全氟烷氧基；在一些實施例中係C1-10 全氟烷氧基。In some embodiments of Formula I, z> 0 and at least one R 3 is C 1-20 perfluoroalkoxy; in some embodiments it is C 1-10 perfluoroalkoxy.

在式I之一些實施例中，z > 0且至少一個R3 係SiH3 。In some embodiments of Formula I, z> 0 and at least one R 3 is SiH 3 .

在式I之一些實施例中，z > 0且至少一個R3 係C1-12 矽基；在一些實施例中係C3-6 矽基。In some embodiments of Formula I, z> 0 and at least one R 3 is C 1-12 silicon-based; in some embodiments it is C 3-6 silicon-based.

在式I之一些實施例中，z > 0且至少一個R3 係C1-12 矽烷氧基；在一些實施例中係C3-6 矽烷氧基。In some embodiments of Formula I, z> 0 and at least one R 3 is a C 1-12 silaneoxy group; in some embodiments, it is a C 3-6 silaneoxy group.

在式I之一些實施例中，z > 0且至少一個R3 係未取代或取代的C6-30 烴芳基；在一些實施例中係未取代或取代的C6-18 烴芳基；在一些實施例中係未取代的。In some embodiments of Formula I, z>0 and at least one R 3 is an unsubstituted or substituted C 6-30 hydrocarbon aryl group; in some embodiments, it is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; In some embodiments it is unsubstituted.

在式I之一些實施例中，z > 0且至少一個R3 係未取代或取代的C3‑30 雜芳基；在一些實施例中係未取代或取代的C3‑18 雜芳基；在一些實施例中係未取代的。In some embodiments of Formula I, z> 0 and at least one R 3 is unsubstituted or substituted C 3-30 heteroaryl; in some embodiments, it is unsubstituted or substituted C 3-18 heteroaryl; In some embodiments it is unsubstituted.

在式I之一些實施例中，z > 0且至少一個R3 係未取代或取代的C6-30 烴芳氧基；在一些實施例中係未取代或取代的C6-18 烴芳氧基；在一些實施例中係未取代的。In some embodiments of Formula I, z> 0 and at least one R 3 is an unsubstituted or substituted C 6-30 hydrocarbon aryloxy; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryloxy Radical; in some embodiments it is unsubstituted.

在一些實施例中，以上烴芳基、雜芳基、以及芳氧基基團中的任一個進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

在式I之一些實施例中，Rx = Ry 。In some embodiments of Formula I, R x = R y .

在式I之一些實施例中，Rx ≠ Ry 。In some embodiments of Formula I, R x ≠ R y .

在式I之一些實施例中，Rx = Ry = H。In some embodiments of Formula I, R x = R y = H.

在式I之一些實施例中，Rx 係R6 。In some embodiments of Formula I, R x is R 6 .

在式I之一些實施例中，Rx 係H。In some embodiments of Formula I, R x is H.

在式I之一些實施例中，Rx 係F。In some embodiments of Formula I, R x is F.

在式I之一些實施例中，Rx 係CN。In some embodiments of Formula I, R x is CN.

在式I之一些實施例中，Rx 係C1-20 烷基；在一些實施例中係C1-10 烷基。In some embodiments of Formula I, R x is C 1-20 alkyl; in some embodiments, it is C 1-10 alkyl.

在式I之一些實施例中，Rx 係C1-20 氟烷基；在一些實施例中係C1-10 氟烷基。In some embodiments of Formula I, R x is C 1-20 fluoroalkyl; in some embodiments, it is C 1-10 fluoroalkyl.

在式I之一些實施例中，Rx 係C1-20 全氟烷基；在一些實施例中係C1-10 全氟烷基。In some embodiments of Formula I, R x is C 1-20 perfluoroalkyl; in some embodiments, it is C 1-10 perfluoroalkyl.

在式I之一些實施例中，Rx 係C1-20 烷氧基；在一些實施例中係C1-10 烷氧基。In some embodiments of Formula I, R x is C 1-20 alkoxy; in some embodiments, it is C 1-10 alkoxy.

在式I之一些實施例中，Rx 係C1-20 氟烷氧基；在一些實施例中係C1-10 氟烷氧基。In some embodiments of Formula I, R x is C 1-20 fluoroalkoxy; in some embodiments, it is C 1-10 fluoroalkoxy.

在式I之一些實施例中，Rx 係C1-20 全氟烷氧基；在一些實施例中係C1-10 全氟烷氧基。In some embodiments of Formula I, R x is C 1-20 perfluoroalkoxy; in some embodiments, it is C 1-10 perfluoroalkoxy.

在式I之一些實施例中，Rx 係SiH3 。In some embodiments of Formula I, R x is SiH 3 .

在式I之一些實施例中，Rx 係C1-12 矽基；在一些實施例中係C3-6 矽基。In some embodiments of Formula I, R x is C 1-12 silicon-based; in some embodiments, it is C 3-6 silicon-based.

在式I之一些實施例中，Rx 係C1-12 矽烷氧基；在一些實施例中係C3-6 矽烷氧基。In some embodiments of Formula I, R x is C 1-12 silaneoxy; in some embodiments, it is C 3-6 silaneoxy.

在式I之一些實施例中，Rx 係未取代或取代的C6-30 烴芳基；在一些實施例中係C6-18 烴芳基；在一些實施例中係未取代的。In some embodiments of Formula I, R x is an unsubstituted or substituted C 6-30 hydrocarbon aryl group; in some embodiments, a C 6-18 hydrocarbon aryl group; in some embodiments, it is unsubstituted.

在式I之一些實施例中，Rx 係未取代或取代的C3-30 雜芳基；在一些實施例中係C3-18 雜芳基；在一些實施例中係未取代的。In some embodiments of Formula I, R x is unsubstituted or substituted C 3-30 heteroaryl; in some embodiments, C 3-18 heteroaryl; in some embodiments, unsubstituted.

在式I之一些實施例中，Rx 係未取代或取代的C6-30 烴芳氧基；在一些實施例中係C6-18 烴芳氧基；在一些實施例中係未取代的。In some embodiments of Formula I, R x is an unsubstituted or substituted C 6-30 hydrocarbon aryloxy group; in some embodiments, it is a C 6-18 hydrocarbon aryloxy group; in some embodiments, it is unsubstituted .

在一些實施例中，以上烴芳基、雜芳基、以及芳氧基基團中的任一個進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

在式I之一些實施例中，Ry 係R7 。In some embodiments of Formula I, R y is R 7 .

在式I之一些實施例中，Ry 係H。In some embodiments of Formula I, R y is H.

在式I之一些實施例中，Ry 係F。In some embodiments of Formula I, R y is F.

在式I之一些實施例中，Ry 係CN。In some embodiments of Formula I, R y is CN.

在式I之一些實施例中，Ry 係C1-20 烷基；在一些實施例中係C1-10 烷基。In some embodiments of Formula I, R y is C 1-20 alkyl; in some embodiments, it is C 1-10 alkyl.

在式I之一些實施例中，Ry 係C1-20 氟烷基；在一些實施例中係C1-10 氟烷基。In some embodiments of Formula I, R y is C 1-20 fluoroalkyl; in some embodiments, it is C 1-10 fluoroalkyl.

在式I之一些實施例中，Ry 係C1-20 全氟烷基；在一些實施例中係C1-10 全氟烷基。In some embodiments of Formula I, R y is C 1-20 perfluoroalkyl; in some embodiments, it is C 1-10 perfluoroalkyl.

在式I之一些實施例中，Ry 係C1-20 烷氧基；在一些實施例中係C1-10 烷氧基。In some embodiments of Formula I, R y is C 1-20 alkoxy; in some embodiments, it is C 1-10 alkoxy.

在式I之一些實施例中，Ry 係C1-20 氟烷氧基；在一些實施例中係C1-10 氟烷氧基。In some embodiments of Formula I, R y is C 1-20 fluoroalkoxy; in some embodiments, it is C 1-10 fluoroalkoxy.

在式I之一些實施例中，Ry 係C1-20 全氟烷氧基；在一些實施例中係C1-10 全氟烷氧基。In some embodiments of Formula I, R y is C 1-20 perfluoroalkoxy; in some embodiments, it is C 1-10 perfluoroalkoxy.

在式I之一些實施例中，Ry 係SiH3 。In some embodiments of Formula I, R y is SiH 3 .

在式I之一些實施例中，Ry 係C1-12 矽基；在一些實施例中係C3-6 矽基。In some embodiments of Formula I, R y is C 1-12 silicon-based; in some embodiments, it is C 3-6 silicon-based.

在式I之一些實施例中，Ry 係C1-12 矽烷氧基；在一些實施例中係C3-6 矽烷氧基。In some embodiments of Formula I, R y is a C 1-12 silaneoxy group; in some embodiments, it is a C 3-6 silaneoxy group.

在式I之一些實施例中，Ry 係未取代或取代的C6-30 烴芳基；在一些實施例中係C6-18 烴芳基；在一些實施例中係未取代的。In some embodiments of Formula I, R y is an unsubstituted or substituted C 6-30 hydrocarbon aryl group; in some embodiments, a C 6-18 hydrocarbon aryl group; in some embodiments, it is unsubstituted.

在式I之一些實施例中，Ry 係未取代或取代的C3-30 雜芳基；在一些實施例中係C3-18 雜芳基；在一些實施例中係未取代的。In some embodiments of Formula I, R y is unsubstituted or substituted C 3-30 heteroaryl; in some embodiments, C 3-18 heteroaryl; in some embodiments, unsubstituted.

在式I之一些實施例中，Ry 係未取代或取代的C6-30 烴芳氧基；在一些實施例中係C6-18 烴芳氧基；在一些實施例中係未取代的。In some embodiments of Formula I, R y is an unsubstituted or substituted C 6-30 hydrocarbon aryloxy group; in some embodiments, it is a C 6-18 hydrocarbon aryloxy group; in some embodiments, it is unsubstituted .

在一些實施例中，以上烴芳基、雜芳基、以及芳氧基基團中的任一個進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

在式I之一些實施例中，R6 係NH2 。In some embodiments of Formula I, R 6 is NH 2 .

在式I之一些實施例中，R6 係ArNH2 。In some embodiments of Formula I, R 6 is ArNH 2 .

在式I之一些實施例中，R6 係OArNH2 。In some embodiments of Formula I, R 6 is OArNH 2 .

在式I之一些實施例中，R7 係NH2 。In some embodiments of Formula I, R 7 is NH 2 .

在式I之一些實施例中，R7 係ArNH2 。In some embodiments of Formula I, R 7 is ArNH 2 .

在式I之一些實施例中，R7 係OArNH2 。In some embodiments of Formula I, R 7 is OArNH 2 .

在式I之一些實施例中，Ar具有式a，

Figure 02_image027
其中： R10 和R11 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R10 和/或R11 基團可以連接在一起以形成稠環； p和q係相同或不同的並且是從0~4的整數； s係從0~3的整數；以及 *表示附接點。In some embodiments of formula I, Ar has formula a,
Figure 02_image027
Wherein: R 10 and R 11 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, Alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy groups, where adjacent R 10 and/or R 11 groups can be joined together to form Condensed ring; p and q are the same or different and are integers from 0 to 4; s is an integer from 0 to 3; and * represents the attachment point.

在式I之一些實施例中，Ar選自由苯基、聯苯基、以及萘基所組成的群組，其可以是未取代的或取代的。在一些實施例中，Ar具有至少一個選自以下群組的取代基，該群組由以下組成：F、烷基、氟烷基、烷氧基、以及氟烷氧基。In some embodiments of Formula I, Ar is selected from the group consisting of phenyl, biphenyl, and naphthyl, which may be unsubstituted or substituted. In some embodiments, Ar has at least one substituent selected from the group consisting of F, alkyl, fluoroalkyl, alkoxy, and fluoroalkoxy.

在式I之一些實施例中，Qa = CRx 並且Rx 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula I, Q a = CR x and R x is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl Group.

在式I之一些實施例中，Qa = CRx 並且Rx 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula I, Q a = CR x and R x is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式I之一些實施例中，Qb = CRy 並且Ry 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula I, Q b = CR y and R y is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl Group.

在式I之一些實施例中，Qb = CRy 並且Ry 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula I, Q b = CR y and R y is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式I之一些實施例中，a > 0並且R1 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula I, a> 0 and R 1 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式I之一些實施例中，a > 0並且R1 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula I, a>0 and R 1 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式I之一些實施例中，二胺具有式IA，

Figure 02_image029
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q2 選自由CR5 、SiR5 、GeR5 、PR5 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數；以及 d和e係相同或不同的，並且是從0~3的整數。In some embodiments of Formula I, the diamine has Formula IA,
Figure 02_image029
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 2 is selected from the group consisting of CR 5 , SiR 5 , GeR 5 , PR 5 , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R 4 and R 5 are the same or different, and are selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy , Fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy; R 6 and R 7 are the same or different, and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2. The group consisting of 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; a is an integer from 0 to 4; and d and e are the same or Different, and is an integer from 0~3.

在式IA的一些實施例中，Q1 = Q2 。In some embodiments of Formula IA, Q 1 = Q 2 .

在式IA的一些實施例中，Q1 ≠ Q2 。In some embodiments of formula IA, Q 1 ≠ Q 2 .

在式IA的一些實施例中，Q1 = CR4 。In some embodiments of Formula IA, Q 1 = CR 4 .

在式IA的一些實施例中，Q1 = SiR4 。In some embodiments of Formula IA, Q 1 = SiR 4 .

在式IA的一些實施例中，Q1 = GeR4 。In some embodiments of Formula IA, Q 1 =GeR 4 .

在式IA的一些實施例中，Q1 = PR4 。In some embodiments of Formula IA, Q 1 = PR 4 .

在式IA的一些實施例中，Q1 = N。In some embodiments of Formula IA, Q 1 =N.

在式IA的一些實施例中，Q2 = CR5 。In some embodiments of Formula IA, Q 2 = CR 5 .

在式IA的一些實施例中，Q2 = SiR5 。In some embodiments of Formula IA, Q 2 = SiR 5 .

在式IA的一些實施例中，Q2 = GeR5 。In some embodiments of Formula IA, Q 2 = GeR 5 .

在式IA的一些實施例中，Q2 = PR5 。In some embodiments of Formula IA, Q 2 = PR 5 .

在式IA的一些實施例中，Q2 = N。In some embodiments of Formula IA, Q 2 =N.

在式IA的一些實施例中，a = 0。In some embodiments of Formula IA, a=0.

在式IA的一些實施例中，a = 1。In some embodiments of Formula IA, a=1.

在式IA的一些實施例中，a = 2。In some embodiments of Formula IA, a=2.

在式IA的一些實施例中，a = 3。In some embodiments of Formula IA, a=3.

在式IA的一些實施例中，a = 4。In some embodiments of Formula IA, a=4.

在式IA的一些實施例中，a > 0。In some embodiments of Formula IA, a>0.

在式IA的一些實施例中，d = 0。In some embodiments of Formula IA, d=0.

在式IA的一些實施例中，d = 1。In some embodiments of Formula IA, d=1.

在式IA的一些實施例中，d = 2。In some embodiments of Formula IA, d=2.

在式IA的一些實施例中，d = 3。In some embodiments of Formula IA, d=3.

在式IA的一些實施例中，d > 0。In some embodiments of Formula IA, d>0.

在式IA的一些實施例中，e = 0。In some embodiments of Formula IA, e=0.

在式IA的一些實施例中，e = 1。In some embodiments of Formula IA, e=1.

在式IA的一些實施例中，e = 2。In some embodiments of Formula IA, e=2.

在式IA的一些實施例中，e = 3。In some embodiments of formula IA, e=3.

在式IA的一些實施例中，e > 0。In some embodiments of Formula IA, e>0.

在式IA的一些實施例中，R4 = R5 。In some embodiments of Formula IA, R 4 = R 5 .

在式IA的一些實施例中，R4 ≠ R5 。In some embodiments of formula IA, R 4 ≠ R 5 .

在式IA的一些實施例中，R4 = R5 = H。In some embodiments of Formula IA, R 4 = R 5 = H.

在式IA的一些實施例中，R4 係H。In some embodiments of Formula IA, R 4 is H.

在式IA的一些實施例中，R4 係F。In some embodiments of Formula IA, R 4 is F.

在式IA的一些實施例中，R4 係CN。In some embodiments of Formula IA, R 4 is CN.

在式IA的一些實施例中，R4 係C1-20 烷基；在一些實施例中係C1-10 烷基。In some embodiments of Formula IA, R 4 is C 1-20 alkyl; in some embodiments, it is C 1-10 alkyl.

在式IA的一些實施例中，R4 係C1-20 氟烷基；在一些實施例中係C1-10 氟烷基。In some embodiments of Formula IA, R 4 is C 1-20 fluoroalkyl; in some embodiments, it is C 1-10 fluoroalkyl.

在式IA的一些實施例中，R4 係C1-20 全氟烷基；在一些實施例中係C1-10 全氟烷基。In some embodiments of Formula IA, R 4 is C 1-20 perfluoroalkyl; in some embodiments, it is C 1-10 perfluoroalkyl.

在式IA的一些實施例中，R4 係C1-20 烷氧基；在一些實施例中係C1-10 烷氧基。In some embodiments of Formula IA, R 4 is C 1-20 alkoxy; in some embodiments it is C 1-10 alkoxy.

在式IA的一些實施例中，R4 係C1-20 氟烷氧基；在一些實施例中係C1-10 氟烷氧基。In some embodiments of Formula IA, R 4 is C 1-20 fluoroalkoxy; in some embodiments, it is C 1-10 fluoroalkoxy.

在式IA的一些實施例中，R4 係C1-20 全氟烷氧基；在一些實施例中係C1-10 全氟烷氧基。In some embodiments of Formula IA, R 4 is C 1-20 perfluoroalkoxy; in some embodiments, it is C 1-10 perfluoroalkoxy.

在式IA的一些實施例中，R4 係SiH3 。In some embodiments of Formula IA, R 4 is SiH 3 .

在式IA的一些實施例中，R4 係C1-12 矽基；在一些實施例中係C3-6 矽基。In some embodiments of Formula IA, R 4 is C 1-12 silicon-based; in some embodiments, it is C 3-6 silicon-based.

在式IA的一些實施例中，R4 係C1-12 矽烷氧基；在一些實施例中係C3-6 矽烷氧基。In some embodiments of Formula IA, R 4 is C 1-12 silaneoxy; in some embodiments, it is C 3-6 silaneoxy.

在式IA的一些實施例中，R4 係未取代或取代的C6-30 烴芳基；在一些實施例中係C6-18 烴芳基；  在一些實施例中係未取代的。In some embodiments of formula IA, R 4 is unsubstituted or substituted C 6-30 hydrocarbon aryl; in some embodiments it is C 6-18 hydrocarbon aryl; in some embodiments it is unsubstituted.

在式IA的一些實施例中，R4 係未取代或取代的C3-30 雜芳基；在一些實施例中係C3-18 雜芳基；在一些實施例中係未取代的。In some embodiments of Formula IA, R 4 is unsubstituted or substituted C 3-30 heteroaryl; in some embodiments, C 3-18 heteroaryl; in some embodiments, unsubstituted.

在式IA的一些實施例中，R4 係未取代或取代的C6-30 烴芳氧基；在一些實施例中係C6-18 烴芳氧基；在一些實施例中係未取代的。In some embodiments of Formula IA, R 4 is unsubstituted or substituted C 6-30 hydrocarbon aryloxy; in some embodiments it is C 6-18 hydrocarbon aryloxy; in some embodiments it is unsubstituted .

在一些實施例中，以上烴芳基、雜芳基、以及芳氧基基團中的任一個進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

式IA中的R4 的所有以上描述的實施例同樣適用於式IA中的R5 。All the above-described embodiments of R 4 in formula IA also apply to R 5 in formula IA.

式I中的x > 0時的R1 的所有以上描述的實施例同樣適用於式IA中的a > 0時的R1 。All the above-described embodiments of R 1 when x> 0 in Formula I are also applicable to R 1 when a> 0 in Formula IA.

式I中的y > 0時的R2 的所有以上描述的實施例同樣適用於式IA中的d > 0時的R2 。All the above-described embodiments of R 2 when y> 0 in Formula I are also applicable to R 2 when d> 0 in Formula IA.

式I中的z > 0時的R3 的所有以上描述的實施例同樣適用於式IA中的e > 0時的R3 。All the above-described embodiments of R 3 when z> 0 in Formula I are also applicable to R 3 when e> 0 in Formula IA.

式I中的R6 、R7 、以及Ar的所有以上描述的實施例同樣適用於式IA中的R6 、R7 、以及Ar。All the above-described embodiments of R 6 , R 7 , and Ar in Formula I are also applicable to R 6 , R 7 , and Ar in Formula IA.

在式IA的一些實施例中，Q1 = CR4 並且R4 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IA, Q 1 = CR 4 and R 4 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl Group.

在式IA的一些實施例中，Q1 = CR4 並且R4 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IA, Q 1 = CR 4 and R 4 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IA的一些實施例中，Q2 = CR5 並且R5 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IA, Q 2 = CR 5 and R 5 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl Group.

在式IA的一些實施例中，Q2 = CR5 並且R5 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IA, Q 2 = CR 5 and R 5 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IA的一些實施例中，a > 0並且R1 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IA, a>0 and R 1 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IA的一些實施例中，a > 0並且R1 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IA, a>0 and R 1 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IA的一些實施例中，d > 0並且R2 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IA, d>0 and R 2 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IA的一些實施例中，d > 0並且R2 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IA, d>0 and R 2 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IA的一些實施例中，e > 0並且R3 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IA, e>0 and R 3 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IA的一些實施例中，e > 0並且R3 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IA, e>0 and R 3 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式I之一些實施例中，二胺具有式IB，

Figure 02_image031
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q2 選自由CR5 、SiR5 、GeR5 、PR5 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R7 在每次出現時是相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數； c係從0~2的整數；以及 f係從0~4的整數。In some embodiments of Formula I, the diamine has Formula IB,
Figure 02_image031
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 2 is selected from the group consisting of CR 5 , SiR 5 , GeR 5 , PR 5 , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R 4 and R 5 are the same or different, and are selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy , Fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy; R 7 is the same or different at each occurrence and is selected from NH 2 , ArNH 2 , And the group formed by OArNH 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; a is an integer from 0 to 4; c is from 0 to An integer of 2; and f is an integer from 0 to 4.

在式IB的一些實施例中，c = 0。In some embodiments of formula IB, c=0.

在式IB的一些實施例中，c = 1。In some embodiments of formula IB, c=1.

在式IB的一些實施例中，c = 2。In some embodiments of formula IB, c=2.

在式IB的一些實施例中，c > 0。In some embodiments of formula IB, c>0.

在式IB的一些實施例中，f = 0。In some embodiments of formula IB, f=0.

在式IB的一些實施例中，f = 1。In some embodiments of Formula IB, f=1.

在式IB的一些實施例中，f = 2。In some embodiments of Formula IB, f=2.

在式IB的一些實施例中，f = 3。In some embodiments of Formula IB, f=3.

在式IB的一些實施例中，f = 4。In some embodiments of formula IB, f=4.

在式IB的一些實施例中，f > 0。In some embodiments of formula IB, f>0.

式IA中的Q1 、Q2 、R4 、R5 、以及a的所有以上描述的實施例同樣適用於式IB中的Q1 、Q2 、R4 、R5 、以及a。All the above-described embodiments of Q 1 , Q 2 , R 4 , R 5 , and a in Formula IA are also applicable to Q 1 , Q 2 , R 4 , R 5 , and a in Formula IB.

式I中的x > 0時的R1 的所有以上描述的實施例同樣適用於式IB中的a > 0時的R1 。All the above-described embodiments of R 1 when x> 0 in Formula I are also applicable to R 1 when a> 0 in Formula IB.

式I中的y > 0時的R2 的所有以上描述的實施例同樣適用於式IB中的f > 0時的R2 。All the above-described embodiments of R 2 when y> 0 in Formula I are also applicable to R 2 when f> 0 in Formula IB.

式I中的z > 0時的R3 的所有以上描述的實施例同樣適用於式IB中的c > 0時的R3 。All the above-described embodiments of R 3 when z> 0 in Formula I are also applicable to R 3 when c> 0 in Formula IB.

式I中的R7 和Ar的所有以上描述的實施例同樣適用於式IB中的R7 和Ar。All the above-described embodiments of R 7 and Ar in Formula I are equally applicable to R 7 and Ar in Formula IB.

在式IB的一些實施例中，Q1 = CR4 並且R4 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IB, Q 1 = CR 4 and R 4 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl Group.

在式IB的一些實施例中，Q1 = CR4 並且R4 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IB, Q 1 = CR 4 and R 4 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IB的一些實施例中，Q2 = CR5 並且R5 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IB, Q 2 = CR 5 and R 5 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl Group.

在式IB的一些實施例中，Q2 = CR5 並且R5 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IB, Q 2 = CR 5 and R 5 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IB的一些實施例中，a > 0並且R1 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IB, a>0 and R 1 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IB的一些實施例中，a > 0並且R1 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IB, a>0 and R 1 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IB的一些實施例中，f > 0並且R2 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of formula IB, f> 0 and R 2 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IB的一些實施例中，f > 0並且R2 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IB, f>0 and R 2 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IB的一些實施例中，c > 0並且R3 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of Formula IB, c>0 and R 3 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IB的一些實施例中，c > 0並且R3 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula IB, c>0 and R 3 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式I之一些實施例中，二胺具有式IC，

Figure 02_image033
其中： Q3 選自由CR6 、SiR6 、GeR6 、以及PR6 所組成的群組； Q4 選自由CR7 、SiR7 、GeR7 、以及PR7 所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數；以及 f和g係相同或不同的，並且是從0~4的整數。In some embodiments of Formula I, the diamine has Formula IC,
Figure 02_image033
Q 3 is selected from the group consisting of CR 6 , SiR 6 , GeR 6 , and PR 6 ; Q 4 is selected from the group consisting of CR 7 , SiR 7 , GeR 7 , and PR 7 ; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy Groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic ring; R 6 It is the same as or different from R 7 and is selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar is the same or different at each occurrence, and is unsubstituted or substituted C 6-18 Hydrocarbon aryl; a is an integer from 0 to 4; and f and g are the same or different and are integers from 0 to 4.

在式IC的一些實施例中，Q3 = Q2 。In some embodiments of the IC, Q 3 = Q 2 .

在式IC的一些實施例中，Q3 ≠ Q2 。In some embodiments of the IC, Q 3 ≠ Q 2 .

在式IC的一些實施例中，Q3 = CR6 。In some embodiments of the IC, Q 3 = CR 6 .

在式IC的一些實施例中，Q3 = SiR6 。In some embodiments of the IC, Q 3 = SiR 6 .

在式IC的一些實施例中，Q3 = GeR6 。In some embodiments of Formula IC, Q 3 = GeR 6 .

在式IC的一些實施例中，Q3 = PR6 。In some embodiments of the formula IC, Q 3 = PR 6 .

在式IC的一些實施例中，Q4 = CR7 。In some embodiments of Formula IC, Q 4 = CR 7 .

在式IC的一些實施例中，Q4 = SiR7 。In some embodiments of the IC, Q 4 = SiR 7 .

在式IC的一些實施例中，Q4 = GeR7 。In some embodiments of the IC, Q 4 = GeR 7 .

在式IC的一些實施例中，Q4 = PR7 。In some embodiments of Formula IC, Q 4 = PR 7 .

在式IC的一些實施例中，f = 0。In some embodiments of the IC, f=0.

在式IC的一些實施例中，f = 1。In some embodiments of the IC, f=1.

在式IC的一些實施例中，f = 2。In some embodiments of the IC, f=2.

在式IC的一些實施例中，f = 3。In some embodiments of the IC, f=3.

在式IC的一些實施例中，f = 4。In some embodiments of the IC, f=4.

在式IC的一些實施例中，f > 0。In some embodiments of the IC, f>0.

在式IC的一些實施例中，g = 0。In some embodiments of Formula IC, g=0.

