CN112424204A

CN112424204A - Polymers for use in electronic devices

Info

Publication number: CN112424204A
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: 2021-02-26
Anticipated expiration: 2039-05-15
Also published as: CN112424204B; WO2019222304A1; TW202409041A; TWI833752B; TW201946925A; KR20200144150A

Abstract

An acid dianhydride having the formula IV is disclosed. In formula IV: r^dRepresents a tetracarboxylic acid component residue; r^eRepresents a diamine residue(ii) a And m is an integer from 1 to 20.

Description

Polymers for use in electronic devices

Claim of benefit of prior application

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

Background information

Technical Field

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

Background

Materials used in electronic applications often have stringent requirements with respect to their structural, optical, thermal, electronic and other properties. As the number of commercial electronic applications continues to increase, the breadth and specificity of desired properties requires innovation of materials with new and/or improved properties. 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 properties. These materials are useful as components of liquid crystal displays ("LCDs"), where their modest electrical power consumption, light weight, and layer flatness are key characteristics for practical utility. Other uses in electronic display devices where such parameters are preferentially set include device substrates, substrates for optical 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"). OLEDs are promising for many display applications due to high power conversion efficiency and applicability to a wide range of end uses. They are increasingly used in cell phones, tablet devices, handheld/laptop computers, and other commercial products. In addition to low power consumption, these applications require displays with high information content, full color, and fast video rate response times.

Polyimide films generally have sufficient thermal stability, high glass transition temperature, and mechanical toughness to make such use worth considering. Moreover, polyimides do not typically 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 conventional amber colored polyimides in some display applications such as optical filters and touch screen panels is hampered by the priority of optical transparency. Furthermore, polyimides are generally hard, highly aromatic materials; 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, producing light retardation that may adversely affect display performance. If additional uses of polyimides are sought in the display market, solutions are needed that maintain their desirable properties while improving their optical clarity and reducing amber color and birefringence leading to optical 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^arepresents a tetracarboxylic acid component residue;

R^brepresents a diamine residue; and is

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^drepresents a tetracarboxylic acid component residue;

R^erepresents a diamine residue; and is

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 polyamic acid described above and (b) at least one high-boiling aprotic solvent.

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

Also provided is a polyimide film comprising the above polyimide.

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

Also provided is a flexible replacement for glass in an electronic device, wherein the flexible replacement for glass is the polyimide film described above.

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

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 illustrated in the accompanying drawings to improve 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.

Skilled artisans appreciate that elements 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 to improve understanding of embodiments.

Detailed Description

Many aspects and embodiments have been described above and are merely exemplary and non-limiting. After reading this description, the skilled person will understand that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and benefits of any one or more embodiments will be apparent from the detailed description below and from the claims. Detailed description first relates to the definition and illustration of terms followed by an imide-containing monomer, a diamine having formula I, an acid dianhydride having formula IV, a polyamic acid, a polyimide, a method for preparing a polyimide film, an electronic device, and examples.

1. Definition and clarification of terms

Before addressing details of the following examples, some terms are defined or clarified.

As defined in "termsAnd as used in clarification, "R, R^a、R^bR', R "and any other variables are generic names and may be the same 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 the molecules closest to each plate as a result of its rubbing onto 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 hydrocarbon groups. In some embodiments, alkyl groups may be mono-, di-, and tri-substituted. An example of a substituted alkyl group is trifluoromethyl. Other substituted alkyl groups are formed from one or more of the substituents described herein. In certain embodiments, the alkyl group has 1 to 20 carbon atoms. In other embodiments, the group has 1 to 6 carbon atoms. The term is intended to include heteroalkyl groups. The heteroalkyl group can have from 1 to 20 carbon atoms.

The term "aprotic" refers to a class of solvents that lack an acidic hydrogen atom and therefore cannot act as a hydrogen donor. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), 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, which have only carbon and hydrogen atoms, and heteroaromatic compounds in which one or more carbon atoms within a cyclic group have been replaced by another atom, such as nitrogen, oxygen, sulfur, and the like.

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

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

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

The term "allyl" is intended to mean the radical-CH₂-CH＝CH₂。

The term "vinyl" is intended to mean the radical-CH ═ CH₂。

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-alkoxyalkyl, (R ') (R') N-alkylaryloxyalkyl, -S (O)_s-aryl (wherein s ═ 0-2), or-s (o)_s-heteroaryl (wherein s ═ 0-2). Each R' and R "is independently an optionally substituted alkyl, cycloalkyl or aryl group. R' and R ", together with the nitrogen atom to which they are bound, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

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-NH₂-NHR or-NR₂Wherein R is the same or different at each occurrence and may be alkyl or aryl. 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 "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 a moiety bonded to two isocyanate groups in an aromatic diisocyanate compound. This is further explained below.

The term "b" is intended to mean the b axis representing the yellow/blue opponent color in the CIELab color space. Yellow is represented by positive b values and blue by negative b values. The measured b-value may be affected by the solvent, in particular because solvent selection may affect the colour measured on materials exposed to high temperature processing conditions. This may occur as a result of the inherent characteristics of the solvent and/or characteristics associated with low levels of impurities contained in the various solvents. The particular solvent is typically pre-selected to achieve the b values desired for a particular application.

The term "birefringence" is intended to mean the difference in refractive index in different directions in a polymer film or coating. The term generally refers to the difference between the x-or y-axis (in-plane) and z-axis (out-of-plane) refractive indices.

The term "charge transport," when referring to a layer, material, member, or structure, is intended to mean that such layer, material, member, or structure facilitates the migration of such charges through the thickness of such layer, material, member, or structure with relative efficiency and small charge loss. The hole transport material favors positive charge; the electron transport material favors negative charges. Although a light emitting 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 further including atoms, wherein the atoms cannot be separated from their corresponding molecules by physical means without breaking chemical bonds. The term is intended to include oligomers and polymers.

The term "coefficient of linear thermal expansion (CTE or a)" is intended to refer to a parameter that defines 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 via known methods during the first or second heating scan. Understanding the relative expansion/contraction characteristics of materials can be an important consideration in the manufacture and/or reliability of electronic devices.

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

The term "electroactive" when referring to a layer or material 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 a charge, which can be an electron or a hole, or a material that emits radiation or exhibits a change in the concentration of electron-hole pairs 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 refer to the percentage increase in length that occurs in a material before the material breaks under an applied tensile stress. It can be measured, for example, by 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 mean the temperature at which a reversible change occurs in an amorphous polymer or in amorphous regions 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 coiled, stationary polymer chains become free to rotate and can move past each other. T can be measured using Differential Scanning Calorimetry (DSC), thermomechanical analysis (TMA), or Dynamic Mechanical Analysis (DMA), or other methods_g。

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 transmit, receive, or filter radiation. In some embodiments, the host material is present in a higher concentration.

The term "isothermal weight loss" is intended to mean a material property directly related to its thermal stability. It is typically measured at a constant temperature of interest via thermogravimetric analysis (TGA). Materials with high thermal stability typically exhibit very low isothermal weight loss percentages over a desired period of time at 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 a 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 mean the temperature at which 1% of the original polymer weight is lost due to decomposition (excluding absorbed water).

The term "optical retardation (or R)_TH) "is intended to mean the difference between the average in-plane refractive index and the out-of-plane refractive index (i.e., birefringence), which is then multiplied by the thickness of the film or coating. 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 that includes 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 performed on the solution itself or on finished materials (sheets, films, etc.) made from those films. Various optical methods can be used to assess 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 and with or without an applied bias voltage (as in a photodetector or photovoltaic cell).

The term "polyamic acid solution" refers to a solution of a polymer containing amic acid units having the ability to cyclize intramolecularly to form an imide group.

The term "polyimide" refers to condensates 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.

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

The term "soft bake" is intended to refer to a process commonly used in electronics manufacturing in which a spin-coated material is heated to drive off solvents and cure the film. Soft baking is usually carried out on a hot plate or in an exhaust oven at a temperature between 90 ℃ and 110 ℃ as a preparation step for the subsequent heat treatment of the coating layer or film.

