阅读说明：本技术 聚酰亚胺-聚亚芳基聚合物 (Polyimide-polyarylene polymers ) 是由 A·A·拉什福德 C·R·坎齐 M·K·加拉格尔 C·吉尔摩 金映锡 于 2020-11-13 设计创作，主要内容包括：公开了一种双-酰亚胺化合物,其包含被乙炔基部分所取代的两个或更多个芳基部分、和各自具有一个或多个极性取代基的两个或更多个芳基部分。进一步公开了一种聚合物组合物,其包含由以下的单体混合物聚合的共聚物：(a)包含双-酰亚胺化合物的一种或多种第一单体,所述双-酰亚胺化合物包含被乙炔基部分所取代的两个或更多个芳基部分、和各自具有一个或多个极性取代基的两个或更多个芳基部分；以及(b)包含两个或更多个环戊二烯酮部分的一种或多种第二单体。所述聚合物组合物在电子产品和显示器应用的使用中表现出有利的特性。(Disclosed is a bis-imide compound comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents. Further disclosed is a polymer composition comprising a copolymer polymerized from a monomer mixture of: (a) one or more first monomers comprising a bis-imide compound comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents; and (b) one or more second monomers comprising two or more cyclopentadienone moieties. The polymer compositions exhibit advantageous properties in use in electronic and display applications.)

1. A bis-imide compound comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents; wherein the bis-imide compound is selected from the group consisting of: a compound having formula 1a, a compound having formula 1b, and a compound having formula 1c,

wherein:

L¹is a quilt (Z)²)_yA substituted divalent aromatic linking group;

L²is a fused aromatic or alicyclic ring;

L³is a divalent linking group;

Z¹and Z²Is the same or different at each occurrence and is a polar group;

Ar¹is the same or different at each occurrence and is selected from the group consisting of C₆-C₃₀Aryl groups;

x1, x2, x3 and y are the same or different and are integers of 0 to 4;

v is an integer from 0 to 2, with the proviso that when L²V is 0 when it is an alicyclic ring;

w is an integer of 0 to 3;

x1+ y is an integer from 2 to 6;

x2+ v is an integer from 2 to 4; and is

x3+ w is an integer from 2 to 6.

2. The bis-imide compound of claim 1 wherein L¹Selected from the group consisting of: hydrocarbon aryl groups, heteroaryl groups, and substituted derivatives thereof.

3. The bis-imide compound of claim 2 wherein L²Selected from the group consisting of: a 4-to 6-membered alicyclic ring, a benzene ring, and a naphthalene ring.

4. The bis-imide compound as claimed in claim 3 wherein the polar group Z¹And Z²Selected from the group consisting of: OH, CO₂H、CO₂R、OR、CF₃、F、Cl、SH、SR、S(O)_nR、S(O)₂OH、S(O)₂OR、S₂R、NR₂NH (O) R, and

wherein:

r is selected from the group consisting of: H. halogen, C_1-30Alkyl radical, C_1-C30Heteroalkyl group, C_2-30Alkenyl radical, C_7-30Aralkyl radical, C_6-30Aryl, and C_4-30A heteroaryl group;

and:

n is an integer of 1 to 2.

5. The bis-imide compound as claimed in claim 4, wherein Ar¹Is the same or different at each occurrence and is selected from the group consisting of C₆-C₁₈Aryl groups.

6. A polymer composition comprising a copolymer polymerized from a monomer mixture of: (a) one or more first monomers comprising a bis-imide compound comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents; and (b) one or more second monomers comprising two or more cyclopentadienone moieties.

7. The polymer composition of claim 6, wherein the one or more first monomers are selected from the group consisting of: a compound having formula 1a, a compound having formula 1b, and a compound having formula 1c,

wherein:

L¹is a quilt (Z)²)_yA substituted divalent aromatic linking group;

L²is a fused aromatic or alicyclic ring;

L³is a divalent linking group;

Z¹and Z²Is the same or different at each occurrence and is a polar group;

Ar¹is the same or different at each occurrence and is selected from the group consisting of C₆-C₃₀Aryl groups;

x1, x2, x3 and y are the same or different and are integers of 0 to 3;

v is an integer from 0 to 2, with the proviso that when L²V is 0 when it is an alicyclic ring;

w is an integer of 0 to 3;

x1+ y is an integer from 2 to 6;

x2+ v is an integer from 2 to 4; and is

x3+ w is an integer from 2 to 6.

8. The polymer composition of claim 7, wherein the one or more second monomers are of formula 3,

wherein:

R⁷is the same or different at each occurrence and is selected from the group consisting of: H. substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_6-20Aryl, and substituted or unsubstituted C_4-20(ii) a heteroaryl group, wherein,

and:

Ar²is substituted or unsubstituted C_6-20An aryl group.

9. The polymer composition according to claim 8, wherein,wherein Ar is²Has the formula (4) shown in the specification,

wherein:

q is an integer of 1 to 3;

r is an integer of 0 to 2;

Ar³is the same or different at each occurrence and is selected from the group consisting of formula 5 and formula 6,

wherein:

R⁸is the same or different at each occurrence and is selected from the group consisting of: halogen, substituted or unsubstituted C_1-6Alkyl, aryl, and aryloxy groups;

c is an integer of 0 to 4;

d and e are the same or different at each occurrence and are each an integer from 0 to 3;

z is the same or different at each occurrence and is selected from the group consisting of:

covalent single bond, alkyl group, O, C (O), C (S), CF₂And C (CF)₃)₂。

10. The polymer composition of claim 9, wherein the copolymer is selected from the group consisting of:

Background

1. Field of the disclosure and claimed inventive concepts

The presently disclosed process (es), procedure(s), method(s), product(s), result(s), and/or concept (hereinafter collectively referred to as "the present disclosure") generally relate to novel organic compounds that can be used as monomer components for preparing polymers. In particular, functionalized bis-imide compounds can be copolymerized with cyclopentadienone-containing materials to produce polymers having characteristics well suited for electronic and display applications.

2. Background and applicable aspects of one or more inventive concepts of the present disclosure and claims

Polymers are increasingly used in electronic and display applications due to their widely variable properties and processability over conventional, existing materials. Polyphenylene polymers represent one such material. They can exhibit good chemical resistance, high T, required for many electronic and display applications_gAnd mechanical toughness. In addition, the polyphenylene polymer molecular weight and solution concentration can be adjusted to enable precise and convenient deposition by spin coating, a widely important industrial process. The aromatic structure of the cured film provides low dielectric constant, high thermal stability and low moisture absorption. The synthetic flexibility provided by heteroatom inclusion, copolymer formation, etc. makes available a family of materials that can be used to prepare highly specific applications.

