KR20200144150A - Polymers for use in electronic devices - Google Patents

Abstract

를 갖는 산 이무수물이 개시된다. 화학식 IV에서, R^d는 테트라카르복실산 성분 잔기를 나타내고; R^e는 디아민 잔기를 나타내고; m은 1 내지 20의 정수이다.Formula IV:
[Formula IV]

An acid dianhydride is disclosed. In formula IV, R ^d represents a tetracarboxylic acid component moiety; R ^e represents a diamine moiety; m is an integer from 1 to 20.

Description

Polymers for use in electronic devices

Claim of profit on prior application

This application claims the benefit of U.S. Provisional Application No. 62/672,272, filed May 16, 2018, which U.S. Provisional Application is incorporated herein by reference in its entirety.

Technical field

The present invention relates to novel polymeric compounds. The invention also relates to a method for producing such a polymer compound, and to an electronic device having at least one layer comprising such a material.

Materials for use in electronic device applications often have stringent requirements in terms of their structural properties, optical properties, thermal properties, electronic properties and other properties. As the number of commercial electronics applications continues to increase, innovative materials with new and/or improved properties in the breadth and specificity of essential properties are required. Polyimides represent a class of polymer compounds that have been widely used in a variety of electronics applications. Polyimide can serve as a flexible glass substitute in electronic display devices if it has appropriate properties. Such a material can function as a component of a liquid crystal display ("LCD") where moderate power consumption, light weight, and layer flatness are important properties for efficient use. Other uses in electronic display devices that value these parameters include device substrates, substrates for color filter sheets, cover films, touch screen panels, and the like.

Many of these components are also important for the construction and operation of organic electronic devices with organic light-emitting diodes ("OLEDs"). OLEDs are promising for many display applications because they have high power conversion efficiency and can be applied to a wide range of end uses. The use of OLEDs in mobile phones, tablet devices, portable/notebook computers, and other commercial products is increasing. In addition to low power consumption, these applications require displays that can hold a lot of information, are full color, and have a fast video rate response time.

Polyimide films generally have sufficient thermal stability, high glass transition temperatures, and mechanical toughness to contemplate these applications. In addition, since polyimide generally does not generate haze when bending is repeated, it is often preferred over other transparent substrates such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) in flexible display applications.

However, the conventional amber polyimide cannot be used in some display applications such as color filters and touch screen panels where light transmission is important. In addition, polyimides are generally rigid, highly aromatic materials, and when the film/coating is being formed, the polymer chains tend to be oriented on the side of the film/coating. This causes a difference in refractive index (birefringence) between the parallel direction and the vertical direction of the film, resulting in an optical phase delay that may negatively affect display performance. To find further applications of polyimide in the display market, there is a need for solutions to improve light transmittance and reduce amber and birefringence (causing optical phase delay) while maintaining the desired properties of polyimide.

Therefore, there is a continuing need for low-chrominance materials suitable for use in electronic devices.

Imide-containing monomers for polyimides are provided.

Also provided are diamines having the formula (I):

[Formula I]

here,

R ^a represents a tetracarboxylic acid component residue;

R ^b represents a diamine moiety;

m is an integer from 1 to 20.

Further provided is a polyamic acid composition, which is the reaction product of at least one tetracarboxylic acid component and at least one diamine, wherein the diamine comprises 1 to 100 mole% of a diamine having formula (I).

There is further provided an acid dianhydride having formula IV:

[Formula IV]

here,

R ^d represents a tetracarboxylic acid component residue;

R ^e represents a diamine moiety;

m is an integer from 1 to 20.

A polyamic acid composition, which is a reaction product of at least one tetracarboxylic acid component and at least one diamine, is further provided, wherein the tetracarboxylic acid component comprises 1 to 100 mol% of a tetracarboxylic dianhydride having formula IV. Include.

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

A polyimide produced by imidation of any one of the polyamic acids is further provided.

A polyimide film comprising the polyimide is further provided.

One or more methods for making the polyimide film are further provided.

As a flexible glass substitute in an electronic device, a flexible glass substitute which is the polyimide film is further provided.

An electronic device having at least one layer including the polyimide film is further provided.

An organic electronic device such as an OLED, further provided is an organic electronic device comprising the flexible glass substitute disclosed herein.

The foregoing general description and the following detailed description are illustrative and illustrative only, and do not limit the invention as defined in the appended claims.

Embodiments are illustrated in the accompanying drawings to enhance the understanding of the concepts presented herein.
1 includes an illustration of an example of a polyimide film that can serve as a flexible glass substitute.
2 includes an illustration of an example of an electronic device including a flexible glass substitute.
Those skilled in the art will understand that the objects in the drawings have been drawn for conciseness and clarity and are not necessarily drawn to scale. For example, in the drawings, dimensions of some objects may be exaggerated compared to other objects to help improve understanding of the embodiments.

Many aspects and embodiments have been described above, which are illustrative only and not limiting. After reading this specification, those skilled in the art understand that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and advantages of any one or more embodiments will become apparent from the following detailed description and claims. The detailed description first includes definition and description of terms, followed by an imide-containing monomer, a diamine having the formula I, an acid dianhydride having the formula IV, a polyamic acid, a polyimide, a method for preparing a polyimide film, an electronic device, and examples. Deals with

1. Definition and explanation of terms

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

As used in "Definition and Description of Terms", R, R ^a , R ^b , R', R", and any other variables are generic names and may be the same as or different from those defined in the formula.

The term "alignment layer" is intended to mean a layer of organic polymers in an LCD that aligns molecules closest to each plate by rubbing the plate against the LCD glass in one preferred direction during the liquid crystal device (LCD) manufacturing process. .

As used herein, the term “alkyl” includes branched and straight chain saturated aliphatic hydrocarbon groups. Unless otherwise specified, this term is also intended to include cyclic groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl, and the like. The term “alkyl” further includes both substituted and unsubstituted hydrocarbon groups. In some embodiments, alkyl groups can be single, double, and triple 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 alkyl group has 1 to 6 carbon atoms. This term is intended to include heteroalkyl groups. Heteroalkyl groups can have 1 to 20 carbon atoms.

The term “aprotic” refers to a class of solvents that lack acidic hydrogen atoms and thus cannot act as hydrogen donors. Common aprotic solvents include alkanes, carbon tetrachloride (CCl4), benzene, dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and many others.

The term "aromatic compound" is intended to mean an organic compound comprising at least one unsaturated cyclic group having 4n+2 delocalized π electrons. The term is intended to include both aromatic compounds having only carbon and hydrogen atoms, and heteroaromatic compounds in which at least one of the carbon atoms in the cyclic group is replaced with another atom such as nitrogen, oxygen, sulfur, and the like.

The term "aryl" or "aryl group" refers to a moiety formed by removing one or more hydrogen ("H") or deuterium ("D") from an aromatic compound. The aryl group may be a single ring (monocyclic), or may have multiple rings (bicyclic or more) fused together or covalently bonded. “Hydrocarbon aryl” has only carbon atoms in the aromatic ring(s). “Heteroaryl” has one or more heteroatoms within at least one aromatic ring. In some embodiments, hydrocarbon aryl groups have 6 to 60 ring carbon atoms, and in some embodiments 6 to 30 ring carbon atoms. In some embodiments, heteroaryl groups have 4 to 50 ring carbon atoms, and in some embodiments 4 to 30 ring carbon atoms.

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

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

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

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

Unless otherwise specified, all groups may be substituted or unsubstituted. An optionally substituted group, 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"), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryl Oxy, 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 (where s is 0 to 2), or -S(O) _s -heteroaryl (where s is 0 to 2). Each of R'and R" is independently, optionally Substituted alkyl, cycloalkyl, or aryl groups. In certain embodiments, R'and R", together with the nitrogen atom to which they are attached, may form a ring system. The substituent may also be a crosslinking group.

).The term “amine” is intended to mean containing basic nitrogen atoms with lone pairs. The term “amino” refers to the functional group -NH ₂ , -NHR, or -NR ₂ , where R is the same or different at each occurrence and may be an alkyl group or an aryl group. The term "diamine" is intended to mean a compound containing two basic nitrogen atoms with lone pairs bonded. 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 bonded lone pairs are arranged asymmetrically around the center of symmetry of the corresponding compound or functional group (eg m -phenylenediamine:

).

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

The term “b*” is intended to mean the b* axis in the CIELab color space representing the complementary colors of yellow/blue. Yellow is represented by a positive b* value, and blue is represented by a negative b* value. The measured b* value can be influenced by the solvent, especially since the choice of solvent can affect the chromaticity measured in materials exposed to high temperature processing conditions. This can occur as a result of the inherent properties of the solvent and/or the properties associated with the low levels of impurities contained in the various solvents. Certain solvents are often preselected to achieve the required b* value 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. This term generally refers to the difference between the index of refraction in the x-axis or y-axis (in-plane) and the index of refraction in the z-axis (out of plane).

When referring to a layer, material, member, or structure, the term "charge transport" means that such a layer, material, member or structure is It is intended to mean that it facilitates the transfer of charges. The hole transport material facilitates the transfer of positive charges, and the electron transport material facilitates the transfer of negative charges. Light-emitting materials may also have some charge transport properties, but the term "charge transport layer, charge transport material, charge transport member, or charge transport structure" is intended to include a layer, material, member or structure whose main function is light emission. It is not.

The term "compound" is intended to mean an electrically uncharged material consisting of molecules that further contain atoms that cannot be separated from the molecule by physical means without breaking a chemical bond. The term is intended to include oligomers and polymers.

The term "linear coefficient of thermal expansion (CTE or α)" is intended to mean a parameter defining the amount by which a material expands or contracts as a function of temperature. This is expressed as a change in length per 1°C, and is generally expressed in units of μm/m/°C or ppm/°C.

The CTE measurements disclosed herein are those measured during the first or second heating scan through known methods. Understanding the relative expansion/contraction properties of a material can be an important consideration in the fabrication and/or reliability of electronic devices.

The term “dopant” refers to the electronic property(s) of that layer, or the target wavelength(s) of radiation emission, absorption, or filtering, within a layer comprising a host material, the electronic properties of a layer in which such material is not present ( S), or a material that changes relative to the wavelength(s) of radiation emission, absorption, or filtering.

The term “electroactive” when referring to a layer or material is intended to refer to a layer or material that electronically facilitates the operation of the device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charges, which may be electrons or holes, or materials that exhibit a change in concentration of electron-hole pairs or emit radiation upon absorption of radiation. no. Examples of inert materials include, but are not limited to, planarizing materials, insulating materials, and environmental shielding materials.

The term "tensile elongation" or "tensile strain" is intended to mean the percentage of length increase that occurs before the material breaks upon application of tensile stress. This can be measured, for example, by ASTM method D882.

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

The term “glass transition temperature (or T _g )” refers to a reversible change in the amorphous polymer or in the amorphous region of a semi-crystalline polymer, ie a sudden change in material from a hard, glassy, or brittle state to a flexible or elastic state. I want to mean the temperature that occurs. Microscopically, the glass transition occurs when the normally wound, immobile polymer chains are free to rotate and can move past each other. T _g can be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA), or dynamic mechanical analysis (DMA), or other methods.

The prefix "hetero" indicates that one or more carbon atoms have been replaced by another atom. In some embodiments, the heteroatom is O, N, S, or combinations thereof.

The term “high boiling point” is intended to denote a boiling point higher than 130°C.

The term "host material" is intended to mean a material to which a dopant is added. The host material may or may not have electronic property(s) or the ability to emit, absorb, 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 property of a material that is directly related to the thermal stability of the material. This is generally measured via thermogravimetric analysis (TGA) at a constant temperature of interest. Materials with high thermal stability generally exhibit very low isothermal weight loss rates at the required use or processing temperatures for the required period of time, and therefore in applications at these temperatures without significant loss of strength, outgassing, and/or structural changes. Can be used.

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 the material is dispersed to form a dispersion, or a liquid medium in which the material is suspended to form a suspension or emulsion.

The term "matrix" is intended to mean the basis on which one or more layers are deposited, for example during 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 phase delay (or R _TH )" is intended to mean the product of the difference between the average in-plane and out-of-plane refractive index (ie, birefringence) and the thickness of the film or coating. Optical phase delay is typically measured for a given frequency of light, and the units are reported in nanometers. This can be measured with Metricon or Axoscan.

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

The term "particle content" is intended to mean the number or number of insoluble particles present in the solution. The particle content can be measured for the solution itself, or it can be measured for the final material (piece, film, etc.) made from such a film. Various optical methods can be used to evaluate these properties.

The term “photoactive” means emit light when activated by an applied voltage (such as in a light-emitting diode or chemical cell), or after absorbing a photon (as in a down-converting phosphor device), or ( Refers to a material or layer that generates a signal in the presence or absence of an applied bias voltage in response to radiant energy (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 form imide groups by intramolecular cyclization.

The term “polyimide” refers to a condensation polymer resulting from the reaction of at least one difunctional carboxylic acid component with at least one primary diamine or diisocyanate. They contain the imide structure -CO-NR-CO- as linear or heterocyclic units along the backbone of the polymer.