The term "substrate" refers to a base material that may be rigid or flexible and may include one or more layers of one or more materials, which may include, but are not limited to, glass, 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 R₃SiOR₂Si-, wherein R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

The term "siloxy" refers to the group R₃SiO-, wherein R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl.

The term "silyl" refers to the group R₃Si-, wherein R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons in the R alkyl group are replaced with Si.

The term "spin coating" is intended to refer to a process 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, which is rotated at a low speed or not rotated at all. The substrate is then rotated at a prescribed speed to uniformly spread the coating material 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 a5 "silicon wafer and soft baked/dried. The particle content of the films thus prepared is evaluated by any number of standard measurement techniques. Such techniques include laser particle detection and other techniques known in the art.

The term "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 monoanhydride, tetracarboxylic dianhydride, tetracarboxylic monoester, and tetracarboxylic diester.

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

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

The term "yellowness index (or YI)" refers to the magnitude of yellowness relative to a standard. Positive values of YI indicate the presence and magnitude of yellow. Materials with negative YI appear bluish. Especially 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 a solvent may be different from the magnitude of the color introduced using NMP as a solvent. This may occur as a result of the inherent characteristics of the solvent and/or characteristics associated with low levels of impurities contained in the various solvents. The particular solvent is typically pre-selected to achieve the YI value desired for a particular application.

In structures where the substituent bonds shown below pass through one or more rings,

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

The phrase "adjacent," when used in reference to a layer in a device, 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 the formula that are immediately adjacent to each other (i.e., R groups on atoms that are bonded by a bond). Exemplary adjacent R groups are shown below:

in this specification, unless the context of usage clearly dictates otherwise or indicates to the contrary, where an embodiment of the inventive 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 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 here. Another alternative embodiment of the subject matter described is described as consisting of certain features or elements, in which embodiment, or in insubstantial variations thereof, only the features or elements specifically stated or described are present.

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

Also, the use of "a" or "an" is used 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 within the periodic Table of the elements use the convention "New Notation" as seen in the CRC Handbook of Chemistry and Physics [ Handbook of Chemistry and Physics ], 81 th edition (2000-2001).

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 specific passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specific materials, processing 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

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

It has been found that the imide-containing monomers described herein can be used to overcome the problems of monomers with low reactivity to control polymer structure (e.g., local order and tacticity) in order to achieve imidization with a smaller number of defects for polyimides with 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 with precisely defined oligomeric structures can be used as monomers.

In some embodiments, the imide-containing monomer is used in the form formed and is a mixture of pre-imidized compounds.

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

In some embodiments, the imide-containing monomer is a diamine and the reactive end group is an amino group, -NH₂。

In some embodiments, the imide-containing monomer is a diisocyanate and the reactive end group is an isocyanate group — 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 "imides".

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

Disclosed herein is a method of synthesizing a precisely defined imide-containing polymer obtained 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 dicarboxylic anhydride with an excess of the first diamine. The pre-imidized diamine monomer thus formed can 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 than the first dianhydride) 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 a polyimide polymer using conventional imidization techniques (e.g., thermal curing). An 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 a 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 greater than 50.

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

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

In scheme II, the first step is pre-imidization of 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 a polyimide polymer using conventional imidization techniques (e.g., thermal curing). An embodiment of scheme II is shown below, where the second diamine is different from the first diamine.

Scheme II: one embodiment

In the above scheme, Y represents a residue from a tetracarboxylic acid component (dianhydride), Z represents a residue from a first diamine, X2 represents a residue from a 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 dicarboxylic anhydride 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 with different values of m1 may be present. In polyamic acids and polyimides, m1 can 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 to pre-imidize 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 having the formula I

The diamines described herein have the formula I

Wherein:

R^arepresents a tetracarboxylic acid component residue;

R^brepresents a diamine residue; and is

m is an integer from 1 to 20.

In some embodiments of formula I, m ═ 1.

In some embodiments of formula I, m is 2-20.

In some embodiments of formula I, m is 2-5.

In some embodiments of formula I, m is 6-10.

In some embodiments of formula I, m is 11-20.

In some embodiments of formula I, R^aIs aromatic.

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

In some embodiments of formula I, R^aIs a polycyclic cycloaliphatic radical.

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

In some embodiments of formula I, R^aHaving an aromatic group and an alicyclic group.

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

In some embodiments of formula I, R^aRepresents a residue of a tetracarboxylic dianhydride selected from the group consisting of: pyromellitic dianhydride (PMDA), 3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 4,4' -oxydiphthalic anhydride (ODPA), 4,4' -hexafluoroisopropylidenediphthalic anhydride (6FDA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3',4,4' -diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4' -bisphenol-a dianhydride (BPADA), hydroquinone diphthalic anhydride (hq), 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; and so on. 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, perfluoroalkaneOxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -S (O)₂-, -C (═ O) -N (R ') (R'), (R ') (R') N-alkyl, (R ') (R') N-alkoxyalkyl, (R ') (R') N-alkylaryloxyalkyl, -S (O)_s-aryl (where s ═ 0-2) or-s (o)_s-heteroaryl (wherein s ═ 0-2). Each R' and R "is independently an optionally substituted alkyl, cycloalkyl or aryl group. R' and R ", together with the nitrogen atom to which they are bound, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

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

In some embodiments of formula I, R^aSelected from the group consisting of: formulae A1 to A36

Wherein:

R¹is the same or different at each occurrence and is selected from the group consisting of: alkyl, fluoroalkyl and silyl, where adjacent R¹Groups may be linked together to form a double bond;

R²、R³and R⁴Is the same or different at each occurrence and is selected from the group consisting of: F. alkyl, fluoroalkyl, and silyl;

R⁵selected from the group consisting of: H. halogen, cyano, hydroxy, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, alkylaryl, substituted alkylaryl, heteroaryl, substituted heteroaryl, vinyl, and allyl;

R⁶selected from the group consisting of: halogen, cyano, hydroxy, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, alkylaryl, substituted alkylaryl, heteroaryl, substituted heteroaryl, vinyl, and allyl;

R⁸and R⁹Is the same or different at each occurrence and is selected from the group consisting of: H. f, alkyl, fluoroalkyl, and silyl;

q is selected from the group consisting of: CR⁸R⁹、SiR⁸R⁹、S、SR⁸R⁹、S＝O、SO₂And 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 0-2;

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 is

Denotes the attachment point.

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

In some embodiments of formula I, R^bIs a polycyclic aliphatic group.

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

In some embodiments of formula I, R^bHaving alicyclic groupsRadicals and aromatic radicals.

In some embodiments of formula I, R^bRepresents the residue of a diamine of formula D1

Wherein:

R¹⁰is the same or different at each occurrence and is selected from the group consisting of: fluoroalkyl and fluoroalkoxy;

R¹¹is 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 0-2; and is

y is an integer from 0-2.

In some embodiments of formula D1, R¹⁰Is C_1-5A perfluoroalkyl group.

In some embodiments of formula D1, y is 0.

In some embodiments of formula D1, y is 1.

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

In some embodiments of formula I, R^bRepresents the residue of an aromatic diamine selected from the group consisting of: p-phenylenediamine (PPD), 2 '-dimethyl-4, 4' -diaminobiphenyl (m-toluidine), 3 '-dimethyl-4, 4' -diaminobiphenyl (o-toluidine), 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 (3355TMB), 2' -bis (trifluoromethyl) benzidine (22TFMB or TFMB), 2-bis [4- (4-aminophenoxy) phenyl.]Propane (BAPP), 4 '-Methylenedianiline (MDA), 4' - [1, 3-phenylenebis (1-methyl-ethylene)]Bis-aniline (Bis-M), 4' - [1, 4-phenylenebis(1-methyl-ethylene)]Dianiline (Bis-P), 4' -oxydianiline (4, 4' -ODA), m-phenylenediamine (MPD), 3,4' -oxydianiline (3, 4' -ODA), 3' -diaminodiphenyl sulfone (3,3' -DDS), 4' -diaminodiphenyl sulfone (4, 4' -DDS), 4' -diaminodiphenyl sulfide (ASD), 2-Bis [4- (4-amino-phenoxy) phenyl group]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 (DA5MG), 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 '-Bis (4-amino-2-trifluoromethylphenoxy) biphenyl (6BFBAPB), 3',5 '-tetramethyl-4, 4' -diaminodiphenylmethane (TMMDA) and the like.