Polyimides are another class of polymeric materials that have found widespread use in electronic and display applications since their first introduction (see, e.g., U.S.8,653,512b2). These materials can exhibit low dielectric constants, low moisture absorption, high T_gGood thermal stability, low Coefficient of Thermal Expansion (CTE), excellent chemical resistance, and flexible processability.

In view of the importance of these two types of polymeric materials, efforts have been made to produce hybrid polyphenylene-polyimide polymers for electronic and display applications. The polyphenylenes are generally recognized for their favorable low dielectric constant contribution, while polyimides can contribute to a high degree of modularity and tunable thermal and mechanical properties. The two types of materials can be combined into a single, unbranched polymer chain that can exhibit the strength of both polymer types with hybrid properties that can be tailored to specific end-use electronic and display applications. Polyphenylene-polyimide polymers are also known to exhibit spin-and slot-die coater compatibility, high coating uniformity, low defects and surface roughness, low outgassing, short cure times and low post-cure stress, among other useful properties. Films associated with these compositions can be prepared that exhibit a high degree of flexibility and toughness, high elongation, and thermal stability at elevated temperatures associated with processing conditions typical in electronic and display applications.

However, the broader industrial use of polyphenylene-polyimide polymers may be limited due to the relative insolubility of typical compositions in solvent systems commonly used in electronics and display applications. For example, certain polar, protic solvent systems are ineffective at solubilizing polyphenylene-polyimide polymers. Therefore, previous work has been directed to improving the solubility of polyphenylene-polyimide polymers in such industrially important solvents while maintaining the advantages of the overall material. The use of low molecular weight polymers and/or functionalization of the monomers have found limited effectiveness in this regard.

There is therefore a continuing need for new polyphenylene-polyimide polymers that exhibit enhanced solubility in polar, protic solvents, while retaining properties that make them useful in electronic and display applications.

Detailed Description

Before explaining at least one embodiment of the disclosure in detail, it is to be understood that the disclosure is not limited in its application to the details of construction and to the arrangements of the components or steps or methods set forth in the following description. The disclosure is capable of other embodiments or of being practiced or carried out in various ways. It is also to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.

Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have meanings that are commonly understood by those of ordinary skill in the art. Furthermore, unless the context requires otherwise, singular terms shall include the plural, and plural terms shall include the singular.

All patents, published patent applications, and non-patent publications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this disclosure pertains. All patents, published patent applications, and non-patent publications cited in any section of this application are expressly incorporated herein by reference in their entirety to the same extent as if each individual patent or publication were specifically and individually indicated to be incorporated by reference.

All of the terms and/or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. Although the terms and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations may be applied to the terms and/or methods and in the steps or in the series of steps of one or more methods described herein without departing from the concept, spirit and scope of the present disclosure. It will be apparent to those skilled in the art that all such similar substitutes and modifications are deemed to be within the spirit, scope and concept of the disclosure.

As used in accordance with the present disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.

The use of the word "a" or "an" when used in conjunction with the term "comprising" can mean "one," but it is also consistent with the meaning of "one or more," at least one, "and" one or more than one. The use of the term "or" is intended to mean "and/or" unless explicitly indicated to refer to an alternative (only when such alternatives are mutually exclusive), although the present disclosure supports the definition that the term "or" refers to an alternative only and "and/or". Throughout this application, the term "about" is used to indicate a value that includes an inherent change in the device used to quantify the change, one or more methods employed to determine the value, or a change that exists between study objects. For example, and not by way of limitation, when the term "about" is used, the specified value may vary by plus or minus twelve percent, or eleven percent, or ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent. The use of the term "at least one" will be understood to include one as well as any number of more than one, including but not limited to 1,2,3,4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term "at least one" may extend to 100 or 1000 or more, depending on the term to which it is attached. Further, the amount of 100/1000 is not considered limiting, as lower or higher limits may also produce satisfactory results. Further, use of the term "X, Y and at least one of Z" will be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y and Z. The use of ordinal number terms (i.e., "first," "second," "third," "fourth," etc.) is merely to distinguish two or more items and, unless otherwise specified, is not intended to imply any order or sequence or importance to one item relative to another or any order of addition.

As used herein, the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "include" and "include"), or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. The terms "or combinations thereof" and/or combinations thereof "as used herein refer to all permutations and combinations of the listed items preceding the term. For example, "A, B, C, or a combination thereof," is intended to include at least one of: a. B, C, AB, AC, BC, or ABC, and BA, CA, CB, CBA, BCA, ACB, BAC, or CAB if the order is important in a particular context. Continuing with this example, expressly included are combinations containing one or more repetitions of the term or term, e.g., BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, and the like. Those of skill in the art will understand that there is typically no limit to the number of items or terms in any combination, unless otherwise apparent from the context.

As used herein, the term "substantially" means that the subsequently described event occurs entirely or that the subsequently described event occurs to a large extent or degree.

For the purposes of the following detailed description, unless in any operating example or otherwise indicated, numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". The numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by practicing the present invention.

The term "alicyclic" refers to a cyclic group that is not aromatic. The group may be saturated or unsaturated, but it does not exhibit aromatic character.

The term "alkyl" refers to a saturated straight or branched chain hydrocarbon group of 1 to 50 carbons. It further includes both substituted and unsubstituted hydrocarbyl groups. The term is further intended to include heteroalkyl groups.

The term "aprotic" refers to a class of solvents that lack an acidic hydrogen atom and therefore cannot act as a hydrogen donor. Common aprotic solvents include alkanes, carbon tetrachloride (CCl)₄) Benzene, Dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), Propylene Glycol Methyl Ether Acetate (PGMEA), anisole, cyclohexanone, benzyl benzoate, and the like.

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

The term "aryl" or "aryl group" refers to a moiety formed by the removal of one or more hydrogens ("H") or deuterons ("D") from an aromatic compound. The aryl group can be a single ring (monocyclic) or have multiple rings (bicyclic, or more) fused together or covalently linked. "carbocyclic aryl" has only carbon atoms in one or more aromatic rings. "heteroaryl" has one or more heteroatoms in at least one aromatic ring.

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

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

Unless otherwise indicated, all groups may be substituted or unsubstituted. Optionally substituted groups, such as but not limited to alkyl or aryl, may be substituted with one or more substituents which may be the same or different. Suitable substituents include alkyl, aryl, nitro, cyano, -N (R') (R "), halogen, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, silylalkoxy, siloxane, thioalkoxy, -S (O)₂-, -C (═ O) -N (R ') (R'), (R ') (R') N-alkyl, (R ') (R') N-alkoxyalkyl, (R ') (R') N-alkylaryloxyalkyl, -S (O)_s-aryl (where s ═ 0-2), or-s (o)_s-heteroaryl (wherein s ═ 0-2). Each R' and R "is independently an optionally substituted alkyl, cycloalkyl or aryl group. R' and R ", together with the nitrogen atom to which they are bound, may form a ring system in certain embodiments. The substituent may also be a crosslinking group.