在式IC的一些實施例中，g = 1。In some embodiments of Formula IC, g=1.

在式IC的一些實施例中，g = 2。In some embodiments of Formula IC, g=2.

在式IC的一些實施例中，g = 3。In some embodiments of Formula IC, g=3.

在式IC的一些實施例中，g = 4。In some embodiments of Formula IC, g=4.

在式IC的一些實施例中，g >0。In some embodiments of Formula IC, g>0.

式IA中的a的所有以上描述的實施例同樣適用於式IC中的a。All the above-described embodiments of a in formula IA also apply to a in formula IC.

式I中的x > 0時的R1 的所有以上描述的實施例同樣適用於式IC中的a > 0時的R1 。All of the above-described embodiments of R 1 when x> 0 in Formula I are also applicable to R 1 when a> 0 in Formula IC.

式I中的y > 0時的R2 的所有以上描述的實施例同樣適用於式IC中的f > 0時的R2 。All the above-described embodiments of R 2 when y> 0 in Formula I are also applicable to R 2 when f> 0 in Formula IC.

式I中的z > 0時的R3 的所有以上描述的實施例同樣適用於式IC中的g > 0時的R3 。All of the above-described embodiments of R 3 when z> 0 in Formula I are also applicable to R 3 when g> 0 in Formula IC.

式I中的R6 、R7 、以及Ar的所有以上描述的實施例同樣適用於式IC中的R6 、R7 、以及Ar。All the above-described embodiments of R 6 , R 7 , and Ar in Formula I are also applicable to R 6 , R 7 , and Ar in Formula IC.

在式IC的一些實施例中，a > 0並且R1 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of formula IC, a> 0 and R 1 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IC的一些實施例中，a > 0並且R1 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of formula IC, a>0 and R 1 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IC的一些實施例中，f > 0並且R2 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of formula IC, f> 0 and R 2 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IC的一些實施例中，f > 0並且R2 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of formula IC, f>0 and R 2 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式IC的一些實施例中，g > 0並且R3 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of formula IC, g>0 and R 3 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式IC的一些實施例中，g > 0並且R3 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of formula IC, g>0 and R 3 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式I之一些實施例中，二胺具有式ID，

Figure 02_image035
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q4 選自由CR7 、SiR7 、GeR7 、以及PR7 所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數； d係從0~3的整數；以及 g係從0~4的整數。In some embodiments of formula I, the diamine has the formula ID,
Figure 02_image035
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 4 is selected from the group consisting of CR 7 , SiR 7 , GeR 7 , and PR 7 ; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, Alkoxy group, fluoroalkoxy group, unsubstituted or substituted aryloxy group, silyl group, and siloxy group, wherein adjacent R 1 groups can be connected together to form a fused aromatic ring; R 4 is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryl Oxygen, silyl, and silaneoxy groups; R 6 and R 7 are the same or different, and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar appears at each occurrence Are the same or different, and are unsubstituted or substituted C 6-18 hydrocarbon aryl; a is an integer from 0 to 4; d is an integer from 0 to 3; and g is an integer from 0 to 4.

式I中的x > 0時的R1 的所有以上描述的實施例同樣適用於式ID中的a > 0時的R1 。All the above-described embodiments of R 1 when x> 0 in Formula I are also applicable to R 1 when a> 0 in Formula ID.

式I中的y > 0時的R2 的所有以上描述的實施例同樣適用於式ID中的d > 0時的R2 。All the above-described embodiments of R 2 when y> 0 in Formula I are also applicable to R 2 when d> 0 in Formula ID.

式I中的z > 0時的R3 的所有以上描述的實施例同樣適用於式ID中的g > 0時的R3 。All the above-described embodiments of R 3 when z> 0 in Formula I are also applicable to R 3 when g> 0 in Formula ID.

式IA中的Q1 、a、以及d的所有以上描述的實施例同樣適用於式ID中的Q1 、a、以及d。All the above-described embodiments of Q 1 , a, and d in Formula IA are also applicable to Q 1 , a, and d in Formula ID.

式IC中的Q4 和g的所有以上描述的實施例同樣適用於式ID中的Q4 和g。All the above-described embodiments of Q 4 and g in Formula IC are also applicable to Q 4 and g in Formula ID.

式IA中的R4 的所有以上描述的實施例同樣適用於式ID中的R4 。All the above-described embodiments of R 4 in formula IA are equally applicable to R 4 in formula ID.

式I中的R6 、R7 、以及Ar的所有以上描述的實施例同樣適用於式ID中的R6 、R7 、以及Ar。All the above-described embodiments of R 6 , R 7 , and Ar in Formula I are also applicable to R 6 , R 7 , and Ar in Formula ID.

在式ID的一些實施例中，a > 0並且R1 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of formula ID, a> 0 and R 1 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式ID的一些實施例中，a > 0並且R1 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula ID, a>0 and R 1 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式ID的一些實施例中，d > 0並且R2 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of formula ID, d>0 and R 2 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式ID的一些實施例中，d > 0並且R2 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula ID, d>0 and R 2 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式ID的一些實施例中，g > 0並且R3 選自由F、氟烷基、全氟烷基、未取代或取代的烴芳基、以及未取代或取代的雜芳基所組成的群組。In some embodiments of formula ID, g>0 and R 3 is selected from the group consisting of F, fluoroalkyl, perfluoroalkyl, unsubstituted or substituted hydrocarbon aryl, and unsubstituted or substituted heteroaryl group.

在式ID的一些實施例中，g > 0並且R3 選自由F、三氟甲基、苯基、以及聯苯基所組成的群組。In some embodiments of Formula ID, g>0 and R 3 is selected from the group consisting of F, trifluoromethyl, phenyl, and biphenyl.

在式I之一些實施例中，二胺具有式IA-1，

Figure 02_image037
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q2 選自由CR5 、SiR5 、GeR5 、PR5 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數；以及 d和e係相同或不同的，並且是從0~3的整數。In some embodiments of Formula I, the diamine has Formula IA-1,
Figure 02_image037
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 2 is selected from the group consisting of CR 5 , SiR 5 , GeR 5 , PR 5 , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R 4 and R 5 are the same or different, and are selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy , Fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy; R 6 and R 7 are the same or different, and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2. The group consisting of 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; a is an integer from 0 to 4; and d and e are the same or Different, and is an integer from 0~3.

式IA中的Q1 、Q2 、R1 至R7 、Ar、a、d、以及e的所有以上描述的實施例同樣適用於式IA-1中的Q1 、Q2 、R1 至R7 、Ar、a、d、以及e。All the above-described embodiments of Q 1 , Q 2 , R 1 to R 7 , Ar, a, d, and e in formula IA are also applicable to Q 1 , Q 2 , R 1 to R in formula IA-1 7 , Ar, a, d, and e.

在式I之一些實施例中，二胺具有式IB-1，

Figure 02_image039
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q2 選自由CR5 、SiR5 、GeR5 、PR5 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R7 在每次出現時是相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數； c係從0~2的整數；以及 f係從0~4的整數。In some embodiments of Formula I, the diamine has Formula IB-1,
Figure 02_image039
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 2 is selected from the group consisting of CR 5 , SiR 5 , GeR 5 , PR 5 , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R 4 and R 5 are the same or different, and are selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy , Fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy; R 7 is the same or different at each occurrence and is selected from NH 2 , ArNH 2 , And the group formed by OArNH 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; a is an integer from 0 to 4; c is from 0 to An integer of 2; and f is an integer from 0 to 4.

式IB中的Q1 、Q2 、R1 至R5 、R7 、Ar、a、c、以及f的所有以上描述的實施例同樣適用於式IB-1中的Q1 、Q2 、R1 至R5 、R7 、Ar、a、c、以及f。All the above described embodiments of Q 1 , Q 2 , R 1 to R 5 , R 7 , Ar, a, c, and f in formula IB are also applicable to Q 1 , Q 2 , R in formula IB-1 1 to R 5 , R 7 , Ar, a, c, and f.

在式I之一些實施例中，二胺具有式ID-1，

Figure 02_image041
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q4 選自由CR7 、SiR7 、GeR7 、以及PR7 所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數； d係從0~3的整數；以及 g係從0~4的整數。In some embodiments of Formula I, the diamine has Formula ID-1,
Figure 02_image041
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 4 is selected from the group consisting of CR 7 , SiR 7 , GeR 7 , and PR 7 ; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, Alkoxy group, fluoroalkoxy group, unsubstituted or substituted aryloxy group, silyl group, and siloxy group, wherein adjacent R 1 groups can be connected together to form a fused aromatic ring; R 4 is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryl Oxygen, silyl, and silaneoxy groups; R 6 and R 7 are the same or different, and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar appears at each occurrence Are the same or different, and are unsubstituted or substituted C 6-18 hydrocarbon aryl; a is an integer from 0 to 4; d is an integer from 0 to 3; and g is an integer from 0 to 4.

式ID中的Q1 、Q4 、R1 至R4 、R6 、R7 、Ar、a、d、以及g的所有以上描述的實施例同樣適用於式ID-1中的Q1 、Q4 、R1 至R4 、R6 、R7 、Ar、a、d、以及g。All the above-described embodiments of Q 1 , Q 4 , R 1 to R 4 , R 6 , R 7 , Ar, a, d, and g in Formula ID are also applicable to Q 1 , Q in Formula ID-1 4, R 1 to R 4, R 6, R 7 , Ar, a, d, and g.

在式I之一些實施例中，二胺具有式ID-2，

Figure 02_image043
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q4 選自由CR7 、SiR7 、GeR7 、以及PR7 所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數； d係從0~3的整數；以及 g係從0~4的整數。In some embodiments of Formula I, the diamine has Formula ID-2,
Figure 02_image043
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 4 is selected from the group consisting of CR 7 , SiR 7 , GeR 7 , and PR 7 ; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, Alkoxy group, fluoroalkoxy group, unsubstituted or substituted aryloxy group, silyl group, and siloxy group, wherein adjacent R 1 groups can be connected together to form a fused aromatic ring; R 4 is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryl Oxygen, silyl, and silaneoxy groups; R 6 and R 7 are the same or different, and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar appears at each occurrence Are the same or different, and are unsubstituted or substituted C 6-18 hydrocarbon aryl; a is an integer from 0 to 4; d is an integer from 0 to 3; and g is an integer from 0 to 4.

式ID中的Q1 、Q4 、R1 至R4 、R6 、R7 、Ar、a、d、以及g的所有以上描述的實施例同樣適用於式ID-2中的Q1 、Q4 、R1 至R4 、R6 、R7 、Ar、a、d、以及g。All the above-described embodiments of Q 1 , Q 4 , R 1 to R 4 , R 6 , R 7 , Ar, a, d, and g in Formula ID are also applicable to Q 1 , Q in Formula ID-2 4, R 1 to R 4, R 6, R 7 , Ar, a, d, and g.

在式I之一些實施例中，二胺具有式IA-1a，

Figure 02_image045
其中： R8 和R9 係相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R8 和/或R9 基團可以連接在一起以形成稠環； h和i係相同或不同的，並且是從0~4的整數；以及 R1 -R5 、a、d、以及e如式IA中所定義。In some embodiments of Formula I, the diamine has Formula IA-1a,
Figure 02_image045
Wherein: R 8 and R 9 are the same or different, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluorine Alkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy groups, where adjacent R 8 and/or R 9 groups can be joined together to form a fused ring; h and i is the same or different, and is an integer from 0 to 4; and R 1 -R 5 , a, d, and e are as defined in formula IA.

在式IA-1a的一些實施例中，h = 0。In some embodiments of Formula IA-1a, h=0.

在式IA-1a的一些實施例中，h = 1。In some embodiments of Formula IA-1a, h=1.

在式IA-1a的一些實施例中，h = 2。In some embodiments of Formula IA-1a, h=2.

在式IA-1a的一些實施例中，h = 3。In some embodiments of Formula IA-1a, h=3.

在式IA-1a的一些實施例中，h = 4。In some embodiments of Formula IA-1a, h=4.

在式IA-1a的一些實施例中，h > 0。In some embodiments of Formula IA-1a, h>0.

在式IA-1a的一些實施例中，i = 0。In some embodiments of Formula IA-1a, i=0.

在式IA-1a的一些實施例中，i = 1。In some embodiments of Formula IA-1a, i=1.

在式IA-1a的一些實施例中，i = 2。In some embodiments of Formula IA-1a, i=2.

在式IA-1a的一些實施例中，i = 3。In some embodiments of Formula IA-1a, i=3.

在式IA-1a的一些實施例中，i = 4。In some embodiments of Formula IA-1a, i=4.

在式IA-1a的一些實施例中，i > 0。In some embodiments of Formula IA-1a, i>0.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係F。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is F.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係CN。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is CN.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C1-20 烷基；在一些實施例中係C1-10 烷基。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is C 1-20 alkyl; in some embodiments it is C 1-10 alkyl.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C1-20 氟烷基；在一些實施例中係C1-10 氟烷基。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is C 1-20 fluoroalkyl; in some embodiments it is C 1-10 fluoroalkyl.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C1-20 全氟烷基；在一些實施例中係C1-10 全氟烷基。In some embodiments of formula IA-1a, h>0 and at least one R 8 is C 1-20 perfluoroalkyl; in some embodiments it is C 1-10 perfluoroalkyl.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C1-20 烷氧基；在一些實施例中係C1-10 烷氧基。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is C 1-20 alkoxy; in some embodiments it is C 1-10 alkoxy.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C1-20 氟烷氧基；在一些實施例中係C1-10 氟烷氧基。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is C 1-20 fluoroalkoxy; in some embodiments it is C 1-10 fluoroalkoxy.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C1-20 全氟烷氧基；在一些實施例中係C1-10 全氟烷氧基。In some embodiments of formula IA-1a, h>0 and at least one R 8 is C 1-20 perfluoroalkoxy; in some embodiments it is C 1-10 perfluoroalkoxy.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係SiH3 。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is SiH 3 .

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C1-12 矽基；在一些實施例中係C3-6 矽基。In some embodiments of formula IA-1a, h> 0 and at least one R 8 is C 1-12 silicon-based; in some embodiments it is C 3-6 silicon-based.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C1-12 矽烷氧基；在一些實施例中係C3-6 矽烷氧基。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is C 1-12 silaneoxy; in some embodiments it is C 3-6 silaneoxy.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係未取代或取代的C6-30 烴芳基；在一些實施例中係未取代或取代的C6-18 烴芳基；在一些實施例中係未取代的。In some embodiments of formula IA-1a, h>0 and at least one R 8 is an unsubstituted or substituted C 6-30 hydrocarbon aryl group; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryl group Radical; in some embodiments it is unsubstituted.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C3‑30 雜芳基；在一些實施例中係未取代或取代的C3‑18 雜芳基；在一些實施例中係未取代的。In some embodiments of Formula IA-1a, h> 0 and at least one R 8 is C 3-30 heteroaryl; in some embodiments it is unsubstituted or substituted C 3-18 heteroaryl; in some implementations In the case of unsubstituted.

在式IA-1a的一些實施例中，h > 0且至少一個R8 係C6-30 烴芳氧基；在一些實施例中係未取代或取代的C6-18 烴芳氧基；在一些實施例中係未取代的。In some embodiments of Formula IA-1a, h>0 and at least one R 8 is a C 6-30 hydrocarbon aryloxy group; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryloxy group; In some embodiments, it is unsubstituted.

在一些實施例中，以上烴芳基、雜芳基、以及芳氧基基團中的任一個進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係F。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is F.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係CN。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is CN.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C1-20 烷基；在一些實施例中係C1-10 烷基。In some embodiments of formula IA-1a, i>0 and at least one R 9 is C 1-20 alkyl; in some embodiments it is C 1-10 alkyl.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C1-20 氟烷基；在一些實施例中係C1-10 氟烷基。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is C 1-20 fluoroalkyl; in some embodiments it is C 1-10 fluoroalkyl.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C1-20 全氟烷基；在一些實施例中係C1-10 全氟烷基。In some embodiments of formula IA-1a, i>0 and at least one R 9 is C 1-20 perfluoroalkyl; in some embodiments it is C 1-10 perfluoroalkyl.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C1-20 烷氧基；在一些實施例中係C1-10 烷氧基。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is C 1-20 alkoxy; in some embodiments it is C 1-10 alkoxy.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C1-20 氟烷氧基；在一些實施例中係C1-10 氟烷氧基。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is C 1-20 fluoroalkoxy; in some embodiments it is C 1-10 fluoroalkoxy.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C1-20 全氟烷氧基；在一些實施例中係C1-10 全氟烷氧基。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is C 1-20 perfluoroalkoxy; in some embodiments it is C 1-10 perfluoroalkoxy.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係SiH3 。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is SiH 3 .

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C1-12 矽基；在一些實施例中係C3-6 矽基。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is C 1-12 silicon-based; in some embodiments it is C 3-6 silicon-based.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C1-12 矽烷氧基；在一些實施例中係C3-6 矽烷氧基。In some embodiments of Formula IA-1a, i>0 and at least one R 9 is C 1-12 silaneoxy; in some embodiments it is C 3-6 silaneoxy.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係未取代或取代的C6-30 烴芳基；在一些實施例中係未取代或取代的C6-18 烴芳基；在一些實施例中係未取代的。In some embodiments of formula IA-1a, i>0 and at least one R 9 is an unsubstituted or substituted C 6-30 hydrocarbon aryl group; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryl group Radical; in some embodiments it is unsubstituted.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C3‑30 雜芳基；在一些實施例中係未取代或取代的C3‑18 雜芳基；在一些實施例中係未取代的。In some embodiments of Formula IA-1a, i> 0 and at least one R 9 is C 3-30 heteroaryl; in some embodiments it is unsubstituted or substituted C 3-18 heteroaryl; in some implementations In the case of unsubstituted.

在式IA-1a的一些實施例中，i > 0且至少一個R9 係C6-30 烴芳氧基；在一些實施例中係未取代或取代的C6-18 烴芳氧基；在一些實施例中係未取代的。In some embodiments of formula IA-1a, i>0 and at least one R 9 is a C 6-30 hydrocarbon aryloxy group; in some embodiments is an unsubstituted or substituted C 6-18 hydrocarbon aryloxy group; In some embodiments, it is unsubstituted.

在一些實施例中，以上烴芳基、雜芳基、以及芳氧基基團中的任一個進一步被一個或多個選自以下群組的取代基取代，該群組由以下組成：F、CN、烷基、氟烷基、烷氧基、氟烷氧基、矽基、以及矽烷氧基。In some embodiments, any of the above hydrocarbon aryl, heteroaryl, and aryloxy groups is further substituted with one or more substituents selected from the group consisting of: F, CN, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, silyl, and siloxy.

式IA中的R1 -R5 、a、d、以及e的所有以上描述的實施例同樣適用於式IA-1a中的R1 -R5 、a、d、以及e。In Formula IA R 1 -R 5, a, d , e, and all the embodiments described above apply equally to formula IA-1a is R 1 -R 5, a, d , and e.

在式I之一些實施例中，二胺具有式IA-1b，

Figure 02_image047
其中R1 -R5 、R8 、R9 、a、d、以及e如式IA-1a中所定義。In some embodiments of Formula I, the diamine has Formula IA-1b,
Figure 02_image047
Wherein R 1 -R 5 , R 8 , R 9 , a, d, and e are as defined in formula IA-1a.

式IA-1a中的R1 -R5 、R8 、R9 、a、d、e、h、以及i的所有以上描述的實施例同樣適用於式IA-1b中的R1 -R5 、R8 、R9 、a、d、e、h、以及i。All of the above described embodiments of R 1 -R 5 , R 8 , R 9 , a, d, e, h, and i in formula IA-1a are also applicable to R 1 -R 5 in formula IA-1b, R 8 , R 9 , a, d, e, h, and i.

在式I之一些實施例中，二胺具有式IB-1a，

Figure 02_image049
其中： R1 -R5 、a、c、以及f如式IB中所定義；以及 R8 、R9 、h以及i如式IA-1a中所定義。In some embodiments of Formula I, the diamine has Formula IB-1a,
Figure 02_image049
Wherein: R 1 -R 5 , a, c, and f are as defined in formula IB; and R 8 , R 9 , h, and i are as defined in formula IA-1a.

式IB中的R1 -R5 、a、c、以及f的所有以上描述的實施例同樣適用於式IB-1a中的R1 -R5 、a、c、以及f。Formula IB R 1 -R 5, a, c , f and all embodiments described above apply equally to formula IB-1a is R 1 -R 5, a, c , and f.

式IA-1a中的R8 、R9 、h、以及i的所有以上描述的實施例同樣適用於式IB-1a中的R8 、R9 、h、以及i。All the above-described embodiments of R 8 , R 9 , h, and i in Formula IA-1a are also applicable to R 8 , R 9 , h, and i in Formula IB-1a.

在式I之一些實施例中，二胺具有式IB-1b，

Figure 02_image051
其中R1 -R5 、R8 、R9 、a、c、f、h、以及i如式IB-1a中所定義。In some embodiments of Formula I, the diamine has Formula IB-1b,
Figure 02_image051
Where R 1 -R 5 , R 8 , R 9 , a, c, f, h, and i are as defined in formula IB-1a.

式IB-1a中的R1 -R5 、R8 、R9 、a、c、f、h、以及i的所有以上描述的實施例同樣適用於式IB-1b中的R1 -R5 、R8 、R9 、a、c、f、h、以及i。All the above-described embodiments of R 1 -R 5 , R 8 , R 9 , a, c, f, h, and i in formula IB-1a are also applicable to R 1 -R 5 in formula IB-1b, R 8 , R 9 , a, c, f, h, and i.

在式IC的一些實施例中，二胺具有式IC-1a，

Figure 02_image053
其中： R1 -R3 、a、f、以及g如式IC中所定義；以及 R8 、R9 、h以及i如式IA-1a中所定義。In some embodiments of formula IC, the diamine has the formula IC-1a,
Figure 02_image053
Wherein: R 1 -R 3 , a, f, and g are as defined in formula IC; and R 8 , R 9 , h, and i are as defined in formula IA-1a.

式IC中的R1 -R3 、a、f、以及g的所有以上描述的實施例同樣適用於式IC-1a中的R1 -R3 、a、f、以及g。Formula IC in which R 1 -R 3, a, f, and apply equally to the IC-1a R g embodiments described above all 1 -R 3, a, f, and g.

式IA-1a中的R8 、R9 、h、以及i的所有以上描述的實施例同樣適用於式IC-1a中的R8 、R9 、h、以及i。All the above-described embodiments of R 8 , R 9 , h, and i in Formula IA-1a are also applicable to R 8 , R 9 , h, and i in Formula IC-1a.

在式I之一些實施例中，二胺具有式IC-1b，

Figure 02_image055
其中R1 -R3 、R8 、R9 、a、f、g、h、以及i如式IC‑1a中所定義。In some embodiments of Formula I, the diamine has the formula IC-1b,
Figure 02_image055
Where R 1 -R 3 , R 8 , R 9 , a, f, g, h, and i are as defined in formula IC‑1a.

式IC-1a中的R1 -R3 、R8 、R9 、a、f、g、h、以及i的所有以上描述的實施例同樣適用於式IC-1b中的R1 -R3 、R8 、R9 、a、f、g、h、以及i。All the above-described embodiments of R 1 -R 3 , R 8 , R 9 , a, f, g, h, and i in formula IC-1a are also applicable to R 1 -R 3 in formula IC-1b, R 8 , R 9 , a, f, g, h, and i.

在式I之一些實施例中，二胺具有式ID‑1a，

Figure 02_image057
其中： R1 ‑R3 、a、d、以及g如式ID中所定義；以及 R8 、R9 、h以及i如式IA-1a中所定義。In some embodiments of formula I, the diamine has the formula ID-1a,
Figure 02_image057
Where: R 1 ‑R 3 , a, d, and g are as defined in formula ID; and R 8 , R 9 , h, and i are as defined in formula IA-1a.

式ID中的R1 至R3 、a、d、以及g的所有以上描述的實施例同樣適用於式ID‑1a中的R1 至R3 、a、d、以及g。Of formula ID, R 1 to R 3, a, d, g and all embodiments described above apply equally to ID-1a is R 1 to R 3, a, d, and g.

式IA-1a中的R8 、R9 、h、以及i的所有以上描述的實施例同樣適用於式ID-1a中的R8 、R9 、h、以及i。All the above-described embodiments of R 8 , R 9 , h, and i in Formula IA-1a are also applicable to R 8 , R 9 , h, and i in Formula ID-1a.

在式I之一些實施例中，二胺具有式ID‑1b，

Figure 02_image059
其中R1 -R3 、R8 、R9 、a、d、g、h、以及i如式ID-1a中所定義。In some embodiments of formula I, the diamine has the formula ID-1b,
Figure 02_image059
Where R 1 -R 3 , R 8 , R 9 , a, d, g, h, and i are as defined in formula ID-1a.

式ID-1a中的R1 -R3 、R8 、R9 、a、d、g、h、以及i的所有以上描述的實施例同樣適用於式ID-1b中的R1 -R3 、R8 、R9 、a、d、g、h、以及i。All of the above described embodiments of R 1 -R 3 , R 8 , R 9 , a, d, g, h, and i in formula ID-1a are also applicable to R 1 -R 3 in formula ID-1b, R 8 , R 9 , a, d, g, h, and i.

在式I之一些實施例中，二胺具有式ID-2a，

Figure 02_image061
其中： R1 ‑R3 、a、d、以及g如式ID中所定義；以及 R8 、R9 、h以及i如式IA-1a中所定義。In some embodiments of Formula I, the diamine has Formula ID-2a,
Figure 02_image061
Where: R 1 ‑R 3 , a, d, and g are as defined in formula ID; and R 8 , R 9 , h, and i are as defined in formula IA-1a.

式ID中的R1 至R3 、a、d、以及g的所有以上描述的實施例同樣適用於式ID‑2a中的R1 至R3 、a、d、以及g。Of formula ID, R 1 to R 3, a, d, g and all embodiments described above apply equally to the ID-2a R 1 to R 3, a, d, and g.

式IA-1a中的R8 、R9 、h、以及i的所有以上描述的實施例同樣適用於式ID-2a中的R8 、R9 、h、以及i。All the above-described embodiments of R 8 , R 9 , h, and i in Formula IA-1a are also applicable to R 8 , R 9 , h, and i in Formula ID-2a.

在式I之一些實施例中，二胺具有式ID-2b，

Figure 02_image063
其中R1 -R3 、R8 、R9 、a、d、h、i、以及k如式IB-1a中所定義。In some embodiments of Formula I, the diamine has Formula ID-2b,
Figure 02_image063
Where R 1 -R 3 , R 8 , R 9 , a, d, h, i, and k are as defined in formula IB-1a.

式ID-2a中的R1 -R3 、R8 、R9 、a、d、h、i、以及k的所有以上描述的實施例同樣適用於式ID-2b中的R1 -R3 、R8 、R9 、a、d、h、i、以及k。All the above described embodiments of R 1 -R 3 , R 8 , R 9 , a, d, h, i, and k in formula ID-2a are also applicable to R 1 -R 3 in formula ID-2b, R 8 , R 9 , a, d, h, i, and k.

新化合物可以使用將產生C-C或C-N鍵、或其他希望的鍵的任何技術製備。已知多種此類技術，如鈴木（Suzuki）、山本（Yamamoto）、施蒂勒（Stille）、根岸（Negishi）和金屬催化的C-N偶聯以及金屬催化和氧化的直接芳基化。示例性製備在實例中給出。The new compound can be prepared using any technique that will produce a C-C or C-N bond, or other desired bond. A variety of such technologies are known, such as Suzuki, Yamamoto, Stille, Negishi, and metal-catalyzed C-N coupling, and metal-catalyzed and oxidized direct arylation. Exemplary preparations are given in the examples.