In some embodiments of formula I, R^bRepresents the 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, so long as they are not mutually exclusive.

In some embodiments of formula I, the diamine is selected from the group consisting of: compound 1 to compound 24

Compound 1

Compound 2

Compound 3

Compound 4

Compound 5

Compound 6

Compound 6a

Compound 7

Compound 8

Compound 9

Compound 10

Compound 11

Compound 12

Compound 13

Compound 14

Compound 15

Compound 16

Compound 17

Compound 18

Compound 19

Compound 20

Compound 21

Compound 22

Compound 23

Compound 24

4. Dianhydrides of the formula IV

The dianhydrides described herein have the formula IV

Wherein:

R^drepresents a tetracarboxylic acid component residue;

R^erepresents a diamine residue; and is

m is an integer from 1 to 20.

In some embodiments of formula IV, m ═ 1.

In some embodiments of formula IV, m is 2-20.

In some embodiments of formula IV, m is 2-5.

In some embodiments of formula IV, m is 6-10.

In some embodiments of formula IV, m is 11-20.

Suitable for forming the residue R in formula I^aAny of the tetracarboxylic dianhydrides listed above are also suitable for forming the residue R in formula IV^d。

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

Suitable for forming the residue R in formula I^bAny of the above-listed diamines are also suitable for forming the residue R in formula IV^e。

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

In some embodiments of formula IV, R^eSelected from the group consisting of: formulae E1 to E16

Wherein:

R⁷is the same or different at each occurrence and is selected from the group consisting of: F. alkyl, aryl, R_fAnd OR_f；

R_fis C_1-3A perfluoroalkyl group;

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 0-2;

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 is

Denotes the attachment point.

In some embodiments of E1-E16, R⁷Selected from the group consisting of: F. r_fAnd OR_f。

In some embodiments of E1-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, so long as they are not mutually exclusive.

In some embodiments of formula IV, the dianhydride is selected from the group consisting of: compound 25 to compound 38

Compound 25

Compound 26

Compound 27

Compound 28

Compound 29

Compound 30

Compound 31

Compound 32

Compound 33

Compound 34

Compound 35

Compound 36

Compound 37

Compound 38

5. Polyamic acid

Polyamic acids described herein are reaction products of one or more tetracarboxylic acid components and one or more diamines, wherein (a) the diamines comprise 1 to 100 mole% of a diamine having formula I, and/or (b) the tetracarboxylic acid components comprise 1 to 100 mole% of a tetracarboxylic dianhydride 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: (a) these diamines comprise from 1 to 100 mol% of a diamine of the formula I, or (b) the tetracarboxylic acid components comprise from 1 to 100 mol% of a tetracarboxylic dianhydride of the 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 1-5 mol% of the total diamine; in some embodiments, 6 to 10 mol%; in some embodiments, 10 to 25 mol%; in some embodiments, 25 to 50 mol%; in some embodiments, 50 to 75 mol%; in some embodiments, 75 to 100 mol%; in some embodiments, 100 mol%.

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, there are three tetracarboxylic acid components.

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^aand R^cAre the same or different and represent a tetracarboxylic acid component residue;

R^brepresents a diamine residue; and is

m is an integer from 1 to 20.

For R in formula I^a、R^bAll of the above-described embodiments of m apply equally to R in formula II^a、R^bAnd m.

Suitable for forming the residue R in formula I^aAny of the tetracarboxylic dianhydrides listed above are also suitable for forming the residue R in formula II^c。

In some embodiments of formula II, R^cRepresents 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 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 to 10 mol%; in some embodiments, 10 to 25 mol%; in some embodiments, 25 to 50 mol%; in some embodiments, 50 to 75 mol%; in some embodiments, 75 to 100 mol%; in some embodiments, 100 mol%.

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

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

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

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^drepresents a tetracarboxylic acid component residue;

R^eand R^fAre the same or different and represent a diamine residue; and is

m is an integer from 1 to 20.

For R in formula IV^d、R^eAll of the above-described embodiments of m apply equally to R in formula V^d、R^eAnd m.

Suitable for forming the residue R in formula IV^eAny of the above-listed diamines are also suitable for forming the residue R in formula V^f。

In some embodiments of formula V, R^fRepresents the 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 foregoing polyamic acids, the moiety derived from the monoanhydride monomer is present as an end 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 mol% of the total tetracarboxylic acid composition.

In some embodiments of the foregoing polyamic acids, the moiety derived from the monoamine monomer is present as an end capping group.

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

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

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

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

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

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

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

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

In some embodiments, the polyamic acid has a weight average molecular weight (M) between 150,000 and 350,000 based on gel permeation chromatography and polystyrene standards_W)。

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

The overall polyamic acid composition can be named via symbols commonly used in the art. For example, a polyamic acid having a tetracarboxylic acid component of 100% ODPA and a diamine component of 90 mol% Bis-P and 10 mol% TFMB may be represented 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. This 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-butyl pyrrolidone (NBP), N-diethylacetamide (DEAc), tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, gamma-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 of the identified high boiling aprotic solvents is used in the liquid composition.

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

In some embodiments, the liquid composition is < 1% by weight polyamic acid in > 99% by weight 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 1-5% by weight polyamic acid in 95-99% by weight one or more high boiling aprotic solvents.

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

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

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

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

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

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

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

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

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

In some embodiments, the liquid composition is 50% by weight polyamic acid in 50% by weight high boiling aprotic solvent or solvents.

The polyamic acid solution may optionally further contain any 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 deleteriously affect the desired polyimide properties.

The polyamic acid solution can be prepared using various available methods with respect to the introduction of the 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 previously mixed together and then the mixture is added to a solvent in portions while stirring.

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

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

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

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

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

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

(i) A method of first reacting one of the dianhydride components with one of the diamine components to obtain a first polyamic acid. Another dianhydride component is then reacted with another amine component to provide a second polyamic acid. These polyamic acids are then combined in any of a variety of ways prior to film formation.

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

The polyamic acid solution can then be filtered one or more times to reduce the particle content. Polyimide membranes produced from such filtered solutions may exhibit a reduced number of defects, and thus yield superior performance in the electronic applications disclosed herein. Evaluation of filtration efficiency can be performed by a laser particle counter test, in which a representative sample of the polyamic acid solution is cast onto a5 "silicon wafer. After soft-bake/dry, the particle content of the film is evaluated by any number of laser particle counting techniques on commercially available and art-known 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 yield 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 yield 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 yield 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 yield a particle content between 4 particles and 6 particles, as measured by a laser particle counter test.

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

6. Polyimide, polyimide resin composition and polyimide resin composition

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

Wherein:

R^brepresents a diamine residue; and is

m is an integer from 1 to 20.

For R in formula II^a、R^b、R^cAll of the above-described embodiments of m apply equally to R in formula III^a、R^b、R^cAnd m.

A second polyimide having a repeating unit structure of formula VI is provided

Wherein:

R^drepresents a tetracarboxylic acid component residue;

R^eand R^fAre the same or different and represent a diamine residue; and is

m is an integer from 1 to 20.

For R in formula IV^d、R^e、R^fAll of the above-described embodiments of m apply equally to R in formula V^d、R^e、R^fAnd m.

Also provided is a polyimide film, wherein the polyimide has a repeating unit structure of formula III or formula VI as described above.

The polyimide film may be made by coating a polyimide precursor onto a substrate and then imidizing. This can be achieved by thermal or chemical conversion methods.

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

In some embodiments of the polyimide film, the coefficient of thermal expansion in plane (CTE) is less than 45 ppm/deg.c between 50 deg.c and 200 deg.c; in some embodiments, less than 30 ppm/deg.C; in some embodiments, less than 20 ppm/deg.C; in some embodiments, less than 15 ppm/deg.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) is for polyimide films cured at temperatures in excess of 300 deg.C_g) Is greater than 250 ℃; in some embodiments, greater than 300 ℃; and in some embodiments, greater than 350 deg.c.