The term "amine" refers to a compound containing a basic nitrogen atom with a lone pair of electrons. The term "amino" refers to the functional group-NH₂-NHR or-NR₂Wherein R is the same or different at each occurrence and can be an alkyl group or an aryl group. The term "diamine" refers to a compound containing two basic nitrogen atoms with associated lone pair electrons. The term "aromatic diamine" refers to an aromatic compound having two amino groups.

The term "aromatic diamine residue" refers to a moiety bonded to two amino groups in an aromatic diamine. This is further explained below.

The term "diamine residue" refers to a moiety bonded to two amino groups, wherein the moiety is aliphatic or aromatic.

The term "coefficient of linear thermal expansion (CTE or a)" refers to a parameter that defines the amount by which a material expands or contracts as a function of temperature. It is expressed as a change in length per degree celsius and is typically expressed in units of μm/m/° c or ppm/° c.

α＝(ΔL/L0)/ΔT

CTE values are measured via known methods during the first or second heating scan. Understanding the relative expansion/contraction characteristics of materials can be an important consideration in the manufacture and/or reliability of electronic and display devices.

The term "electroactive" when referring to a layer or material, refers to a layer or material that electronically facilitates operation of the device. Examples of electroactive materials include, but are not limited to, materials that conduct, inject, transport, or block charges, which may be electrons or holes, or materials that emit radiation or exhibit a change in the concentration of electron-hole pairs upon receiving radiation.

The term "fused" when applied to an aromatic or alicyclic ring refers to an aromatic or alicyclic material containing two or more connecting rings that may share an atom, two adjacent atoms, or 3 or more atoms.

The term "glass transition temperature (or T)_g) "refers to the temperature at which a reversible change occurs in an amorphous polymer or in amorphous regions of a semi-crystalline polymer, wherein the material suddenly changes from a hard, glassy, or brittle state to a flexible or elastic state. On a microscopic level, glass transition occurs when normally coiled, stationary polymer chains become free to rotate and can move past each other. T can be measured using Differential Scanning Calorimetry (DSC), thermomechanical analysis (TMA), Dynamic Mechanical Analysis (DMA), or other methods_g。

The term "haloalkyl" refers to an alkyl group having one or more hydrogen atoms replaced with a halogen atom.

The term "haloalkoxy" refers to an alkoxy group having one or more hydrogen atoms replaced with a halogen atom.

The prefix "hetero" refers to a condition where one or more carbon atoms have been replaced with a different atom. In some embodiments, the heteroatom is O, N, S, or a combination thereof.

The term "high boiling point" refers to a boiling point above 130 ℃.

The term "imide" refers to a functional group containing two acyl groups bonded to the central nitrogen, i.e., RCO-NR' -COR. The term "bis-imide" refers to the presence of two identical but separate imide groups in a single molecule, polymer, or other substance.

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

The term "monomer" refers to a small molecule that is chemically bonded to one or more monomers of the same or different species during polymerization to form a polymer.

The term "non-polar" refers to a molecule, solvent, or other substance in which the electron distribution between covalent bond atoms is uniform and thus there is no net charge between them. In some embodiments; when the constituent atoms have the same or similar electronegativity, a nonpolar molecule, solvent, or other species is formed.

The term "organic electronic device" or sometimes "electronic device" refers to a device that includes one or more organic semiconductor layers or one or more materials.

The term "polar" refers to molecules, solvents, or other substances in which the electron distribution between covalent bond atoms is non-uniform. Thus, these species exhibit large dipole moments, which may be caused by bonding between atoms characterized by significantly different electronegativities.

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

The term "polymer" refers to a macromolecule comprising one or more types of monomeric residues (repeating units) linked by covalent chemical bonds. According to this definition, polymers encompass compounds in which the number of monomer units can range from very few (more commonly referred to as oligomers) to very many. Non-limiting examples of polymers include homopolymers and non-homopolymers, such as copolymers, terpolymers, tetrapolymers, and the like.

The term "polyarylene" refers to a class of polymers containing aromatic components of the benzene type directly linked to each other by carbon-carbon bonds along the backbone of the polymer backbone.

The term "proton" refers to a class of solvents that contain an acidic hydrogen atom and thus can act as a hydrogen donor. Common protic solvents include formic acid, n-butanol, isopropanol, ethanol, methanol, acetic acid, water, propylene glycol methyl ether acetic acid (PGME), Propylene Glycol Methyl Ether Acetate (PGMEA), and the like. The protic solvents may be used alone or in various combinations.

The term "satisfactory" when referring to a material property or characteristic is intended to mean that the property or characteristic meets all of the requirements/requirements of the material in use. For example, a 30:1 diluted polymer solution exhibiting an impact test rating of 4.5 at 12 wt% in the context of the polymers disclosed herein may be considered a non-limiting example of a "satisfactory" property.

The term "impact test" refers to a method of assessing the solubility of a polymer, wherein the polymer is formulated in an appropriate solvent system at a specified concentration, optionally filtered, diluted, and subjected to a solvent system test of interest. The polymer/solvent system was turned to mix and the solubility rating was evaluated by visual inspection of the degree of mixing and the amount of precipitation. In some embodiments, a suitable solubility rating scale is the rating scale disclosed in detail herein.

The term "solubility" refers to the maximum amount of solute that can be dissolved in a solvent at a given temperature. In some embodiments, solubility can be determined or assessed by any number of qualitative or quantitative methods.

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

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

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

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

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

The phrase "adjacent," when used in reference to a layer in a device, does not necessarily mean that one layer is immediately adjacent to another layer. On the other hand, the phrase "adjacent R groups" is used to refer to R groups in the formula that are immediately adjacent to each other (i.e., R groups on atoms that are bound by a bond). Exemplary vicinal R groups are shown below:

all percentages, ratios, and proportions used herein are by weight unless otherwise specified.

The present disclosure relates to bis-imide compounds comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents. The aryl moiety is selected from any number of groups including 6 to 60 ring carbon atoms and may also include heteroatoms. The ethynyl moiety is any moiety containing a carbon-carbon triple bond. Polar substituents are substituents in which the electron distribution between any covalently bonded atoms as disclosed herein is not uniform.

In one non-limiting embodiment, the bis-imide compounds of the present disclosure may be represented by formula 1 a:

wherein L is¹Is a quilt (Z)²)_yA substituted divalent linking group; z¹And Z²Is a polar group;

x1 and y are the same or different and are integers from 0 to 4, thus x1+ y is an integer from 2 to 6.