式I之以上實施例中的任一個可以與其他實施例中的一個或多個組合，只要它們不是互相排斥的。例如，其中二胺具有式IA的實施例可以與其中Q1 係CR4 的實施例、其中R1 係C1-3 烷基的實施例、以及其中d = 0的實施例組合。所屬技術領域具有通常知識者將理解哪些實施例係相互排斥的並且因此將容易地能夠確定本申請所考慮的實施例的組合。Any of the above embodiments of Formula I can be combined with one or more of the other embodiments as long as they are not mutually exclusive. For example, an embodiment in which the diamine has Formula IA may be combined with an embodiment in which Q 1 is CR 4 , an embodiment in which R 1 is C 1-3 alkyl, and an embodiment in which d=0. Those of ordinary skill in the art will understand which embodiments are mutually exclusive and therefore will easily be able to determine the combination of embodiments considered in this application.

在下面示出了具有式I之化合物的一些非限制性實例。 化合物1

Figure 02_image065
化合物2
Figure 02_image067
化合物3
Figure 02_image069
化合物4
Figure 02_image071
化合物5
Figure 02_image073
Some non-limiting examples of compounds of formula I are shown below. Compound 1
Figure 02_image065
Compound 2
Figure 02_image067
Compound 3
Figure 02_image069
Compound 4
Figure 02_image071
Compound 5
Figure 02_image073

3.   具有式II之重複單元結構的聚醯胺酸3. Polyamide with repeating unit structure of formula II

本文所述的聚醯胺酸具有式II之重複單元結構，

Figure 02_image075
其中： Ra 在每次出現時是相同或不同的，並且表示一個或多個四羧酸組分殘基；並且 Rb 在每次出現時是相同或不同的，並且表示一個或多個芳香族二胺殘基； 其中10-100 mol%的Rb 係來自一種或多種具有式I之二胺的殘基。The polyamic acid described herein has a repeating unit structure of formula II,
Figure 02_image075
Where: R a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R b is the same or different at each occurrence and represents one or more aromatics Group diamine residues; where 10-100 mol% of R b are derived from one or more residues of the diamine of formula I.

在式II之一些實施例中，Ra 表示單個四羧酸組分殘基。In some of the embodiments of formula II, R a represents a single tetracarboxylic acid component residue.

在式II之一些實施例中，Ra 表示兩個四羧酸組分殘基。In some embodiments of Formula II, R a represents two tetracarboxylic acid component residues.

在式II之一些實施例中，Ra 表示三個四羧酸殘基。In some of the embodiments of formula II, R a represents a three tetracarboxylic acid residue.

在式II之一些實施例中，Ra 表示四個四羧酸殘基。In some of the embodiments of formula II, R a represents a four tetracarboxylic acid residue.

在式II之一些實施例中，Ra 表示一個或多個四羧酸二酐殘基。In some of the embodiments of formula II, R a represents one or more tetracarboxylic dianhydride residue.

合適的芳香族四羧酸二酐的實例包括但不限於均苯四甲酸二酐（PMDA）、3,3',4,4'-聯苯四甲酸二酐（BPDA）、4,4'-氧雙鄰苯二甲酸酐（ODPA）、4,4'-六氟異亞丙基雙鄰苯二甲酸二酐（6FDA）、3,3',4,4'-二苯甲酮四甲酸二酐（BTDA）、雙(1,3-二側氧基-1,3-二氫異苯并呋喃-5-羧酸)1,4-伸苯基酯（TAHQ）、3,3',4,4'-二苯碸四甲酸二酐（DSDA）、4,4'-雙酚-A二酐（BPADA）、氫醌二鄰苯二甲酸酐（HQDEA）、乙二醇雙(偏苯三酸酐)（TMEG-100）、4-(2,5-二側氧基四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二甲酸酐（DTDA）；4,4’-雙酚A二酐（BPADA）等及其組合。該等芳香族二酐可以視需要被本領域已知的基團取代，該等基團包括烷基、芳基、硝基、氰基、-N(R’)(R’’)、鹵素、羥基、羧基、烯基、炔基、環烷基、雜芳基、烷氧基、芳氧基、雜芳氧基、烷氧基羰基、全氟烷基、全氟烷氧基、芳基烷基、矽基、矽烷氧基、矽氧烷、硫代烷氧基、-S(O)2 -、-C(=O)-N(R’)(R’’)、(R’)(R’’)N-烷基、(R’)(R’’)N-烷氧基烷基、(R’)(R’’)N-烷基芳氧基烷基、-S(O)s -芳基（其中s = 0~2）或-S(O)s -雜芳基（其中s = 0~2）。每個R’和R’’獨立地是視需要取代的烷基、環烷基或芳基基團。R’和R’’，與它們所結合的氮原子一起，在某些實施例中可以形成環系統。取代基還可以是交聯基團。Examples of suitable aromatic tetracarboxylic dianhydrides include, but are not limited to, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'- Oxydiphthalic anhydride (ODPA), 4,4'-hexafluoroisopropylidene bisphthalic dianhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic acid dicarboxylic acid Anhydride (BTDA), bis(1,3-bi- pendant-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene ester (TAHQ), 3,3',4 ,4'-Diphenyltetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis (trimellitic anhydride) ( TMEG-100), 4-(2,5-bi- pendant tetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (DTDA); 4,4' -Bisphenol A dianhydride (BPADA), etc. and combinations thereof. The aromatic dianhydrides may be substituted with groups known in the art as needed, such groups include alkyl, aryl, nitro, cyano, -N(R')(R''), halogen, Hydroxy, carboxyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl Group, silyl group, siloxyl group, siloxane, thioalkoxy group, -S(O) 2 -, -C(=O)-N(R')(R''), (R')( R'')N-alkyl, (R')(R'')N-alkoxyalkyl, (R')(R'')N-alkylaryloxyalkyl, -S(O) s -aryl (where s = 0~2) or -S(O) s -heteroaryl (where s = 0~2). Each R'and R'' is independently an optionally substituted alkyl, cycloalkyl, or aryl group. R'and R'', together with the nitrogen atom to which they are bound, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

在式II之一些實施例中，Ra 表示一個或多個來自四羧酸二酐的殘基，該四羧酸二酐選自由PMDA、BPDA、6FDA、以及BTDA所組成的群組。In some embodiments of Formula II, R a represents one or more residues from tetracarboxylic dianhydride selected from the group consisting of PMDA, BPDA, 6FDA, and BTDA.

在式II之一些實施例中，Ra 表示PMDA殘基。In some of the embodiments of formula II, R a represents a residue of PMDA.

在式II之一些實施例中，Ra 表示BPDA殘基。In some of the embodiments of formula II, R a represents a residue of BPDA.

在式II之一些實施例中，Ra 表示6FDA殘基。In some of the embodiments of formula II, R a represents a residue of 6FDA.

在式II之一些實施例中，Ra 表示BTDA殘基。In some of the embodiments of formula II, R a represents a residue BTDA.

在式II之一些實施例中，Ra 表示PMDA殘基和BPDA殘基。In some of the embodiments of formula II, R a represents a residue of PMDA and BPDA residues.

在式II之一些實施例中，Ra 表示PMDA殘基和6FDA殘基。In some of the embodiments of formula II, R a represents a residue of PMDA and 6FDA residues.

在式II之一些實施例中，Ra 表示PMDA殘基和BTDA殘基。In some of the embodiments of formula II, R a represents a residue of PMDA and BTDA residues.

在式II之一些實施例中，Ra 表示BPDA殘基和6FDA殘基。In some of the embodiments of formula II, R a represents a residue BPDA and 6FDA residues.

在式II之一些實施例中，Ra 表示BPDA殘基和BTDA殘基。In some of the embodiments of formula II, R a represents a residue of BPDA and BTDA residues.

在式II之一些實施例中，Ra 表示6FDA殘基和BTDA殘基。In some of the embodiments of formula II, R a represents a residue, and BTDA 6FDA residues.

在式II之一些實施例中，Ra 表示PMDA殘基、BPDA殘基、以及6FDA殘基。In some of the embodiments of formula II, R a represents a residue PMDA, BPDA residues, and residues 6FDA.

在式II中，10-100 mol%的Rb 表示來自一種或多種具有如以上示出的式I之二胺的二胺殘基。In formula II, 10-100 mol% of R b represents a diamine residue from one or more diamines having formula I as shown above.

在式II之一些實施例中，10-100 mol%的Rb 表示來自一種具有如以上示出的式I之二胺的二胺殘基。In some embodiments of Formula II, 10-100 mol% of R b represents a diamine residue from a diamine having Formula I as shown above.

在式II之一些實施例中，10-100 mol%的Rb 表示來自兩種不同的、二者均具有如以上示出的式I之二胺的二胺殘基。In some embodiments of formula II, 10-100 mol% of R b represents diamine residues from two different, both of which have the diamine of formula I as shown above.

在式II之一些實施例中，10-100 mol%的Rb 表示來自三種不同的、全部都具有如以上示出的式I之二胺的二胺殘基。In some embodiments of formula II, 10-100 mol% of R b represents diamine residues from three different, all having the diamine of formula I as shown above.

在式II之一些實施例中，10-100 mol%的Rb 表示來自四種或更多種不同的、全部都具有如以上示出的式I之二胺的二胺殘基。In some embodiments of formula II, 10-100 mol% of R b represents diamine residues from four or more different, all having the diamine of formula I as shown above.

在式II之一些實施例中，20-100 mol%的Rb 係來自一種或多種具有式I之二胺的殘基；在一些實施例中，30-100 mol%；在一些實施例中，40-100 mol%；在一些實施例中，50-100 mol%；在一些實施例中，60-100 mol%；在一些實施例中，70-100 mol%；在一些實施例中，80-100 mol%；在一些實施例中，90-100 mol%；在一些實施例中，100%。In some embodiments of formula II, 20-100 mol% of R b is derived from one or more residues having a diamine of formula I; in some embodiments, 30-100 mol%; in some embodiments, 40-100 mol%; in some embodiments, 50-100 mol%; in some embodiments, 60-100 mol%; in some embodiments, 70-100 mol%; in some embodiments, 80- 100 mol%; in some embodiments, 90-100 mol%; in some embodiments, 100%.

式II中的式I之以上實施例中的任一個可以與其他實施例中的一個或多個組合，只要它們不是互相排斥的。Any of the above embodiments of Formula I in Formula II may be combined with one or more of the other embodiments as long as they are not mutually exclusive.

在式II之一些實施例中，Rb 表示來自一種或多種具有式I之二胺的二胺殘基以及至少一個附加的二胺殘基。In some embodiments of Formula II, R b represents a diamine residue from one or more diamines having Formula I and at least one additional diamine residue.

在式II之一些實施例中，Rb 表示來自一種或多種具有式I之二胺的二胺殘基以及一個附加的二胺殘基。In some embodiments of Formula II, R b represents a diamine residue from one or more diamines having Formula I and an additional diamine residue.

在式II之一些實施例中，Rb 表示來自一種或多種具有式I之二胺的二胺殘基以及兩個附加的二胺殘基。In some embodiments of Formula II, R b represents a diamine residue from one or more diamines having Formula I and two additional diamine residues.

在式II之一些實施例中，Rb 表示來自一種或多種具有式I之二胺的二胺殘基以及三個附加的二胺殘基。In some embodiments of Formula II, R b represents a diamine residue from one or more diamines having Formula I and three additional diamine residues.

在一些實施例中，附加的芳香族二胺選自下組，該群組由以下組成：對苯二胺（PPD）、2,2'-二甲基-4,4'-二胺基聯苯（間聯甲苯胺）、3,3'-二甲基-4,4'-二胺基聯苯（鄰聯甲苯胺）、3,3'-二羥基-4,4'-二胺基聯苯（HAB）、9,9'-雙(4-胺基苯基)茀（FDA）、鄰聯甲苯胺碸（TSN）、2,3,5,6-四甲基-1,4-伸苯基二胺（TMPD）、2,4-二胺基-1,3,5-三甲苯（DAM）、3,3',5,5'-四甲基聯苯胺（3355TMB）、2,2'-雙(三氟甲基)聯苯胺（22TFMB或TFMB）、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷（BAPP）、4,4'-亞甲基二苯胺（MDA）、4,4'-[1,3-伸苯基雙(1-甲基-亞乙基)]雙苯胺（Bis-M）、4,4'-[1,4-伸苯基雙(1-甲基-亞乙基)]雙苯胺（Bis-P）、4,4'-氧基二苯胺（4,4’-ODA）、間伸苯基二胺（MPD）、3,4'-氧基二苯胺（3,4’-ODA）、3,3'-二胺基二苯碸（3,3’-DDS）、4,4'-二胺基二苯碸（4,4’-DDS）、4,4'-二胺基二苯硫醚（ASD）、2,2-雙[4-(4-胺基-苯氧基)苯基]碸（BAPS）、2,2-雙[4-(3-胺基苯氧基)-苯基]碸（m-BAPS）、1,4'-雙(4-胺基苯氧基)苯（TPE-Q）、1,3'-雙(4-胺基苯氧基)苯（TPE-R）、1,3'-雙(4-胺基-苯氧基)苯（APB-133）、4,4'-雙(4-胺基苯氧基)聯苯（BAPB）、4,4'-二胺基苯醯替苯胺（DABA）、亞甲基雙(鄰胺基苯甲酸)（MBAA）、1,3'-雙(4-胺基苯氧基)-2,2-二甲基丙烷（DANPG）、1,5-雙(4-胺基苯氧基)戊烷（DA5MG）、2,2'-雙[4-(4-胺基苯氧基苯基)]六氟丙烷（HFBAPP）、2,2-雙(4-胺基苯基)六氟丙烷（Bis-A-AF）、2,2-雙(3-胺基-4-羥苯基)六氟丙烷（Bis-AP-AF）、2,2-雙(3-胺基-4-甲基苯基)六氟丙烷（Bis-AT-AF）、4,4'-雙(4-胺基-2-三氟甲基苯氧基)聯苯（6BFBAPB）、3,3'5,5'-四甲基-4,4'-二胺基二苯基甲烷（TMMDA）等及其組合。In some embodiments, the additional aromatic diamine is selected from the group consisting of p-phenylenediamine (PPD), 2,2'-dimethyl-4,4'-diamine Benzene (m-tolidine), 3,3'-dimethyl-4,4'-diaminobiphenyl (o-tolidine), 3,3'-dihydroxy-4,4'-diamino Biphenyl (HAB), 9,9'-bis(4-aminophenyl) stilbene (FDA), o-toluidine (TSN), 2,3,5,6-tetramethyl-1,4- Phenylenediamine (TMPD), 2,4-diamino-1,3,5-trimethylbenzene (DAM), 3,3',5,5'-tetramethylbenzidine (3355TMB), 2, 2'-bis(trifluoromethyl)benzidine (22TFMB or TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-methylene Diphenylamine (MDA), 4,4'-[1,3-phenylene bis(1-methyl-ethylene)] bisaniline (Bis-M), 4,4'-[1,4- Phenylbis(1-methyl-ethylene)] bisaniline (Bis-P), 4,4'-oxydiphenylamine (4,4'-ODA), m-phenylene diamine (MPD) , 3,4'-oxydiphenylamine (3,4'-ODA), 3,3'-diaminodiphenylbenzene (3,3'-DDS), 4,4'-diaminodiphenylbenzene (4,4'-DDS), 4,4'-diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-amino-phenoxy)phenyl] benzene (BAPS) , 2,2-bis[4-(3-aminophenoxy)-phenyl] benzene (m-BAPS), 1,4'-bis(4-aminophenoxy)benzene (TPE-Q) , 1,3'-bis(4-aminophenoxy)benzene (TPE-R), 1,3'-bis(4-aminophenoxy)benzene (APB-133), 4,4' -Bis(4-aminophenoxy)biphenyl (BAPB), 4,4'-diaminobenzidine (DABA), methylene bis(o-aminobenzoic acid) (MBAA), 1, 3'-bis(4-aminophenoxy)-2,2-dimethylpropane (DANPG), 1,5-bis(4-aminophenoxy)pentane (DA5MG), 2,2' -Bis[4-(4-aminophenoxyphenyl)] hexafluoropropane (HFBAPP), 2,2-bis(4-aminophenyl) hexafluoropropane (Bis-A-AF), 2, 2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (Bis-AP-AF), 2,2-bis(3-amino-4-methylphenyl) hexafluoropropane (Bis- AT-AF), 4,4'-bis(4-amino-2-trifluoromethylphenoxy) biphenyl (6BFBAPB), 3,3'5,5'-tetramethyl-4,4' -Diaminodiphenylmethane (TMMDA), etc. and combinations thereof.

在式II之一些實施例中，Rb 表示來自一種或多種具有式I之二胺的二胺殘基以及來自至少一種附加的二胺的二胺殘基，其中該附加的二胺選自由PPD、4,4’-ODA、3,4’-ODA、TFMB、Bis-A-AF、Bis-AT-AF、以及Bis-P所組成的群組。In some embodiments of formula II, R b represents a diamine residue from one or more diamines having the diamine of formula I and a diamine residue from at least one additional diamine, wherein the additional diamine is selected from PPD , 4,4'-ODA, 3,4'-ODA, TFMB, Bis-A-AF, Bis-AT-AF, and Bis-P.

在式II之一些實施例中，由單酐單體得到的部分作為封端基團存在。In some embodiments of Formula II, the moiety derived from the monoanhydride monomer is present as a capping group.

在一些實施例中，該等單酐單體選自下組，該組由鄰苯二甲酸酐和類似物以及其衍生物組成。In some embodiments, the monoanhydride monomers are selected from the group consisting of phthalic anhydride and analogs and derivatives thereof.

在一些實施例中，該等單酐以全部四羧酸組成物的最高達5 mol%的量存在。In some embodiments, the monoanhydrides are present in an amount of up to 5 mol% of the total tetracarboxylic acid composition.

在式II之一些實施例中，由單胺單體得到的部分作為封端基團存在。In some embodiments of formula II, the moiety derived from the monoamine monomer is present as a capping group.

在一些實施例中，該等單胺單體選自下組，該組由苯胺和類似物以及其衍生物組成。In some embodiments, the monoamine monomers are selected from the group consisting of aniline and analogs and derivatives thereof.

在一些實施例中，該等單胺以全部胺組成物的最高達5 mol%的量存在。In some embodiments, the monoamines are present in an amount of up to 5 mol% of the total amine composition.

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有大於100,000的重量平均分子量（MW ）。In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight greater than 100,000 (M W).

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有大於150,000的重量平均分子量（MW ）。In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M W ) greater than 150,000.

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有大於200,000的重量平均分子量（MW ）。In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M W ) greater than 200,000.

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有大於250,000的重量平均分子量（MW ）。In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight greater than 250,000 (M W).

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有大於300,000的重量平均分子量（MW ）。In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M W ) greater than 300,000.

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有在100,000與400,000之間的重量平均分子量（MW ）。In some embodiments, gel permeation chromatography with polystyrene standards, polyamide acid having a weight average molecular weight (M W) of between 100,000 and 400,000.

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有在200,000與400,000之間的重量平均分子量（MW ）。In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M W ) between 200,000 and 400,000.

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有在250,000與350,000之間的重量平均分子量（MW ）。In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M W ) between 250,000 and 350,000.

在一些實施例中，基於凝膠滲透層析法與聚苯乙烯標準品，聚醯胺酸具有在200,000與300,000之間的重量平均分子量（MW ）。In some embodiments, based on gel permeation chromatography and polystyrene standards, the polyamic acid has a weight average molecular weight (M W ) between 200,000 and 300,000.

聚醯胺酸的以上實施例中的任一個可以與其他實施例中的一個或多個組合，只要它們不是互相排斥的。Any of the above embodiments of polyamic acid may be combined with one or more of other embodiments as long as they are not mutually exclusive.

總體聚醯胺酸組成可以經由本領域通常使用的符號來命名。例如，可以將具有100% ODPA的四羧酸組分以及90 mol%的Bis-P和10 mol%的TFMB的二胺組分的聚醯胺酸表示為： ODPA//Bis-P/22TFMB  100//90/10。The overall polyamide composition can be named via symbols commonly used in the art. For example, a polyamic acid having a tetracarboxylic acid component of 100% ODPA and a diamine component of 90 mol% Bis-P and 10 mol% TFMB can be expressed as: ODPA//Bis-P/22TFMB 100//90/10.

還提供了一種液體組成物，其包含 (a) 具有式II之重複單元的聚醯胺酸和 (b) 高沸點非質子溶劑。該液體組成物在文本中還被稱為「聚醯胺酸溶液」。Also provided is a liquid composition comprising (a) a polyamic acid having a repeating unit of formula II and (b) a high-boiling aprotic solvent. This liquid composition is also called "polyamide solution" in the text.

在一些實施例中，該高沸點非質子溶劑具有150ºC或更高的沸點。In some embodiments, the high-boiling aprotic solvent has a boiling point of 150°C or higher.

在一些實施例中，該高沸點非質子溶劑具有175ºC或更高的沸點。In some embodiments, the high-boiling aprotic solvent has a boiling point of 175°C or higher.

在一些實施例中，該高沸點非質子溶劑具有200ºC或更高的沸點。In some embodiments, the high-boiling aprotic solvent has a boiling point of 200°C or higher.

在一些實施例中，該高沸點非質子溶劑係極性溶劑。在一些實施例中，該溶劑具有大於20的介電常數。In some embodiments, the high-boiling aprotic solvent is a polar solvent. In some embodiments, the solvent has a dielectric constant greater than 20.

高沸點非質子溶劑的一些實例包括但不限於N-甲基-2-吡咯啶酮（NMP）、二甲基乙醯胺（DMAc）、二甲亞碸（DMSO）、二甲基甲醯胺（DMF）、γ-丁內酯、二丁基卡必醇、丁基卡必醇乙酸酯、二甘醇單***乙酸酯、丙二醇單甲醚乙酸酯等及其組合。Some examples of high-boiling aprotic solvents include, but are not limited to, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), dimethylformamide (DMF), γ-butyrolactone, dibutyl carbitol, butyl carbitol acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. and combinations thereof.

在液體組成物的一些實施例中，該溶劑選自由NMP、DMAc、和DMF組成的組。In some embodiments of the liquid composition, the solvent is selected from the group consisting of NMP, DMAc, and DMF.

在液體組成物的一些實施例中，該溶劑係NMP。In some embodiments of the liquid composition, the solvent is NMP.

在液體組成物的一些實施例中，該溶劑係DMAc。In some embodiments of the liquid composition, the solvent is DMAc.

在液體組成物的一些實施例中，該溶劑係DMF。In some embodiments of the liquid composition, the solvent is DMF.

在液體組成物的一些實施例中，該溶劑係γ‑丁內酯。In some embodiments of the liquid composition, the solvent is γ-butyrolactone.

在液體組成物的一些實施例中，該溶劑係二丁基卡必醇。In some embodiments of the liquid composition, the solvent is dibutyl carbitol.

在液體組成物的一些實施例中，該溶劑係丁基卡必醇乙酸酯。In some embodiments of the liquid composition, the solvent is butyl carbitol acetate.

在液體組成物的一些實施例中，該溶劑係二甘醇單***乙酸酯。In some embodiments of the liquid composition, the solvent is diethylene glycol monoethyl ether acetate.

在液體組成物的一些實施例中，該溶劑係丙二醇單***乙酸酯。In some embodiments of the liquid composition, the solvent is propylene glycol monoethyl ether acetate.

在一些實施例中，在液體組成物中使用超過一種以上指出的高沸點非質子溶劑。In some embodiments, more than one high boiling aprotic solvent indicated above is used in the liquid composition.

在一些實施例中，在液體組成物中使用附加的共溶劑。In some embodiments, additional co-solvents are used in the liquid composition.

在一些實施例中，該液體組成物係在 > 99重量%的高沸點非質子溶劑中的 > 1重量%的聚醯胺酸。In some embodiments, the liquid composition is> 1% by weight of polyamide in> 99% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在95重量%~99重量%的高沸點非質子溶劑中的1重量%~5重量%的聚醯胺酸。In some embodiments, the liquid composition is 1% to 5% by weight of polyamide in 95% to 99% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在90重量%~95重量%的高沸點非質子溶劑中的5重量%~10重量%的聚醯胺酸。In some embodiments, the liquid composition is 5% to 10% by weight of polyamide in 90% to 95% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在85重量%~90重量%的高沸點非質子溶劑中的10重量%~15重量%的聚醯胺酸。In some embodiments, the liquid composition is 10% to 15% by weight of polyamide in 85% to 90% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在80重量%~85重量%的高沸點非質子溶劑中的15重量%~20重量%的聚醯胺酸。In some embodiments, the liquid composition is 15%-20% by weight of polyamide in 80%-85% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在75重量%~80重量%的高沸點非質子溶劑中的20重量%~25重量%的聚醯胺酸。In some embodiments, the liquid composition is 20% to 25% by weight of polyamide in 75% to 80% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在70重量%~75重量%的高沸點非質子溶劑中的25重量%~30重量%的聚醯胺酸。In some embodiments, the liquid composition is 25% to 30% by weight of polyamide in 70% to 75% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在65重量%~70重量%的高沸點非質子溶劑中的30重量%~35重量%的聚醯胺酸。In some embodiments, the liquid composition is 30% to 35% by weight of polyamide in 65% to 70% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在60重量%~65重量%的高沸點非質子溶劑中的35重量%~40重量%的聚醯胺酸。In some embodiments, the liquid composition is 35% to 40% by weight of polyamide in 60% to 65% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在55重量%~60重量%的高沸點非質子溶劑中的40重量%~45重量%的聚醯胺酸。In some embodiments, the liquid composition is 40% to 45% by weight of polyamide in 55% to 60% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在50重量%~55重量%的高沸點非質子溶劑中的45重量%~50重量%的聚醯胺酸。In some embodiments, the liquid composition is 45% to 50% by weight of polyamide in 50% to 55% by weight of a high-boiling aprotic solvent.

在一些實施例中，該液體組成物係在50重量%的高沸點非質子溶劑中的50重量%的聚醯胺酸。In some embodiments, the liquid composition is 50% by weight of polyamide in 50% by weight of a high-boiling aprotic solvent.

聚醯胺酸溶液可以視需要進一步含有許多添加劑中的任一種。此類添加劑可以是：抗氧化劑、熱穩定劑、粘合促進劑、偶聯劑（例如矽烷）、無機填料或各種增強劑，只要它們不有害地影響所希望的聚醯亞胺特性。The polyamide solution may further contain any one of many additives as necessary. Such additives may be: antioxidants, heat stabilizers, adhesion promoters, coupling agents (such as silanes), inorganic fillers, or various reinforcing agents, as long as they do not deleteriously affect the desired properties of the polyimide.

聚醯胺酸溶液可以使用關於引入組分（即，單體和溶劑）的各種可供使用的方法進行製備。生產聚醯胺酸溶液的一些方法包括： (a) 一種方法，其中將二胺組分和二酐組分預先混合在一起且然後將該混合物在攪拌同時分批加入到溶劑中。The polyamic acid solution can be prepared using various methods available for introducing components (ie, monomers and solvents). Some methods for producing polyamide solutions include: (a) A method in which the diamine component and the dianhydride component are mixed together in advance and then the mixture is added to the solvent in portions while stirring.

(b) 一種方法，其中將溶劑加入到二胺和二酐組分的攪拌混合物中。（與上面的 (a) 相反） (c) 一種方法，其中將二胺單獨地溶解在溶劑中，且然後以允許控制反應速率的比例向其中加入二酐。(b) A method in which a solvent is added to a stirred mixture of diamine and dianhydride components. (Contrary to (a) above) (c) A method in which the diamine is separately dissolved in a solvent, and then the dianhydride is added thereto in a ratio that allows the reaction rate to be controlled.

(d) 一種方法，其中將二酐組分單獨地溶解在溶劑中，且然後以允許控制反應速率的比例向其中加入胺組分。(d) A method in which the dianhydride component is separately dissolved in a solvent, and then the amine component is added thereto in a ratio that allows the reaction rate to be controlled.

(e) 一種方法，其中將二胺組分和二酐組分分別溶解在溶劑中且然後將該等溶液在反應器中混合。(e) A method in which the diamine component and the dianhydride component are separately dissolved in a solvent and then such solutions are mixed in the reactor.