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

In some embodiments of the polyimide film, the birefringence at 550 or 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 the polyimide film, the transmittance at 430nm is greater than 60%; in some embodiments, greater than 70%.

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

In some embodiments of the polyimide film, 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, so long as they are not mutually exclusive.

4. Method for producing polyimide film

Generally, 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. The polyimide films disclosed herein (particularly when used as flexible replacements for glass in electronic devices) are prepared by a thermal conversion process.

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

Chemical conversion processes are described in U.S. Pat. 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, etc.). The anhydride dehydrating material is typically used in a slight molar excess of the amount of amic 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. Generally, a substantial amount of tertiary amine catalyst is used.

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

The specific process parameters are pre-selected considering that not only the film composition yields the properties of interest. Conversely, the curing temperature and temperature ramp profile also play an important role in achieving the most desirable characteristics for the intended use disclosed herein. The polyamic acid should be imidized at or above the maximum temperature of any subsequent processing step (e.g., deposition of the inorganic or other layer(s) required to produce a functional display), but at a temperature below the temperature at which significant thermal degradation/discoloration of the polyimide occurs. It should also be noted that inert atmospheres are generally preferred, particularly when higher processing temperatures are employed for imidization.

For the polyamic acids/polyimides disclosed herein, temperatures of 300 ℃ to 400 ℃ are typically employed when subsequent processing temperatures in excess of 300 ℃ are required. Selecting proper curing temperature allowsTo 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, it should adopt<100ppm of furnace oxygen level. Very low oxygen levels enable the use of the highest curing temperatures without significant degradation/discoloration of the polymer. Catalysts that accelerate the imidization process are effective at achieving higher levels of imidization at curing temperatures between about 200 ℃ and 300 ℃. If the flexible device is below the T of the polyimide_gMay optionally be used.

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

In some embodiments, the 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-bake 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-bake 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-bake thickness of less than 30 μm.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the thermal conversion method, the soft-baked spin-coated substrate is then cured at 8 preselected temperatures for 8 preselected time intervals, where each of 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, where 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, where 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 are 10 minutes.

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

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

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

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

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

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

In some embodiments of the thermal conversion process, one or more of the preselected time intervals are 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 a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits properties that are satisfactory for use in electronic applications such as those disclosed herein.

In some embodiments of the thermal conversion process, the process for preparing a polyimide film consists 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 a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits properties that are satisfactory for use in 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 a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits properties that are satisfactory for use in electronic applications such as those disclosed herein.

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

Improved thermal conversion processes are also provided wherein the conversion catalyst generally allows the imidization reaction to be carried out at lower temperatures than would be possible in the absence of such conversion catalysts.

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 contains 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 weight percent 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 contains dimethylethanolamine as a conversion catalyst.

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

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

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

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

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

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

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

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

In some embodiments of the improved thermal conversion process, the polyamic acid solution further contains 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-bake 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-bake 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-bake 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-bake thickness of less than 20 μm.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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 at 3 preselected temperatures for 3 preselected time intervals, where 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, where 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, where 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, where 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, where 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, where 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, where 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, where 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 are 2 minutes.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the improved thermal conversion process, one or more of the preselected time intervals are 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 a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits properties that are satisfactory for use in 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, 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 a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits properties that are satisfactory for use in 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 a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits properties that are satisfactory for use in electronic applications such as those disclosed herein.

5. Electronic device

The polyimide films disclosed herein can be suitable for use in a variety of layers in electronic display devices, such as OLED and LCD displays. Non-limiting examples of such layers include device substrates, touch panels, substrates for optical filters, cover films, and the like. The specific material property requirements 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 a repeating unit of formula III as described in detail above.

Organic electronic devices that may benefit from having one or more layers that include at least one compound as described herein include, but are not limited to: (1) a device that converts electrical energy to radiation (e.g., a light emitting diode display, a lighting device, a light source, or a diode laser), (2) a device that detects signals by electronic means (e.g., a photodetector, a photoconductive cell, a photoresistor, a photorelay, a phototransistor, a phototube, an IR detector, a biosensor), (3) a device that converts radiation to electrical energy (e.g., a photovoltaic device or a solar cell), (4) a device that converts light of one wavelength to light of a longer wavelength (e.g., a down-conversion phosphor device); and (5) devices that include one or more electronic components that include one or more organic semiconductor layers (e.g., transistors or diodes). Other uses of the composition according to the present invention include coating materials for memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolytic capacitors, energy storage devices (such as rechargeable batteries), and electromagnetic shielding 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 that can serve as flexible substitutes for glass are included in electronic devices. Fig. 2 illustrates the case when the electronic device 200 is an organic electronic device. The device 200 has a substrate 100, an anode layer 110 and a second electrical contact layer, a cathode layer 130, and a photoactive layer 120 therebetween. Additional layers may optionally be present. Adjacent 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 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 or hole transport layers (not shown) proximate to anode 110 and/or one or more additional electron injection 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 film disclosed herein.

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

In some embodiments, the different layers have the following thickness ranges: substrate 100, 5-100 microns, anode 110,

in some embodiments of the present invention, the,

a hole injection layer (not shown),

in some embodiments of the present invention, the,

a hole-transporting layer (not shown),

in some embodiments of the present invention, the,

the photoactive layer (120) is disposed on the substrate,

in some embodiments of the present invention, the,

an electron transport layer (not shown),

in some embodiments of the present invention, the,

the cathode(s) 130 are provided,

in some embodiments of the present invention, the,

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.

The anode 110 is an electrode that is particularly effective for injecting positive charge carriers. It may be made of, for example, a material containing a metal, mixed metal, alloy, metal oxide or 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 to 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-emitting diodes made of soluble conductive polymers", Nature [ Nature ], volume 357, page 477-479 (11.6.1992). At least one of the anode and cathode should be at least partially transparent to allow the light generated 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 underlying layers, charge transport and/or charge injection properties, 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 injection material may be a polymer, oligomer, or small molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

The hole injection layer may be formed from a polymeric material, such as Polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), which are typically doped with a protic acid. The protonic acid may be, for example, poly (styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid), or the like. The hole injection layer 120 may include a charge transfer compound, etc., such as copper phthalocyanine and tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In some embodiments, the 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, 2004-0127637 and 2005-0205860.

Other layers may include hole transport materials. Examples of hole transport materials for hole transport layers are outlined in, for example, Kirk-Othmer Encyclopedia of Chemical Technology, Kock. Oas Encyclopedia of Chemical engineering, fourth edition, Vol.18, p.837-. Both hole transporting small molecules and polymers can 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-diphenylaminostyrene (TPS); p- (diethylamino) benzaldehyde Diphenylhydrazone (DEH); triphenylamine (TPA); bis [4- (N, N-diethylamino) -2-methylphenyl ] (4-methylphenyl) methane (MPMP); 1-phenyl-3- [ p- (diethylamino) styryl ] -5- [ p- (diethylamino) phenyl ] 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 transport polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl) polysilane, poly (dioxythiophene), polyaniline, and polypyrrole. It is also possible to obtain hole-transporting polymers by incorporating hole-transporting molecules such as those described above into polymers such as polystyrene and polycarbonate. In some cases, triarylamine polymers, especially triarylamine-fluorene copolymers, are used. In some cases, the polymers and copolymers are crosslinkable. Examples of crosslinkable hole-transporting polymers can be 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 tetrafluorotetracyanoquinodimethane and perylene-3, 4,9, 10-tetracarboxyl-3, 4,9, 10-dianhydride.

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

In some embodiments, the photoactive layer comprises a compound comprising an emissive compound that is a photoactive material. In some embodiments, the photoactive layer further comprises a host material. Examples of host materials include, but are not limited to

Phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, carbazole, indolocarbazole, furan, benzofuran, dibenzofuran, benzodifuran, 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 includes only (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, wherein there are no additional materials that would substantially alter the operating principle or distinguishing characteristics of the layer.

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

In some embodiments, the weight ratio of the first host to the second host in the photoactive layer is in the range of 10:1 to 1: 10. In some embodiments, the weight ratio is between 6:1 and 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-emitting dopant, (b) a first host compound, and (c) a second host compound.