The term "satisfied" with respect to a property or characteristic of a material is intended to mean that the property or characteristic meets all requirements/requirements for the material being used. For example, an isothermal weight loss of less than 1% for 3 hours at 350° C. in nitrogen can be considered as a non-limiting example of “satisfactory” properties with respect to the polyimide films disclosed herein.

The term "soft baking" is a process commonly used in the manufacture of electronic devices, and is intended to mean a process of heating a spin-coated material to remove a solvent and solidify a film. Soft baking is a preparatory step for the subsequent heat treatment of the coated layer or film and is generally carried out in a hot plate or vented oven at a temperature of 90°C to 110°C.

The term “substrate” is a base material that may be rigid or flexible, and includes 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. It refers to a substrate that may be included. The substrate may or may not include electronic components, circuits, or conductive members.

The term “siloxane” refers to the group R ₃ SiOR ₂ Si-, where R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons of the R alkyl group are replaced with Si.

The term “siloxy” refers to the group R ₃ SiO-, where R is the same or different at each occurrence and is H, C1-20 alkyl, fluoroalkyl, or aryl.

The term “silyl” refers to the group R ₃ Si-, 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 of the R alkyl group are replaced with Si.

The term “spin coating” is intended to mean a process used to deposit a uniform thin film on a flat substrate. Typically, a small amount of coating material is applied to the center of a substrate that rotates at low speed or does not rotate at all. Then, the substrate is rotated at a specific speed in order to uniformly apply the coating material by centrifugal force.

The term "laser particle counter test" refers to a method used to evaluate the particle content of polyamic acid and other polymer solutions by spin coating a representative sample of the test solution onto a 5" silicon wafer and soft baking/drying. Films are evaluated for particle content by a number of standard measurement techniques, including laser particle detection and other techniques known in the art.

The term "tensile modulus" is intended to mean a measure of the stiffness of a solid material, defining the initial relationship between stress (force per unit area) and strain (proportional strain) in a film-like material. A commonly used unit is Giga Pascal (GPa).

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

The term “tetracarboxylic acid component moiety” is intended to mean that the moiety is bonded to four carboxy groups in the tetracarboxylic acid component. This is further illustrated below.

The term "transmittance" refers to a ratio of light of a predetermined wavelength incident on the film that can pass through the film and be detected from the other side. Measurement of light transmittance in the visible region (380 nm to 800 nm) is particularly useful for characterizing film chromaticity properties that are most important for understanding the in-use properties of the polyimide films disclosed herein.

The term “yellowing degree (or YI)” refers to the degree of yellowing relative to the standard. Positive YI values indicate the presence and grade of yellow. Materials with negative YI have a bluish tint. It should also be noted that YI can be solvent dependent, especially for polymerization and/or curing processes carried out at high temperatures. For example, the grade of color introduced using DMAC as a solvent may differ from that introduced using NMP as a solvent. This can occur as a result of the inherent properties of the solvent and/or the properties associated with the low levels of impurities contained in the various solvents. Certain solvents are often preselected to achieve the YI values required for a particular application.

In structures in which substituent bonds penetrate more than one ring as shown below, it means that substituent R may be bonded at any effective position on one or more rings:

.

.

The phrase “adjacent to” when used to refer to a layer within a device does not necessarily mean that one layer is immediately next to another. On the other hand, the phrase "adjacent R group" is used to refer to an R group adjacent to each other in the formula (ie, an R group on an atom linked by a bond). Exemplary adjacent R groups are illustrated below:

.

.

In this specification, unless expressly stated otherwise or indicated to the contrary in the context of usage, embodiments of the subject matter include, contain, contain, have, consist of, or are made by or by certain features or elements. When stated or described as being constituted, one or more features or elements other than those explicitly stated or described may be present in an embodiment. Alternative embodiments of the disclosed subject matter are described as consisting essentially of specific features or elements, in which there are no features or elements that substantially change the principle of operation or distinct features of the embodiments. Another alternative embodiment of the disclosed subject matter is described as consisting of specific features or elements, in which only those features or elements specifically mentioned or described are present in such embodiments or non-substantial variations thereof.

Moreover, unless explicitly stated to the contrary, "or" refers to an inclusive'or' and not an exclusive'or'. For example, condition A'or' B is satisfied by any of the following: A is true (or exists), B is false (or does not exist), A is false (or does not exist), and B is true (or is not present). ), and both A and B are true (or present).

In addition, singular nouns are used to describe the elements and components described herein. This is done for convenience only and to give a general meaning of the scope of the invention. Such descriptions should be read as including one or at least one, and the singular also includes the plural unless explicitly meant to be singular.

The group numbers corresponding to the columns in the periodic table of the elements use the "New Notation" rule in CRC Handbook of Chemistry and Physics , 81 ^st Edition (2000-2001).

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

Unless described herein, many details of specific materials, processing operations and circuits are conventional and can be found in textbooks and other materials in the field of organic light emitting diode displays, photodetectors, photovoltaic and semiconductor member technologies.

2. Imide-containing monomer

Difficulties due to low reactivity, processability, and ability to control polymer structure hinder the application of some potentially useful classes of monomers in polyimide synthesis. Both dianhydride monomers and diamine monomers can cause problems. Some monomers with low reactivity can only be polymerized under severe reaction conditions. These conditions can promote the formation of side reactions that adversely affect the quality of the final polyimide film. Both optical and mechanical properties can be reduced.

The imide-containing monomer described herein overcomes the problem due to the low reactivity monomer, and controls the polymer structure (e.g., regioregularity and tacticity) to provide a polyimide having improved properties. It has been found that it can be used to achieve imidization with fewer defects.

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

In some embodiments, the imide-containing monomer is isolated and purified from defects and by-products. Thus, high-purity compounds with precisely defined oligomer structures can be used as monomers.

In some embodiments, the imide-containing monomer is used as formed and is a mixture of pre-imidated compounds.

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

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

In some embodiments, the imide-containing monomer is a diisocyanate and the reactive end 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 “di-imide”).

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

A method for the synthesis of precisely defined imide-containing polymers obtained from pre-imide-imide-containing monomers is disclosed herein. This is described below as Scheme I and Scheme II.

In Scheme I, the first step is the preimidation of the first dianhydride with an excess of the second diamine. The preimidated diamine monomer so formed can be isolated and purified. The pre-imidated diamine has sufficient reactivity to react in step 2 with one or more additional dianhydrides, which may be the same or different from the first dianhydride, to form an imide-containing polyamic acid. Even in the presence of a high molar ratio of imide groups, these imide-containing polymers are soluble and processable. Step 3 is the final imidization to form the polyimide polymer using conventional imidization techniques such as thermosetting. One embodiment of Scheme I is shown below, wherein the second dianhydride is different from the first dianhydride.

[Scheme I] One embodiment

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

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

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

In Scheme II, the first step is the pre-imidization of the first diamine with an excess of dianhydride. The pre-imide dianhydride monomer so formed has sufficient reactivity to react in step 2 with one or more additional diamines, which may be the same or different from the first diamine, to form an imide-containing polyamic acid. Even in the presence of a high molar ratio of imide groups, these imide-containing polymers are soluble and processable. Step 3 is the final imidization to form the polyimide polymer using conventional imidization techniques such as thermosetting. One embodiment of Scheme II is shown below, wherein the second diamine is different from the first diamine.

[Scheme II] One embodiment

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

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

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

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

In Scheme III, the first step is the preimidation of the first dianhydride with a large excess of the second diamine. The resulting mixture of pre-imidated diamine and excess first diamine is reacted in step 2 with one or more dianhydrides and, optionally, one or more additional diamines. The resulting imide-containing polyamic acid is imidized in step 3 using a conventional imidization technique.

In Scheme III, the pre-imidated diamine prepared in step 1 has the formula shown below:

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

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

In Scheme IV, the pre-imidated dianhydride prepared in step 1 has the formula shown below:

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

3. Diamine of Formula I

The diamines described herein have formula I:

[Formula I]

here,

R ^a represents a tetracarboxylic acid component residue;

R ^b represents a diamine moiety;

m is an integer from 1 to 20.

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

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

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

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

In some embodiments of Formula I, R ^a has both an aromatic group and an alicyclic group.

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

In some embodiments of Formula I, R ^a is pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic acid. Anhydride (ODPA), 4,4'-hexafluoroiso-propylidenebisphthalic dianhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ',4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4'-bisphenol-A dianhydride (BPADA), hydroquinone diphthalic anhydride (HQDEA), ethylene glycol bis (trimellitic anhydride) )(TMEG-100), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (DTDA); 4,4'-bisphenol A dianhydride (BPADA); Cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA); It represents a residue of a tetracarboxylic dianhydride selected from the group consisting of xanthene tetracarboxylic dianhydride and the like. These aromatic dianhydrides are alkyl, aryl, nitro, cyano, -N(R')(R ^" ), halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, hetero Aryloxy, alkoxycarbonyl, fluoroalkyl, perfluoroalkyl, fluoroalkoxy, 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-alkylaryl Known in the art, including oxyalkyl, -S(O) _s -aryl (where s is 0 to 2), or -S(O) _s -heteroaryl, where s is 0 to 2 May be optionally substituted with a group. Each of R′ and R″ is independently an optionally substituted alkyl, cycloalkyl, or aryl group. In certain embodiments, R'and R", together with the nitrogen atom to which they are attached, may form a ring system. The substituent may also be a crosslinking group.

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

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

In some embodiments of Formula I, R ^a is selected from the group consisting of Formulas A1-A36:

here,

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

R ² , R ³ , and R ⁴ are the same or different at each occurrence and are selected from the group consisting of F, alkyl, fluoroalkyl, and silyl;

R ⁵ is H, halogen, cyano, hydroxyl, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, hydrocarbon aryl, substituted hydrocarbon aryl, heteroaryl, substituted heteroaryl, vinyl, and allyl Is selected from the group consisting of;

R ⁶ is a group consisting of halogen, cyano, hydroxyl, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, hydrocarbon aryl, substituted hydrocarbon aryl, heteroaryl, substituted heteroaryl, vinyl, and allyl Is selected from;

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

Q is selected from the group consisting of CR ⁸ R ⁹ , SiR ⁸ R ⁹ , S, SR ⁸ R ⁹ , S=O, SO ₂ , and C=O;

a is an integer from 0 to 6;

b is an integer from 0 to 3;

c, d, and e are the same or different and are integers from 0 to 2;

f is an integer from 0 to 4;

z is an integer from 1 to 6;

z1 is an integer from 0 to 6;

* Indicates the point of attachment.

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

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

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

In some embodiments of Formula I, R ^b has both alicyclic and aromatic groups.

In some embodiments of Formula I, R ^b represents a moiety of a diamine having Formula D1:

[Formula D1]

here,

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

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

b is the same or different in each case and is an integer from 0 to 3;

c is the same or different in each case and is an integer from 0 to 2;

y is an integer from 0 to 2.

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

In some embodiments of Formula D1, y 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 ^b is p-phenylene diamine (PPD), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 3,3'-dimethyl- 4,4'-diaminobiphenyl (o-tolidine), 3,3'-dihydroxy-4,4'-diaminobiphenyl (HAB), 9,9'-bis (4-aminophenyl) Fluorene (FDA), o-tolidine sulfone (TSN), 2,3,5,6-tetramethyl-1,4-phenylenediamine (TMPD), 2,4-diamino-1,3,5- Trimethyl benzene (DAM), 3,3',5,5'-tetramethylbenzidine (3355TMB), 2,2'-bis(trifluoromethyl) benzidine (22TFMB or TFMB), 2,2-bis[4- (4-aminophenoxy)phenyl]propane (BAPP), 4,4'-methylene dianiline (MDA), 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline (Bis-M), 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline (bis-P), 4,4'-oxydianiline (4,4'- ODA), m-phenylene diamine (MPD), 3,4'-oxydianiline (3,4'-ODA), 3,3'-diaminodiphenyl sulfone (3,3'-DDS), 4, 4'-diaminodiphenyl sulfone (4,4'-DDS), 4,4'-diaminodiphenyl sulfide (ASD), 2,2-bis[4-(4-amino-phenoxy)phenyl] Sulfone (BAPS), 2,2-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(4-amino-phenoxy)benzene (APB-133), 4,4'-bis(4- Aminophenoxy)biphenyl (BAPB), 4,4'-diaminobenzanilide (DABA), methylene bis(anthranylic acid) (MBAA), 1,3'-bis(4-aminophenoxy)-2,2 -Dimethylpropane (DANPG), 1,5-bis(4-aminophenoxy)pentane (DA5MG), 2,2'-bis[4-(4-aminophenoxy phenyl)]hexafluoropropane (HFBAPP), 2,2-bis(4-aminophenyl) hexafluoropropane (bis-A-AF), 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (bis-AP-AF) , 2,2-bis(3-amino -4-methylphenyl) hexafluoropropane (bis-AT-AF), 4,4'-bis (4-amino-2-trifluoromethyl phenoxy) biphenyl (6BFBAPB), 3,3'5,5 It represents a residue of an aromatic diamine selected from the group consisting of'-tetramethyl-4,4'-diamino diphenylmethane (TMMDA) and the like.

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

Any of the above embodiments for Formula I may be combined with one or more other embodiments, unless 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. Anhydrides having Formula IV

The dianhydrides described herein have formula IV:

[Formula IV]

here,

R ^d represents a tetracarboxylic acid component residue;

R ^e represents a diamine moiety;

m is an integer from 1 to 20.

