TWI833752B - Polymers for use in electronic devices - Google Patents

Abstract

There is disclosed an acid dianhydride having Formula IV. In Formula IV: R^d represents a tetracarboxylic acid component residue; R^e represents a diamine residue; and m is an integer from 1-20.

Description

Polymers used in 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 low-color materials suitable for electronic devices.

Imide-containing monomers for polyimides are provided.

Also provided is a diamine of formula I wherein: R ^a represents a tetracarboxylic acid component residue; R ^b represents a diamine residue; and m is an integer from 1 to 20.

Also provided is a polyamic acid composition, which is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the diamines comprise 1-100 mol% of the diamine having formula I.

Also provided is an acid dianhydride having formula IV wherein: R ^d represents a tetracarboxylic acid component residue; R ^e represents a diamine residue; and m is an integer from 1 to 20.

Also provided is a polyamic acid composition, which is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the tetracarboxylic acid components comprise 1-100 mol% of a compound having formula IV Tetracarboxylic dianhydride.

Also provided is a composition comprising (a) the above-described polyamide and (b) at least one high boiling aprotic solvent.

Also provided is a polyimide obtained by imidization of any of the above-mentioned polyamide acids.

A polyimide film including the above polyimide is also provided.

One or more methods for preparing the polyimide membranes described above are also provided.

A flexible substitute for glass in electronic devices is also provided, wherein the flexible substitute for glass is the above-mentioned polyimide film.

Also provided is an electronic device having at least one layer including the polyimide film described above.

Also provided is an organic electronic device, such as an OLED, 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.

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 relates first to the definition and clarification of terms and then to the amide-imine-containing monomers, diamines of formula I, acid dianhydrides of formula IV, polyamide acids, polyimides, used in the preparation of polyamides Imine membrane methods, electronic devices, and 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, cyclopentyl Hexyl, 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. The term is intended to include heteroalkyl. 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 Replaced by another atom 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. An aryl group 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, the hydrocarbyl group has 6 to 60 ring carbon atoms; in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, a heteroaryl group has from 4-50 ring carbon atoms; in some embodiments, 4-30 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.

The term "allyl" is intended to refer to the group _-CH2 -CH= _CH2 .

The term "vinyl" is intended to refer to the group -CH= _CH2 .

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" is 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 alkyl or aryl. 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 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/°C or ppm/°C. 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 ruptures 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 130°C.

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 usually measured via thermogravimetric analysis (TGA) at a constant temperature of interest. 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 "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 R _TH )" 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. Optical delay can be measured with Metricon or Axoscan.

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 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% at 350°C for 3 hours in nitrogen 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 spin-coated material is heated to drive off the solvent and cure the film. Soft baking is usually performed on a hot plate or in an exhaust oven at a temperature between 90°C and 110°C as a preparation step for subsequent heat treatment of the coating 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, C1-20 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, C1-20 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, C1-20 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 "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 membranes thus prepared are evaluated for particle content by any number of standard measurement techniques. Such techniques include laser particle detection and other techniques known in the art.

The term "tensile modulus" is intended to refer to a measure of the stiffness of a solid material that 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 features or elements. , 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, the term "a" or "an" is used to describe the 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 to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are hereby 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. Monomers containing amide imine

Difficulties with low reactivity, processability, and the ability to control polymer structure have hindered the use of some potentially useful classes of monomers for the synthesis of polyimides. Both dianhydride monomers and diamine monomers present problems. Some monomers with low reactivity can only polymerize under harsh reaction conditions. Such conditions can promote the formation of side reactions, which adversely affect the quality of the final polyimide film. Both optical and mechanical properties can be degraded.

It has been found that the amide-containing monomers described herein can be used to overcome the problems of monomers with low reactivity to control polymer structure (such as local order and tacticity) in order to achieve less Imination in the presence of a number of defects is used for polyimides with improved properties.

In some embodiments, the imine-containing monomers described herein can be used to provide polyimides with reduced stress.

In some embodiments, the imine-containing monomers are separated from defects and by-products and purified. Therefore, highly pure compounds with precisely defined oligomer structures can be used as monomers.

In some embodiments, the imine-containing monomers are used in the form formed and are mixtures of pre-imidized compounds.

The imine-containing monosystems described herein are compounds having a reactive end-group imidized core.

In some embodiments, the reactive terminal group of the imine-containing monosystem diamine is an amine group, -NH ₂ .

In some embodiments, the imine-containing monosystem diisocyanate and the reactive end group are isocyanate groups -NCO.

In some embodiments, the acyl imine-containing monosystem tetracarboxylic dianhydride, and the reactive end group is an anhydride.

In some embodiments, the imidized core contains two imidized groups, hereafter referred to as "dimides."

In some embodiments, the imidized core is a polyimide oligomer having 4 to 20 imidimine groups.

Disclosed herein is a method for the synthesis of precisely defined amide-imine-containing polymers obtained from pre-imidized (amide-imine-containing) monomers. This is described below as Scheme I and Scheme II.

In scheme I, the first step is to pre-imidize the first dianhydride with an excess of the first diamine. The preiminated diamine monomer so formed can be isolated and purified. The pre-imidized diamine is sufficiently reactive to react in step 2 with one or more additional dianhydrides (which may or may not be the same as the first dianhydride) to form an imine-containing polyamic acid. Despite the presence of imine groups even at high molar ratios, such imine-containing polymers are soluble and processable. Step 3 is the final imidization to form a polyimide polymer using conventional imidization techniques such as thermal curing. One embodiment of Scheme I is shown below, wherein the second dianhydride is different from the first dianhydride. Option I: An Implementation Mode

In the above scheme, Y represents a residue from the first tetracarboxylic acid component (dianhydride), Z represents a residue from a diamine, X1 represents a residue from the second tetracarboxylic acid component (dianhydride), n1 represents an integer from 1 to 20, and n represents an integer greater than 50.

In some embodiments of Scheme I, n1 = 1 and the diamine has a single imidized core.

In some embodiments of Scheme I, n1 = 2-20, and the diamine has an oligomeric imidized core. In some embodiments, n1 = 2-5; in some embodiments, 6-10; in some embodiments, 11-20.

In Scheme II, the first step involves pre-imidization of the first diamine with an excess of dianhydride. The preiminated dianhydride monomer thus formed is sufficiently reactive to react with one or more additional diamines (which may be the same as or different from the first diamine) in step 2 to form the amide-containing imine of polyamide. Despite the presence of imine groups even at high molar ratios, such imine-containing polymers are soluble and processable. Step 3 is the final imidization to form a polyimide polymer using conventional imidization techniques such as thermal curing. One embodiment of Scheme II is shown below, wherein the second diamine is different from the first diamine. Option II: An Implementation

In the above scheme, Y represents the residue from the tetracarboxylic acid component (dianhydride), Z represents the residue from the first diamine, X2 represents the residue from the second diamine, and n1 represents from 1-20 Integers, and n represents an integer greater than 50.

In some embodiments of Scheme II, n1 = 1 and the dianhydride has a single imidized core.

In some embodiments of Scheme II, n1 = 2-20, and the dianhydride has an oligomeric imidized core. In some embodiments, n1 = 2-5; in some embodiments, 6-10; in some embodiments, 11-20.

Alternatively, pre-imidized monomers can be used in situ without isolation and characterization. This is described below as Scheme III and Scheme IV.

In Scheme III, the first step involves pre-imidization of the first dianhydride with a large excess of the first diamine. In step 2, the resulting mixture of pre-imidized diamine and excess first diamine is reacted with one or more dianhydrides and optionally one or more additional diamines. The resulting amide imine-containing polyamide acid is imidized in step 3 using conventional imidization techniques.

In Scheme III, the preimidated diamine prepared in step 1 has the formula shown below where m1 represents an integer from 1-20. Mixtures of monomers with different m1 values may exist. In polyamides and polyimides, m1 can be the same or different on each occurrence. In some embodiments, m1 is 2-5; in some embodiments, 6-10; in some embodiments, 11-20. Y represents a residue derived from the first tetracarboxylic acid component (dianhydride), and Z represents a residue derived from the first diamine.

In Scheme IV, the first step involves pre-imidization of the first diamine with a large excess of the first dianhydride. In step 2, the resulting mixture of pre-imidized dianhydride monomer and excess first dianhydride is reacted with one or more diamines and optionally one or more additional dianhydrides. The resulting amide imine-containing polyamide acid is imidized in step 3 using conventional imidization techniques.

In Scheme IV, the pre-imidized dianhydride prepared in step 1 has the formula shown below where m1 represents an integer from 1-20. Mixtures of monomers with different m1 values may exist. In polyamides and polyimides, m1 can be the same or different on each occurrence. In some embodiments, m1 is 2-5; in some embodiments, 6-10; in some embodiments, 11-20. Y represents a residue derived from the first tetracarboxylic acid component (dianhydride), and Z represents a residue derived from the first diamine. 3. Diamines of formula I

The diamines described herein have formula I wherein: R ^a represents a tetracarboxylic acid component residue; R ^b represents a diamine residue; and m is an integer from 1 to 20.

In some embodiments of Formula I, m = 1.

In some embodiments of Formula I, m = 2-20.

In some embodiments of Formula I, m = 2-5.

In some embodiments of Formula I, m = 6-10.

In some embodiments of Formula I, m = 11-20.

In some embodiments of Formula I, R ^a is aromatic.

In some embodiments of Formula I, R ^a is aliphatic; in some embodiments, cycloaliphatic.

In some embodiments of Formula I, R ^a is a polycyclic alicyclic group.

In some embodiments of Formula I, R ^a is aromatic; in some embodiments, polycyclic aromatic.

In some embodiments of Formula I, ^Ra has an aromatic group and an alicyclic group.

In some embodiments of Formula I, ^R represents a residue of tetracarboxylic dianhydride.

