TWI813704B - Polymers for use in electronic devices - Google Patents

Abstract

Disclosed is a diamine having Formula I. In Formula I: Q is a group having a spiro atom; R⁷ and R⁸ are the same or different at each occurrence and are F, CN, alkyl, fluoroalkyl, hydrocarbon aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, or silyl, where adjacent R⁷ and/or R⁸ groups can be joined together to form an aromatic ring; c and d are the same or different at each occurrence and are an integer from 0-4; and m and q are the same or different and are an integer from 0-6.

Description

Polymers for electronic devices

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 comprising such materials.

Materials used in electronic applications often have stringent requirements regarding their structural properties, optical properties, thermal properties, electronic properties and other properties. As the number of commercial electronics applications continues to increase, the breadth and specificity of required properties require innovation in materials with new and/or improved properties. Polyimides represent a class of polymeric compounds widely used in a variety of electronic applications. They can serve as flexible alternatives to glass in electronic display devices, provided they have the right properties. These materials find use as components in liquid crystal displays ("LCDs"), where their modest electrical power consumption, light weight, and layer flatness are key properties for practical utility. Other uses in electronic display devices where setting such parameters are preferred include device substrates, optical filter substrates, cover films, touch screen panels, etc.

Many of these components are also important in the construction and operation of organic electronic devices with organic light-emitting diodes ("OLEDs"). OLEDs are promising for many display applications due to their high power conversion efficiency and suitability for a wide range of end uses. They are increasingly used in cell phones, tablet devices, handheld/laptop computers, and other business products. In addition to low power consumption, these applications require displays with high information content, full color, and fast video rate response times.

Polyimide membranes generally have sufficient thermal stability, high glass transition temperature, and mechanical toughness to merit consideration for this type of use. Furthermore, polyimide generally does not develop haze when subjected to repeated flexing, so it is relatively less dense than other transparent substrates like polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). ), they are often preferred in flexible display applications.

However, prioritizing optical transparency has prevented the use of traditional amber polyimides in some display applications such as optical filters and touch screen panels. Furthermore, polyimides are typically hard, highly aromatic materials; and as the film/coating forms, the polymer chains tend to orient in the plane of the film/coating. This results in a difference in refractive index between the parallel and perpendicular directions of the film (birefringence), creating light retardation that may adversely affect display performance. If additional uses for polyimide are to be found in the display market, solutions are needed that maintain its desired properties while improving its optical clarity and reducing amber coloration and birefringence causing light retardation.

There is therefore a continuing need for polymer materials suitable for use in electronic devices.

A diamine of formula I is provided Where: Q is a group with a spiro atom; R ⁷ and R ⁸ are the same or different each time they occur, and are selected from the group consisting of: F, CN, alkyl, fluoroalkyl, hydrocarbon aromatic group, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and siloxy, wherein adjacent R ⁷ and/or R ⁸ groups can be connected together to form an aromatic ring; c and d are the same or different on each occurrence and are integers from 0 to 4; and m and q are the same or different and are integers from 0 to 6. Further provided is a polyamide having repeating units of formula II where: R ^a is the same or different on each occurrence and represents one or more tetracarboxylic acid component residues; and R ^b is the same or different on each occurrence and represents one or more aromatic residues family diamine residues; wherein 10 mol% to 100 mol% of R ^b is a diamine residue derived from one or more diamines of formula I.

Further provided is a composition comprising (a) a polyamic acid having repeating units of Formula II and (b) a high boiling aprotic solvent.

Further provided is a polyimide, the repeating unit of the polyimide having the structure in Formula IV where R ^a and R ^b are as defined in Formula II.

Further provided is a polyimide film comprising repeating units of Formula IV.

One or more methods for preparing polyimide films are further provided, wherein the polyimide films have repeating units of Formula IV.

Further provided is a flexible replacement for glass in an electronic device, wherein the flexible replacement for glass is a polyimide film having repeating units of Formula IV.

Further provided is an electronic device having at least one layer comprising a polyimide film having repeating units of Formula IV.

An organic electronic device, such as an OLED, is further provided, wherein the organic electronic device contains a flexible replacement for glass as disclosed herein.

Both the foregoing general description and the following detailed description are exemplary and explanatory only and are not limiting of the invention, as defined by the appended claims.

A diamine of formula I is provided as described in detail below.

Further provided is a polyamide having repeating units of Formula II as described in detail below.

Further provided is a composition comprising (a) a polyamic acid having repeating units of Formula II and (b) a high boiling aprotic solvent.

Further provided is a polyimide as described in detail below, the repeating units of the polyimide having a structure in Formula IV.

One or more methods for preparing a polyimide membrane are further provided, wherein the polyimide membrane has repeating units of Formula IV.

Further provided is a flexible replacement for glass in an electronic device, wherein the flexible replacement for glass is a polyimide film having repeating units of Formula IV.

Further provided is an electronic device having at least one layer comprising a polyimide film having repeating units of Formula IV.

An organic electronic device, such as an OLED, is further provided, wherein the organic electronic device contains a flexible replacement for glass as disclosed herein.

Many aspects and embodiments have been described above and are illustrative and non-limiting only. After reading this specification, the skilled artisan will understand that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and benefits of any one or more embodiments will be apparent from the following detailed description, and from the claims. The detailed description first presents definitions and clarifications of terms, followed by diamines having the formula I, polyamide acids having the repeating unit structure of the formula II, polyimides having the repeating unit structure of the formula IV, and methods for preparing polyamides. Imine membrane methods, electronic devices, and final examples. 1. Definition and clarification of terms

Before presenting the details of the embodiments described below, some terms are defined or clarified.

As used in Definition and Clarification of Terms, R, R ^a , R ^b , R', R'' and any other variables are generic names and may or may not be the same as those defined in the formula.

The term "alignment layer" is intended to refer to the organic polymer layer in a liquid crystal device (LCD) that brings the molecules closest to each other as a result of its rubbing onto the LCD glass in a preferred direction during the LCD manufacturing process. Align the boards.

As used herein, the term "alkyl" includes branched and straight chain saturated aliphatic hydrocarbon groups. Unless otherwise specified, 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 hydrocarbyl groups. In some embodiments, alkyl groups 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, alkyl groups have 1 to 20 carbon atoms. In other embodiments, the group has 1 to 6 carbon atoms. This term is intended to include heteroalkyl groups. Heteroalkyl groups can have from 1 to 20 carbon atoms.

The term "aprotic" refers to a class of solvents that lack acidic hydrogen atoms and therefore cannot act as hydrogen donors. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc )wait.

The term "aromatic compound" is intended to mean an organic compound containing at least one unsaturated cyclic group having 4n + 2 delocalized pi electrons. The term is intended to cover both aromatic compounds having only carbon and hydrogen atoms and heteroaromatic compounds in which one or more carbon atoms within a cyclic group have been replaced by another Replacement of atoms such as nitrogen, oxygen, sulfur, etc.

The term "aryl" or "aryl group" refers to a moiety formed by the removal of one or more hydrogen ("H") or deuterium ("D") from an aromatic compound. Aryl groups can be a single ring (monocyclic) or have multiple rings fused together or covalently linked (bicyclic, or more). "Hydrocarbyl" 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, a hydrocarbyl group has 6 to 60 ring carbon atoms; in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, heteroaryl groups have from 4 to 50 ring carbon atoms; in some embodiments, 4 to 30 ring carbon atoms.

The term "alkoxy" is intended to refer to the group -OR, where R is alkyl.

The term "aryloxy" is intended to refer to the group -OR, where R is aryl.

Unless otherwise specified, all groups may be substituted or unsubstituted. Optionally substituted groups, such as, but not limited to, alkyl or aryl, may be substituted by 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, alkoxy group, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, silyloxy, siloxane, thioalkoxy, - S(O) ₂ -, -C(=O)-N(R')(R"), (R')(R")N-alkyl, (R')(R")N-alkoxy Alkyl, (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" are independently an optionally substituted alkyl, cycloalkyl or aryl group. R' and R", together with the nitrogen atoms to which they are bonded, can form a ring system in certain embodiments. Substituents can also be cross-linking groups.

The term "amine" is intended to refer to compounds containing basic nitrogen atoms with lone pairs of electrons. The term "amine" refers to the functional group _-NH2 , -NHR or _-NR2 , where R is the same or different on each occurrence and can be an alkyl group or an aryl group. The term "diamine" is intended to refer to compounds containing two basic nitrogen atoms with associated lone pairs of electrons. The term "aromatic diamine" is intended to refer to aromatic compounds having two amine groups. The term "bent diamine" is intended to refer to diamines in which the two basic nitrogen atoms and the associated lone pair of electrons are arranged asymmetrically around the center of symmetry of the corresponding compound or functional group, e.g. m-phenylene Diamine: The term "aromatic diamine residue" is intended to refer to the moiety bonded to two amine groups in the aromatic diamine. The term "aromatic diisocyanate residue" is intended to mean a moiety bonded to two isocyanate groups in an aromatic diisocyanate compound. This is explained further below.

The terms "diamine residue" and "diisocyanate residue" are intended to mean a moiety bonded to two amine groups or two isocyanate groups, respectively, where the moiety is aliphatic or aromatic.

The term "b*" is intended to refer to the b* axis in CIELab color space that represents the yellow/blue opposition. Yellow is represented by positive b* values, and blue is represented by negative b* values. The measured b* value can be affected by the solvent, especially since solvent selection can affect the color measured on materials exposed to high temperature processing conditions. This can occur as a result of inherent properties of the solvent and/or properties associated with the low levels of impurities contained in various solvents. Specific solvents are often pre-selected to achieve the desired b* value for a specific application.

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- or y-axis (in-plane) and the z-axis (out-of-plane) refractive index.

When referring to a layer, material, component, or structure, the term "charge transport" is intended to mean that such layer, material, component, or structure facilitates the movement of such charges across such layer, material, with relative efficiency and little charge loss. Migration in the thickness of a , member, or structure. Hole transport materials favor positive charges; electron transport materials favor negative charges. Although luminescent materials may also have some charge transport properties, the term "charge transport layer, material, component, or structure" is not intended to include layers, materials, components, or structures whose primary function is to emit light.

The term "compound" is intended to mean an uncharged substance composed of molecules further including atoms, wherein the atoms cannot be separated from their corresponding molecules by physical means without breaking chemical bonds. The term is intended to include oligomers and polymers.

The term "coefficient of linear thermal expansion (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 change in length per degree Celsius and is usually expressed in units of µm/m/ºC or ppm/ºC. α = (ΔL/L ₀ )/ΔT

The measured CTE values disclosed herein were generated during the first or second heating scan via known methods. Understanding the relative expansion/contraction characteristics of materials can be an important consideration in the manufacturing and/or reliability of electronic devices.