In some embodiments of Formula IV, m is 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.

Any of the above listed tetracarboxylic dianhydrides suitable for forming moieties R ^a of formula I are also suitable for forming moieties R ^d of formula IV.

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

Any of the diamines listed above, suitable for forming the moiety R ^b of formula I, are also suitable for forming the moiety R ^e of formula IV.

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

In some embodiments of Formula IV, R ^e is selected from the group consisting of Formulas E1-E16:

here,

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

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

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

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

R _f is C _1-3 perfluoroalkyl;

Q is selected from the group consisting of CR ⁸ R ⁹ , SiR ⁸ R ⁹ , S, SR ⁸ R ⁹ , S=O, SO ₂ , and C=O;

b is the same or different in each case and is an integer from 0 to 3;

c is the same or different in each case and is an integer from 0 to 2;

g is an integer from 0 to 4;

h is an integer from 0 to 6;

p is an integer from 1 to 10;

q is an integer from 0 to 5;

y is an integer from 0 to 2;

* Indicates the point of attachment.

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

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

Unless mutually exclusive, any of the above embodiments for Formula IV may be combined with one or more other embodiments.

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

Compound 25

Compound 26

Compound 27

Compound 28

Compound 29

Compound 30

Compound 31

Compound 32

Compound 33

Compound 34

Compound 35

Compound 36

Compound 37

Compound 38

5. Polyamic acid

The polyamic acid described herein is the reaction product of at least one tetracarboxylic acid component and at least one diamine, wherein (a) the diamine comprises 1 to 100 mol% of a diamine having formula I, and/or (b) a tetracarboxylic acid The acid component comprises from 1 to 100 mole percent of a tetracarboxylic dianhydride having formula IV. In some embodiments, the polyamic acid is the reaction product of at least one tetracarboxylic acid component and at least one diamine, and (a) the diamine comprises 1 to 100 mole percent of a diamine having Formula I, or (b) a tetracar The acid component comprises from 1 to 100 mole percent of a tetracarboxylic dianhydride having formula IV.

The first polyamic acid is the reaction product of at least one tetracarboxylic acid component and at least one diamine, and the diamine comprises 1 to 100 mol% of a diamine having formula (I).

In some embodiments of the first polyamic acid, the diamine having Formula (I) comprises 1 to 5 mole percent of the total diamine; In some embodiments, 6-10 mole percent; In some embodiments, 10 to 25 mole percent; From 25 to 50 mole percent in some embodiments; In some embodiments, 50-75 mole percent; In some embodiments, 75 to 100 mole percent; In some embodiments, it is 100 mole percent.

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:

[Formula II]

here,

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

R ^b represents a diamine moiety;

m is an integer from 1 to 20.

The embodiments described above for R ^a , R ^b , and m in Formula I all apply equally to R ^a , R ^b , and m in Formula II.

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

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

The second polyamic acid is a reaction product of at least one tetracarboxylic acid component and at least one diamine, and the tetracarboxylic acid component comprises 1 to 100 mol% of a tetracarboxylic dianhydride having formula IV.

In some embodiments of the second polyamic acid, the dianhydride having Formula IV comprises 1 to 5 mole percent of the total dianhydride; In some embodiments, 6-10 mole percent; In some embodiments, 10 to 25 mole percent; From 25 to 50 mole percent in some embodiments; In some embodiments, 50-75 mole percent; In some embodiments, 75 to 100 mole percent; In some embodiments, it is 100 mole percent.

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

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

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

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

The second polyamic acid has a repeating unit of formula V:

[Formula V]

here,

R ^d represents a tetracarboxylic acid component residue;

R ^e and R ^f are the same or different and represent a diamine moiety;

m is an integer from 1 to 20.

The embodiments described above for R ^d , R ^e , and m in Formula IV all apply equally to R ^d , R ^e , and m in Formula V.

Any of the diamines listed above, suitable for forming the moiety R ^e of Formula IV, are also suitable for forming the moiety R ^f of Formula V.

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

In some embodiments of the above polyamic acid, moieties resulting from monoanhydride monomers are present as end-capping groups.

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

In some embodiments, the monoanhydride is present in an amount of 5 mole percent or less of the total tetracarboxylic acid composition.

In some embodiments of the above polyamic acid, moieties resulting from monoamine monomers are present as end-capping groups.

In some embodiments, the monoamine monomer is selected from the group consisting of aniline and the like and derivatives thereof.

In some embodiments, the monoamine is present in an amount of 5 mole percent or less of the total amine composition.

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

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

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

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

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

In some embodiments, the polyamic acid has a weight average molecular weight (M _W ) of 100,000 to 400,000 based on gel permeation chromatography using polystyrene standards.

In some embodiments, the polyamic acid has a weight average molecular weight (M _W ) of 150,000 to 350,000 based on gel permeation chromatography using polystyrene standards.

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

The overall polyamic acid composition may be indicated through a notation commonly used in the art. For example, a polyamic acid with a tetracarboxylic acid component of 100% ODPA and a diamine component of 90 mol% bis-P and 10 mol% TFMB would be represented as follows:

ODPA//bis-P/22TFMB 100//90/10.

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

There is also provided a second liquid composition comprising (a) a polyamic acid having repeating units of formula (V) and (b) at least one high boiling point aprotic solvent. The second liquid composition is also referred to herein as “second polyamic acid solution”.

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

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

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

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

Some examples of high boiling point aprotic solvents include N-methyl-2-pyrrolidone (NMP), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), and N-butylpyrrolidinone. (NBP), N,N-diethylacetamide (DEAc), tetramethylurea, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, dibutyl carbitol, butyl carbitol acetate, di Ethylene 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 γ-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 high boiling point aprotic solvents identified above are used in the liquid composition.

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

In some embodiments, the liquid composition is less than 1% by weight polyamic acid in greater than 99% by weight high boiling point aprotic solvent(s). As used herein, the term “solvent(s)” refers to one or more solvents.

In some embodiments, the liquid composition is 1 to 5% by weight of polyamic acid in 95 to 99% by weight of high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 5-10% by weight polyamic acid in 90-95% by weight high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 10-15% by weight polyamic acid in 85-90% by weight high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 15-20% polyamic acid by weight in 80-85% by weight high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 20-25% by weight polyamic acid in 75-80% by weight high boiling aprotic solvent(s).

In some embodiments, the liquid composition is 25 to 30 weight percent polyamic acid in 70 to 75 weight percent high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 30 to 35 weight percent polyamic acid in 65 to 70 weight percent high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 35 to 40 weight percent polyamic acid in 60 to 65 weight percent high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 40 to 45 weight percent polyamic acid in 55 to 60 weight percent high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 45 to 50% by weight polyamic acid in 50 to 55% by weight of high boiling point aprotic solvent(s).

In some embodiments, the liquid composition is 50% by weight polyamic acid in 50% by weight high boiling point aprotic solvent(s).

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

Polyamic acid solutions can be prepared using a variety of methods available in connection with the introduction of components (ie, monomers and solvents). Some methods of preparing polyamic acid solutions include the following methods:

(a) After mixing the diamine component and the dianhydride component together in advance, the mixture is gradually added to the solvent while stirring.

(b) Method of adding a solvent to the stirring mixture of diamine and dianhydride component (as opposed to (a) above)

(c) a method of dissolving only diamine in a solvent, and then adding a dianhydride thereto at a rate such that the reaction rate can be controlled;

(d) a method of dissolving only the dianhydride component in a solvent, and then adding the amine component thereto in a ratio such that the reaction rate can be controlled;

(e) a method of separately dissolving a diamine component and a dianhydride component in a solvent and then mixing these solutions in a reactor;

(f) a polyamic acid having an excess of amine component and another polyamic acid having an excess of dianhydride component are formed in advance, and then reacted with each other in a reactor, especially in a manner to produce a non-random copolymer or block copolymer. Way;

(g) a method of first reacting a specific portion of an amine component with a dianhydride component and then reacting with the remaining diamine component, or vice versa;

(h) adding the components to some or all of the solvent partially or wholly in any order (and also allowing some or all of the optional components to be added to some or all of the solvent as a solution);

(i) one of the dianhydride components is first reacted with one of the diamine components to provide a first polyamic acid, and then the other dianhydride component is reacted with another amine component to provide a second polyamic acid, and then before film formation A method of combining polyamic acids in any one of a number of ways.

In general, the polyamic acid solution can be obtained from any one of the methods for preparing the polyamic acid solution disclosed above.

Subsequently, the polyamic acid solution may be filtered one or more times to reduce the particle content. The polyimide film produced from such a filtered solution may exhibit a reduction in the number of defects, thereby exhibiting excellent performance in the electronic device applications disclosed herein. Evaluation of the filtration efficiency can be performed by a laser particle counter test in which a representative sample of a polyamic acid solution is cast onto a 5" silicon wafer. After soft baking/drying, the film is evaluated for particle content by a number of laser particle counting techniques in equipment commercially available and known in the art.

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

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

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

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

An exemplary preparation of a polyamic acid solution is provided in the Examples.

6. Polyimide

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

[Formula III]

here,

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

R ^b represents a diamine moiety;

m is an integer from 1 to 20.

The embodiment described in the above for ^{R a, R b, R c} , and m in formula II are all the same for ^{R a, R b, R c} , and m in formula III.

There is provided a second polyimide having a repeating unit structure of formula (VI):

[Formula VI]

here,

R ^d represents a tetracarboxylic acid component residue;

R ^e and R ^f are the same or different and represent a diamine moiety;

m is an integer from 1 to 20.

The embodiments described above for R ^d , R ^e , R ^f , and m in Formula IV all apply equally to R ^d , R ^e , R ^f , and m in Formula V.

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

Polyimide films can be prepared by coating a polyimide precursor on a substrate and subsequently imidizing. This can be achieved by a thermal conversion process or a chemical conversion process.

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

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

In some embodiments of the polyimide film, the glass transition temperature (T _g ) is greater than 250° C., in some embodiments, greater than 300° C., and in some embodiments, greater than 350° C. for a polyimide film cured at a temperature greater than 300° C. to be.

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

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

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

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

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

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

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

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

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

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

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

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

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

Unless mutually exclusive, any of the above embodiments for a polyimide film may be combined with one or more other embodiments.

4. Manufacturing method of polyimide film

In general, polyimide films can be prepared by chemical or thermal conversion from a polyimide precursor. In some embodiments, the film is made by a chemical or thermal conversion process from the corresponding polyamic acid solution. The polyimide films disclosed herein are produced by a thermal conversion process, particularly when used as a flexible glass substitute in electronic devices.

In general, polyimide films can be prepared from a corresponding polyamic acid solution by a chemical or thermal conversion process. The polyimide films disclosed herein are produced by a thermal conversion process or a modified thermal conversion process compared to a chemical conversion process, particularly when used as a flexible glass substitute in an electronic device.

Chemical conversion processes are described in US Pat. Nos. 5,166,308 and 5,298,331, which are incorporated by reference in their entirety. In this process, a conversion chemical is added to the polyamic acid solution. Conversion chemicals found to be useful in the present invention include (i) one or more dehydrating agents, such as aliphatic acid anhydrides (such as acetic anhydride) and acid anhydrides; And (ii) one or more catalysts such as aliphatic tertiary amines (such as triethylamine), tertiary amines (such as dimethylaniline), and heterocyclic tertiary amines (such as pyridine, picoline, isoquinoline, etc.). Not limited. The anhydrous dehydration material is typically used in a somewhat molar excess than the amount of amic acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically 2.0 to 3.0 moles per equivalent of polyamic acid. In general, similar amounts of tertiary amine catalyst are used.

The thermal conversion process may or may not use conversion chemicals (ie, catalysts) to convert the polyamic acid casting solution to polyimide. If conversion chemicals are used, the process can be considered a modified thermal conversion process. In both types of thermal conversion processes, only thermal energy is used to heat the film, drying the solvent in the film and performing the imidation reaction. A thermal conversion process is generally used with or without a conversion catalyst to prepare the polyimide films disclosed herein.

Specific method parameters are preselected taking into account that it is not just the film composition that yields the properties of interest. rather,

The curing temperature and temperature-ramp profile also play an important role in achieving the most desirable properties for the intended use disclosed herein. Polyamic acid is above the highest temperature of any subsequent processing steps (e.g., deposition of inorganic or other layer(s) required to manufacture a functional display), but above the temperature at which severe thermal degradation/discoloration of the polyimide occurs. It should be imidized at low temperatures. It should also be noted that an inert atmosphere is generally preferred, and is particularly preferred when higher processing temperatures are used for imidization.

For the polyamic acid/polyimide disclosed herein, temperatures of 300° C. to 400° C. are typically used if subsequent processing temperatures in excess of 300° C. are required. Choosing an appropriate curing temperature can result in a fully cured polyimide with an optimal balance of thermal and mechanical properties. Because of this very high temperature, an inert atmosphere is required. Typically, oxygen levels of less than 100 ppm should be used within the oven. At very low oxygen levels the highest curing temperature can be used without significant degradation/discoloration of the polymer. Catalysts that promote the imidation process are effective in achieving higher levels of imidation at curing temperatures of about 200°C to 300°C. This approach can optionally be used if the flexible device is made with an upper cure temperature that is less than the T _g of the polyimide.