In one non-limiting embodiment; l is¹Is a divalent aromatic linking group selected from the group consisting of: hydrocarbon aryl groups, heteroaryl groups, and substituted derivatives thereof. In another non-limiting embodiment; l is¹Is a divalent linking group which may be an unsubstituted hydrocarbon aryl group or a hydrocarbon aryl group having from 6 to 30 ring carbons or a hydrocarbon aryl group having from 6 to 18 ring carbons. In another non-limiting embodiment; l is¹Selected from the group consisting of: phenyl, biphenyl, terphenyl, naphthyl, and substituted derivatives thereof.

In another non-limiting embodiment; l is¹Selected from the group consisting of heteroaryl, wherein the heteroaryl has at least one ring atom selected from the group consisting of O, N, and S. In one non-limiting embodiment; l is¹Is an O-heteroaryl group having at least one ring atom that is O. In another non-limiting embodiment; the O-heteroaryl is derived from a compound selected from the group consisting of: furan, benzofuran, isobenzofuran, dibenzofuran, and substituted derivatives thereof. In one non-limiting embodiment; l is¹Is an S-heteroaryl group having at least one ring atom which is S. In another non-limiting embodiment; the S-heteroaryl is derived from a compound selected from the group consisting of: thiophenes, benzothiophenes, isobenzothiophenes, dibenzothiophenes, and substituted derivatives thereof.

In another non-limiting embodiment of formula 1a, L¹Having formula 2 a:

wherein Z²And y is as defined elsewhere herein; and is^*Represents the point of attachment to the imide nitrogen of formula 1 a.

In another non-limiting embodiment of formula 1a, L¹Having formula 2 b:

wherein Z²And y is as defined elsewhere herein; and is^*Represents the point of attachment to the imide nitrogen of formula 1 a.

In another non-limiting embodiment of formula 1a, L¹Having formula 2c or 2 d:

wherein R is^1aAnd R^1bAre the same or different and may be selected from the group consisting of: H. halogen, C_1-30Alkyl radical, C_1-C30Heteroalkyl group, C_2-30Alkenyl radical, C_7-30Aralkyl radical, C_6-30Aryl, and C_4-30A heteroaryl group; and Z²Y and^*as defined elsewhere herein.

In another non-limiting embodiment of formulas 2c and 2 d; r^1aAnd R^1bIs F or CF₃。

In another non-limiting embodiment; l is¹Is a cycloaliphatic ring selected from the group consisting of: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, bicycloundecane, decalin, atriane, and the like.

In another non-limiting embodiment of formula 1 a; l is¹May be selected from the group consisting of:

wherein n is the same or different at each occurrence and is 0, 1 or 2; and m is 0 or 1.

In another non-limiting embodiment of formula 1 a; formula 1a is derived from formula 1 a':

wherein the Ar groups are the same or different at each occurrence and are selected from the group consisting of C₆-C₃₀Aryl groups; z¹At each timeAre the same or different at each occurrence and are polar groups; x is selected from the group consisting of S, O, SO₂And NR; and R is selected from the group consisting of: H. halogen, C_1-30Alkyl radical, C_1-C30Heteroalkyl group, C_2-30Alkenyl radical, C_7-30Aralkyl radical, C_6-30Aryl, and C_4-30A heteroaryl group.

In some non-limiting embodiments of formula 1 a'; ar groups are the same or different at each occurrence and are selected from the group consisting of C₅-C₃₀Heteroaryl groups. In some non-limiting embodiments of formula 1 a'; ar groups are the same or different at each occurrence and are selected from the group consisting of C₆-C₁₈Aryl groups. In some non-limiting embodiments of formula 1 a'; the Ar groups are the same or different at each occurrence and are selected from the group consisting of: benzyl, naphthyl, phenanthryl, and terphenyl. In some non-limiting embodiments of formula 1 a; x is S, or O, or SO₂Or NR. In some non-limiting embodiments of formula 1 a; r is H, or halogen, or C_1-30Alkyl, or C_1-30Heteroalkyl, or C_2-30Alkenyl, or C_7-30Aralkyl, or C_6-30Aryl, or C_4-30A heteroaryl group.

In some non-limiting embodiments of formula 1a or formula 1 a'; polar group Z¹And Z²The same at each occurrence. In other non-limiting embodiments of formula 1a or formula 1 a'; polar group Z¹And Z²Different at each occurrence. In some non-limiting embodiments of formula 1a or formula 1 a'; polar group Z¹And Z²May be selected from the group consisting of: OH, CO₂H、CO₂R、OR、CX₃、F、Cl、Br、SH、CONH₂、CONHR、CONR₂And SR; wherein R is as disclosed elsewhere herein, and X is halogen.

In other non-limiting embodiments of formula 1a or formula 1 a'; polar group Z¹And Z²Selected from the group consisting of: NR (nitrogen to noise ratio)₂、

And

wherein R is as disclosed elsewhere herein, and n ═ 1 or n ═ 2.

In some non-limiting embodiments of formula 1 a; x1 ═ 0, or x1 ═ 1, or x1 ═ 2, or x1 ═ 3, or x1 ═ 4; y is 0, or y is 1, or y is 2, or y is 3, or y is 4; x1+ y 2, x1+ y 3, x1+ y 4, x1+ y 5, or x1+ y 6.

Any of the above embodiments of formulas 1a and 1 a' may be combined with one or more of the other embodiments, so long as they are not mutually exclusive. For example, where L¹Embodiments of formula 1a that are hydrocarbon aryl groups may be substituted with those wherein Z¹Example combination of formula 1a that is OH. The same is true for the other non-mutually exclusive embodiments discussed above. Those skilled in the art will understand which embodiments are mutually exclusive and will therefore be readily able to determine combinations of embodiments contemplated herein.

Some non-limiting examples of compounds having formula 1a are:

in one non-limiting embodiment, the bis-imide compounds of the present disclosure may be represented by formula 1 b:

wherein L is²Being condensed aromatic or aliphaticA ring family ring; z¹And Z²Is a polar group; ar (Ar)¹Is the same or different at each occurrence, and is C₆-C₃₀An aryl group; x2 is an integer from 0 to 4; v is an integer of 0 to 2, with the proviso that when L²V is 0 when it is an alicyclic ring; and x2+ v is an integer from 2 to 4.

In one non-limiting embodiment of formula 1b, L²Is a fused aromatic ring selected from the group consisting of: benzene, naphthalene, phenanthrene, phenalene, naphthacene,Triphenylene, pyrene, pentacene, and the like, and include substances having more fused rings. In another non-limiting embodiment, L²Is a phenyl group. In another non-limiting embodiment of formula 1b, L²Is a naphthyl group. In another non-limiting embodiment of formula 1b, L²Are fused aromatic ring structures containing one or more heteroatoms. In another non-limiting embodiment of formula 1 b; l is²May be selected from the group consisting of:

wherein n is the same or different at each occurrence and is 0, 1 or 2; and m is 0 or 1.

