CN112424204B

CN112424204B - Polymer for use in electronic devices

Info

Publication number: CN112424204B
Application number: CN201980047528.5A
Authority: CN
Inventors: V·V·戴夫; N·S·拉杜; J·T·梅耶; C·K·盖; J·R·小克洛普顿
Original assignee: DuPont Electronics Inc
Current assignee: DuPont Electronics Inc
Priority date: 2018-05-16
Filing date: 2019-05-15
Publication date: 2024-04-30
Anticipated expiration: 2039-05-15
Also published as: CN112424204A; KR20200144150A; TW201946925A; WO2019222304A1

Abstract

An acid dianhydride of formula IV is disclosed. In formula IV: r ^d represents a tetracarboxylic acid component residue; r ^e represents a diamine residue; and m is an integer from 1 to 20.

Description

Polymer for use in electronic devices

Claim of benefit of the previous application

The present application claims the benefit of U.S. provisional application No. 62/672,272, filed on 5/16 of 2018, which is incorporated herein by reference in its entirety.

Background information

Technical Field

The present disclosure relates to novel polymeric compounds. The disclosure further relates to methods for preparing such polymeric compounds and electronic devices having at least one layer comprising these materials.

Background

Materials for electronic applications generally have stringent requirements in terms of their structural, optical, thermal, electronic and other properties. As the number of commercial electronic applications continues to increase, the breadth and specificity of the desired characteristics requires innovation in materials with new and/or improved characteristics. Polyimides represent a class of polymeric compounds that are widely used in a variety of electronic applications. They can serve as flexible substitutes for glass in electronic display devices, provided they have suitable characteristics. These materials are useful as components of liquid crystal displays ("LCDs") where their moderate electrical power consumption, light weight and layer flatness are key features of practical utility. Other uses in electronic display devices that prefer to set such parameters include device substrates, substrates for filters, cover films, touch screen panels, and the like.

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

Polyimide films generally have sufficient thermal stability, high glass transition temperatures, and mechanical toughness to be desirable for such uses. Moreover, polyimide generally does not produce haze when subjected to repeated flexing, so they are often preferred in flexible display applications over other transparent substrates like polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).

However, the use of traditional amber polyimide in some display applications such as filters and touch screen panels is hampered by the priority of optical transparency. Furthermore, polyimide is typically a hard, highly aromatic material; and as the film/coating is formed, the polymer chains tend to orient in the plane of the film/coating. This results in a difference in refractive index (birefringence) between the parallel and perpendicular directions of the film, creating an optical retardation that may adversely affect display performance. If additional uses for polyimides were sought in the display market, there is a need for solutions that maintain their desirable properties while improving their optical clarity and reducing amber color and birefringence that results in light retardation.

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

Disclosure of Invention

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 that is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the diamines comprise 1 to 100 mole% of a 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 that is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the tetracarboxylic acid components comprise 1 to 100 mole% of a tetracarboxylic dianhydride having formula IV.

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

Also provided is a polyimide obtained by imidization of any of the above polyamic acids.

Also provided is a polyimide film comprising the polyimide.

One or more methods for preparing the polyimide film are also provided.

A flexible substitute for glass in an electronic device is also provided, wherein the flexible substitute for glass is the polyimide film described above.

An electronic device having at least one layer comprising the polyimide film described above is also provided.

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

The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.

Drawings

Embodiments are shown in the drawings to enhance understanding of the concepts as presented herein.

Fig. 1 includes an illustration of one example of a polyimide film that can serve as a flexible substitute for glass.

Fig. 2 includes an illustration of one example of an electronic device including a flexible substitute for glass.

The skilled artisan will appreciate that the objects in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the objects in the figures may be exaggerated relative to other objects to help improve understanding of embodiments.

Detailed Description

Many aspects and embodiments have been described above and are merely illustrative and not restrictive. After reading this specification, the skilled artisan will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and advantages of any one or more embodiments will be apparent from the following detailed description, and from the claims. The detailed description first refers to the definition and elucidation of terms, followed by imide-containing monomers, diamines of formula I, acid dianhydrides of formula IV, polyamic acids, polyimides, methods for preparing polyimide films, electronic devices, and examples.

1. Definition and elucidation of terms

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

As used in the definition and elucidation of the term, R, R ^a、R^b, R', R "and any other variables are common names and may be the same as or different from those defined in the formula.

The term "alignment layer" is intended to mean an organic polymer layer in a Liquid Crystal Device (LCD) that aligns molecules closest to each plate as a result of its rubbing against the LCD glass in one preferred direction during the LCD manufacturing process.

As used herein, the term "alkyl" includes both branched and straight chain saturated aliphatic hydrocarbon groups. Unless otherwise indicated, the term is also intended to include cyclic groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl and the like. The term "alkyl" further includes both substituted and unsubstituted hydrocarbyl groups. In some embodiments, alkyl groups may be mono-, di-, and tri-substituted. One example of a substituted alkyl group is trifluoromethyl. Other substituted alkyl groups are formed from one or more of the substituents described herein. In certain embodiments, the alkyl 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 groups. The heteroalkyl group may 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 (CCl 4), benzene, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and the like.

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

The term "aryl (aryl)" or "aryl (aryl group)" refers to moieties formed by the removal of one or more of hydrogen ("H") or deuterium ("D") from an aromatic compound. Aryl groups may be single rings (monocyclic) or have multiple rings (bicyclic, or more) fused together or covalently linked. "Hydrocarbon aryl" has only carbon atoms in one or more aromatic rings. "heteroaryl" groups have one or more heteroatoms in at least one aromatic ring. In some embodiments, hydrocarbon aryl groups have 6 to 60 ring carbon atoms; in some embodiments, 6 to 30 ring carbon atoms. In some embodiments, heteroaryl groups have from 4 to 50 ring carbon atoms; in some embodiments, 4-30 ring carbon atoms.

The term "alkoxy" is intended to mean the radical-OR, wherein R is an alkyl group.

The term "aryloxy" is intended to mean the radical-OR, wherein R is aryl.

The term "allyl" is intended to mean the group-CH ₂-CH＝CH₂.

The term "vinyl" is intended to mean the group-ch=ch ₂.

Unless otherwise indicated, all groups may be substituted or unsubstituted. Optionally substituted groups, such as but not limited to alkyl or aryl, may be substituted with one or more substituents, which may be the same or different. Suitable substituents include alkyl, aryl, nitro, cyano, -N (R ') (R "), halogen, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -S (O) ₂ -, -C (=o) -N (R ') (R"), (R ') (R ") N-alkyl, (R ') (R") N-alkoxyalkyloxy, (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 optionally substituted alkyl, cycloalkyl or aryl. R' and R ", together with the nitrogen atom to which they are attached, may form a ring system in certain embodiments. The substituents may also be crosslinking groups.

The term "amine" is intended to mean a compound containing a basic nitrogen atom with a lone pair of electrons. The term "amino" refers to the functional group-NH ₂, -NHR or-NR ₂, where R is the same or different at each occurrence and may be an alkyl or aryl group. The term "diamine" is intended to mean a compound containing two basic nitrogen atoms with associated lone pair electrons. The term "aromatic diamine" is intended to mean an aromatic compound having two amino groups. The term "curved diamine (bent diamine)" is intended to mean a diamine in which two basic nitrogen atoms and associated lone pair electrons are asymmetrically disposed about the center of symmetry of the corresponding compound or functional group, such as m-phenylenediamine:

The term "aromatic diamine residue" is intended to mean a moiety bonded to two amino groups in an aromatic diamine. The term "aromatic diisocyanate residue" is intended to mean the moiety bonded to two isocyanate groups in an aromatic diisocyanate compound. This is further described below.

The term "b x" is intended to mean the b x axis representing the yellow/blue counter color in the CIELab color space. Yellow is represented by a positive b-value and blue is represented by a negative b-value. The measured b-value may be affected by the solvent, particularly because solvent selection may affect the color measured on materials exposed to high temperature processing conditions. This may occur as a result of inherent characteristics of the solvent and/or characteristics associated with low levels of impurities contained in the various solvents. The particular solvent is typically preselected to achieve the desired b value for the particular 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 generally refers to the difference between the refractive index in the x-axis or y-axis (in-plane) and the z-axis (out-of-plane).

When referring to a layer, material, member, or structure, the term "charge transport" is intended to mean that such layer, material, member, or structure facilitates migration of such charge through the thickness of such layer, material, member, or structure with relative efficiency and small loss of charge. The hole transport material facilitates positive charge; the electron transport material favors negative charges. Although the luminescent material may also have some charge transport properties, the term "charge transport layer, material, member, or structure" is not intended to include a layer, material, member, or structure whose primary function is to emit light.

The term "compound" is intended to mean an uncharged substance consisting of molecules which further comprise atoms, wherein the atoms cannot be separated from their corresponding molecules by physical means which do not break 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 specifies the amount of expansion or contraction of a material with temperature. It is expressed as a change in length per degree celsius and is typically expressed in units of μm/m/°c or ppm/°c.

α＝(ΔL/L₀)/ΔT

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

The term "dopant" is intended to mean a material within a layer comprising a host material that alters the one or more electronic properties or one or more target wavelengths of radiation emission, reception, or filtration of the layer compared to the one or more electronic properties or one or more wavelengths of radiation emission, reception, or filtration of the layer in the absence of such material.

When referring to a layer or material, the term "electroactive" is intended to mean a layer or material that electronically facilitates operation of the device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block electrical charges, where the electrical charges may be electrons or holes, or materials that emit radiation or exhibit a change in electron-hole pair concentration upon receiving radiation. Examples of inactive materials include, but are not limited to, planarization 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 the material breaks under an applied tensile stress. It may be measured by, for example, ASTM method D882.

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

The term "glass transition temperature (or T _g)" is intended to refer to the temperature at which a reversible change occurs in an amorphous polymer or in an amorphous region of a semi-crystalline polymer, wherein the material suddenly changes from a hard, glassy or brittle state to a flexible or elastic state. Under a microscope, glass transition occurs when normally wound stationary polymer chains become free to rotate and can pass each other. T _g may 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, the heteroatom is O, N, S, or a combination thereof.

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

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

The term "isothermal weightlessness" is intended to mean a material property directly related to its thermal stability. It is typically measured via thermogravimetric analysis (TGA) at a constant temperature of interest. Materials with high thermal stability typically exhibit very low isothermal weight loss percentages over a desired period of time at the required use or processing temperatures, and thus can be used for applications at these temperatures without significant strength loss, outgassing 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 foundation 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 (excluding absorbed water) due to decomposition.

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., the birefringence), which is then multiplied by the thickness of the film or coating. The optical delay is typically measured for light of a given frequency and reported in nanometers. The optical retardation can be measured by Metricon or Axoscan.

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

The term "particle content" is intended to mean the number or count of insoluble particles present in a solution. The measurement of the particle content can be carried out on the solution itself or on the finished material (sheet, film, etc.) prepared from those films. Various optical methods may be used to evaluate this property.

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

The term "polyamic acid solution" refers to a solution containing a polymer having amic acid units that have the ability to intramolecular cyclization to form imide groups.

The term "polyimide" refers to a condensate resulting from the reaction of one or more difunctional carboxylic acid components with one or more primary diamines or diisocyanates. They contain the imide structure-CO-NR-CO-as a linear or heterocyclic unit along the backbone of the polymer backbone.

When referring to a material property or characteristic, the term "satisfactory" is intended to mean that the property or characteristic meets all of the requirements/demands of the material in use. For example, isothermal weight loss of less than 1% in nitrogen at 350 ℃ for 3 hours in the context of the polyimide films disclosed herein can be considered a non-limiting example of "satisfactory" characteristics.

The term "soft bake" is intended to refer to a process commonly used in electronic manufacturing in which a spin-coated material is heated to drive off a solvent and cure the film. Soft baking is typically performed on a hot plate or in an exhaust oven at a temperature between 90 ℃ and 110 ℃ 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 is not limited to, glass, polymer, metal, 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 R ₃SiOR₂ Si-, where R is the same or different at each occurrence and is H, C-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

The term "siloxy" refers to the group R ₃ SiO-, where R is the same or different at each occurrence and is H, C-20 alkyl, fluoroalkyl, or aryl.

The term "silyl" refers to the group R ₃ Si-where R is the same or different at each occurrence and is H, C-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 for depositing a uniform thin film onto a flat substrate. Generally, a small amount of coating material is applied on the center of a substrate that rotates at a low speed or does not rotate at all. The substrate is then rotated at a prescribed speed so as to spread the coating material uniformly by centrifugal force.