The amount of time for each potential curing step is also an important process consideration. In general, the time used for curing at the highest temperature should be kept to a minimum. For example, in the case of curing at 320° C., the curing time may be up to 1 hour in an inert atmosphere, but at higher curing temperatures this time should be shortened to avoid thermal degradation. In general, the higher the temperature, the shorter the time should be. One of skill in the art will recognize the balance between temperature and time to optimize the properties of a polyimide for a particular end use.

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

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

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

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked on the hotplate in proximity mode, and nitrogen gas is used to hold the spin coated matrix directly above the hotplate.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked on the hotplate in full contact mode, and the spin coated matrix is in direct contact with the hotplate surface.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked on a hotplate using a combination of proximity mode and full contact mode.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 80°C.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 90°C.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 100°C.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 110°C.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 120°C.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 130°C.

In some embodiments of the thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 140°C.

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the spin coated matrix 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 matrix is subsequently cured at two preselected temperatures for two preselected time intervals, and the preselected time intervals may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin coated matrix is subsequently cured for three preselected time intervals at three preselected temperatures, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin coated matrix is subsequently cured for four preselected time intervals at four preselected temperatures, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin coated matrix is subsequently cured for five preselected time intervals at five preselected temperatures, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin coated matrix is subsequently cured for six preselected time intervals at six preselected temperatures, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin coated matrix is subsequently cured at 7 preselected temperatures for 7 preselected time intervals, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin coated matrix is subsequently cured at eight preselected temperatures for eight preselected time intervals, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin coated matrix is subsequently cured at nine preselected temperatures for nine preselected time intervals, each of which may be the same or different.

In some embodiments of the thermal conversion process, the soft baked spin coated matrix is subsequently cured at 10 preselected temperatures for 10 preselected time intervals, each of which may be the same or different.

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

In some embodiments of the thermal conversion process, the preselected temperature is 100°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 150°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 200°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 250°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 300°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 350°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 400°C.

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

In some embodiments of the thermal conversion process, the preselected temperature is 450°C.

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

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

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

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

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

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

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

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

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

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

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

In some embodiments of the thermal conversion process, at least one of the preselected time intervals is 50 minutes.

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

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

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

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

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

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

In some embodiments of the thermal conversion process, the method of making a polyimide film comprises the following steps in sequence: a polyamic acid solution comprising at least two tetracarboxylic acid components and at least one diamine component in a high boiling point aprotic solvent is matrixed. Spin coating on the top; Soft baking the spin coated matrix; Treating the soft baked spin coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic device applications as disclosed herein. Show.

In some embodiments of the thermal conversion process, the method of making a polyimide film comprises the following steps in sequence: a polyamic acid solution comprising at least two tetracarboxylic acid components and at least one diamine component in a high boiling point aprotic solvent is matrixed. Spin coating on the top; Soft baking the spin coated matrix; It consists of treating the soft baked spin coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film has satisfactory properties for use in electronic device applications as disclosed herein. Show.

In some embodiments of the thermal conversion process, the method of making a polyimide film comprises the following steps in sequence: a polyamic acid solution comprising at least two tetracarboxylic acid components and at least one diamine component in a high boiling point aprotic solvent is matrixed. Spin coating on the top; Soft baking the spin coated matrix; It consists essentially of processing the soft baked spin coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film is satisfactory for use in electronic device applications as disclosed herein. Characteristics.

Typically, the polyamic acid solution/polyimide disclosed herein is coated/cured onto a supporting glass substrate to facilitate processing through the rest of the display manufacturing process. At some point in the process as determined by the display manufacturer, the polyimide coating is peeled off the supporting glass substrate by a mechanical or laser lift off process. This process separates the polyimide from the glass as a film on which the display layer is deposited, thereby enabling a flexible form. Usually, this polyimide film with a deposited layer is then bonded to a thicker but still flexible plastic film to provide support for the subsequent manufacture of the display.

A modified thermal conversion process is also provided wherein the conversion catalyst generally causes the imidation reaction at a temperature lower than the temperature at which the imidation reaction can occur without such conversion catalyst.

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

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

In some embodiments of the modified 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 modified thermal conversion process, the polyamic acid solution is tributylamine, dimethylethanolamine, isoquinoline, 1,2-dimethylimidazole, N-methylimidazole, 2-methylimidazole, 2 -A conversion catalyst selected from the group consisting of ethyl-4-imidazole, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 5-methylbenzimidazole, and the like is further contained.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present at no more than 5% by weight of the polyamic acid solution.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present at no more than 3% by weight of the polyamic acid solution.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present at no more than 1% by weight of the polyamic acid solution.

In some embodiments of the modified thermal conversion process, the conversion catalyst is present at 1% by weight of the polyamic acid solution.

In some embodiments of the modified thermal conversion process,

The polyamic acid solution further contains tributylamine as a conversion catalyst.

In some embodiments of the modified thermal conversion process,

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

In some embodiments of the modified thermal conversion process,

The polyamic acid solution further contains isoquinoline as a conversion catalyst.

In some embodiments of the modified thermal conversion process,

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

In some embodiments of the modified thermal conversion process,

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

In some embodiments of the modified thermal conversion process,

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

In some embodiments of the modified thermal conversion process,

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

In some embodiments of the modified thermal conversion process,

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

In some embodiments of the modified thermal conversion process,

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

In some embodiments of the modified thermal conversion process,

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

In some embodiments of the modified thermal conversion process,

The polyamic acid solution further contains 2,5-dimethylpyridine as a conversion catalyst.

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

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

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

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

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

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

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

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

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked on the hotplate in proximity mode, and nitrogen gas is used to hold the spin coated matrix directly above the hotplate.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked on the hotplate in full contact mode, and the spin coated matrix is in direct contact with the hotplate surface.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked on a hotplate using a combination of proximity mode and full contact mode.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 80°C.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 90°C.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 100°C.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 110°C.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 120°C.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 130°C.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked using a hotplate set at 140°C.

In some embodiments of the modified thermal conversion process, the spin coated matrix is soft baked for a total time greater than 10 minutes.

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

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

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

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

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

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

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured for two preselected time intervals at two preselected temperatures, and the preselected time intervals may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured for three preselected time intervals at three preselected temperatures, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured for four preselected time intervals at four preselected temperatures, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured at 5 preselected temperatures for 5 preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured at six preselected temperatures for six preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured at 7 preselected temperatures for 7 preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured at eight preselected temperatures for eight preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured at nine preselected temperatures for nine preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the soft baked spin coated matrix is subsequently cured at 10 preselected temperatures for 10 preselected time intervals, each of which may be the same or different.

In some embodiments of the modified thermal conversion process, the preselected temperature is above 80°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 100°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 150°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 200°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is above 200°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 220°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 230°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is above 230°C.

In some embodiments of the modified thermal conversion process, the preselected temperature is 240°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 250°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 260°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 270°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 280°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 290°C.

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

In some embodiments of the modified thermal conversion process, the preselected temperature is 300°C.

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

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

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

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

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

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

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 2 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 5 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 10 minutes.

In some embodiments of the modified conversion process, at least one of the preselected time intervals is 15 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 20 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 25 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 30 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 35 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 40 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 45 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 50 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 55 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is 60 minutes.

In some embodiments of the modified thermal conversion process, at least one of the preselected time intervals is greater than 60 minutes.

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

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

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

In some embodiments of the modified thermal conversion process, the method of making a polyimide film comprises the following steps in sequence: at least two tetracarboxylic acid components and at least one diamine component and conversion chemicals in a high boiling point aprotic solvent. Spin coating the resulting polyamic acid solution onto a matrix; Soft baking the spin coated matrix; Treating the soft baked spin coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film exhibits satisfactory properties for use in electronic device applications as disclosed herein. Show.

In some embodiments of the modified thermal conversion process, the method of making a polyimide film comprises the following steps in sequence: at least two tetracarboxylic acid components and at least one diamine component and conversion chemicals in a high boiling point aprotic solvent. Spin coating the resulting polyamic acid solution onto a matrix; Soft baking the spin coated matrix; It consists of treating the soft baked spin coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film has satisfactory properties for use in electronic device applications as disclosed herein. Show.

In some embodiments of the modified thermal conversion process, the method of making a polyimide film comprises the following steps in sequence: at least two tetracarboxylic acid components and at least one diamine component and conversion chemicals in a high boiling point aprotic solvent. Spin coating the resulting polyamic acid solution onto a matrix; Soft baking the spin coated matrix; It consists essentially of processing the soft baked spin coated matrix at a plurality of preselected temperatures for a plurality of preselected time intervals, whereby the polyimide film is satisfactory for use in electronic device applications as disclosed herein. Characteristics.

5. Electronic device

The polyimide films disclosed herein may be suitable for use in various layers of electronic display devices such as OLED and LCD displays. Non-limiting examples of such layers include device substrates, touch panels, substrates for color filter sheets, cover films, and the like. The specific material property requirements for each application are unique and can be addressed by the composition(s) and processing condition(s) appropriate for the polyimide films disclosed herein.

In some embodiments, the flexible glass substitute in the electronic device is a polyimide film having repeating units of Formula III as detailed above.

Organic electronic devices that can benefit from having one or more layers containing at least one compound as described herein include (1) devices that convert electrical energy into radiation (e.g., light-emitting diodes, light-emitting diode displays, lighting devices) (lighting device, luminaire, or diode laser); (2) a device that detects a signal through an electronic process (eg, a photodetector, a photoconductive battery, a photoresistor, an optical switch, a phototransistor, an optical tube, an IR detector, a biosensor); (3) devices that convert radiation into electrical energy (eg, photovoltaic devices or solar cells); (4) a device for converting light of one wavelength into light of a longer wavelength (eg, a downconverting phosphorescent device); And (5) a device (eg, a transistor or a diode) comprising one or more electronic components comprising one or more organic semiconductor layers. Other uses of the composition according to the invention include memory storage devices, antistatic films, biosensors, electrochromic devices, solid electrolyte capacitors, energy storage devices such as rechargeable batteries, and coating materials for electromagnetic shielding applications.

An example of a polyimide film that can serve as a flexible glass substitute, as described herein, is shown in FIG. 1. The flexible film 100 may have properties as described in the embodiments of the present invention. In some embodiments, a polyimide film that can function as a flexible glass substitute is included in the electronic device. 2 illustrates a case where 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 to the anode, there may be a hole injection layer (not shown), sometimes referred to as a buffer layer. Adjacent to the hole injection layer, there may be a hole transport layer (not shown) comprising a hole transport material. Adjacent to the cathode, there may be an electron transport layer (not shown) comprising an electron transport material. Optionally, the device includes one or more additional hole injection layers or hole transport layers (not shown) next to the anode 110, and/or one or more additional electron injection layers or electron transport layers (not shown) next to the cathode 130. Not) can be used. The layers between 110 and 130 individually and collectively are referred to as the organic active layer. Additional layers that may or may not be present include color filters, touch panels, and/or cover sheets. In addition to the substrate 100, one or more of these layers may also be made of the polyimide film disclosed herein.

Different layers will be discussed further herein with reference to FIG. 2. However, the discussion also applies to other configurations.

In some embodiments, the different layers have the following thickness range: substrate 100, 5-100 microns; Anode 110, 500-5000 Å, in some embodiments, 1000-2000 Å; Hole injection layer (not shown), 50-2000 Å, in some embodiments 200-1000 Å); Hole transport layer (not shown), 50-3000 Å, in some embodiments 200-2000 Å; Photoactive layer 120, 10-2000 Å, in some embodiments 100-1000 Å; Electron transport layer (not shown), 50-2000 Å, in some embodiments 100-1000 Å); Cathode 130, 200-10000 Å, in some embodiments 300-5000 Å. The preferred ratio of layer thickness will depend on the exact nature of the material used.

In some embodiments, the organic electronic device (OLED) contains a flexible glass substitute, as disclosed herein.

In some embodiments, the organic electronic device includes a substrate, an anode, a cathode, and a photoactive layer between the anode and the cathode, 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 a particularly efficient electrode for injecting positive charge carriers. It can be made, for example, of 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, Groups 4, 5 and 6 metals, and transition metals of Groups 8 to 10. When the anode is to be light-transmitting, mixed metal oxides of Group 12, Group 13 and Group 14 metals such as indium-tin-oxide are generally used. The anode is also described in "Flexible light-emitting diodes made from soluble conducting polymer," Nature vol. 357, pp 477 479 (11 June 1992)], and may include organic materials such as polyaniline. At least one of the anode and cathode must be at least partially transparent so that the generated light can 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 mean an electrically conductive or semiconducting material, and one or more functions in organic electronic devices (planarization of the underlying layer, charge transport and/or charge injection properties, oxygen or metal ions Removal of impurities such as, and other aspects for promoting or improving the performance of organic electronic devices). The hole injection material may be a polymer, oligomer, or small molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

The hole injection layer may be formed of a polymeric material such as polyaniline (PANI) or polyethylenedioxythiophene (PEDOT), which is usually doped with protonic acid. The protonic acid may be, for example, poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), or the like. The hole injection layer 120 may include a charge transport compound such as copper phthalocyanine and tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In some embodiments, hole injection layer 120 is made of a dispersion of a conductive polymer and a colloid-forming polymeric acid. Such materials are described in, for example, published US patent applications 2004-0102577, 2004-0127637, and 2005-0205860.