(f) 一種方法，其中預先形成具有過量胺組分的聚醯胺酸和具有過量二酐組分的另一聚醯胺酸，且然後使其在反應器中彼此反應，特別是以產生非無規或嵌段共聚物的這樣的方式彼此反應。(f) A method in which a polyamic acid having an excess amine component and another polyamic acid having an excess dianhydride component are formed in advance, and then reacted with each other in the reactor, in particular to produce Random or block copolymers react with each other in this way.

(g) 一種方法，其中首先使特定部分的胺組分和二酐組分反應，且然後使殘餘的二胺組分反應，或反之亦然。(g) A method in which a specific portion of the amine component and the dianhydride component are reacted first, and then the residual diamine component is reacted, or vice versa.

(h) 一種方法，其中將該等組分以部分或整體按任何順序加入到部分或全部溶劑中，此外其中部分或全部任何組分可以作為部分或全部溶劑中的溶液加入。(h) A method in which these components are added to part or all of the solvent in any order in part or in whole, and in addition part or all of any of the components may be added as a solution in part or all of the solvent.

(i) 一種方法，其中首先使二酐組分之一與二胺組分之一反應，從而得到第一聚醯胺酸。然後使另一種二酐組分與另一種胺組分反應以得到第二聚醯胺酸。然後在成膜之前以多種方式中的任一種將該等聚醯胺酸組合。(i) A method in which one of the dianhydride components and one of the diamine components are first reacted to obtain the first polyamic acid. Then another dianhydride component is reacted with another amine component to obtain a second polyamide. This polyamic acid is then combined in any of a variety of ways before film formation.

一般來說，由以上揭露的聚醯胺酸溶液製備方法中的任一種可以獲得聚醯胺酸溶液。Generally speaking, a polyamic acid solution can be obtained from any of the above disclosed methods for preparing a polyamic acid solution.

然後可以將聚醯胺酸溶液過濾一次或多次以便減少顆粒含量。由這種經過濾的溶液產生的聚醯亞胺膜可以顯示出減少的缺陷數量，且由此在本文揭露的電子應用中產生優異性能。可以藉由雷射粒子計數器測試來進行對過濾效率的評估，其中將聚醯胺酸溶液的代表性樣品澆注到5’’矽晶圓上。在軟烘/乾燥之後，藉由任何數量的雷射粒子計數技術在可商購且本領域已知的儀器上評估膜的顆粒含量。The polyamide solution can then be filtered one or more times to reduce the particle content. The polyimide membrane produced from this filtered solution can show a reduced number of defects, and thus produce excellent performance in the electronic applications disclosed herein. Filtration efficiency can be evaluated by laser particle counter testing, where a representative sample of polyamide solution is cast onto a 5’’ silicon wafer. After soft baking/drying, the particle content of the film is evaluated by any number of laser particle counting techniques on commercially available and known in the art instruments.

在一些實施例中，製備聚醯胺酸溶液並過濾以產生小於40個顆粒的顆粒含量，如藉由雷射粒子計數器測試所測量。In some embodiments, a polyamide solution is prepared and filtered to produce a particle content of less than 40 particles, as measured by a laser particle counter test.

在一些實施例中，製備聚醯胺酸溶液並過濾以產生小於30個顆粒的顆粒含量，如藉由雷射粒子計數器測試所測量。In some embodiments, a polyamide solution is prepared and filtered to produce a particle content of less than 30 particles, as measured by a laser particle counter test.

在一些實施例中，製備聚醯胺酸溶液並過濾以產生小於20個顆粒的顆粒含量，如藉由雷射粒子計數器測試所測量。In some embodiments, a polyamide solution is prepared and filtered to produce a particle content of less than 20 particles, as measured by a laser particle counter test.

在一些實施例中，製備聚醯胺酸溶液並過濾以產生小於10個顆粒的顆粒含量，如藉由雷射粒子計數器測試所測量。In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content of less than 10 particles, as measured by a laser particle counter test.

在一些實施例中，製備聚醯胺酸溶液並過濾以產生在2個顆粒與8個顆粒之間的顆粒含量，如藉由雷射粒子計數器測試所測量。In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content between 2 particles and 8 particles, as measured by a laser particle counter test.

在一些實施例中，製備聚醯胺酸溶液並過濾以產生在4個顆粒與6個顆粒之間的顆粒含量，如藉由雷射粒子計數器測試所測量。In some embodiments, a polyamic acid solution is prepared and filtered to produce a particle content between 4 particles and 6 particles, as measured by a laser particle counter test.

聚醯胺酸溶液的示例性製備在實例中給出。Exemplary preparations of polyamic acid solutions are given in the examples.

4.   具有式III的重複單元結構的聚醯亞胺4. Polyimide with repeating unit structure of formula III

提供了一種具有式III的重複單元結構的聚醯亞胺，

Figure 02_image077
其中： Ra 在每次出現時是相同或不同的，並且表示一個或多個四羧酸組分殘基；以及 Rb 在每次出現時是相同或不同的，並且表示一個或多個芳香族二胺殘基； 其中10~100 mol%的Rb 係來自一種或多種具有式I之二胺的殘基。Provided is a polyimide having a repeating unit structure of formula III,
Figure 02_image077
Where: R a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R b is the same or different at each occurrence and represents one or more aromatics Group diamine residues; where 10 to 100 mol% of R b is derived from one or more residues of the diamine of formula I.

式II中的Ra 和Rb 的所有以上描述的實施例同樣適用於式III中的Ra 和Rb 。All Formula II R a and R b are the same applies to the above embodiment of Formula III R a and R b are described.

式III中的式I之以上實施例中的任一個可以與其他實施例中的一個或多個組合，只要它們不是互相排斥的。Any of the above embodiments of Formula I in Formula III may be combined with one or more of the other embodiments as long as they are not mutually exclusive.

聚醯亞胺可以由任何合適的聚醯亞胺先質（如聚醯胺酸、聚醯胺酸酯、聚異醯亞胺、和聚醯胺酸鹽）製成。The polyimide can be made of any suitable polyimide precursor (such as polyamic acid, polyamic acid ester, polyisoimide, and polyamidate).

還提供了一種聚醯亞胺膜，其中該聚醯亞胺具有如以上描述的式III的重複單元結構。There is also provided a polyimide film, wherein the polyimide has a repeating unit structure of formula III as described above.

聚醯亞胺膜可以藉由將聚醯亞胺先質塗覆到基板上並且隨後醯亞胺化來製成。這可以藉由熱轉化方法或化學轉化方法來實現。The polyimide film can be made by coating a precursor of polyimide onto a substrate and then subjecting it to imidization. This can be achieved by thermal conversion methods or chemical conversion methods.

此外，如果聚醯亞胺可溶於適合的塗覆溶劑中，則它可以作為溶解在適合的塗覆溶劑中的已經醯亞胺化的聚合物提供並且作為聚醯亞胺塗覆。In addition, if the polyimide is soluble in a suitable coating solvent, it can be provided as a polymer that has been imidized in a suitable coating solvent and coated as a polyimide.

在一些實施例中，具有式III的重複單元的聚醯亞胺膜具有高玻璃化轉變溫度和低光延遲兩者。In some embodiments, the polyimide film having a repeating unit of Formula III has both a high glass transition temperature and low light retardation.

在聚醯亞胺膜的一些實施例中，對於在超過350ºC的溫度下固化的聚醯亞胺膜，玻璃化轉變溫度（Tg ）係大於300ºC；在一些實施例中，係大於370ºC；在一些實施例中，係大於380ºC。In some embodiments of the polyimide film, the glass transition temperature (T g ) is greater than 300ºC for the polyimide film cured at a temperature exceeding 350ºC; in some embodiments, it is greater than 370ºC; In some embodiments, it is greater than 380ºC.

在聚醯亞胺膜的一些實施例中，光延遲在550 nm處係小於120；在一些實施例中，係小於100；在一些實施例中，係小於90。In some embodiments of the polyimide film, the optical retardation is less than 120 at 550 nm; in some embodiments, it is less than 100; in some embodiments, it is less than 90.

在聚醯亞胺膜的一些實施例中，對於第一次測量，平面內熱膨脹係數（CTE）在50ºC與200ºC之間係小於45 ppm/ºC；在一些實施例中，係小於30 ppm/ºC；在一些實施例中，係小於20 ppm/ºC；在一些實施例中，係小於15 ppm/ºC。In some embodiments of the polyimide film, for the first measurement, the in-plane thermal expansion coefficient (CTE) between 50ºC and 200ºC is less than 45 ppm/ºC; in some embodiments, it is less than 30 ppm/ºC ; In some embodiments, it is less than 20 ppm/ºC; in some embodiments, it is less than 15 ppm/ºC.

在聚醯亞胺膜的一些實施例中，對於第二次測量，平面內熱膨脹係數（CTE）在50ºC與200ºC之間係小於75 ppm/ºC；在一些實施例中，係小於65 ppm/ºC。In some embodiments of the polyimide film, for the second measurement, the coefficient of in-plane thermal expansion (CTE) between 50ºC and 200ºC is less than 75 ppm/ºC; in some embodiments, it is less than 65 ppm/ºC .

在聚醯亞胺膜的一些實施例中，1% TGA失重溫度係大於350ºC；在一些實施例中，係大於400ºC；在一些實施例中，係大於450ºC。In some embodiments of the polyimide film, the 1% TGA weightlessness temperature is greater than 350ºC; in some embodiments, it is greater than 400ºC; in some embodiments, it is greater than 450ºC.

在聚醯亞胺膜的一些實施例中，拉伸模量係在1.5 GPa與15.0 GPa之間；在一些實施例中，係在1.5 GPa與10.0 GPa之間；在一些實施例中，係在1.5 GPa與7.5 GPa之間；在一些實施例中，係在1.5 GPa與5.0 GPa之間。In some embodiments of the polyimide film, the tensile modulus is between 1.5 GPa and 15.0 GPa; in some embodiments, it is between 1.5 GPa and 10.0 GPa; in some embodiments, it is Between 1.5 GPa and 7.5 GPa; in some embodiments, between 1.5 GPa and 5.0 GPa.

在聚醯亞胺膜的一些實施例中，斷裂伸長率係大於10%。In some embodiments of the polyimide film, the elongation at break is greater than 10%.

在聚醯亞胺膜的一些實施例中，霧度係小於1.0%；在一些實施例中，係小於0.5%。In some embodiments of the polyimide film, the haze is less than 1.0%; in some embodiments, it is less than 0.5%.

在聚醯亞胺膜的一些實施例中，b*係小於7.5；在一些實施例中，係小於5.0。In some embodiments of the polyimide film, b* is less than 7.5; in some embodiments, it is less than 5.0.

在聚醯亞胺膜的一些實施例中，YI係小於12；在一些實施例中，係小於10。In some embodiments of the polyimide film, YI is less than 12; in some embodiments, it is less than 10.

在聚醯亞胺膜的一些實施例中，在400 nm處的透射率係大於40%；在一些實施例中，係大於50%。In some embodiments of the polyimide film, the transmittance at 400 nm is greater than 40%; in some embodiments, it is greater than 50%.

在聚醯亞胺膜的一些實施例中，在430 nm處的透射率係大於60%；在一些實施例中，係大於70%。In some embodiments of the polyimide film, the transmission at 430 nm is greater than 60%; in some embodiments, it is greater than 70%.

在聚醯亞胺膜的一些實施例中，在450 nm處的透射率係大於70%；在一些實施例中，係大於80%。In some embodiments of the polyimide film, the transmittance at 450 nm is greater than 70%; in some embodiments, it is greater than 80%.

在聚醯亞胺膜的一些實施例中，在550 nm處的透射率係大於70%；在一些實施例中，係大於80%。In some embodiments of the polyimide film, the transmittance at 550 nm is greater than 70%; in some embodiments, it is greater than 80%.

在聚醯亞胺膜的一些實施例中，在750 nm處的透射率係大於70%；在一些實施例中，係大於80%。In some embodiments of the polyimide film, the transmittance at 750 nm is greater than 70%; in some embodiments, it is greater than 80%.

聚醯亞胺膜的以上實施例中的任一個可與其他實施例中的一個或多個組合，只要它們不是互相排斥的。Any of the above embodiments of the polyimide film can be combined with one or more of the other embodiments as long as they are not mutually exclusive.

5.   用於製備聚醯亞胺膜的方法5. Method for preparing polyimide film

一般來說，聚醯亞胺膜可以藉由化學或熱轉化由聚醯亞胺先質製備。在一些實施例中，該等膜藉由化學或熱轉化方法由相應的聚醯胺酸溶液製備。本文揭露的聚醯亞胺膜（特別是當用作電子裝置中的玻璃的可撓性替代物時）藉由熱轉化方法來製備。In general, polyimide membranes can be prepared from polyimide precursors by chemical or thermal conversion. In some embodiments, the membranes are prepared from corresponding polyamide solutions by chemical or thermal conversion methods. The polyimide film disclosed herein (especially when used as a flexible substitute for glass in electronic devices) is prepared by a thermal conversion method.

一般來說，聚醯亞胺膜可以藉由化學或熱轉化方法由相應的聚醯胺酸溶液製備。本文揭露的聚醯亞胺膜（特別是當用作電子裝置中的玻璃的可撓性替代物時）藉由熱轉化或改進型熱轉化方法與化學轉化方法來製備。In general, polyimide membranes can be prepared from corresponding polyamic acid solutions by chemical or thermal conversion methods. The polyimide film disclosed herein (especially when used as a flexible substitute for glass in electronic devices) is prepared by thermal conversion or improved thermal conversion methods and chemical conversion methods.

化學轉化方法描述於美國專利號5,166,308和5,298,331中，將該等專利藉由援引以其全文併入本文。在此類方法中，將轉化化學品添加到聚醯胺酸溶液中。發現可用於本發明的轉化化學品包括但不限於：(i) 一種或多種脫水劑，如脂肪族酸酐（乙酸酐等）和酸酐；以及 (ii) 一種或多種催化劑，如脂肪族三級胺（三乙胺等）、三級胺（二甲基苯胺等）和雜環三級胺（吡啶、甲基吡啶、異喹啉（isoquinoilne）等）。酸酐脫水材料典型地以聚醯胺酸溶液中存在的醯胺酸基團的量的稍微莫耳過量使用。所使用的乙酸酐的量典型地是每當量聚醯胺酸約2.0~3.0莫耳。一般來說，使用相當量的三級胺催化劑。Chemical conversion methods are described in US Patent Nos. 5,166,308 and 5,298,331, which are incorporated herein by reference in their entirety. In such methods, conversion chemicals are added to the polyamide solution. Conversion chemicals found to be useful in the present invention include, but are not limited to: (i) one or more dehydrating agents, such as aliphatic anhydrides (acetic anhydride, etc.) and acid anhydrides; and (ii) one or more catalysts, such as aliphatic tertiary amines (Triethylamine, etc.), tertiary amines (dimethylaniline, etc.) and heterocyclic tertiary amines (pyridine, picoline, isoquinoilne, etc.). Anhydride dehydrating materials are typically used in a slight molar excess of the amount of amidic acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically about 2.0 to 3.0 moles per equivalent of polyamide. Generally, a considerable amount of tertiary amine catalyst is used.

熱轉化方法可以或可以不採用轉化化學品（即催化劑）來將聚醯胺酸澆注溶液轉化為聚醯亞胺。如果使用轉化化學品，則該方法可被認為係改進型熱轉化方法。在兩種類型的熱轉化方法中，僅使用熱能來加熱膜以不僅乾燥溶劑的膜而且進行醯亞胺化反應。通常使用有或無轉化催化劑的熱轉化方法來製備本文揭露的聚醯亞胺膜。The thermal conversion method may or may not use conversion chemicals (ie, catalysts) to convert the polyamic acid casting solution to polyimide. If conversion chemicals are used, this method can be considered as an improved thermal conversion method. In the two types of thermal conversion methods, only the thermal energy is used to heat the membrane to not only dry the membrane of the solvent but also perform the amide imidization reaction. Thermal conversion methods with or without conversion catalysts are generally used to prepare the polyimide membranes disclosed herein.

考慮到不僅僅是膜組成產生感興趣的特性，具體的方法參數係預先選擇的。相反，固化溫度和溫度斜升曲線在實現本文揭露的預期用途的最希望的特性中也起到重要作用。聚醯胺酸應在任何後續加工步驟（例如沈積產生功能性顯示器所需的一個或多個無機或其他層）的最高溫度或高於該最高溫度的溫度下、但在低於聚醯亞胺出現顯著熱降解/變色時的溫度的溫度下醯亞胺化。還應該指出，惰性氣氛通常是較佳的，特別是當採用較高的加工溫度進行醯亞胺化時。Considering that not only the composition of the film produces the characteristics of interest, the specific method parameters are pre-selected. Conversely, curing temperature and temperature ramp curves also play an important role in achieving the most desirable characteristics of the intended use disclosed herein. The polyamic acid should be at or above the maximum temperature of any subsequent processing steps (such as deposition of one or more inorganic or other layers required to produce a functional display), but below the polyimide Acetylimidization at a temperature where significant thermal degradation/discoloration occurs. It should also be noted that an inert atmosphere is generally preferred, especially when higher processing temperatures are used for imidateization.

對於本文揭露的聚醯胺酸/聚醯亞胺，當需要超過300ºC的後續加工溫度時，典型地採用300ºC至320ºC的溫度。選擇適當的固化溫度允許得到實現熱特性和機械特性的最佳平衡的完全固化的聚醯亞胺。由於這種非常高的溫度，需要惰性氣氛。典型地，應採用 > 100 ppm的爐中氧水平。非常低的氧水平使得能夠使用最高的固化溫度而無聚合物的顯著降解/變色。加速醯亞胺化過程的催化劑在約200ºC與300ºC之間的固化溫度下有效地實現更高水平的醯亞胺化。如果可撓性裝置在低於聚醯亞胺的Tg 的較高固化溫度下製備，則可以視需要採用此方法。For the polyamic acid/polyimide disclosed herein, when a subsequent processing temperature exceeding 300ºC is required, a temperature of 300ºC to 320ºC is typically used. The selection of an appropriate curing temperature allows to obtain a fully cured polyimide that achieves the best balance of thermal and mechanical properties. Due to this very high temperature, an inert atmosphere is required. Typically, furnace oxygen levels> 100 ppm should be used. The very low oxygen level enables the highest curing temperature to be used without significant degradation/discoloration of the polymer. The catalyst that accelerates the imidate process effectively achieves a higher level of imidate at a curing temperature between about 200ºC and 300ºC. If the apparatus for preparing a flexible curing at a higher temperature, T g is lower than the polyimide, it is possible to use this method as needed.

每個可能的固化步驟的時間量也是重要的製程考慮因素。一般來說，用於最高溫度固化的時間應該保持在最小值。例如，對於320ºC固化，在惰性氣氛下固化時間可長達一小時左右；但在更高固化溫度下，這一時間應被縮短以避免熱降解。一般來說，較高的溫度指示較短的時間。所屬技術領域具有通常知識者將認識到溫度與時間之間的平衡以便優化用於特定最終用途的聚醯亞胺的特性。The amount of time for each possible curing step is also an important process consideration. In general, the time for curing at the highest temperature should be kept to a minimum. For example, for 320ºC curing, the curing time can be up to about an hour in an inert atmosphere; but at higher curing temperatures, this time should be shortened to avoid thermal degradation. In general, a higher temperature indicates a shorter time. Those of ordinary skill in the art will recognize the balance between temperature and time in order to optimize the characteristics of the polyimide for a specific end use.

在一些實施例中，聚醯胺酸溶液經由熱轉化方法轉化成聚醯亞胺膜。In some embodiments, the polyamic acid solution is converted into a polyimide film via a thermal conversion method.

在熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於50 µm。In some embodiments of the thermal conversion method, a polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is less than 50 µm.

在熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於40 µm。In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 40 µm.

在熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於30 µm。In some embodiments of the thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is less than 30 µm.

在熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於20 µm。In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 20 µm.

在熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度在10 µm與20 µm之間。In some embodiments of the thermal conversion method, a polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is between 10 µm and 20 µm.

在熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度在15 µm與20 µm之間。In some embodiments of the thermal conversion method, a polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is between 15 µm and 20 µm.

在熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度係18 µm。In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of 18 µm.

在熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於10 µm。In some embodiments of the thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 10 µm.

在熱轉化方法的一些實施例中，在熱板上以接近模式軟烘經塗覆的基體，其中使用氮氣來將經塗覆的基體恰好保持在熱板上方。In some embodiments of the thermal conversion method, the coated substrate is soft baked in a proximity mode on a hot plate, wherein nitrogen is used to hold the coated substrate just above the hot plate.

在熱轉化方法的一些實施例中，在熱板上以完全接觸模式軟烘經塗覆的基體，其中經塗覆的基體與熱板表面直接接觸。In some embodiments of the thermal conversion method, the coated substrate is soft baked in a full contact mode on the hot plate, where the coated substrate is in direct contact with the surface of the hot plate.

在熱轉化方法的一些實施例中，使用接近模式和完全接觸模式的組合在熱板上軟烘經塗覆的基體。In some embodiments of the thermal conversion method, a combination of proximity mode and full contact mode is used to soft bake the coated substrate on a hot plate.

在熱轉化方法的一些實施例中，使用設定在80o C的熱板軟烘經塗覆的基體。In some embodiments, the thermal conversion process, a set of 80 o C hot plate soft baking the coated substrate.

在熱轉化方法的一些實施例中，使用設定在90o C的熱板軟烘經塗覆的基體。In some embodiments, the thermal conversion process, a set of 90 o C hot plate soft baking the coated substrate.

在熱轉化方法的一些實施例中，使用設定在100o C的熱板軟烘經塗覆的基體。In some embodiments, the thermal conversion process, using a hot plate set at 100 o C soft baking the coated substrate.

在熱轉化方法的一些實施例中，使用設定在110o C的熱板軟烘經塗覆的基體。In some embodiments, the thermal conversion process, using a hot plate set at 110 o C of the soft baking the coated substrate.

在熱轉化方法的一些實施例中，使用設定在120o C的熱板軟烘經塗覆的基體。In some embodiments, the thermal conversion process, using a hot plate set at 120 o C of the soft baking the coated substrate.

在熱轉化方法的一些實施例中，使用設定在130o C的熱板軟烘經塗覆的基體。In some embodiments, the thermal conversion process, using a hot plate set at 130 o C of the soft baking the coated substrate.

在熱轉化方法的一些實施例中，使用設定在140o C的熱板軟烘經塗覆的基體。In some embodiments, the thermal conversion process, using a hot plate set at 140 o C of the soft baking the coated substrate.

在熱轉化方法的一些實施例中，將經塗覆的基體軟烘超過10分鐘的總時間。In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of more than 10 minutes.

在熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於10分鐘的總時間。In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 10 minutes.

在熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於8分鐘的總時間。In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 8 minutes.

在熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於6分鐘的總時間。In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 6 minutes.

在熱轉化方法的一些實施例中，將經塗覆的基體軟烘4分鐘的總時間。In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of 4 minutes.

在熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於4分鐘的總時間。In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 4 minutes.

在熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於2分鐘的總時間。In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 2 minutes.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在2個預先選擇的溫度下固化2個預先選擇的時間間隔，其中該等時間間隔可以是相同或不同的。In some embodiments of the thermal conversion method, the soft-baked coated substrate is subsequently cured at 2 pre-selected temperatures for 2 pre-selected time intervals, where the time intervals may be the same or different.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在3個預先選擇的溫度下固化3個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the thermal conversion method, the soft-baked coated substrate is subsequently cured at 3 pre-selected temperatures for 3 pre-selected time intervals, wherein each of these time intervals may be the same or different.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在4個預先選擇的溫度下固化4個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 4 pre-selected temperatures at 4 pre-selected time intervals, wherein each of these time intervals may be the same or different.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在5個預先選擇的溫度下固化5個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 5 pre-selected temperatures for 5 pre-selected time intervals, wherein each of these time intervals may be the same or different.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在6個預先選擇的溫度下固化6個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 6 pre-selected temperatures for 6 pre-selected time intervals, wherein each of these time intervals may be the same or different.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在7個預先選擇的溫度下固化7個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 7 pre-selected temperatures for 7 pre-selected time intervals, wherein each of these time intervals may be the same or different.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在8個預先選擇的溫度固化8個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 8 pre-selected temperatures and 8 pre-selected time intervals, wherein each of these time intervals may be the same or different of.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在9個預先選擇的溫度下固化9個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 9 pre-selected temperatures for 9 pre-selected time intervals, wherein each of these time intervals may be the same or different.

在熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在10個預先選擇的溫度下固化10個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the thermal conversion method, the soft baked coated substrate is subsequently cured at 10 pre-selected temperatures for 10 pre-selected time intervals, wherein each of these time intervals may be the same or different.

在熱轉化方法的一些實施例中，預先選擇的溫度大於80ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 80ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度等於100ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 100°C.

在熱轉化方法的一些實施例中，預先選擇的溫度大於100ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 100ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度等於150ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 150ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度大於150ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 150ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度等於200ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 200ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度大於200ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 200ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度等於250ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 250ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度大於250ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 250ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度等於300ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 300ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度大於300ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 300ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度等於350ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 350ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度大於350ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 350ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度等於400ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 400ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度大於400ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 400ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度等於450ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is equal to 450ºC.

在熱轉化方法的一些實施例中，預先選擇的溫度大於450ºC。In some embodiments of the thermal conversion method, the pre-selected temperature is greater than 450ºC.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係2分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 2 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係5分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 5 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係10分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 10 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係15分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 15 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係20分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 20 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係25分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 25 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係30分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 30 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係35分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 35 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係40分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 40 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係45分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 45 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係50分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 50 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係55分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 55 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係60分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is 60 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個大於60分鐘。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is greater than 60 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個在2分鐘與60分鐘之間。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is between 2 minutes and 60 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個在2分鐘與90分鐘之間。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is between 2 minutes and 90 minutes.

在熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個在2分鐘與120分鐘之間。In some embodiments of the thermal conversion method, one or more of the pre-selected time intervals is between 2 minutes and 120 minutes.

在熱轉化方法的一些實施例中，用於製備聚醯亞胺膜的方法按順序包括以下步驟：將以上描述的聚醯胺酸溶液塗覆到基體上；軟烘該經塗覆的基體；在多個預先選擇的溫度下將該軟烘的經塗覆的基體處理多個預先選擇的時間間隔，由此該聚醯亞胺膜表現出滿足用於如本文揭露的那些電子應用的特性。In some embodiments of the thermal conversion method, the method for preparing the polyimide film includes the following steps in order: applying the above-described polyamic acid solution to the substrate; soft-baking the coated substrate; The soft-baked coated substrate is treated at a plurality of pre-selected temperatures for a plurality of pre-selected time intervals, whereby the polyimide film exhibits characteristics satisfactory for those electronic applications as disclosed herein.

在熱轉化方法的一些實施例中，用於製備聚醯亞胺膜的方法按順序由以下步驟組成：將以上描述的聚醯胺酸溶液塗覆到基體上；軟烘該經塗覆的基體；在多個預先選擇的溫度下將該軟烘的經塗覆的基體處理多個預先選擇的時間間隔，由此該聚醯亞胺膜表現出滿足用於如本文揭露的那些電子應用的特性。In some embodiments of the thermal conversion method, the method for preparing the polyimide film consists of the following steps in order: applying the above-described polyamic acid solution to the substrate; soft-baking the coated substrate ; Processing the soft-baked coated substrate at a plurality of pre-selected temperatures at a plurality of pre-selected time intervals, whereby the polyimide film exhibits characteristics suitable for those electronic applications as disclosed herein .

在熱轉化方法的一些實施例中，用於製備聚醯亞胺膜的方法按順序主要由以下步驟組成：將以上描述的聚醯胺酸溶液塗覆到基體上；軟烘該經塗覆的基體；在多個預先選擇的溫度下將該軟烘的經塗覆的基體處理多個預先選擇的時間間隔，由此該聚醯亞胺膜表現出滿足用於如本文揭露的那些電子應用的特性。In some embodiments of the thermal conversion method, the method for preparing the polyimide film is composed of the following steps in order: apply the polyamic acid solution described above to the substrate; soft-bake the coated Substrate; the soft-baked coated substrate is treated at a plurality of pre-selected temperatures at a plurality of pre-selected time intervals, whereby the polyimide film appears to be satisfactory for electronic applications such as those disclosed herein characteristic.