The term "dopant" is intended to mean a material within a layer including a host material that is similar to one or more electronic properties or one or more wavelengths of radiation that would be emitted, received, or filtered by that layer in the absence of such material. The material alters one or more electronic properties or one or more target wavelengths of radiation emission, reception, or filtering of the layer.

The term "electroactive" when referring to a layer or material is intended to mean a layer or material that electronically facilitates the operation of a device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charges, where the charges may be electrons or holes, or materials that emit radiation or exhibit changes in concentration of electron-hole pairs when receiving radiation. Examples of inactive materials include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials.

The term "tensile elongation" or "tensile strain" is intended to mean the percentage increase in length that occurs in a material before it breaks under an applied tensile stress. It can be measured by, for example, ASTM method D882.

The prefix "fluoro" is intended to indicate that one or more hydrogens in the group have been replaced by fluorine.

The term "glass transition temperature (or T _g )" is intended to mean the temperature at which a reversible change occurs in an amorphous polymer or in the amorphous region of a semi-crystalline polymer, where the material suddenly changes from a hard, glassy, or brittle state Become flexible or elastic. Under a microscope, the glass transition occurs when normally coiled, stationary polymer chains become free to rotate and can move past each other. T _g can be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA) or dynamic mechanical analysis (DMA) or other methods.

The prefix "hetero" indicates that one or more carbon atoms have been replaced by a different atom. In some embodiments, heteroatoms are O, N, S, or combinations thereof.

The term "high boiling point" is intended to mean a boiling point above 130ºC.

The term "host material" is intended to refer to the material to which dopants are added. The host material may or may not have one or more electronic properties or abilities to emit, receive, or filter radiation. In some embodiments, the host material is present in a higher concentration.

The term "isothermal weight loss" is intended to refer to a material property directly related to its thermal stability. It is typically measured via thermogravimetric analysis (TGA) at a constant target temperature. Materials with high thermal stability generally exhibit very low percent isothermal weight loss over a desired period of time at the required use or processing temperatures, and can therefore be used in applications at such temperatures without significant loss of strength. , degassing and/or structural changes.

The term "laser particle counter test" refers to a method used to evaluate 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-baked. /Dry. The particle content of the films thus prepared is evaluated by any number of standard measurement techniques. Such techniques include laser particle detection and other techniques known in the art.

The term "liquid composition" is intended to mean a liquid medium in which a material is dissolved to form a solution, a liquid medium in which a material is dispersed to form a dispersion, or a liquid medium in which a material is suspended to form a suspension or emulsion.

The term "substrate" is intended to refer to the base upon which one or more layers are deposited, for example, in the formation of an electronic device. Non-limiting examples include glass, silicon, and the like.

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 (excluding absorbed water).

The term "optical retardation (or _RTH )" is intended to refer to the difference between the average in-plane refractive index and the out-of-plane refractive index (i.e., birefringence), which is then multiplied by the thickness of the film or coating . Optical retardation is typically measured for a given frequency of light and is reported in nanometers.

The term "organic electronic device" or sometimes "electronic device" is intended herein to refer to a device including one or more organic semiconductor layers or one or more materials.

The term "particle content" is intended to refer to the number or count of insoluble particles present in a solution. Measurements of particle content can be made on the solution itself or on the finished material (sheets, films, etc.) prepared from those membranes. Various optical methods can be used to evaluate this property.

The term "photoactive" means emitting light when activated by an applied voltage (as in a light-emitting diode or chemical cell), emitting light after absorbing photons (as in a down-converting phosphor device), or in response to A material or layer that radiates energy and generates a signal with or without an applied bias voltage (as in a photodetector or photovoltaic cell).

The term "polyamide solution" refers to a solution of a polymer containing amide units that have the ability to intramolecular cyclize to form amide imine groups.

The term "polyimide" refers to the condensate obtained by reacting one or more bifunctional carboxylic acid components with one or more primary diamines or diisocyanates. They contain the imine structure -CO-NR-CO- as linear or heterocyclic units along the main chain of the polymer backbone.

The term "satisfactory" when referring to a material property or characteristic is intended to mean that the property or characteristic satisfies all requirements/needs of the material in use. For example, in the context of the polyimide films disclosed herein, an isothermal weight loss of less than 1% in nitrogen at 350°C for 3 hours may be considered a non-limiting example of a "satisfactory" property.

The term "soft bake" is intended to refer to a process commonly used in electronics manufacturing in which the coated material is heated to drive off the solvent and cure the film. Soft baking is usually performed on a hot plate or in a vented oven at temperatures between 90ºC and 110ºC as a preparatory step for subsequent heat treatment of the coated layer or film.

The term "substrate" refers to a base material that may be rigid or flexible and may include one or more layers of one or more materials, which may include, but are not limited to, glass, polymers, metallic or ceramic materials, or combinations thereof. The substrate may or may not include electronic components, circuitry, or conductive members.

The term "siloxane" refers to the group _R3SiOR2Si- , where R on each occurrence is the same or different _and is H, C1-C20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

The term "silyloxy" refers to the group _R3SiO- , where R on each occurrence is the same or different and is H, C1-C20 alkyl, fluoroalkyl, or aryl.

The term "silyl" refers to the group _R3Si- , where R on each occurrence is the same or different and is H, C1-C20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

The term "spin coating" is intended to refer to a process used to deposit a uniform thin film onto a flat substrate. Generally, a small amount of coating material is applied to the center of the substrate, which is rotated at a low speed or not at all. The substrate is then rotated at a prescribed speed to evenly spread the coating material by centrifugal force.

The term "spiro group" refers to a group having a bicyclic organic moiety in which the two rings have a common atom. The rings may be different or identical in nature, and may form part of other ring systems. The shared atoms have two bonds in each ring and are called spiro atoms. In some embodiments, the spiro atoms are selected from the group consisting of C and Si.

The term "tensile modulus" is intended to refer to a measure of the stiffness of a solid material, which defines the initial relationship between stress (force per unit area) and strain (proportional deformation) in a material such as a membrane. The commonly used unit is the gigapascal (GPa).

The term "tetracarboxylic acid component" is intended to mean any one or more of: tetracarboxylic acid, tetracarboxylic acid monoanhydride, tetracarboxylic acid dianhydride, tetracarboxylic acid monoester, and tetracarboxylic acid diester.

The term "tetracarboxylic acid component residue" is intended to mean a moiety bonded to the four carboxyl groups in the tetracarboxylic acid component. This is explained further below.

The term "transmittance" refers to the percentage of light of a given wavelength that strikes a film and passes through it so that it is detectable on the other side. Light transmittance measurements in the visible region (380 nm to 800 nm) are particularly useful for characterizing film color characteristics that are most important to understanding the in-service properties of the polyimide films disclosed herein.

The term "yellowness index (or YI)" refers to the magnitude of yellowness relative to a standard. Positive values of YI indicate the presence and magnitude of yellow. Materials with negative YI appear blue. Particularly 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 color introduced using DMAC as the solvent may be different from the magnitude of color introduced using NMP as the solvent. This can occur as a result of inherent properties of the solvent and/or properties associated with the low levels of impurities contained in various solvents. Specific solvents are often pre-selected to achieve the desired YI value for a specific application.

In a structure in which a substituent bond passes through one or more rings as shown below, This means that the substituent R can be bonded at any available position on the ring or rings.

When used to refer to layers in a device, the phrase "adjacent" does not necessarily mean that one layer is immediately adjacent to another layer. On the other hand, the phrase "adjacent R groups" is used to refer to R groups that are immediately adjacent to each other in a chemical formula (i.e., R groups on atoms that are bonded together). Exemplary adjacent R groups are shown below: In this specification, unless otherwise expressly indicated otherwise or indicated to the contrary by the context of use, embodiments thereof are stated or described as comprising, including, containing, having certain characteristics, 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 the embodiment. Alternative embodiments of the disclosed inventive subject matter are described as consisting essentially of certain features or elements, wherein implementation features or elements that would materially alter the principles of operation or distinguishing features of the embodiments are not present herein. Another alternative embodiment of the inventive subject matter is described as consisting of certain features or elements, in which embodiment or in inessential variations thereof only those features or elements specifically stated or described are present.

Furthermore, unless expressly stated to the contrary, "or" shall mean an inclusive "or" and not 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).

Furthermore, "a/an" is used to describe elements and components described herein. This is done for convenience only and to give a general sense of the scope of the invention. The description should be read to include one or at least one, and the singular also includes the plural unless it is clearly stated otherwise.

Group numbers corresponding to columns within the periodic table use the "New Notation" convention as found in the CRC Handbook of Chemistry and Physics , 81st Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specific materials, processing behavior, 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. Diamines of Formula I The diamines described herein are of Formula I Where: Q is a group with a spiro atom; R ⁷ and R ⁸ are the same or different each time they occur, and are selected from the group consisting of: F, CN, alkyl, fluoroalkyl, hydrocarbon aromatic group, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and siloxy, wherein adjacent R ⁷ and/or R ⁸ groups can be connected together to form an aromatic ring; c and d are the same or different on each occurrence and are integers from 0 to 4; and m and q are the same or different and are integers from 0 to 6.

In some embodiments of Formula I, Q has the formula Q1 wherein: R ¹ - R ⁴ are the same or different and selected from the group consisting of: H, alkyl, alkoxy, hydrocarbyl, heteroaryl, aryloxy, silyl, and silyloxy ; R ⁵ and R ⁶ are the same or different on each occurrence and are selected from the group consisting of: F, CN, alkyl, fluoroalkyl, hydrocarbon aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and silyloxy; a and b are the same or different and are integers from 0 to 3; and * indicates the point of attachment.

In some embodiments of Formula Q1, R ¹ = R ² = R ³ = R ⁴ .

In some embodiments of Formula Q1, R ¹ ≠ R ² .

In some embodiments of Formula Q1, R ¹ = R ³ and R ² = R ⁴ .

In some embodiments of Formula Q1, R ¹ =H.

In some embodiments of Formula Q1, R ¹ is C _1-10 alkyl; in some embodiments, R 1 is C _1-5 alkyl.

In some embodiments of Formula Q1, R ¹ is C _1-10 alkoxy; in some embodiments, R 1 is C _1-5 alkoxy.

In some embodiments of Formula Q1, R ¹ is C _3-10 silyl; in some embodiments, R 1 is C _3-6 silyl.

In some embodiments of Formula Q1, ^R1 is C _6-18 hydrocarbyl.

All the embodiments described above for R ¹ in formula Q1 apply equally to R ² , R ³ and R ⁴ in formula Q1.