In some embodiments of Formula I, ^R represents a residue of a tetracarboxylic dianhydride selected from the group consisting of: pyromellitic dianhydride (PMDA), 3,3', 4,4'-Biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-hexafluoroisopropylidenebisphthalic dianhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (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-dilateral oxytetrahydrofuran- 3-yl)-1,2,3,4-tetralin-1,2-dicarboxylic anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA); cyclobutane-1,2, 3,4-tetracarboxylic dianhydride (CBDA); 𠮿 (oral star) tetracarboxylic dianhydride; etc. These aromatic dianhydrides may be optionally substituted by 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, fluoroalkyl, perfluoroalkyl, fluoroalkoxy , perfluoroalkoxy, arylalkyl, silyl, silyloxy, siloxane, thioalkoxy, -S(O) ₂ -, -C(=O)-N(R')( R”), (R’)(R”)N-alkyl, (R’)(R”)N-alkoxyalkyl, (R’)(R”)N-alkylaryloxyalkyl , -S(O) _s -aryl (where s = 0-2) or -S(O) _s -heteroaryl (where s = 0-2). Each R' and R'' are independently optional Substituted alkyl, cycloalkyl or aryl. 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 I, ^R represents a residue from a tetracarboxylic dianhydride selected from the group consisting of: PMDA, BPDA, 6FDA, BTDA, and CBDA.

In some embodiments of Formula I, ^R represents a residue of an aliphatic tetracarboxylic dianhydride or a polycyclic tetracarboxylic dianhydride.

In some embodiments of Formula I, R ^a is selected from the group consisting of: Formulas A1 to A36 where: R ¹ is the same or different on each occurrence and is selected from the group consisting of: alkyl, fluoroalkyl and silyl, where adjacent R ¹ groups may be linked together to form Double bond; R ² , R ³ and R ⁴ are the same or different on each occurrence and are selected from the group consisting of: F, alkyl, fluoroalkyl and silyl; R ⁵ is selected from Group consisting of: H, halogen, cyano, hydroxy, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, hydrocarbyl, substituted hydrocarbyl , heteroaryl, substituted heteroaryl, vinyl, and allyl; R ⁶ is selected from the group consisting of: halogen, cyano, hydroxyl, alkyl, heteroalkyl, alkoxy, hetero Alkoxy, fluoroalkyl, silyl, hydrocarbyl, substituted hydrocarbyl, heteroaryl, substituted heteroaryl, vinyl, and allyl; R ⁸ and R ⁹ on each occurrence are the same or different and are selected from the group consisting of: H, F, alkyl, fluoroalkyl and silyl; Q is selected from the group consisting of: CR ⁸ R ⁹ , SiR ⁸ R ⁹ , S, SR ⁸ R ⁹ , S=O, SO ₂ and C=O; a is an integer from 0-6; b is an integer from 0-3; c, d and e are the same or different, and is an integer from 0 to 2; f is an integer from 0 to 4; z is an integer from 1 to 6; z1 is an integer from 0 to 6; and * represents an attachment point.

In some embodiments of Formula I, R ^b is aliphatic; in some embodiments, cycloaliphatic.

In some embodiments of Formula I, R ^b is a polycyclic aliphatic group.

In some embodiments of Formula I, R ^b is aromatic; in some embodiments, polycyclic aromatic.

In some embodiments of Formula I, R ^b has an alicyclic group and an aromatic group. In some embodiments of Formula I, R ^b represents a residue of a diamine of Formula D1 where: R ¹⁰ is the same or different on each occurrence and is selected from the group consisting of: fluoroalkyl and fluoroalkoxy; R ¹¹ is the same or different on each occurrence, and is selected from the group consisting of: F, alkyl, fluoroalkyl, and silyl; b is the same or different on each occurrence and is an integer from 0 to 3; c is on each occurrence are the same or different and are integers from 0 to 2; and y is an integer from 0 to 2.

In some embodiments of Formula D1, R ¹⁰ is C _1-5 perfluoroalkyl.

In some embodiments of Formula D1, y = 0.

In some embodiments of formula D1, y = 1.

In some embodiments of formula D1, b = c = 0.

In some embodiments of Formula I, R ^b represents a residue of an aromatic diamine selected from the group consisting of p-phenylenediamine (PPD), 2,2'-dimethyl -4,4'-Diaminobiphenyl (m-toluidine), 3,3'-Dimethyl-4,4'-diaminobiphenyl (o-toluidine), 3,3'-di Hydroxy-4,4'-diaminobiphenyl (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'-tetrakis Methylbenzidine (3355TMB), 2,2'-bis(trifluoromethyl)benzidine (22TFMB or TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]propane ( BAPP), 4,4'-methylenedianiline (MDA), 4,4'-[1,3-phenylenebis(1-methyl-ethylene)]bis-aniline (Bis-M), 4,4'-[1,4-phenylenebis(1-methyl-ethylene)]bisaniline (Bis-P), 4,4'-oxydiphenylamine (4,4'-ODA) , m-phenylenediamine (MPD), 3,4'-oxydiphenylamine (3,4'-ODA), 3,3'-diaminodiphenylamine (3,3'-DDS), 4,4 '-Diaminodiphenylsulfide (4,4'-DDS), 4,4'-diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-amino-phenoxy base)phenyl]sine (BAPS), 2,2-bis[4-(3-aminophenoxy)-phenyl]sine (m-BAPS), 1,4'-bis(4-aminobenzene) Oxy)benzene (TPE-Q), 1,3'-bis(4-aminophenoxy)benzene (TPE-R), 1,3'-bis(3-amino-phenoxy)benzene ( APB-133), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 4,4'-diaminobenzoaniline (DABA), methylene bis(o-amino) Benzoic acid) (MBAA), 1,3'-bis(4-aminophenoxy)-2,2-dimethylpropane (DANPG), 1,5-bis(4-aminophenoxy)pentane alkane (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-methyl) Phenyl) hexafluoropropane (Bis-AT-AF), 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl (6BFBAPB), 3,3'5,5'-Tetramethyl-4,4'-diaminodiphenylmethane (TMMDA), etc.

In some embodiments of Formula I, R ^b represents a residue of an aromatic diamine selected from the group consisting of: PPD, MPD, m-toluidine, o-toluidine, Benzidine and TFMB.

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.

In some embodiments of Formula I, the diamine is selected from the group consisting of: Compound 1 to Compound 24 Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Compound 6a Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Compound 13 Compound 14 Compound 15 Compound 16 Compound 17 Compound 18 Compound 19 Compound 20 Compound 21 Compound 22 Compound 23 Compound 24 4. Dianhydrides of formula IV

The dianhydrides described herein have formula IV wherein: R ^d represents a tetracarboxylic acid component residue; R ^e represents a diamine residue; and m is an integer from 1 to 20.

In some embodiments of Formula IV, m = 1.

In some embodiments of Formula IV, m = 2-20.

In some embodiments of Formula IV, m = 2-5.

In some embodiments of Formula IV, m = 6-10.

In some embodiments of Formula IV, m = 11-20.

Any of the above-listed tetracarboxylic dianhydrides suitable for forming residue R ^a in formula I is also suitable for forming residue R ^d in formula IV.

In some embodiments of Formula IV, R ^d represents a residue from a tetracarboxylic dianhydride selected from the group consisting of: PMDA, BPDA, 6FDA, BTDA, and CBDA.

Any of the above listed diamines suitable for forming residue ^Rb in formula I are also suitable for forming residue ^Re in formula IV.

In some embodiments of Formula IV, ^Re represents a residue of a fluorinated aromatic diamine. In some embodiments of Formula IV, Re ^is selected from the group consisting of: Formulas E1 to E16 where: R ⁷ is the same or different on each occurrence and is selected from the group consisting of: F, alkyl, aryl, R _f and OR _f ; R ⁸ and R ⁹ are on each occurrence are the same or different and are selected from the group consisting of: H, F, alkyl, fluoroalkyl, and silyl; R ¹⁰ is the same or different on each occurrence and is selected from the group consisting of: The group consisting of: fluoroalkyl and fluoroalkoxy; R ¹¹ is the same or different on each occurrence and is selected from the group consisting of: F, alkyl, fluoroalkyl and silicon group; R _f is C _1-3 perfluoroalkyl group; Q is selected from the group consisting of: CR ⁸ R ⁹ , SiR ⁸ R ⁹ , S, SR ⁸ R ⁹ , S=O, SO ₂ and C=O; b is the same or different in each occurrence and is an integer from 0-3; c is the same or different in each occurrence and is an integer from 0-2; g is an integer from 0- h is an integer from 0 to 6; p is an integer from 1 to 10; q is an integer from 0 to 5; y is an integer from 0 to 2; and * represents an attachment point.

In some embodiments of E1 to E16, ^R7 is selected from the group consisting of: F, _Rf , and _ORf .

In some embodiments of E1 to E16, g is an integer from 1-4.

Any of the above embodiments of Formula IV may be combined with one or more of the other embodiments as long as they are not mutually exclusive. In some embodiments of Formula IV, the dianhydride is selected from the group consisting of: Compound 25 to Compound 38 Compound 25 Compound 26 Compound 27 Compound 28 Compound 29 Compound 30 Compound 31 Compound 32 Compound 33 Compound 34 Compound 35 Compound 36 Compound 37 Compound 38 5. Polyamide

The polyamic acid described herein is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein (a) the diamines comprise 1 to 100 mol % of the diamine of formula I, and /or (b) the tetracarboxylic acid components comprise 1-100 mol% of the tetracarboxylic dianhydride of formula IV. In some embodiments, the polyamic acid is a reaction product of one or more tetracarboxylic acid components and one or more diamines, which conforms to one of the following: (a) the diamines comprise 1-100 mol% of Diamine of formula I, or (b) The tetracarboxylic acid component contains 1 to 100 mol % of the tetracarboxylic dianhydride of formula IV.

The first polyamide is a reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the diamines comprise 1-100 mol% of the diamine of formula I.

In some embodiments of the first polyamide, 1-5 mol% of the total diamine of the diamine series having Formula I; in some embodiments, 6-10 mol%; in some embodiments, 10- 25 mol%; in some embodiments, 25-50 mol%; in some embodiments, 50-75 mol%; in some embodiments, 75-100 mol%; in some embodiments, 100 mol%.

In some embodiments of the first polyamide, a single tetracarboxylic acid component is present.

In some embodiments of the first polyamide, two tetracarboxylic acid components are present.

In some embodiments of the first polyamide, three tetracarboxylic acid components are present.

In some embodiments, the first polyamic acid system has the reaction product of a single diamine and a single tetracarboxylic acid component of Formula I.