典型地，將本文揭露的聚醯胺酸溶液/聚醯亞胺塗覆/固化到支承玻璃基板上以在其餘的顯示器製作過程中有助於加工。在由顯示器製造商確定的過程中的某個時刻，藉由機械或雷射剝離製程將聚醯亞胺塗層從支承玻璃基板上移除。該等製程使作為具有沈積的顯示層的膜的聚醯亞胺與玻璃分開，並實現可撓性形式。通常，然後將具有沈積層的該聚醯亞胺膜粘合到較厚但仍然可撓性的塑膠膜上，以為顯示器的隨後製作提供支承。Typically, the polyamic acid solution/polyimide disclosed herein is coated/cured onto a supporting glass substrate to facilitate processing during the rest of the display manufacturing process. At some point in the process determined by the display manufacturer, the polyimide coating is removed from the supporting glass substrate by mechanical or laser lift-off processes. These processes separate the polyimide, which is the film with the deposited display layer, from the glass and realize a flexible form. Typically, the polyimide film with the deposited layer is then bonded to a thicker but still flexible plastic film to provide support for subsequent fabrication of the display.

還提供了改進型熱轉化方法，其中轉化催化劑通常使醯亞胺化反應在比此類轉化催化劑不存在下有可能的更低的溫度下進行。An improved thermal conversion process is also provided, in which the conversion catalyst generally allows the amide imidization reaction to be carried out at a lower temperature than is possible in the absence of such conversion catalysts.

在一些實施例中，聚醯胺酸溶液經由改進型熱轉化方法轉化成聚醯亞胺膜。In some embodiments, the polyamic acid solution is converted to a polyimide film via a modified thermal conversion method.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains a conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有選自由三級胺組成的組的轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains a conversion catalyst selected from the group consisting of tertiary amines.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有選自以下群組的轉化催化劑，該群組由以下組成：三丁胺、二甲基乙醇胺、異喹啉、1,2-二甲基咪唑、N-甲基咪唑、2-甲基咪唑、2-乙基-4-咪唑、3,5-二甲基吡啶、3,4-二甲基吡啶、2,5-二甲基吡啶、5-甲基苯并咪唑等。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains a conversion catalyst selected from the group consisting of tributylamine, dimethylethanolamine, isoquinoline, 1, 2-Dimethylimidazole, N-methylimidazole, 2-methylimidazole, 2-ethyl-4-imidazole, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5- Dimethylpyridine, 5-methylbenzimidazole, etc.

在改進型熱轉化方法的一些實施例中，轉化催化劑以聚醯胺酸溶液的5重量%或更少存在。In some embodiments of the improved thermal conversion method, the conversion catalyst is present as 5 wt% or less of the polyamic acid solution.

在改進型熱轉化方法的一些實施例中，轉化催化劑以聚醯胺酸溶液的3重量%或更少存在。In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 3% by weight or less of the polyamic acid solution.

在改進型熱轉化方法的一些實施例中，轉化催化劑以聚醯胺酸溶液的1重量%或更少存在。In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 1% by weight or less of the polyamic acid solution.

在改進型熱轉化方法的一些實施例中，轉化催化劑以聚醯胺酸溶液的1重量%存在。In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 1% by weight of the polyamic acid solution.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有三丁胺作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains tributylamine as the conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有二甲基乙醇胺作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains dimethylethanolamine as a conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有異喹啉作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains isoquinoline as the conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有1,2-二甲基咪唑作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 1,2-dimethylimidazole as a conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有3,5-二甲基吡啶作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 3,5-lutidine as the conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有5-甲基苯并咪唑作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 5-methylbenzimidazole as a conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有N-甲基咪唑作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains N-methylimidazole as a conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有2-甲基咪唑作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 2-methylimidazole as a conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有2-乙基-4-咪唑作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 2-ethyl-4-imidazole as the conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有3,4-二甲基吡啶作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 3,4-lutidine as the conversion catalyst.

在改進型熱轉化方法的一些實施例中，聚醯胺酸溶液進一步含有2,5-二甲基吡啶作為轉化催化劑。In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 2,5-lutidine as the conversion catalyst.

在改進型熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於50 µm。In some embodiments of the improved thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 50 µm.

在改進型熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於40 µm。In some embodiments of the improved thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 40 µm.

在改進型熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於30 µm。In some embodiments of the improved thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is less than 30 µm.

在改進型熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於20 µm。In some embodiments of the improved thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 20 µm.

在改進型熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度在10 µm與20 µm之間。In some embodiments of the improved thermal conversion method, the polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is between 10 µm and 20 µm.

在改進型熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度在15 µm與20 µm之間。In some embodiments of the improved thermal conversion method, a polyamic acid solution is applied to the substrate so that the soft-baking thickness of the resulting film is between 15 µm and 20 µm.

在改進型熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度係18 µm。In some embodiments of the improved thermal conversion method, a polyamic acid solution is applied to the substrate so that the soft baking thickness of the resulting film is 18 µm.

在改進型熱轉化方法的一些實施例中，將聚醯胺酸溶液塗覆到基體上，以使得所得膜的軟烘厚度小於10 µm。In some embodiments of the improved thermal conversion method, the polyamide solution is applied to the substrate so that the resulting film has a soft bake thickness of less than 10 µm.

在改進型熱轉化方法的一些實施例中，在熱板上以接近模式軟烘經塗覆的基體，其中使用氮氣來將經塗覆的基體恰好保持在熱板上方。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked in proximity mode on a hot plate, where nitrogen is used to hold the coated substrate just above the hot plate.

在改進型熱轉化方法的一些實施例中，在熱板上以完全接觸模式軟烘經塗覆的基體，其中經塗覆的基體與熱板表面直接接觸。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked in a full contact mode on the hot plate, where the coated substrate is in direct contact with the surface of the hot plate.

在改進型熱轉化方法的一些實施例中，使用接近模式和完全接觸模式的組合在熱板上軟烘經塗覆的基體。In some embodiments of the improved thermal conversion method, a combination of proximity mode and full contact mode is used to soft bake the coated substrate on a hot plate.

在改進型熱轉化方法的一些實施例中，使用設定在80ºC的熱板軟烘經塗覆的基體。In some embodiments of the improved thermal conversion method, a hot plate set at 80°C is used to soft bake the coated substrate.

在改進型熱轉化方法的一些實施例中，使用設定在90ºC的熱板軟烘經塗覆的基體。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked using a hot plate set at 90ºC.

在改進型熱轉化方法的一些實施例中，使用設定在100ºC的熱板軟烘經塗覆的基體。In some embodiments of the improved thermal conversion method, a hot plate set at 100°C is used to soft bake the coated substrate.

在改進型熱轉化方法的一些實施例中，使用設定在110ºC的熱板軟烘經塗覆的基體。In some embodiments of the improved thermal conversion method, the coated substrate is soft-baked using a hot plate set at 110°C.

在改進型熱轉化方法的一些實施例中，使用設定在120ºC的熱板軟烘經塗覆的基體。In some embodiments of the improved thermal conversion method, a hot plate set at 120°C is used to soft bake the coated substrate.

在改進型熱轉化方法的一些實施例中，使用設定在130ºC的熱板軟烘經塗覆的基體。In some embodiments of the improved thermal conversion method, the coated substrate is soft-baked using a hot plate set at 130ºC.

在改進型熱轉化方法的一些實施例中，使用設定在140ºC的熱板軟烘經塗覆的基體。In some embodiments of the improved thermal conversion method, a hot plate set at 140°C is used to soft bake the coated substrate.

在改進型熱轉化方法的一些實施例中，將經塗覆的基體軟烘超過10分鐘的總時間。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked for a total time of more than 10 minutes.

在改進型熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於10分鐘的總時間。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked for a total time of less than 10 minutes.

在改進型熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於8分鐘的總時間。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked for a total time of less than 8 minutes.

在改進型熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於6分鐘的總時間。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked for a total time of less than 6 minutes.

在改進型熱轉化方法的一些實施例中，將經塗覆的基體軟烘4分鐘的總時間。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked for a total time of 4 minutes.

在改進型熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於4分鐘的總時間。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked for a total time of less than 4 minutes.

在改進型熱轉化方法的一些實施例中，將經塗覆的基體軟烘少於2分鐘的總時間。In some embodiments of the improved thermal conversion method, the coated substrate is soft baked for a total time of less than 2 minutes.

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在2個預先選擇的溫度下固化2個預先選擇的時間間隔，其中該等時間間隔可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is subsequently cured at 2 pre-selected temperatures at 2 pre-selected time intervals, where the time intervals may be the same or different .

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在3個預先選擇的溫度下固化3個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft baked coated substrate is subsequently cured at 3 pre-selected temperatures for 3 pre-selected time intervals, wherein each of these time intervals may be Same or different.

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在4個預先選擇的溫度下固化4個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft baked coated substrate is subsequently cured at 4 preselected temperatures at 4 preselected time intervals, wherein each of these time intervals may be Same or different.

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在5個預先選擇的溫度下固化5個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft baked coated substrate is subsequently cured at 5 pre-selected temperatures for 5 pre-selected time intervals, wherein each of these time intervals may be Same or different.

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在6個預先選擇的溫度下固化6個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft baked coated substrate is subsequently cured at 6 pre-selected temperatures for 6 pre-selected time intervals, wherein each of these time intervals may be Same or different.

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在7個預先選擇的溫度下固化7個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft baked coated substrate is subsequently cured at 7 pre-selected temperatures for 7 pre-selected time intervals, wherein each of these time intervals may be Same or different.

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在8個預先選擇的溫度下固化8個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft baked coated substrate is subsequently cured at 8 pre-selected temperatures for 8 pre-selected time intervals, wherein each of these time intervals may be Same or different.

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在9個預先選擇的溫度下固化9個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft-baked coated substrate is subsequently cured at 9 pre-selected temperatures for 9 pre-selected time intervals, wherein each of these time intervals may be Same or different.

在改進型熱轉化方法的一些實施例中，將軟烘的經塗覆的基體隨後在10個預先選擇的溫度下固化10個預先選擇的時間間隔，其中該等時間間隔中的每一個可以是相同或不同的。In some embodiments of the improved thermal conversion method, the soft baked coated substrate is subsequently cured at 10 pre-selected temperatures for 10 pre-selected time intervals, wherein each of these time intervals may be Same or different.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於80ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 80ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於100ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 100°C.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於100ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 100ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於150ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 150ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於150ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 150ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於200ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 200ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於200ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 200ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於220ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 220ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於220ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 220ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於230ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 230ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於230ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 230ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於240ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 240°C.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於240ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 240ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於250ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 250ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於250ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 250ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於260ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 260ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於260ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 260ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於270ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 270ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於270ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 270ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於280ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 280°C.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於280ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 280°C.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於290ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 290ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度大於290ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is greater than 290°C.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度等於300ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is equal to 300ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度小於300ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 300ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度小於290ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 290ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度小於280ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 280°C.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度小於270ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 270ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度小於260ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 260ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的溫度小於250ºC。In some embodiments of the improved thermal conversion method, the pre-selected temperature is less than 250ºC.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係2分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 2 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係5分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 5 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係10分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 10 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係15分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 15 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係20分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 20 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係25分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 25 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係30分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 30 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係35分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 35 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係40分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 40 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係45分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 45 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係50分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 50 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係55分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 55 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個係60分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is 60 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個大於60分鐘。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is greater than 60 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個在2分鐘與60分鐘之間。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is between 2 minutes and 60 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個在2分鐘與90分鐘之間。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is between 2 minutes and 90 minutes.

在改進型熱轉化方法的一些實施例中，預先選擇的時間間隔中的一個或多個在2分鐘與120分鐘之間。In some embodiments of the improved thermal conversion method, one or more of the pre-selected time intervals is between 2 minutes and 120 minutes.

在改進型熱轉化方法的一些實施例中，用於製備聚醯亞胺膜的方法按順序包括以下步驟：將以上描述的包含轉化化學品的聚醯胺酸溶液塗覆到基體上；軟烘該經塗覆的基體；在多個預先選擇的溫度下將該軟烘的經塗覆的基體處理多個預先選擇的時間間隔，由此該聚醯亞胺膜表現出滿足用於如本文揭露的那些電子應用的特性。In some embodiments of the improved thermal conversion method, the method for preparing the polyimide film includes the following steps in sequence: applying the above-described conversion chemical-containing polyamic acid solution to the substrate; soft baking The coated substrate; treating the soft-baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film appears to be satisfactory for use as disclosed herein Characteristics of those electronic applications.

在改進型熱轉化方法的一些實施例中，用於製備聚醯亞胺膜的方法按順序由以下步驟組成：將以上描述的包含轉化化學品的聚醯胺酸溶液塗覆到基體上；軟烘該經塗覆的基體；在多個預先選擇的溫度下將該軟烘的經塗覆的基體處理多個預先選擇的時間間隔，由此該聚醯亞胺膜表現出滿足用於如本文揭露的那些電子應用的特性。In some embodiments of the improved thermal conversion method, the method for preparing the polyimide film is composed of the following steps in order: applying the above-described conversion chemical-containing polyamic acid solution to the substrate; soft Baking the coated substrate; treating the soft-baked coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film appears to be satisfactory for use as described herein Uncovered features of those electronic applications.

在改進型熱轉化方法的一些實施例中，用於製備聚醯亞胺膜的方法按順序主要由以下步驟組成：將以上描述的包含轉化化學品的聚醯胺酸溶液塗覆到基體上；軟烘該經塗覆的基體；在多個預先選擇的溫度下將該軟烘的經塗覆的基體處理多個預先選擇的時間間隔，由此該聚醯亞胺膜表現出滿足用於如本文揭露的那些電子應用的特性。In some embodiments of the improved thermal conversion method, the method for preparing the polyimide film is mainly composed of the following steps in sequence: applying the polyamic acid solution containing the conversion chemical described above to the substrate; Soft-baking the coated substrate; treating the soft-baking coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film appears to be satisfactory for applications such as The characteristics of those electronic applications disclosed in this article.

6.   電子裝置6. Electronic devices

本文揭露的聚醯亞胺膜可以適用於電子顯示裝置（如OLED和LCD顯示器）中的多個層。此類層的非限制性實例包括裝置基板、觸摸面板、濾色片的基板、覆蓋膜等。每種應用的特定材料的特性要求係獨特的，並且可以藉由本文揭露的聚醯亞胺膜的一種或多種適當組成和一種或多種加工條件解決。The polyimide film disclosed herein can be applied to multiple layers in electronic display devices, such as OLED and LCD displays. Non-limiting examples of such layers include device substrates, touch panels, color filter substrates, cover films, and the like. The specific material requirements for each application are unique and can be solved by one or more suitable compositions and one or more processing conditions of the polyimide film disclosed herein.

在一些實施例中，電子裝置中玻璃的可撓性替代物係如以上詳細描述的具有式III的重複單元的聚醯亞胺膜。In some embodiments, the flexible alternative to glass in the electronic device is a polyimide film having a repeating unit of formula III as described in detail above.

在一些實施例中，提供了一種具有至少一個層的有機電子裝置，該至少一個層包含具有如以上詳述所描述的式III的重複單元的聚醯亞胺膜。In some embodiments, there is provided an organic electronic device having at least one layer comprising a polyimide film having a repeating unit of formula III as described in detail above.

可得益於具有一個或多個包括至少一種如本文所述的化合物的層的有機電子裝置包括但不限於：(1) 將電能轉換為輻射的裝置（例如發光二極體、發光二極體顯示器、照明裝置、光源、或二極體雷射器），(2) 藉由電子方法檢測訊號的裝置（例如光電偵測器、光導電池、光敏電阻器、光控繼電器、光電電晶體、光電管、IR檢測器、生物感測器），(3) 將輻射轉換為電能的裝置（例如光伏裝置或太陽能電池），(4) 將一個波長的光轉換成更長波長的光的裝置（例如，下變頻磷光體裝置）；以及 (5) 包括一個或多個電子部件的裝置，該一個或多個電子部件包括一個或多個有機半導體層（例如，電晶體或二極體）。根據本發明的組成物的其他用途包括用於記憶存儲裝置的塗覆材料、抗靜電膜、生物感測器、電致變色裝置、固體電解電容器、儲能裝置（如可再充電電池）和電磁遮罩應用。Organic electronic devices that may benefit from having one or more layers including at least one compound as described herein include, but are not limited to: (1) Devices that convert electrical energy into radiation (eg, light-emitting diodes, light-emitting diodes Displays, lighting devices, light sources, or diode lasers), (2) Devices that detect signals by electronic methods (such as photodetectors, photoconductive cells, photoresistors, photocontrol relays, phototransistors, photocells) , IR detectors, biosensors), (3) Devices that convert radiation into electrical energy (such as photovoltaic devices or solar cells), (4) Devices that convert one wavelength of light to longer wavelengths of light (for example, Down-converted phosphor device); and (5) a device including one or more electronic components including one or more organic semiconductor layers (eg, transistors or diodes). Other uses of the composition according to the invention include coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolytic capacitors, energy storage devices (such as rechargeable batteries) and electromagnetic Mask application.

圖1中示出可以充當如本文所述的玻璃的可撓性替代物的聚醯亞胺膜的一個圖示。可撓性膜100可以具有如本揭露的實施例中所述的特性。在一些實施例中，可以充當玻璃的可撓性替代物的聚醯亞胺膜被包括在電子裝置中。圖2說明電子裝置200係有機電子裝置時的情況。裝置200具有基板100、陽極層110和第二電接觸層、陰極層130、以及在它們之間的光主動層(photoactive layer)120。可以視需要存在附加的層。鄰近陽極的可以是電洞注入層（未示出），有時稱為緩衝層。鄰近電洞注入層的可以是包含電洞傳輸材料的電洞傳輸層（未示出）。鄰近陰極的可以是包含電子傳輸材料的電子傳輸層（未示出）。作為一種選擇，裝置可以使用一個或多個緊鄰陽極110的附加的電洞注入層或電洞傳輸層（未示出）和/或一個或多個緊鄰陰極130的附加的電子注入層或電子傳輸層（未示出）。在110與130之間的層單獨地且統稱為有機主動層(organic active layer)。可以或可以不存在的附加的層包括濾色片、觸摸面板和/或護板。該等層中的一個或多個（除了基板100外）也可以由本文揭露的聚醯亞胺膜製成。An illustration of a polyimide film that can serve as a flexible substitute for glass as described herein is shown in FIG. The flexible film 100 may have the characteristics as described in the embodiments of the present disclosure. In some embodiments, a polyimide film that can serve as a flexible substitute for glass is included in the electronic device. FIG. 2 illustrates the case when the electronic device 200 is an organic electronic device. The device 200 has a substrate 100, an anode layer 110 and a second electrical contact layer, a cathode layer 130, and a photoactive layer 120 therebetween. There may be additional layers as needed. Adjacent to the anode may be a hole injection layer (not shown), sometimes referred to as a buffer layer. Adjacent to the hole injection layer may be a hole transport layer (not shown) containing hole transport material. Adjacent to the cathode may be an electron transport layer (not shown) containing an electron transport material. Alternatively, the device may use one or more additional hole injection layers or hole transport layers (not shown) next to the anode 110 and/or one or more additional electron injection layers or electron transport next to the cathode 130 Layer (not shown). The layers between 110 and 130 are individually and collectively referred to as organic active layers. Additional layers that may or may not be present include color filters, touch panels, and/or shields. One or more of these layers (other than the substrate 100) may also be made of the polyimide film disclosed herein.

這裡將參照圖2進一步討論該等不同的層。然而，該討論同樣適用於其他構型。The different layers will be further discussed here with reference to FIG. 2. However, the discussion is equally applicable to other configurations.

在一些實施例中，不同的層具有以下厚度範圍：基板100，5~100微米，陽極110，500~5000 Å，在一些實施例中，1000~2000 Å；電洞注入層（未示出），50~2000 Å，在一些實施例中，200~1000 Å；電洞傳輸層（未示出），50~3000 Å，在一些實施例中，200~2000 Å；光主動層120，10~2000 Å，在一些實施例中，100~1000 Å；電子傳輸層（未示出），50~2000 Å，在一些實施例中，100~1000 Å；陰極130，200~10000 Å，在一些實施例中，300~5000 Å。所希望的層厚度的比率將取決於所用材料的確切性質。In some embodiments, the different layers have the following thickness ranges: substrate 100, 5-100 microns, anode 110, 500-5000 Å, and in some embodiments, 1000-2000 Å; hole injection layer (not shown) , 50~2000 Å, in some embodiments, 200~1000 Å; hole transmission layer (not shown), 50~3000 Å, in some embodiments, 200~2000 Å; photoactive layer 120, 10~ 2000 Å, in some embodiments, 100-1000 Å; electron transport layer (not shown), 50-2000 Å, in some embodiments, 100-1000 Å; cathode 130, 200-10000 Å, in some implementations In the example, 300~5000 Å. The desired ratio of layer thickness will depend on the exact nature of the materials used.

在一些實施例中，有機電子裝置（OLED）含有如本文揭露的玻璃的可撓性替代物。In some embodiments, the organic electronic device (OLED) contains a flexible alternative to glass as disclosed herein.

在一些實施例中，提供了一種有機電子裝置，其中該裝置基板包含本文揭露的聚醯亞胺膜。在一些實施例中，該裝置係有機發光二極體（OLED）。In some embodiments, an organic electronic device is provided, wherein the device substrate comprises the polyimide film disclosed herein. In some embodiments, the device is an organic light emitting diode (OLED).

在一些實施例中，有機電子裝置包括基板、陽極、陰極和在其間的光主動層，並且進一步包括一個或多個附加的有機主動層。在一些實施例中，該附加的有機主動層係電洞傳輸層。在一些實施例中，該附加的有機主動層係電子傳輸層。在一些實施例中，該附加的有機主動層係電洞傳輸層和電子傳輸層兩者。In some embodiments, the organic electronic device includes a substrate, an anode, a cathode, and a light active layer therebetween, and further includes one or more additional organic active layers. In some embodiments, the additional organic active layer is a hole transport layer. In some embodiments, the additional organic active layer is an electron transport layer. In some embodiments, the additional organic active layer is both a hole transport layer and an electron transport layer.

陽極110係對於注入正電荷載體尤其有效的電極。其可由例如含有金屬、混合金屬、合金、金屬氧化物或混合金屬氧化物的材料製成，或者其可為導電聚合物、以及它們的混合物。合適的金屬包括第11族金屬，第4、5和6族中的金屬和第8~10族的過渡金屬。如果陽極係要透光的，則一般使用第12、13和14族金屬的混合金屬氧化物，如氧化銦錫。陽極還可包含有機材料如聚苯胺，如在「Flexible light-emittingdiodes made from soluble conducting polymer [由可溶性導電聚合物製成的可撓性發光二極體]」，Nature [自然]，第357卷，第477-479頁（1992年6月11日）中所述。陽極和陰極中的至少一個應係至少部分透明的以允許產生的光被觀察到。The anode 110 is an electrode that is particularly effective for injecting positive charge carriers. It can be made of, for example, materials containing metals, mixed metals, alloys, metal oxides, or mixed metal oxides, or it can be conductive polymers, and mixtures thereof. Suitable metals include Group 11 metals, metals in Groups 4, 5 and 6, and transition metals in Groups 8-10. If the anode is to be transparent, a mixed metal oxide of Group 12, 13 and 14 metals, such as indium tin oxide, is generally used. The anode may also contain organic materials such as polyaniline, as described in "Flexible light-emitting diodes made from soluble conducting polymer", Nature [Natural], Volume 357, Pages 477-479 (June 11, 1992). At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.

視需要的電洞注入層可以包括電洞注入材料。術語「電洞注入層」或「電洞注入材料」旨在係指導電或半導電材料，並且在有機電子裝置中可具有一種或多種功能，包括但不限於下層的平面化、電荷傳輸和/或電荷注入特性、雜質如氧或金屬離子的清除、以及有利於或改善有機電子裝置的性能的其他方面。電洞注入材料可以是聚合物、低聚物或小分子，並且可以是呈溶液、分散體、懸浮液、乳液、膠體混合物或其他組成物的形式。The hole injection layer as needed may include a hole injection material. The term "hole injection layer" or "hole injection material" is intended to guide electrical or semi-conductive materials, and may have one or more functions in organic electronic devices, including but not limited to planarization of lower layers, charge transport and/or Or charge injection characteristics, the removal of impurities such as oxygen or metal ions, and other aspects that facilitate or improve the performance of organic electronic devices. The hole injection material may be a polymer, oligomer, or small molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

電洞注入層可用聚合物材料形成，如聚苯胺（PANI）或聚乙烯二氧噻吩（PEDOT），該等聚合物材料通常摻雜有質子酸。質子酸可以是例如聚(苯乙烯磺酸)、聚(2-丙烯醯胺基-2-甲基-1-丙磺酸)等。電洞注入層120可包含電荷轉移化合物等，如銅酞青和四硫富瓦烯-四氰基對苯二醌二甲烷系統（TTF-TCNQ）。在一些實施例中，電洞注入層120由導電聚合物和形成膠體的聚合物酸的分散體製成。此類材料已經在例如公佈的美國專利申請2004-0102577、2004-0127637和2005-0205860中描述。The hole injection layer may be formed of a polymer material, such as polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), which is usually doped with protonic acid. The protonic acid may be, for example, poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), or the like. The hole injection layer 120 may include a charge transfer compound and the like, such as copper phthalocyanine and tetrathiofulvalene-tetracyano-p-phthalodiquinone dimethane system (TTF-TCNQ). In some embodiments, the hole injection layer 120 is made of a dispersion of a conductive polymer and a colloid-forming polymer acid. Such materials have been described in, for example, published US patent applications 2004-0102577, 2004-0127637, and 2005-0205860.