In some embodiments of Formula Q1, a = 0.

In some embodiments of Formula Q1, a = 1.

In some embodiments of Formula Q1, a = 2.

In some embodiments of Formula Q1, a = 3.

In some embodiments of Formula Q1, a > 0.

In some embodiments of Formula Q1, b = 0.

In some embodiments of Formula Q1, b = 1.

In some embodiments of Formula Q1, b = 2.

In some embodiments of Formula Q1, b = 3.

In some embodiments of Formula Q1, b > 0.

In some embodiments of Formula Q1, a > 0 and at ^least one R is F.

In some embodiments of Formula Q1, a > 0 and at ^least one R is CN.

In some embodiments of Formula Q1, a > 0 and at least one R ⁵ is C _1-10 alkyl; in some embodiments, is C _1-5 alkyl.

In some embodiments of Formula Q1, a > 0 and at least one R ⁵ is C _1-10 alkoxy; in some embodiments, is C _1-5 alkoxy.

In some embodiments of Formula Q1, a > 0 and at ^least one R is C _1-10 fluoroalkyl; in some embodiments, is C _1-5 fluoroalkyl; in some embodiments, is C _{1 -5} perfluoroalkyl.

In some embodiments of Formula Q1, a > 0 and at ^least one R is C _3-10 silyl; in some embodiments, is C _3-6 silyl.

In some embodiments of Formula Q1, a > 0 and at least one R ⁵ is C _3-10 silyloxy; in some embodiments, is C _3-6 silyloxy.

All the embodiments described above for R ⁵ in formula Q1 also apply to R ⁶ in formula Q1.

In some embodiments of Formula I, Q has the formula Q2 where: R ⁵ and R ⁶ are the same or different on each occurrence and are selected from the group consisting of: F, CN, alkyl, fluoroalkyl, hydrocarbyl, heteroaryl, alkoxy , fluoroalkoxy, aryloxy, silyl, and silyloxy; a and b are the same or different and are integers from 0 to 3; and * represents the point of attachment.

All the embodiments described above for R ⁵ , R ⁶ , a, and b in formula Q1 also apply to R ⁵ , R ⁶ , a, and b in formula Q2.

In some embodiments of Formula I, Q has the formula Q3 wherein: R ¹ - R ⁴ are the same or different and selected from the group consisting of: H, alkyl, alkoxy, hydrocarbyl, heteroaryl, aryloxy, silyl, and silyloxy ; R ⁵ and R ⁶ are the same or different on each occurrence and are selected from the group consisting of: F, CN, alkyl, fluoroalkyl, hydrocarbon aryl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and silyloxy; a and b are the same or different and are integers from 0 to 3; and * indicates the point of attachment.

All the embodiments described above for R ¹ to R ⁶ , a, and b in formula Q1 also apply to R ¹ to R ⁶ , a, and b in formula Q3.

In some embodiments of Formula I, m = 0.

In some embodiments of Formula I, m = 1.

In some embodiments of Formula I, m = 2.

In some embodiments of Formula I, m = 3.

In some embodiments of Formula I, m = 4.

In some embodiments of Formula I, m = 5.

In some embodiments of Formula I, m = 6.

In some embodiments of Formula I, q = 0.

In some embodiments of Formula I, q = 1.

In some embodiments of Formula I, q = 2.

In some embodiments of Formula I, q = 3.

In some embodiments of Formula I, q = 4.

In some embodiments of Formula I, q = 5.

In some embodiments of Formula I, q = 6.

In some embodiments of Formula I, m = q.

In some embodiments of Formula I, m ≠ q.

In some embodiments of Formula I, m = q = 1.

In some embodiments of Formula I, c = 0.

In some embodiments of Formula I, c = 1.

In some embodiments of Formula I, c = 2.

In some embodiments of Formula I, c = 3.

In some embodiments of Formula I, c = 4.

In some embodiments of Formula I, c > 0.

In some embodiments of Formula I, d = 0.

In some embodiments of Formula I, d = 1.

In some embodiments of Formula I, d = 2.

In some embodiments of Formula I, d = 3.

In some embodiments of Formula I, d = 4.

In some embodiments of Formula I, d > 0.

In some embodiments of Formula I, c > 0 and at ^least one R is F.

In some embodiments of Formula I, c > 0 and at ^least one R is CN.

In some embodiments of Formula I, c > 0 and at least one R ⁷ is C _1-10 alkyl; in some embodiments, is C _1-5 alkyl.

In some embodiments of Formula I, c > 0 and at least one R ⁷ is C _1-10 alkoxy; in some embodiments, is C _1-5 alkoxy.

In some embodiments of Formula I, c > 0 and at ^least one R is C _1-10 fluoroalkyl; in some embodiments, is C _1-5 fluoroalkyl; in some embodiments, is C _{1 -5} perfluoroalkyl.

In some embodiments of Formula I, c > 0 and at least one ^R is C _3-10 silyl; in some embodiments, is C _3-6 silyl.

In some embodiments of Formula I, c > 0 and at least one R ⁷ is C _3-10 silyloxy; in some embodiments, is C _3-6 silyloxy.

All the embodiments described above for R ⁷ in formula I apply equally to R ⁸ in formula I.

In some embodiments of Formula I, the diamine has Formula Ia wherein R ¹ to R ⁶ , a, and b are as defined in Formula Q1.

In some embodiments of Formula I, the diamine has Formula Ib or Formula Ic wherein R ¹ to R ⁶ , a, and b are as defined in Formula Q1.

In some embodiments of Formula I, the diamine has Formula Id Wherein R ¹ to R ⁶ , a, and b are as defined in Formula Q1; R ⁷ , R ⁸ , c and d are as defined in Formula I.

In some embodiments of Formula I, the diamine has Formula Ie or Formula If Wherein R ¹ to R ⁶ , a, and b are as defined in Formula Q1; R ⁷ , R ⁸ , c and d are as defined in Formula I.

In some embodiments of Formula I, the diamine has Formula Ig Where R ⁵ , R ⁶ , a, and b are as defined in Formula Q2.

In some embodiments of Formula I, the diamine has Formula Ih or Formula Ii Where R ⁵ , R ⁶ , a, and b are as defined in Formula Q2.

In some embodiments of Formula I, the diamine has Formula Ij Wherein R ⁵ , R ⁶ , a, and b are as defined in Formula Q2; R ⁷ , R ⁸ , c and d are as defined in Formula I.

In some embodiments of Formula I, the diamine has Formula Ik or Formula Im Wherein R ⁵ , R ⁶ , a, and b are as defined in Formula Q2; R ⁷ , R ⁸ , c and d are as defined in Formula I.

In some embodiments of Formula I, the diamine has Formula In wherein R ¹ to R ⁶ , a, and b are as defined in Formula Q1.

In some embodiments of Formula I, the diamine has Formula Io or Formula Ip wherein R ¹ to R ⁶ , a, and b are as defined in Formula Q1.

In some embodiments of Formula I, the diamine has Formula Iq Wherein R ¹ to R ⁶ , a, and b are as defined in Formula Q1; R ⁷ , R ⁸ , c and d are as defined in Formula I.

In some embodiments of Formula I, the diamine has Formula Ir or Formula Is Wherein R ¹ to R ⁶ , a, and b are as defined in Formula Q1; R ⁷ , R ⁸ , c and d are as defined in Formula I.

New compounds can be prepared using any technique that will produce C-C or C-N bonds. Several such techniques are known, such as Suzuki, Yamamoto, Stille, Negishi and metal-catalyzed C-N coupling as well as metal-catalyzed and oxidative direct arylation. Exemplary preparations are given in the Examples.

One synthesis scheme for compounds of formula Ib is shown below.

In the above scheme: Tf represents triflate; Tf ₂ O represents trifluoromethanesulfonic anhydride; BOC represents tertiary butoxycarbonyl.

Compound A can be prepared according to the procedures reported by Chen, W.-F.; Lin, H.-Y.; Dai, SA Org. Letters [Organic Chemistry Letters] 2004 , 6 , 2341.

One synthesis scheme for compounds of formula Id is shown below. Any of the above embodiments of Formula I may be combined with one or more of the other embodiments as long as they are not mutually exclusive. For example, embodiments in which R ¹ is C _1-3 alkyl can be combined with embodiments in which R ¹ = R ² = R ³ = R ⁴ , and embodiments in which m = q = 1. Those skilled in the art will understand which embodiments are mutually exclusive and will therefore readily be able to determine the combinations of embodiments contemplated by this application.

Some non-limiting examples of compounds of formula I are shown below. Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Compound 13 Compound 14 Compound 15 Compound 16 Compound 17 3. Polyamic acid having a repeating unit structure of Formula II The polyamic acid described herein has a repeating unit structure of Formula II where: R ^a is the same or different on each occurrence and represents one or more tetracarboxylic acid component residues; and R ^b is the same or different on each occurrence and represents one or more aromatic residues family diamine residues; wherein 10 mol% to 100 mol% of R ^b is derived from residues of one or more diamines of formula I.

In some embodiments of Formula II, ^Ra represents a single tetracarboxylic acid component residue.

In some embodiments of Formula II, ^Ra represents two tetracarboxylic acid component residues.

In some embodiments of Formula II, ^Ra represents three tetracarboxylic acid residues.

In some embodiments of Formula II, ^Ra represents four tetracarboxylic acid residues.

In some embodiments of Formula II, ^Ra represents one or more tetracarboxylic dianhydride residues.

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'-hexafluoroisopropylidenediphthalic anhydride (6FDA), 3,3',4,4'-benzophenonetetracarboxylic Dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic acid Formic anhydride (HQDEA), ethylene glycol bis(trimellitic anhydride) (TMEG-100), 4-(2,5-bisoxytetrahydrofuran-3-yl)-1,2,3,4-tetralin-1 , 2-dicarboxylic anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA), etc. and their combinations. The aromatic dianhydrides may be optionally substituted with groups known in the art, including alkyl, aryl, nitro, cyano, -N(R')(R ^" ), halogen, and hydroxyl. , carboxyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl , silicone group, silyloxy 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" are independently an optionally substituted alkyl, cycloalkyl or aryl group group. R' and R", together with the nitrogen atoms to which they are bonded, can form a ring system in certain embodiments. Substituents can also be cross-linking groups.

In some embodiments of Formula II, ^Ra represents one or more residues from a tetracarboxylic dianhydride selected from the group consisting of: PMDA, BPDA, 6FDA, and BTDA.

In some embodiments of Formula II, ^Ra represents a PMDA residue.

In some embodiments of Formula II, ^Ra represents a BPDA residue.

In some embodiments of Formula II, ^Ra represents a 6FDA residue.