The term "laser particle counter test" refers to a method for evaluating the particle content of polyamic acid and other polymer solutions whereby a representative sample of the test solution is spin coated onto a 5 "silicon wafer and soft baked/dried. The particle content of the films thus prepared was evaluated 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, which defines the initial relationship between stress (force per unit area) and strain (proportional deformation) in a material such as a film. The unit commonly used is gigapascal (GPa).

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

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

The term "transmittance" refers to the percentage of light of a given wavelength that impinges on a film that passes through the film so as to be 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 for understanding the in-use characteristics 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 bluish. In particular for polymerization and/or curing processes operating at high temperatures, it should also be noted that YI may be solvent dependent. For example, the magnitude of the color introduced using DMAC as solvent may be different from the magnitude of the color introduced using NMP as solvent. This may occur as a result of inherent characteristics of the solvent and/or characteristics associated with low levels of impurities contained in the various solvents. The particular solvent is typically preselected to achieve the desired YI value for the particular application.

In structures wherein the substituent bonds are through one or more rings as shown below,

This means that the substituents R may be bonded at any available position on one or more rings.

When used in reference 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 in close proximity to each other in the formula (i.e., R groups on atoms bonded through bonds). Exemplary adjacent R groups are shown below:

In this specification, unless the context clearly indicates otherwise or indicated to the contrary, where an embodiment of the subject matter is stated or described as comprising, including, containing, having, consisting of, or consisting of certain features or elements, one or more features or elements other than those explicitly stated or described may also be present in that embodiment. Alternative embodiments of the disclosed inventive subject matter are described as consisting essentially of certain features or elements, wherein embodiment features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiments are not present herein. Another alternative embodiment of the described inventive subject matter is described as consisting of certain features or elements, only the features or elements specifically recited or described being present in that embodiment or in a non-essential variation thereof.

Furthermore, unless explicitly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or". For example, the condition a or B is satisfied by any one of the following: a is true (or present) and B is false (or absent), a is false (or absent) and B is true (or present), and a and B are both true (or present).

Moreover, the use of "a" or "an" to describe elements and components described herein. This is done merely for convenience 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 obvious that it is meant otherwise.

The group numbers corresponding to columns in the periodic Table of the elements use the "New Notification [ New nomenclature ]" convention as seen in CRC Handbook of CHEMISTRY AND PHYSICS [ CRC Handbook of chemistry and Physics ], 81 (2000-2001) th edition.

Unless defined otherwise, 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 present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety unless a particular paragraph 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 acts, and circuits are conventional and may be found in textbooks and other sources within the organic light-emitting diode display, photodetector, photovoltaic, and semiconductor component arts.

2. Imide-containing monomers

The difficulty in low reactivity, processability, and ability to control polymer structure has 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 severe 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 reduced.

It has been found that the imide-containing monomers described herein can be used to overcome the problem of monomers having low reactivity to control polymer structure (e.g., local order and tacticity) in order to achieve imidization with a reduced number of defects for polyimides having improved properties.

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

In some embodiments, the imide-containing monomers are separated from defects and byproducts and purified. Thus, highly pure compounds having precisely defined oligomer structures can be used as monomers.

In some embodiments, the imide-containing monomers are used in the form of a formation and are a mixture of pre-imidized compounds.

The imide-containing monomers described herein are compounds having an imidized core with reactive end groups.

In some embodiments, the imide-containing monomer is a diamine and the reactive end group is an amino group, -NH ₂.

In some embodiments, the imide-containing monomer is a diisocyanate and the reactive end groups are isocyanate groups-NCO.

In some embodiments, the imide-containing monomer is a tetracarboxylic dianhydride and the reactive end group is an anhydride.

In some embodiments, the imidized core contains two imide groups, hereinafter referred to as "diimides".

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

Disclosed herein is a method of synthesizing a precisely defined imide-containing polymer derived from pre-imidized (imide-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 pre-imidized diamine monomer thus formed may be isolated and purified. The pre-imidized diamine is sufficiently reactive to react with one or more additional dianhydrides (which may be the same or different from the first dianhydride) in step2 to form an imide-containing polyamic acid. Such imide-containing polymers are soluble and processable, despite the presence of imide groups even in high molar ratios. Step 3 is a final imidization to form polyimide polymers using conventional imidization techniques (e.g., thermal curing). One embodiment of scheme I is shown below, wherein the second dianhydride is different from the first dianhydride.

Scheme I: one embodiment

In the above scheme, Y represents a residue from the first tetracarboxylic acid component (dianhydride), Z represents a residue from the diamine, X1 represents a residue from the second tetracarboxylic acid component (dianhydride), n1 represents an integer of 1 to 20, and n represents an integer of more 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 is to pre-imidize the first diamine with an excess of dianhydride. The pre-imidized dianhydride monomer thus formed is sufficiently reactive to react with one or more additional diamines (which may be the same or different from the first diamine) in step 2 to form an imide-containing polyamic acid. Such imide-containing polymers are soluble and processable, despite the presence of imide groups even in high molar ratios. Step 3 is a final imidization to form polyimide polymers using conventional imidization techniques (e.g., thermal curing). One embodiment of scheme II is shown below, wherein the second diamine is different from the first diamine.

Scheme II: one embodiment

In the above scheme, Y represents a residue from the tetracarboxylic acid component (dianhydride), Z represents a residue from the first diamine, X2 represents a residue from the second diamine, n1 represents an integer from 1 to 20, 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, the pre-imidized monomer may be used in situ without isolation and characterization. This is described below as scheme III and scheme IV.

In scheme III, the first step is to pre-imidize 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 imide-containing polyamic acid is imidized in step 3 using conventional imidization techniques.

In scheme III, the pre-imidized diamine prepared in step 1 has the formula shown below

Wherein m1 represents an integer from 1 to 20. Mixtures of monomers having different m1 values may be present. In the polyamic acid and polyimide, m1 may be the same or different at each occurrence. In some embodiments, m1 is 2-5; in some embodiments, 6-10; in some embodiments, 11-20.Y represents a residue from the first tetracarboxylic acid component (dianhydride), and Z represents a residue from the first diamine.

In scheme IV, the first step is a 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 imide-containing polyamic 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

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, alicyclic.

In some embodiments of formula I, R ^a is a polycyclic cycloaliphatic group.

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

In some embodiments of formula I, R ^a has an aromatic group and a cycloaliphatic group.

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

In some embodiments of formula I, R ^a represents a residue of a tetracarboxylic dianhydride selected from the group consisting of: pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride (BPDA), 4' -oxydiphthalic anhydride (ODPA), 4' -hexafluoroisopropylidene diphthalic dianhydride (6 FDA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3',4,4' -diphenylsulfone tetracarboxylic dianhydride (DSDA), 4' -bisphenol-a dianhydride (BPADA), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis (trimellitic anhydride) (TMEG-100), 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride (DTDA); 4,4' -bisphenol-a dianhydride (BPADA); cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (CBDA); xanthene tetracarboxylic dianhydride; etc. These aromatic dianhydrides may be optionally substituted with groups known in the art including alkyl, aryl, nitro, cyano, -N (R ') (R "), halogen, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, fluoroalkyl, perfluoroalkyl, fluoroalkoxy, perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -S (O) ₂ -, -C (=o) -N (R') (R"), (R ') (R ") N-alkyl, (R") N-alkoxyalkyl, (R') (R ") N-alkylaryloxyalkyl, -S (O) _s -aryl (where s=0-2), or-S (O) _s -heteroaryl (where s=0-2). Each R' and R "is independently optionally substituted alkyl, cycloalkyl or aryl. R' and R ", together with the nitrogen atom to which they are attached, may form a ring system in certain embodiments. The substituents may also be crosslinking groups.

In some embodiments of formula I, R ^a 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 ^a represents the 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: formulae A1 to A36

/>

Wherein:

R ¹ is the same or different at each occurrence and is selected from the group consisting of: alkyl, fluoroalkyl, and silyl groups, wherein adjacent R ¹ groups may be linked together to form a double bond;

r ²、R³ and R ⁴ are the same or different at each occurrence and are selected from the group consisting of: F. alkyl, fluoroalkyl, and silyl;

R ⁵ is selected from the group consisting of: H. halo, cyano, hydroxy, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, alkylaryl, substituted alkylaryl, heteroaryl, substituted heteroaryl, vinyl, and allyl;

R ⁶ is selected from the group consisting of: halo, cyano, hydroxy, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, alkylaryl, substituted alkylaryl, heteroaryl, substituted heteroaryl, vinyl, and allyl;

R ⁸ and R ⁹ are the same or different at each occurrence and are selected from the group consisting of: H. f, alkyl, fluoroalkyl, and silyl;

Q is selected from the group consisting of: CR ⁸R⁹、SiR⁸R⁹、S、SR⁸R⁹、S＝O、SO₂ and c=o;

a is an integer from 0 to 6;

b is an integer from 0 to 3;

c. d and e are the same or different and are integers 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

* Indicating the attachment point.

In some embodiments of formula I, R ^b is aliphatic; in some embodiments, alicyclic.

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, the polycyclic aromatic is aromatic.

In some embodiments of formula I, R ^b has a cycloaliphatic group and an aromatic group.

In some embodiments of formula I, R ^b represents the residue of a diamine having formula D1

Wherein:

R ¹⁰ is the same or different at each occurrence and is selected from the group consisting of: fluoroalkyl and fluoroalkoxy;

R ¹¹ is the same or different at each occurrence and is selected from the group consisting of: F. alkyl, fluoroalkyl, and silyl;

b is the same or different at each occurrence and is an integer from 0 to 3;

c is the same or different at each occurrence and is an integer 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' -dimethyl-4, 4' -diaminobiphenyl (M-tolidine), 3' -dimethyl-4, 4' -diaminobiphenyl (o-tolidine), 3' -dihydroxy-4, 4' -diaminobiphenyl (HAB), 9' -Bis (4-aminophenyl) Fluorene (FDA), o-Tolidine Sulfone (TSN), 2,3,5, 6-tetramethyl-1, 4-phenylenediamine (TMPD), 2, 4-diamino-1, 3, 5-trimethylbenzene (DAM), 3',5,5' -tetramethylbenzidine (3355 TMB), 2' -Bis (trifluoromethyl) benzidine (22 TFMB or TFMB), 2-Bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 4' -Methylenedianiline (MDA), 4' - [1, 3-phenylenebis (1-methyl-ethylene) ] dianiline (Bis-M) 4,4' - [1, 4-phenylenebis (1-methyl-ethylene) ] Bis-aniline (Bis-P), 4' -oxydiphenylamine (4, 4' -ODA), M-phenylenediamine (MPD), 3,4' -oxydiphenylamine (3, 4' -ODA), 3' -diaminodiphenyl sulfone (3, 3' -DDS), 4' -diaminodiphenyl sulfone (4, 4' -DDS), 4,4 '-diaminodiphenyl sulfide (ASD), 2-Bis [4- (4-amino-phenoxy) phenyl ] sulfone (BAPS), 2-Bis [4- (3-aminophenoxy) -phenyl ] sulfone (m-BAPS), 1,4' -Bis (4-aminophenoxy) benzene (TPE-Q), 1,3 '-Bis (4-aminophenoxy) benzene (TPE-R), 1,3' -Bis (3-amino-phenoxy) benzene (APB-133), 4 '-Bis (4-aminophenoxy) biphenyl (BAPB), 4' -Diaminobenzanilide (DABA), methylenebis (anthranilic acid) (MBAA), 1,3 '-Bis (4-aminophenoxy) -2, 2-Dimethylpropane (DANPG), 1, 5-Bis (4-aminophenoxy) pentane (DA 5 MG), 2' -Bis [4- (4-aminophenoxyphenyl) ] Hexafluoropropane (HFBAPP), 2-Bis (4-aminophenyl) hexafluoropropane (Bis-A-AF), 2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Bis-AP-aF), 2-Bis (3-amino-4-methylphenyl) hexafluoropropane (Bis-AT-aF), 4,4 '-bis (4-amino-2-trifluoromethylphenoxy) biphenyl (6 BFBAPB), 3',5 '-tetramethyl-4, 4' -diaminodiphenylmethane (TMMDA), and the like.

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

Any of the above embodiments of formula I may be combined with one or more of the other embodiments, provided they are not mutually exclusive.

In some embodiments of formula I, the diamine is selected from the group consisting of: compounds 1 through 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. Dianhydride of formula IV

The dianhydrides described herein have the 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 are 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 diamines listed above that are suitable for forming residue R ^b in formula I are also suitable for forming residue R ^e in formula IV.