其他層可包含電洞傳輸材料。用於電洞傳輸層的電洞傳輸材料的實例已概述於例如Y. Wang的Kirk-Othmer Encyclopedia of Chemical Technology [柯克•奧思默化工百科全書]，第四版，第18卷，第837-860頁，1996中。電洞傳輸小分子和聚合物二者均可使用。常用的電洞傳輸分子包括但不限於：4,4’,4’’-三(N,N-二苯基-胺基)-三苯胺（TDATA）；4,4’,4’’-三(N-3-甲基苯基-N-苯基-胺基)-三苯胺（MTDATA）；N,N’-二苯基-N,N'-雙(3-甲基苯基)-[1,1'-聯苯基]-4,4'-二胺（TPD）；4,4’-雙(咔唑-9-基)聯苯（CBP）；1,3-雙(咔唑-9-基)苯（mCP）；1,1-雙[(二-4-甲苯基胺基)苯基]環己烷（TAPC）；N,N'-雙(4-甲基苯基)-N,N'-雙(4-乙基苯基)-[1,1'-(3,3'-二甲基)聯苯基]-4,4'-二胺（ETPD）；四-(3-甲基苯基)-N,N,N',N'-2,5-苯二胺（PDA）；α-苯基-4-N,N-二苯基胺基苯乙烯（TPS）；對‑(二乙基胺基)苯甲醛二苯腙（DEH）；三苯胺（TPA）；雙[4-(N,N-二乙基胺基)-2-甲基苯基](4-甲基苯基)甲烷（MPMP）；1-苯基-3-[對-(二乙基胺基)苯乙烯基]-5-[對-(二乙基胺基)苯基]吡唑啉（PPR或DEASP）；1,2-反式-雙(9H-咔唑-9-基)環丁烷（DCZB）；N,N,N'，N'‑四(4-甲基苯基)-(1,1'-聯苯基）-4,4'-二胺（TTB)；N,N’-雙(萘-1-基)-N,N’-雙-(苯基)聯苯胺（α-NPB）；以及卟啉化合物，如銅酞青。常用的電洞傳輸聚合物包括但不限於聚乙烯咔唑、(苯基甲基)聚矽烷、聚(二氧噻吩)、聚苯胺、以及聚吡咯。還可能藉由將電洞傳輸分子如上述那些摻入聚合物如聚苯乙烯和聚碳酸酯中來獲得電洞傳輸聚合物。在一些情況下，使用三芳基胺聚合物，尤其是三芳基胺-茀共聚物。在一些情況下，該聚合物和共聚物係可交聯的。可交聯的電洞傳輸聚合物的實例可在例如公佈的美國專利申請2005-0184287和公佈的PCT申請WO 2005/052027中找到。在一些實施例中，電洞傳輸層摻雜有p型摻雜劑，如四氟四氰基喹啉二甲烷和苝-3,4,9,10-四羧基-3,4,9,10-二酐。Other layers may contain hole transport materials. Examples of hole-transporting materials used in hole-transporting layers have been outlined in, for example, Kirk-Othmer Encyclopedia of Chemical Technology by Y. Wang [Kirk-Othmer Encyclopedia of Chemical Technology], Fourth Edition, Volume 18, 837 -860 pages, 1996. Both hole transporting small molecules and polymers can be used. Commonly used hole transport molecules include, but are not limited to: 4,4',4"-tri(N,N-diphenyl-amino)-triphenylamine (TDATA); 4,4',4''-tri (N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA); N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[ 1,1'-biphenyl]-4,4'-diamine (TPD); 4,4'-bis(carbazol-9-yl)biphenyl (CBP); 1,3-bis(carbazole- 9-yl)benzene (mCP); 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC); N,N'-bis(4-methylphenyl)- N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD); tetra-( 3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA); α-phenyl-4-N,N-diphenylaminostyrene (TPS) ; P-(diethylamino) benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis[4-(N,N-diethylamino)-2-methylphenyl] (4 -Methylphenyl)methane (MPMP); 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazole Porphyrin (PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N'‑tetra(4-methylphenyl )-(1,1'-biphenyl)-4,4'-diamine (TTB); N,N'-bis(naphthalene-1-yl)-N,N'-bis-(phenyl)bi Aniline (α-NPB); and porphyrin compounds, such as copper phthalocyanine. Commonly used hole transport polymers include but are not limited to polyvinylcarbazole, (phenylmethyl) polysilane, poly(dioxythiophene), polyaniline, and polypyrrole. It is also possible to obtain hole transport polymers by incorporating hole transport molecules such as those described above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers are used, especially triarylamine-stilbene copolymers. In some cases, the polymer and copolymer systems are crosslinkable. Examples of crosslinkable hole transport polymers can be found in, for example, published US patent application 2005-0184287 and published PCT application WO 2005/052027. In some embodiments, the hole transport layer is doped with p-type dopants, such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxy-3,4,9,10 -Dianhydride.

根據裝置的應用，光主動層120可以是由所施加的電壓激活的發光層（如在發光二極體或發光電化學電池中）、吸收光並且發射具有更長波長的光的材料層（如在下變頻磷光體裝置中）、或響應於輻射能並且在或不在所施加的偏壓下生成訊號的材料層（如在光電偵測器或光伏裝置中）。Depending on the application of the device, the photoactive layer 120 may be a light-emitting layer activated by the applied voltage (as in a light-emitting diode or light-emitting electrochemical cell), a material layer that absorbs light and emits light with a longer wavelength (such as In a down-converted phosphor device), or a layer of material that responds to radiant energy and generates a signal with or without an applied bias (such as in a photodetector or photovoltaic device).

在一些實施例中，光主動層包含化合物，該化合物包含作為光主動材料的發射化合物。在一些實施例中，光主動層進一步包含主體材料。主體材料的實例包括但不限於䓛、菲、苯并菲、啡啉、萘、蒽、喹啉、異喹啉、喹㗁啉、苯基吡啶、咔唑、吲哚并咔唑、呋喃、苯并呋喃、二苯并呋喃、苯并二呋喃和金屬喹啉錯合物。在一些實施例中，主體材料係氘代的。In some embodiments, the photoactive layer includes a compound that includes an emitting compound as a photoactive material. In some embodiments, the photoactive layer further includes a host material. Examples of host materials include, but are not limited to, phenanthrene, phenanthrene, benzophenanthrene, morpholine, naphthalene, anthracene, quinoline, isoquinoline, quinoline, phenylpyridine, carbazole, indolocarbazole, furan, benzene Pyrofuran, dibenzofuran, benzodifuran and metal quinoline complexes. In some embodiments, the host material is deuterated.

在一些實施例中，光主動層包含 (a) 能夠具有在380與750 nm之間的發射最大值的電致發光的摻雜劑，(b) 第一主體化合物，以及 (c) 第二主體化合物。上文描述了合適的第二主體化合物。In some embodiments, the photoactive layer contains (a) an electroluminescent dopant capable of having an emission maximum between 380 and 750 nm, (b) a first host compound, and (c) a second host Compound. The suitable second host compound is described above.

在一些實施例中，光主動層僅包括 (a) 能夠具有在380與750 nm之間的發射最大值的電致發光的摻雜劑，(b) 第一主體化合物，以及 (c) 第二主體化合物，其中不存在將實質上改變層的操作原理或區別特徵的附加材料。In some embodiments, the photoactive layer includes only (a) an electroluminescent dopant capable of having an emission maximum between 380 and 750 nm, (b) a first host compound, and (c) a second The host compound, where there are no additional materials that will substantially change the operating principle or distinguishing characteristics of the layer.

在一些實施例中，基於在光主動層中的重量，第一主體以比第二主體更高的濃度存在。In some embodiments, based on the weight in the photoactive layer, the first body is present at a higher concentration than the second body.

在一些實施例中，光主動層中第一主體與第二主體的重量比在10 : 1至1 : 10的範圍內。在一些實施例中，該重量比在6 : 1至1 : 6；在一些實施例中，5 : 1至1 : 2；在一些實施例中，3 : 1至1 : 1的範圍內。In some embodiments, the weight ratio of the first body to the second body in the photoactive layer is in the range of 10:1 to 1:10. In some embodiments, the weight ratio is in the range of 6:1 to 1:6; in some embodiments, 5:1 to 1:2; in some embodiments, 3:1 to 1:1.

在一些實施例中，摻雜劑與總主體的重量比在1 : 99至20 : 80；在一些實施例中，5 : 95至15 : 85的範圍內。In some embodiments, the weight ratio of dopant to total host is in the range of 1:99 to 20:80; in some embodiments, in the range of 5:95 to 15:85.

在一些實施例中，光主動層包含 (a) 發射紅光的摻雜劑，(b) 第一主體化合物，以及 (c) 第二主體化合物。In some embodiments, the photoactive layer includes (a) a red-emitting dopant, (b) a first host compound, and (c) a second host compound.

在一些實施例中，光主動層包含 (a) 發射綠光的摻雜劑，(b) 第一主體化合物，以及 (c) 第二主體化合物。In some embodiments, the photoactive layer includes (a) a green-emitting dopant, (b) a first host compound, and (c) a second host compound.

在一些實施例中，光主動層包含 (a) 發射黃光的摻雜劑，(b) 第一主體化合物，以及 (c) 第二主體化合物。In some embodiments, the photoactive layer includes (a) a yellow-emitting dopant, (b) a first host compound, and (c) a second host compound.

視需要的層可以同時起到促進電子傳輸的作用，並且還用作約束層以防止激子在層介面處淬滅。較佳的是，該層促進電子移動性並減少激子淬滅。The optional layer can simultaneously promote electron transport and also serve as a confinement layer to prevent the exciton from quenching at the layer interface. Preferably, this layer promotes electron mobility and reduces exciton quenching.

在一些實施例中，此類層包括其他電子傳輸材料。可用於視需要的電子傳輸層的電子傳輸材料的實例包括金屬螯合的類喔星（oxinoid）化合物，包括金屬喹啉鹽衍生物如三(8-羥基喹啉合)鋁（AlQ）、雙(2-甲基-8-羥基喹啉合)(對苯基苯酚合)鋁（BAlq）、四-(8-羥基喹啉合)鉿（HfQ）和四-(8-羥基喹啉合)鋯（ZrQ）；以及唑類化合物，如2-(4-聯苯基)-5-(4-三級丁基苯基)-1,3,4-㗁二唑（PBD）、3-(4-聯苯基)-4-苯基-5-(4-三級丁基苯基)-1,2,4-***（TAZ）以及1,3,5-三(苯基-2-苯并咪唑)苯（TPBI）；喹㗁啉衍生物，如2,3-雙(4-氟苯基)喹㗁啉；啡啉，如4,7-二苯基-1,10-啡啉（DPA）和2,9-二甲基-4,7-二苯基-1,10-啡啉（DDPA）；三𠯤；富勒烯；及其混合物。在一些實施例中，該電子傳輸材料選自由金屬喹啉鹽和啡啉衍生物所組成的群組。在一些實施例中，該電子傳輸層進一步包含n型摻雜劑。N型摻雜劑材料係眾所周知的。n型摻雜劑包括但不限於第1族和第2族金屬；第1族和第2族金屬鹽，如LiF、CsF和Cs2 CO3 ；第1族和第2族金屬有機化合物，如喹啉鋰；以及分子n型摻雜劑，如隱色染料、金屬錯合物，如W2 (hpp)4 （其中hpp = 1,3,4,6,7,8-六氫-2H-嘧啶并-[1,2-a]-嘧啶）和二茂鈷、四硫并四苯、雙(伸乙基二硫代)四硫富瓦烯、雜環基團或二價基團、以及雜環基團或二價基團的二聚體、低聚物、聚合物、二螺化合物和多環化物。In some embodiments, such layers include other electron transport materials. Examples of electron transport materials that can be used in the optional electron transport layer include metal chelated oxinoid compounds, including metal quinoline salt derivatives such as tris(8-hydroxyquinoline) aluminum (AlQ), bis (2-methyl-8-hydroxyquinoline) (p-phenylphenolo) aluminum (BAlq), tetra-(8-hydroxyquinoline) hafnium (HfQ) and tetra-(8-hydroxyquinoline) Zirconium (ZrQ); and azole compounds, such as 2-(4-biphenyl)-5-(4-tertiary butylphenyl)-1,3,4-㗁diazole (PBD), 3-( 4-biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ) and 1,3,5-tris(phenyl-2- Benzimidazole)benzene (TPBI); quinoline derivatives, such as 2,3-bis(4-fluorophenyl)quinoline; morpholine, such as 4,7-diphenyl-1,10-morpholine (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-morpholine (DDPA); three 𠯤; fullerene; and mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinoline salts and morpholine derivatives. In some embodiments, the electron transport layer further includes an n-type dopant. N-type dopant materials are well known. n-type dopants include, but are not limited to, Group 1 and Group 2 metals; Group 1 and Group 2 metal salts, such as LiF, CsF, and Cs 2 CO 3 ; Group 1 and Group 2 metal organic compounds, such as Lithium quinoline; and molecular n-type dopants, such as leuco dyes, metal complexes, such as W 2 (hpp) 4 (where hpp = 1,3,4,6,7,8-hexahydro-2H- Pyrimido-[1,2-a]-pyrimidine) and cobaltocene, tetrathiotetraphenyl, bis(ethylidenedithio)tetrathiofulvalene, heterocyclic or divalent groups, and Dimers, oligomers, polymers, dispiro compounds and polycyclic compounds of heterocyclic groups or divalent groups.

可以在電子傳輸層上沈積視需要的電子注入層。電子注入材料的實例包括但不限於含Li的有機金屬化合物，LiF、Li2 O、喹啉鋰；含Cs的有機金屬化合物，CsF、Cs2 O和Cs2 CO3 。該層可與下面的電子傳輸層、上面覆蓋的陰極或兩者反應。當存在電子注入層時，沈積的材料的量通常在1~100 Å的範圍內，在一些實施例中1~10 Å。An optional electron injection layer can be deposited on the electron transport layer. Examples of electron injection materials include, but are not limited to, organometallic compounds containing Li, LiF, Li 2 O, and lithium quinoline; organometallic compounds containing Cs, CsF, Cs 2 O, and Cs 2 CO 3 . This layer can react with the underlying electron transport layer, the overlying cathode or both. When an electron injection layer is present, the amount of material deposited is usually in the range of 1-100 Å, in some embodiments 1-10 Å.

陰極130係對於注入電子或負電荷載體尤其有效的電極。陰極可以是具有低於陽極的功函的任何金屬或非金屬。用於陰極的材料可以選自第1族的鹼金屬（例如，Li、Cs），第2族（鹼土）金屬，第12族金屬，包括稀土元素和鑭系元素，以及錒系元素。可以使用如鋁、銦、鈣、鋇、釤和鎂、以及組合的材料。The cathode 130 is an electrode that is particularly effective for injecting electrons or negative charge carriers. The cathode can be any metal or non-metal with a lower work function than the anode. The material used for the cathode may be selected from Group 1 alkali metals (eg, Li, Cs), Group 2 (alkaline earth) metals, Group 12 metals, including rare earth elements and lanthanides, and actinides. Materials such as aluminum, indium, calcium, barium, samarium, and magnesium, and combinations can be used.

已知在有機電子裝置中具有其他層。例如，在陽極110與電洞注入層（未示出）之間可存在多個層（未示出）以控制注入的正電荷的量和/或提供層的帶隙匹配，或用作保護層。可以使用本領域中已知的層，如銅酞菁、氮氧化矽、碳氟化合物、矽烷、或金屬（如Pt）的超薄層。可替代地，可以對陽極層110、主動層120或陰極層130中的一些或全部進行表面處理以增加電荷載體傳輸效率。較佳的是藉由平衡發射極層中的正電荷和負電荷來確定每個部件層的材料的選擇，以提供具有高電致發光效率的裝置。It is known to have other layers in organic electronic devices. For example, there may be multiple layers (not shown) between the anode 110 and the hole injection layer (not shown) to control the amount of positive charge injected and/or to provide band gap matching of the layers, or to serve as a protective layer . Layers known in the art may be used, such as ultra-thin layers of copper phthalocyanine, silicon oxynitride, fluorocarbon, silane, or metals (such as Pt). Alternatively, some or all of the anode layer 110, the active layer 120, or the cathode layer 130 may be surface-treated to increase charge carrier transfer efficiency. It is preferable to determine the material selection of each component layer by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescence efficiency.

應當理解，每個功能層可由多於一個層構成。It should be understood that each functional layer may be composed of more than one layer.

裝置層通常可以藉由任何沈積技術或技術的組合形成，包括氣相沈積、液相沈積和熱轉移。可使用如玻璃、塑膠和金屬的基板。可使用常規的氣相沈積技術，如熱蒸發、化學氣相沈積等。可使用常規的塗覆或印刷技術，包括但不限於塗覆、浸塗、卷對卷技術、噴墨印刷、連續噴嘴印刷、網版印刷、凹版印刷等，由合適溶劑中的溶液或分散體來施用有機層。The device layer can generally be formed by any deposition technique or combination of techniques, including vapor deposition, liquid deposition, and thermal transfer. Substrates such as glass, plastic and metal can be used. Conventional vapor deposition techniques such as thermal evaporation, chemical vapor deposition, etc. can be used. Conventional coating or printing techniques can be used, including but not limited to coating, dip coating, roll-to-roll technology, inkjet printing, continuous nozzle printing, screen printing, gravure printing, etc., from solutions or dispersions in suitable solvents To apply the organic layer.

對於液相沈積方法，所屬技術領域具有通常知識者可容易地確定用於特定化合物或相關類別化合物的合適溶劑。對於一些應用，希望該等化合物溶解於非水溶劑中。此類非水溶劑可以是相對極性的，如C1 至C20 醇、醚和酸酯，或可以是相對非極性的，如C1 至C12 烷烴或芳香族化合物如甲苯、二甲苯、三氟甲苯等。其他合適的用於製造包括新化合物的液體組成物（如本文所述的作為溶液或分散體）的液體包括但不限於氯化烴（如二氯甲烷、氯仿、氯苯）、芳烴（如取代的和未取代的甲苯和二甲苯，包括三氟甲苯）、極性溶劑（如四氫呋喃（THP）、N-甲基吡咯啶酮）、酯（如乙酸乙酯）、醇（異丙醇）、酮（環戊酮）、以及它們的混合物。用於電致發光材料的合適溶劑已經在例如公佈的PCT申請WO 2007/145979中進行了描述。For the liquid-phase deposition method, those skilled in the art can easily determine a suitable solvent for a specific compound or a related class of compounds. For some applications, it is desirable to dissolve these compounds in non-aqueous solvents. Such non-aqueous solvents may be relatively polar, such as C 1 to C 20 alcohols, ethers, and acid esters, or may be relatively non-polar, such as C 1 to C 12 alkanes or aromatic compounds such as toluene, xylene, tris Fluorotoluene, etc. Other suitable liquids for manufacturing liquid compositions including new compounds (as described herein as solutions or dispersions) include, but are not limited to, chlorinated hydrocarbons (such as methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (such as substituted And unsubstituted toluene and xylene, including trifluorotoluene), polar solvents (such as tetrahydrofuran (THP), N-methylpyrrolidone), esters (such as ethyl acetate), alcohols (isopropanol), ketones (Cyclopentanone), and their mixtures. Suitable solvents for electroluminescent materials have been described in, for example, published PCT application WO 2007/145979.

在一些實施例中，該裝置藉由將電洞注入層、電洞傳輸層和光主動層液相沈積，以及藉由將陽極、電子傳輸層、電子注入層和陰極氣相沈積到可撓性基板上而製成。In some embodiments, the device is by liquid deposition of a hole injection layer, a hole transport layer, and a photoactive layer, and by vapor deposition of an anode, an electron transport layer, an electron injection layer, and a cathode onto a flexible substrate Made from above.

應當理解，可藉由優化裝置中的其他層來提高裝置的效率。例如，可使用更有效的陰極如Ca、Ba或LiF。導致操作電壓降低或增加量子效率的成型基板和新型電洞傳輸材料也是可應用的。還可增加附加層以定製各個層的能級並且促進電致發光。It should be understood that the efficiency of the device can be improved by optimizing other layers in the device. For example, a more effective cathode such as Ca, Ba or LiF can be used. Molded substrates and new hole-transporting materials that lead to reduced operating voltage or increased quantum efficiency are also applicable. Additional layers can also be added to customize the energy level of each layer and promote electroluminescence.

在一些實施例中，該裝置按順序具有以下結構：基板、陽極、電洞注入層、電洞傳輸層、光主動層、電子傳輸層、電子注入層、陰極。In some embodiments, the device has the following structure in order: substrate, anode, hole injection layer, hole transport layer, photoactive layer, electron transport layer, electron injection layer, cathode.

儘管與本文所述的那些類似或等同的方法和材料可用於本發明的實踐或測試中，但是在下面描述了合適的方法和材料。此外，材料、方法和實例僅為說明性的並且不旨在係限制性的。本文提及的所有的公開物、專利申請、專利、以及其他參考文獻均藉由援引以其全文併入本文。Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.

實例Examples

本文所述的概念將在以下實例中進一步說明，該等實例不限制申請專利範圍中所述的本發明的範圍。The concepts described herein will be further illustrated in the following examples, which do not limit the scope of the invention described in the patent application.

合成實例1Synthesis Example 1

此實例說明了具有式I之化合物（化合物1）的製備。This example illustrates the preparation of the compound of formula I (Compound 1).

根據在文獻（J. Mater. Chem. A [材料化學雜誌A],2014 ,2 , 13309-13320）中報導的方法製備4,4'-[(9,10-二氫-9,10[1',2']-苯并蒽-1,4-二基)雙(氧基)]雙[3-(三氟甲基)苯胺。According to the method reported in the literature ( J. Mater. Chem. A [Journal of Materials Chemistry A], 2014 , 2 , 13309-13320), 4,4'-[(9,10-dihydro-9,10[1 ',2']-Benzanthracene-1,4-diyl)bis(oxy)]bis[3-(trifluoromethyl)aniline.

合成實例2Synthesis Example 2

此實例說明了具有式I之化合物（化合物2）的製備。

Figure 02_image079
This example illustrates the preparation of the compound of formula I (Compound 2).
Figure 02_image079

步驟1：蒽-2,6-二醇： 向裝配有機械攪拌器、內部溫度計以及氮氣鼓泡器的10 L的4頸圓底燒瓶中裝入在2600 mL的1 M碳酸鈉溶液中的硼氫化鈉（122 g，3330.0 mmol）。之後，在室溫下經5 h將2,6-二羥基蒽-9,10-二酮（50 g，208.1 mmol，以10等份）添加至溶液中。在2,6-二羥基蒽-9,10-二酮添加完成後，使反應混合物在室溫下經受攪拌。24 h後，在0ºC~5ºC下將反應混合物倒入6 M HCl和乙酸乙酯的混合物（200 mL，1 : 1比例）中。用乙酸乙酯（100 x 3次）萃取水層。將組合的有機層用飽和碳酸氫鈉溶液（100 mL）洗滌、經無水硫酸鈉乾燥、過濾、並且在減壓下濃縮以獲得黃色固體，將其在50ºC下在真空下乾燥8 h以產生呈黃色固體的蒽-2,6-二醇（14035.0 g，80%）。1H NMR (400 MHz, DMSO-d6) δ: 9.65 (s, 2H), 8.15 (s, 2H), 7.83 (d, J = 9.2 Hz, 2H), 7.14 (d, J = 2.4 Hz, 2H), 7.08 (dd, J = 2.4 Hz和9.2 Hz, 2H)；UPLC：95.25%純度。Step 1: Anthracene-2,6-diol: A 10 L 4-neck round bottom flask equipped with a mechanical stirrer, internal thermometer, and nitrogen bubbler was charged with sodium borohydride (122 g, 3330.0 mmol) in 2600 mL of a 1 M sodium carbonate solution. After that, 2,6-dihydroxyanthracene-9,10-dione (50 g, 208.1 mmol, in 10 equal parts) was added to the solution over 5 h at room temperature. After the addition of 2,6-dihydroxyanthracene-9,10-dione was completed, the reaction mixture was subjected to stirring at room temperature. After 24 h, the reaction mixture was poured into a mixture of 6 M HCl and ethyl acetate (200 mL, 1:1 ratio) at 0ºC~5ºC. The aqueous layer was extracted with ethyl acetate (100 x 3 times). The combined organic layer was washed with saturated sodium bicarbonate solution (100 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a yellow solid, which was dried under vacuum at 50ºC for 8 h to produce Anthracene-2,6-diol as a yellow solid (14035.0 g, 80%). 1H NMR (400 MHz, DMSO-d6) δ: 9.65 (s, 2H), 8.15 (s, 2H), 7.83 (d, J = 9.2 Hz, 2H), 7.14 (d, J = 2.4 Hz, 2H), 7.08 (dd, J = 2.4 Hz and 9.2 Hz, 2H); UPLC: 95.25% purity.

步驟2：2,6-二甲氧基蒽： 向裝配有機械攪拌器、內部溫度計以及氮氣鼓泡器的10 L的4頸圓底燒瓶中裝入在丙酮（7500 mL）中的蒽-2,6-二醇（140.0 g，665.9 mmol）和碳酸鉀（1194.0 g，8656.0 mmol）。之後，在室溫下滴加硫酸二甲酯（1258.0 g，9988.0 mmol）。在硫酸二甲酯添加完成後，將反應混合物加熱至70ºC~75ºC。持續16 h後，將反應混合物冷卻至室溫並且倒入水（1000 mL）中。所得固體藉由過濾收集，用水（100 mL）洗滌，並且在真空下乾燥。向固體中添加乙酸乙酯（250 mL）並且在室溫下攪拌30 min。固體材料藉由過濾收集並且在真空下乾燥，以產生呈黃色固體的2,6-二甲氧基蒽（130.0 g，82%）。1H NMR (400 MHz, CDCl3) δ: 8.20 (s, 2H), 7.84 (d, J = 9.2 Hz, 2H), 7.18-7.13 (m, 4H), 3.96 (s, 6H)；UPLC：96.87%純度。Step 2: 2,6-Dimethoxyanthracene: A 10-L 4-neck round bottom flask equipped with a mechanical stirrer, internal thermometer, and nitrogen bubbler was charged with anthracene-2,6-diol (140.0 g, 665.9 mmol) in acetone (7500 mL) and Potassium carbonate (1194.0 g, 8656.0 mmol). After that, dimethyl sulfate (1258.0 g, 9988.0 mmol) was added dropwise at room temperature. After the addition of dimethyl sulfate is completed, the reaction mixture is heated to 70ºC~75ºC. After continuing for 16 h, the reaction mixture was cooled to room temperature and poured into water (1000 mL). The resulting solid was collected by filtration, washed with water (100 mL), and dried under vacuum. Ethyl acetate (250 mL) was added to the solid and stirred at room temperature for 30 min. The solid material was collected by filtration and dried under vacuum to produce 2,6-dimethoxyanthracene (130.0 g, 82%) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ: 8.20 (s, 2H), 7.84 (d, J = 9.2 Hz, 2H), 7.18-7.13 (m, 4H), 3.96 (s, 6H); UPLC: 96.87% purity .

步驟3：(9R,10R)-2,6-二甲氧基-9,10-二氫-9,10-[1,2]苯并蒽9,10-二氫-2,6-二甲氧基-9,10[1',2']-苯并蒽： 向裝配有機械攪拌器、內部溫度計以及氮氣鼓泡器的10 L的4頸圓底燒瓶中裝入在二氯乙烷（5000 mL）中的2,6-二甲氧基蒽（50 g，209.8 mmol）和1,2-環氧丙烷（621 mL，8895 mmol）。在合成重氮鹽的同時將以上反應混合物靜置。在室溫下，向另一個裝配有機械攪拌器、內部溫度計以及氮氣鼓泡器的5 L的4頸圓底燒瓶中裝入在乙醇（1275 mL）中的鄰胺基苯甲酸（115 g，839.0 mmol）。之後，在0ºC~5ºC下添加濃HCl（84 mL）以及亞硝酸異戊酯（210 mL）。在0ºC~5ºC下將混合物攪拌10 min，然後添加二***（1200 mL），並且在25ºC~27ºC下繼續攪拌10 min。將所得重氮鹽 (4) 小心地濾出，用二***（50 mL）洗滌並且在真空下輕度乾燥2 min（注意：因為作為重氮鹽的化合物4係對熱敏感且對衝擊敏感的材料，所以在後處理過程中應採取防範措施，並且濾餅不應完全乾燥）。將所得鹽轉移至以上含有在二氯乙烷中的2,6-二甲氧基蒽和1,2-環氧丙烷的10 L燒瓶中。在1 h內將反應混合物緩慢加熱至80ºC~85ºC。16 h後，將反應混合物在減壓下濃縮以獲得粗殘餘物。將粗化合物殘餘物藉由矽膠柱層析法（100~200矽膠和二氯甲烷/己烷作為洗脫液）純化以獲得淡黃色固體，將其在真空下在40ºC下乾燥1 h，以產生呈淡黃色固體的(9R,10R)-2,6-二甲氧基-9,10-二氫-9,10-[1,2]苯并蒽9,10-二氫-2,6-二甲氧基-9,10[1',2']-苯并蒽（32.0 g，60%）。1H NMR (400 MHz, CDCl3) δ: 7.35-7.33 (m, 2H), 7.25-7.24 (m, 2H), 6.98-6.96 (m, 4H), 6.48-6.46 (m, 2H), 5.29 (s, 2H), 3.72 (s, 6H)；LCMS：315.15 [M+H]+；UPLC：90.90%純度。Step 3: (9R,10R)-2,6-dimethoxy-9,10-dihydro-9,10-[1,2]benzoanthracene 9,10-dihydro-2,6-dimethyl Oxo-9,10[1',2']-benzoanthracene: A 10-L 4-neck round bottom flask equipped with a mechanical stirrer, internal thermometer, and nitrogen bubbler was charged with 2,6-dimethoxyanthracene (50 g, in dichloroethane (5000 mL) 209.8 mmol) and 1,2-propylene oxide (621 mL, 8895 mmol). The above reaction mixture was allowed to stand while synthesizing the diazonium salt. At room temperature, another 5 L 4-neck round bottom flask equipped with a mechanical stirrer, internal thermometer, and nitrogen bubbler was charged with o-aminobenzoic acid (115 g, in ethanol (1275 mL), 839.0 mmol). After that, add concentrated HCl (84 mL) and isoamyl nitrite (210 mL) at 0ºC~5ºC. Stir the mixture at 0ºC~5ºC for 10 min, then add diethyl ether (1200 mL), and continue stirring at 25ºC~27ºC for 10 min. The resulting diazonium salt (4) was carefully filtered out, washed with diethyl ether (50 mL) and lightly dried under vacuum for 2 min (Note: because Compound 4 as the diazonium salt is heat-sensitive and shock-sensitive Materials, so precautions should be taken during post-processing, and the filter cake should not be completely dried). The resulting salt was transferred to the above 10 L flask containing 2,6-dimethoxyanthracene and 1,2-propylene oxide in dichloroethane. The reaction mixture was slowly heated to 80ºC~85ºC within 1 h. After 16 h, the reaction mixture was concentrated under reduced pressure to obtain a crude residue. The crude compound residue was purified by silica gel column chromatography (100-200 silica gel and dichloromethane/hexane as eluents) to obtain a pale yellow solid, which was dried under vacuum at 40ºC for 1 h to produce (9R,10R)-2,6-dimethoxy-9,10-dihydro-9,10-[1,2]benzoanthracene 9,10-dihydro-2,6- Dimethoxy-9,10[1',2']-benzoanthracene (32.0 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 7.35-7.33 (m, 2H), 7.25-7.24 (m, 2H), 6.98-6.96 (m, 4H), 6.48-6.46 (m, 2H), 5.29 (s, 2H), 3.72 (s, 6H); LCMS: 315.15 [M+H]+; UPLC: 90.90% purity.