In some embodiments of Formula II, ^Ra represents a BTDA residue.

In some embodiments of Formula II, ^Ra represents a PMDA residue and a BPDA residue.

In some embodiments of Formula II, ^Ra represents a PMDA residue and a 6FDA residue.

In some embodiments of Formula II, ^Ra represents a PMDA residue and a BTDA residue.

In some embodiments of Formula II, ^Ra represents a BPDA residue and a 6FDA residue.

In some embodiments of Formula II, ^Ra represents a BPDA residue and a BTDA residue.

In some embodiments of Formula II, ^Ra represents a 6FDA residue and a BTDA residue.

In some embodiments of Formula II, ^Ra represents a PMDA residue, a BPDA residue, and a 6FDA residue.

In formula II, 10 mol% to 100 mol% of R ^b represents a diamine residue from one or more diamines of formula I as shown above.

In some embodiments of Formula II, 10 mol% to 100 mol% of R ^b represents a diamine residue from a diamine having Formula I as shown above.

In some embodiments of Formula II, 10 mol% to 100 mol% of R ^b represents diamine residues from two different diamines, both of Formula I as shown above.

In some embodiments of Formula II, 10 mol% to 100 mol% of R ^b represents diamine residues from three different diamines, all having Formula I as shown above.

In some embodiments of Formula II, 10 mol% to 100 mol% of R ^b represents diamine residues from four or more different diamines, all having Formula I as shown above.

In some embodiments of Formula II, 20 mol%-100 mol% of R ^b is derived from residues of one or more diamines of Formula I; in some embodiments, 30 mol%-100 mol%; in some In embodiments, 40 mol%-100 mol%; in some embodiments, 50 mol%-100 mol%; in some embodiments, 60 mol%-100 mol%; in some embodiments, 70 mol%- 100 mol%; in some embodiments, 80 mol%-100 mol%; in some embodiments, 90 mol%-100 mol%; in some embodiments, 100%.

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.

In some embodiments of Formula II, R ^b represents a diamine residue from one or more diamines of Formula I and at least one additional diamine residue.

In some embodiments of Formula II, R ^b represents a diamine residue from one or more diamines of Formula I and one additional diamine residue.

In some embodiments of Formula II, R ^b represents a diamine residue from one or more diamines of Formula I as well as two additional diamine residues.

In some embodiments of Formula II, R ^b represents a diamine residue from one or more diamines of Formula I and three additional diamine residues.

In some embodiments, the additional aromatic diamine is selected from the group consisting of: p-phenylenediamine (PPD), 2,2'-dimethyl-4,4'-diamine Biphenyl (m-toluidine), 3,3'-dimethyl-4,4'-diaminobiphenyl (o-toluidine), 3,3'-dihydroxy-4,4'-diamine HAB (HAB), 9,9'-bis(4-aminophenyl)fluoride (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'-benzidine Methyldiphenylamine (MDA), 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline (Bis-M), 4,4'-[1,4 -phenylenebis(1-methyl-ethylidene)]bis-phenyleneamine (Bis-P), 4,4'-oxydiphenylamine (4,4'-ODA), m-phenylenediamine (MPD) ), 3,4'-oxydiphenylamine (3,4'-ODA), 3,3'-diaminodiphenylsine (3,3'-DDS), 4,4'-diaminodiphenyl Trisine (4,4'-DDS), 4,4'-diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-amino-phenoxy)phenyl]sine (BAPS ), 2,2-bis[4-(3-aminophenoxy)-phenyl]sine (m-BAPS), 1,4'-bis(4-aminophenoxy)benzene (TPE-Q ), 1,3'-bis(4-aminophenoxy)benzene (TPE-R), 1,3'-bis(4-amino-phenoxy)benzene (APB-133), 4,4 '-Bis(4-aminophenoxy)biphenyl (BAPB), 4,4'-diaminobenzoaniline (DABA), methylenebis(anthralaminobenzoic 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 their combinations.

In some embodiments of Formula II, R ^b represents a diamine residue from one or more diamines of Formula I and a diamine residue from at least one additional diamine, wherein the additional diamine is selected from the group consisting of: Group consisting of: PPD, 4,4'-ODA, 3,4'-ODA, TFMB, Bis-A-AF, Bis-AT-AF, and Bis-P.

In some embodiments of Formula II, the moiety derived from the monoanhydride monomer is present as a capping group.

In some embodiments, the monoanhydride monomers are selected from the group consisting of phthalic anhydride and the like and derivatives thereof.

In some embodiments, the monoanhydrides are present in an amount up to 5 mol% of the total tetracarboxylic acid composition.

In some embodiments of Formula II, the moiety derived from the monoamine monomer is present as a capping group.

In some embodiments, the monoamine monomers are selected from the group consisting of anilines and analogs and derivatives thereof.

In some embodiments, the monoamines are present in an amount up to 5 mol% of the total amine composition.

In some embodiments, the polyamic acid has a weight average molecular weight ( _MW ) greater than 100,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight ( _MW ) greater than 150,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a molecular weight ( _MW ) greater than 200,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight ( _MW ) greater than 250,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight ( _MW ) greater than 300,000 based on gel permeation chromatography with polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight ( _MW ) between 100,000 and 400,000 based on gel permeation chromatography and polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight ( _MW ) between 200,000 and 400,000 based on gel permeation chromatography and polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight ( _MW ) between 250,000 and 350,000 based on gel permeation chromatography and polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight ( _MW ) between 200,000 and 300,000 based on gel permeation chromatography and polystyrene standards.

Any of the above embodiments of polyamides may be combined with one or more of the other embodiments so long as they are not mutually exclusive.

The overall polyamide composition may be named via symbols commonly used in the art. For example, a polyamic acid with 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.

Also provided is a liquid composition comprising (a) a polyamic acid having repeating units of Formula II and (b) a high boiling aprotic solvent. This liquid composition is also referred to in the text as "polyamide solution".

In some embodiments, the high boiling aprotic solvent has a boiling point of 150ºC or higher.

In some embodiments, the high boiling aprotic solvent has a boiling point of 175ºC or higher.

In some embodiments, the high boiling aprotic solvent has a boiling point of 200ºC or higher.

In some embodiments, the high boiling aprotic solvent is a polar solvent. In some embodiments, the solvent has a dielectric constant greater than 20.

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 their combinations.

In some embodiments of the liquid composition, the solvent is selected from the group consisting of NMP, DMAc, and DMF.

In some embodiments of the liquid composition, the solvent is NMP.

In some embodiments of the liquid composition, the solvent is DMAc.

In some embodiments of the liquid composition, the solvent is DMF.

In some embodiments of the liquid composition, the solvent is gamma-butyrolactone.

In some embodiments of the liquid composition, the solvent is dibutyl carbitol.

In some embodiments of the liquid composition, the solvent is butyl carbitol acetate.

In some embodiments of the liquid composition, the solvent is diethylene glycol monoethyl ether acetate.

In some embodiments of the liquid composition, the solvent is propylene glycol monoethyl ether acetate.

In some embodiments, more than one of the above noted high boiling point aprotic solvents is used in the liquid composition.

In some embodiments, additional co-solvents are used in the liquid composition.

In some embodiments, the liquid composition is >1 wt% polyamic acid in >99 wt% high boiling aprotic solvent.

In some embodiments, the liquid composition is 1 to 5 wt % polyamic acid in 95 to 99 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 5 to 10 wt % polyamic acid in 90 to 95 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 10 to 15 wt % polyamic acid in 85 to 90 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 15 to 20 wt % polyamic acid in 80 to 85 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 20 to 25 wt % polyamic acid in 75 to 80 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 25 to 30 wt % polyamic acid in 70 to 75 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 30 to 35 wt % polyamic acid in 65 to 70 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 35 to 40 wt % polyamic acid in 60 to 65 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 40 to 45 wt % polyamic acid in 55 to 60 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 45 to 50 wt % polyamic acid in 50 to 55 wt % of a high boiling aprotic solvent.

In some embodiments, the liquid composition is 50 wt% polyamic acid in 50 wt% high boiling aprotic solvent.

The polyamide solution may further contain any of a number of additives, if desired. Such additives may be: antioxidants, heat stabilizers, adhesion promoters, coupling agents (eg silanes), inorganic fillers or various reinforcing agents, as long as they do not deleteriously affect the desired polyimide properties.

Polyamide solutions can be prepared using a variety of available methods regarding the introduction of components (ie, monomers and solvents). Some methods of producing polyamide solutions include:

(a) A method in which the diamine component and the dianhydride component are premixed together and then the mixture is added to the solvent in portions while stirring.

(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 dissolved separately in a solvent and the dianhydride is then added thereto in a ratio that allows control of the reaction rate.

(d) A method in which the dianhydride component is separately dissolved in a solvent, and the amine component is then added thereto in a ratio that allows control of the reaction rate.

(e) A method in which the diamine component and the dianhydride component are separately dissolved in a solvent and the solutions are then mixed in a reactor.

(f) A method in which a polyamic acid having an excess of an amine component and another polyamic acid having an excess of a dianhydride component are previously formed and then reacted with each other in a reactor, in particular to produce a non- Random or block copolymers react with each other in such a way.

(g) A method in which a specific portion of the amine component and the dianhydride component are reacted first, and then the remaining diamine component is reacted, or vice versa.

(h) A process wherein the components are added in part or in whole and in any order to part or all of the solvent, further wherein part or all of any component may be added as a solution in part or all of the solvent.

(i) A method in which one of the dianhydride components and one of the diamine components are first reacted to obtain a first polyamic acid. The other dianhydride component is then reacted with the other amine component to provide a second polyamic acid. The polyamides are then combined in any of a variety of ways prior to film formation.

Generally speaking, a polyamic acid solution can be obtained by any of the polyamic acid solution preparation methods disclosed above.

The polyamide solution can then be filtered one or more times to reduce particulate content. Polyimide membranes produced from such filtered solutions can exhibit a reduced number of defects and thereby produce superior performance in the electronic applications disclosed herein. Evaluation of filtration efficiency can be performed by laser particle counter testing, in which representative samples of polyamide solutions are cast onto 5" silicon wafers. After soft bake/drying, by any number of laser Particle counting techniques evaluate the particle content of films on instruments that are commercially available and known in the art.

In some embodiments, a polyamic acid solution is prepared and filtered to yield a particle content of less than 40 particles, as measured by laser particle counter testing.

In some embodiments, a polyamic acid solution is prepared and filtered to yield a particle content of less than 30 particles, as measured by laser particle counter testing.

In some embodiments, a polyamic acid solution is prepared and filtered to yield a particle content of less than 20 particles, as measured by laser particle counter testing.