In another non-limiting embodiment of formula 1b, L²Is a cycloaliphatic group. In another non-limiting embodiment of formula 1b, L²Is a cycloaliphatic ring selected from the group consisting of: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, bicycloundecane, decalin, atriane, and the like. In another non-limiting embodiment of formula 1b, L²Selected from the group consisting of cyclobutane, cyclopentane and cyclohexane. In another non-limiting embodiment of formula 1b, L²Selected from the group consisting of 4-to 6-membered alicyclic rings, benzene rings and naphthalene rings. Another non-limiting embodiment in formula 1bIn the examples, L²Containing one or more heteroatoms. In another non-limiting embodiment of formula 1b,

l containing hetero atoms²Selected from the group consisting of N, O and S.

In another non-limiting embodiment of formula 1b, L²The method comprises the following steps:

wherein A and B are the same or different at each occurrence and are selected from the group consisting of: CH (CH)₂、CF₂、C(CH₃)₂、C(CH₃)(CF₃)、C(CF₃)₂、C(O)、O、S、SO、SO₂And a fluorenyl group.

In another non-limiting embodiment of formula 1 b; formula 1b is derived from formula 1 b':

wherein the Ar groups are the same or different at each occurrence and are selected from the group consisting of C₆-C₃₀Aryl groups; z¹Is a polar group; x is selected from the group consisting of S, O, SO₂And NR; and R is selected from the group consisting of: H. halogen, C_1-30Alkyl radical, C_1-C30Heteroalkyl group, C_2-30Alkenyl radical, C_7-30Aralkyl radical, C_6-30Aryl, and C_4-30A heteroaryl group.

Ar, Z in formula 1b¹Non-limiting specific embodiments of, and X are the same as those identified in the context of formula 1 a' disclosed herein.

In one non-limiting embodiment of formula 1b, Ar¹Is the same or different at each occurrence and is selected from the group consisting of C₆-C₃₀Aryl groups. In another non-limiting embodiment of formula 1b, Ar¹Is the same or different at each occurrenceAnd is selected from the group consisting of: benzyl, naphthyl, phenanthryl, triphenyl, and the like, and includes materials having more fused rings. In another non-limiting embodiment of formula 1b, Ar¹Is the same or different at each occurrence and is selected from the group consisting of₅-C₃₀Heteroaryl groups. In another non-limiting embodiment of formula 1b, Ar¹Is the same or different at each occurrence and contains N, O, or S as a heteroatom.

In some non-limiting embodiments of formula 1 b'; x is S, or O, or SO₂Or NR. In some non-limiting embodiments of formula 1 b'; r is H, or halogen, or C_1-30Alkyl, or C_1-30Heteroalkyl, or C_2-30Alkenyl, or C_7-30Aralkyl, or C_6-30Aryl, or C_4-30A heteroaryl group.

In some non-limiting embodiments of formula 1b or formula 1 b'; polar group Z¹And Z²The same at each occurrence. In other non-limiting embodiments of formula 1b or formula 1 b'; polar group Z¹And Z²Different at each occurrence. In some non-limiting embodiments of formula 1b or formula 1 b'; the polar groups Z1 and Z2 may be selected from the group consisting of: OH, CO₂H、CO₂R、OR、 CX₃、F、Cl、Br、SH、CONH₂、CONHR、CONR₂And SR; wherein R is as disclosed elsewhere herein, and X is halogen.

In other non-limiting embodiments of formula 1b or formula 1 b'; the polar groups Z1 and Z2 are selected from the group consisting of: NR (nitrogen to noise ratio)₂、

And

wherein R is as disclosed elsewhere herein, and n ═ 1 or n ═ 2.

In some non-limiting embodiments of formula 1 b; x2 ═ 0, or x2 ═ 1, or x2 ═ 2, or x2 ═ 3, or x2 ═ 4; when L is²When it is a fused aromatic ring, v is 0, or when L²When is a fused alicyclic ring, v ═ 0, or v ═ 1, or v ═ 2; x2+ v 2, or x2+ v 3, or x2+ v 4.

Any of the above embodiments of formula 1b or formula 1 b' may be combined with one or more of the other embodiments, so long as they are not mutually exclusive. For example, where L²Embodiments of formula 1b that are fused aromatic rings can be substituted with wherein Z¹Is CF₃In combination with the embodiments of formula 1 b. The same is true for the other non-mutually exclusive embodiments discussed above. Those skilled in the art will understand which embodiments are mutually exclusive and will therefore be readily able to determine combinations of embodiments contemplated herein.

Some non-limiting examples of compounds having formula 1b are:

in one non-limiting embodiment, the bis-imide compounds of the present disclosure may be represented by formula 1 c:

wherein L is³Is a divalent linking group; ar for formula 1a and formula 1b disclosed herein¹、Z¹And Z²All of the examples of (1) apply equally to Ar in formula 1c¹、Z¹And Z²(ii) a x3 is an integer from 0 to 4; and w is an integer from 0 to 3, so x3+ w is an integer from 2 to 6.

In one non-limiting embodiment of formula 1 c; l is³Is selected from the group consisting ofGroup consisting of: covalent single bond, alkyl group, O, S, C (O), C (S), S (O), SO₂、CF₂And C (CF)₃)₂。

In some non-limiting embodiments of formula 1 c; x3 ═ 0, or x3 ═ 1, or x3 ═ 2, or x3 ═ 3, or x3 ═ 4; w is 0, w is 1, w is 2, or w is 3; x3+ w is 2, or x3+ w is 3, or x3+ w is 4, or x3+ w is 5, or x3+ w is 6.

Any of the above embodiments of equation 1c may be combined with one or more of the other embodiments, as long as they are not mutually exclusive. For example, where L³is-C (CF)₃)₂May be combined with embodiments in which x3 is 2. The same is true for the other non-mutually exclusive embodiments discussed above. Those skilled in the art will understand which embodiments are mutually exclusive and will therefore be readily able to determine combinations of embodiments contemplated herein.

Some non-limiting examples of compounds having formula 1c are:

the present disclosure further relates to a polymer composition comprising a copolymer polymerized from a monomer mixture of: (a) one or more first monomers comprising a bis-imide compound comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents; and (b) one or more second monomers comprising two or more cyclopentadienone moieties. The one or more first monomers comprising a bis-imide compound are selected from the group consisting of: disclosed herein are compounds having formula 1a, compounds having formula 1b, and compounds having formula 1c, the bis-imide compounds comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents.

The one or more second monomers comprising two or more cyclopentadienone moieties of the polymer composition may be represented by formula 3:

wherein R is⁷Is the same or different at each occurrence and is selected from the group consisting of: H. substituted or unsubstituted C_1-6Alkyl, substituted or unsubstituted C_6-20Aryl, and substituted or unsubstituted C_4-20A heteroaryl group; and Ar²Is substituted or unsubstituted C_6-20An aryl group.