步驟4：(9R,10R)-9,10-二氫-9,10-[1’,2’]苯并蒽-2,6-二醇： 在室溫下，向裝配有機械攪拌器、內部溫度計以及CaCl2防護管的3 L的4頸圓底燒瓶中裝入在二氯甲烷（1200 mL）中的(9R,10R)-2,6-二甲氧基-9,10-二氫-9,10-[1,2]苯并蒽9,10-二氫-2,6-二甲氧基-9,10[1',2']-苯并蒽（40 g，127.2 mmol）。在0ºC~5ºC下滴加三溴化硼（191 g，763.0 mmol）。使混合物達到室溫並且繼續攪拌。2 h後，用冰冷水（100 mL）淬滅反應，並且用乙酸乙酯-二氯甲烷（1 : 1）的混合物（100 mL x 3次）萃取。將組合的有機相經無水硫酸鈉乾燥、過濾並且在減壓下濃縮。將粗化合物溶解在乙酸乙酯中，將其穿過中性氧化鋁-Florisil® 墊並且在減壓下濃縮，以獲得固體。將固體藉由使用Et2 O-DCM二***-二氯甲烷的共沈澱進一步純化，以產生呈灰白色固體的9,10-二氫-9,10-[1’,2’]苯并蒽-2,6-二醇(9R,10R)-9,10-二氫-9,10-[1,2]苯并蒽-2,6-二醇（30.0 g，82%）。1H NMR (400 MHz, DMSO-d6) δ: 9.15 (s, 2H), 7.36-7.32 (m, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.97-6.94 (m, 2H), 6.82 (d, J = 2.4 Hz, 2H), 6.31 (dd, J = 2.4 Hz和8.0 Hz, 2H), 5.33 (s, 2H)；UPLC：99.03%純度。Step 4: (9R,10R)-9,10-dihydro-9,10-[1',2']benzoanthracene-2,6-diol: At room temperature, a mechanical stirrer, A 3-L 4-neck round bottom flask with an internal thermometer and a CaCl2 protective tube was charged with (9R,10R)-2,6-dimethoxy-9,10-dihydro- in dichloromethane (1200 mL) 9,10-[1,2]benzoanthracene 9,10-dihydro-2,6-dimethoxy-9,10[1',2']-benzoanthracene (40 g, 127.2 mmol). Boron tribromide (191 g, 763.0 mmol) was added dropwise at 0ºC~5ºC. Bring the mixture to room temperature and continue stirring. After 2 h, the reaction was quenched with ice cold water (100 mL), and extracted with a mixture of ethyl acetate-dichloromethane (1:1) (100 mL x 3 times). The combined organic phase was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude compound was dissolved in ethyl acetate, which was passed through a pad of neutral alumina -Florisil ® and concentrated under reduced pressure to obtain a solid. The solid was further purified by co-precipitation using Et 2 O-DCM diethyl ether-dichloromethane to produce 9,10-dihydro-9,10-[1′,2′]benzoanthracene- as an off-white solid 2,6-diol (9R,10R)-9,10-dihydro-9,10-[1,2]benzoanthracene-2,6-diol (30.0 g, 82%). 1H NMR (400 MHz, DMSO-d6) δ: 9.15 (s, 2H), 7.36-7.32 (m, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.97-6.94 (m, 2H), 6.82 (d, J = 2.4 Hz, 2H), 6.31 (dd, J = 2.4 Hz and 8.0 Hz, 2H), 5.33 (s, 2H); UPLC: 99.03% purity.

步驟5：(9R,10R)-9,10-二氫-9,10-[1’,2’]苯并蒽-2,6-二基雙(三氟甲磺酸酯)： 在室溫下，向裝配有機械攪拌器、內部溫度計以及氮氣鼓泡器的2 L的4頸圓底燒瓶中裝入在二氯甲烷（600 mL）中的9,10-二氫-9,10-[1’,2’]苯并蒽-2,6-二醇(9R,10R)-9,10-二氫-9,10-[1,2]苯并蒽-2,6-二醇（30 g，104.7 mmol）、吡啶（101.5 mL，1256.4 mmol）。之後，在0ºC~5ºC下經20 min滴加三氟甲烷磺酸酐（106.2 mL，628.2 mmol）。在三氟甲烷磺酸酐添加完成後，將反應混合物在室溫下攪拌。2 h後，將反應混合物用二氯甲烷（300 mL）稀釋並且用水（500 mL）和鹽水（250 mL）洗滌。將有機層經無水硫酸鈉乾燥、經Na2 SO4 過濾、並且在減壓下濃縮。將殘餘物藉由矽膠柱層析法（100~200矽膠和2%-30%乙酸乙酯/己烷作為洗脫液）純化，以產生灰白色固體。向固體中添加乙醇（60 mL）並且在室溫下攪拌30 min。固體材料在室溫下藉由過濾收集並且在真空下乾燥，以產生呈白色固體的9,10-二氫-9,10-[1’,2’]苯并蒽-2,6-二基雙(三氟甲磺酸酯)(9R,10R)-9,10-二氫-9,10-[1,2]苯并蒽-2,6-二基雙(三氟甲磺酸酯)（32 g，66%）。熔點：106ºC~108ºC；FT-IR：1210.22 cm-1 （C-F）；1H NMR (400 MHz, CDCl3) δ: 7.44-7.40 (m, 4H), 7.31 (d, J = 2.0 Hz, 2H), 7.08-7.06 (m, 2H), 6.94 (dd, J = 2.4 Hz和8.4 Hz, 2H), 5.48 (s, 2H)；GCMS：550.1 [M]+ ；UPLC：99.51%純度。Step 5: (9R,10R)-9,10-dihydro-9,10-[1',2']benzoanthracene-2,6-diylbis(trifluoromethanesulfonate): at room temperature Next, a 2-L 4-neck round bottom flask equipped with a mechanical stirrer, internal thermometer, and nitrogen bubbler was charged with 9,10-dihydro-9,10-[ in dichloromethane (600 mL) 1',2'] Benzoanthracene-2,6-diol (9R,10R)-9,10-dihydro-9,10-[1,2]benzoanthracene-2,6-diol (30 g, 104.7 mmol), pyridine (101.5 mL, 1256.4 mmol). After that, trifluoromethanesulfonic anhydride (106.2 mL, 628.2 mmol) was added dropwise at 0ºC~5ºC for 20 min. After the addition of trifluoromethanesulfonic anhydride was completed, the reaction mixture was stirred at room temperature. After 2 h, the reaction mixture was diluted with dichloromethane (300 mL) and washed with water (500 mL) and brine (250 mL). The organic layer was dried over anhydrous sodium sulfate, filtered through Na 2 SO 4 , and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (100-200 silica gel and 2%-30% ethyl acetate/hexane as eluent) to produce an off-white solid. Ethanol (60 mL) was added to the solid and stirred at room temperature for 30 min. The solid material was collected by filtration at room temperature and dried under vacuum to produce 9,10-dihydro-9,10-[1',2']benzoanthracene-2,6-diyl as a white solid Bis(trifluoromethanesulfonate)(9R,10R)-9,10-dihydro-9,10-[1,2]benzoanthracene-2,6-diylbis(trifluoromethanesulfonate) (32 g, 66%). Melting point: 106ºC~108ºC; FT-IR: 1210.22 cm -1 (CF); 1H NMR (400 MHz, CDCl3) δ: 7.44-7.40 (m, 4H), 7.31 (d, J = 2.0 Hz, 2H), 7.08 -7.06 (m, 2H), 6.94 (dd, J = 2.4 Hz and 8.4 Hz, 2H), 5.48 (s, 2H); GCMS: 550.1 [M] + ; UPLC: 99.51% purity.

步驟6：(9R,10R)-2,6-雙(4,4,5,5-四甲基-1,3,2-二氧雜戊硼烷-2-基)-9,10-二氫-9,10-[1’,2’]苯并蒽： 在室溫下，向裝配有磁力攪拌器的1 L鋼製反應釜中裝入在1,4-二㗁𠮿（225 mL）中的9,10-二氫-9,10-[1’,2’]苯并蒽-2,6-二基雙(三氟甲磺酸酯)(9R,10R)-9,10-二氫-9,10-[1,2]苯并蒽-2,6-二基雙(三氟甲磺酸酯)（15 g，27.2 mmol）、雙(頻哪醇合)二硼（17.3 g，68.1 mmol）以及乙酸鉀（16.0 g，163.5 mmol）。將混合物用氬氣吹掃15 min，然後將1,1'-雙[(二苯基膦基)二茂鐵]二氯化鈀(II)（與二氯甲烷複合）（2.2 g，2.72 mmol）添加至反應混合物中，並且繼續氬氣吹掃10 min。將反應混合物加熱至95ºC~100ºC。16 h後，將反應混合物冷卻至室溫，通過Celite®床過濾，並將該床用乙酸乙酯（500 mL）洗滌。將組合的濾液用水（300 mL）、鹽水（100 mL）洗滌、經無水硫酸鈉乾燥、經Na2 SO4 過濾並且在減壓下濃縮。向固體中添加乙醇（25 mL）並且在室溫下攪拌30 min。固體材料藉由過濾收集並且在真空下乾燥，以產生呈灰白色固體的2,6-雙(4,4,5,5-四甲基-1,3,2-二氧雜戊硼烷-2-基)-9,10-二氫-9,10-[1’,2’]苯并蒽(9R,10R)-2,6-雙(4,4,5,5-四甲基-1,3,2-二氧雜戊硼烷-2-基)-9,10-二氫-9,10-[1,2]苯并蒽（12.0 g，87%）。1H NMR (400 MHz, CDCl3) δ: 7.81 (s, 2H), 7.47 (dd, J = 1.2 Hz和7.6 Hz, 2H), 7.37-7.32 (m, 4H), 6.96-6.94 (m, 2H), 5.43 (s, 2H), 1.29 (s, 24H)；GCMS：506.0 [M]+ ；UPLC：98.37%純度。Step 6: (9R,10R)-2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-di Hydrogen-9,10-[1',2'] Benzoanthracene: At room temperature, a 1 L steel reactor equipped with a magnetic stirrer was charged with 1,4-two㗁𠮿 (225 mL) 9,10-dihydro-9,10-[1',2']benzoanthracene-2,6-diylbis(trifluoromethanesulfonate)(9R,10R)-9,10-di Hydrogen-9,10-[1,2]benzoanthracene-2,6-diylbis(trifluoromethanesulfonate) (15 g, 27.2 mmol), bis(pinacolate) diboron (17.3 g , 68.1 mmol) and potassium acetate (16.0 g, 163.5 mmol). The mixture was purged with argon for 15 min, then 1,1'-bis[(diphenylphosphino)ferrocene]palladium(II) dichloride (complexed with dichloromethane) (2.2 g, 2.72 mmol ) Add to the reaction mixture and continue the argon purge for 10 min. Heat the reaction mixture to 95ºC~100ºC. After 16 h, the reaction mixture was cooled to room temperature, filtered through a Celite® bed, and the bed was washed with ethyl acetate (500 mL). The combined filtrate was washed with water (300 mL), brine (100 mL), dried over anhydrous sodium sulfate, filtered through Na 2 SO 4 and concentrated under reduced pressure. Ethanol (25 mL) was added to the solid and stirred at room temperature for 30 min. The solid material was collected by filtration and dried under vacuum to produce 2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2 as an off-white solid -Yl)-9,10-dihydro-9,10-[1',2']benzoanthracene(9R,10R)-2,6-bis(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzoanthracene (12.0 g, 87%). 1H NMR (400 MHz, CDCl3) δ: 7.81 (s, 2H), 7.47 (dd, J = 1.2 Hz and 7.6 Hz, 2H), 7.37-7.32 (m, 4H), 6.96-6.94 (m, 2H), 5.43 (s, 2H), 1.29 (s, 24H); GCMS: 506.0 [M] + ; UPLC: 98.37% purity.

步驟7：4,4'-((9R,10R)-9,10-二氫-9,10-[1’,2’]苯并蒽-2,6-二基)雙(3-(三氟甲基)苯胺)（化合物2）： 在室溫下，向裝配有磁力攪拌器、內部溫度計以及氮氣鼓泡器的3 L的4頸圓底燒瓶中裝入在甲苯（800 mL）中的2,6-雙(4,4,5,5-四甲基-1,3,2-二氧雜戊硼烷-2-基)-9,10-二氫-9,10-[1’,2’]苯并蒽(9R,10R)-2,6-雙(4,4,5,5-四甲基-1,3,2-二氧雜戊硼烷-2-基)-9,10-二氫-9,10-[1,2]苯并蒽（40.0 g，79.0 mmol）、4-溴-3-(三氟甲基)苯胺（47.4 g，197.5 mmol）、2 M碳酸鈉Na2 CO3 水溶液（480 mL）以及Aliquat-336（2 mL）。氬氣吹掃通過混合物持續15 min，然後將四(三苯基膦)鈀(0)（9.1 g，7.9 mmol）添加至混合物中，並且再次吹掃氬氣10 min。將反應混合物加熱至100ºC~110ºC。16 h後，將反應混合物冷卻至室溫，通過Celite®床過濾，並將該床用乙酸乙酯（500 mL）洗滌。將組合的濾液用水（500 mL）、鹽水（100 mL）洗滌、經無水硫酸鈉乾燥、經Na2 SO4 過濾並且在減壓下濃縮。將殘餘物藉由矽膠柱層析法（100~200二氧化矽和15%~30%乙酸乙酯/己烷作為洗脫液）純化，隨後用二氯甲烷洗滌，以產生呈灰白色固體的4,4'-(9,10-二氫-9,10-[1’,2’]苯并蒽-2,6-二基)雙(3-(三氟甲基)苯胺)4,4'-((9R,10R)-9,10-二氫-9,10-[1,2]苯并蒽-2,6-二基)雙(3-(三氟甲基)苯胺)（26.2 g，57%）。熔點：192ºC~197ºC；FT-IR：1338.79 cm-1 （C-F）；1H NMR (400 MHz, DMSO-d6) δ: 7.47-7.45 (m, 2H), 7.42 (d, J = 7.2 Hz, 2H), 7.34 (s, 2H), 7.03-7.01 (m, 2H), 6.96 (d, J = 8.4 Hz, 2H), 6.92 (d, J = 2.0 Hz, 2H), 6.87 (d, J = 7.6 Hz, 2H), 6.75 (dd, J = 2.0 Hz和8.4 Hz, 2H), 5.68 (s, 2H), 5.60 (s, 4H)；19F NMR (376 MHz, DMSO-d6) δ: -55.31；LCMS：573.47 [M+H]+；UPLC：99.55%純度。Step 7: 4,4'-((9R,10R)-9,10-dihydro-9,10-[1',2']benzoanthracene-2,6-diyl)bis(3-(tri (Fluoromethyl)aniline) (Compound 2): At room temperature, a 3 L 4-neck round bottom flask equipped with a magnetic stirrer, internal thermometer, and nitrogen bubbler was charged with toluene (800 mL) 2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-(1',2']benzoanthracene (9R,10R)-2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9 ,10-dihydro-9,10-[1,2]benzoanthracene (40.0 g, 79.0 mmol), 4-bromo-3-(trifluoromethyl)aniline (47.4 g, 197.5 mmol), 2 M carbonic acid Sodium Na 2 CO 3 aqueous solution (480 mL) and Aliquat-336 (2 mL). Argon was purged through the mixture for 15 min, then tetrakis(triphenylphosphine)palladium(0) (9.1 g, 7.9 mmol) was added to the mixture, and argon was purged again for 10 min. Heat the reaction mixture to 100ºC~110ºC. After 16 h, the reaction mixture was cooled to room temperature, filtered through a Celite® bed, and the bed was washed with ethyl acetate (500 mL). The combined filtrate was washed with water (500 mL), brine (100 mL), dried over anhydrous sodium sulfate, filtered through Na 2 SO 4 and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (100-200 silica and 15%-30% ethyl acetate/hexane as eluent), followed by washing with dichloromethane to produce 4 as an off-white solid ,4'-(9,10-dihydro-9,10-[1',2']benzoanthracene-2,6-diyl)bis(3-(trifluoromethyl)aniline)4,4' -((9R,10R)-9,10-dihydro-9,10-[1,2]benzoanthracene-2,6-diyl)bis(3-(trifluoromethyl)aniline) (26.2 g , 57%). Melting point: 192ºC~197ºC; FT-IR: 1338.79 cm -1 (CF); 1H NMR (400 MHz, DMSO-d6) δ: 7.47-7.45 (m, 2H), 7.42 (d, J = 7.2 Hz, 2H) , 7.34 (s, 2H), 7.03-7.01 (m, 2H), 6.96 (d, J = 8.4 Hz, 2H), 6.92 (d, J = 2.0 Hz, 2H), 6.87 (d, J = 7.6 Hz, 2H), 6.75 (dd, J = 2.0 Hz and 8.4 Hz, 2H), 5.68 (s, 2H), 5.60 (s, 4H); 19F NMR (376 MHz, DMSO-d6) δ: -55.31; LCMS: 573.47 [M+H]+; UPLC: 99.55% purity.

合成實例3Synthesis Example 3

此實例說明了具有式I之化合物（化合物3）的製備。

Figure 02_image081
This example illustrates the preparation of the compound of formula I (Compound 3).
Figure 02_image081

步驟-1：9,10-二氫-9,10[1',2']-苯并蒽-1,4-二酮： 在室溫下，向裝配有機械攪拌器和內部溫度計的10 L的4頸圓底燒瓶中裝入在冰乙酸（2000 mL）中的蒽（200 g，1122.1 mmol）和對苯醌（424.6 g，3927.5 mmol）。將反應混合物加熱至110ºC~120ºC。4 h後，將反應混合物冷卻至室溫並且倒入水（6000 mL）中。將所得懸浮液在室溫下攪拌1 h。固體材料藉由過濾收集並且在真空下乾燥。在室溫下將乙醇（2000 mL）添加至固體中並且攪拌1 h。固體材料藉由過濾收集並且在真空下乾燥，以產生呈深棕色固體的9,10-二氫-9,10[1',2']-苯并蒽-1,4-二酮（243 g，76%）。熔點：292ºC~296ºC；1H NMR (400 MHz, CDCl3) δ: 7.45-7.40 (m, 4H), 7.06-7.02 (m, 4H), 6.60 (s, 2H), 5.79 (s, 2H)；MS：m/z = 285.2[M+H]+；LCMS：66.69%純度（3.41 min RT）；UPLC：79.56%純度。Step-1: 9,10-dihydro-9,10[1',2']-benzoanthracene-1,4-dione: At room temperature, a 10-L 4-neck round bottom flask equipped with a mechanical stirrer and internal thermometer was charged with anthracene (200 g, 1122.1 mmol) and p-benzoquinone (424.6 g in glacial acetic acid (2000 mL) , 3927.5 mmol). Heat the reaction mixture to 110ºC~120ºC. After 4 h, the reaction mixture was cooled to room temperature and poured into water (6000 mL). The resulting suspension was stirred at room temperature for 1 h. The solid material was collected by filtration and dried under vacuum. Ethanol (2000 mL) was added to the solid at room temperature and stirred for 1 h. The solid material was collected by filtration and dried under vacuum to produce 9,10-dihydro-9,10[1',2']-benzoanthracene-1,4-dione (243 g) as a dark brown solid , 76%). Melting point: 292ºC~296ºC; 1H NMR (400 MHz, CDCl3) δ: 7.45-7.40 (m, 4H), 7.06-7.02 (m, 4H), 6.60 (s, 2H), 5.79 (s, 2H); MS: m/z = 285.2 [M+H]+; LCMS: 66.69% purity (3.41 min RT); UPLC: 79.56% purity.

步驟-2：9,10-二氫-9,10[1',2']-苯并蒽-1,4-二醇： 在氬氣氣氛下，向2 L高壓釜反應器中裝入在乙酸乙酯（1250 mL）中的9,10-二氫-9,10[1',2']-苯并蒽-1,4-二酮（100 g，351.7 mmol）和10% Pd/C（10 g，9.4 mmol）。之後，將高壓釜密封並且用氫氣脫氣兩次。在25ºC~30ºC下在50 psi氫氣下攪拌反應混合物。16 h後，將反應混合物通過Celite®床過濾，並將該床用乙酸乙酯（1000 mL）洗滌。在減壓下將組合的濾液濃縮，然後添加二氯甲烷（300 mL）並且在室溫下攪拌1 h。固體材料藉由過濾收集並且在真空下乾燥，以產生呈棕色固體的9,10-二氫-9,10[1',2']-苯并蒽-1,4-二醇（44.31 g，44%）。熔點：245ºC~249ºC：1H NMR (400 MHz, DMSO-d6) δ: 8.81 (s, 2H), 7.39-7.37 (m, 4H), 6.98-6.96 (m, 4H), 6.30 (s, 2H), 5.80 (s, 2H)；MS：m/z = 287.3 [M+H]+；LCMS：89.21%純度（2.84 min RT）；UPLC：94.38%純度。Step-2: 9,10-dihydro-9,10[1',2']-benzoanthracene-1,4-diol: Under an argon atmosphere, a 2 L autoclave reactor was charged with 9,10-dihydro-9,10[1',2']-benzoanthracene-1 in ethyl acetate (1250 mL) 4-diketone (100 g, 351.7 mmol) and 10% Pd/C (10 g, 9.4 mmol). After that, the autoclave was sealed and degassed twice with hydrogen. The reaction mixture was stirred under 50 psi hydrogen at 25ºC~30ºC. After 16 h, the reaction mixture was filtered through a Celite® bed, and the bed was washed with ethyl acetate (1000 mL). The combined filtrate was concentrated under reduced pressure, and then dichloromethane (300 mL) was added and stirred at room temperature for 1 h. The solid material was collected by filtration and dried under vacuum to produce 9,10-dihydro-9,10[1',2']-benzoanthracene-1,4-diol (44.31 g, 44%). Melting point: 245ºC~249ºC: 1H NMR (400 MHz, DMSO-d6) δ: 8.81 (s, 2H), 7.39-7.37 (m, 4H), 6.98-6.96 (m, 4H), 6.30 (s, 2H), 5.80 (s, 2H); MS: m/z = 287.3 [M+H]+; LCMS: 89.21% purity (2.84 min RT); UPLC: 94.38% purity.

步驟-3：9,10-二氫-9,10-[1,2]苯并蒽-1,4-二基雙(三氟甲磺酸酯)： 在室溫下，向裝配有機械攪拌器、內部溫度計以及氮氣鼓泡器的3 L的4頸圓底燒瓶中裝入在二氯甲烷（1000 mL）中的9,10-二氫-9,10[1',2']-苯并蒽-1,4-二醇（50 g，174.6 mmol）、吡啶（70.3 mL、873.1 mmol），並且在0ºC下經20 min裝入三氟甲烷磺酸酐（73.3 mL，436.6 mmol）。在三氟甲烷磺酸酐添加完成後，將反應混合物在室溫下攪拌16 h。16 h後，將反應混合物用二氯甲烷（500 mL）稀釋並且用水（1000 mL）和鹽水（500 mL）洗滌。將有機層經無水硫酸鈉乾燥、過濾並且在減壓下濃縮。藉由矽膠柱層析法（2%~30%乙酸乙酯/己烷作為洗脫液）純化殘餘物，以產生淺棕色固體。向固體中添加乙醇（150 mL）並且在50ºC下攪拌30 min。固體材料在室溫下藉由過濾收集並且在真空下乾燥，以產生呈灰白色固體的9,10-二氫-9,10-[1,2]苯并蒽-1,4-二基雙(三氟甲磺酸酯)（64 g，66%）。熔點：199ºC~203ºC；FT-IR：1216.63 cm-1 （C-F）；1H NMR (400 MHz, DMSO-d6) δ: 7.58-7.55 (m, 4H), 7.42 (s, 2H), 7.13-7.09 (m, 4H); 5.96 (s, 2H)；19F NMR (376 MHz, DMSO-d6) δ: -72.60；LCMS：550.0 [M]+ ；UPLC：99.54%。Step-3: 9,10-dihydro-9,10-[1,2]benzoanthracene-1,4-diyl bis(trifluoromethanesulfonate): At room temperature, the machine is equipped with mechanical stirring 3 L 4-neck round-bottomed flask equipped with a pressure vessel, internal thermometer and nitrogen bubbler was charged with 9,10-dihydro-9,10[1',2']-benzene in dichloromethane (1000 mL) Phenanthrene-1,4-diol (50 g, 174.6 mmol), pyridine (70.3 mL, 873.1 mmol), and trifluoromethanesulfonic anhydride (73.3 mL, 436.6 mmol) was charged at 0ºC for 20 min. After the addition of trifluoromethanesulfonic anhydride was completed, the reaction mixture was stirred at room temperature for 16 h. After 16 h, the reaction mixture was diluted with dichloromethane (500 mL) and washed with water (1000 mL) and brine (500 mL). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (2%~30% ethyl acetate/hexane as eluent) to produce a light brown solid. Add ethanol (150 mL) to the solid and stir at 50ºC for 30 min. The solid material was collected by filtration at room temperature and dried under vacuum to produce 9,10-dihydro-9,10-[1,2]benzoanthracene-1,4-diylbis( Trifluoromethanesulfonate) (64 g, 66%). Melting point: 199ºC~203ºC; FT-IR: 1216.63 cm -1 (CF); 1H NMR (400 MHz, DMSO-d6) δ: 7.58-7.55 (m, 4H), 7.42 (s, 2H), 7.13-7.09 ( m, 4H); 5.96 (s, 2H); 19F NMR (376 MHz, DMSO-d6) δ: -72.60; LCMS: 550.0 [M] + ; UPLC: 99.54%.