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

The optional layer may simultaneously serve to facilitate electron transport and also serve as a confinement layer to prevent quenching of excitons at layer interfaces. Preferably, this layer promotes electron mobility and reduces exciton quenching.

In some embodiments, such layers include other electron transport materials. Examples of electron transport materials that may be used in the optional electron transport layer include metal chelated oxinoid (oxinoid) compounds, including metal quinolinate derivatives such as tris (8-hydroxyquinolinato) aluminum (AlQ), bis (2-methyl-8-hydroxyquinolinato) (p-phenylphenolato) aluminum (BAlq), tetrakis- (8-hydroxyquinolinato) hafnium (HfQ), and tetrakis- (8-hydroxyquinolinato) zirconium (ZrQ); and azole compounds such as 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ), and 1,3, 5-tris (phenyl-2-benzimidazole) benzene (TPBI); quinoxaline derivatives, e.g. 2, 3-bis (4-fluoro)Phenyl) quinoxaline; phenanthrolines, such as 4, 7-diphenyl-1, 10-phenanthroline (DPA) and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (DDPA); a 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 2 metal salts, e.g. LiF, CsF and Cs₂CO₃(ii) a Group 1 and group 2 metal organic compounds, such as lithium quinolinate; and molecular n-type dopants, e.g. leuco dyes, metal complexes, e.g. W₂(hpp)₄(wherein hpp ═ 1,3,4,6,7, 8-hexahydro-2H-pyrimido- [1, 2-a)]-pyrimidines) and cobaltocenes, tetrathiatetracenes, bis (ethylenedithio) tetrathiafulvalenes, heterocyclic or divalent radicals, and dimers, oligomers, polymers, dispiro compounds and polycyclics of the heterocyclic or divalent radicals.

An optional electron injection layer may be deposited on the electron transport layer. Examples of electron injecting materials include, but are not limited to, Li-containing organometallic compounds, LiF, Li₂O, lithium quinolinate; organometallic compounds containing Cs, CsF, Cs₂O and Cs₂CO₃. 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 generally at

In some embodiments

The 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 material for the cathode may be selected from group 1 alkali metals (e.g., Li, Cs), group 2 (alkaline earth) metals, group 12 metals, including rare earths and lanthanides, and actinides. Materials such as aluminum, indium, calcium, barium, samarium, and magnesium, and combinations may be used.

It is known to have other layers in organic electronic devices. For example, multiple layers (not shown) may be present between the anode 110 and the hole injection layer (not shown) to control the amount of positive charge injected and/or to provide band gap matching of the layers, or to serve as a protective layer. Layers known in the art, such as ultra-thin layers of copper phthalocyanine, silicon oxynitride, fluorocarbons, silanes, 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 layer 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 layers may be applied from solutions or dispersions in suitable solvents 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 non-aqueous solvent. Such non-aqueous solvents may be relatively polar, e.g. C₁To C₂₀Alcohols, ethers and acid esters, or may be relatively non-polar, e.g. C₁To C₁₂Alkane or aromatic compounds such as toluene, xylene, trifluorotoluene, etc. Other suitable liquids (as solutions or dispersions as described herein) for making liquid compositions comprising the novel compounds include, but are not limited to, chlorinated hydrocarbons (e.g., dichloromethane, chloroform, chlorobenzene), aromatic hydrocarbons (e.g., substituted and unsubstituted toluene and xylenes, including trifluorotoluene) Polar solvents (such as Tetrahydrofuran (THP), N-methylpyrrolidone), esters (such as ethyl acetate), alcohols (isopropanol), 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 made by liquid phase deposition of a hole injection layer, a hole transport layer, and a photoactive layer, and vapor deposition of an anode, an electron transport layer, an electron injection layer, and a cathode onto a flexible substrate.

It will 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 may be used. Shaped substrates and novel hole transport materials that result in a reduction in operating voltage or increase in quantum efficiency are also applicable. Additional layers may also be added to tailor the energy levels of the various layers and to facilitate electroluminescence.

In some embodiments, the device has the following structure in order: the light-emitting diode comprises a substrate, an anode, a hole injection layer, a hole transport layer, a light active 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 of the invention

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

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

BPDA (3,3', 4,4' -Biphenyltetracarboxylic dianhydride)

4,4 '-DDS ═ 4,4' -diaminodiphenyl sulfone

6FDA ═ 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 ] xanthene-1, 3,7,9(11H) -tetraone,

synthesis examples

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']dipyrrole-1, 3,5,7(2H,6H) -tetrone (2).

A mixture of 2,2' -bis (trifluoromethyl) benzidine (171.4g, 535.3mmol, 4 equiv.), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (5g), pyridine (50ml) and N-methylpyrrolidone (200ml) was heated at 130 ℃ under nitrogen for 1 hour. Thereafter, the remaining amount of 1,2,4, 5-cyclohexanetetracarboxylic 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 the excess 2,2' -bis (trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). Combining the fractions containing the diimide-diamine, evaporating the eluent and dissolving the residue in ethyl acetate and hexane 1:1To the mixture, 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 way, a mixture of 2,2' -bis (trifluoromethyl) benzidine (171.4g, 535.3mmol, 4 equiv.), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (5g), pyridine (50ml) and N-methylpyrrolidone (200ml) was heated at 130 ℃ under a nitrogen atmosphere for 1 hour. Thereafter, an additional amount of 1,2,4, 5-cyclohexanetetracarboxylic dianhydride was 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 give 33.36g of the product. The product may additionally be recrystallized from propyl acetate.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-d₆470MHz) 57.4, 57.1. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry ("MALDI TOF MS"): 829.1671(MH +).

Synthesis example 2

2, 6-bis (2,2' -bis (trifluoromethyl) -4' -amino-1, 1' -biphenyl-4-yl) -hexahydro-4, 8-ethyl-bridged benzene And [1,2-c:4,5-c']Dipyrrole-1, 3,5,7(2H,6H) -tetrone (4).

The method A comprises the following steps:

to a stirred solution of 2,2' -bis (trifluoromethyl) benzidine (76.86g, 240mmol, 4 equiv.) in pyridine (30ml) and N-methylpyrrolidone (150ml) under nitrogen atmosphere was added portionwise a 50ml suspension of bicyclo [2.2.2] octane-2, 3:5, 6-tetracarboxylic dianhydride ("bicyclooctanetetracarboxylic dianhydride") (15g, 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 the excess 2,2' -bis (trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent was evaporated and dried in vacuo to give 21.23g of compound 4.

The method B comprises the following steps:

a mixture of 2,2' -bis (trifluoromethyl) benzidine (51.2g, 4 equivalents) and bicyclo [2.2.2] octane-2, 3:5, 6-tetracarboxylic dianhydride (10g, 39.97mmol) was heated at 220 ℃ for 2 hours under an inert atmosphere. The mixture was cooled to ambient temperature, dissolved in ethyl acetate, adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of propyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent 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-ethenylene Benzo [1,2-c:4,5-c']Dipyrrole-1, 3,5,7(2H,6H) -tetraone (5).

To a stirred solution of 2,2' -bis (trifluoromethyl) benzidine (77.43g, 241.8mmol, 4 equiv.) in pyridine (30ml) and N-methylpyrrolidone (150ml) under nitrogen was added a suspension of bicyclooctane tetracarboxylic dianhydride (15g, 60.45mmol) in 50ml N-methylpyrrolidone in portions. 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 the excess 2,2' -bis (trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent was evaporated and dried in vacuo to give 21.23g of 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-ethenylbenzo [1,2-c:4,5-c'] Dipyrrole-1, 3,5,7(2H,6H) -tetrone](7).

2,2' -bis (trifluoromethyl) benzidine (77.43g, 241.8mmol, 2 equiv.), pyridine (20ml), N-methylpyrrolidone (100ml) and bicycloA mixture of octanetetracarboxylic dianhydride (15g, 60.45mmol) was stirred under nitrogen at 180 ℃ for 6 days under heating. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, the residue was absorbed onto celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent was evaporated and dried in vacuo to give 14.8g of compound 5. The fractions containing the tetraamide-diamine were combined, the eluent evaporated and dried in vacuo to give 8.75g of compound 7. Compound 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,4,4a,7a,8,8a,8 b-octahydro-9- (1, 1-dimethylethyl) -4, 8-ethenylidenefuro [3', 4':3,4]cyclobutanes [1,2-f ]]Isobenzofuran-1, 3,5, 7-tetraone.