In some embodiments of formula IV, R ^e represents the residue of a fluorinated aromatic diamine.

In some embodiments of formula IV, R ^e is selected from the group consisting of: e1 to E16

/>

Wherein:

r ⁷ is the same or different at each occurrence and is selected from the group consisting of: F. alkyl, aryl, R _f, and OR _f;

R _f is C _1-3 perfluoroalkyl;

b is the same or different at each occurrence and is an integer from 0 to 3;

c is the same or different at each occurrence and is an integer from 0 to 2;

g is an integer from 0 to 4;

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

* Indicating the attachment point.

In some embodiments of E1 to E16, R ⁷ is selected from the group consisting of: F. r _f and OR _f.

In some embodiments of E1 through 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, provided they are not mutually exclusive.

In some embodiments of formula IV, the dianhydride is selected from the group consisting of: compound 25 through 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. Polyamic acid

The polyamic acids described herein are the reaction products of one or more tetracarboxylic acid components with one or more diamines, wherein (a) these diamines comprise 1 to 100 mole% of diamines having formula I, and/or (b) these tetracarboxylic acid components comprise 1 to 100 mole% of tetracarboxylic dianhydrides having formula IV. In some embodiments, the polyamic acid is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein one of the following: (a) These diamines comprise from 1 to 100mol% of diamines of formula I, or (b) these tetracarboxylic acid components comprise from 1 to 100mol% of tetracarboxylic dianhydrides of formula IV.

The first polyamic acid is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the diamines comprise 1 to 100 mole% of a diamine having formula I.

In some embodiments of the first polyamic acid, the diamine having formula I is 1 to 5 mole% of the total diamine; in some embodiments, 6-10mol%; in some embodiments, 10-25mol%; in some embodiments, 25-50mol%; in some embodiments, 50-75mol%; in some embodiments, 75-100mol%; in some embodiments, 100mol%.

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

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

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

In some embodiments, the first polyamic acid is the reaction product of a single diamine having formula I and a single tetracarboxylic acid component.

The first polyamic acid has a repeating unit of formula II

Wherein:

R ^a and R ^c are the same or different and represent the residue of a tetracarboxylic acid component;

r ^b represents a diamine residue; and

M is an integer from 1 to 20.

All the above-described embodiments for R ^a、R^b and m in formula I apply equally to R ^a、R^b and m in formula II.

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

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

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

In some embodiments of the second polyamic acid, the dianhydride having formula IV is 1 to 5 mole% of the total dianhydride; in some embodiments, 6-10mol%; in some embodiments, 10-25mol%; in some embodiments, 25-50mol%; in some embodiments, 50-75mol%; in some embodiments, 75-100mol%; in some embodiments, 100mol%.

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

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

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

In some embodiments, the second polyamic acid is the reaction product of a single dianhydride and a single diamine component having formula IV.

The second polyamic acid has a repeating unit 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 above-described embodiments for R ^d、R^e and m in formula IV apply equally to R ^d、R^e and m in formula V.

Any of the diamines listed above that are suitable for forming residue R ^e in formula IV are also suitable for forming residue R ^f 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-tolidine, o-tolidine, benzidine and TFMB.

In some embodiments of the polyamide acids described above, the moiety derived from the monoanhydride monomer is present as a capping group.

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

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

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

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

In some embodiments, these monoamines are present in an amount of up to 5 mole% of the entire amine composition.

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

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

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

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

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

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

The overall polyamic acid composition may be named via symbols commonly used in the art. For example, a polyamic acid having a tetracarboxylic acid component of 100% odpa and a diamine component of 90mol% Bis-P and 10mol% TFMB can be expressed as:

ODPA//Bis-P/22TFMB 100//90/10。

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

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

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

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

In some embodiments, the high boiling aprotic solvent has a boiling point of 200 ℃ 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-diethylacetamide (DEAc), tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, 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-imidazolidinone.

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 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 < 1wt% polyamic acid in >99 wt% of 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 wt% to 5 wt% polyamic acid in 95 wt% to 99 wt% of one or more high boiling aprotic solvents.

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

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

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

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

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

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

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

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

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

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

The polyamic acid solution may optionally further contain any one of a number of additives. Such additives may be: antioxidants, heat stabilizers, adhesion promoters, coupling agents (e.g., silanes), inorganic fillers, or various reinforcing agents, so long as they do not adversely affect the desired polyimide properties.

The polyamic acid solution can be prepared using various methods available with respect to the introduction components (i.e., monomers and solvents). Some methods of producing polyamic acid solutions include:

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

(B) A method wherein a solvent is added to a stirred mixture of diamine and dianhydride components. (contrary to (a) above)

(C) A process in which a diamine is dissolved separately in a solvent and then a dianhydride is added thereto in such a ratio as to allow control of the reaction rate.

(D) A method in which the dianhydride component is dissolved separately in a solvent and then the amine component is added thereto in such a ratio as to allow control of the reaction rate.

(E) A process wherein the diamine component and the dianhydride component are separately dissolved in a solvent and then these solutions are mixed in a reactor.

(F) A process wherein a polyamic acid having an excess amine component and another polyamic acid having an excess dianhydride component are preformed and then reacted with each other in a reactor, particularly in such a way as to produce a non-random or block copolymer.

(G) A process wherein a specific portion of the amine component and dianhydride component are reacted first, and then the residual diamine component is reacted, or vice versa.

(H) A process wherein these components are added to part or all of the solvent in any order, in part or in whole, and further wherein part or all of any component 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 a first polyamic acid. The other dianhydride component is then reacted with the other amine component to yield a second polyamic acid. These polyamic acids are then combined in any one of a variety of ways prior to film formation.

In general, a polyamic acid solution can be obtained from any one of the above-disclosed polyamic acid solution production methods.

The polyamic acid solution may then be filtered one or more times to reduce the particle content. Polyimide films produced from such filtered solutions can exhibit reduced numbers of defects and thereby yield excellent performance in the electronic applications disclosed herein. The evaluation of filtration efficiency can be performed by a laser particle counter test, in which a representative sample of polyamic acid solution is cast onto a5 "silicon wafer. After soft baking/drying, the particle content of the film was assessed by any number of laser particle counting techniques on commercially available and known in the art instruments.

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

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

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

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

In some embodiments, the polyamic acid solution is prepared and filtered to produce a particle content between 2 particles and 8 particles, as measured by a laser particle counter test.

In some embodiments, the polyamic acid solution is prepared and filtered to produce a particle content between 4 particles and 6 particles, as measured by a laser particle counter test.

An exemplary preparation of polyamic acid solution is given in the examples.

6. Polyimide resin

There is provided a first polyimide having a repeating unit structure of formula III

Wherein:

r ^b represents a diamine residue; and

M is an integer from 1 to 20.

All the above-described embodiments for R ^a、R^b、R^c and m in formula II apply equally to R ^a、R^b、R^c and m in formula III.

There is provided 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 above-described embodiments for R ^d、R^e、R^f and m in formula IV apply equally to R ^d、R^e、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 then imidizing. This can be achieved by thermal or chemical conversion methods.

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

In some embodiments of the polyimide film, the coefficient of in-plane thermal expansion (CTE) is less than 45ppm/°c between 50 ℃ and 200 ℃; in some embodiments, less than 30ppm/°c; in some embodiments, less than 20ppm/°c; in some embodiments, less than 15ppm/°c; in some embodiments, between 0 ppm/DEG C and 15 ppm/DEG C.

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

In some embodiments of polyimide films, the 1% tga weight loss temperature is greater than 350 ℃; in some embodiments, greater than 400 ℃; in some embodiments, greater than 450 ℃.

In some embodiments of the polyimide film, the tensile modulus is between 1.5GPa and 8.0 GPa; in some embodiments, between 1.5GPa and 5.0 GPa.

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

In some embodiments of polyimide films, the optical retardation is less than 2000nm; in some embodiments, less than 1500nm; in some embodiments, less than 1000nm; in some embodiments, less than 500nm.

In some embodiments of the polyimide film, the birefringence at 550 or 633nm 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 film, 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 film, 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 transmittance at 400nm is greater than 40%; in some embodiments, greater than 50%; in some embodiments, greater than 60%.

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

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

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

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

Any of the above embodiments of polyimide films may be combined with one or more of the other embodiments, provided they are not mutually exclusive.

4. Method for producing polyimide film

In general, polyimide films can be prepared from polyimide precursors by chemical or thermal conversion methods. In some embodiments, these films are prepared from the corresponding polyamic acid solutions by chemical or thermal conversion methods. Polyimide films disclosed herein (particularly when used as flexible substitutes for glass in electronic devices) are prepared by a thermal conversion process.

In general, polyimide films can be prepared from the corresponding polyamic acid solutions by chemical or thermal conversion methods. Polyimide films disclosed herein (particularly when used as flexible substitutes for glass in electronic devices) are prepared by thermal or modified thermal and chemical conversion processes.

Chemical conversion processes are described in U.S. patent nos. 5,166,308 and 5,298,331, which are incorporated herein by reference in their entirety. In such processes, a conversion chemical is added to the polyamic acid solution. Conversion chemicals found useful in the present invention include, but are not limited to: (i) One or more dehydrating agents such as aliphatic acid anhydrides (acetic anhydride, etc.) and acid anhydrides; and (ii) one or more catalysts such as aliphatic tertiary amines (triethylamine, etc.), tertiary amines (dimethylaniline, etc.), and heterocyclic tertiary amines (pyridine, picoline, isoquinoline (isoquinoilne, etc.). The anhydride dehydrating material is typically used in a slight molar excess of the amount of amidic acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically about 2.0 to 3.0 moles per equivalent of polyamic acid. In general, a considerable amount of tertiary amine catalyst is used.

The thermal conversion process may or may not employ a conversion chemical (i.e., catalyst) to convert the polyamic acid casting solution to polyimide. If conversion chemicals are used, the process can be considered an improved thermal conversion process. In both types of thermal conversion processes, only thermal energy is used to heat the film to simultaneously dry the solvent film and perform the imidization reaction. The polyimide films disclosed herein are typically prepared using a thermal conversion process with or without a conversion catalyst.

The specific process parameters are preselected in view of not just film composition to produce the properties of interest. Conversely, cure temperature and temperature ramp-up curves also play an important role in achieving the most desirable characteristics of the intended use disclosed herein. The polyamic acid should be imidized at or above the highest temperature of any subsequent processing step (e.g., deposition of one or more inorganic or other layers needed to produce a functional display), but at a temperature below that at which significant thermal degradation/discoloration of the polyimide occurs. It should also be noted that an inert atmosphere is generally preferred, particularly when imidization is performed with higher processing temperatures.

For the polyamic acids/polyimides disclosed herein, when subsequent processing temperatures in excess of 300 ℃ are required, temperatures of 300 ℃ to 400 ℃ are typically employed. The selection of an appropriate curing temperature allows to obtain a fully cured polyimide that achieves an optimal balance of thermal and mechanical properties. Due to this very high temperature, an inert atmosphere is required. Typically, an oxygen level in the furnace of <100ppm should be employed. The very low oxygen level enables the highest curing temperatures to be used without significant degradation/discoloration of the polymer. The catalyst that accelerates the imidization process is effective to achieve higher levels of imidization at curing temperatures between about 200 ℃ and 300 ℃. This approach may optionally be employed if the flexible device is prepared at a higher cure temperature below T _g of the polyimide.

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

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

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 50 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 40 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 30 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 20 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft-baked thickness of between 10 μm and 20 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft-baked thickness of between 15 μm and 20 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of 18 μm.

In some embodiments of the thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 10 μm.

In some embodiments of the thermal conversion method, the spin-coated substrate is soft baked in a close-up mode on a hotplate, wherein nitrogen is used to hold the spin-coated substrate just above the hotplate.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the soft baked spin-coated substrate is then cured at 3 preselected temperatures for 3 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin-coated substrate is then cured at 4 preselected temperatures for 4 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin-coated substrate is then cured at 5 preselected temperatures for 5 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin-coated substrate is then cured at 6 preselected temperatures for 6 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin-coated substrate is then cured at 7 preselected temperatures for 7 preselected time intervals, wherein each of these time intervals may be the same or different.

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

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

In some embodiments of the thermal conversion process, the soft baked spin-coated substrate is then cured at 10 preselected temperatures for 10 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 80 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is equal to 100 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 100 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is equal to 150 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 150 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is equal to 200 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 200 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is equal to 250 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 250 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is equal to 300 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 300 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is equal to 350 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 350 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is equal to 400 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 400 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is equal to 450 ℃.