The first polyamide has repeating units of formula II Where: R ^a and R ^c are the same or different and represent a tetracarboxylic acid component residue; R ^b represents a diamine residue; and m is an integer from 1 to 20.

All the embodiments described above for Ra ^{, Rb} and m in formula I apply equally to Ra, ^{Rb and} m in formula II.

Any of the above-listed tetracarboxylic dianhydrides suitable for forming residue R ^a in formula I is also suitable for forming residue R ^c in formula II.

In some embodiments of Formula II, ^Rc represents a residue from a tetracarboxylic dianhydride selected from the group consisting of: PMDA, BPDA, 6FDA, BTDA, and CBDA.

The second polyamic acid is a reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the tetracarboxylic acid components comprise 1-100 mol% of the tetracarboxylic dianhydride of formula IV.

In some embodiments of the second polyamide, 1-5 mol% of the total dianhydride of the dianhydride system having Formula IV; in some embodiments, 6-10 mol%; in some embodiments, 10- 25 mol%; in some embodiments, 25-50 mol%; in some embodiments, 50-75 mol%; in some embodiments, 75-100 mol%; in some embodiments, 100 mol%.

In some embodiments of the second polyamide, a single diamine component is present.

In some embodiments of the second polyamide, two diamine components are present.

In some embodiments of the second polyamide, three diamine components are present.

In some embodiments, the second polyamic acid system has the reaction product of a single dianhydride and a single diamine component of Formula IV.

The second polyamide has repeating units of formula V wherein: R ^d represents a tetracarboxylic acid component residue; R ^e and R ^f are the same or different and represent a diamine residue; and m is an integer from 1 to 20.

All the embodiments described above for R ^d , Re ^and m in formula IV also apply to R ^d , Re ^and m in formula V.

Any of the above listed diamines suitable for forming the residue ^Re in Formula IV is also suitable for forming the residue ^Rf in Formula V.

In some embodiments of Formula V, R ^f represents a residue of an aromatic diamine selected from the group consisting of: PPD, MPD, m-toluidine, o-toluidine, Benzidine and TFMB.

In some embodiments of the polyamides described above, moieties derived from the monoanhydride monomers are present as end-capping groups.

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 entire tetracarboxylic acid composition.

In some embodiments of the polyamides described above, moieties derived from monoamine monomers are present as end-capping groups.

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 entire 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 150,000 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.

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/22TFMB100//90/10.

Also provided is a first liquid composition comprising (a) a polyamic acid having repeating units of Formula II and (b) at least one high boiling aprotic solvent. The first liquid composition is also referred to herein as the "first polyamide solution."

Also provided is a second liquid composition comprising (a) a polyamic acid having repeating units of Formula V and (b) at least one high boiling aprotic solvent. The second liquid composition is also referred to herein as the "second polyamide solution."

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

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

In some embodiments, the high boiling aprotic solvent has a boiling point of 200°C 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), N-butylpyrrolidone (NBP), N,N-diethyl acetamide (DEAc), tetramethylurea, 1,3-dimethyl-2-imidazolinone, γ- Butyrolactone, dibutyl carbitol, butyl carbitol acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like and combinations thereof.

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 NBP.

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

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

In some embodiments of the liquid composition, the solvent is 1,3-dimethyl-2-imidazolinone.

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 identified high boiling point aprotic solvent 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 >99 wt% polyamic acid in one or more high boiling aprotic solvents. As used herein, the term "solvent(s)" refers to one or more solvents.

In some embodiments, the liquid composition is 1 to 5 wt % polyamic acid in 95 to 99 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 5 to 10 wt % polyamic acid in 90 to 95 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 10 to 15 wt % polyamic acid in 85 to 90 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 15 to 20 wt % polyamic acid in 80 to 85 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 20 to 25 wt % polyamic acid in 75 to 80 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 25 to 30 wt % polyamic acid in 70 to 75 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 30 to 35 wt % polyamic acid in 65 to 70 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 35 to 40 wt % polyamic acid in 60 to 65 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 40 to 45 wt % polyamic acid in 55 to 60 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 45 to 50 wt % polyamic acid in 50 to 55 wt % of one or more high boiling aprotic solvents.

In some embodiments, the liquid composition is 50 wt% polyamic acid in one or more high boiling aprotic solvents.

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 dissolved separately in a solvent, and the amine component is then added thereto in such a ratio as to allow 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 preformed 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 of the components may be added as a solution in part or all of the solvent. (i) A method of first reacting one of the dianhydride components with one of the diamine components to obtain the first polyamide. 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, the filtration efficiency is measured 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. 6. Polyimide

Provided is a first polyimide having a repeating unit structure of Formula III Where: R ^a and R ^c are the same or different and represent a tetracarboxylic acid component residue; R ^b represents a diamine residue; and m is an integer from 1 to 20.

All the embodiments described above for Ra ^{, Rb} , ^Rc and m in formula II apply equally to Ra, ^{Rb , Rc} and m in formula III.

Provided is a second polyimide having a repeating unit structure of Formula VI wherein: R ^d represents a tetracarboxylic acid component residue; R ^e and R ^f are the same or different and represent a diamine residue; and m is an integer from 1 to 20.

All the embodiments described above for R ^d , ^Re , R ^f and m in formula IV also apply to R ^d , ^Re , R ^f and m in formula V.

Also provided is a polyimide film, wherein the polyimide has a repeating unit structure of Formula III or Formula VI 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 of the polyimide film, the in-plane coefficient of thermal expansion (CTE) is less than 45 ppm/°C between 50°C and 200°C; in some embodiments, less than 30 ppm/°C; in some embodiments In some embodiments, it is less than 20 ppm/°C; in some embodiments, it is less than 15 ppm/°C; in some embodiments, it is between 0 ppm/°C and 15 ppm/°C.

In some embodiments of the polyimide film, the glass transition temperature (T _g ) is greater than 250° C. for polyimide films cured at temperatures in excess of 300° C.; in some embodiments, is greater than 300° C. ° C; in some embodiments, greater than 350 ° C.

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

In some embodiments of the polyimide film, the tensile modulus is between 1.5 GPa and 8.0 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 optical retardation is less than 2000 nm; in some embodiments, less than 1500 nm; in some embodiments, less than 1000 nm; in some embodiments, less than 500 nm.

In some embodiments of the polyimide film, the birefringence at 550 or 633 nm is less than 0.15; in some embodiments, less than 0.10; in some embodiments, less than 0.05; in some embodiments, Less than 0.010; in some embodiments, less than 0.005.

In some embodiments of the polyimide film, the haze is less than 1.0%; in some embodiments, less than 0.5%; in some embodiments, less than 0.1%.

In some embodiments of the polyimide membrane, b* is less than 10; in some embodiments, less than 7.5; in some embodiments, less than 5.0; in some embodiments, less than 3.0.

In some embodiments of the polyimide membrane, the YI is less than 12; in some embodiments, less than 10; in some embodiments, less than 5.

In some embodiments of the polyimide film, the transmission at 400 nm is greater than 40%; in some embodiments, greater than 50%; in some embodiments, greater than 60%.

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

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

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

In some embodiments of the polyimide film, the transmission at 750 nm is greater than 70%; in some embodiments, greater than 80%; in some embodiments, greater than 90%.

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. 4. Method for preparing polyimide membrane

Generally speaking, polyimide membranes can be prepared from polyimide precursors through chemical or thermal conversion methods. 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 simultaneously dry the film of the solvent and 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 300°C are required, temperatures of 300°C to 400°C 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 about 200°C and 300°C. 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 320°C cure, the cure time can be as long as about 1 hour under an inert atmosphere; but 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 spin-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 spin-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 spin-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 spin-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 spin-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 thermal conversion method, a polyamide solution is spin-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, a polyamide solution is spin-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, a polyamide solution is spin-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 spin-coated substrate is soft-baked in proximity mode on a hot plate, with nitrogen gas used to hold the spin-coated substrate just above the hot plate.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the thermal conversion method, the spin-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 spin-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 spin-coated substrate is then 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 spin-coated substrate is then 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 spin-coated substrate is then cured at 5 pre-selected temperatures for 5 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 spin-coated substrate is then 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 spin-coated substrate is then cured at 7 pre-selected temperatures for 7 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 spin-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 spin-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 spin-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 80°C.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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, a method for preparing a polyimide membrane sequentially includes the steps of: containing two or more tetracarboxylic acid components and one or more tetracarboxylic acid components in a high boiling aprotic solvent. spin coating a polyamide solution of the diamine component onto a substrate; soft baking the spin coated substrate; treating the soft baked spin coated substrate at a plurality of preselected temperatures for a plurality of preselected times spacing, whereby the polyimide film exhibits properties satisfactory for electronic applications such as those disclosed herein.

In some embodiments of the thermal conversion method, a method for preparing a polyimide membrane consists of the following steps in sequence: containing two or more tetracarboxylic acid components and one or more in a high boiling aprotic solvent. A polyamide solution of a plurality of diamine components is spin-coated onto a substrate; the spin-coated substrate is soft-baked; and the soft-baked spin-coated substrate is treated with a plurality of preselected temperatures at a plurality of preselected temperatures. time interval 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 membrane mainly consists of the following steps in sequence: two or more tetracarboxylic acid components and one or a polyamide solution of multiple diamine components onto a substrate; soft-baking the spin-coated substrate; treating the soft-baked spin-coated substrate at a plurality of preselected temperatures for a plurality of preselected time interval, whereby the polyimide film exhibits characteristics satisfactory for electronic applications such as those disclosed herein.

Typically, the polyamic acid solution/polyimide disclosed herein is coated/cured onto a supporting glass substrate to facilitate processing through 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, the polyimide film with the deposited layer is then bonded to a thicker but still flexible plastic film to provide support for subsequent fabrication of the display.

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 polyamic acid solution further contains tributylamine as a conversion catalyst.

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

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

In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 1,2-dimethylimidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 3,5-lutidine as a conversion catalyst.

In some embodiments of the improved thermal conversion method, the polyamic acid 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 polyamic acid solution further contains 2-methylimidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 2-ethyl-4-imidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 3,4-lutidine as a conversion catalyst.