步驟-4：1,4-雙(4,4,5,5-四甲基-1,3,2-二氧雜戊硼烷-2-基)-9,10-二氫-9,10-[1,2]苯并蒽： 在室溫下，向裝配有磁力攪拌器的450 mL鋼製反應釜中裝入在1,4-二㗁𠮿（270 mL）中的9,10-二氫-9,10-[1,2]苯并蒽-1,4-二基雙(三氟甲磺酸酯)（18 g，32.7 mmol）、雙(頻哪醇合)二硼（24.9 g，98.1 mmol）以及乙酸鉀（22.5 g，228.9 mmol）。將混合物用氬氣吹掃15 min，然後添加1,1'-雙[(二苯基膦基)二茂鐵]二氯化鈀(II)（與二氯甲烷複合）（2.9 g，3.5 mmol），並且將反應混合物進一步用氬氣吹掃10 min。將反應混合物加熱至110ºC~120ºC。16 h後，將反應混合物冷卻至室溫，通過Celite®床過濾，並將該床用乙酸乙酯（600 mL）洗滌。將組合的濾液用水（500 mL）、鹽水（300 mL）洗滌，經無水硫酸鈉乾燥，過濾，並且在減壓下濃縮。藉由矽膠柱層析法（2%~10%乙酸乙酯/己烷作為洗脫液）純化殘餘物，以產生灰白色固體。向固體中添加乙醇（20 mL）並且在室溫下攪拌30 min。固體材料藉由過濾收集並且在真空下乾燥，以產生呈白色固體的1,4-雙(4,4,5,5-四甲基-1,3,2-二氧雜戊硼烷-2-基)-9,10-二氫-9,10-[1,2]苯并蒽（9.9 g，60%）。1H NMR (400 MHz, CDCl3) δ: 7.39-7.36 (m, 6H), 6.97-6.95 (m, 4H), 6.52 (s, 2H); 1.43 (s, 24H)；GCMS：506.0 [M]+ ；UPLC：95.50%純度。Step-4: 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10 -[1,2]Benzanthracene: At room temperature, a 450 mL steel reactor equipped with a magnetic stirrer was charged with 9,10-II in 1,4-dioxane (270 mL) Hydrogen-9,10-[1,2]benzoanthracene-1,4-diylbis(trifluoromethanesulfonate) (18 g, 32.7 mmol), bis(pinacolate) diboron (24.9 g , 98.1 mmol) and potassium acetate (22.5 g, 228.9 mmol). The mixture was purged with argon for 15 min, then 1,1'-bis[(diphenylphosphino)ferrocene]palladium(II) dichloride (complexed with dichloromethane) (2.9 g, 3.5 mmol ), and the reaction mixture was further purged with argon for 10 min. Heat the reaction mixture to 110ºC~120ºC. After 16 h, the reaction mixture was cooled to room temperature, filtered through a Celite® bed, and the bed was washed with ethyl acetate (600 mL). The combined filtrate was washed with water (500 mL), brine (300 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (2%~10% ethyl acetate/hexane as eluent) to produce an off-white solid. Ethanol (20 mL) was added to the solid and stirred at room temperature for 30 min. The solid material was collected by filtration and dried under vacuum to produce 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2 as a white solid -Yl)-9,10-dihydro-9,10-[1,2]benzoanthracene (9.9 g, 60%). 1H NMR (400 MHz, CDCl3) δ: 7.39-7.36 (m, 6H), 6.97-6.95 (m, 4H), 6.52 (s, 2H); 1.43 (s, 24H); GCMS: 506.0 [M] + ; UPLC: 95.50% purity.

步驟-5：4,4'-(9,10-二氫-9,10-[1,2]苯并蒽-1,4-二基)雙(3-(三氟甲基)苯胺)（化合物2）： 在室溫下，向裝配有磁力攪拌器、內部溫度計以及氮氣鼓泡器的1 L的4頸圓底燒瓶中裝入在甲苯（400 mL）中的1,4-雙(4,4,5,5-四甲基-1,3,2-二氧雜戊硼烷-2-基)-9,10-二氫-9,10-[1,2]苯并蒽（20.0 g，39.5 mmol）、4-溴-3-(三氟甲基)苯胺（19.9 g，83.0 mmol）、2 M碳酸鈉水溶液（120 mL）以及Aliquat-336（2 mL）。將混合物用氬氣吹掃15 min，然後添加四(三苯基膦)鈀(0)（4.6 g，3.9 mmol），並且再繼續氬氣吹掃10 min。將反應混合物加熱至110ºC~120ºC。16 h後，將反應混合物冷卻至室溫，通過Celite®床過濾，並將該床用乙酸乙酯（400 mL）沖洗。將組合的濾液用水（500 mL）、鹽水（250 mL）洗滌，經無水硫酸鈉乾燥，過濾，並且在減壓下濃縮。藉由矽膠柱層析法（10%~35%乙酸乙酯/己烷作為洗脫液）純化殘餘物，以產生黃色固體。用在正己烷中的乙酸乙酯（1 : 5）將固體共沈澱，隨後乙腈洗滌（15 mL）以獲得淡黃色固體，將其在真空下乾燥，以產生4,4'-(9,10-二氫-9,10-[1,2]苯并蒽-1,4-二基)雙(3-(三氟甲基)苯胺)（10.8 g，48%）。熔點：181ºC~185ºC；FT-IR：1336.91 cm-1 （C-F）；1H NMR (400 MHz, DMSO-d6) δ: 7.25-7.21 (m, 2H), 7.17-7.09 (m, 4H), 6.99-6.89 (m, 6H), 6.85-6.82 (m, 2H), 6.76 (d, J = 6.0 Hz, 2H), 5.75 (s, 4H), 5.17 (s, 2H)；19F NMR (376 MHz, DMSO-d6) δ: -57.00、-57.13；LCMS：573.2 [M+H]+；UPLC：99.73%純度。Step-5: 4,4'-(9,10-dihydro-9,10-[1,2]benzoanthracene-1,4-diyl)bis(3-(trifluoromethyl)aniline)( Compound 2): At room temperature, a 1 L 4-neck round bottom flask equipped with a magnetic stirrer, an internal thermometer, and a nitrogen bubbler was charged with 1,4-bis(4 in toluene (400 mL) ,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,10-dihydro-9,10-[1,2]benzoanthracene (20.0 g, 39.5 mmol), 4-bromo-3-(trifluoromethyl)aniline (19.9 g, 83.0 mmol), 2 M aqueous sodium carbonate solution (120 mL) and Aliquat-336 (2 mL). The mixture was purged with argon for 15 min, then tetrakis(triphenylphosphine)palladium(0) (4.6 g, 3.9 mmol) was added, and the argon purge was continued for another 10 min. Heat the reaction mixture to 110ºC~120ºC. After 16 h, the reaction mixture was cooled to room temperature, filtered through a Celite® bed, and the bed was rinsed with ethyl acetate (400 mL). The combined filtrate was washed with water (500 mL), brine (250 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (10% to 35% ethyl acetate/hexane as eluent) to produce a yellow solid. The solid was co-precipitated with ethyl acetate (1:5) in n-hexane, followed by washing with acetonitrile (15 mL) to obtain a pale yellow solid, which was dried under vacuum to produce 4,4′-(9,10 -Dihydro-9,10-[1,2]benzoanthracene-1,4-diyl)bis(3-(trifluoromethyl)aniline) (10.8 g, 48%). Melting point: 181ºC~185ºC; FT-IR: 1336.91 cm -1 (CF); 1H NMR (400 MHz, DMSO-d6) δ: 7.25-7.21 (m, 2H), 7.17-7.09 (m, 4H), 6.99- 6.89 (m, 6H), 6.85-6.82 (m, 2H), 6.76 (d, J = 6.0 Hz, 2H), 5.75 (s, 4H), 5.17 (s, 2H); 19F NMR (376 MHz, DMSO- d6) δ: -57.00, -57.13; LCMS: 573.2 [M+H]+; UPLC: 99.73% purity.

聚合物實例1Polymer Example 1

此實例說明了使用具有式I之二酐（化合物1）製備聚醯胺酸。This example illustrates the use of a dianhydride of Formula I (Compound 1) for the preparation of polyamide.

向裝配有氮氣入口和出口、機械攪拌器以及熱電偶的250-mL反應燒瓶中裝入6.73 g的2,2'-雙(三氟甲基)聯苯胺（TFMB）（0.021莫耳）、5.44 g的化合物1（0.009莫耳）以及108.5 g的二甲基乙醯胺（DMAc）。將混合物在氮氣下在室溫下在150 rpm下攪拌約30分鐘。之後，向二胺的攪拌溶液中分批緩慢添加9.12 g（0.0294莫耳）的4,4'-氧雙鄰苯二甲酸酐（ODPA）。控制二酐的添加速率，以保持最高反應溫度> 30ºC。在二酐添加完成後，使用另外12.1 g的DMAc洗滌來自容器和反應燒瓶的壁的任何剩餘的二酐粉末。在7天的過程中，增量地添加另外0.165 g的ODPA（0.0005莫耳，在DMAc中的5%溶液），以增加聚合物的分子量和聚合物溶液的粘度。使用博勒飛（Brookfield）錐板式粘度計以藉由從反應燒瓶中取出小樣品進行測試來監測溶液粘度。聚合物溶液的最終粘度係在25ºC下389 cps。A 250-mL reaction flask equipped with a nitrogen inlet and outlet, a mechanical stirrer, and a thermocouple was charged with 6.73 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) (0.021 mol), 5.44 g of compound 1 (0.009 mol) and 108.5 g of dimethylacetamide (DMAc). The mixture was stirred under nitrogen at room temperature at 150 rpm for about 30 minutes. Thereafter, 9.12 g (0.0294 mol) of 4,4′-oxydiphthalic anhydride (ODPA) was slowly added to the stirred solution of diamine in portions. Control the rate of dianhydride addition to maintain the highest reaction temperature> 30ºC. After the dianhydride addition was completed, an additional 12.1 g of DMAc was used to wash any remaining dianhydride powder from the walls of the vessel and reaction flask. Over the course of 7 days, an additional 0.165 g of ODPA (0.0005 moles, 5% solution in DMAc) was added incrementally to increase the molecular weight of the polymer and the viscosity of the polymer solution. A Brookfield cone-plate viscometer was used to monitor the solution viscosity by taking a small sample from the reaction flask for testing. The final viscosity of the polymer solution is 389 cps at 25ºC.

膜實例1Membrane example 1

此實例說明了聚醯亞胺膜的製備。This example illustrates the preparation of polyimide membranes.

將來自聚合物實例1的聚醯胺酸溶液通過微型過濾器過濾，旋塗到乾淨的矽晶圓上，在熱板上在90ºC下軟烘，放入爐中。在空氣中，將爐分階段加熱至最高固化溫度260ºC。將晶圓從爐中取出，浸泡在水中並手動分層以產生9.81 µm厚度的聚醯亞胺膜樣品。The polyamide solution from Polymer Example 1 was filtered through a micro filter, spin-coated onto a clean silicon wafer, soft-baked on a hot plate at 90ºC, and placed in an oven. In air, heat the furnace in stages to the maximum curing temperature of 260ºC. The wafer was removed from the furnace, soaked in water and layered manually to produce a sample of polyimide film with a thickness of 9.81 µm.

使用Hunter Lab分光光度計在360 nm~780 nm的波長範圍內測量b*和黃度指數以及透射率%（%T）。使用如適於本文報導的具體參數的熱重量分析和熱機械分析的組合進行對膜的熱測量。使用來自英斯特朗公司（Instron）的設備測量機械特性。 以下給出了膜特性： 拉伸模量                           3.22 GPa 拉伸強度                           124.10 MPa 斷裂伸長率                        16.66% Tg                                       273ºC CTE                                    35.50 ppm/ºC（第一次加熱50ºC~200ºC） 59.45 ppm/ºC（第二次加熱50ºC~250ºC） 0.5% TGA質量損失           447.93ºC 1.0 % TGA質量損失          485.31ºC 平均透射率                        87.03 （380~780 nm） 霧度                                   0.21% 在550 nm處的光延遲        74 b* 1.78 YI                                       3.10A Hunter Lab spectrophotometer was used to measure b*, yellowness index, and% transmittance (%T) in the wavelength range of 360 nm to 780 nm. The thermal measurement of the film was performed using a combination of thermogravimetric analysis and thermomechanical analysis as specific parameters as reported herein. Mechanical properties were measured using equipment from Instron. The film properties are given below: Tensile modulus 3.22 GPa Tensile strength 124.10 MPa Elongation at break 16.66% Tg 273ºC CTE 35.50 ppm/ºC (first heating 50ºC~200ºC) 59.45 ppm/ºC (second heating 50ºC~ 250ºC) 0.5% TGA mass loss 447.93ºC 1.0% TGA mass loss 485.31ºC Average transmission 87.03 (380~780 nm) Haze 0.21% Optical retardation at 550 nm 74 b * 1.78 YI 3.10

應注意的是，並不是所有的以上在一般性描述或實例中所描述的活動都是必需的，一部分具體活動可能不是必需的，並且除了所描述的那些以外，還可進行一個或多個其他活動。此外，所列舉的活動的順序不必是它們實施的順序。It should be noted that not all of the activities described in the general description or examples above are necessary, some specific activities may not be necessary, and in addition to those described, one or more other activities activity. Furthermore, the order of the listed activities need not be the order in which they are carried out.

在前述說明書中，已參考具體實施例描述了概念。然而，所屬技術領域具有通常知識者理解，在不背離以下申請專利範圍中所規定的本發明範圍的情況下可作出各種修改和改變。因此，說明書和圖式應被認為係示例性的而非限制意義，並且所有的此類修改均旨在包括於本發明的範圍內。In the foregoing specification, the concepts have been described with reference to specific embodiments. However, those of ordinary skill in the art understand that various modifications and changes can be made without departing from the scope of the invention as defined in the following patent applications. Therefore, the description and drawings should be considered exemplary rather than limiting, and all such modifications are intended to be included within the scope of the present invention.

上面已經關於具體實施例描述了益處、其他優點和問題的解決方案。然而，益處、優點、問題的解決方案、以及可能引起任何益處、優點、或解決方案出現或使其變得更明顯的一個或多個任何特徵不會被解釋為任何或所有申請專利範圍的關鍵的、必要的或基本的特徵。The benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, benefits, advantages, solutions to problems, and one or more any features that may cause or make any benefits, advantages, or solutions appear will not be interpreted as the key to the scope of any or all patent applications , Necessary or basic characteristics.

要理解的是，為清楚起見，在單獨實施例的背景下本文所述的某些特徵還可以以組合形式在單個實施例中提供。相反地，為了簡潔起見，在單個實施例的背景下所述的各個特徵也可以單獨地或以任何子組合提供。本文指定的各個範圍內的數值的使用表述為近似值，就像所述範圍內的最小值和最大值二者前面都有單詞「約」。以這種方式，可以使用高於和低於所述範圍的輕微變化來實現與該等範圍內的值基本上相同的結果。而且，該等範圍的揭露旨在作為包括在最小與最大平均值之間的每個值的連續範圍，包括當一個值的一些分量與不同值的分量混合時可產生的分數值。此外，當揭露更寬和更窄的範圍時，在本發明的期望內，使來自一個範圍的最小值與來自另一個範圍的最大值匹配，並且反之亦然。It is understood that for clarity, certain features described herein may also be provided in combination in a single embodiment in the context of separate embodiments. Conversely, for the sake of brevity, the various features described in the context of a single embodiment may also be provided individually or in any subcombination. The use of numerical values in each range specified herein is expressed as an approximate value, just as both the minimum and maximum values in the range are preceded by the word "about". In this way, slight variations above and below the stated ranges can be used to achieve substantially the same results as the values within these ranges. Moreover, the disclosure of such ranges is intended as a continuous range of each value included between the minimum and maximum average values, including the fractional value that can be generated when some components of a value are mixed with components of different values. Furthermore, when wider and narrower ranges are disclosed, it is within the expectations of the present invention to match the minimum value from one range to the maximum value from another range, and vice versa.

無no

所附圖式中示出了實施例，以提高對如本文提出的概念的理解。Embodiments are shown in the attached drawings to improve understanding of concepts as presented herein.

圖1包括可充當玻璃的可撓性替代物的聚醯亞胺膜的一個實例之圖示。Figure 1 includes an illustration of one example of a polyimide film that can serve as a flexible substitute for glass.

圖2包括對包括玻璃的可撓性替代物的電子裝置的一個實例之圖示。FIG. 2 includes an illustration of an example of an electronic device that includes a flexible alternative to glass.

熟練的技術人員應理解，圖中的物體係為了簡化和清楚而示出的，並且不一定按比例繪製。例如，圖中的一些物體的尺寸相對於其他物體可能有所放大，以幫助提高對實施例的理解。A skilled technician should understand that the object systems in the figures are shown for simplicity and clarity, and are not necessarily drawn to scale. For example, the size of some objects in the figure may be enlarged relative to other objects to help improve the understanding of the embodiments.

Claims (10)

一種具有式I之二胺，
Figure 03_image003
其中： Qa 選自由CRx 、SiRx 、GeRx 、PRx 、以及N所組成的群組； Qb 選自由CRy 、SiRy 、GeRy 、PRy 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； Rx 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、矽烷氧基、以及R6 所組成的群組； Ry 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、矽烷氧基、以及R7 所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； m和n係相同或不同的，並且是從0~2的整數，使得m + n ≤ 2； x係從0~4的整數； y和z係相同或不同的，並且是從0至可用最大值的整數； 其前提係： (i) 如果m + n = 2，則Rx ≠ R6 且Ry ≠ R7 ； (ii) 如果m + n = 1，則Rx ≠ R6 ，Qb ≠ N，並且Ry = R7 ； (iii) 如果m + n = 0，則Qa ≠ N，Qb ≠ N，Rx = R6 ，並且Ry = R7 。A diamine of formula I,
Figure 03_image003
Where Q a is selected from the group consisting of CR x , SiR x , GeR x , PR x , and N; Q b is selected from the group consisting of CR y , SiR y , GeR y , PR y , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R x is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted Aryloxy, silyl, silaneoxy, and R 6 ; R y is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or The group consisting of substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, silaneoxy, and R 7 ; R 6 and R 7 are the same or different , And is selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; m and n are The same or different, and an integer from 0~2, such that m + n ≤ 2; x is an integer from 0~4; y and z are the same or different, and are integers from 0 to the maximum value available; The premise is: (i) If m + n = 2, then R x ≠ R 6 and R y ≠ R 7 ; (ii) If m + n = 1, then R x ≠ R 6 , Q b ≠ N, and R y = R 7 ; (iii) If m + n = 0, then Q a ≠ N, Q b ≠ N, R x = R 6 , and R y = R 7 . 如申請專利範圍第1項所述之二胺，其具有式IA，
Figure 03_image084
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q2 選自由CR5 、SiR5 、GeR5 、PR5 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數；以及 d和e係相同或不同的，並且是從0~3的整數。The diamine described in item 1 of the patent application scope has the formula IA,
Figure 03_image084
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 2 is selected from the group consisting of CR 5 , SiR 5 , GeR 5 , PR 5 , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R 4 and R 5 are the same or different, and are selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy , Fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy; R 6 and R 7 are the same or different, and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2. The group consisting of 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; a is an integer from 0 to 4; and d and e are the same or Different, and is an integer from 0~3. 如申請專利範圍第1項所述之二胺，其具有式IB，
Figure 03_image086
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q2 選自由CR5 、SiR5 、GeR5 、PR5 、以及N所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R7 在每次出現時是相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數； c係從0~2的整數；以及 f係從0~4的整數。The diamine as described in item 1 of the patent application scope, which has the formula IB,
Figure 03_image086
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 2 is selected from the group consisting of CR 5 , SiR 5 , GeR 5 , PR 5 , and N; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl Groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups, where adjacent R 1 groups can be linked together to form a fused aromatic Ring; R 4 and R 5 are the same or different, and are selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy , Fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy; R 7 is the same or different at each occurrence and is selected from NH 2 , ArNH 2 , And the group formed by OArNH 2 ; Ar is the same or different at each occurrence, and is an unsubstituted or substituted C 6-18 hydrocarbon aryl group; a is an integer from 0 to 4; c is from 0 to An integer of 2; and f is an integer from 0 to 4. 如申請專利範圍第1項所述之二胺，其具有式IC，
Figure 03_image088
其中： Q3 選自由CR6 、SiR6 、GeR6 、以及PR6 所組成的群組； Q4 選自由CR7 、SiR7 、GeR7 、以及PR7 所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數；以及 f和g係相同或不同的，並且是從0~4的整數。The diamine as described in item 1 of the patent application scope has the formula IC,
Figure 03_image088
Q 3 is selected from the group consisting of CR 6 , SiR 6 , GeR 6 , and PR 6 ; Q 4 is selected from the group consisting of CR 7 , SiR 7 , GeR 7 , and PR 7 ; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy Group, fluoroalkoxy group, unsubstituted or substituted aryloxy group, silyl group, and siloxy group, where adjacent R 1 groups can be connected together to form a fused aromatic ring; R 4 It is the same as or different from R 5 and is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy Group, unsubstituted or substituted aryloxy group, silyl group, and silaneoxy group; R 6 and R 7 are the same or different, and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 Group; Ar is the same or different at each occurrence and is an unsubstituted or substituted C 6-18 hydrocarbon aryl; a is an integer from 0 to 4; and f and g are the same or different, and It is an integer from 0~4. 如申請專利範圍第1項所述之二胺，其具有式ID，
Figure 03_image035
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q4 選自由CR7 、SiR7 、GeR7 、以及PR7 所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R7 選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a係從0~4的整數； d係從0~3的整數；以及 g係從0~4的整數。The diamine as described in item 1 of the patent application scope has the formula ID,
Figure 03_image035
Where: Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 4 is selected from the group consisting of CR 7 , SiR 7 , GeR 7 , and PR 7 ; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, Alkoxy group, fluoroalkoxy group, unsubstituted or substituted aryloxy group, silyl group, and siloxy group, wherein adjacent R 1 groups can be connected together to form a fused aromatic ring; R 4 is selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryl Oxygen, silyl, and silaneoxy; R 7 is selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar is the same or different each time it appears, and is not Substituted or substituted C 6-18 hydrocarbon aryl; a is an integer from 0 to 4; d is an integer from 0 to 3; and g is an integer from 0 to 4. 如申請專利範圍第1項所述之二胺，其具有式IA-1、式IB-1、式ID-1、以及式ID-2之一，
Figure 03_image091
Figure 03_image093
Figure 03_image095
Figure 03_image097
其中： Q1 選自由CR4 、SiR4 、GeR4 、PR4 、以及N所組成的群組； Q2 選自由CR5 、SiR5 、GeR5 、PR5 、以及N所組成的群組； Q4 選自由CR7 、SiR7 、GeR7 、以及PR7 所組成的群組； R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R6 和R7 係相同或不同的，並且選自由NH2 、ArNH2 、以及OArNH2 所組成的群組； Ar在每次出現時是相同或不同的，並且是未取代或取代的C6-18 烴芳基； a、f、以及g係相同或不同的，並且是從0~4的整數； c係從0~2的整數；以及 d和e係相同或不同的，並且是從0~3的整數。The diamine as described in item 1 of the patent application scope has one of formula IA-1, formula IB-1, formula ID-1, and formula ID-2,
Figure 03_image091
Figure 03_image093
Figure 03_image095
Figure 03_image097
Q 1 is selected from the group consisting of CR 4 , SiR 4 , GeR 4 , PR 4 , and N; Q 2 is selected from the group consisting of CR 5 , SiR 5 , GeR 5 , PR 5 , and N; Q 4 is selected from the group consisting of CR 7 , SiR 7 , GeR 7 , and PR 7 ; R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from the group consisting of F, CN, and alkane Group, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy Group consisting of adjacent R 1 groups can be connected together to form a fused aromatic ring; R 4 and R 5 are the same or different, and are selected from H, F, CN, alkyl, fluoroalkyl , Unsubstituted or substituted hydrocarbon aryl groups, unsubstituted or substituted heteroaryl groups, alkoxy groups, fluoroalkoxy groups, unsubstituted or substituted aryloxy groups, silyl groups, and siloxy groups; R 6 and R 7 are the same or different, and are selected from the group consisting of NH 2 , ArNH 2 , and OArNH 2 ; Ar is the same or different at each occurrence, and is unsubstituted or substituted C 6 -18 hydrocarbon aryl groups; a, f, and g are the same or different and are integers from 0 to 4; c is an integer from 0 to 2; and d and e are the same or different and are from 0 Integer of ~3. 如申請專利範圍第1項所述之二胺，其具有式IA-1a、式IA-1b、式IB-1a、式IC-1a、式IC-1b、式ID-1a、式ID-1b、式ID-2a、以及式ID-2b之一，
Figure 03_image099
Figure 03_image101
Figure 03_image103
Figure 03_image105
Figure 03_image107
Figure 03_image109
Figure 03_image111
Figure 03_image113
Figure 03_image115
其中： R1 、R2 、和R3 在每次出現時是相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R1 基團可以連接在一起以形成稠合芳環； R4 和R5 係相同或不同的，並且選自由H、F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組； R8 和R9 係相同或不同的，並且選自由F、CN、烷基、氟烷基、未取代或取代的烴芳基、未取代或取代的雜芳基、烷氧基、氟烷氧基、未取代或取代的芳氧基、矽基、以及矽烷氧基所組成的群組，其中相鄰的R8 和/或R9 基團可以連接在一起以形成稠環； a、f、以及g係相同或不同的，並且是從0~4的整數； c係從0~2的整數； d和e係相同或不同的，並且是從0~3的整數；以及 h、i、以及k係相同或不同的，並且是從0~4的整數。The diamine as described in item 1 of the patent application scope has formula IA-1a, formula IA-1b, formula IB-1a, formula IC-1a, formula IC-1b, formula ID-1a, formula ID-1b, One of formula ID-2a and formula ID-2b,
Figure 03_image099
Figure 03_image101
Figure 03_image103
Figure 03_image105
Figure 03_image107
Figure 03_image109
Figure 03_image111
Figure 03_image113
Figure 03_image115
Wherein: R 1 , R 2 , and R 3 are the same or different at each occurrence, and are selected from F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted Heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy groups, where adjacent R 1 groups can be joined together to form a thick Aromatic ring; R 4 and R 5 are the same or different, and are selected from H, F, CN, alkyl, fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkyl Oxygen, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy; R 8 and R 9 are the same or different, and are selected from the group consisting of F, CN, alkyl , Fluoroalkyl, unsubstituted or substituted hydrocarbon aryl, unsubstituted or substituted heteroaryl, alkoxy, fluoroalkoxy, unsubstituted or substituted aryloxy, silyl, and siloxy Group where adjacent R 8 and/or R 9 groups can be joined together to form a fused ring; a, f, and g are the same or different and are integers from 0 to 4; c is from Integers from 0 to 2; d and e are the same or different and are integers from 0 to 3; and h, i, and k are the same or different and are integers from 0 to 4. 一種具有式II之重複單元結構的聚醯胺酸，
Figure 03_image075
其中： Ra 在每次出現時是相同或不同的，並且表示一個或多個四羧酸組分殘基；以及 Rb 在每次出現時是相同或不同的，並且表示一個或多個芳香族二胺殘基； 其中10~100 mol%的Rb 係來自一種或多種如申請專利範圍第1項所述之具有式I之二胺的殘基。A polyamide having a repeating unit structure of formula II,
Figure 03_image075
Where: R a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R b is the same or different at each occurrence and represents one or more aromatics Group diamine residues; wherein 10 to 100 mol% of R b is derived from one or more residues of the diamine of formula I as described in item 1 of the patent application scope. 一種聚醯亞胺膜，其中該聚醯亞胺具有式III的重複單元結構，
Figure 03_image077
其中： Ra 在每次出現時是相同或不同的，並且表示一個或多個四羧酸組分殘基；以及 Rb 在每次出現時是相同或不同的，並且表示一個或多個芳香族二胺殘基； 其中10~100 mol%的Rb 係來自一種或多種如申請專利範圍第1項所述之具有式I之二胺的殘基。A polyimide film, wherein the polyimide has a repeating unit structure of formula III,
Figure 03_image077
Where: R a is the same or different at each occurrence and represents one or more residues of tetracarboxylic acid components; and R b is the same or different at each occurrence and represents one or more aromatics Group diamine residues; wherein 10 to 100 mol% of R b is derived from one or more residues of the diamine of formula I as described in item 1 of the patent application scope. 一種具有至少一個層的有機電子裝置，該至少一個層包含具有如申請專利範圍第9項所述之式III的重複單元的聚醯亞胺膜。An organic electronic device having at least one layer, the at least one layer comprising a polyimide film having a repeating unit of formula III as described in item 9 of the patent application.
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