In some embodiments of the thermal conversion process, the preselected temperature is greater than 450 ℃.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the process for preparing a polyimide film comprises the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components in a high-boiling aprotic solvent onto a substrate; soft baking the spin-coated substrate; the soft baked spin-coated substrate is treated at preselected temperatures for preselected time intervals whereby the polyimide film exhibits properties that are satisfactory for electronic applications such as those disclosed herein.

In some embodiments of the thermal conversion process, the process for preparing a polyimide film consists of the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components in a high-boiling aprotic solvent onto a substrate; soft baking the spin-coated substrate; the soft baked spin-coated substrate is treated at preselected temperatures for preselected time intervals whereby the polyimide film exhibits properties that are satisfactory for electronic applications such as those disclosed herein.

In some embodiments of the thermal conversion process, the process for preparing a polyimide film consists essentially of, in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components in a high-boiling aprotic solvent onto a substrate; soft baking the spin-coated substrate; the soft baked spin-coated substrate is treated at preselected temperatures for preselected time intervals whereby the polyimide film exhibits properties that are 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 manufacturing process. At some point during 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 polyimide from glass as a film with a deposited display layer and achieve a flexible form. Typically, this polyimide film with the deposited layer is then bonded to a thicker but still flexible plastic film to provide support for subsequent fabrication of the display.

Also provided are improved thermal conversion processes wherein the conversion catalyst generally allows the imidization reaction to be conducted at lower temperatures than would be possible in the absence of such conversion catalyst.

In some embodiments, the polyamic acid solution is converted to a polyimide film via a modified thermal conversion process.

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

In some embodiments of the improved thermal conversion process, the polyamic acid solution further comprises a conversion catalyst selected from the group consisting of tertiary amines.

In some embodiments of the improved thermal conversion process, the polyamic acid solution further comprises a conversion catalyst selected from the group consisting of: tributylamine, dimethylethanolamine, isoquinoline, 1, 2-dimethylimidazole, N-methylimidazole, 2-ethyl-4-imidazole, 3, 5-lutidine, 3, 4-lutidine, 2, 5-lutidine, 5-methylbenzimidazole, and the like.

In some embodiments of the improved thermal conversion process, the conversion catalyst is present at 5 wt% or less of the polyamic acid solution.

In some embodiments of the improved thermal conversion process, the conversion catalyst is present at 3 wt% or less of the polyamic acid solution.

In some embodiments of the improved thermal conversion process, the conversion catalyst is present at 1 wt% or less of the polyamic acid solution.

In some embodiments of the improved thermal conversion process, the conversion catalyst is present at 1 wt% of the polyamic acid solution.

In some embodiments of the improved thermal conversion process, the polyamic acid solution further comprises tributylamine as a conversion catalyst.

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

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

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

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

In some embodiments of the improved thermal conversion process, the polyamic acid solution further comprises 5-methylbenzimidazole as a conversion catalyst.

In some embodiments of the improved thermal conversion process, the polyamic acid solution further comprises N-methylimidazole as a conversion catalyst.

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

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

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

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

In some embodiments of the improved thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 50 μm.

In some embodiments of the improved thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 40 μm.

In some embodiments of the improved thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 30 μm.

In some embodiments of the improved thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 20 μm.

In some embodiments of the improved thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of between 10 μm and 20 μm.

In some embodiments of the improved thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of between 15 μm and 20 μm.

In some embodiments of the improved thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of 18 μm.

In some embodiments of the improved thermal conversion process, the polyamic acid solution is spin-coated onto the substrate such that the resulting film has a soft baked thickness of less than 10 μm.

In some embodiments of the improved thermal conversion method, the spin-coated substrate is soft baked in a near pattern on a hot plate, wherein nitrogen is used to hold the spin-coated substrate just above the hot plate.

In some embodiments of the improved thermal conversion process, the spin-coated substrate is soft baked in full contact mode on a hotplate, wherein the spin-coated substrate is in direct contact with the hotplate surface.

In some embodiments of the improved thermal conversion method, a combination of a proximity mode and a full contact mode is used to soft bake the spin-coated substrate on a hot plate.

In some embodiments of the improved thermal conversion process, a hot plate set at 80 ℃ is used to soft bake the spin-coated substrate.

In some embodiments of the improved thermal conversion process, a hot plate set at 90 ℃ is used to soft bake the spin-coated substrate.

In some embodiments of the improved thermal conversion process, a hot plate set at 100 ℃ is used to soft bake the spin-coated substrate.

In some embodiments of the improved thermal conversion process, a hot plate set at 110 ℃ is used to soft bake the spin-coated substrate.

In some embodiments of the improved thermal conversion process, a spin-coated substrate is soft baked using a hot plate set at 120 ℃.

In some embodiments of the improved thermal conversion process, a hot plate set at 130 ℃ is used to soft bake the spin-coated substrate.

In some embodiments of the improved thermal conversion process, a hot plate set at 140 ℃ is used to soft bake the spin-coated substrate.

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

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

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

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

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

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

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

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

In some embodiments of the improved thermal conversion process, the soft baked spin-coated substrate is then cured at3 preselected temperatures for 3 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the improved thermal conversion process, the soft baked spin-coated substrate is then cured at 4 preselected temperatures for 4 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the improved thermal conversion process, the soft baked spin-coated substrate is then cured at 5 preselected temperatures for 5 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the improved thermal conversion process, the soft baked spin-coated substrate is then cured at 6 preselected temperatures for 6 preselected time intervals, wherein each of these time intervals may be the same or different.

In some embodiments of the improved thermal conversion process, the soft baked spin-coated substrate is then cured at 7 preselected temperatures for 7 preselected time intervals, wherein each of these time intervals may be the same or different.

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

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

In some embodiments of the improved thermal conversion process, the soft baked spin-coated substrate is then cured at 10 preselected temperatures for 10 preselected time intervals, wherein each of these time intervals may be the same or different.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the improved thermal conversion process, the process for preparing a polyimide film comprises the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components and a conversion chemical in a high boiling aprotic solvent onto a substrate; soft baking the spin-coated substrate; the soft baked spin-coated substrate is treated at preselected temperatures for preselected time intervals whereby the polyimide film exhibits properties that are satisfactory for electronic applications such as those disclosed herein.

In some embodiments of the improved thermal conversion process, the process for preparing a polyimide film consists of the following steps in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components and a conversion chemical in a high boiling aprotic solvent onto a substrate; soft baking the spin-coated substrate; the soft baked spin-coated substrate is treated at preselected temperatures for preselected time intervals whereby the polyimide film exhibits properties that are satisfactory for electronic applications such as those disclosed herein.

In some embodiments of the improved thermal conversion process, the process for preparing a polyimide film consists essentially of, in order: spin-coating a polyamic acid solution comprising two or more tetracarboxylic acid components and one or more diamine components and a conversion chemical in a high boiling aprotic solvent onto a substrate; soft baking the spin-coated substrate; the soft baked spin-coated substrate is treated at preselected temperatures for preselected time intervals whereby the polyimide film exhibits properties that are satisfactory for electronic applications such as those disclosed herein.

5. Electronic device

Polyimide films disclosed herein can be suitable for use in 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 filters, cover films, and the like. The property requirements of the particular materials for each application are unique and can be addressed by one or more suitable compositions and one or more processing conditions of the polyimide films disclosed herein.

In some embodiments, the flexible substitute for glass in an electronic device is a polyimide film having repeating units of formula III as described in detail above.

Organic electronic devices that may benefit from having one or more layers comprising at least one compound as described herein include, but are not limited to: (1) means for converting electrical energy into radiation (e.g. light emitting diode, light emitting diode display, illumination means, light source, or diode laser), (2) means for electronically detecting a signal (e.g. photo detector, photoconductive cell, photoresistor, photo relay, phototransistor, phototube, IR detector, biosensor), (3) means for converting radiation into electrical energy (e.g. photovoltaic device or solar cell), (4) means for converting light of one wavelength into light of a longer wavelength (e.g. down-converting phosphor device); and (5) devices comprising one or more electronic components comprising one or more organic semiconductor layers (e.g., transistors or diodes). Other uses of the composition according to the invention include coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolytic capacitors, energy storage devices (such as rechargeable batteries) and electromagnetic shielding applications.

One illustration of a polyimide film that can serve as a flexible substitute for glass as described herein is shown in fig. 1. The flexible film 100 may have the characteristics as described in embodiments of the present disclosure. In some embodiments, polyimide films, which may serve as flexible substitutes for glass, are included in electronic devices. Fig. 2 illustrates a case when the electronic device 200 is an electronic device. The device 200 has a substrate 100, an anode layer 110 and a second electrical contact layer, a cathode layer 130, and a photoactive layer 120 therebetween. Additional layers may optionally be present. Adjacent to the anode may be a hole injection layer (not shown), sometimes referred to as a buffer layer. Adjacent to the hole injection layer may be a hole transport layer (not shown) comprising a hole transport material. Adjacent to the cathode may be an electron transport layer (not shown) comprising an electron transport material. Alternatively, the device may use one or more additional hole injection layers or hole transport layers (not shown) proximate to anode 110 and/or one or more additional electron injection layers or electron transport layers (not shown) proximate to cathode 130. 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 (in addition to the substrate 100) may also be made of the polyimide films disclosed herein.

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

In some embodiments, the different layers have the following thickness ranges: the substrate 100,5-100 microns, anode 110,In some embodiments,/>Hole injection layer (not shown)/>In some embodiments,/>Hole transport layer (not shown)/>In some embodiments,/>Photoactive layer 120,/>In some embodiments,/>Electron transport layer (not shown)/>In some embodiments,/> Cathode 130,/>In some embodiments,/>The ratio of layer thicknesses desired will depend on the exact nature of the materials used.

In some embodiments, an organic electronic device (OLED) contains a flexible substitute for 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 may be made of a material containing, for example, a metal, a mixed metal, an alloy, a metal oxide or a mixed metal oxide, or it may be a conductive polymer, and mixtures thereof. Suitable metals include group 11 metals, metals from groups 4, 5 and 6 and transition metals from groups 8-10. If the anode is to be light transmissive, mixed metal oxides of group 12, 13 and 14 metals, such as indium tin oxide, are typically used. The anode may also comprise an organic material such as polyaniline, as described in "Flexible light-emittingdiodes made from soluble conducting polymer [ Flexible light emitting diode made of soluble conductive polymer ]", nature, volume 357, pages 477-479 (1992, 6, 11). 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 a hole injection material. The term "hole injection layer" or "hole injection material" is intended to refer to a conductive or semiconductive material and may have one or more functions in an organic electronic device, including, but not limited to, planarization of an underlying layer, charge transport and/or charge injection characteristics, scavenging of impurities such as oxygen or metal ions, and other aspects that facilitate or improve the performance of the organic electronic device. The hole injecting material may be a polymer, oligomer or small molecule and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture or other composition.

The hole injection layer may be formed of a polymeric material, such as Polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), which is typically doped with a protic acid. The protic acid may be, for example, poly (styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid), and the like. The hole injection layer 120 may include a charge transfer compound, etc., such as copper phthalocyanine and tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In some embodiments, hole injection layer 120 is made from a dispersion of a conductive polymer and a colloid-forming polymeric acid. Such materials have been described, for example, in published U.S. patent applications 2004-0102577, 2004-0127377 and 2005-0205860.

The other layer may comprise a hole transporting material. Examples of hole-transporting materials for the hole-transporting layer have been outlined in, for example, kirk-Othmer Encyclopedia of Chemical Technology of Y.Wang [ Ke Ke Ocimer encyclopedia ], fourth edition, volume 18, pages 837-860, 1996. Both hole transporting small molecules and polymers may be used. Common 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 (carbazol-9-yl) benzene (mCP); 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); n, N ' -bis (4-methylphenyl) -N, N ' -bis (4-ethylphenyl) - [1,1' - (3, 3' -dimethyl) biphenyl ] -4,4' -diamine (ETPD); tetrakis- (3-methylphenyl) -N, N' -2, 5-Phenylenediamine (PDA); alpha-phenyl-4-N, N-diphenyl aminostyrene (TPS); p- (diethylamino) benzaldehyde diphenyl hydrazone (DEH); triphenylamine (TPA); bis [4- (N, N-diethylamino) -2-methylphenyl ] (4-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 ' -tetrakis (4-methylphenyl) - (1, 1' -biphenyl) -4,4' -diamine (TTB); n, N '-bis (naphthalen-1-yl) -N, N' -bis- (phenyl) benzidine (α -NPB); and porphyrin compounds such as copper phthalocyanine. Common hole-transporting 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, especially triarylamine-fluorene copolymers, are used. In some cases, the polymers and copolymers are crosslinkable. Examples of crosslinkable hole-transporting polymers are found, for example, in published U.S. 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 tetrafluorotetracyanoquinoline dimethane and perylene-3, 4,9, 10-tetracarboxylic-3, 4,9, 10-dianhydrides.