In some embodiments of the improved thermal conversion method, the polyamic acid solution further contains 2,5-lutidine as a conversion catalyst.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the modified thermal conversion method, the spin-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 spin-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 spin-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 spin-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 spin-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 spin-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 spin-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 spin-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.

In some embodiments of the modified thermal conversion method, the soft-baked spin-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 spin-coated substrate is then 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 80°C.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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, a method for preparing a polyimide membrane sequentially includes the following steps: containing two or more tetracarboxylic acid components and one in a high-boiling aprotic solvent. Spin-coating a polyamide solution of a diamine component or a plurality of diamine components and a conversion chemical onto a substrate; soft-baking the spin-coated substrate; treating the soft-baked spin-coated substrate at a plurality of preselected temperatures A plurality of preselected time intervals whereby the polyimide film exhibits characteristics satisfactory for use in electronic applications such as those disclosed herein.

In some embodiments of the improved thermal conversion method, a method for preparing a polyimide membrane consists of the following steps in sequence: containing two or more tetracarboxylic acid components and Spin-coating a polyamide solution of one or more diamine components and conversion chemicals onto a substrate; soft-bake the spin-coated substrate; and bake the soft-bake spin-coated substrate at a plurality of preselected temperatures The polyimide film is treated for a plurality of preselected time intervals whereby the polyimide film exhibits properties satisfactory for use in electronic applications such as those disclosed herein.

In some embodiments of the improved thermal conversion method, the method for preparing a polyimide membrane mainly consists of the following steps in sequence: two or more tetracarboxylic acid components are included in a high-boiling aprotic solvent. Spin-coat a polyamide solution with one or more diamine components and conversion chemicals onto a substrate; soft-bake the spin-coated substrate; and bake the soft-bake spin-coated substrate at a plurality of preselected temperatures. The substrate is treated for a plurality of preselected time intervals whereby the polyimide film exhibits properties satisfactory for electronic applications such as those disclosed herein. 5. 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 III 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 shielding hood 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 made from a dispersion of a conductive polymer and a colloid-forming polymer 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, 4th 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); Tetra-(3- Methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA); α-phenyl-4-N,N-diphenylaminostyrene (TPS); p -(diethylamino)benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis[4-(N,N-diethylamino)-2-methylphenyl](4-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 is from 6:1 to 1:6; in some embodiments, from 5:1 to 1:2; in some embodiments, from 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-pyrimidine and -[1,2-a]-pyrimidine) and cobaltinocene, tetrathiotetracene, bis(ethylidenedithio)tetrathiafulvalene, a heterocyclic group or a divalent group, 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 spin coating, dip coating, roll-to-roll techniques, inkjet printing, continuous nozzle printing, screen printing, gravure printing, etc., from solutions or dispersions in suitable solvents. Apply an 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 making liquid compositions including novel compounds (as described herein as solutions or dispersions) include, but are not limited to, chlorinated hydrocarbons (e.g., methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (e.g., Substituted and unsubstituted toluenes and xylenes, 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 fabricated 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. become.

It will be appreciated 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 efficiencies are also applicable. Additional layers can also be added to tailor the energy levels of the various layers 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 described in the following examples, which do not limit the scope of the invention as described in the claimed claims.

In an example, Mw is the weight average molecular weight; Mn is the number average molecular weight; Mz is the Z-average molecular weight; and Mp is the peak molecular weight. Abbreviation APB-133 = 1,3’-bis(3-amino-phenoxy)benzene BPDA = 3,3’,4,4’-biphenyltetracarboxylic dianhydride 4,4’-DDS = 4,4’-Diaminodiphenylsine 6FDA = 4,4’-Hexafluoroisopropylidenebisphthalic dianhydride ODPA =4,4’-oxydiphthalic anhydride PMDA = pyromellitic dianhydride TFMB = 2,2’-bis(trifluoromethyl)benzidine XFDA = 11-methyl-11-(trifluoromethyl)-1H-difluoro[3,4-b:3',4'-i] 𠮿(口星)-1,3,7,9 (11H )-tetraketone, Synthetic example

These examples illustrate the preparation of compounds of formula I. Synthesis example 1 2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-benzo[1,2-c :4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetraketone (2).

Combine 2,2'-bis(trifluoromethyl)benzidine (171.4 g, 535.3 mmol, 4 equivalents), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (5 g), pyridine (50 ml ) and N-methylpyrrolidone (200 ml) was heated at 130 °C under nitrogen atmosphere for 1 h. Afterwards, the remaining amount of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in 5 g portions (30 g total, 133.8 mmol total) at 130 °C over a period of 5 hours. Afterwards, the mixture was heated at 150°C for 2 days and at 180°C for 1 day. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% ethyl acetate and heptane to recover excess 2,2'-bis(trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing diimide-diamine were combined, the eluent was evaporated, the residue was dissolved in a 1:1 mixture of ethyl acetate and hexane, the crystallized products were combined by filtration, and dried under vacuum to obtain 40.2 g of the compound. 2 . Compound 2 can also be obtained by direct crystallization from the crude reaction mixture. In this way, 2,2'-bis(trifluoromethyl)benzidine (171.4 g, 535.3 mmol, 4 equivalents), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (5 g) A mixture of , pyridine (50 ml) and N-methylpyrrolidone (200 ml) was heated at 130°C under a nitrogen atmosphere for 1 hour. Afterwards, an additional amount of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in 5 g portions (total 30 g) at 130 °C over a period of 5 hours. Afterwards, the mixture was heated at 150°C for 16 hours. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, the residue was dissolved in 1L 1:1 ethyl acetate and hexane, and left to stand at ambient temperature, and the precipitated product was collected periodically to obtain 33.36 g of product. . The product can additionally be recrystallized from propyl acetate. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 2.02-2.09 (m, 2H), 2.29-2.34 (m, 2H), 3.25-3.30 (m, 4H), 5.71 (s, 4H), 6.77 ( dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.94-6.96 (m, 4H), 7.39-7.41 (m, 2H), 7.52 (2, 2H, J = 9 Hz), 7.68-7.70 (m , 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 178.4, 149.5, 138.4, 133.6, 132.6, 132.1, 130.1, 128.3, 122.8, 122.2, 116.1, 110.7, 38.4, 22.3. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.4, 57.1. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry ("MALDI TOF MS"): 829.1671 (MH+). Synthesis example 2 2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-4,8-ethylbenzene And [1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetraketone (4). Method A:

To 2,2'-bis(trifluoromethyl)benzidine (76.86 g, 240 mmol, 4 equiv) in pyridine (30 ml) and N-methylpyrrolidone (150 ml) under nitrogen atmosphere Add 50 ml of bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride ("bicyclooctanetetracarboxylic dianhydride") (15 g, 60 mmol) in portions to the stirring solution. suspension. The resulting mixture was heated at 180°C for 2 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% ethyl acetate and heptane to recover excess 2,2'-bis(trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the dicarboxylimine-diamine were combined, the eluent evaporated, and dried under vacuum to give 21.23 g of compound 4 . Method B:

2,2'-Bis(trifluoromethyl)benzidine (51.2 g, 4 equivalents) and bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride (10 g, 39.97 mmol) was heated at 220 °C for 2 h under an inert atmosphere. The mixture was cooled to ambient temperature, dissolved in ethyl acetate, adsorbed on celite, and chromatographed on silica gel (gradient elution with a mixture of propyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent evaporated, and dried under vacuum to give 21.82 g of compound 4 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 1.53 (s, 4H), 2.61 (s, 2H), 3.40 (s, 4H), 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 2 Hz, J2 = 8 Hz), 6.97 (s, 2H), 6.98 (d, 2H, J = 7 Hz), 7.46 (d, 2H, J = 8 Hz), 7.67 (dd, 2H, J1 = 2 Hz , J2 = 8 Hz), 7.80 (d, 2H, J = 2 Hz). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 177.9, 149.6, 138.6, 133.8, 132.6, 132.2, 130.3, 129.0, 128.8, 128.2, 128.0, 125.7, 125.0, 124.7, 1 23.5, 122.9, 122.2, 116.2, 110.7, 43.1, 28.8, 17.6. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.3, 57.0. MALDI TOF MS: 855.1810 (MH+). Synthesis example 3 2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-4,8-vinylidenebenzene And [1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetraketone (5).

To 2,2'-bis(trifluoromethyl)benzidine (77.43 g, 241.8 mmol, 4 equiv) in pyridine (30 ml) and N-methylpyrrolidone (150 ml) under nitrogen atmosphere A suspension of bicyclooctanetetracarboxylic dianhydride (15 g, 60.45 mmol) in 50 ml N-methylpyrrolidone was added portionwise to the stirred solution. The resulting mixture was heated at 180°C for 7 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% ethyl acetate and heptane to recover excess 2,2'-bis(trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the dicarboxylimine-diamine were combined, the eluent evaporated, and dried under vacuum to give 21.23 g of compound 5 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 3.49 (s, 4H), 3.57 (br.S, 2H), 5.72 (s, 4H), 6.37 (t, 2H, J = 4 Hz), 6.78 (dd, 2H, J1 = 8Hz, J2 = 2 Hz), 6.95-6.97 (m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.47 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.61 (d, 2H, J = 2 Hz). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 176.9, 149.6, 138.5, 133.5, 133.9, 132.6, 132.0, 131.6, 129.9, 129.0, 128.7, 128.2, 128.0, 125.7, 1 25.0, 124.2, 123.5, 122.8, 122.1, 116.2, 110.6, 43.0, 34.5. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.4, 57.1. MALDI TOF MS: 853.1654 (MH+). Synthesis example 4 2,2'-(6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4,4'-diyl)bis[6- Bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-4,8-vinylidenebenzo[1, 2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetraketone](7).