Another layer may include a hole transport material. Examples of hole transport materials for the hole transport layer are summarized, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p.837-860, 1996, by Y. Wang. . Both hole transporting small molecules and polymers can be used. Commonly used hole transport molecules include, but are not limited to: 4,4',4"-tris(N,N-diphenyl-amino)-triphenylamine (TDATA); 4,4',4 "-Tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA); N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD); 4,4'-bis(carbazol-9-yl)biphenyl (CBP); 1,3-bis(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,N',N'-2,5-phenylenediamine (PDA); α-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehyde diphenylhydrazone (DEH); Triphenylamine (TPA); Bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP); 1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl] pyrazoline (PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TTB); N,N'-bis(naphthalen-1-yl)-N,N'-bis-(phenyl)benzidine (α-NPB); And porphyrin compounds such as copper phthalocyanine. Hole transport polymers commonly used include, but are not limited to, polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophene), polyaniline, and polypyrrole. It is also possible to obtain a hole transport polymer by doping a polymer such as polystyrene and polycarbonate with hole transport molecules such as those mentioned above. In some cases, triarylamine polymers, especially triarylamine-fluorene copolymers are used. In some cases, the polymer and copolymer are crosslinkable. Examples of crosslinkable hole transport polymers can be found in, for example, US Patent Application Publication No. 2005-0184287 and International Patent Application Publication No. WO 2005/052027. In some embodiments, the hole transport layer is a p-dopant such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxylic acid-3,4,9,10-dianhydride. Doped with.

Depending on the application of the device, the photoactive layer 120 is a light-emitting layer that is activated by an applied voltage (as in a light-emitting diode or a light-emitting electrochemical cell), and absorbs light (as in a down-converting phosphorescent device) to a longer wavelength Or a layer of material that generates a signal in the presence or absence of an applied bias voltage in response to radiant energy (as in photodetectors or photovoltaic devices).

In some embodiments, the photoactive layer comprises a compound comprising a light emitting compound having a photoactive material. In some embodiments, the photoactive layer further comprises a host material. Examples of host materials include chrysene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, carbazole, indolocarbazole, furan, benzofuran, dibenzofuran. , Benzodifuran, and metal quinolinate complexes. In some embodiments, the host material is deuterated.

In some embodiments, the photoactive layer includes (a) a dopant capable of electroluminescence having a maximum emission value from 380 nm to 750 nm, (b) a first host compound, and (c) a second host compound. Suitable second host compounds are described above.

In some embodiments, the photoactive layer comprises only (a) an electroluminescent dopant having an emission maximum from 380 nm to 750 nm, (b) a first host compound, and (c) a second host compound, and the layer There are no additional materials that substantially alter the principle of operation or the distinguishing characteristics of the.

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

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

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

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

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

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

The optional layer not only facilitates electron transport, but can also function to serve as a confinement layer preventing quenching of excitons at the layer interface. Preferably, this layer promotes electron mobility and reduces exciton quenching.

In some embodiments, these layers include other electron transport materials. Examples of electron transport materials that can be used in the optional electron transport layer include tris(8-hydroxyquinolato)aluminum (AlQ), bis(2-methyl-8-quinolinolato)(p-phenylphenolato) Metal chelates comprising metal quinolate derivatives such as aluminum (BAlq), tetrakis-(8-hydroxyquinolato)hafnium (HfQ), and tetrakis-(8-hydroxyquinolato)zirconium (ZrQ) Oxinoid compounds; 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5- Azole compounds such as (4-t-butylphenyl)-1,2,4-triazole (TAZ), and 1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); Quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline; Phenanthrolines such as 4,7-diphenyl-1,10-phenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); Triazine; Fullerene; And mixtures thereof. In some embodiments, the electron transport material is selected from the group consisting of metal quinolate and phenanthroline derivatives. In some embodiments, the electron transport layer further comprises an n-dopant. n-dopant materials are well known. n-dopants are Group 1 and Group 2 metals; Group 1 and Group 2 metal salts such as LiF, CsF, and Cs ₂ CO ₃ ; Group 1 and Group 2 metal organic compounds such as Li quinolate; And molecular n-dopants such as leuco dyes, metal complexes such as W ₂ (hpp) ₄ (where hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2- a)-pyrimidine) and cobaltocene, tetrathianapthacene, bis(ethylenedithio)tetrathiafulvalene, heterocyclic radical or diradical, and heterocyclic radical or diradical dimer, oligomer, polymer , Dispyro compounds, and polycycles.

An optional electron injection layer may be deposited on the electron transport layer. Examples of electron injection materials include, but are not limited to, Li-containing organometallic compounds, LiF, Li ₂ O, Li quinolate, Cs-containing organometallic compounds, CsF, Cs ₂ O, and Cs ₂ CO ₃ . This layer can react with the lower electron transport layer, the upper cathode, or both. When an electron injection layer is present, the amount of material deposited is generally in the range of 1 to 100 Å, in some embodiments 1 to 10 Å.

The cathode 130 is a particularly efficient electrode for injecting electron or negative charge carriers. The cathode can be any metal or non-metal with a lower work function than the anode. The material for the cathode may be selected from a group 1 alkali metal (eg Li, Cs), a group 2 metal (alkaline earth metal), a rare earth element and a group 12 metal including a lanthanide element, and an actinium group element. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations thereof, can be used.

Organic electronic devices are known to have different layers. For example, between the anode 110 and the hole injection layer (not shown), a layer (not shown) that controls the injection amount of positive charge and/or provides bandgap matching of the layers, or functions as a protective layer is provided. There may be. Layers known in the art such as copper phthalocyanine, silicon oxynitride, fluorocarbon, silane, or ultra-thin layers of 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 is understood that each functional layer may consist of more than one layer.

The device layers may generally be formed by any deposition technique or combination of techniques, including vapor deposition, liquid deposition, and thermal transfer. Substrates such as glass, plastic, and metal can be used. Conventional vapor deposition techniques such as thermal evaporation, chemical vapor deposition and the like can be used. The organic layer is a suitable solvent using conventional coating or printing techniques including, but not limited to, spin-coating, dip-coating, roll-to-roll technology, inkjet printing, continuous nozzle printing, screen printing, gravure printing, and the like. It can be applied from a solution or dispersion in.

In the case of liquid deposition methods, suitable solvents for a particular compound or a related class of compounds can be readily determined by a person skilled in the art. For some applications, it is desirable for the compound to be dissolved in a non-aqueous solvent. Such non-aqueous solvents may be relatively polar, such as C ₁ to C ₂₀ alcohols, ethers, and acid esters, or relatively non-polar, such as C ₁ to C ₁₂ alkanes, or aromatics such as toluene, xylene, and trifluorotoluene. Can be Other liquids suitable for use in preparing liquid compositions comprising the novel compounds as solutions or dispersions as described herein include chlorinated hydrocarbons (e.g. methylene chloride, chloroform, chlorobenzene), aromatic hydrocarbons (e.g. trifluoro. Substituted and unsubstituted toluene and xylene, including rotoluene), polar solvents (e.g. tetrahydrofuran (THP), N-methyl pyrrolidone), esters (e.g. ethyl acetate), alcohols (isopropanol), Ketones (cyclopentanone), and mixtures thereof are included, but are not limited thereto. Suitable solvents for electroluminescent materials are described, for example, in WO 2007/145979.

In some embodiments, the device is fabricated by liquid phase deposition of a hole injection layer, a hole transport layer, and a photoactive layer on a flexible substrate, and by vapor deposition of an anode, an electron transport layer, an electron injection layer, and a cathode.

It is understood that the efficiency of the device can be improved by optimizing the different layers of the device. For example, more efficient cathodes such as Ca, Ba or LiF can be used. New hole transport materials and molded substrates that reduce the operating voltage or increase quantum efficiency are also applicable. Additional layers may also be added to match the energy levels of the various layers and facilitate electroluminescence.

In some embodiments, the device has the following structures in order: a substrate, an anode, a hole injection layer, a hole transport layer, a photoactive layer, an electron transport layer, an electron injection layer, a cathode.

Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety.

Example

The concepts described herein are further illustrated in the following examples, but this does not limit the scope of the invention as set forth 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; Mp is the peak molecular weight.

Abbreviation

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

BPDA =3,3',4,4'-biphenyl tetracarboxylic dianhydride

4,4'-DDS = 4,4'-diaminodiphenyl sulfone

6FDA = 4,4'-hexafluoroiso-propylidenebisphthalic acid dianhydride

ODPA = 4,4'-oxydiphthalic anhydride

PMDA = pyromellitic dianhydride

TFMB = 2,2'-bis (trifluoromethyl) benzidine

XFDA = 1H-difuro[3,4-b:3',4'-i]xanthene-1,3,7,9(11H)-tetron, 11-methyl-11-(trifluoromethyl)-

Synthetic Example

These examples illustrate the preparation of compounds having Formula I.

Synthesis Example 1

2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-benzo[1,2-c:4, 5-c']dipyrrole-1,3,5,7(2H,6H)-tetron (2).

2,2'-bis(trifluoromethyl)benzidine (171.4 g, 535.3 mmol, 4 eq), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (5 g), pyridine (50 ml) And a mixture of N-methylpyrrolidinone (200 ml) was heated at 130° C. for 1 hour under a nitrogen atmosphere. Thereafter, the remaining amount of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in portions of 5 g at 130° C. over a period of 5 hours (total 30 g, total 133.8 mmol). The mixture was then heated at 150° C. for 2 days and at 180° C. for 1 day. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% ethyl acetate and heptane to give an excess of 2,2'-bis(trifluoromethyl)benzidine. Was recovered. The residue was taken up on celite and subjected to chromatography on silica gel using gradient elution with a mixture of ethyl acetate and hexane. Fractions containing diimide-diamine were combined, the eluent was evaporated, the residue was dissolved in a mixture of ethyl acetate and hexane 1:1, and the crystallized product was combined by filtration and dried in vacuo to give 40.2 g of compound 2 Got it. Compound 2 can also be obtained by direct crystallization from a crude reaction mixture. In this way, 2,2'-bis(trifluoromethyl)benzidine (171.4 g, 535.3 mmol, 4 eq), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (5 g), pyridine A mixture of (50 ml) and N-methylpyrrolidinone (200 ml) was heated at 130° C. for 1 hour under a nitrogen atmosphere. Then, an additional amount of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in portions of 5 g each over a period of 5 hours at 130°C (total 30 g). The mixture was then heated at 150° C. for 16 hours. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was dissolved in 1 L of 1:1 ethyl acetate and hexane and allowed to stand at ambient temperature to periodically collect the precipitated product to collect 33.36 g of the product. The product was obtained. The product can be further recrystallized from propyl acetate. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 2.02-2.09 (m, 2H), 2.29-2.34 (m, 2H), 3.25-3.30 (m, 4H), 5.71 (s, 4H), 6.77 ( dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.94-6.96 (m, 4H), 7.39-7.41 (m, 2H), 7.52 (2, 2H, J = 9 Hz), 7.68-7.70 (m , 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 178.4, 149.5, 138.4, 133.6, 132.6, 132.1, 130.1, 128.3, 122.8, 122.2, 116.1, 110.7, 38.4, 22.3. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.4, 57.1. Matrix Assisted Laser Desorption/Ionization time-of-flight mass spectrometry ("MALDI TOF MS"): 829.1671 (MH+).

Synthesis Example 2

2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-4,8-ethanobenzo[1, 2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetron (4).

Method A:

In a stirred solution of 2,2'-bis(trifluoromethyl)benzidine (76.86 g, 240 mmol, 4 equivalents) in pyridine (30 ml) and N-methylpyrrolidinone (150 ml) 50 ml under nitrogen atmosphere A suspension of bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride ("bicyclooctanetetracarboxylic dianhydride") (15 g, 60 mmol) was added little by little. . The resulting mixture was heated at 180° C. for 2 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% ethyl acetate and heptane to give an excess of 2,2'-bis(trifluoromethyl)benzidine. Was recovered. The residue was taken up on celite and subjected to chromatography on silica gel using gradient elution with a mixture of ethyl acetate and hexane. Fractions containing diimide-diamine were combined and the eluent was evaporated and dried in vacuo to give 21.23 g of compound 4 .

Method B:

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

¹ H-NMR (DMSO-d ₆ , 500 MHz): 1.53 (s, 4H), 2.61 (s, 2H), 3.40 (s, 4H), 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 2 Hz, J2 = 8 Hz), 6.97 (s, 2H), 6.98 (d, 2H, J = 7 Hz), 7.46 (d, 2H, J = 8 Hz), 7.67 (dd, 2H, J1 = 2 Hz , J2 = 8 Hz), 7.80 (d, 2H, J = 2 Hz). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 177.9, 149.6, 138.6, 133.8, 132.6, 132.2, 130.3, 129.0, 128.8, 128.2, 128.0, 125.7, 125.0, 124.7, 123.5, 122.9, 122.2, 116.2, 110.7, 43.1, 28.8, 17.6. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.3, 57.0. MALDI TOF MS: 855.1810 (MH+).