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 light emitting electrochemical cell), a material layer that absorbs light and emits light having a longer wavelength (as in a down-converting phosphor device), or a material layer 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 comprises a compound comprising an emissive compound as the photoactive material. In some embodiments, the photoactive layer further comprises a host material. Examples of host materials include, but are not limited toPhenanthrene, benzophenanthrene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, carbazole, indolocarbazole, furan, benzofuran, dibenzofuran, and metal quinoline complexes. In some embodiments, the host material is deuterated.

In some embodiments, the photoactive layer comprises (a) an electroluminescent dopant capable of having an emission maximum between 380 and 750nm, (b) a first host compound, and (c) a second host compound. Suitable second host compounds are described above.

In some embodiments, the photoactive layer comprises only (a) a dopant capable of electroluminescence having an emission maximum between 380 and 750nm, (b) a first host compound, and (c) a second host compound, wherein no additional material is present that would substantially alter the operating principle or distinguishing characteristics of the layer.

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

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

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

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

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

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

The optional layer may also function to facilitate electron transport and also act as a confinement layer to prevent quenching of excitons at the layer interface. Preferably, the layer promotes electron mobility and reduces exciton quenching.

In some embodiments, such layers include other electron transporting materials. Examples of electron transport materials that can be used for the optional electron transport layer include metal chelated oxinoid (oxinoid) compounds including metal quinoline salt derivatives such as tris (8-quinolinolato) aluminum (AlQ), bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum (BAlq), tetrakis- (8-quinolinolato) hafnium (HfQ), and tetrakis- (8-quinolinolato) zirconium (ZrQ); and azole compounds such as 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ) and 1,3, 5-tris (phenyl-2-benzimidazole) benzene (TPBI); quinoxaline derivatives such as 2, 3-bis (4-fluorophenyl) quinoxaline; phenanthrolines such as 4, 7-diphenyl-1, 10-phenanthroline (DPA) and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (DDPA); triazine; a 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 comprises an n-type dopant. N-type dopant materials are well known. n-type dopants include, but are not limited to, group 1 and group 2 metals; group 1 and group 2 metal salts, such as LiF, csF and Cs ₂CO₃; group 1 and group 2 metal organic compounds such as lithium quinolinolates; and molecular n-type dopants such as leuco dyes, metal complexes such as W ₂(hpp)₄ (where hpp= 1,3,4,6,7,8-hexahydro-2H-pyrimido- [1,2-a ] -pyrimidine) and cobaltocene, tetrathiatetracene, bis (ethylenedithio) tetrathiafulvalene, heterocyclic or divalent groups, and dimers, oligomers, polymers, dispiro compounds and polycycles of heterocyclic or divalent groups.

An optional electron injection layer may 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 quinolinate; cs-containing organometallic compounds, csF, cs ₂ O and Cs ₂CO₃. This layer may 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 typicallyWithin the scope of/>, in some embodiments

Cathode 130 is an electrode that is particularly effective for injecting electrons or negative charge carriers. The cathode may be any metal or nonmetal having a work function lower than that of the anode. The materials used for the cathode may be selected from the group consisting of alkali metals of group 1 (e.g., 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 thereof may be used.

It is known to have other layers in an organic electronic device. For example, there may be multiple layers (not shown) between anode 110 and the hole injection layer (not shown) to control the amount of positive charge injected and/or to provide band gap matching of the layers, or to act as a protective layer. Layers known in the art, such as ultra-thin layers of copper phthalocyanine, silicon oxynitride, fluorocarbon, silane, or metals such as Pt, may be used. 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 transport efficiency. The choice of material for each component layer is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescent efficiency.

It should be understood that each functional layer may be comprised of more than one layer.

The 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 may be used. Conventional vapor deposition techniques such as thermal evaporation, chemical vapor deposition, and the like may be used. The organic layer may be applied from a solution or dispersion in a suitable solvent using conventional coating or printing techniques including, but not limited to, spin coating, dip coating, roll-to-roll techniques, ink jet printing, continuous nozzle printing, screen printing, gravure printing, and the like.

For liquid phase deposition methods, one skilled in the art can readily determine suitable solvents for a particular compound or related class of compounds. For some applications, it is desirable that these compounds be dissolved in a nonaqueous solvent. Such nonaqueous solvents may be relatively polar, such as C ₁ to C ₂₀ alcohols, ethers, and acid esters, or may be relatively nonpolar, such as C ₁ to C ₁₂ alkanes or aromatic compounds such as toluene, xylene, benzotrifluoride, and the like. Other suitable liquids (as described herein as solutions or dispersions) for making the liquid compositions comprising the novel compounds include, but are not limited to, chlorinated hydrocarbons (such as methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (such as substituted and unsubstituted toluene and xylenes, including benzotrifluoride), polar solvents (such as Tetrahydrofuran (THP), N-methylpyrrolidone), esters (such as ethyl acetate), alcohols (isopropyl alcohol), ketones (cyclopentanone), and mixtures thereof. 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 phase deposition of the hole injection layer, the hole transport layer, and the photoactive layer, and by vapor phase deposition of the anode, the electron transport layer, the electron injection layer, and the cathode onto the flexible substrate.

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

In some embodiments, the apparatus has the following structure in order: the device comprises a substrate, an anode, a hole injection layer, a hole transport layer, a photoactive layer, an electron transport layer, an electron injection layer and a 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.

Examples

The concepts described herein will be further described in the following examples, which do not limit the scope of the invention as described in the claims.

In examples, 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.

Abbreviations (abbreviations)

APB-133=1, 3' -bis (3-amino-phenoxy) benzene

Bpda=3, 3', 4' -biphenyltetracarboxylic dianhydride

4,4 '-Dds=4, 4' -diaminodiphenyl sulfone

6 Fda=4, 4' -hexafluoroisopropylidene diphthalic 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 ] xanthen-1, 3,7,9 (11H) -tetraone,

Synthesis example

These examples illustrate the preparation of compounds having 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' ] bipyrrolidinyl-1, 3,5,7 (2H, 6H) -tetraone (2).

A mixture of 2,2' -bis (trifluoromethyl) benzidine (171.4 g,535.3mmol,4 eq.), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (5 g), pyridine (50 ml) and N-methylpyrrolidone (200 ml) was heated at 130℃under nitrogen atmosphere for 1 hour. Thereafter, the remaining amount of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride was added in 5g portions (30 g in total, 133.8mmol in total) at 130℃over a period of 5 hours. Thereafter, the mixture was heated at 150 ℃ for 2 days and at 180 ℃ 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 onto celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent was evaporated, and the residue was dissolved in a mixture of ethyl acetate and hexane 1:1, and the crystalline product was combined by filtration and dried in vacuo to give 40.2g of compound 2. Compound 2 can also be obtained by direct crystallization from the crude reaction mixture. In this manner, a mixture of 2,2' -bis (trifluoromethyl) benzidine (171.4 g,535.3mmol,4 eq.), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (5 g), pyridine (50 ml) and N-methylpyrrolidone (200 ml) was heated at 130℃under nitrogen atmosphere for 1 hour. Thereafter, additional amounts of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride were added in 5g portions (30 g total) at 130℃over a period of 5 hours. Thereafter, the mixture was heated at 150℃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 of 1:1 ethyl acetate and hexane, and left to stand at ambient temperature, and the precipitated product was collected periodically to obtain 33.36g of product. The product may additionally be recrystallized .¹H-NMR(DMSO-d₆,500MHz):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＝9Hz,J2＝2Hz),6.94-6.96(m,4H),7.39-7.41(m,2H),7.52(2,2H,J＝9Hz),7.68-7.70(m,2H).¹³C-NMR(DMSO-d₆,125MHz):178.4,149.5,138.4,133.6,132.6,132.1,130.1,128.3,122.8,122.2,116.1,110.7,38.4,22.3.¹⁹F-NMR(DMSO-d₆,470MHz):57.4,57.1. matrix-assisted laser desorption/ionization time-of-flight mass spectrometry ("MALDI TOF MS") from propyl acetate: 829.1671 (MH+).

Synthesis example 2

2, 6-Bis (2, 2 '-bis (trifluoromethyl) -4' -amino-1, 1 '-biphenyl-4-yl) -hexahydro-4, 8-ethylbridge benzo [1,2-c:4,5-c' ] bipyrrolidinyl-1, 3,5,7 (2H, 6H) -tetralone (4).

Method A:

To a stirred solution of 2,2' -bis (trifluoromethyl) benzidine (76.86 g,240mmol,4 eq.) in pyridine (30 ml) and N-methylpyrrolidone (150 ml) under a nitrogen atmosphere was added in portions 50ml of a suspension of bicyclo [2.2.2] octane-2, 3:5, 6-tetracarboxylic dianhydride ("bicyclooctane tetracarboxylic dianhydride") (15 g,60 mmol). The resulting mixture was heated at 180℃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 onto celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluate was evaporated, and dried in vacuo to give 21.23g of compound 4.

Method B:

A mixture of 2,2' -bis (trifluoromethyl) benzidine (51.2 g,4 eq.) and bicyclo [2.2.2] octane-2, 3:5, 6-tetracarboxylic dianhydride (10 g,39.97 mmol) was heated at 220℃under an inert atmosphere for 2 hours. The mixture was cooled to ambient temperature, dissolved in ethyl acetate, adsorbed onto celite, and chromatographed on silica gel (gradient elution using a mixture of propyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluate was evaporated, and dried in vacuo to give 21.82g of compound 4.

¹H-NMR(DMSO-d₆,500MHz):1.53(s,4H),2.61(s,2H),3.40(s,4H),5.73(s,4H),6.80(dd,2H,J1＝2Hz,J2＝8Hz),6.97(s,2H),6.98(d,2H,J＝7Hz),7.46(d,2H,J＝8Hz),7.67(dd,2H,J1＝2Hz,J2＝8Hz),7.80(d,2H,J＝2Hz).¹³C-NMR(DMSO-d₆,125MHz):177.9,149.6,138.6,133.8,132.6,132.2,130.3,129.0,128.8,128.2,128.0,125.7,125.0,124.7,123.5,122.9,122.2,116.2,110.7,43.1,28.8,17.6.¹⁹F-NMR(DMSO-d₆,470MHz):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-vinylidene benzo [1,2-c:4,5-c' ] bipyrrolidinyl-1, 3,5,7 (2H, 6H) -tetralone (5).

To a stirred solution of 2,2' -bis (trifluoromethyl) benzidine (77.43 g,241.8mmol,4 eq.) in pyridine (30 ml) and N-methylpyrrolidone (150 ml) under a nitrogen atmosphere was added in portions a suspension of bicyclooctane tetracarboxylic dianhydride (15 g,60.45 mmol) in 50ml of N-methylpyrrolidone. The resulting mixture was heated at 180℃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 onto celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluate was evaporated, and vacuum dried to give 21.23g of the compound 5.¹H-NMR(DMSO-d₆,500MHz):3.49(s,4H),3.57(br.S,2H),5.72(s,4H),6.37(t,2H,J＝4Hz),6.78(dd,2H,J1＝8Hz,J2＝2Hz),6.95-6.97(m,4H),7.43(d,2H,J＝8Hz),7.47(dd,2H,J1＝8Hz,J2＝2Hz),7.61(d,2H,J＝2Hz).¹³C-NMR(DMSO-d₆,125MHz):176.9,149.6,138.5,133.5,133.9,132.6,132.0,131.6,129.9,129.0,128.7,128.2,128.0,125.7,125.0,124.2,123.5,122.8,122.1,116.2,110.6,43.0,34.5.¹⁹F-NMR(DMSO-d₆,470MHz):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-vinylidene benzo [1,2-c:4,5-c ' ] bipyrrolidinyl-1, 3,5,7 (2 h,6 h) -tetraketone ] (7).