Combine 2,2'-bis(trifluoromethyl)benzidine (77.43 g, 241.8 mmol, 2 equivalents), pyridine (20 ml), N-methylpyrrolidone (100 ml) and bicyclooctanetetracarboxylic acid A mixture of dianhydride (15 g, 60.45 mmol) was stirred under nitrogen atmosphere with heating at 180 °C for 6 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, the residue was absorbed onto celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the dicarboxylimine-diamine were combined, the eluent evaporated, and dried under vacuum to give 14.8 g of compound 5 . The fractions containing tetracarboxylimine-diamine were combined, the eluent was evaporated and dried under vacuum to give 8.75 g of compound 7 . Compound 7 : ¹ H-NMR (DMSO-d ₆ , 500 MHz): 3.50 (s, 4H), 3.51 (s, 4H), 3.58 (br.S, 4H), 5.72 (s, 4H), 6.38 (t , 4H, J = 4 Hz), 6.78 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.95-6.97 (m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.47 (dd , 2H, J1 = 8 Hz, J2 = 2 Hz), 7.56-7.61 (m, 6H), 7.72 (s, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 176.92, 176.86, 149.6, 138.6, 136.1, 133.9, 133.0, 132.9, 132.6, 132.0, 131.7, 130.2, 129.9, 128.2, 128.0, 125.7, 1245.0, 124.8, 124.5, 124.4, 124.2, 123.5, 122.8, 122.6, 122.1, 116.2, 110.67, 110.62, 48.9, 43.00, 42.96, 34.5. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.4, 57.2, 57.1. MALDI TOF MS: 1385.2532 (MH+). Synthesis example 5 3a,3b,4,4a,7a,8,8a,8b-octahydro-9-(1,1-dimethylethyl)-4,8-vinylidenefuro[3',4':3 ,4]cyclobutan[1,2-f]isobenzofuran-1,3,5,7-tetraone.

Maleic anhydride (37.4 g, 0.38 mol) and acetophenone (22.9 g, 0.191 mol) were dissolved in tertiary butylbenzene (approximately 0.8 L) and placed in a 1 L photochemical reactor using borosilicate The salt glass impregnated wells were illuminated with a 200 W medium pressure Hanovia mercury lamp. The precipitate was collected by filtration. Yield of crude product after 42 hours of irradiation - 33.3 g. The product can be recrystallized from hot acetone. ¹ H-NMR (acetone-d ₆ , 500 MHz): 1.14 (s, 9H), 2.99-3.09 (m, 4H), 3.31 (dd, 1H, J1 = 9 Hz, J2 = 3 Hz), 3.41 (dd , 1H, J1 = 9 Hz, J2 = 3 Hz), 3.45-3.48 (m, 1H), 3.71-3.72 (m, 1H), 6.29 (dd, 1H, J1 = 7 Hz, J2 = 2 Hz).

In control experiments, it was found that tertiary butyltricyclotetradecenetetracarboxylic dianhydride did not react with BPDA even at elevated temperatures. 2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-9-(1,1-dimethylethyl base)-3a,3b,4,4a,7a,8,8a,8b-octahydro-4,8-vinylidenepyrrolo[3',4':3,4]cyclobuta[1,2-f ] Isoindole-1,3,5,7(2H,6H)-tetraketone (6).

2,2'-bis(trifluoromethyl)benzidine (19.4 g, 60.55 mmol, 4 equiv) was dissolved in pyridine (10 ml) and N-methylpyrrolidone ( A solution of tertiary butyltricyclotetradecenetetracarboxylic dianhydride (5 g, 15.14 mmol)) in N-methylpyrrolidone (50 ml) was added dropwise to a stirred solution in 80 ml). Afterwards, the mixture was heated at 180°C for 8 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, the residue was absorbed onto celite and chromatographed on silica gel (using a mixture gradient of hexane-dichloromethane and hexane-ethyl acetate elution). The fractions containing the diimide-diamine were combined, the eluent was evaporated and the residue was dried under vacuum to give 8.7 g of compound 6 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 1.06 (s, 9H), 2.77 (dd, 1H, J1 = 7 Hz, J2 = 3 Hz), 2.83 - 2.85 (m, 1H), 2.93-2.96 (m, 2H), 3.02 (dd, 1H, J1= 9 Hz, J2 = 2 Hz), 3.07-3.09 (m, 1H), 3.33-3.35 (m, 1H), 3.52 (br.s, 1H), 5.73 (s, 4H), 6.22 (dd, 1H, J1 = 7 Hz, J2= 1.5 Hz), 6.80 (t, 2H, J = 8 Hz), 6.97-7.00 (m, 4H), 7.45-7.47 (m , 3H), 7.59-7.61 (m, 2H), 7.80 (s, 1H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 177.9, 177.85, 177.5, 177.1, 152.1, 149.57, 149.54, 138.44, 138.37, 134.0, 133.7, 132.8, 132.6, 132 .2, 130.2, 129.8, 129.7, 129.9, 128.96, 128.3, 128.0, 125.7, 125.68, 125.11, 1245.0, 124.9, 124.8, 123.53, 123.5, 122.9, 122.8, 122.3, 122.2, 122.1, 116.2, 110.7, 110.66, 43.3, 43.2, 41.8, 41.2, 36.4, 34.5, 34.0, 29.8. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.6, 57.3, 57.1, 57.0. MALDI TOF MS: 935.2439 (MH+). Synthesis example 6 3a,3b,4,4a,7a,8,8a,8b-octahydro-9-methyl-4,8-vinylidenefuro[3',4':3,4]cyclobuta[1,2 -f]isobenzofuran-1,3,5,7-tetraone.

Maleic anhydride (37.4 g, 0.38 mol) and acetophenone (22.9 g, 0.191 mol) were dissolved in toluene (about 0.8 L), placed in a 1 L photochemical reactor, and used with 200 W medium pressure Hanovia Mercury lamp irradiation. The precipitate was collected by filtration. Yield of crude product after 28.5 hours of irradiation - 24 g, as a mixture of 9-methyl and 3-methyl regioisomers. The product can be recrystallized from hot acetone. Data for 9-methyl regioisomer: ¹ H-NMR (acetone-d ₆ , 500 MHz): 1.97 (s, 3H), 2.96-3.00 (m, 2H), 3.02-3.05 (m, 1H), 3.10-3.12 (m, 1H), 3.31-3.34 (m, 2H), 3.40-3.44 (m, 2H), 6.18 (d, 1H, J = 6 Hz). ¹³ C-NMR (acetone-d ₆ , 125 MHz): 173.1, 173.0, 172.5, 172.3, 142.2, 123.6, 43.1, 42.8, 41,7, 41.5, 39.9, 38.8, 38.4, 35.0, 22.0.

In control experiments, it was found that methyltricyclotetradecenetetracarboxylic dianhydride did not react with BPDA even at elevated temperatures. 2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-9-(1,1-dimethylethyl base)-3a,3b,4,4a,7a,8,8a,8b-octahydro-4,8-vinylidenepyrrolo[3',4':3,4]cyclobuta[1,2-f ] Isoindole-1,3,5,7(2H,6H)-tetraketone (6a).

2,2'-Bis(trifluoromethyl)benzidine (66.66 g, 208.15 mmol, 4 equivalents), methyltricyclotetradecenetetracarboxylic dianhydride (2.5 g, 9-methyl and 3-methyl A mixture of regioisomers in a ratio of 1:0.2), pyridine (20 ml) and N-methylpyrrolidone (100 ml) was heated at 150 °C for 1 h under a nitrogen atmosphere. Afterwards, an additional amount of methyltricyclotetradecenetetracarboxylic dianhydride was added in 2.5 g portions (total 15 g) at 130° C. over a period of 5 hours. Afterwards, the mixture was heated at 180°C for 6 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% propyl acetate and heptane to recover excess 2,2'-bis(trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of propyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent evaporated and dried under vacuum to give 20.1 g of compound 6a . Data for 9-methyl regioisomer: ¹ H-NMR (DMSO-d ₆ , 500 MHz): 1.92 (s, 3H), 2.72-2.74 (m, 1H), 2.84-2.86 (m, 1H), 2.89-2.92 (m, 1H), 2.94-2.98 (m, 1H), 3.03 (dd, 1H, J1 = 8 Hz, J2 = 3 Hz), 3.11 (dd, 1H, J1 = 8 Hz, J2 = 3 Hz ), 3.16 (br. s, 1H), 3.25 (p, 1H, J = 3 Hz), 7.73 (s, 4H), 6.11 (br. s, 1H), 6.78-6.81 (m, 2H), 6.97- 6.99 (m, 4H), 7.41-7.47 (m, 3H), 7.56-7.62 (m, 2H), 7.80 (d, 1H, J = 1.5 Hz). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 177.9, 177.8, 177.5, 177.3, 149.58, 149.55, 141.2, 138.5, 138.4, 134.0, 133.7, 132.7, 132.6, 132.2, 130.3, 129.9, 128.9, 128.7, 128.3, 128.0, 127.3, 125.7, 125.1, 125.0, 124.9, 124.8, 124.2, 123.5, 122.9, 122.8, 122.3, 122.1, 116.2, 110.7, 43.11, 42.3 5, 41.6, 41.3, 39.2, 35.7, 22.8. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.5, 57.3, 57.04, 57.02. MALDI TOF: 893.1969 (MH+). Synthesis example 7 2,5-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-benzo[1,2-c :4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetraketone (8). 2,2'-bis(trifluoromethyl)benzidine (153 g, 477.8 mmol), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (5 g), pyridine (20 ml) and N-methylpyrrolidone (150 ml) was heated at 150°C under a nitrogen atmosphere 1 hour. Afterwards, the remaining amount of 1,2,3,4-cyclohexanetetracarboxylic dianhydride was added in 5 g portions (total 25 g, total 118.97 mmol) at 150 °C over a period of 4 hours. Afterwards, the mixture was heated at 180°C for 2.5 weeks. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 20% ethyl acetate and heptane to recover excess 2,2'-bis(trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexanes) (2 times). The fractions containing the diimide-diamine were combined, the eluent evaporated, and dried under vacuum to give 3 g of compound 8 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 2.56 (t, 2H, J = 9 Hz), 3.73 (q, 2H, J = 8 Hz), 3.80 (d, 2H, J = 8 Hz), 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.97-6.99 (m, 4H), 7.46 (d, 2H, J = 9 Hz), 7.65 (d, 2H , J = 9 Hz), 7.85 (s, 2H). ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.0, 57.2. Synthesis example 8

Compound 9. Combine 2,2'-bis(trifluoromethyl)benzidine (132.6 g, 414.08 mmol), 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxy A mixture of methyl-3-furyl)-naphtho[1,2-c]furan-1,3-dione (5 g), pyridine (20 ml) and N-methylpyrrolidone (150 ml) was Heat at 150°C for 1 hour under nitrogen atmosphere. Afterwards, the remaining amount of dianhydride was added in 5 g portions (30 g total, 118.97 mmol total) at 150 °C over a period of 2.5 hours. Afterwards, the mixture was heated at 180°C for 3 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% propyl acetate and heptane to recover excess 2,2'-bis(trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of propyl acetate and hexane). The fractions containing the dicarboxylimine-diamine were combined, the eluates evaporated and dried under vacuum to give a total of 34.1 g of compound 9 . Synthesis example 9 5,5'-oxybis[2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl]-1H-isoindole-1, 3(2H)-diketone ( 10 ) and compound 11 . A mixture of 2,2'-bis(trifluoromethyl)benzidine (61.94 g, 6 equiv) and oxydiphthalic dianhydride (10 g, 32.24 mmol) was heated at 220 °C under an inert atmosphere for 1 hours. Afterwards, the excess diamine was vacuum sublimated at 260°C-265°C. The residue was dissolved in 150 ml of ethyl acetate, adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing the pure trimer were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried under vacuum at 150°C for 1 hour in a glovebox to give 16.13 g of product 10 . The fractions containing a little impure trimer were combined, the eluent was evaporated, and the residue was dried using a rotary evaporator to give 3.53 g of compound 10 . The fractions containing pure compound 11 were combined, the eluent was evaporated and the residue was dried under vacuum at 150°C to give 2.24 g of compound 11 .