Maleic anhydride (37.4g, 0.38mol) and acetophenone (22.9g, 0.191mol) were dissolved in tert-butylbenzene (ca. 0.8L), placed in a 1L photochemical reactor, and the wells were impregnated with borosilicate glass and irradiated with a 200W medium pressure Heluowei mercury lamp (Hanovia mercury lamp). The precipitate was collected by filtration. Yield of crude product after 42 hours of irradiation-33.3 g. The product can be recrystallized from hot acetone.¹H-NMR (acetone-d)₆,500MHz):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 the control experiment, it was found that t-butyl tricyclodecatriene 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 Yl) -3a,3b,4,4a,7a,8,8a,8 b-octahydro-4, 8-ethenopyrrolo [3',4':3,4]Cyclobutanes [1,2-f ]]Isoindole derivatives Indole-1, 3,5,7(2H,6H) -tetrone (6).

To a stirred solution of 2,2' -bis (trifluoromethyl) benzidine (19.4g, 60.55mmol, 4 equiv.) in pyridine (10ml) and N-methylpyrrolidone (80ml) was added dropwise a solution of tert-butyltricyclodecatriene tetracarboxylic dianhydride (5g, 15.14mmol)) in N-methylpyrrolidone (50ml) under a nitrogen atmosphere at 100 ℃ over 6 hours. 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 absorbed onto 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 eluent was evaporated and the residue was dried in vacuo to give 8.7g of 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 examples6

3a,3b,4,4a,7a,8,8a,8 b-octahydro-9-methyl-4, 8-ethenylidenefuro [3',4':3,4]Ring D [1,2-f]Isobenzofuran-1, 3,5, 7-tetraone.

Maleic anhydride (37.4g, 0.38mol) and acetophenone (22.9g, 0.191mol) were dissolved in toluene (ca. 0.8L), placed in a 1L photochemical reactor and irradiated with a 200W medium pressure Enoky mercury lamp. The precipitate was collected by filtration. The yield of the crude product after 28.5 hours of irradiation was-24 g, as a mixture of 9-methyl and 3-methyl regioisomers. The product can be recrystallized from hot acetone. Data for the 9-methyl regioisomer:¹H-NMR (acetone-d)₆,500MHz):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-d)₆,125MHz):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 the control experiment, it was found that methyltricyclooctadecene 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 Yl) -3a,3b,4,4a,7a,8,8a,8 b-octahydro-4, 8-ethenopyrrolo [3',4':3,4]Cyclobutanes [1,2-f ]]Isoindole derivatives Indole-1, 3,5,7(2H,6H) -tetrone (6a).

A mixture of 2,2' -bis (trifluoromethyl) benzidine (66.66g, 208.15mmol, 4 equiv.), methyltricyclotetraenoic dianhydride (2.5g, a mixture of 1:0.2 ratio of the 9-methyl and 3-methyl regioisomers), pyridine (20ml) and N-methylpyrrolidone (100ml) was heated at 150 ℃ for 1 hour under a nitrogen atmosphere. Thereafter, an additional amount of methyltricyclodecanetetracarboxylic dianhydride was added at 130 ℃ in 2.5g portions (15g total) over a period of 5 hours. Thereafter, the mixture was heated at 180 ℃ for 6 days. Will be mixed withThe 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 the excess 2,2' -bis (trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of propyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent was evaporated and dried in vacuo to give 20.1g of compound 6 a. Data for the 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']dipyrrole-1, 3,5,7(2H,6H) -tetraone (8)A mixture of 2,2' -bis (trifluoromethyl) benzidine (153g, 477.8mmol), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (5g), pyridine (20ml) and N-methylpyrrolidone (150ml) was heated at 150 ℃ for 1 hour under a nitrogen atmosphere. Thereafter, the remaining amount of 1,2,3, 4-cyclohexanetetracarboxylic 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. Cooling the mixture to ambient temperature using rotationThe solvent was distilled off by an evaporator and the residue was extracted several times with a hot mixture of 20% ethyl acetate and heptane to recover the excess 2,2' -bis (trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of ethyl acetate and hexane) (2 times). The fractions containing the diimide-diamine were combined, the eluent was evaporated and dried in vacuo to give 3g of 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 (132.6g, 414.08mmol), 3a,4,5,9 b-tetrahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c ] furan-1, 3-dione (5g), pyridine (20ml) and N-methylpyrrolidone (150ml) was heated at 150 ℃ under a 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 the excess 2,2' -bis (trifluoromethyl) benzidine. The residue was adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of propyl acetate and hexane). The fractions containing the diimide-diamine were combined, the eluent was evaporated and dried in vacuo to give a total of 34.1g of compound 9.

Synthesis example 9

5,5 '-oxybis [2,2' -bis (trifluoromethyl) -4 '-amino-1, 1' -biphenyl-4-yl]-1H-isoindole-1, 3 (2H) -diketone (10) and compound 11.A mixture of 2,2' -bis (trifluoromethyl) benzidine (61.94g, 6 equivalents) and oxydiphthalic dianhydride (10g, 32.24mmol) was heated at 220 ℃ for 1 hour under an inert atmosphere. Thereafter, the excess diamine is sublimed under vacuum at 260 ℃ to 265 ℃. The residue is dissolved in 150ml of ethyl acetate, adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing pure trimer were combined, the eluent evaporated using a rotary evaporator and the residue dried in a glovebox under vacuum at 150 ℃ for 1 hour to give 16.13g of product 10. Fractions containing a little impure trimer were combined, the eluent 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 eluent evaporated and the residue dried under vacuum at 150 ℃ to give 2.24g of compound 11.

Compound 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。

compound 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-phenylenebis (oxy-3, 1-phenylene) yl]-1H-isoindole-1, 3(2H) -dione (12)。A mixture of 1, 3-bis (3-aminophenoxy) benzene (56.55g, 193.44mmol, 6 equivalents) and oxydiphthalic dianhydride (10g, 32.24mmol) was heated at 220 ℃ under an inert atmosphere for 1 hour and then at 265 ℃ under vacuum. The residue was dissolved in 150ml of ethyl acetate, adsorbed on celite and purified by partial chromatography on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing pure trimer were combined, the eluent evaporated using a rotary evaporator and the residue dried in a glovebox under vacuum at 150 ℃ for 1 hour. Compound 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, 3' -pentaoxydiro [4, 7-methano-5H-isoindole-5, 1' -cyclopentane-3 ',5 ″)”-[4,7]Bridged methylene [5H ]]Isoindole derivatives Indole (A)(13) A mixture of 2,2' -bis (trifluoromethyl) benzidine (41.66g, 130.08mmol, 10 equivalents) and the corresponding spiro dianhydride (5g, 13.01mmol) was reacted at 220 ℃ under an inert atmosphereThe mixture was heated for 1.5 hours. The residue was dissolved in ethyl acetate, adsorbed on celite and chromatographed on silica gel (gradient elution with hexane and a mixture of ethyl acetate and hexane-propyl acetate). The fractions containing pure product were combined, the eluent was evaporated using a rotary evaporator and the residue was dried in a glove box under vacuum at 150 ℃ for 1 hour to give 8.59g of 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' -bi-1H-isoindole Indole (A)]-1,1',3,3' (2H,2' H) -tetrone(14) A mixture of 2,2' -bis (trifluoromethyl) benzidine (113.7g, 355.1mmol, 6.3 equivalents) and biphenyltetracarboxylic dianhydride (16.58g, 56.35mmol) with a small amount of N-methylpyrrolidone was heated at 220 ℃ for 1 hour under an inert atmosphere and then at the same temperature for 3 hours in vacuo. The mixture was cooled, dissolved in ethyl acetate, adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing the pure product were combined, the eluent was evaporated to a volume of 200ml using a rotary evaporator, and the crystalline product was collected by filtration to give 17.57g of compound 14. The fractions containing the less pure product are combined, the eluent is evaporated,the residue was dissolved in ethyl acetate, then one volume of hexane was added and allowed to stand at ambient temperature for slow crystallization. The precipitated product containing 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' -binaphthyl- 1H-isoindoles]-1,1',3,3' (2H,2' H) -tetrone(15) A mixture of 2,2' -bis (trifluoromethyl) benzidine (52.27g, 163.24mmol, 10 equivalents), dicyclohexyl-3, 4, 3',4' -tetracarboxylic dianhydride (5g, 16.32mmol) and N-methylpyrrolidone (5ml) was heated at 220 ℃ under an inert atmosphere for 1 hour and then at the same temperature under vacuum for 1 hour. The mixture was cooled, dissolved in ethyl acetate, adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing pure product were combined, the eluent 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