A mixture of 2,2' -bis (trifluoromethyl) benzidine (77.43 g,241.8mmol,2 eq.), pyridine (20 ml), N-methylpyrrolidone (100 ml) and dicyclohexyl octane tetracarboxylic dianhydride (15 g,60.45 mmol) was stirred under heating at 180℃for 6 days under nitrogen atmosphere. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, the residue was taken up on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluate was evaporated, and dried in vacuo to give 14.8g of compound 5. The fractions containing the tetra-imide-diamine were combined, the eluate evaporated and dried in vacuo to give 8.75g of compound 7. Compounds of formula (I) 7：¹H-NMR(DMSO-d₆,500MHz):3.50(s,4H),3.51(s,4H),3.58(br.S,4H),5.72(s,4H),6.38(t,4H,J＝4Hz),6.78(dd,2H,J1＝8Hz,J2＝2Hz),6.95-6.97(m,4H),7.43(d,2H,J＝8Hz),7.47(dd,2H,J1＝8Hz,J2＝2Hz),7.56-7.61(m,6H),7.72(s,2H).¹³C-NMR(DMSO-d₆,125MHz):176.92,176.86,149.6,138.6,136.1,133.9,133.0,132.9,132.6,132.0,131.7,130.2,129.9,128.2,128.0,125.7,1245.0,124.8,124.5,124.4,124.2,123.5,122.8,122.6,122.1,116.2,110.67,110.62,48.9,43.00,42.96,34.5.¹⁹F-NMR(DMSO-d₆,470MHz):57.4,57.2,57.1.MALDI TOF MS:1385.2532(MH+).

Synthesis example 5

3A,3b, 4a,7a, 8a,8 b-octahydro-9- (1, 1-dimethylethyl) -4, 8-vinylidene furo [3',4':3,4] cyclobut [1,2-f ] isobenzofuran-1, 3,5, 7-dione.

Maleic anhydride (37.4 g,0.38 mol) and acetophenone (22.9 g,0.191 mol) were dissolved in t-butylbenzene (about 0.8L) and placed in a 1L photochemical reactor and the wells were irradiated with 200W medium pressure Hainowei mercury lamp (Hanovia mercury lamp) using borosilicate glass immersion. The precipitate was collected by filtration. Yield of crude product after 42 hours of irradiation-33.3 g. The product may be recrystallized from hot acetone. ¹ H-NMR (acetone -d₆,500MHz):1.14(s,9H),2.99-3.09(m,4H),3.31(dd,1H,J1＝9Hz,J2＝3Hz),3.41(dd,1H,J1＝9Hz,J2＝3Hz),3.45-3.48(m,1H),3.71-3.72(m,1H),6.29(dd,1H,J1＝7Hz,J2＝2Hz).)

In control experiments, it was found that tert-butyl tricyclotetradecene tetracarboxylic dianhydride does 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) -3a,3b, 4a,7a, 8a,8 b-octahydro-4, 8-vinylidene pyrrolo [3',4':3,4] cyclobut [1,2-f ] isoindole-1, 3,5,7 (2 h,6 h) -tetraon (6).

To a stirred solution of 2,2' -bis (trifluoromethyl) benzidine (19.4 g,60.55mmol,4 eq.) in pyridine (10 ml) and N-methylpyrrolidone (80 ml) was added dropwise a solution of tert-butyltricyclotetradecene tetracarboxylic dianhydride (5 g,15.14 mmol)) in N-methylpyrrolidone (50 ml) at 100℃over 6 hours under nitrogen atmosphere. Thereafter, the mixture was heated at 180℃for 8 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, the residue was taken up on celite and chromatographed on silica gel (gradient elution with a mixture of hexane-dichloromethane and hexane-ethyl acetate). The fractions containing the diimide-diamine were combined, the eluate was evaporated, and the residue was dried in vacuo to give 8.7g of the compound 6.¹H-NMR(DMSO-d₆,500MHz):1.06(s,9H),2.77(dd,1H,J1＝7Hz,J2＝3Hz),2.83–2.85(m,1H),2.93-2.96(m,2H),3.02(dd,1H,J1＝9Hz,J2＝2Hz),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＝7Hz,J2＝1.5Hz),6.80(t,2H,J＝8Hz),6.97-7.00(m,4H),7.45-7.47(m,3H),7.59-7.61(m,2H),7.80(s,1H).¹³C-NMR(DMSO-d₆,125MHz):177.9,177.85,177.5,177.1,152.1,149.57,149.54,138.44,138.37,134.0,133.7,132.8,132.6,132.2,130.2,129.8,129.7,129.9,128.96,128.3,128.0,125.7,125.68,125.11,1245.0,124.9,124.8,123.53,123.5,122.9,122.8,122.3,122.2,122.1,116.2,110.7,110.66,43.3,43.2,41.8,41.2,36.4,34.5,34.0,29.8.¹⁹F-NMR(DMSO-d₆,470MHz):57.6,57.3,57.1,57.0.MALDI TOF MS:935.2439(MH+).

Synthesis example 6

3A,3b, 4a,7a, 8a,8 b-octahydro-9-methyl-4, 8-vinylidene furo [3',4':3,4] cyclobut [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 0.8L) and placed in a 1L photochemical reactor and irradiated with a 200W medium pressure Hmong lamp. 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 may be recrystallized from hot acetone. Data for 9-methyl regioisomer: ¹ H-NMR (acetone -d₆,500MHz):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＝6Hz).¹³C-NMR( acetone -d₆,125MHz):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 methyltricyclotetradecene tetracarboxylic dianhydride does 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) -3a,3b, 4a,7a, 8a,8 b-octahydro-4, 8-vinylidene pyrrolo [3',4':3,4] cyclobut [1,2-f ] isoindole-1, 3,5,7 (2 h,6 h) -tetraon (6 a).

A mixture of 2,2' -bis (trifluoromethyl) benzidine (66.66 g,208.15mmol,4 eq.), methyltricyclotetradecene tetracarboxylic dianhydride (2.5 g, a mixture of 9-methyl and 3-methyl regioisomers in a ratio of 1:0.2), pyridine (20 ml) and N-methylpyrrolidone (100 ml) was heated under nitrogen at 150℃for 1 hour. Thereafter, an additional amount of methyltricyclotetradecene tetracarboxylic dianhydride was added in 2.5g portions (15 g total) over a period of 5 hours at 130 ℃. Thereafter, the mixture was heated at 180℃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 onto celite and chromatographed on silica gel (gradient elution using a mixture of propyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluate was evaporated, and dried in vacuo to give 20.1g of compound 6a. Data for 9-methyl regioisomer ：¹H-NMR(DMSO-d₆,500MHz):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＝8Hz,J2＝3Hz),3.11(dd,1H,J1＝8Hz,J2＝3Hz),3.16(br.s,1H),3.25(p,1H,J＝3Hz),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＝1.5Hz).¹³C-NMR(DMSO-d₆,125MHz):177.9,177.8,177.5,177.3,149.58,149.55,141.2,138.5,138.4,134.0,133.7,132.7,132.6,132.2,130.3,129.9,128.9,128.7,128.3,128.0,127.3,125.7,125.1,125.0,124.9,124.8,124.2,123.5,122.9,122.8,122.3,122.1,116.2,110.7,43.11,42.35,41.6,41.3,39.2,35.7,22.8.¹⁹F-NMR(DMSO-d₆,470MHz):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 ' ] bipyrrolidinyl-1, 3,5,7 (2H, 6H) -tetralone (8). A mixture of 2,2' -bis (trifluoromethyl) benzidine (153 g,477.8 mmol), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (5 g), pyridine (20 ml) and N-methylpyrrolidone (150 ml) was heated at 150℃for 1 hour under a nitrogen atmosphere. Thereafter, the remaining amount of 1,2,3, 4-cyclohexane tetracarboxylic dianhydride was added in 5g portions (25 g in total, 118.97mmol in total) at 150℃over a period of 4 hours. Thereafter, the mixture was heated at 180℃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 onto celite and chromatographed on silica gel (elution with a mixture gradient of ethyl acetate and hexane) (2 times). The fractions containing the diimide-diamine were combined, the eluate was evaporated, and vacuum dried to give 3g of the compound 8.¹H-NMR(DMSO-d₆,500MHz):2.56(t,2H,J＝9Hz),3.73(q,2H,J＝8Hz),3.80(d,2H,J＝8Hz),5.73(s,4H),6.80(dd,2H,J1＝9Hz,J2＝2Hz),6.97-6.99(m,4H),7.46(d,2H,J＝9Hz),7.65(d,2H,J＝9Hz),7.85(s,2H).¹⁹F-NMR(DMSO-d₆,470MHz):57.0,57.2.

Synthesis example 8

Compound 9A mixture of 2,2' -bis (trifluoromethyl) benzidine (132.6 g,414.08 mmol), 3a,4,5,9 b-tetrahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c ] furan-1, 3-dione (5 g), pyridine (20 ml) and N-methylpyrrolidone (150 ml) was heated at 150℃under nitrogen atmosphere for 1 hour. Thereafter, the remaining amount of dianhydride was added in 5g portions (30 g total, 118.97mmol total) at 150℃over a period of 2.5 hours. Thereafter, the mixture was heated at 180℃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 onto celite and chromatographed on silica gel (gradient elution using a mixture of propyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluate was evaporated, and dried in vacuo to give 34.1g of compound 9 in total.

Synthesis example 9

5,5 '-Oxybis [2,2' -bis (trifluoromethyl) -4 '-amino-1, 1' -biphenyl-4-yl ] -1H-isoindole-1, 3 (2H) -dione (10) and compound 11. A mixture of 2,2' -bis (trifluoromethyl) benzidine (61.94 g,6 eq.) and oxydiphthalic dianhydride (10 g,32.24 mmol) was heated at 220℃under an inert atmosphere for 1 hour. Thereafter, excess diamine is sublimated in vacuo at 260 ℃ to 265 ℃. The residue was dissolved in 150ml of ethyl acetate, adsorbed onto 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 eluate was evaporated using a rotary evaporator, and the residue was dried in a glove box at 150 ℃ under vacuum for 1 hour to give 16.13g of product 10. Fractions containing a few impure trimer were combined, the eluate was evaporated, and the residue was dried using a rotary evaporator to give 3.53g of compound 10. The fractions containing pure compound 11 were combined, the eluate was evaporated, and the residue was dried under vacuum at 150 ℃ to give 2.24g of compound 11.

Compounds of formula (I) 10：¹H-NMR(DMSO-d₆,500MHz):5.73(s,4H),6.80(dd,2H,J1＝9Hz,J2＝2Hz),6.98(d,2H,J＝3Hz),7.00(d,2H,J＝9Hz),7.48(d,2H,J＝8Hz),7.65-7.68(m,4H),7.75(dd,2H,J1＝8Hz,J2＝2Hz),7.94(d,2H,J＝2Hz),8.11-8.13(m,2H).¹³C-NMR(DMSO-d₆,125MHz):166.4,166.3,161.4,149.5,138.0,135.0,133.7,132.7,132.0,130.0,129.0,128.7,128.3,128.0,127.7,126.7,125.7,125.6,125.1,124.8,123.6,122.6,122.9,122.33,122.31,116.2,114.3,110.69,110.65,110.61.¹⁹F-NMR(DMSO-d₆,470MHz):56.97,56.98,57.3.

Compounds of formula (I) 11：¹H-NMR(DMSO-d₆,500MHz):5.73(s,4H),6.80(dd,2H,J1＝8Hz,J2＝2Hz),6.98(d,2H,J＝2Hz),7.00(d,2H,J＝8Hz),7.48(d,2H,J＝9Hz),7.67-7.69(m,10H),7.75(dd,2H,J1＝8Hz,J2＝2Hz),7.86(dd,2H,J1＝8Hz,J2＝2Hz),7.94(d,2H,J＝2Hz),8.05(d,2H,J＝2Hz),8.11-8.15(m,4H).

Synthesis example 10

5,5' -Oxybis [1, 3-phenylenedi (oxy-3, 1-phenylene) yl ] -1H-isoindole-1, 3 (2H) -dione (12). A mixture of 1, 3-bis (3-aminophenoxy) benzene (56.55 g,193.44mmol,6 eq.) and oxydiphthalic dianhydride (10 g,32.24 mmol) was heated at 220℃under an inert atmosphere for 1 hour and then at 265℃in vacuo. The residue was dissolved in 150ml of ethyl acetate, adsorbed onto celite, and purified by partial chromatography on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing the pure trimer were combined, the eluate was evaporated using a rotary evaporator, and the residue was dried in a glove box under vacuum at 150 ℃ for 1 hour. Compounds of formula (I) 12：¹H-NMR(DMSO-d₆,500MHz):5.21(s,4H),6.16(dd,2H,J1＝8Hz,J2＝3Hz),6.22(t,2H,J＝2Hz),6.33(dd,2H,J1＝8Hz,J2＝2Hz),6.66(t,2H,J＝2Hz),6.74-6.78(m,4H),6.98(t,2H,J＝8Hz),7.11(dd,2H,J1＝8Hz,J2＝2Hz),7.16(t,2H,J＝2Hz),7.23(br d,2H,J＝8Hz),7.36(t,2H,J＝8Hz),7.53(t,2H,J＝8Hz),7.59-7.52(m,4H),8.04(d,2H,J＝).¹³C-NMR(DMSO-d₆,125MHz):166.5,166.3,161.3,159.0,157.7,157.3,156.9,156.0,134.9,133.7,131.5,130.7,130.6,127.6,126.56,125.4,122.9,118.6,117.9,114.2,114.0,113.4,110.4,109.4,106.6,104.6.