In some embodiments, a polyamic acid solution is prepared and filtered to yield a particle content of less than 10 particles, as measured by laser particle counter testing.

In some embodiments, a polyamide solution is prepared and filtered to yield a particle content between 2 particles and 8 particles, as measured by laser particle counter testing.

In some embodiments, a polyamide solution is prepared and filtered to yield a particle content between 4 particles and 6 particles, as measured by laser particle counter testing.

Exemplary preparations of polyamide solutions are given in the Examples. 4. Polyimide having a repeating unit structure of Formula IV. Provided is a polyimide having a repeating unit structure of Formula IV. wherein R ^a is the same or different on each occurrence and represents one or more tetracarboxylic acid component residues; and R ^b is the same or different on each occurrence and represents one or more aromatic Diamine residues; wherein 10 mol% to 100 mol% of R ^b are residues from one or more diamines of formula I.

All the embodiments described above for R ^a and R ^b in formula II apply equally to R ^a and R ^b in formula IV.

Any of the above embodiments of formula I in formula IV may be combined with one or more of the other embodiments as long as they are not mutually exclusive.

Polyamides can be made from any suitable polyamide precursors such as polyamide acids, polyamide esters, polyisoamides, and polyamide salts.

Also provided is a polyimide film, wherein the polyimide has a repeating unit structure of Formula IV as described above.

Polyimide films can be made by coating a polyimide precursor onto a substrate and subsequently imidizing it. This can be achieved by thermal conversion methods or chemical conversion methods.

Furthermore, if the polyimide is soluble in a suitable coating solvent, it can be provided as an already imidized polymer dissolved in a suitable coating solvent and coated as the polyimide.

In some embodiments, polyimide films having repeating units of Formula IV have both a high glass transition temperature and low optical retardation.

In some embodiments of the polyimide film, the glass transition temperature ( _Tg ) is greater than 300ºC; in some embodiments, greater than 370ºC; for polyimide films cured at temperatures in excess of 350ºC; In some embodiments, it is greater than 380ºC.

In some embodiments of the polyimide film, the optical retardation at 550 nm is less than 120; in some embodiments, less than 100; in some embodiments, less than 90.

In some embodiments of the polyimide film, for the first measurement, the in-plane coefficient of thermal expansion (CTE) is less than 45 ppm/ºC between 50ºC and 200ºC; in some embodiments, is less than 30 ppm/ºC ; In some embodiments, less than 20 ppm/ºC; in some embodiments, less than 15 ppm/ºC.

In some embodiments of the polyimide film, for the second measurement, the in-plane coefficient of thermal expansion (CTE) is less than 75 ppm/ºC between 50ºC and 200ºC; in some embodiments, is less than 65 ppm/ºC .

In some embodiments of the polyimide membrane, the 1% TGA weight loss temperature is greater than 350ºC; in some embodiments, it is greater than 400ºC; in some embodiments, it is greater than 450ºC.

In some embodiments of the polyimide film, the tensile modulus is between 1.5 GPa and 15.0 GPa; in some embodiments, between 1.5 GPa and 10.0 GPa; in some embodiments, between Between 1.5 GPa and 7.5 GPa; in some embodiments, between 1.5 GPa and 5.0 GPa.

In some embodiments of the polyimide film, the elongation at break is greater than 10%.

In some embodiments of the polyimide film, the haze is less than 1.0%; in some embodiments, it is less than 0.5%.

In some embodiments of the polyimide membrane, b* is less than 7.5; in some embodiments, is less than 5.0.

In some embodiments of the polyimide membrane, the YI is less than 12; in some embodiments, it is less than 10.

In some embodiments of the polyimide film, the transmission at 400 nm is greater than 40%; in some embodiments, is greater than 50%.

In some embodiments of the polyimide film, the transmission at 430 nm is greater than 60%; in some embodiments, is greater than 70%.

In some embodiments of the polyimide film, the transmission at 450 nm is greater than 70%; in some embodiments, is greater than 80%.

In some embodiments of the polyimide film, the transmission at 550 nm is greater than 70%; in some embodiments, is greater than 80%.

In some embodiments of the polyimide film, the transmission at 750 nm is greater than 70%; in some embodiments, is greater than 80%.

Any of the above embodiments of polyimide membranes may be combined with one or more of the other embodiments as long as they are not mutually exclusive. 5. Methods for Preparing Polyimide Membranes

Generally speaking, polyimide membranes can be prepared from polyimide precursors through chemical or thermal conversion. In some embodiments, the membranes are prepared from corresponding polyamide solutions by chemical or thermal conversion methods. The polyimide films disclosed herein, particularly when used as flexible replacements for glass in electronic devices, are prepared by thermal conversion methods.

Generally speaking, polyimide membranes can be prepared from corresponding polyamide acid solutions by chemical or thermal conversion methods. The polyimide films disclosed herein, particularly when used as flexible replacements for glass in electronic devices, are prepared by thermal conversion or modified thermal conversion methods and chemical conversion methods.

Chemical transformation methods are described in US Patent Nos. 5,166,308 and 5,298,331, which patents are incorporated herein by reference in their entirety. In this type of method, conversion chemicals are added to the polyamide solution. Transformation chemicals found 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 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.). The anhydride dehydration material is typically used in a slight molar excess to the amount of amide groups present in the polyamic acid solution. The amount of acetic anhydride used is typically about 2.0-3.0 moles per equivalent of polyamide acid. Generally, a considerable amount of tertiary amine catalyst is used.

Thermal conversion methods may or may not employ conversion chemicals (i.e., catalysts) to convert the polyamic acid casting solution to polyimide. If conversion chemicals are used, the method can be considered a modified thermal conversion method. In both types of thermal conversion methods, only thermal energy is used to heat the film to not only dry the film of the solvent but also to perform the imidization reaction. The polyimide membranes disclosed herein are typically prepared using thermal conversion methods with or without conversion catalysts.

Specific method parameters were preselected taking into account that it is not just the membrane composition that produces the properties of interest. Conversely, the cure temperature and temperature ramp profile also play an important role in achieving the most desirable properties for the intended uses disclosed herein. The polyamide should be processed at or above the maximum temperature of any subsequent processing steps (such as the deposition of one or more inorganic or other layers required to produce a functional display), but at a temperature lower than that of the polyimide. Significant thermal degradation/discoloration occurs at temperatures below which imidization occurs. It should also be noted that an inert atmosphere is generally preferred, especially when higher processing temperatures are used for the imidization.

For the polyamic acids/polyimides disclosed herein, when subsequent processing temperatures in excess of 300ºC are required, temperatures of 300ºC to 320ºC are typically used. Selecting an appropriate curing temperature allows for a fully cured polyimide that achieves an optimal balance of thermal and mechanical properties. Due to these very high temperatures, an inert atmosphere is required. Typically, a furnace oxygen level of >100 ppm should be used. The very low oxygen levels enable the use of the highest curing temperatures without significant degradation/discoloration of the polymer. Catalysts that accelerate the imidization process effectively achieve higher levels of imidization at cure temperatures between approximately 200ºC and 300ºC. This approach can be optionally used if the flexible device is prepared at a higher curing temperature below the _Tg of the polyimide.

The amount of time for each possible curing step is also an important process consideration. In general, the time used for maximum temperature cure should be kept to a minimum. For example, for a 320ºC cure, the cure time can be as long as about 1 hour under an inert atmosphere; however, at higher cure temperatures, this time should be shortened to avoid thermal degradation. Generally speaking, higher temperatures indicate shorter times. Those skilled in the art will recognize the balance between temperature and time in order to optimize the properties of the polyimide for a particular end use.

In some embodiments, the polyamide acid solution is converted into a polyimide film via a thermal conversion process.

In some embodiments of the thermal conversion method, the polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 50 µm.

In some embodiments of the thermal conversion method, the polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 40 µm.

In some embodiments of the thermal conversion method, the polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 30 µm.

In some embodiments of the thermal conversion method, the polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 20 µm.

In some embodiments of the thermal conversion method, a polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of between 10 µm and 20 µm.

In some embodiments of the thermal conversion method, a polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of between 15 µm and 20 µm.

In some embodiments of the thermal conversion method, the polyamide solution is coated onto the substrate such that the resulting film has a soft bake thickness of 18 µm.

In some embodiments of the thermal conversion method, the polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 10 µm.

In some embodiments of the thermal conversion method, the coated substrate is soft baked in proximity mode on a hot plate, with nitrogen gas used to hold the coated substrate just above the hot plate.

In some embodiments of the thermal conversion method, the coated substrate is soft baked in full contact mode on a hot plate, where the coated substrate is in direct contact with the hot plate surface.

In some embodiments of the thermal conversion method, the coated substrate is soft baked on a hot plate using a combination of proximity mode and full contact mode.

In some embodiments of the thermal conversion method, the coated substrate is soft baked using a hot plate set at 80 ^° C.

In some embodiments of the thermal conversion method, the coated substrate is soft baked using a hot plate set at 90 ^° C.

In some embodiments of the thermal conversion method, the coated substrate is soft baked using a hot plate set at 100 ^° C.

In some embodiments of the thermal conversion method, the coated substrate is soft baked using a hot plate set at 110 ^° C.

In some embodiments of the thermal conversion method, the coated substrate is soft baked using a hot plate set at 120 ^° C.

In some embodiments of the thermal conversion method, the coated substrate is soft baked using a hot plate set at 130 ^° C.

In some embodiments of the thermal conversion method, the coated substrate is soft baked using a hot plate set at 140 ^° C.

In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of more than 10 minutes.

In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 10 minutes.

In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 8 minutes.

In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 6 minutes.

In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of 4 minutes.

In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 4 minutes.

In some embodiments of the thermal conversion method, the coated substrate is soft baked for a total time of less than 2 minutes.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 2 preselected temperatures for 2 preselected time intervals, where the time intervals may be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is subsequently cured at 3 preselected temperatures for 3 preselected time intervals, where each of the time intervals may be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is subsequently cured at 4 preselected temperatures for 4 preselected time intervals, where each of the time intervals may be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is subsequently cured at 5 preselected temperatures for 5 preselected time intervals, where each of the time intervals may be the same or different.

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, where each of the time intervals may be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is subsequently cured at 7 preselected temperatures for 7 preselected time intervals, where each of the time intervals may be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 8 preselected temperatures for 8 preselected time intervals, where each of the time intervals may be the same or different of.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is then cured at 9 preselected temperatures for 9 preselected time intervals, where each of the time intervals may be the same or different.