11-methyl-2, 8-bis (2,2' -bis (trifluoromethyl) -4' -amino-1, 1' -biphenyl-4-yl) -11- (trifluoromethyl) Aryl) -1H-pyrano [2,3-f:5,6-f']Diisoindole-1, 3,7,9(2H,8H,11H) -tetrones(16) A mixture of 2,2' -bis (trifluoromethyl) benzidine (51g, 159.26mmol, 10 equivalents), the corresponding xanthene tetracarboxylic dianhydride (10.2g, 25.23mmol) and N-methylpyrrolidone (25ml) was heated at 220 ℃ for 1 hour under an inert atmosphere and then at the same temperature for 1 hour under vacuum. The mixture was diluted with ethyl acetate, adsorbed on celite and chromatographed on silica gel (gradient elution with a mixture of hexane and ethyl acetate). The fractions containing pure product were combined, the eluent 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 group]Phenyl radical]-benzo [1,2-c:4,5-c']Dipyrrole-1, 3,5,7 (2H,6H) -tetrones(17) Reacting 4,4' -sulfonyl bis [ aniline](56.92g, 229.2mmol, 5 equiv.), pyromellitic dianhydride (10g, 45.84mmol) and N-methylpyrrolidone (100ml) were heated under nitrogen at 177 ℃ for 1.5 hours with stirring. The reaction mixture was cooled, diluted with ethyl acetate (200ml), filtered, washed with ethyl acetate and dried in vacuo to give 26g of crude product containing about 10% of higher oligomeric product used 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 (0.07mol) 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 (0.06mol) of 6FDA were slowly added in portions to the stirred diamine solution. After the dianhydride addition was complete, any residual dianhydride powder from the vessel and flask walls was washed with an additional 27.86g of NMP and the resulting mixture was stirred at room temperature overnight. Then, 80mL of m-xylene was added to the mixture and refluxed for 8 hours to remove water with a dean-Stark trap. The mixture was cooled to room temperature and then precipitated into 1,500mL of methanol with stirring, the resulting suspension was filtered, and the collected solid was dried in vacuo.

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

Synthesis example 17

6,6' - (Sulfonylbis-4, 1-phenylene) bis-1H-furo [3, 4-f)]Isoindole-1, 3,5,7(6H) -tetrones(33) Synthesis of pyromellitic monoanhydride. To a stirred solution of pyromellitic dianhydride (43.6g, 0.2mol) in 400ml of THF was added a mixture of 30ml of tetrahydrofuran and 5ml of water at ambient temperature over a period of 48 hours. Thereafter, 250ml of tetrahydrofuran was evaporated using a rotary evaporator, and the resulting solution was treated with hexane (100ml) until precipitation occurred. The precipitate was removed by filtration. The filtrate was held 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.¹H-NMR (acetone-d)₆,500MHz):6.39(s 2H),12.46(br.s,2H)。

The pyromellitic monoanhydride (28.16g, 119.26mmol, 2.3 equivalents) was reacted with 4,4' -sulfonylbis [ aniline ]](12.97g, 52.2mmol) was stirred in 200ml of anhydrous tetrahydrofuran at ambient temperature for 1 hour. The mixture was diluted with acetone (100ml), passed through a column packed with silica gel, and washed with acetone. The product containing fractions were combined, the solvent evaporated using a rotary evaporator, the residue treated with approximately 500ml water, the fine precipitate filtered, washed with water and dried in vacuo to give the amide hexa acid (31.1 g):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 hexaamic acid (31.1g) was stirred under heating under nitrogen in acetic anhydride (300ml) under reflux for 2 hours. The hot reaction mixture was filtered, washed with 50ml acetic anhydride, dichloromethane (50ml), suspended in 150ml chloroform, filtered and dried in vacuo to give 20.9g of compound 33:¹H-NMR(DMSO-d₆,500MHz):7.81(d,4H,J＝9Hz),8.23(d,4H,J＝9Hz),8.57(s,4H)。

examples of polymers

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

Polymer example 1

Polymer 1 polymerization of compound 6 with BPDA:

imide-diamine monomer 6(5.23g, 5.60mmol), BPDA (1.616g, 5.488mmol) and N-methylpyrrolidinone (38ml) were added to a 250ml glass reactor and the mixture stirred at ambient temperature under nitrogen atmosphere until the final viscosity of the polyamic acid was 7283 cP. GPC: mn is 73713, Mw is 139448, Mp is 121967, Mz is 222437, and PDI is 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:

diimide-diamine monomer 2(2g, 2.41mmol) (obtained by direct crystallization from the crude reaction mixture and recrystallization from propyl acetate), BPDA (0.689g, 2.34mmol) and N-methylpyrrolidinone (15.2g) were mixed using a roller and allowed to react at ambient temperature until the final viscosity of polyamic acid was 11620 cP. GPC: mn is 127781, Mw is 300128, Mp is 258512, Mz is 496954, and PDI is 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(6.70g, 7.84mmol), BPDA (2.237g, 7.60mmol) and N-methylpyrrolidinone (50ml) were added to a 250ml glass reactor, the mixture was stirred at ambient temperature under nitrogen atmosphere, and then the final PMDA (39mg) was added until the final viscosity of the polyamic acid was 7890 cP. GPC: mn is 88795, Mw is 175396, Mp is 168430, Mz is 282955, and PDI is 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(6.71g, 7.87mmol), BPDA (2.246g, 7.63mmol) and N-methylpyrrolidinone (50ml) were added to a 250ml glass reactor, the mixture stirred at ambient temperature under nitrogen atmosphere, then final PMDA (39mg) was added until the final viscosity of the polyamic acid was 6033 cP. GPC: mn is 93567, Mw is 184524, Mp is 178922, Mz is 297891, and PDI is 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(3g, 3.316mmol), BPDA (0.956g, 3.25mmol) and N-methylpyrrolidinone (22.6g) were mixed using a roller under an inert atmosphere and allowed to react at ambient temperature, then PMDA (7mg) was added until the final viscosity of the polyamic acid was 3135 cP. GPC: mn is 106690, Mw is 240045, Mp is 210783, Mz is 420038, and PDI is 2.25.

Polymer example 6

Polymer 6 polymerization of Compound 8 with BPDA

Imide-diamine monomer 8(2.572g, 3.157mmol), BPDA (0.91g, 3.093mmol) and N-methylpyrrolidinone (19.8g) were mixed using a roller under an inert atmosphere and allowed to react at ambient temperature, then PMDA (10mg) was added until the final viscosity of the polyamic acid was 7779 cP. GPC: mn is 92903, Mw is 175925, Mp is 165061, Mz is 278182, and PDI is 1.89.

Polymer example 7

Polymer 7 polymerization of Compounds 11 and 12 with oxydiphthalic anhydride

Imide-diamine monomer 11(1.799g, 1.192mmol), imide monomer 12(0.171g, 0.199mmol), oxydiphthalic anhydride (0.42g, 1.354mmol), and N-methylpyrrolidinone (13.6g) were mixed under an inert atmosphere using a roller and allowed to react at ambient temperature, then oxydiphthalic anhydride (10mg) was added. GPC: mn 52301, Mw 124710, Mp 109452, Mz 205698, and PDI 2.38.