Synthesis example 11

2,2' -Bis (2, 2' -bis (trifluoromethyl) -4' -amino-1, 1' -biphenyl-4-yl) (dodecahydro-1, 1', 2', 3' -pentaoxo-dispiro [4, 7-methano-5H-isoindole-5, 1' -cyclopentane-3 ',5 ' - [4,7] methano [5H ] isoindole (13). A mixture of 2,2' -bis (trifluoromethyl) benzidine (41.66 g,130.08mmol,10 eq.) and the corresponding spirocyclic dianhydride (5 g,13.01 mmol) was heated at 220 ℃ C. Under an inert atmosphere for 1.5 hours, the residue was dissolved in ethyl acetate, adsorbed on celite, and the fractions containing the pure product were chromatographed on silica gel (gradient elution using a mixture of hexane and ethyl acetate and hexane-propyl acetate) were combined, the residue was evaporated using a rotary evaporator and dried in vacuo at 150 ℃ C. In a glove box for 1 hour to give 8.59g of the compound 13.¹H-NMR(DMSO-d₆,500MHz):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＝9Hz),6.96-6.97(m,4H),7.43(d,2H,J＝8Hz),7.58(d,2H,J＝8Hz),7.74(s,2H).¹³C-NMR(DMSO-d₆,125MHz):223.8,223.3,117.97,117.93,117.75,117.81,149.5,138.5,133.8,132.6,132.3,130.2,130.1,129.2,129.0,128.75,128.5,128.0,127.9,127.8,127.2,125.7,125.0,124.7,124.6,123.5,122.9,122.2,121.3,120.7,120.0,116.2,110.7,110.6,66.7,53.6,48.0,47.9,47.4,46.7,45.6,45.1,42.0,33.2,21.2,31.9,30.8,21.9,21.1,10.7.¹⁹F-NMR(DMSO-d₆,470MHz):57.3,57.0.

Synthesis example 12

2,2 '-Bis (trifluoromethyl) -4' -amino-1, 1 '-biphenyl-4-yl) - [5,5' -bis-1H-isoindole ] -1,1', 3' (2H, 2 'H) -tetraon (14). A mixture of 2,2' -bis (trifluoromethyl) benzidine (113.7 g,355.1mmol,6.3 eq.) and biphenyl tetracarboxylic dianhydride (16.58 g,56.35 mmol) with a small amount of N-methylpyrrolidone was heated at 220℃under an inert atmosphere for 1 hour and then under vacuum at the same temperature for 3 hours. The mixture was cooled, dissolved in ethyl acetate, adsorbed onto celite, and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). Fractions containing the pure product were combined, the eluate was evaporated to a volume of 200ml using a rotary evaporator, and the crystalline product was collected by filtration to give 17.57g of compound 14. Fractions containing the lower purity product were combined, the eluate was evaporated, the residue was dissolved in ethyl acetate, then one volume of hexane was added, and allowed to stand at ambient temperature to slowly crystallize. The precipitated product containing oligomeric impurities was collected by filtration to give 12.95g of lower purity material. Products containing small amounts of oligomers can also be obtained by direct crystallization according to the following: the initial crude mixture was dissolved in ethyl acetate, one volume of hexane was added and the precipitate formed was collected .¹H-NMR(DMSO-d₆,500MHz):5.73(s,4H),6.81(dd,2H,J1＝8Hz,J2＝2Hz),6.99(d,2H,J＝2Hz),7.02(d,2H,J＝9Hz),7.50(d,2H,J＝8Hz),7.79(dd,2H,J1＝8Hz,J2＝2Hz),7.98(d,2H,J＝2Hz),8.14(d,2H,J＝8Hz),8.43(dd,2H,J1＝8Hz,J2＝2Hz),8.50(s,2H).¹³C-NMR(DMSO-d₆,125MHz):166.8,149.6,144.9,138.0,134.4,133.7,133.2,132.7,132.1,131.9,130.3,128.9,128.3,125.1,124.8,124.8,123.0,122.9,116.2,110.7,110.66.¹⁹F-NMR(DMSO-d₆,470MHz):57.3,57.0.

Synthesis example 13

Dodecahydro-2, 2 '-bis (trifluoromethyl) -4' -amino-1, 1 '-biphenyl-4-yl) - [5,5' -bis-1H-isoindole ] -1,1', 3' (2H, 2 'H) -tetralone (15) A mixture of 2,2' -bis (trifluoromethyl) benzidine (52.27 g,163.24mmol,10 eq.), dicyclohexyl-3, 4,3',4' -tetracarboxylic dianhydride (5 g,16.32 mmol) and N-methylpyrrolidone (5 ml) was heated at 220℃under an inert atmosphere for 1 hour and then in vacuo at the same temperature. The mixture was cooled, dissolved in ethyl acetate, adsorbed onto celite, and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). Fractions containing pure product were combined, the eluate was evaporated using a rotary evaporator, and the residue was dried under vacuum at 150 ℃ to give 8.92g of compound 15.¹H-NMR(DMSO-d₆,500MHz):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＝9Hz,J2＝2Hz),6.96-6.97(m,4H),7.42(d,2H,J＝8Hz),7.61(d,2H,J＝8Hz),7.78(s,2H).¹³C-NMR(DMSO-d₆,125MHz):179.0,178.4,149.5,138.1,133.6,132.64,132.57,132.55,130.1,128.3,125.7,123.5,122.3,120.0,116.2,110.67,110.63,110.59,29.34,29.25,25.52,21.69,21.66.¹⁹F-NMR(DMSO-d₆,470MHz):57.25,57.22,57.06,57.04.

Synthesis example 14

A mixture of 11-methyl-2, 8-bis (2, 2' -bis (trifluoromethyl) -4' -amino-1, 1' -biphenyl-4-yl) -11- (trifluoromethyl) -1H-pyrano [2,3-f:5,6-f ' ] diisoindole-1, 3,7,9 (2H, 8H, 11H) -tetralone (16) A mixture of 2,2' -bis (trifluoromethyl) benzidine (51 g,159.26mmol,10 eq.) corresponding xanthenetetracarboxylic dianhydride (10.2 g,25.23 mmol) and N-methylpyrrolidone (25 ml) was heated at 220℃for 1 hour under an inert atmosphere and then in vacuo at the same temperature for 1 hour. The mixture was diluted with ethyl acetate, adsorbed onto celite, and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). Fractions containing pure product were combined, the eluate was evaporated using a rotary evaporator, and the residue was dried in vacuo to give 16.62g of compound 16.¹H-NMR(DMSO-d₆,500MHz):2.39(s,3H),5.74(s,4H),6.82(d,2H,J＝8Hz),7.00-7.03(m,4H),7.51(d,2H,J＝8Hz),7.78(d,2H,J＝8Hz),7.91(s,2H),7.97(d,2H,J＝2Hz),8.51(s,2H).¹³C-NMR(DMSO-d₆,125MHz):170.8,166.1,165.7,155.5,149.6,138.2,134.8,133.8,132.7,132.0,130.3,128.8,128.1,127.9,125.8,125.6,125.1,124.9,124.6,123.6,122.6,122.3,121.4,120.8,116.2,112.9,110.73,110.69,110.64,45.0,19.8.¹⁹F-NMR(DMSO-d₆,470MHz):75.5,57,4,57.0.

Synthesis example 15

2, 6-Bis [4- [ (4-aminophenyl) sulfonyl ] phenyl ] -benzo [1,2-c:4,5-c '] bipyrrolidinyl-1, 3,5,7 (2H, 6H) -tetraketone (17). 4,4' -sulfonylbis [ aniline ] (56.92 g,229.2mmol,5 eq.), pyromellitic dianhydride (10 g,45.84 mmol) and N-methylpyrrolidone (100 ml) were heated under stirring at 177℃for 1.5 hours. The reaction mixture was cooled, diluted with ethyl acetate (200 ml), filtered, washed with ethyl acetate, and dried in vacuo to give 26g of crude product containing about 10% of higher oligomeric product for polymerization without further purification .¹H-NMR(DMSO-d₆,500MHz):6.22(s 4H),6.64(d,4H,J＝9Hz),7.59(d,4H,J＝9Hz),7.72(d,4H,J＝9Hz),8.02(d,4H,J＝9Hz),8.40(s,2H).

Synthesis example 16

A500 mL round bottom flask equipped with a Dean-Stark trap (Dean-STARK TRAP) was charged with 22.41g of TFMB (0.07 mol) and 250.71g of 1-methyl-2-pyrrolidone (NMP) under a nitrogen purge. The mixture was stirred at room temperature under nitrogen for about 30 minutes. Then, 26.74g (0.06 mol) of 6FDA was slowly added to the stirred diamine solution in portions. After the dianhydride addition was complete, the vessel and any residual dianhydride powder on the flask wall was washed with an additional 27.86g of NMP and the resulting mixture was stirred at room temperature overnight. Then, 80mL of meta-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, then precipitated into 1,500ml of methanol under stirring, the resulting suspension was filtered, and the collected solids were dried in vacuo.

The molecular weight of the resulting diamine monomer was about 5,000Da. Thus, there are about 7 repeating imides in the core (m is about 7 in formula I). The solids are used in the reaction with one or more dianhydrides without further isolation or purification to form the polyamic acid polymer.

Synthesis example 17

Synthesis of 6,6' - (sulfonylbis-4, 1-phenylene) bis-1H-furo [3,4-f ] isoindole-1, 3,5,7 (6H) -tetralone (33). Homopolylhydroxybenzoic acid monoanhydride. To a stirred solution of pyromellitic dianhydride (43.6 g,0.2 mol) in 400ml THF was added a mixture of 30ml tetrahydrofuran and 5ml water over a period of 48 hours at ambient temperature. After that, 250ml of tetrahydrofuran was 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℃for 3 hours. The precipitate was filtered and dried in vacuo to give 14.9g of product. An additional amount of product formed overnight at-24 ℃ was filtered and dried in vacuo to give 6.85g of product. ¹ H-NMR (acetone-d ₆, 500 MHz): 6.39 (s 2H), 12.46 (br.s, 2H).

The above pyromellitic dianhydride (28.16 g,119.26mmol,2.3 eq.) was stirred with 4,4' -sulfonylbis [ aniline ] (12.97 g,52.2 mmol) in 200ml dry tetrahydrofuran at ambient temperature for 1 hour. The mixture was diluted with acetone (100 ml), passed through a column packed with silica gel and washed with acetone. Combining the product-containing fractions, evaporating the solvent using a rotary evaporator, treating the residue with about 500ml of water, filtering the fine precipitate, washing with water, and drying in vacuo to give the amidohexaacid (31.1g)：¹H-NMR(DMSO-d₆,500MHz):7.78(s,2H),7.86(d,4H,J＝9Hz),7.91(d,4H,J＝9Hz),8.16(s,2H),10.89(s,2H),13.56(br.s,6H).

The above-mentioned amide hexaoic acid (31.1 g) was stirred under reflux in acetic anhydride (300 ml) under heating for 2 hours under nitrogen atmosphere. The hot reaction mixture was filtered, washed with 50ml acetic anhydride, dichloromethane (50 ml), suspended in 150ml chloroform, filtered and dried under vacuum to give 20.9g of compound 33: ¹H-NMR(DMSO-d₆ 500 MHz) 7.81 (d, 4H, j=9 Hz), 8.23 (d, 4H, j=9 Hz), 8.57 (s, 4H).

Examples of polymers

These examples illustrate the preparation of polyamic acids having formula II.