Compound 10 : ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.98 (d, 2H, J = 3 Hz), 7.00 (d, 2H, J = 9 Hz), 7.48 (d, 2H, J = 8 Hz), 7.65-7.68 (m, 4H), 7.75 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.94 (d, 2H, J = 2 Hz), 8.11-8.13 (m, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 166.4, 166.3, 161.4, 149.5, 138.0, 135.0, 133.7, 132.7, 132.0, 130.0, 129.0, 128.7, 128.3, 128.0, 1 27.7, 126.7, 125.7, 125.6, 125.1, 124.8, 123.6, 122.6, 122.9, 122.33, 122.31, 116.2, 114.3, 110.69, 110.65, 110.61. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 56.97, 56.98, 57.3.

Compound 11 : ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.98 (d, 2H, J = 2 Hz), 7.00 (d, 2H, J = 8 Hz), 7.48 (d, 2H, J = 9 Hz), 7.67-7.69 (m, 10 H), 7.75 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.86 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.94 (d, 2H, J = 2 Hz), 8.05 (d, 2H, J = 2 Hz), 8.11-8.15 (m , 4H). Synthesis example 10 5,5'-oxybis[1,3-phenylenebis(oxy-3,1-phenylene)yl]-1H-isoindole-1,3(2H)-dione (12) . A mixture of 1,3-bis(3-aminophenoxy)benzene (56.55 g, 193.44 mmol, 6 equivalents) and oxydiphthalic dianhydride (10 g, 32.24 mmol) was heated at 220 °C in an inert atmosphere. Heat for 1 hour under atmosphere and then in vacuum at 265°C. The residue was dissolved in 150 ml of ethyl acetate, adsorbed on celite and purified by partial chromatography on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing pure trimer were combined, the eluate was evaporated using a rotary evaporator, and the residue was dried under vacuum at 150°C for 1 hour in a glove box. Compound 12 : ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.21 (s, 4H), 6.16 (dd, 2H, J1 = 8 Hz, J2 = 3 Hz), 6.22 (t, 2H, J = 2 Hz), 6.33 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.66 (t, 2H, J = 2 Hz), 6.74-6.78 (m, 4H), 6.98 (t, 2H, J= 8 Hz), 7.11 (dd, 2H, J1 = 8Hz, J2 = 2 Hz), 7.16 (t, 2H, J = 2Hz), 7.23 (br d, 2H, J = 8 Hz), 7.36 (t, 2H, J = 8 Hz), 7.53 (t, 2H, J = 8 Hz), 7.59-7.52 (m, 4H), 8.04 (d, 2H, J = ). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 166.5, 166.3, 161.3, 159.0, 157.7, 157.3, 156.9, 156.0, 134.9, 133.7, 131.5, 130.7, 130.6, 127.6, 1 26.56, 125.4, 122.9, 118.6, 117.9, 114.2, 114.0, 113.4, 110.4, 109.4, 106.6, 104.6. Synthesis example 11 2,2''-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)(dodecahydro-1,1'',2',3,3''-Pentaoxydisspiro[4,7-bridgemethylene-5H-isoindole-5,1'-cyclopentane-3',5''-[4 ,7]Bismethylene[5H]isoindole ( 13 ). Combine 2,2'-bis(trifluoromethyl)benzidine (41.66 g, 130.08 mmol, 10 equivalents) and the corresponding spirocyclic dianhydride ( 5 g, 13.01 mmol) was heated at 220 °C under an inert atmosphere for 1.5 h. The residue was dissolved in ethyl acetate, adsorbed on celite and purified by chromatography on silica gel (using hexane and Gradient elution with a mixture of ethyl acetate and hexane-propyl acetate). The fractions containing the pure product were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried under vacuum at 150 °C for 1 h in a glovebox to 8.59 g of compound 13 was obtained. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 1.30-1.47 (m, 4H), 1.75-2.13 (m, 8H), 2.65 (br. s, 4H), 2.97-3.26 (m, 4H), 5.72 (s, 4H), 6.79 (d, 2H, J = 9 Hz), 6.96-6.97 (m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.58 (d, 2H, J = 8 Hz), 7.74 (s ,2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 223.8, 223.3, 117.97, 117.93, 117.75, 117.81, 149.5, 138.5, 133.8, 132.6, 132.3 , 130.2, 130.1, 129.2, 129.0, 128.75, 128.5, 128.0, 127.9, 127.8, 127.2, 125.7, 125.0, 124.7, 124.6, 123.5, 122.9, 122.2, 1 21.3, 120.7, 120.0, 116.2, 110.7, 110.6, 66.7, 53.6 , 48.0, 47.9, 47.4, 46.7, 45.6, 45.1, 42.0, 33.2, 21.2, 31.9, 30.8, 21.9, 21.1, 10.7. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.3, 57.0. Synthesis Example 12 2,2'-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-[5,5'-bi-1H- Isoindole]-1,1',3,3'(2H,2'H)-tetraketone ( 14 ). 2,2'-Bis(trifluoromethyl)benzidine (113.7 g, 355.1 mmol, 6.3 equiv) and biphenyltetracarboxylic dianhydride (16.58 g, 56.35 mmol) with a small amount of N-methylpyrrolidone were heated at 220 °C for 1 h under an inert atmosphere and then at the same temperature in vacuo Heat for 3 hours. The mixture was cooled, dissolved in ethyl acetate, adsorbed on celite, and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing the pure product were combined, the eluate was evaporated using a rotary evaporator to a volume of 200 ml, and the crystallized product was collected by filtration to give 17.57 g of compound 14 . The fractions containing the lower purity product were combined, the eluent was evaporated, the residue was dissolved in ethyl acetate, then one volume of hexane was added and allowed to stand at ambient temperature for slow crystallization. The precipitated product containing oligomer impurities was collected by filtration to obtain 12.95 g of lower purity material. Products containing small amounts of oligomers can also be obtained by direct crystallization as follows: Dissolve the initial crude mixture in ethyl acetate, add a volume of hexane, and collect the precipitate formed. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.73 (s, 4H), 6.81 (dd, 2H, J1 = 8 Hz, J2= 2 Hz), 6.99 (d, 2H, J = 2 Hz), 7.02 (d, 2H, J = 9 Hz), 7.50 (d, 2H, J = 8 Hz), 7.79 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.98 (d, 2H, J = 2 Hz), 8.14 (d, 2H, J = 8 Hz), 8.43 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 8.50 (s, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 166.8, 149.6, 144.9, 138.0, 134.4, 133.7, 133.2, 132.7, 132.1, 131.9, 130.3, 128.9, 128.3, 125.1, 1 24.8, 124.8, 123.0, 122.9, 116.2, 110.7, 110.66. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.3, 57.0. Synthesis example 13 Dodecahydro-2,2'-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-[5,5'- Bi-1H-isoindole]-1,1',3,3'(2H,2'H)-tetraketone ( 15 ). 2,2'-Bis(trifluoromethyl)benzidine (52.27 g , 163.24 mmol, 10 equivalents), a mixture of dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride (5 g, 16.32 mmol) and N-methylpyrrolidone (5 ml) at 220°C Heated for 1 hour under an inert atmosphere and then heated at the same temperature for 1 hour under vacuum. The mixture was cooled, dissolved in ethyl acetate, adsorbed on celite, and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing the pure product were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried under vacuum at 150°C to give 8.92 g of compound 15 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 0.99 (br s, 2H), 1.32 (br. s, 4H), 1.61-1.63 (m, 4H), 1.97-2.04 (m, 2H), 2.14 -2.17 (m, 2H), 2.99-3.05 (m, 2H), 3.22-3.26 (m, 2H), 5.71 (s, 4H), 6.79 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.96-6.97 (m, 4H), 7.42 (d, 2H, J = 8 Hz), 7.61 (d, 2H, J = 8 Hz), 7.78 (s, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 179.0, 178.4, 149.5, 138.1, 133.6, 132.64, 132.57, 132.55,130.1, 128.3, 125.7, 123.5, 122.3, 120.0, 116.2, 110.67, 110.63, 110.59, 29.34, 29.25, 25.52, 21.69, 21.66. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.25, 57.22, 57.06, 57.04. Synthesis example 14 11-methyl-2,8-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-11-(trifluoromethyl base)-1H-pirano[2,3-f:5,6-f']diisoindole-1,3,7,9(2H,8H,11H)-tetraketone ( 16 ). Convert 2 , 2'-bis(trifluoromethyl)benzidine (51 g, 159.26 mmol, 10 equivalents), the corresponding 𠮿(口星)tetracarboxylic dianhydride (10.2 g, 25.23 mmol) and N-methylpyrrolidone (25 ml) of the mixture was heated at 220 °C for 1 h under an inert atmosphere and then in vacuo at the same temperature for 1 h. The mixture was diluted with ethyl acetate, adsorbed on celite, and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). Fractions containing pure product were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried under vacuum to give 16.62 g of compound 16 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 2.39 (s, 3H), 5.74 (s, 4H), 6.82 (d, 2H, J = 8 Hz), 7.00-7.03 (m, 4H), 7.51 (d, 2H, J = 8 Hz), 7.78 (d, 2H, J = 8 Hz), 7.91 (s, 2H), 7.97 (d, 2H, J = 2 Hz), 8.51 (s, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 170.8, 166.1, 165.7, 155.5, 149.6, 138.2, 134.8, 133.8, 132.7, 132.0, 130.3, 128.8, 128.1, 127.9, 1 25.8, 125.6, 125.1, 124.9, 124.6, 123.6, 122.6, 122.3, 121.4, 120.8, 116.2, 112.9, 110.73, 110.69, 110.64, 45.0, 19.8. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 75.5, 57,4, 57.0. Synthesis example 15 2,6-bis[4-[(4-aminophenyl)sulfonyl]phenyl]-benzo[1,2-c:4,5-c']dipyrrole-1,3,5, 7(2H,6H)-tetraketone ( 17 ). Combine 4,4'-sulfonyl bis[aniline] (56.92 g, 229.2 mmol, 5 equivalents) and pyromellitic dianhydride (10 g, 45.84 mmol) and N-methylpyrrolidone (100 ml) were heated at 177 °C under a nitrogen atmosphere with stirring for 1.5 h. The reaction mixture was cooled, diluted with ethyl acetate (200 ml), filtered, washed with ethyl acetate and dried under vacuum to obtain 26 g of crude product, which contained approximately 10% of the higher oligomeric product used in the polymerization without further purification. . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 6.22 (s 4H), 6.64 (d, 4H, J = 9 Hz), 7.59 (d, 4H, J = 9 Hz), 7.72 (d, 4H, J = 9 Hz), 8.02 (d, 4H, J = 9 Hz), 8.40 (s, 2H). Synthesis example 16