Polymer example 8

Polymer 8 polymerization of Compound 15 with BPDA

Imide-diamine monomer 15(8.5g, 9.33mmol), BPDA (2.73g, 9.29mmol) and N-methylpyrrolidinone (63.6g) were added to a 250ml glass reactor and the mixture stirred at ambient temperature under nitrogen atmosphere until the final viscosity of the polyamic acid was 4339 cP. GPC: mn 104310, Mw 234898, Mp 222275, Mz 378468, and 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 (0.0108mol), 6.51g of Compound 9(0.0072mol) 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 (0.009mol) XFDA were slowly added in portions to the stirred diamine solution, followed by 3.76g (0.00846mol)6 FDA. After dianhydride addition was complete, and an additional 9.84g of NMP was used to wash any remaining dianhydride powder from the walls of the vessel and reaction flask. And the resulting mixture was stirred for 6 days. Separately, a 5% solution of 6FDA in NMP was prepared and added in small amounts (about 0.8g) over time to increase the molecular weight of the polymer and the viscosity of the polymer solution. The solution viscosity was monitored using a Bohler fly (Brookfield) cone and plate viscometer 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 overnight with gentle stirring to allow the polymer to equilibrate. The final viscosity of the polymer solution was 1,100cp at 25 ℃.

Polymer examples 10 to 14

Polymers 10-14 were prepared using a procedure similar to 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 (11.902g, 37.17mmol), bicyclo [2.2.2] octane-2, 3:5, 6-tetracarboxylic dianhydride (6.51g, 26.02mmol) and 20ml N-methylpyrrolidone was heated with a Dean Stark apparatus (Dean Stark apparatus) under an inert atmosphere at 180 ℃ for 2.5 hours. Thereafter, the N-methylpyrrolidone was distilled in vacuo. NMR spectroscopic data of the resulting glassy residue showed complete imidization. The solid was redissolved in N-methylpyrrolidone at 150 ℃, transferred to a glass reactor and stirred with 3,3',4,4' -biphenyltetracarboxylic dianhydride BPDA (1.094g, 3.717mmol), 4,4' -hexafluoroisopropylidene bisphthalic dianhydride 6FDA (2.808g, 6.32mmol) under nitrogen atmosphere at ambient temperature with a total of 129g of N-methylpyrrolidone. An additional amount of 6FDA (480 m g total, 1.08mmol) was then added until the final viscosity was 10430 cP. GPC: 88006, 205641, Mp 201618, 335818, and PDI 2.34.

Polymer example 16

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

2,2 '-bis (trifluoromethyl) benzidine (5.95g, 18.58mmol), norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride CpODA (5.0g, 13.08mmol) and 6ml N-methylpyrrolidone were heated with a dean-Stark apparatus under an inert atmosphere at 180 ℃ for 3 hours, then 6ml N-methylpyrrolidone was added and the mixture was heated for an additional 3 hours. Thereafter, the N-methylpyrrolidone was distilled in vacuo. The solid was redissolved in N-methylpyrrolidone (71g), transferred to a glass reactor and stirred at ambient temperature under nitrogen atmosphere with 3,3',4,4' -biphenyltetracarboxylic dianhydride BPDA (1.53g, 5.20mmol), then pyromellitic dianhydride PMDA (62mg) was added until the final viscosity was 22860 cP. GPC: mn 80956, Mw 188020, Mp 169907, Mz 313930, and 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 PMDA was used instead of 6 FDA.

Polymer example 18

Polymer 18:

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

Examples of membranes

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

B and yellowness index and% transmission (% T) were measured in the wavelength range 350nm-780nm using a Hunter Lab spectrophotometer. Thermal measurements of the film were made using a combination of thermogravimetric and thermomechanical analyses as appropriate to the specific parameters reported herein. Mechanical properties were measured using equipment from Instron (Instron).

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 onto a clean silicon wafer, soft baked on a hot plate at 90 ℃ and placed in an oven. The furnace was purged with nitrogen and heated in stages to the maximum curing temperature. The wafer was removed from the oven, soaked in water and hand layered 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	Polymer and method of making same	Curing temperature of 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 measured in degrees Celsius; CTE is measured in ppm/deg.C on a second scan; Δ η is the birefringence at 633 nm; td is the temperature in degrees celsius at which 1% weight loss occurs; t.m. tensile modulus in GPa; t.s. tensile strength in MPa; elong is the elongation at break in%.

As can be seen from the above examples, the use of pre-imidized monomers allows the use of conventional polymerization techniques to obtain high molecular weight polymers.

As can be seen from table 3, the polyimide film obtained from the pre-imidized imide-containing monomer has beneficial properties such as reduced coloration b/yellowness index YI, increased thermal stability Td (1%), improved mechanical properties and other properties.

Film examples 8-13

The foregoing polyamic acids were used to prepare polyimide films having 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	Polymer and method of making same	Curing temperature of 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 measured in degrees Celsius; CTE is measured in ppm/deg.C on a second scan; td is the temperature in degrees celsius at which 1% weight loss occurs; t.m. tensile modulus in GPa; t.s. 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	Polymer and method of making same	Curing temperature of 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 measured in degrees Celsius; CTE is measured in ppm/deg.C on a second scan; Δ η is the birefringence at 633 nm; td is the temperature in degrees celsius at which 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. Further, the order of activities listed are not necessarily the order in which they are performed.

In the foregoing specification, the 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. Accordingly, the specification and figures are 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 are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. The use of numerical values in the various ranges specified herein is stated to be approximate as if both the minimum and maximum values in the ranges were preceded by the word "about". In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Moreover, the disclosure of these ranges is intended as a continuous range including every value between the minimum and maximum average values, including fractional values that may result when some components of one value are mixed with components of a different value. Further, when broader and narrower ranges are disclosed, it is within the contemplation of the invention to match the minimum values from one range with the maximum values from the other range, and vice versa.

Claims

1. Diamine with formula I

Wherein:

R^arepresents a tetracarboxylic acid component residue;

R^brepresents a diamine residue; and is

m is an integer from 1 to 20.

2. The diamine of claim 1, wherein R^aRepresents a residue of an aliphatic tetracarboxylic dianhydride or a polycyclic tetracarboxylic dianhydride.

3. The diamine of claim 1, wherein R^aSelected from the group consisting of: formulae A1 to A36

Wherein:

R¹is the same or different at each occurrence and is selected from the group consisting of: alkyl, fluoroalkyl and silyl, where adjacent R¹Radical (I)May be linked together to form a double bond;

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 0-2;

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 is

Denotes the attachment point.

4. The diamine of claim 1, selected from the group consisting of: compound 1 to compound 24

Compound 1

Compound 2

Compound 3

Compound 4

Compound 5

Compound 6

Compound 6a

Compound 7

Compound 8

Compound 9

Compound 10

Compound 11

Compound 12

Compound 13

Compound 14

Compound 15

Compound 16

Compound 17

Compound 18

Compound 19

Compound 20

Compound 21

Compound 22

Compound 23

Compound 24

5. An acid dianhydride of formula IV

Wherein:

R^drepresents a tetracarboxylic acid component residue;

R^erepresents a diamine residue; and is

m is an integer from 1 to 20.

6. The dianhydride of claim 5, wherein R^eRepresents the residue of a fluorinated aromatic diamine.

7. The dianhydride of claim 5, wherein R^eSelected from the group consisting of: formulae E1 to E16

(E13)

(E14)

(E15)

(E16)

Wherein:

R_fis C_1-3A perfluoroalkyl group;

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 0-2;

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 is

Denotes the attachment point.

8. The dianhydride according to claim 5, selected from the group consisting of: compound 25 to compound 38

Compound 25

Compound 26

Compound 27

Compound 28

Compound 29

Compound 30

Compound 31

Compound 32

Compound 33

Compound 34

Compound 35

Compound 36

Compound 37

Compound 38

9. A polyamic acid composition that is the reaction product of one or more tetracarboxylic acid components and one or more diamines, wherein either (a) the diamines comprise 1-100 mol% of the diamine of formula I as recited in claim 1, or (b) the tetracarboxylic acid components comprise 1-100 mol% of the tetracarboxylic dianhydride of formula IV as recited in claim 5.

10. A polyimide produced by imidization of the polyamic acid according to claim 9.