In one non-limiting embodiment of formula 3; r⁷And may be the same or different at each occurrence. In another non-limiting embodiment; r⁷Can be H, or unsubstituted C_1-6Alkyl, or substituted C_1-6Alkyl, or unsubstituted C_6-30Aryl, or substituted C_6-30Aryl, or unsubstituted C_5-30Heteroaryl, or substituted C_5-30A heteroaryl group.

In one non-limiting embodiment of formula 3; ar (Ar)²Is substituted or unsubstituted C_6-20An aryl group. Various aromatic moieties are suitable for use as Ar². Many of these aromatic moieties are disclosed in U.S. patent No. 5,965,679.

In one non-limiting embodiment of formula 3; ar (Ar)²Has the formula 4:

wherein q is an integer of 1 to 3; r is an integer of 0 to 2; ar (Ar)³Is the same or different at each occurrence and is selected from the group consisting of formula 5 and formula6:

wherein R is⁸Is the same or different at each occurrence and is selected from the group consisting of: halogen, substituted or unsubstituted C_1-6Alkyl, aryl, and aryloxy groups; c is an integer of 0 to 4; d and e are the same or different at each occurrence and are each an integer from 0 to 3; z is the same or different at each occurrence and is selected from the group consisting of: single covalent bond, alkyl group, O, C (O), C (S), CF₂And C (CF)₃)₂。

In another non-limiting embodiment of formula 4; z is the same or different at each occurrence and is selected from the group consisting of: CH (CH)₂、CF₂、C(CH₃)₂、C(CF₃)₂Fluorenyl, O, S, SO₂、NR⁹、PR⁹、P(＝O)R⁹、C(＝O)、CR¹⁰R¹¹、SiR¹⁰R¹¹，

Wherein R is as defined elsewhere herein; and R is⁹、R¹⁰And R¹¹Are the same or different and are selected from the group consisting of H, substituted or unsubstituted C_1-4Alkyl, and aryl.

In some non-limiting embodiments of formulas 5 and 6, R⁸Is selected from the group consisting of: halogen, C_1-4Haloalkyl, C_1-4Haloalkoxy, phenyl, phenoxy, fluorine, C_1-4Alkyl radical, C_1-4Fluoroalkyl, and C_1-4A fluoroalkoxy group.

In some non-limiting embodiments of formula 5 and formula 6, c is 0, or c is 1, or c is 2, or c is 3.

In some non-limiting embodiments of formulas 5 and 6, d and e are each independently 0, or 1, or 2.

In another non-limiting embodiment of formulas 5 and 6, d + e is 0, or 1, or 2, or 3, or 4.

In some non-limiting embodiments of formula 4, q-1 or q-2.

In some non-limiting embodiments of formula 4, r-0 or r-1.

In another non-limiting embodiment of formula 4, each Z is independently selected from the group consisting of: o, S, NR⁹、C(O)、C¹⁰R¹¹And SiR¹⁰R¹¹(ii) a Wherein R is⁹、R¹⁰And R¹¹Each independently is H, or C_1-4Alkyl, or C_1-2Fluoroalkyl, or phenyl.

Some non-limiting examples of the one or more first monomers comprising a bis-imide compound are selected from the group consisting of: disclosed herein are compounds having formula 1a, compounds having formula 1b, and compounds having formula 1c, the bis-imide compounds comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents.

Some non-limiting examples of the one or more second monomers comprising two or more cyclopentadienone moieties are:

comprising a reaction product of (a) one or more first monomers comprising a bis-imide compound comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents; and (b) one or more second monomers comprising two or more cyclopentadienone moieties are the following:

the present disclosure further relates to polymer compositions comprising terpolymers and higher copolymers polymerized from a monomer mixture of: (a) two or more first monomers each comprising a bis-imide compound comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents; and (b) one or more second monomers comprising two or more cyclopentadienone moieties. The two or more first monomers each comprising a bis-imide compound are selected from the group consisting of: disclosed herein are compounds having formula 1a, compounds having formula 1b, and compounds having formula 1c, the bis-imide compounds comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents.

Such polymer compositions have examples that offer the potential to produce new materials that can provide additional flexibility in terms of the final polymer properties that can be optimized for electronic and display applications. The materials disclosed herein, produced via careful selection of the monomeric materials and corresponding relative amounts, may be tailored for their processability, thermal stability, CTE, solubility, and other properties disclosed herein. Comprising two or more first monomers consisting of (a) two or more first monomers each comprising a bis-imide compound comprising two or more aryl moieties substituted with an ethynyl moiety, and two or more aryl moieties each having one or more polar substituents; and (b) one or more second monomers comprising two or more cyclopentadienone moieties are non-limiting examples of polymer compositions of ternary and higher polymers polymerized from monomer mixtures of:

in some embodiments, the polymer compositions disclosed herein exhibit enhanced solubility in polar protic solvents due to the introduction of additional polar groups on their constituents relative to existing polyphenylene-polyimide polymers. When incorporated into the copolymer compositions disclosed herein, functionalized bis-imide compounds and monomers improve the solubility of the materials without sacrificing other desirable properties for various electronic and display applications. The particular synthetic methods disclosed herein are applicable to a broader array of polar protic groups and may therefore also find application in other end uses.

In some embodiments, the methods disclosed herein for introducing polar functionality into the monomer make-up of a copolymer composition employ a synthesis scheme based on diamine residues containing one or more polar groups. In some non-limiting embodiments, the bis-imide monomers can be prepared using hydroxylated or carboxylated diamines and can be further reacted to form the corresponding polymers with enhanced solubility in polar protic solvents relative to existing materials. In some non-limiting embodiments, a general synthetic route begins with:

the appropriate functionalized diamine is reacted with two equivalents of 4-ethylphthalic anhydride to form the desired bis-imide monomer. Some non-limiting examples of diamines having residues with polar functionality are:

wherein X and Y may be the same or different and are selected from the group consisting of: single bond, CO, S, SO₂、C(CF₃)₂、C(CH₃)₂Or fluorenyl; z is as elsewhere herein for Z¹And Z²Disclosed is a composition comprising; etc., and combinations thereof, wherein others may be selected based on the characteristics of the material, the solvent of interest, etc.

In another non-limiting embodiment, functionalization of the dianhydride monomer provides a route to the compounds and polymer compositions disclosed herein. In some non-limiting embodiments, two carboxylic acid groups are introduced per bis-imide monomer by reacting two equivalents of AEBzOH with any number of commercially available dianhydrides:

some non-limiting examples of suitable dianhydrides include

And further pyromellitic dianhydride (PMDA), 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride (BPDA), 2,3,3 ', 4 ' -biphenyltetracarboxylic dianhydride (s-BPDA), 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride (BTDA), 1, 4-phenylene bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylate) (TAHQ), 3,3 ', 4,4 ' -diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 ' -bisphenol-A dianhydride (BPADA), 1,3,3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-c ] Tetracarboxylic Dianhydride (TDA), Norbornane-2-spiro- α -cyclopentanone- α '-spiro-2 "-norbornane-5, 5", 6,6 "-tetracarboxylic dianhydride (CpODA), 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' -bisphenol-A dianhydride (BPADA), xanthene tetracarboxylic dianhydride, and the like, and combinations thereof.