A 500 mL round-bottom flask equipped with a Dean-Stark trap was charged with 22.41 g TFMB (0.07 mol) and 250.71 g 1-methyl-2-pyrrole under nitrogen purge. nidinone (NMP). The mixture was stirred at room temperature under nitrogen for about 30 minutes. Then, 26.74 g (0.06 mol) 6FDA was slowly added to the stirring diamine solution in batches. After the dianhydride addition was complete, an additional 27.86 g of NMP was used to wash the vessel and flask walls of any remaining dianhydride powder, and the resulting mixture was stirred at room temperature overnight. Then, 80 mL m-xylene was added to the mixture and refluxed for 8 hours to remove water using a Dean-Stark trap. The mixture was cooled to room temperature and then precipitated into 1,500 mL of methanol with stirring, the resulting suspension was filtered, and the collected solids were dried under vacuum.

The resulting diamine monomer has a molecular weight of approximately 5,000 Da. Therefore, there are approximately 7 repeating diimides in the core (m in Formula I is approximately 7). The solid is used in reaction with one or more dianhydrides without further isolation or purification to form the polyamic acid polymer. Synthesis example 17 6,6'-(Sulfonylbis-4,1-phenylene)bis-1H-furo[3,4-f]isoindole-1,3,5,7(6H)-tetraone ( 33 ).Synthesis of pyromellitic acid monoanhydride. To a stirred solution of pyromellitic dianhydride (43.6 g, 0.2 mol) in 400 ml THF was added over a period of 48 hours a mixture of 30 ml tetrahydrofuran and 5 ml water at ambient temperature. Afterwards, 250 ml of tetrahydrofuran were evaporated using a rotary evaporator and the resulting solution was treated with hexane (100 ml) until precipitation occurred. The precipitate was removed by filtration. The filtrate was kept at -24°C for 3 hours. The precipitate was filtered and dried under vacuum to obtain 14.9 g of product. The additional amount of product formed overnight at -24°C was filtered and dried under vacuum to give 6.85 g of product. ¹ H-NMR (acetone-d ₆ , 500 MHz): 6.39 (s 2H), 12.46 (br. s, 2H).

The above pyromellitic acid monoanhydride (28.16 g, 119.26 mmol, 2.3 equivalents) and 4,4'-sulfonyl bis[aniline] (12.97 g, 52.2 mmol) were stirred in 200 ml anhydrous tetrahydrofuran at ambient temperature for 1 hours. The mixture was diluted with acetone (100 ml), passed through a column packed with silica gel, and washed with acetone. The product-containing fractions were combined, the solvent was evaporated using a rotary evaporator, the residue was treated with approximately 500 ml of water, the fine precipitate was filtered, washed with water and dried in vacuo to give amide hexanoic acid (31.1 g): ¹ H-NMR ( DMSO-d ₆ , 500 MHz): 7.78 (s, 2H), 7.86 (d, 4H, J = 9 Hz), 7.91 (d, 4H, J = 9 Hz), 8.16 (s, 2H), 10.89 (s , 2H), 13.56 (br. s, 6H).

The above-mentioned amide hexanoic acid (31.1 g) was stirred with heating in acetic anhydride (300 ml) under a nitrogen atmosphere for 2 hours under reflux. The hot reaction mixture was filtered, washed with 50 ml acetic anhydride, dichloromethane (50 ml), suspended in 150 ml chloroform, filtered, and dried under vacuum to obtain 20.9 g of compound 33 : ¹ H-NMR (DMSO-d ₆ , 500 MHz): 7.81 (d, 4H, J = 9 Hz), 8.23 (d, 4H, J = 9 Hz), 8.57 (s, 4H). Polymer Examples

These examples illustrate the preparation of polyamic acids of formula II. Polymer Example 1 Polymer 1. Polymerization of compound 6 and BPDA:

Diamine-diamine monomer 6 (5.23 g, 5.60 mmol), BPDA (1.616 g, 5.488 mmol) and N-methylpyrrolidone (38 ml) were added to a 250 ml glass reactor under nitrogen. The mixture was stirred at ambient temperature until the final viscosity of the polyamide was 7283 cP. GPC: Mn = 73713, Mw = 139448, Mp = 121967, Mz = 222437, PDI = 1.89. ¹ H-NMR: (DMSO-d ₆ , 500 MHz): 1.08 (s, 9H), 2.78-3.10 (m, 6H), 3.36 (br. s, 1H), 3.54 (br. s, 1H), 6.24 (br. d, 1H, J = 6 Hz), 7.44-8.36 (m, 18H), 10.90 (br. s, 2H), 13.30 (br. s, 2H). Polymer Example 2 Polymer 2. Polymerization of compound 2 with BPDA:

Diamine-diamine monomer 2 (2 g, 2.41 mmol) (obtained by direct crystallization from the crude reaction mixture and recrystallization from propyl acetate), BPDA (0.689 g, 2.34 mmol) and N- Methylpyrrolidone (15.2 g) was mixed using a roller and allowed to react at ambient temperature until the final viscosity of the polyamide was 11620 cP. GPC: Mn=127781, Mw=300128, Mp=258512, Mz=496954, PDI=2.35. ¹ H-NMR: (DMSO-d ₆ , 500 MHz): 2.05 (br. s, 2H), 2.35 (br. s, 24H), 3.30 (br. s, 4H), 7.41-8.34 (m, 18H) , 10.89 (br. s, 2H), 13.30 (br. s, 2H). Polymer Example 3 Polymer 3. Polymerization of compound 4 and BPDA:

Diamine-diamine monomer 4 (6.70 g, 7.84 mmol), BPDA (2.237 g, 7.60 mmol) and N-methylpyrrolidone (50 ml) were added to a 250 ml glass reactor under nitrogen. The mixture was stirred at ambient temperature under atmosphere and then the final PMDA (39 mg) was added until the final viscosity of the polyamide was 7890 cP. GPC: Mn = 88795, Mw = 175396, Mp = 168430, Mz = 282955, PDI = 1.98. ¹ H-NMR: (DMSO-d ₆ , 500 MHz): 1.56 (br. s, 4H), 2.63 (br. s, 2H), 3.43 (br. s, 4H), 7.44-8.36 (m, 18H) , 10.90 (br. s, 2H), 13.30 (br. s, 2H). Polymer Example 4 Polymer 4. Polymerization of compound 5 and BPDA:

Diamine-diamine monomer 5 (6.71 g, 7.87 mmol), BPDA (2.246 g, 7.63 mmol) and N-methylpyrrolidone (50 ml) were added to a 250 ml glass reactor under nitrogen. The mixture was stirred at ambient temperature and then the final PMDA (39 mg) was added until the final viscosity of the polyamide was 6033 cP. GPC: Mn = 93567, Mw = 184524, Mp = 178922, Mz = 297891, PDI = 1.97. ¹ H-NMR: (DMSO-d ₆ , 500 MHz): 3.49 (br. s, 4H), 3.59 (br. s, 2H), 6.40 (s, 2H), 7.41-8.34 (m, 18H), 10.89 (br. s, 2H), 13.26 (br. s, 2H). Polymer Example 5 Polymer 5. Polymerization of Compound 9 and BPDA

Mix diimide-diamine monomer 9 (3 g, 3.316 mmol), BPDA (0.956 g, 3.25 mmol) and N-methylpyrrolidone (22.6 g) under an inert atmosphere using a roller and allow to temperature, then PMDA (7 mg) was added until the final viscosity of the polyamide was 3135 cP. GPC: Mn= 106690, Mw= 240045, Mp= 210783, Mz= 420038, PDI=2.25. Polymer Example 6 Polymer 6. Polymerization of Compound 8 and BPDA

Mix diimide-diamine monomer 8 (2.572 g, 3.157 mmol), BPDA (0.91 g, 3.093 mmol) and N-methylpyrrolidone (19.8 g) under an inert atmosphere using a roller and allow to temperature, then PMDA (10 mg) was added until the final viscosity of the polyamide was 7779 cP. GPC: Mn= 92903, Mw= 175925, Mp= 165061, Mz= 278182, PDI=1.89. Polymer Example 7 Polymer 7. Polymerization of Compounds 11 and 12 with Oxydiphthalic Anhydride