Synthesis Example 3

2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-4,8-ethenobenzo[1, 2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H)-tetron (5).

In a stirred solution of 2,2'-bis(trifluoromethyl)benzidine (77.43 g, 241.8 mmol, 4 equivalents) in pyridine (30 ml) and N-methylpyrrolidinone (150 ml), 50 ml under nitrogen atmosphere A suspension of bicyclooctenetetracarboxylic dianhydride (15 g, 60.45 mmol) in N-methylpyrrolidinone was added little by little. The resulting mixture was heated at 180° C. for 7 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% ethyl acetate and heptane to give an excess of 2,2'-bis(trifluoromethyl)benzidine. Was recovered. The residue was taken up on celite and subjected to chromatography on silica gel using gradient elution with a mixture of ethyl acetate and hexane. Fractions containing diimide-diamine were combined and the eluent was evaporated and dried in vacuo to give 21.23 g of compound 5 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 3.49 (s, 4H), 3.57 (br.S, 2H), 5.72 (s, 4H), 6.37 (t, 2H, J = 4 Hz), 6.78 (dd, 2H, J1 = 8Hz, J2 = 2 Hz), 6.95-6.97 (m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.47 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.61 (d, 2H, J = 2 Hz). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 176.9, 149.6, 138.5, 133.5, 133.9, 132.6, 132.0, 131.6, 129.9, 129.0, 128.7, 128.2, 128.0, 125.7, 125.0, 124.2, 123.5, 122.8, 122.1, 116.2, 110.6, 43.0, 34.5. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.4, 57.1. MALDI TOF MS: 853.1654 (MH+).

Synthesis Example 4

2,2'-(6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4,4'-diyl)bis[6-bis(2 ,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-4,8-ethenobenzo[1,2-c:4,5 -c']dipyrrole-1,3,5,7(2H,6H)-tetron] (7).

2,2′-bis(trifluoromethyl)benzidine (77.43 g, 241.8 mmol, 2 eq), pyridine (20 ml), N-methylpyrrolidinone (100 ml) and bicyclooctenetetracarboxylic dianhydride A mixture of (15 g, 60.45 mmol) was stirred while heating at 180° C. for 6 days under a nitrogen atmosphere. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was taken up on celite and subjected to chromatography on silica gel using gradient elution with a mixture of ethyl acetate and hexane. . Fractions containing diimide-diamine were combined and the eluent was evaporated and dried in vacuo to give 14.8 g of compound 5 . Fractions containing tetraimide-diamine were combined and the eluent was evaporated and dried in vacuo to give 8.75 g of compound 7 . Compound 7 : ¹ H-NMR (DMSO-d ₆ , 500 MHz): 3.50 (s, 4H), 3.51 (s, 4H), 3.58 (br. S, 4H), 5.72 (s, 4H), 6.38 (t , 4H, J = 4 Hz), 6.78 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.95-6.97 (m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.47 (dd , 2H, J1 = 8 Hz, J2 = 2 Hz), 7.56-7.61 (m, 6H), 7.72 (s, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 176.92, 176.86, 149.6, 138.6, 136.1, 133.9, 133.0, 132.9, 132.6, 132.0, 131.7, 130.2, 129.9, 128.2, 128.0, 125.7, 1245.0, 124.8, 124.5, 124.4, 124.2, 123.5, 122.8, 122.6, 122.1, 116.2, 110.67, 110.62, 48.9, 43.00, 42.96, 34.5. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.4, 57.2, 57.1. MALDI TOF MS: 1385.2532 (MH+).

Synthesis Example 5

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

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

In a control experiment, tert-butyltricyclotetradecenetetracarboxylic dianhydride was found to be non-reactive with BPDA even at elevated temperatures.

2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-9-(1,1-dimethylethyl)-3a, 3b,4,4a,7a,8,8a,8b-octahydro-4,8-ethenopyrrolo[3',4':3,4]cyclobut[1,2-f]isoindole-1,3 ,5,7(2H,6H)-tetron (6).

In a stirred solution of 2,2'-bis(trifluoromethyl)benzidine (19.4 g, 60.55 mmol, 4 equivalents) in pyridine (10 ml) and N-methylpyrrolidinone (80 ml) at 100° C. under nitrogen atmosphere A solution of tert-butyltricyclotetradecenetetracarboxylic dianhydride (5 g, 15.14 mmol) in N-methylpyrrolidinone (50 ml) was added dropwise over 6 hours. Then the mixture was heated at 180° C. for 8 days. The mixture is cooled to ambient temperature, the solvent is distilled off using a rotary evaporator, and the residue is taken up on celite and on silica gel using gradient elution with hexane and dichloromethane and a mixture of hexane and ethyl acetate. It was subjected to chromatography. Fractions containing diimide-diamine were combined, the eluent was evaporated and the residue was dried in vacuo to give 8.7 g of compound 6 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 1.06 (s, 9H), 2.77 (dd, 1H, J1 = 7 Hz, J2 = 3 Hz), 2.83-2.85 (m, 1H), 2.93-2.96 (m, 2H), 3.02 (dd, 1H, J1= 9 Hz, J2 = 2 Hz), 3.07-3.09 (m, 1H), 3.33-3.35 (m, 1H), 3.52 (br.s, 1H), 5.73 (s, 4H), 6.22 (dd, 1H, J1 = 7 Hz, J2 = 1.5 Hz), 6.80 (t, 2H, J = 8 Hz), 6.97-7.00 (m, 4H), 7.45-7.47 (m) , 3H), 7.59-7.61 (m, 2H), 7.80 (s, 1H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 177.9, 177.85, 177.5, 177.1, 152.1, 149.57, 149.54, 138.44, 138.37, 134.0, 133.7, 132.8, 132.6, 132.2, 130.2, 129.8, 129.7, 129.9, 128.96, 128.3, 128.0, 125.7, 125.68, 125.11, 1245.0, 124.9, 124.8, 123.53, 123.5, 122.9, 122.8, 122.3, 122.2, 122.1, 116.2, 110.7, 110.66, 43.3, 43.2, 41.8, 41.2, 36.4, 34.5, 34.0, 29.8. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.6, 57.3, 57.1, 57.0. MALDI TOF MS: 935.2439 (MH+).

Synthesis Example 6

3a,3b,4,4a,7a,8,8a,8b-octahydro-9-methyl-4,8-ethenofuro[3',4':3,4]cyclobut[1,2-f] Isobenzofuran-1,3,5,7-tetron.

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

In control experiments, methyltricyclotetradecenetetracarboxylic dianhydride was found to be non-reactive with BPDA, even at elevated temperatures.

2,6-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-9-(1,1-dimethylethyl)-3a, 3b,4,4a,7a,8,8a,8b-octahydro-4,8-ethenopyrrolo[3',4':3,4]cyclobut[1,2-f]isoindole-1,3 ,5,7(2H,6H)-tetron (6a).

2,2′-bis(trifluoromethyl)benzidine (66.66 g, 208.15 mmol, 4 eq), methyltricyclotetradecenetetracarboxylic dianhydride (2.5 g, 1 :0.2 ratio of 9-methyl and 3- A mixture of methyl regioisomers), a mixture of pyridine (20 ml) and N-methylpyrrolidinone (100 ml) was heated at 150° C. for 1 hour under a nitrogen atmosphere. Thereafter, an additional amount of methyltricyclotetradecenetetracarboxylic dianhydride was added in portions of 2.5 g each over a period of 5 hours at 130°C (total 15 g). Then the mixture was heated at 180° C. for 6 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% propyl acetate and heptane to give an excess of 2,2'-bis(trifluoromethyl)benzidine. Was recovered. The residue was taken up on celite and subjected to chromatography on silica gel using gradient elution with a mixture of propyl acetate and hexane. Fractions containing diimide-diamine were combined and the eluent was evaporated and dried in vacuo to give 20.1 g of compound 6a . Data for 9-methyl regioisomer: ¹ H-NMR (DMSO-d ₆ , 500 MHz): 1.92 (s, 3H), 2.72-2.74 (m, 1H), 2.84-2.86 (m, 1H), 2.89- 2.92 (m, 1H), 2.94-2.98 (m, 1H), 3.03 (dd, 1H, J1 = 8 Hz, J2 = 3 Hz), 3.11 (dd, 1H, J1 = 8 Hz, J2 = 3 Hz), 3.16 (br.s, 1H), 3.25 (p, 1H, J = 3 Hz), 7.73 (s, 4H), 6.11 (br. s, 1H), 6.78-6.81 (m, 2H), 6.97-6.99 ( m, 4H), 7.41-7.47 (m, 3H), 7.56-7.62 (m, 2H), 7.80 (d, 1H, J = 1.5 Hz). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 177.9, 177.8, 177.5, 177.3, 149.58, 149.55, 141.2, 138.5, 138.4, 134.0, 133.7, 132.7, 132.6, 132.2, 130.3, 129.9, 128.9, 128.7, 128.3, 128.0, 127.3, 125.7, 125.1, 125.0, 124.9, 124.8, 124.2, 123.5, 122.9, 122.8, 122.3, 122.1, 116.2, 110.7, 43.11, 42.35, 41.6, 41.3, 39.2, 35.7, 22.8. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.5, 57.3, 57.04, 57.02. MALDI TOF: 893.1969 (MH+).

Synthesis Example 7

2,5-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-hexahydro-benzo[1,2-c:4, 5-c']dipyrrole-1,3,5,7(2H,6H)-tetron (8) . 2,2'-bis(trifluoromethyl)benzidine (153 g, 477.8 mmol), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (5 g), pyridine (20 ml) and N- A mixture of methylpyrrolidinone (150 ml) was heated at 150° C. for 1 hour under a nitrogen atmosphere. Thereafter, the remaining amount of 1,2,3,4-cyclohexanetetracarboxylic dianhydride was added in 5 g portions at 150° C. over a period of 4 hours (total 25 g, total 118.97 mmol). The mixture was then heated at 180° C. for 2.5 weeks. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 20% ethyl acetate and heptane to give an excess of 2,2'-bis(trifluoromethyl)benzidine. Was recovered. The residue was taken up on celite and subjected to chromatography on silica gel (twice) using gradient elution with a mixture of ethyl acetate and hexane. Fractions containing diimide-diamine were combined and the eluent was evaporated and dried in vacuo to give 3 g of compound 8 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 2.56 (t, 2H, J = 9 Hz), 3.73 (q, 2H, J = 8 Hz), 3.80 (d, 2H, J = 8 Hz), 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.97-6.99 (m, 4H), 7.46 (d, 2H, J = 9 Hz), 7.65 (d, 2H , J = 9 Hz), 7.85 (s, 2H). ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.0, 57.2.

Synthesis Example 8

Compound 9 . 2,2'-bis(trifluoromethyl)benzidine (132.6 g, 414.08 mmol), 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl) -A mixture of naphtho[1,2-c]furan-1,3-dione (5 g), pyridine (20 ml) and N-methylpyrrolidinone (150 ml) at 150° C. for 1 hour under a nitrogen atmosphere Heated. Thereafter, the remaining amount of dianhydride was added in portions of 5 g at 150° C. over a period of 2.5 hours (total 30 g, total 118.97 mmol). The mixture was then heated at 180° C. for 3 days. The mixture was cooled to ambient temperature, the solvent was distilled off using a rotary evaporator, and the residue was extracted several times with a hot mixture of 10% propyl acetate and heptane to give an excess of 2,2'-bis(trifluoromethyl)benzidine. Was recovered. The residue was taken up on celite and subjected to chromatography on silica gel using gradient elution with a mixture of propyl acetate and hexane. Fractions containing diimide-diamine were combined, and the eluent was evaporated and dried in vacuo to give a total of 34.1 g of compound 9 .

Synthesis Example 9

5,5'-oxybis[2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl]-1H-isoindole-1,3(2H) -Dione ( 10 ) and compound 11 . A mixture of 2,2'-bis(trifluoromethyl)benzidine (61.94 g, 6 equivalents) and oxydiphthalic dianhydride (10 g, 32.24 mmol) was heated at 220° C. for 1 hour under an inert atmosphere. Thereafter, the excess diamine was sublimed at 260-265° C. in vacuum. The residue was dissolved in 150 ml of ethyl acetate, taken up on celite, and subjected to chromatography on silica gel using gradient elution with a mixture of hexane and ethyl acetate. Fractions containing pure trimer were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried at 150° C. for 1 hour in vacuum in a glovebox to give 16.13 g of product 10 . Fractions containing somewhat impure trimers were combined, the eluent was evaporated and the residue was dried using a rotary evaporator to give 3.53 g of compound 10 . Fractions containing pure compound 11 were combined, the eluent was evaporated and the residue was dried at 150° C. in vacuo to give 2.24 g of compound 11 .

Compound 10 : ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.98 (d, 2H, J = 3 Hz), 7.00 (d, 2H, J = 9 Hz), 7.48 (d, 2H, J = 8 Hz), 7.65-7.68 (m, 4H), 7.75 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.94 (d, 2H, J = 2 Hz), 8.11-8.13 (m, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 166.4, 166.3, 161.4, 149.5, 138.0, 135.0, 133.7, 132.7, 132.0, 130.0, 129.0, 128.7, 128.3, 128.0, 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. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 56.97, 56.98, 57.3.