Polymer example 1

Polymer 1 polymerization of Compound 6 with BPDA:

The diimide-diamine monomer 6 (5.23 g,5.60 mmol), BPDA (1.616 g, 5.08 mmol) and N-methylpyrrolidone (38 ml) were charged into a 250ml glass reactor and the mixture was stirred under a nitrogen atmosphere at ambient temperature until the final viscosity of the polyamic acid was 7283cP.GPC：Mn＝73713,Mw＝139448,Mp＝121967,Mz＝222437,PDI＝1.89.¹H-NMR:(DMSO-d₆,500MHz):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＝6Hz),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:

The diimide-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) were mixed using a roller and allowed to react at ambient temperature until the final viscosity of the polyamic acid was 11620cP.GPC：Mn＝127781,Mw＝300128,Mp＝258512,Mz＝496954,PDI＝2.35.¹H-NMR:(DMSO-d₆,500MHz):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 with BPDA:

Imide-diamine monomer 4 (6.70 g,7.84 mmol), BPDA (2.237 g,7.60 mmol) and N-methylpyrrolidone (50 ml) were charged into a 250ml glass reactor, the mixture was stirred at ambient temperature under a nitrogen atmosphere, and then the final PMDA (39 mg) was added until the final viscosity of the polyamic acid was 7890cP.GPC：Mn＝88795,Mw＝175396,Mp＝168430,Mz＝282955,PDI＝1.98.¹H-NMR:(DMSO-d₆,500MHz):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 with BPDA:

Imide-diamine monomer 5 (6.71 g,7.87 mmol), BPDA (2.246 g,7.63 mmol) and N-methylpyrrolidone (50 ml) were charged into a 250ml glass reactor, the mixture was stirred at ambient temperature under a nitrogen atmosphere, and then the final PMDA (39 mg) was added until the final viscosity of the polyamic acid was 6033cP.GPC：Mn＝93567,Mw＝184524,Mp＝178922,Mz＝297891,PDI＝1.97.¹H-NMR:(DMSO-d₆,500MHz):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 with BPDA

Imide-diamine monomer 9 (3 g,3.316 mmol), BPDA (0.956 g,3.25 mmol) and N-methylpyrrolidone (22.6 g) were mixed under an inert atmosphere using rollers and allowed to react at ambient temperature, then PMDA (7 mg) was added until the final viscosity of the polyamic acid was 3135cP. GPC: mn=106690, mw=240045, mp=210783, mz=420038, pdi=2.25.

Polymer example 6

Polymer 6 polymerization of Compound 8 with BPDA

Imide-diamine monomer 8 (2.578 g,3.157 mmol), BPDA (0.91 g,3.093 mmol) and N-methylpyrrolidone (19.8 g) were mixed under an inert atmosphere using rollers and allowed to react at ambient temperature, then PMDA (10 mg) was added until the final viscosity of the polyamic acid was 7779cP. 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

The diimide-diamine monomer 11 (1.799 g,1.192 mmol), the diimide monomer 12 (0.171 g, 0.199mmol), the oxydiphthalic anhydride (0.42 g,1.354 mmol) and the N-methylpyrrolidone (13.6 g) were mixed under an inert atmosphere using a roller and allowed to react at ambient temperature, followed by the addition of the 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 with BPDA

The diimide-diamine monomer 15 (8.5 g,9.33 mmol), BPDA (2.73 g,9.29 mmol) and N-methylpyrrolidone (63.6 g) were charged into a 250ml glass reactor, and the mixture was stirred under a nitrogen atmosphere at ambient temperature until the final viscosity of the polyamic acid was 4339cP. GPC: mn=104310, mw=234898, mp=222275, mz=378468, pdi=2.25.

Polymer example 9

Polymer 9:

A250 mL reaction flask equipped with nitrogen inlet and outlet and a mechanical stirrer was charged with 3.46g of TFMB (0.0108 mol), 6.51g of Compound 9 (0.0072 mol) and 88.58g of 1-methyl-2-pyrrolidone (NMP). The mixture was stirred at room temperature under nitrogen for about 30 minutes. Then, 3.64g (0.009 mol) XFDA was added slowly in portions to the stirred diamine solution, followed by 3.76g (0.00846 mol) 6FDA. After the dianhydride addition was complete, any remaining dianhydride powder from the walls of the vessel and reaction flask was washed with an additional 9.84g of NMP. And the resulting mixture was stirred for 6 days. Separately, a 5% solution of 6FDA in NMP was prepared and added over time in small amounts (about 0.8 g) to increase the molecular weight of the polymer and the viscosity of the polymer solution. A bohler fly (Brookfield) cone-plate viscometer was used to monitor the solution viscosity by taking a small sample from the reaction flask for testing. A total of 3.2g of this finished solution (0.16g,0.00036mol 6FDA) was added. The reaction was carried out at room temperature with gentle stirring overnight to allow the polymer to equilibrate. The final viscosity of the polymer solution was 1,100cp at 25 ℃.

Polymer examples 10-14

Polymers 10-14 were prepared using a procedure similar to that of polymer example 9. The polymer compositions are given in table 1 below.

TABLE 1 Polymer compositions

Polymer example 15

Polymer 15. Polymerization of in situ pre-imidized bicyclooctane tetracarboxylic dianhydride with 6FDA, BPDA.

A mixture of 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 20ml N-methylpyrrolidone was heated for 2.5 hours under an inert atmosphere at 180℃using a Dean-Stark apparatus (Dean-Stark apparatus). Thereafter, N-methylpyrrolidone was distilled in vacuo. NMR spectral data of the obtained glassy residue showed complete imidization. The solid was redissolved in N-methylpyrrolidone at 150 ℃, transferred to a glass reactor and stirred with 3,3', 4' -biphenyltetracarboxylic dianhydride BPDA (1.094 g, 3.719 mmol), 4' -hexafluoroisopropylidene diphthalic dianhydride 6FDA (2.178 g,6.32 mmol) under nitrogen atmosphere at ambient temperature with a total of 129g of N-methylpyrrolidone. Additional amounts of 6FDA (480 mg total, 1.08 mmol) were then added until the final viscosity was 10430cP. GPC: mn=88006, mw=205641, mp=201618, mz=335818, pdi=2.34.

Polymer example 16

Polymer 16. Polymerization of in situ pre-imidized norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6' -tetracarboxylic dianhydride (CpODA) with BPDA.

2,2' -Bis (trifluoromethyl) benzidine (5.95 g,18.58 mmol), norbornane-2-spiro-alpha-cyclopentanone-alpha ' -spiro-2 ' -norbornane-5, 5 ', 6 ' -tetracarboxylic dianhydride CpODA (5.0 g,13.08 mmol) and 6ml of N-methylpyrrolidone were heated with a dean-Stark apparatus at 180℃for 3 hours, then 6ml of N-methylpyrrolidone were added and the mixture was heated for an additional 3 hours. Thereafter, N-methylpyrrolidone was distilled in vacuo. The solid was redissolved in N-methylpyrrolidone (71 g), transferred to a glass reactor and stirred with 3,3', 4' -biphenyltetracarboxylic dianhydride BPDA (1.53 g,5.20 mmol) at ambient temperature under nitrogen atmosphere, then pyromellitic dianhydride PMDA (62 mg) was added until final viscosity was 22860cP. 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, BPDA.

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

Polymer example 18

Polymer 18:

the imide-dianhydride monomer 33 (2.485 g), 2' -bis (trifluoromethyl) benzidine (1.179 g) and N-methylpyrrolidone (20 g) were dissolved, mixed with a roller under an inert atmosphere, allowed to react at ambient temperature, and then pyromellitic dianhydride (25 mg) was added until the final viscosity was 7112cP. GPC: mn=92432, mw=197099, mp= 173514. Mz=347413, pdi=2.13

Film examples

These examples illustrate the preparation of polyimide films having formula IV.

B and yellowness index (% T) were measured using a Hunter Lab spectrophotometer over a wavelength range of 350nm to 780 nm. Thermal gravimetric analysis and thermomechanical analysis of specific parameters as reported herein were used in combination to make thermal measurements of the films. Mechanical properties were measured using equipment from Instron, inc.

Film examples 1-7

The above polyamic acid is used to prepare a polyimide film having formula IV.

The polyamic acid solution was filtered through a microfilter, spin-coated on a clean silicon wafer, soft-baked on a hot plate at 90 ℃ and placed in an oven. Boiler cleaning-off is purged with nitrogen and heated in stages to the maximum cure temperature. The wafer was removed from the oven, immersed in water and manually delaminated to produce a polyimide film sample. The film compositions are given in table 2 below. The film properties are given in table 3 below.

TABLE 2 polyimide film

Film and method for producing the same	Polymer	Curing temperature, DEG C	Thickness, μm
				1	1	320	10.0
2	2	320	11.8
				3	3	320	10.5
4	4	320	10.6
				5	5	320	12.1
6	6	320	9.9
				7	8	320	10.7

TABLE 3 film Properties

Haze is in%; tg is in degrees Celsius; CTE is the second scan measurement in ppm/°c; Δη is the birefringence at 633 nm; td is the temperature in degrees Celsius at which a 1% weight loss occurs; t.m. is the tensile modulus in GPa; t.s. is the tensile strength in MPa; elong is the elongation at break in%.

From the above examples, it can be seen that 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 films obtained from the pre-imidized imide-containing monomers have beneficial properties such as reduced color b x/yellow index YI, increased thermal stability Td (1%), improved mechanical properties, and other properties.

Film examples 8-13

The above polyamic acid was used to prepare a polyimide film having the formula IV, as described in film examples 1-7, except for film example 9. In film example 9, the film was cured in air at a maximum temperature of 260 ℃.

The film compositions are given in table 4 below. The film properties are given in table 5 below.

TABLE 4 polyimide film

Film and method for producing the same	Polymer	Curing temperature, DEG C	Thickness, μm
				8	9	375	10.21
9	10	260 (Air)	11.03
				10	11	320	10.65
11	12	375	11.00
				12	13	375	10.53
13	14	375	10.21

TABLE 5 film Properties

Haze is in%; tg is in degrees Celsius; CTE is the second scan measurement in ppm/°c; td is the temperature in degrees Celsius at which a 1% weight loss occurs; t.m. is the tensile modulus in GPa; t.s. is the tensile strength in MPa; elong is the elongation at break in%.

Film examples 15-17

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

Polyimide films were prepared as described in film examples 1-7. The film compositions are given in table 6 below. The film properties are given in table 7 below.

TABLE 6 polyimide film

Film and method for producing the same	Polymer	Curing temperature, DEG C	Thickness, μm
				14	15	320	10.6
15	15	375	10.6
				16	17	410	8.70

TABLE 7 film Properties

Haze is in%; tg is in degrees Celsius; CTE is the second scan measurement in ppm/°c; Δη is the birefringence at 633 nm; td is the temperature in degrees Celsius at which a 1% weight loss occurs;

It should be noted that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more other activities may be performed in addition to those described. Moreover, the order of activities recited need not be the order in which they are performed.

In the foregoing specification, concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. The specification and figures are accordingly to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of present invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. The benefits, advantages, solutions to problems, and any feature or features that may cause any benefit, advantage, or solution to occur or become more pronounced, however, are not to be construed as critical, required, or essential features of any or all the claims.

It is appreciated that certain features described herein in the context of separate embodiments may also be provided in combination in a single embodiment for clarity. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. The use of numerical values in the various ranges specified herein are expressed as approximations as if both the minimum and maximum values in the ranges were preceded by the word "about". In this way, slight variations above and below the ranges can be used to achieve substantially the same results as values within these ranges. Moreover, the disclosure of these ranges is intended as a continuous range of each value, including between the minimum and maximum average values, including fractional values that can be produced when some components of one value are mixed with components of a different value. Moreover, when broader and narrower ranges are disclosed, it is within the contemplation of the invention to match the minimum value from one range to the maximum value from another range, and vice versa.

Claims

1. 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 2,

Wherein R ^a is selected from the group consisting of:

Wherein:

R ¹ is the same or different at each occurrence and is selected from the group consisting of: methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl;

R ² is the same or different at each occurrence and is selected from the group consisting of: methyl, ethyl, propyl, isopropyl;

a is an integer from 0 to 6;

c is an integer from 0 to 2;

f is an integer from 0 to 4; and

* Indicating the point of attachment,

Wherein R ^b represents the residue of a diamine having the formula D1

Wherein:

R ¹⁰ is C _1-5 perfluoroalkyl;

b is 0;

c is 0; and

Y is an integer from 0 to 2.

2. The diamine of claim 1, wherein R ¹⁰ is trifluoromethyl.

3. The diamine of claim 2, wherein c in formula a25 is 0.

4. The diamine of claim 2, wherein f in formula a26 is 0.

5. The diamine of any of claims 3 or 4, wherein y in formula D1 is 0.

6. The diamine of claim 1, selected from the group consisting of:

Compound 4

Compound 6

Compound 6a

Compound 8

Compound 9

7. A polyamic acid composition that is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein the diamines comprise 1 to 100 mole% of the diamine of formula I as defined in any one of claims 1 to 6.

8. A polyimide resulting from imidization of the polyamic acid according to claim 7.