In some embodiments of the thermal conversion method, the soft-baked coated substrate is subsequently cured at 10 preselected temperatures for 10 preselected time intervals, where each of the time intervals may be the same or different.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 80ºC.

In some embodiments of the thermal conversion method, the preselected temperature is equal to 100ºC.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 100ºC.

In some embodiments of the thermal conversion method, the preselected temperature is equal to 150ºC.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 150ºC.

In some embodiments of the thermal conversion method, the preselected temperature is equal to 200ºC.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 200ºC.

In some embodiments of the thermal conversion method, the preselected temperature is equal to 250ºC.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 250ºC.

In some embodiments of the thermal conversion method, the preselected temperature is equal to 300ºC.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 300ºC.

In some embodiments of the thermal conversion method, the preselected temperature is equal to 350ºC.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 350ºC.

In some embodiments of the thermal conversion method, the preselected temperature is equal to 400ºC.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 400ºC.

In some embodiments of the thermal conversion method, the preselected temperature is equal to 450ºC.

In some embodiments of the thermal conversion method, the preselected temperature is greater than 450ºC.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 2 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 5 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 10 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 15 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 20 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 25 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 30 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 35 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 40 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 45 minutes.

In some thermal conversion methods, one or more of the preselected time intervals is 50 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 55 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals is 60 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals are greater than 60 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals are between 2 minutes and 60 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals are between 2 minutes and 90 minutes.

In some embodiments of the thermal conversion method, one or more of the preselected time intervals are between 2 minutes and 120 minutes.

In some embodiments of the thermal conversion method, the method for preparing a polyimide film sequentially includes the following steps: coating the polyimide solution described above onto a substrate; soft baking the coated substrate; The soft-bake coated substrate is treated at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits properties satisfactory for electronic applications such as those disclosed herein.

In some embodiments of the thermal conversion method, the method for preparing a polyimide film consists of the following steps in sequence: coating the polyimide solution described above onto a substrate; soft baking the coated substrate ; Treating the soft-bake coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits properties satisfactory for electronic applications such as those disclosed herein .

In some embodiments of the thermal conversion method, the method for preparing a polyimide film mainly consists of the following steps in sequence: coating the polyimide solution described above onto a 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 exhibits satisfactory performance for electronic applications such as those disclosed herein characteristic.

Typically, the polyamic acid solution/polyimide disclosed herein is coated/cured onto a supporting glass substrate to aid processing during the remainder of the display fabrication process. At some point in the process determined by the display manufacturer, the polyimide coating is removed from the supporting glass substrate by a mechanical or laser lift-off process. These processes separate the polyimide, which is the film with the deposited display layer, from the glass and enable a flexible form. Typically, this 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.

Improved thermal conversion processes are also provided in which the conversion catalyst generally causes the imidization reaction to proceed at a lower temperature than would be possible in the absence of such conversion catalyst.

In some embodiments, a polyamide acid solution is converted into a polyimide film via a modified thermal conversion method.

In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains a conversion catalyst.

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.

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.

In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 5% by weight or less of the polyamide solution.

In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 3% by weight or less of the polyamide solution.

In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 1% by weight or less of the polyamide solution.

In some embodiments of the improved thermal conversion method, the conversion catalyst is present at 1% by weight of the polyamide solution.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains tributylamine as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide acid solution further contains dimethylethanolamine as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains isoquinoline as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains 1,2-dimethylimidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains 3,5-dimethylpyridine as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains 5-methylbenzimidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains N-methylimidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains 2-methylimidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains 2-ethyl-4-imidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains 3,4-dimethylpyridine as a conversion catalyst.

In some embodiments of the improved thermal conversion method,

The polyamide solution further contains 2,5-lutidine as a conversion catalyst.

In some embodiments of the modified thermal conversion method, a polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 50 µm.

In some embodiments of the modified thermal conversion method, a polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 40 µm.

In some embodiments of the modified thermal conversion method, a polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 30 µm.

In some embodiments of the modified thermal conversion method, a polyamide solution is coated onto the substrate such that the resulting film has a soft-bake thickness of less than 20 µm.

In some embodiments of the modified thermal conversion method, a polyamide solution is coated onto a substrate such that the resulting film has a soft-bake thickness of between 10 µm and 20 µm.

In some embodiments of the modified thermal conversion method, a polyamide solution is coated onto a substrate such that the resulting film has a soft-bake thickness of between 15 µm and 20 µm.

In some embodiments of the modified thermal conversion method, a polyamide solution is coated onto the substrate such that the resulting film has a soft bake thickness of 18 µm.

In some embodiments of the modified thermal conversion method, a polyamide solution is coated onto a substrate such that the resulting film has a soft-bake thickness of less than 10 µm.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked in proximity mode on a hot plate using nitrogen gas to hold the coated substrate just above the hot plate.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked on a hot plate in full contact mode, where the coated substrate is in direct contact with the hot plate surface.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked on a hot plate using a combination of proximity mode and full contact mode.

In some embodiments of the modified thermal conversion method, the coated substrate is soft-baked using a hot plate set at 80ºC.

In some embodiments of the modified thermal conversion method, the coated substrate is soft-baked using a hot plate set at 90ºC.

In some embodiments of the modified thermal conversion method, the coated substrate is soft-baked using a hot plate set at 100ºC.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked using a hot plate set at 110ºC.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked using a hot plate set at 120ºC.

In some embodiments of the modified thermal conversion method, the coated substrate is soft-baked using a hot plate set at 130ºC.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked using a hot plate set at 140ºC.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked for a total time of more than 10 minutes.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked for a total time of less than 10 minutes.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked for a total time of less than 8 minutes.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked for a total time of less than 6 minutes.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked for a total time of 4 minutes.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked for a total time of less than 4 minutes.

In some embodiments of the modified thermal conversion method, the coated substrate is soft baked for a total time of less than 2 minutes.

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is then cured at 2 preselected temperatures for 2 preselected time intervals, where the time intervals may be the same or different .

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is then cured at 3 pre-selected temperatures for 3 pre-selected time intervals, where each of the time intervals may be Same or different.

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is then cured at 4 preselected temperatures for 4 preselected time intervals, where each of the time intervals may be Same or different.

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is then cured at 5 pre-selected temperatures for 5 pre-selected time intervals, where each of the time intervals may be Same or different.

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is then cured at 6 pre-selected temperatures for 6 pre-selected time intervals, where each of the time intervals may be Same or different.

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is then cured at 7 pre-selected temperatures for 7 pre-selected time intervals, where each of the time intervals may be Same or different.

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is then cured at 8 pre-selected temperatures for 8 pre-selected time intervals, where each of the time intervals may be Same or different.

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is then cured at 9 preselected temperatures for 9 preselected time intervals, where each of the time intervals may be Same or different.

In some embodiments of the modified thermal conversion method, the soft-baked coated substrate is subsequently cured at 10 preselected temperatures for 10 preselected time intervals, where each of the time intervals may be Same or different.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 80ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 100ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 100ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 150ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 150ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 200ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 200ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 220ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 220ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 230ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 230ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 240ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 240ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 250ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 250ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 260ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 260ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 270ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 270ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 280ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 280ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 290ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is greater than 290ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is equal to 300ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is less than 300ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is less than 290ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is less than 280ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is less than 270ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is less than 260ºC.

In some embodiments of the improved thermal conversion method, the preselected temperature is less than 250ºC.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 2 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 5 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 10 minutes.

In some embodiments of the improved transformation method, one or more of the preselected time intervals is 15 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 20 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 25 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 30 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 35 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 40 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 45 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 50 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 55 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals is 60 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals are greater than 60 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals are between 2 minutes and 60 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals are between 2 minutes and 90 minutes.

In some embodiments of the improved thermal conversion method, one or more of the preselected time intervals are between 2 minutes and 120 minutes.

In some embodiments of the improved thermal conversion method, the method for preparing a polyimide film sequentially includes the following steps: applying the above-described polyimide solution containing the conversion chemical to the substrate; soft baking the coated substrate; treating the soft-bake coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory performance for use as disclosed herein characteristics of those electronic applications.

In some embodiments of the improved thermal conversion method, the method for preparing a polyimide film consists of the following steps in sequence: applying the above-described polyimide solution containing the conversion chemical to a substrate; soft Bake the coated substrate; treat the soft-bake coated substrate at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory performance for use as herein Characteristics of those electronic applications disclosed.

In some embodiments of the improved thermal conversion method, the method for preparing a polyimide film consists essentially of the following steps in sequence: applying the above-described polyamide acid solution containing the conversion chemical to a 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 exhibits satisfactory performance for, e.g. This article discloses the characteristics of those electronic applications. 6. Electronic devices

The polyimide films disclosed herein may be suitable for use as multiple layers in electronic display devices such as OLED and LCD displays. Non-limiting examples of such layers include device substrates, touch panels, substrates for optical filters, cover films, and the like. The specific material property requirements of each application are unique and may be addressed by one or more appropriate compositions and one or more processing conditions of the polyimide films disclosed herein.

In some embodiments, flexible alternatives to glass in electronic devices are polyimide films having repeating units of Formula IV as described in detail above.

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 (e.g., light-emitting diodes, light-emitting diodes displays, lighting devices, light sources, or diode lasers), (2) devices that detect signals by electronic means (such as photodetectors, photoconductive cells, photoresistors, photorelays, phototransistors, phototubes, 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 into a longer wavelength (such as frequency conversion 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 compositions according to the present 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.

An illustration of a polyimide film that can serve as a flexible alternative to glass as described herein is shown in Figure 1 . Flexible film 100 may have properties as described in embodiments of the present disclosure. In some embodiments, polyimide films that can serve as flexible alternatives to glass are included in electronic devices. FIG. 2 illustrates the situation when the electronic device 200 is an organic electronic device. 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 between them. Additional layers may be present as needed. Adjacent to the anode may be a hole injection layer (not shown), sometimes called a buffer layer. Adjacent to the hole injection layer may be a hole transport layer (not shown) including a hole transport material. Adjacent to the cathode may be an electron transport layer (not shown) containing electron transport material. As an option, the device may use one or more additional hole injection or hole transport layers (not shown) proximate the anode 110 and/or one or more additional electron injection or electron transport layers proximate 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 filters, touch panels, and/or shields. One or more of these layers (other than substrate 100) may also be made of the polyimide films disclosed herein.

These different layers will be discussed further here with reference to FIG. 2 . However, the discussion applies equally to other configurations.

In some embodiments, the different layers have the following thickness ranges: substrate 100, 5-100 microns, anode 110, 500-5000 Å, in some embodiments 1000-2000 Å; hole injection layer (not shown) , 50-2000 Å, in some embodiments, 200-1000 Å; hole transport 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 embodiments mode, 300-5000 Å. The desired ratio of layer thicknesses will depend on the exact properties of the materials used.