Under an inert atmosphere, diimide-diamine monomer 11 (1.799 g, 1.192 mmol), diimide monomer 12 (0.171 g, 0.199 mmol), and oxydiphthalic anhydride (0.42 g, 1.354 mmol) and N-methylpyrrolidone (13.6 g) were mixed using a roller and allowed to react at ambient temperature before adding oxydiphthalic anhydride (10 mg). GPC: Mn= 52301, Mw= 124710, Mp= 109452, Mz= 205698, PDI=2.38. Polymer Example 8 Polymer 8. Polymerization of Compound 15 and BPDA

Diamine-diamine monomer 15 (8.5 g, 9.33 mmol), BPDA (2.73 g, 9.29 mmol) and N-methylpyrrolidone (63.6 g) were added to a 250 ml glass reactor under nitrogen. The mixture was stirred at ambient temperature until the final viscosity of the polyamide was 4339 cP. GPC: Mn = 104310, Mw = 234898, Mp = 222275, Mz = 378468, PDI = 2.25. Polymer Example 9 Polymer 9:

A 250 mL reaction flask equipped with a nitrogen inlet and outlet and a mechanical stirrer was charged with 3.46 g TFMB (0.0108 mol), 6.51 g compound 9 (0.0072 mol) and 88.58 g 1-methyl-2-pyrrolidinone (NMP). ). The mixture was stirred at room temperature under nitrogen for about 30 minutes. Then, 3.64 g (0.009 mol) XFDA was slowly added into the stirred diamine solution in batches, followed by 3.76 g (0.00846 mol) 6FDA. After the dianhydride addition was complete, an additional 9.84 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 6 days. Separately, a 5% solution of 6FDA in NMP was prepared and added in small amounts (approximately 0.8 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 3.2 g of this completed solution (0.16 g, 0.00036 mol 6FDA) 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 1,100 cp at 25°C. Polymer Examples 10-14

Polymers 10-14 were prepared using procedures similar to Polymer Example 9. The polymer compositions are given in Table 1 below.

[Table 1].Polymer composition Polymer Example 15 Polymer 15. Polymerization of in-situ pre-imidized bicyclooctanetetracarboxylic dianhydride with 6FDA and BPDA.

2,2'-Bis(trifluoromethyl)benzidine (11.902 g, 37.17 mmol), bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride (6.51 g, 26.02 mmol) and 20 ml of N-methylpyrrolidone was heated at 180 °C for 2.5 h using a Dean-Stark apparatus under an inert atmosphere. Afterwards, N-methylpyrrolidone was distilled in vacuo. NMR spectral data of the resulting glassy residue showed complete imidization. The solid was redissolved in N-methylpyrrolidone at 150 °C, transferred to a glass reactor and mixed with 3,3',4,4'-biphenyltetracarboxylic dianhydride BPDA (1.094 g, 3.717 mmol ), 4,4'-hexafluoroisopropylidenebisphthalic dianhydride 6FDA (2.808 g, 6.32 mmol) in a total amount of 129 g of N-methylpyrrolidone at ambient temperature under nitrogen atmosphere Stir in case. Additional amounts of 6FDA (total 480 mg, 1.08 mmol) were then added until the final viscosity was 10430 cP. GPC: Mn = 88006, Mw = 205641, Mp = 201618, Mz = 335818, PDI = 2.34. Polymer Example 16 Polymer 16. In situ preiminated norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''- Polymerization of tetracarboxylic dianhydride (CpODA) and BPDA.

Combine 2,2'-bis(trifluoromethyl)benzidine (5.95 g, 18.58 mmol), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane- 5,5'',6,6''-Tetracarboxylic dianhydride CpODA (5.0 g, 13.08 mmol) and 6 ml N-methylpyrrolidone were heated at 180°C using a Dean-Stark apparatus under an inert atmosphere. 3 hours, then 6 ml of N-methylpyrrolidone were added and the mixture heated for an additional 3 hours. Afterwards, N-methylpyrrolidone was distilled in vacuo. The solid was redissolved in N-methylpyrrolidone (71 g), transferred to a glass reactor and incubated with 3,3',4,4'-biphenyltetracarboxylic acid diphosphate at ambient temperature under nitrogen atmosphere. The anhydride BPDA (1.53 g, 5.20 mmol) was stirred together, then pyromellitic dianhydride PMDA (62 mg) was added until the final viscosity was 22860 cP. GPC: Mn = 80956, Mw = 188020, Mp = 169907, Mz = 313930, PDI = 2.32. Polymer Example 17 Polymer 17. Polymerization of in-situ pre-imidized bicyclooctane tetracarboxylic dianhydride with PMDA and BPDA.

Polymer 17 was prepared as described above for polymer 15, except that PMDA was used instead of 6FDA. Polymer Example 18 Polymer 18:

Dissolve diimide-dianhydride monomer 33 (2.485 g), 2,2'-bis(trifluoromethyl)benzidine (1.179 g) and N-methylpyrrolidone (20 g) in an inert Mix at ambient temperature with a roller and allow to react at ambient temperature, then add pyromellitic dianhydride (25 mg) until the final viscosity is 7112 cP. GPC: Mn = 92432, Mw = 197099, Mp = 173514. Mz = 347413, PDI = 2.13 Membrane Example

These examples illustrate the preparation of polyimide membranes of formula IV.

Measure b* and yellowness index as well as % transmittance (%T) using a Hunter Lab spectrophotometer over the wavelength range 350 nm-780 nm. Thermal measurements of the films were performed using a combination of thermogravimetric and thermomechanical analysis as appropriate for the specific parameters reported here. Mechanical properties were measured using equipment from Instron. Membrane Examples 1-7

The polyamide acid described above is used to prepare a polyimide film of formula IV.

The polyamide solution was filtered through a microfilter, spin-coated on a clean silicon wafer, soft-baked at 90°C on a hot plate, and placed in an oven. Purge the oven with nitrogen and heat in stages to the maximum solidification temperature. The wafers were removed from the furnace, soaked in water and manually layered to produce polyimide film samples. Membrane compositions are given in Table 2 below. Membrane properties are given in Table 3 below.

[Table 2].Polyimide membrane

[Table 3]. Membrane characteristics

Haze is in %; Tg is in °C; CTE is the second scan measurement in ppm/°C; Δη is the birefringence at 633 nm; Td is the temperature in °C at which 1 % weight loss; T.M. is the tensile modulus in GPa; T.S. is the tensile strength in MPa; Elong is the elongation at break in %.

As can be seen from the above examples, the use of pre-imidized monomers can result in high molecular weight polymers using conventional polymerization techniques.

As can be seen from Table 3, the polyimide film obtained from pre-imidized amide-imine-containing monomers has beneficial properties, such as reduced coloration b*/yellowness index YI, increased thermal stability Td ( 1%), improved mechanical and other properties. Membrane Examples 8-13

The polyamides described above were used to prepare polyimide membranes of Formula IV as described in Membrane Examples 1-7, except Membrane Example 9. In Film Example 9, the film was cured in air at a maximum temperature of 260°C.

The membrane compositions are given in Table 4 below. Membrane properties are given in Table 5 below.

[Table 4].Polyimide membrane

[Table 5]. Membrane characteristics

Haze is in %; Tg is in °C; CTE is the second scan measurement in ppm/°C; Td is the temperature in °C at which 1% weight loss occurs; T.M. is in GPa Tensile modulus; T.S. is the tensile strength in MPa; Elong is the elongation at break in %. Membrane Examples 15-17

These examples illustrate the formation of polyimide films from in situ pre-imidized monomers.

Polyimide membranes were prepared as described in Membrane Examples 1-7. The membrane compositions are given in Table 6 below. Membrane properties are given in Table 7 below.

[Table 6].Polyimide membrane

[Table 7]. Membrane characteristics

Haze is in %; Tg is in °C; CTE is the second scan measurement in ppm/°C; Δη is the birefringence at 633 nm; Td is the temperature in °C at which 1 % weight loss;

It should be noted that not all of the activities described above in the general description or examples are required, some specific activities may not be required, and one or more other activities may be performed in addition to those described. Activity. Furthermore, the order in which the 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, those skilled in the art understand 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 each range 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.

without

Embodiments are illustrated in the accompanying drawings to promote 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.

without

Claims (4)

A diamine having formula I

Where R ^a is selected from the residue of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), the residue of 4,4'-oxydiphthalic anhydride (ODPA), and the following Various groups:

R ¹ is the same or different on each occurrence and is selected from the group consisting of alkyl, fluoroalkyl and silyl, where adjacent R ¹ groups may be linked together to form a double bond ; R ² and R ³ are the same or different on each occurrence and are selected from the group consisting of: F, alkyl, fluoroalkyl and silyl; R ⁵ is selected from the group consisting of Groups: H, halogen, cyano, hydroxyl, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, hydrocarbyl, substituted hydrocarbyl, heteroaryl, Substituted heteroaryl, vinyl, and allyl; ^R6 is selected from the group consisting of: halogen, cyano, hydroxy, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluorine Substituted alkyl, silyl, hydrocarbyl, substituted hydrocarbyl, heteroaryl, substituted heteroaryl, vinyl, and allyl; a is an integer from 0 to 6; b in formula A27 is an integer from 0 to 3; c and d in Formulas A8 and A25 are the same or different and are an integer from 0 to 2; f is an integer from 0 to 4; and * represents the attachment point; where R ^b Represents the residue of a diamine of formula D1:

R ¹⁰ is the same or different on each occurrence and is selected from the group consisting of: fluoroalkyl and fluoroalkoxy; R ¹¹ is the same or different on each occurrence and is selected from the group consisting of: fluoroalkyl and fluoroalkoxy; A group consisting of: F, alkyl, fluoroalkyl and silicone; b in formula D1 is the same or different each time it appears and is an integer from 0 to 3; c in formula D1 is Each occurrence is the same or different and is an integer from 0-2; y is an integer from 0-2; and m is an integer from 1-20. For example, the diamine described in item 1 of the patent application scope is selected from the group consisting of the following:

Compound 6

and

A polyamic acid composition, the polyamic acid composition is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the diamines include 1-100 mol% as claimed in claim 1 Diamines of formula I are described. A polyamide produced by the imidization of polyamide acid as described in claim 3.