The compounds and polymer compositions according to the present disclosure and their related properties can be prepared and used according to the examples described below. The examples provided herein are for the purpose of illustrating the present disclosure and are not intended to limit the scope of the invention described in the claims.

Examples of the invention

Synthesis example 1

This example illustrates the preparation of a bis-imide compound having formula 1a (compound 1).

2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bis-AP-AF) (15.00g, 40.95mmol, 1 equiv.) and 4-ethylphthalic anhydride (14.10g, 81.91mmol, 2 equiv.) were combined in glacial acetic acid (200mL, 2M bis-AP-AF) under a nitrogen atmosphere in a 500mL round bottom flask equipped with a magnetic stir bar. The round bottom flask was equipped with a Claisen (Claisen) adapter equipped with a thermometer probe extending into the reaction mixture and a water cooled condenser mounted on a side arm. The mixture temperature was raised to 118 ℃ (reflux) using a thermostatic temperature controller with magnetic stirring for 24 hours.

After cooling to room temperature, the product was precipitated via a separatory funnel by slowly dropping a 100mL portion of the reaction mixture into 800mL of stirred, room temperature deionized water. The solid was vacuum filtered to provide a wet product (pale powder-white solid). Will be provided withThe combined solid precipitate was washed with 750mL of room temperature deionized water in a 1L beaker by magnetic stirring for 1 hour. The vacuum filtered solid was placed in a room temperature vacuum chamber and dried under high vacuum for 48 hours. By passing¹H and¹³c NMR confirmed the solid product (Compound 1) (24.97g, 37.02mmol, 90.39%). If any residual acetic acid is detected, the solid is further washed with deionized water and dried. The process was repeated until no acetic acid was detected.

Synthesis example 2

This example illustrates the preparation of a monomer having formula 3 (compound M2-1). Compound M2-1 is an example of formula 3

Wherein; r⁷Is phenyl and Ar²Obtained by formula 4

Wherein; ar (Ar)³-phenyl, -Z-O, and-x-y-1. The synthesis of such materials has been described, for example, in US 5,965,679 and elsewhere. Compound M2-1 is

Synthesis example 3

This example shows the preparation of a polymer (polymer 1) based on bis-imide monomer 1a and DPO-CPD.

Compound 1 monomer (2.000g, 2.965mmol, 1.1 equivalents) and compound M2-1(2.110 g, 2.696mmol, 1 equivalent) were combined under nitrogen in 16mL of gamma-butyrolactone (GBL) in a 50-mL round bottom flask equipped with a magnetic stir bar. The round bottom flask was equipped with a claisen adapter equipped with a thermometer probe extending into the reaction mixture and a water cooled condenser mounted on a side arm. The temperature of the mixture was raised to 150 ℃ for 24hr under magnetic stirring using a thermostatic temperature controller. After cooling to room temperature, the reaction mixture was diluted with acetone to 4 times the original volume.

The solid polymer was precipitated via a separatory funnel by slowly dropping the diluted solution into 200-mL of stirred, room temperature deionized water. The resulting cloudy suspension of solid polymer was vacuum filtered to provide a wet solid polymer which was washed in a 1L beaker with 500-mL room temperature deionized water for 1 hour by magnetic stirring. The solid was vacuum filtered, placed in a vacuum oven heated at 60 ℃ and dried under high vacuum for 48 hours. The dried polymer (3.358g) was used for formulation and solubility impact testing. Polymer molecular weight was determined using GPC.

Synthesis example 4

This example illustrates the preparation of a bis-imide compound having formula 1c (compound 16).

Synthesis example 4a

Preparation of methyl 3-bromo-5-nitrobenzoate.

3-bromo-5-nitrobenzoic acid (25.00g, 98.6mmol) was dissolved in methanol (400mL) and 0.5mL sulfuric acid was added. In the reflow stripThe mixture was heated under stirring for 24 hr. A small aliquot (about 1mL) was dried on a rotary evaporator and the course of the reaction was assessed using proton NMR. The ratio of ester to acid was determined to be 5 to 1 by NMR spectroscopy. The reaction mixture was refluxed for an additional 24 hours, at which point the conversion of the acid to the ester was complete, as indicated by the same method. The pH was adjusted to pH 4 by addition of aqueous NaOH. Methanol was removed in vacuo on a rotary evaporator. The crude product was extracted with 300mL of ethyl acetate and the organic phase was passed over MgSO₄Dried, filtered, and concentrated on a rotary evaporator in vacuo. Methyl 3-bromo-5-nitrobenzoate (23.17g, 89.1 mmol, 90.38%) was isolated as a pale yellow solid which was used directly in the next step. Use of¹The product was confirmed by H NMR.

Synthesis example 4b

Preparation of methyl 3-nitro-5- (trimethylsilylethynyl) benzoate.

Methyl 3-bromo-5-nitrobenzoate (22.88g, 88.0mmol, 1 eq.) from Synthesis example 4a was dissolved in triethylamine (300 mL). Under a nitrogen atmosphere, copper (I) iodide (335mg, 1.76mmol, 0.02 equiv.), and bis (triphenylphosphine) palladium (ii) dichloride (1.235 g, 1.76 mmol; 0.02 equiv.), and trimethylsilylacetylene (25mL, 17.28g, 175.97 mmol; 2 equiv.) were added at room temperature. The mixture was stirred at room temperature for 20h, then filtered through a plug of silica gel to remove precipitated solids. The silica plug was rinsed (flowed) with 50mL of ethyl acetate. The filtrate was concentrated in vacuo to remove as much triethylamine as possible. The crude residue was dissolved in 300mL ethyl acetate and washed twice with 50mL water and once with 50mL saturated sodium chloride. The organic phase is passed over MgSO₄Dried, filtered and concentrated in vacuo on a rotary evaporator. After drying under high vacuum overnight, the solid methyl 3-nitro-5- (trimethylsilylethynyl) benzoate (24.02g, 86.6mmol, 98.45%) was isolated and used directly in the next step. Make itBy using¹The product was confirmed by H NMR.

Synthesis example 4c

And 3-ethynyl-5-nitrobenzoic acid is prepared.