In some embodiments, organic electronic devices (OLEDs) contain flexible alternatives to glass as disclosed herein.

In some embodiments, an organic electronic device includes a substrate, an anode, a cathode, and a photoactive 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 layer is both a hole transport layer and an electron transport layer.

Anode 110 is an electrode that is particularly effective for injecting positive charge carriers. It can be made of materials containing, for example, metals, mixed metals, alloys, metal oxides or mixed metal oxides, or it can be conductive polymers, and mixtures thereof. Suitable metals include the metals of Group 11, the metals of Groups 4, 5 and 6 and the transition metals of Groups 8-10. If the anode system is to be light-transmissive, mixed metal oxides of Group 12, 13, and 14 metals, such as indium tin oxide, are generally used. The anode may also contain organic materials such as polyaniline, as described in "Flexible light-emittingdiodes made from soluble conducting polymer [Flexible light-emitting diodes made from soluble conducting polymer]", Nature, vol. 357, no. Described on 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.

The optional hole injection layer may include hole injection material. The term "hole injection layer" or "hole injection material" is intended to refer to a conductive or semiconducting material and may have one or more functions in an organic electronic device, including but not limited to planarization of underlying layers, charge transport, and/or or charge injection characteristics, removal of impurities such as oxygen or metal ions, and other aspects that benefit or improve the performance of organic electronic devices. Hole injection materials can be polymers, oligomers, or small molecules, and can be in the form of solutions, dispersions, suspensions, emulsions, colloidal mixtures, or other compositions.

The hole injection layer can be formed of polymer materials, such as polyaniline (PANI) or polyethylenedioxythiophene (PEDOT). These polymer materials are usually doped with protonic acid. The protonic acid may be, for example, poly(styrenesulfonic acid), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), or the like. The hole injection layer 120 may include charge transfer compounds, such as cuprophthalocyanine and tetrathiafulvalene-tetracyanoterephthaloquinodimethane system (TTF-TCNQ). In some embodiments, hole injection layer 120 is comprised of a dispersion of a conductive polymer and a colloid-forming polymeric acid. Such materials have been described, for example, in published US patent applications 2004-0102577, 2004-0127637, and 2005-0205860.

Other layers may contain hole transport materials. Examples of hole transport materials for use in hole transport layers have been summarized, for example, in Y. Wang, Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 18, Page 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"-tris(N,N-diphenyl-amino)-triphenylamine (TDATA); 4,4',4"-tris(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- methyl)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); Tetrakis-(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-methyl methylphenyl)methane (MPMP); 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline ( PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N'-tetrakis(4-methylphenyl)- (1,1'-biphenyl)-4,4'-diamine (TTB); N,N'-bis(naphthyl-1-yl)-N,N'-bis-(phenyl)benzidine (TTB) 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 transporting polymers by incorporating hole transporting molecules such as those described above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers are used, especially triarylamine-fluorine copolymers. In some cases, the polymers and copolymers are cross-linkable. Examples of crosslinkable hole-transporting polymers can be found, for example, in 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 tetrafluorotetracyanoquinolinodimethane and perylene-3,4,9,10-tetracarboxy-3,4,9,10 -Dianhydride.

Depending on the application of the device, the photoactive layer 120 may be a light-emitting layer activated by an applied voltage (as in a light-emitting diode or a light-emitting electrochemical cell), a material layer that absorbs light and emits light with a longer wavelength (as in a light-emitting diode or a light-emitting electrochemical cell). in a downconverting phosphor device), or a layer of material that responds to radiant energy and generates a signal with or without an applied bias voltage (as in a photodetector or photovoltaic device).

In some embodiments, the photoactive layer includes a compound that includes an emissive 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, benzophenanthrene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoline, phenylpyridine, carbazole, indolocarbazole, furan, benzene Furans, dibenzofurans, benzodifurans and metal quinoline complexes. In some embodiments, the host material is deuterated.

In some embodiments, the photoactive layer includes (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. Suitable second host compounds are described above.

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 A host compound in which no additional materials are present that would materially alter the operating principles or distinguishing characteristics of the layer.

In some embodiments, the first host is present at a higher concentration than the second host based on weight in the photoactive layer.

In some embodiments, the weight ratio of the first host to the second host in the photoactive layer is in the range of 10:1 to 1:10. In some embodiments, the weight ratio ranges from 6:1 to 1:6; in some embodiments, 5:1 to 1:2; in some embodiments, 3:1 to 1:1.

In some embodiments, the weight ratio of dopant to total host ranges from 1:99 to 20:80; in some embodiments, from 5:95 to 15:85.

In some embodiments, the photoactive layer includes (a) a red light-emitting dopant, (b) a first host compound, and (c) a second host compound.

In some embodiments, the photoactive layer includes (a) a green light-emitting dopant, (b) a first host compound, and (c) a second host compound.

In some embodiments, the photoactive layer includes (a) a yellow light-emitting dopant, (b) a first host compound, and (c) a second host compound.

Optionally, the layers can function simultaneously to facilitate electron transport and also serve as confinement layers to prevent quenching of excitons at the layer interface. Preferably, this layer promotes electron mobility and reduces exciton quenching.

In some embodiments, such layers include other electron transport materials. Examples of electron transport materials that may be used in the optional electron transport layer include metal-chelated oxinoid compounds, including metal quinolate derivatives such as tris(8-hydroxyquinolate)aluminum (AlQ), bis (2-Methyl-8-hydroxyquinolate)(p-phenylphenolate)aluminum (BAlq), tetrakis-(8-hydroxyquinolate)hafnium (HfQ) and tetrakis-(8-hydroxyquinolate) Zirconium (ZrQ); and azole compounds, such as 2-(4-biphenyl)-5-(4-tertiary butylphenyl)-1,3,4-diadiazole (PBD), 3-( 4-biphenyl)-4-phenyl-5-(4-tertiary butylphenyl)-1,2,4-triazole (TAZ) and 1,3,5-tris(phenyl-2- Benzimidazole)benzene (TPBI); quinziline derivatives, such as 2,3-bis(4-fluorophenyl)quinoline; phenanthroline, such as 4,7-diphenyl-1,10-phenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); trisulfonate; fullerene; and mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinoline salts and phenanthroline 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 2 metals; Group 1 and 2 metal salts such as LiF, CsF and Cs ₂ CO ₃ ; Group 1 and 2 metal organic compounds such as Lithium quinolate; 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 cobaltinocene, tetrathiocene, bis(ethylidenedithio)tetrathiafulvalene, heterocyclic groups or divalent groups, and Dimers, oligomers, polymers, bispiro compounds and polycyclates of heterocyclic groups or divalent groups.

An optional electron injection layer can be deposited on the electron transport layer. Examples of electron injection materials include, but are not limited to, Li-containing organometallic compounds, LiF, Li ₂ O, lithium quinolate; Cs-containing organometallic compounds, 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 typically in the range of 1-100 Å, in some embodiments 1-10 Å.

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 that has a lower work function than the anode. Materials used for the cathode may be selected from the 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 may be used.

It is known to have other layers in organic electronic devices. For example, multiple layers (not shown) may be present between the anode 110 and the hole injection layer (not shown) to control the amount of positive charge injected and/or to provide bandgap matching of the layers, or to serve as protective layers . Layers known in the art may be used, such as ultra-thin layers of copper phthalocyanine, silicon oxynitride, fluorocarbons, 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. The selection of materials for each component layer is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescence efficiency.

It should be understood that each functional layer can be composed of more than one layer.

Device layers may 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 can be used, such as thermal evaporation, chemical vapor deposition, etc. Conventional coating or printing techniques may be used, including but not limited to coating, dip coating, roll-to-roll techniques, inkjet printing, continuous nozzle printing, screen printing, gravure printing, etc., from solutions or dispersions in suitable solvents to apply the organic layer.

For liquid phase deposition methods, one skilled in the art can readily determine suitable solvents for a particular compound or a related class of compounds. For some applications it is desirable that the compounds be soluble 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, trisethylene, Fluorotoluene, etc. Other suitable liquids for use in making liquid compositions including novel compounds (as solutions or dispersions as described herein) include, but are not limited to, chlorinated hydrocarbons (e.g., methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (e.g., substituted and unsubstituted toluene and xylene, including trifluorotoluene), polar solvents (such as tetrahydrofuran (THP), N-methylpyrrolidone), esters (such as ethyl acetate), alcohols (isopropyl alcohol), ketones (cyclopentanone), and their mixtures. Suitable solvents for electroluminescent materials have been described, for example, in published PCT application WO 2007/145979.

In some embodiments, the device is formed 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.

It should be understood that the efficiency of the device can be improved by optimizing other layers in the device. For example, more efficient cathodes such as Ca, Ba or LiF can be used. Shaped substrates and novel hole transport materials that result in lower operating voltages or increased quantum efficiency are also applicable. Additional layers can also be added to tailor the energy levels of each layer and promote electroluminescence.

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.

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 not intended to be limiting. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. Example

The concepts described herein are further illustrated in the following examples, which do not limit the scope of the invention as described in the claimed claims. Example 1

This example shows the synthesis of a compound of formula I (compound 6). (a)

In a 200 mL round bottom flask equipped with a magnetic stirrer and a condenser attached to a nitrogen line, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydrogen -1,1'-Spirobis[indene]-6,6'-diylbis(trifluoromethanesulfonate) (2.00 g, 3.49 mmol), 4,4,4',4',5,5, 5',5'-Octamethyl-2,2'-bis(1,3,2-dioxaborane) (2.66 g, 10.49 mmol), and potassium acetate (1.37 g, 13.97 mmol) were added to anhydrous sodium chloride (40 mL). The mixture was bubbled with nitrogen for 20 min. Then, Pd(dppf)Cl (0.285 g, 0.35 mmol) was added and bubbled for another 10 min. The mixture was stirred and heated at 70ºC under nitrogen for 9 hours. TLC analysis (DCM/hexane, 1/3) indicated that all starting triflate had been consumed. The mixture was cooled to room temperature and concentrated to dryness. DCM (100 mL) and water (100 mL) were added, and the mixture was extracted with additional DCM (100 mL x 2). The organic layers were combined, dried over _Na2SO4 and filtered through florisil to _remove insoluble material and color. The solution was concentrated to dryness and the resulting solid was stirred in hexanes at approximately 45ºC for 10 min and filtered to give 2,2'-(3,3,3',3'-tetramethyl-2 as a white solid ,2',3,3'-tetrahydro-1,1'-spirobis[indene]-6,6'-diyl)bis(4,4,5,5-tetramethyl-1,3,2 -dioxaborane) (1.26 g, 68% yield). NMR analysis showed the material was consistent with the structure. (b)