Compound 11: ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.73 (s, 4H), 6.80 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.98 (d, 2H, J = 2 Hz), 7.00 (d, 2H, J = 8 Hz), 7.48 (d, 2H, J = 9 Hz), 7.67-7.69 (m, 10 H), 7.75 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.86 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.94 (d, 2H, J = 2 Hz), 8.05 (d, 2H, J = 2 Hz), 8.11-8.15 (m , 4H).

Synthesis Example 10.

5,5'-oxybis[1,3-phenylenebis(oxy-3,1-phenylen)yl]-1H-isoindole-1,3(2H)-dione (12) . A mixture of 1,3-bis(3-aminophenoxy)benzene (56.55 g, 193.44 mmol, 6 equivalents) and oxydiphthalic dianhydride (10 g, 32.24 mmol) was heated at 220° C. for 1 hour under an inert atmosphere. Then it was heated at 265° C. in vacuum. The residue was dissolved in 150 ml of ethyl acetate, taken up on celite, and subjected to partial chromatographic purification on silica gel using gradient elution with a mixture of hexane and ethyl acetate. Fractions containing pure trimer were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried at 150° C. for 1 hour in vacuum in a glovebox. Compound 12 : ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.21 (s, 4H), 6.16 (dd, 2H, J1 = 8 Hz, J2 = 3 Hz), 6.22 (t, 2H, J = 2 Hz), 6.33 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.66 (t, 2H, J = 2 Hz), 6.74-6.78 (m, 4H), 6.98 (t, 2H, J= 8 Hz), 7.11 (dd, 2H, J1 = 8Hz, J2 = 2 Hz), 7.16 (t, 2H, J = 2Hz), 7.23 (br d, 2H, J = 8 Hz), 7.36 (t, 2H, J = 8 Hz), 7.53 (t, 2H, J = 8 Hz), 7.59-7.52 (m, 4H), 8.04 (d, 2H, J = ). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 166.5, 166.3, 161.3, 159.0, 157.7, 157.3, 156.9, 156.0, 134.9, 133.7, 131.5, 130.7, 130.6, 127.6, 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''-pentaoxodispiro[4,7-methano-5H-isoindole-5,1'-cyclopentane-3',5''-[4,7]methano[5H] -Isoindole ( 13 ).A mixture of 2,2'-bis(trifluoromethyl)benzidine (41.66 g, 130.08 mmol, 10 eq) and the corresponding spirocyclic dianhydride (5 g, 13.01 mmol) was placed in an inert atmosphere. And heated for 1.5 h at 220° C. The residue was dissolved in ethyl acetate, taken up on celite, and chromatographic purification on silica gel using gradient elution with hexane and ethyl acetate and a mixture of hexane and propyl acetate. Fractions containing pure product were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried in a glovebox in vacuo at 150° C. for 1 hour to give 8.59 g of compound 13. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 1.30-1.47 (m, 4H), 1.75-2.13 (m, 8H), 2.65 (br. s, 4H), 2.97-3.26 (m, 4H), 5.72 (s, 4H), 6.79 (d, 2H, J = 9 Hz), 6.96-6.97 (m, 4H), 7.43 (d, 2H, J = 8 Hz), 7.58 (d, 2H, J = 8 Hz), 7.74 ( ^{. s, 2H) 13 C-} NMR (DMSO-d 6, 125 MHz): 223.8, 223.3, 117.97, 117.93, 117.75, 117.81, 149.5, 138.5, 133.8, 132.6, 132.3, 130.2, 130.1, 129.2, 129.0, 128.75 , 128.5, 128.0, 127.9, 127.8, 127.2, 125.7, 125.0, 124.7, 124.6, 123.5, 122.9, 122.2, 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. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.3, 57.0.

Synthesis Example 12

2,2'-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-[5,5'-bi-1H-isoindole ]-1,1',3,3'(2H,2'H)-tetron ( 14 ). A mixture of 2,2'-bis(trifluoromethyl)benzidine (113.7 g, 355.1 mmol, 6.3 eq) and biphenyltetracarboxylic dianhydride (16.58 g, 56.35 mmol) with a small amount of N-methylpyrrolidinone Was heated at 220° C. for 1 hour in an inert atmosphere and then heated at the same temperature in vacuum for 3 hours. The mixture was cooled, dissolved in ethyl acetate, taken up on celite, and subjected to chromatographic purification on silica gel using gradient elution with a mixture of hexane and ethyl acetate. Fractions containing pure product were combined, the eluent was evaporated to a volume of 200 ml using a rotary evaporator and the crystallized product was collected by filtration to give 17.57 g of compound 14 . Fractions containing the lower purity product were combined, the eluent was evaporated and the residue was dissolved in ethyl acetate, then 1 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 12.95 g of a lower purity material. The product containing a small amount of oligomer can also be obtained by direct crystallization by dissolving the initial crude mixture in ethyl acetate, adding 1 volume of hexane and collecting the formed precipitate. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 5.73 (s, 4H), 6.81 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 6.99 (d, 2H, J = 2 Hz), 7.02 (d, 2H, J = 9 Hz), 7.50 (d, 2H, J = 8 Hz), 7.79 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 7.98 (d, 2H, J = 2 Hz), 8.14 (d, 2H, J = 8 Hz), 8.43 (dd, 2H, J1 = 8 Hz, J2 = 2 Hz), 8.50 (s, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 166.8, 149.6, 144.9, 138.0, 134.4, 133.7, 133.2, 132.7, 132.1, 131.9, 130.3, 128.9, 128.3, 125.1, 124.8, 124.8, 123.0, 122.9, 116.2, 110.7, 110.66. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.3, 57.0.

Synthesis Example 13

Dodecahydro-2,2'-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-[5,5'-bi- 1H-isoindole]-1,1',3,3'(2H,2'H)-tetron ( 15 ). 2,2'-bis(trifluoromethyl)benzidine (52.27 g, 163.24 mmol, 10 eq), dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride (5 g, 16.32 mmol) ) And N-methylpyrrolidinone (5 ml) were heated under an inert atmosphere at 220° C. for 1 hour, and then heated in vacuum at the same temperature for 1 hour. The mixture was cooled, dissolved in ethyl acetate, taken up on celite, and subjected to chromatographic purification on silica gel using gradient elution with a mixture of hexane and ethyl acetate. Fractions containing pure product were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried at 150° C. in vacuo to give 8.92 g of compound 15 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 0.99 (br s, 2H), 1.32 (br. s, 4H), 1.61-1.63 (m, 4H), 1.97-2.04 (m, 2H), 2.14 -2.17 (m, 2H), 2.99-3.05 (m, 2H), 3.22-3.26 (m, 2H), 5.71 (s, 4H), 6.79 (dd, 2H, J1 = 9 Hz, J2 = 2 Hz), 6.96-6.97 (m, 4H), 7.42 (d, 2H, J = 8 Hz), 7.61 (d, 2H, J = 8 Hz), 7.78 (s, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 179.0, 178.4, 149.5, 138.1, 133.6, 132.64, 132.57, 132.55, 130.1, 128.3, 125.7, 123.5, 122.3, 120.0, 116.2, 110.67, 110.63, 110.59, 29.34, 29.25, 25.52, 21.69, 21.66. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 57.25, 57.22, 57.06, 57.04.

Synthesis Example 14

11-Methyl-2,8-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-11-(trifluoromethyl)- 1H-pyrano[2,3-f:5,6-f']diisoindole-1,3,7,9(2H,8H,11H)-tetron ( 16 ). 2,2'-bis(trifluoromethyl)benzidine (51 g, 159.26 mmol, 10 eq), the corresponding xanthene tetracarboxylic dianhydride (10.2 g, 25.23 mmol) and N-methylpyrrolidinone (25 ml) ) Was heated at 220° C. for 1 hour under an inert atmosphere, and then heated in vacuum at the same temperature for 1 hour. The mixture was dissolved in ethyl acetate, taken up on celite, and subjected to chromatographic purification on silica gel using gradient elution with a mixture of hexane and ethyl acetate. Fractions containing pure product were combined, the eluent was evaporated using a rotary evaporator, and the residue was dried in vacuo to give 16.62 g of compound 16 . ¹ H-NMR (DMSO-d ₆ , 500 MHz): 2.39 (s, 3H), 5.74 (s, 4H), 6.82 (d, 2H, J = 8 Hz), 7.00-7.03 (m, 4H), 7.51 (d, 2H, J = 8 Hz), 7.78 (d, 2H, J = 8 Hz), 7.91 (s, 2H), 7.97 (d, 2H, J = 2 Hz), 8.51 (s, 2H). ¹³ C-NMR (DMSO-d ₆ , 125 MHz): 170.8, 166.1, 165.7, 155.5, 149.6, 138.2, 134.8, 133.8, 132.7, 132.0, 130.3, 128.8, 128.1, 127.9, 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. ¹⁹ F-NMR (DMSO-d ₆ , 470 MHz): 75.5, 57,4, 57.0.

Synthesis Example 15

2,6-bis[4-[(4-aminophenyl)sulfonyl]phenyl]-benzo[1,2-c:4,5-c']dipyrrole-1,3,5,7(2H,6H )-Tetron ( 17 ). 4,4'-sulfonylbis[benzeneamine] (56.92 g, 229.2 mmol, 5 eq), pyromellitic dianhydride (10 g, 45.84 mmol) and N-methylpyrrolidinone (100 ml) for 1.5 hours It was heated at 177°C while stirring under a nitrogen atmosphere. The reaction mixture was cooled, diluted with ethyl acetate (200 ml), filtered, washed with ethyl acetate and dried in vacuo to give 26 g of crude product containing approximately 10% higher oligomer product, which It was used for polymerization without further purification. ¹ H-NMR (DMSO-d ₆ , 500 MHz): 6.22 (s 4H), 6.64 (d, 4H, J = 9 Hz), 7.59 (d, 4H, J = 9 Hz), 7.72 (d, 4H, J = 9 Hz), 8.02 (d, 4H, J = 9 Hz), 8.40 (s, 2H).

Synthesis Example 16

A 500 mL round-bottom flask equipped with a Dean-Stark trap under a nitrogen sweep, and a stir bar, with 22.41 g of TFMB (0.07 mol) and 250.71 g of 1-methyl-2-pyrrolidinone (NMP). Charged. The mixture was stirred for about 30 minutes at room temperature under nitrogen. After that, 26.74 g (0.06 mol) of 6FDA was slowly added little by little to the stirring solution of diamine. After completion of the dianhydride addition, an additional 27.86 g of NMP was used to wash any residual dianhydride powder from the walls of the vessel and flask and the resulting mixture was stirred at room temperature overnight. Thereafter, 80 mL of m-xylene was added to the mixture and refluxed for 8 hours to remove water with a Dean-Stark trap. After the mixture was cooled to room temperature, it was precipitated in 1,500 mL of methanol with stirring, the resulting suspension was filtered and the collected solid was dried under vacuum.

The resulting diamine monomer had a molecular weight of about 5,000 Da. Thus, it had about 7 repeating diimides in the core (m is about 7 in Formula I). This solid was used for reaction with the dianhydride(s) without further separation or purification to form a polyamic acid polymer.

Synthesis Example 17

6,6'-(sulfonyldi-4,1-phenylene)bis-1H-furo[3,4-f]isoindole-1,3,5,7(6H)-tetron ( 33 ). Synthesis of pyromellitic anhydride. To a stirred solution of pyromellitic dianhydride (43.6 g, 0.2 mol) in 400 ml THF was added a mixture of 30 ml tetrahydrofuran and 5 ml water over a period of 48 hours at ambient temperature. After that, 250 ml of tetrahydrofuran was evaporated using a rotary evaporator, and the resulting solution was treated with hexane (100 ml) until precipitation occurred. The precipitate was removed by filtration. The filtrate was maintained at -24°C for 3 hours. The precipitate was filtered and dried in vacuo to give 14.9 g of product. An additional amount of product formed overnight at -24° C. was filtered and dried in vacuo to give 6.85 g of product. ¹ H-NMR (acetone-d ₆ , 500 MHz): 6.39 (s 2H), 12.46 (br. s, 2H).

The pyromellitic monoanhydride (28.16 g, 119.26 mmol, 2.3 eq) was added to 4,4'-sulfonylbis[benzeneamine] (12.97 g, 52.2 mmol) in 200 ml of dry tetrahydrofuran for 1 hour at ambient temperature. And stirred together. The mixture was diluted with acetone (100 ml), washed with acetone, and passed through a column packed with silica gel. The fractions containing the product are combined, the solvent is evaporated using a rotary evaporator, the residue is treated with approximately 500 ml of water, the fine precipitate is filtered off, washed with water and dried in vacuo to amic hexaacid ( 31.1 g) was obtained: ¹ H-NMR (DMSO-d ₆ , 500 MHz): 7.78 (s, 2H), 7.86 (d, 4H, J = 9 Hz), 7.91 (d, 4H, J = 9 Hz) , 8.16 (s, 2H), 10.89 (s, 2H), 13.56 (br. s, 6H).