In a 500 mL three-neck round bottom flask equipped with a magnetic stirrer and a condenser attached to a nitrogen line, 2,2'-(3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobis[indene]-6,6'-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxy Heterocyclopentaborane) (10.0 g, 18.9 mmol), N-Boc 4 bromo-2-fluoroaniline (13.67 g, 47.3 mmol, Boc = butoxycarbonyl), and cesium carbonate (18.5 g, 56.8 mmol) were added to a mixture of dimethoxyethane (250 mL), ethanol (125 mL), and water (40 mL). The mixture was bubbled with nitrogen while the system was under continuous nitrogen flow for 20 min. Then, Pd(dppf) ₂ Cl ₂ (1.54 g, 1.89 mmol) was added and bubbled for another 10 min. Thereafter, the mixture was stirred and heated at 70°C under nitrogen for 14 hours. UPLC showed that the starting material had been consumed. The mixture was cooled to room temperature, DCM (100 mL) and water (100 mL) were added, and the mixture was extracted with additional DCM (100 mL x 2). _The organic layers were combined, dried over _Na2SO4 , filtered, and concentrated over celite. The sample was dry packed into a 330 g silica column (hexane:DCM 0%-50%), the fractions were examined by TLC and UPLC, the fractions were concentrated and the hexane slurry was filtered to obtain ((3,3 ,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobis[indene]-6,6'-diyl)bis(2-fluoro-4 ,1-phenylene)) di-tertiary butyl dicarbamate (7.95 g, 60% yield). NMR analysis showed the material was consistent with the structure. (c)

In 250 mL RBF, add ((3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobis[indene]-6,6 Ditertiary butyl '-diyl)bis(2-fluoro-4,1-phenyl))diaminocarboxylate (7.95 g, 11.44 mmol) was dissolved in CH2Cl2 (90 mL). Trifluoroacetic acid (8.76 mL) was added and stirred under nitrogen overnight. After 17 hours, UPLC showed the desired changes in m/z and retention time. Wash the mixture with saturated sodium bicarbonate solution until the pH becomes slightly alkaline (pH approximately 8). The organic layer was dried over _Na2SO4 , filtered, and concentrated _. Acetonitrile was added to create a slurry, filtered and the solid dried in vacuo. Compound 6 was an off-white solid (3.71 g, 65% yield), and NMR was consistent with the expected product. Used as-is in aggregates. Example 2

This example illustrates the preparation of polyamic acid of formula II. Polyamide has the following composition: BPDA/PMDA/6FDA//TFMB/Compound 6 70/10/20//75/25 A 250 mL reaction flask equipped with a nitrogen inlet and outlet, a mechanical stirrer, and a thermocouple was charged with 7.21 g of TFMB (0.0225 mol), 3.71 g of compound 6 from Example 1 (0.0075 mol), and 84.2 g of 1-methyl- 2-pyrrolidinone (NMP). The mixture was stirred at room temperature under nitrogen for about 30 minutes. After that, 6.18 g of BPDA (0.021 mol) was slowly added to the stirring solution of diamine in batches, followed by the addition of 0.46 g of PMDA (0.0021 mol) and 2.67 g of 6FDA (0.006 mol) in batches. Control the dianhydride addition rate to maintain a maximum reaction temperature >30ºC. After the dianhydride addition was complete, an additional 9.35 g of NMP was used to wash any remaining dianhydride powder from the walls of the vessel and reaction flask. And the resulting mixture was stirred for 8 days. Separately, a 5% solution of PMDA in NMP was prepared and added in small amounts (approximately 0.650 g) over time to increase the molecular weight of the polymer and the viscosity of the polymer solution. Use a Brookfield cone and plate viscometer to monitor solution viscosity by testing small samples from the reaction flask. A total of 3.58 g of this completed solution (0.182 g, 0.000825 moles PMDA) was added. The reaction was carried out overnight at room temperature with gentle stirring to allow the polymer to equilibrate. The final viscosity of the polymer solution was 13,210 cps at 25ºC. Example 3

This example illustrates the preparation of a polyimide film, wherein the polyimide has formula IV.

The polyamic acid solution from Example 2 was filtered through a microfilter, spin-coated onto a clean silicon wafer, soft-baked at 90ºC on a hot plate, and placed in an oven. The oven was purged with nitrogen and heated in stages to a maximum curing temperature of 375ºC. The wafers were removed from the furnace, soaked in water and manually layered to produce polyimide film samples. The properties of the film are given below: Thickness: 10.95 µm T _g : 392ºC CTE (2nd scan) 53.23 ppm/ºC Optical retardation 80 b ^* 4.56 YI 7.49 It should be noted that not all of the above are described in a general way or as examples The activities described in are required, some specific activities may not be required, and one or more other activities may be performed in addition to those described. Furthermore, the order in which activities are enumerated is not necessarily the order in which they are performed.

In the foregoing specification, concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the following claims. Accordingly, the specification and drawings are to be regarded in an illustrative and not a restrictive sense, and all such modifications are intended to be included within the scope of the invention.

Benefits, other advantages, and solutions to problems have been described above with respect to specific embodiments. However, benefits, advantages, solutions to problems, and any feature or features which may cause or render more apparent any benefit, advantage, or solution are not to be construed as being critical to the scope of any or all claims. essential, essential or essential characteristics.

It is to be understood that, for clarity, certain features described herein in the context of separate implementations may also be provided in combination in a single implementation. Conversely, for the sake of brevity, various features that are described in the context of a single implementation may also be provided separately or in any sub-combination. The use of numerical values within various ranges specified herein are expressed as approximations as if both the minimum and maximum values within the stated range were preceded by the word "about." In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as values within those ranges. Furthermore, such ranges are intended to be disclosed as a continuous range that includes every value between the minimum and maximum average values, including the fractional values that can result when components of one value are mixed with components of different values. Additionally, when wider and narrower ranges are disclosed, it is within the intent of this invention that the minimum value from one range be matched to the maximum value from the other range, and vice versa.

Embodiments are illustrated in the accompanying drawings to enhance an understanding of the concepts as presented herein.

[Fig. 1] An illustration of an example including a polyimide film that can serve as a flexible substitute for glass.

[Fig. 2] Includes an illustration of an example of an electronic device including a flexible alternative to glass.

Skilled artisans will understand that the objects in the figures are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some objects in the figures may be exaggerated relative to other objects to help improve understanding of the embodiments.

Claims (8)

A diamine having formula I

Among them: Q is selected from the group consisting of the following items: Formula Q2 and Formula Q3;

R ¹ -R ⁴ are the same or different and selected from the group consisting of: H, alkyl, alkoxy, hydrocarbyl, heteroaryl, aryloxy, silyl, and silyloxy; R ⁵ and R ⁶ are the same or different on each occurrence and are selected from the group consisting of: F, CN, alkyl, fluoroalkyl, hydrocarbon aryl, heteroaryl, alkoxy, fluoroalkyl Oxy, aryloxy, silyl, and silyloxy; a and b are the same or different and are integers from 0 to 3; * indicates the point of attachment; R ⁷ and R ⁸ are the same on each occurrence or different and selected from the group consisting of: F, CN, alkyl, fluoroalkyl, hydrocarbyl, heteroaryl, alkoxy, fluoroalkoxy, aryloxy, silyl, and Silyloxy, wherein adjacent R ⁷ and/or R ⁸ groups can be linked together to form an aromatic ring; c and d are the same or different on each occurrence and are an integer from 0 to 4; and m and q are the same or different and are integers from 0 to 6. A polyamide having repeating units of formula II

Where: R ^a is the same or different at each occurrence and represents one or more tetracarboxylic acid component residues; and R ^b is the same or different at each occurrence and represents one or more aromatic residues Family diamine residues; 10 mol% to 100 mol% of R ^b is derived from one or more residues of diamines of formula I according to item 1 of the patent application scope; the remaining R ^b is derived from at least one additional diamine A diamine residue of an amine, the additional diamine being selected from the group consisting of: PPD, 4,4'-ODA, 3,4'-ODA, TFMB, Bis-A-AF, Bis-AT-AF , and Bis-P; the tetracarboxylic acid component includes pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'- Oxydiphthalic anhydride (ODPA), 4,4'-hexafluoroisopropylidene diphthalic anhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic acid di Anhydride (BTDA), 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-bis-oxytetrahydrofuran-3-yl)-1,2,3,4-tetralin-1,2 - Dicarboxylic anhydride (DTDA), 4,4'-bisphenol A dianhydride (BPADA) and combinations thereof. A liquid composition comprising (a) the polyamide as described in item 2 of the patent application, and (b) a high-boiling aprotic solvent. A polyimide having a repeating unit structure of formula IV

wherein R ^a is the same or different on each occurrence and represents one or more tetracarboxylic acid component residues; and R ^b is the same or different on each occurrence and represents one or more aromatic Diamine residues; wherein 10 mol% to 100 mol% of R ^b are derived from one or more diamine residues having formula I as described in item 1 of the patent application scope; the remaining R ^b are derived from at least one additional A diamine residue of a diamine, the additional diamine being selected from the group consisting of: PPD, 4,4'-ODA, 3,4'-ODA, TFMB, Bis-A-AF, Bis-AT- AF, and Bis-P; the tetracarboxylic acid component includes pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4' -Oxydiphthalic anhydride (ODPA), 4,4'-hexafluoroisopropylidenediphthalic anhydride (6FDA), 3,3',4,4'-benzophenonetetracarboxylic acid Dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalate Acid anhydride (HQDEA), ethylene glycol bis(trimellitic anhydride) (TMEG-100), 4-(2,5-bisoxytetrahydrofuran-3-yl)-1,2,3,4-tetralin-1, 2-dicarboxylic anhydride (DTDA), 4,4'-bisphenol A dianhydride (BPADA) and combinations thereof. A method for preparing a polyimide film as described in item 4 of the patent application, the method sequentially includes the following steps: Coating a polyamide solution containing two or more tetracarboxylic acid components and one or more diamine components in a high-boiling aprotic solvent onto the substrate; soft-baking the coated substrate; to The soft-bake coated substrate is treated at a plurality of preselected temperatures for a plurality of preselected time intervals. A flexible substitute for glass in an electronic device, wherein the flexible substitute for glass includes a film of polyimide having formula IV as described in item 4 of the patent application. An electronic device including a flexible substitute for glass as described in claim 6 of the patent application. An electronic device as claimed in claim 7, wherein the flexible substitute for glass is used in a device component selected from the following group consisting of: a device substrate, a substrate of a filter, a cover film, and touch screen panels.