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

Polymer Example

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

Polymer Example 1

Polymer 1. Polymerization of compound 6 and BPDA:

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

Polymer Example 2

Polymer 2. Polymerization of Compound 2 and BPDA:

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

Polymer Example 3

Polymer 3. Polymerization of Compound 4 and BPDA:

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

Polymer Example 4

Polymer 4. Polymerization of compound 5 and BPDA:

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

Polymer Example 5

Polymer 5. Polymerization of compound 9 and BPDA:

Diimide-diamine monomer 9 (3 g, 3.316 mmol), BPDA (0.956 g, 3.25 mmol) and N-methylpyrrolidinone (22.6 g) were mixed using a roller under an inert atmosphere, and 3135 cP of polyamic acid PMDA (7 mg) was added after allowing to react at ambient temperature to final viscosity. GPC: Mn = 106690, Mw = 240045, Mp = 210783, Mz = 420038, PDI = 2.25.

Polymer Example 6

Polymer 6. Polymerization of compound 8 and BPDA:

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

Polymer Example 7

Polymer 7. Polymerization of compounds 11 and 12 with oxydiphthalic anhydride

Diimide-diamine monomer 11 (1.799 g, 1.192 mmol), diimide monomer 12 (0.171 g, 0.199 mmol), oxydiphthalic anhydride (0.42 g, 1.354 mmol) and N-methylpyrrolidinone (13.6 g) are inactive Mixing using a roller under atmosphere, and after allowing to react at ambient temperature, oxydiphthalic anhydride (10 mg) was added. GPC: Mn = 52301, Mw = 124710, Mp = 109452, Mz = 205698, PDI = 2.38.

Polymer Example 8

Polymer 8. Polymerization of compound 15 and BPDA:

Diimide-diamine monomer 15 (8.5 g, 9.33 mmol), BPDA (2.73 g, 9.29 mmol) and N-methylpyrrolidinone (63.6 g) were added to a 250 ml glass reactor, and the final viscosity of 4339 cP polyamic acid Until the mixture was stirred at ambient temperature under a nitrogen atmosphere. GPC: Mn = 104310, Mw = 234898, Mp = 222275, Mz = 378468, PDI = 2.25.

Polymer Example 9

Polymer 9:

In a 250 mL reaction flask equipped with a nitrogen inlet and outlet, and a mechanical stirrer, 3.46 g of TFMB (0.0108 mol), 6.51 g of compound 9 (0.0072 mol), and 88.58 g of 1-methyl-2-pyrrolidinone ( NMP) was charged. The mixture was stirred for about 30 minutes at room temperature under nitrogen. Then, 3.64 g (0.009 mol) of XFDA was slowly added little by little to the stirring solution of diamine, followed by the addition of 3.76 g (0.00846 mol) of 6FDA. After completion of the dianhydride addition, an additional 9.84 g of NMP was used to wash the vessel and any residual dianhydride powder from the walls of the 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 portions (about 0.8 g) over time to increase the molecular weight of the polymer and the viscosity of the polymer solution. For testing, a small sample was taken from the reaction flask and the solution viscosity was monitored using a Brookfield cone and plate viscometry. A total of 3.2 g of this finishing solution was added (0.16 g, 0.00036 mol 6FDA). The reaction was allowed to proceed overnight at room temperature under gentle agitation to bring the polymer to equilibrium. The final viscosity of the polymer solution was 1,100 cP at 25°C.

Polymer Examples 10-14

Polymers 10-14 were prepared using a procedure similar to Polymer Example 9. The polymer composition is provided in Table 1 below.

[Table 1]

Polymer composition

Polymer Example 15

Polymer 15. Polymerization of 6FDA and BPDA with pre-imidated bicyclooctanetetracarboxylic dianhydride in situ.

2,2'-bis(trifluoromethyl)benzidine (11.902 g, 37.17 mmol), bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride (6.51 g, 26.02 mmol) ) And 20 ml of N-methylpyrrolidinone were heated at 180° C. with a Dean-Stark apparatus for 2.5 hours under an inert atmosphere. After that, N-methylpyrrolidinone was distilled off in vacuo. The NMR spectral data of the resulting glassy residue showed complete imidization. The solid was redissolved in N-methylpyrrolidinone at 150° C., transferred to a glass reactor, and 3,3′,4,4′-biphenyltetracarboxylic dianhydride BPDA (1.094 g, under nitrogen atmosphere at ambient temperature, 3.717 mmol), 4,4'-hexafluoroisopropylidenebisphthalic acid dianhydride 6FDA (2.808 g, 6.32 mmol) was stirred, and the total amount of N-methylpyrrolidinone was 129 g. Then, an additional amount of 6FDA (total 480 mg, 1.08 mmol) was added to a final viscosity of 10430 cP. GPC: Mn = 88006, Mw = 205641, Mp = 201618, Mz = 335818, PDI = 2.34.

Polymer Example 16

Polymer 16. Norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracar pre-imidated in situ Polymerization of acid dianhydride (CpODA) and BPDA.

2,2'-bis(trifluoromethyl)benzidine (5.95 g, 18.58 mmol), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5, A mixture of 5``,6,6''-tetracarboxylic dianhydride CpODA (5.0 g, 13.08 mmol) and 6 ml of N-methylpyrrolidinone was added at 180° C. for 3 hours under an inert atmosphere with a Dean-Stark apparatus. After heating at, 6 ml of N-methylpyrrolidinone were added and the mixture was heated for an additional 3 hours. After that, N-methylpyrrolidinone was distilled off in vacuo. The solid was redissolved in N-methylpyrrolidinone (71 g), transferred to a glass reactor, and 3,3',4,4'-biphenyltetracarbosi at ambient temperature under a nitrogen atmosphere to a final viscosity of 22860 cP. After stirring with click dianhydride BPDA (1.53 g, 5.20 mmol), pyromellitic dianhydride PMDA (62 mg) was added. GPC: Mn = 80956, Mw = 188020, Mp = 169907, Mz = 313930, PDI = 2.32.

Polymer Example 17

Polymer 17. Polymerization of PMDA and BPDA with pre-imidated bicyclooctanetetracarboxylic dianhydride in situ.

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

Polymer Example 18

Polymer 18:

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

Film example

These examples illustrate the preparation of a polyimide film having Formula IV.

A Hunter Lab spectrophotometer was used to measure b* and yellowness with% transmittance (%T) over the wavelength range of 350 nm to 780 nm. Thermometry was performed on the film using a combination of thermogravimetric analysis and thermodynamic analysis suitable for the specific parameters reported herein. Mechanical properties were measured using equipment from Instron.

Film Examples 1 to 7

Using the polyamic acid, a polyimide film having Formula IV was prepared.

The polyamic acid solution was filtered through a microfilter, spin coated on a clean silicon wafer, soft-baked at 90° C. on a hot plate, and placed in a furnace. The furnace was purged with nitrogen and heated step by step to the maximum curing temperature. The wafer was removed from the furnace, immersed in water, and manually delaminated to obtain a sample of the polyimide film. The film composition is provided in Table 2 below. Film properties are provided in Table 3 below.

[Table 2]

Polyimide film

[Table 3]

Film properties

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

As can be seen from Table 3, polyimide films obtained from pre-imide-imide-containing monomers have beneficial properties, such as reduced chromaticity b*/yellowing degree YI, increased thermal stability Td (1%), It has improved mechanical properties and other properties.

Film Examples 8-13

Except for Film Example 9, the polyamic acid was used to prepare a polyimide film having Formula IV as described in Film Examples 1 to 7. In Film Example 9, the film was cured in air at a maximum temperature of 260°C.

The film composition is provided in Table 4 below. Film properties are provided in Table 5 below.

[Table 4]

Polyimide film

[Table 5]

Film properties

Film Examples 15-17

These examples illustrate the formation of polyimide films from monomers that have been preimidated in situ.

Polyimide films were prepared as described in Film Examples 1 to 7. The film composition is provided in Table 6 below. Film properties are provided in Table 7 below.

[Table 6]

Polyimide film

[Table 7]

Film properties

Note that not all of the above-described actions are required in the overall description or embodiments, some of the specific actions may not be required, and one or more additional actions may be performed in addition to those described. Also, the order of the listed actions is not necessarily the order in which the actions are performed.

In the foregoing specification, the concept has been described with reference to specific embodiments. However, those skilled in the art understand that various modifications and changes may be made without departing from the scope of the invention as set forth in the following claims. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

Benefits, other advantages, and problem solutions have been described above in connection with specific embodiments. However, any benefit, advantage, problem solution, and any feature(s) that may result in or clarify any benefit, advantage, or solution is an important, essential or essential feature of any or all claims. It should not be interpreted as.

For the sake of clarity, it should be understood that certain features described herein in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, for the sake of brevity the various features described in the context of a single embodiment may also be provided individually or in any subcombination. Use of the numerical ranges of the various ranges specified herein is referred to as an approximation, as if both the minimum and maximum values within the stated range were preceded by the word “about”. In this way, a slight variation above and below the stated range can be used to achieve substantially the same results as the values within the range. Further, the disclosure of these ranges is intended as a continuous range that includes all values between the minimum and maximum average values, including fractional values that may appear when some of the components of one value are mixed with components of different values. . Also, where wider and narrower ranges are disclosed, matching the minimum value of one range to the maximum value of another range and vice versa is within the consideration of the present invention.

Claims (10)

Diamines of Formula I:
[Formula I]

(here,
R ^a represents a tetracarboxylic acid component residue;
R ^b represents a diamine moiety;
m is an integer from 1 to 20). The diamine according to claim 1, wherein R ^a represents a residue of an aliphatic tetracarboxylic dianhydride or a polycyclic tetracarboxylic dianhydride. The diamine of claim 1, wherein R ^a is selected from the group consisting of formulas A1 to A36:

(here,
R ¹ is the same or different at each occurrence and is selected from the group consisting of alkyl, fluoroalkyl and silyl, and adjacent R ¹ groups may be joined together to form a double bond;
R ² , R ³ , and R ⁴ are the same or different at each occurrence and are selected from the group consisting of F, alkyl, fluoroalkyl, and silyl;
R ⁵ is H, halogen, cyano, hydroxyl, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, hydrocarbon aryl, substituted hydrocarbon aryl, heteroaryl, substituted heteroaryl, vinyl, and allyl Is selected from the group consisting of;
R ⁶ is a group consisting of halogen, cyano, hydroxyl, alkyl, heteroalkyl, alkoxy, heteroalkoxy, fluoroalkyl, silyl, hydrocarbon aryl, substituted hydrocarbon aryl, heteroaryl, substituted heteroaryl, vinyl, and allyl Is selected from;
R ⁸ and R ⁹ are the same or different at each occurrence and are selected from the group consisting of H, F, alkyl, fluoroalkyl, and silyl;
Q is selected from the group consisting of CR ⁸ R ⁹ , SiR ⁸ R ⁹ , S, SR ⁸ R ⁹ , S=O, SO ₂ , and C=O;
a is an integer from 0 to 6;
b is an integer from 0 to 3;
c, d, and e are the same or different and are integers from 0 to 2;
f is an integer from 0 to 4;
z is an integer from 1 to 6;
z1 is an integer from 0 to 6;
* Indicates the point of attachment). The diamine of claim 1, selected from the group consisting of compounds 1 to 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

. Acid dianhydride having formula IV:
[Formula IV]

(here,
R ^d represents a tetracarboxylic acid component residue;
R ^e represents a diamine moiety;
m is an integer from 1 to 20). The acid dianhydride of claim 5, wherein R ^e represents the residue of a fluorinated aromatic diamine. The acid dianhydride of claim 5, wherein R ^e is selected from the group consisting of formulas E1 to E16:

(here,
R ⁷ is the same or different at each occurrence and is selected from the group consisting of F, alkyl, aryl, R _f , and OR _f ;
R ⁸ and R ⁹ are the same or different at each occurrence and are selected from the group consisting of H, F, alkyl, fluoroalkyl, and silyl;
R ¹⁰ is the same or different at each occurrence and is selected from the group consisting of fluoroalkyl and fluoroalkoxy;
R ¹¹ is the same or different at each occurrence and is selected from the group consisting of F, alkyl, fluoroalkyl, and silyl;
R _f is C _1-3 perfluoroalkyl;
Q is selected from the group consisting of CR ⁸ R ⁹ , SiR ⁸ R ⁹ , S, SR ⁸ R ⁹ , S=O, SO ₂ , and C=O;
b is the same or different in each case and is an integer from 0 to 3;
c is the same or different in each case and is an integer from 0 to 2;
g is an integer from 0 to 4;
h is an integer from 0 to 6;
p is an integer from 1 to 10;
q is an integer from 0 to 5;
y is an integer from 0 to 2;
* Indicates the point of attachment). The acid dianhydride of claim 5, selected from the group consisting of compounds 25 to 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

. A polyamic acid composition that is a reaction product of at least one tetracarboxylic acid component and at least one diamine, wherein (a) the diamine comprises 1 to 100 mol% of a diamine having the formula I according to claim 1, or (b) The tetracarboxylic acid component comprises 1 to 100 mol% of a tetracarboxylic acid dianhydride having the formula IV according to claim 5, a polyamic acid composition. A polyimide produced by imidization of the polyamic acid of claim 9.

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