Methyl 3-nitro-5- (trimethylsilylethynyl) benzoate from Synthesis example 4b (23.04g, 83.07mmol, 1 eq) was dissolved in methanol (300mL) and LiOH was added_aqSolution (208mL, 2M, 416mmol, 5 equiv.). The mixture was stirred at 60 ℃ for 1 h. The progress of the reaction was monitored by TLC. Disappearance of starting material was observed before the end of the 1 hour heating period. The pH was then adjusted to 4 with dilute aqueous HCl (1M). The product was extracted with ethyl acetate, over MgSO₄Dried, filtered, and concentrated in vacuo on a rotary evaporator. Solid 3-ethynyl-5-nitrobenzoic acid (15.78g, 82.56mmol, 99.38%) was obtained and used directly in the next step. The crude solid retains the pink/purple color produced by the Sonogashira reaction and is used¹H NMR confirmed the identity of the product.

Synthesis example 4d

Preparing 3-amino-5-acetylenyl benzoic acid.

3-ethynyl-5-nitrobenzoic acid from Synthesis example 4c (5.00g, 26.16mmol, 1 eq.) was dissolved in ethyl acetate (100 mL); glacial acetic acid (two drops), SnCl were added₂(24.80 g, 131mmol, 5 equiv.), and water (4.7mL, 262mmol, 10 equiv.). The mixture was refluxed for 2 hours before slowly pouring the mixture into ice-cold water with rapid stirring. Then saturated sodium bicarbonate (NaHCO) is added₃) The aqueous solution adjusted the suspension to pH 5. Subjecting the obtained suspension to H₂O dilution and the product is used200mL (per extraction) of ethyl acetate are extracted 3 times. Washing the combined organic phases with water and saturated sodium chloride; and finally over MgSO₄Dried, filtered and concentrated in vacuo on a rotary evaporator. 3-amino-5-ethynylbenzoic acid (2.17g, 13.46mmol, 51.47%) was formed as a pale yellow solid and the product was confirmed using 1H NMR.

Synthesis example 4e

This example illustrates the final preparation of a bis-imide compound having formula 1c (compound 16).

4, 4' - (Hexafluoroisopropylidene) diphthalic anhydride (6FDA) (1.812g, 4.080mmol, 1 equiv.) and 3-amino-5-acetylenylbenzoic acid from Synthesis example 4d (1.315g, 8.160 mmol, 2 equiv.) were combined in glacial acetic acid (20mL) in a 100-mL round bottom flask equipped with a magnetic stir bar under a nitrogen atmosphere. The round bottom flask was equipped with a claisen adapter equipped with a thermometer probe extending into the reaction mixture and a water cooled condenser mounted on a side arm. The mixture temperature was raised to 118 ℃ (reflux) using a thermostatic temperature controller with magnetic stirring for 24 hours. After cooling to room temperature, the product was precipitated via a separatory funnel by slowly dropping the reaction mixture into 200-mL of stirred, room temperature deionized water. The solid was vacuum filtered to provide a wet product (pale powder-white solid). The combined solid precipitate was washed with 200-mL room temperature deionized water for 1 hour in a 500-mL beaker with stirring. The solid was vacuum filtered, placed in a room temperature vacuum chamber, and dried under high vacuum for 48 hours. Use of¹H and¹³c NMR confirmed the solid monomer product (Compound 16) (2.864g, 3.920mmol, 96.09%) as product. If any residual acetic acid is detected, the solid is further washed with deionized water and dried until undetectable.

Synthesis example 5

This example shows the preparation of a polymer (polymer 2) based on bis-imide monomer 1c and DPO-CPD.

Compound 16 monomer prepared in Synthesis example 4e (2.500g, 3.422mmol, 1.01 equiv.) and compound M2-1(DPO-CPD) (2.653g, 2.696mmol, 1 equiv.) were combined under a nitrogen atmosphere in 25mL of gamma-butyrolactone (GBL) in a 50-mL round bottom flask equipped with a magnetic stir bar. The round bottom flask was equipped with a claisen adapter equipped with a thermometer probe extending into the reaction mixture and a water cooled condenser mounted on a side arm. The temperature of the mixture was raised to 165 ℃ for 24hr under magnetic stirring using a thermostatted temperature controller. After cooling to room temperature, the reaction mixture was diluted to 4 times the original volume with acetone. The solid polymer was precipitated via a separatory funnel by slowly dropping the diluted solution into 200mL of stirred, room temperature deionized water. The resulting cloudy suspension of solid polymer was vacuum filtered to provide a wet solid polymer which was washed with 500mL room temperature deionized water in a 1L beaker by magnetic stirring for 1 hour. The solid was vacuum filtered, placed in a vacuum oven heated at 60 ℃ and dried under high vacuum for 48 hours. The dried polymer (3.641g) was used in the next step for formulation and solubility impact testing. Polymer molecular weight was determined using GPC.

Comparative example Synthesis 1

This example illustrates the preparation of a comparative bis-imide compound (compound a).

4, 4' - (Hexafluoroisopropylidene) diphthalic anhydride (6FDA) (2.000g, 4.502mmol, 1 eq.) and 4-ethynylaniline (1.055g, 9.004mmol, 2 eq.) were placed under nitrogen in a 100-mL round-bottomed flask equipped with a magnetic stir bar,combined in glacial acetic acid (22.5 mL). The round bottom flask was equipped with a claisen adapter equipped with a thermometer probe extending into the reaction mixture and a water cooled condenser mounted on a side arm. The mixture temperature was raised to 118 ℃ (reflux) for 6 hours under magnetic stirring using a thermostatic temperature controller. After cooling to room temperature, the product was precipitated via a separatory funnel by slowly dropping the reaction mixture into 200-mL of stirred, room temperature deionized water. The solid was vacuum filtered to provide a wet product (white solid). The solid precipitate was washed with 200-mL room temperature deionized water for 1 hour in a 500-mL beaker with stirring. The solid was vacuum filtered, placed in a room temperature vacuum chamber, and dried under high vacuum for 48 hours. Use of¹H and¹³c NMR confirmed the solid monomer product (2.775g, 4.319mmol, 95.9%) as product. If any residual acetic acid is detected, the solid is further washed with deionized water and dried until undetectable.

Comparative example Synthesis 2

This example shows the preparation of a polymer based on a bis-imide compound A and DPO-CPD (comparative polymer A).

Compound A monomer prepared in comparative example Synthesis 1 (2.000g, 3.113mmol, 1.01 equiv.) was combined with compound M2-1(DPO-CPD) (2.412g, 3.082mmol, 1 equiv.) under nitrogen in 25mL of gamma-butyrolactone (GBL) in a 50-mL round bottom flask equipped with a magnetic stir bar. The round bottom flask was equipped with a claisen adapter equipped with a thermometer probe extending into the reaction mixture and a water cooled condenser mounted on a side arm. The temperature of the mixture was raised to 165 ℃ for 24hr under magnetic stirring using a thermostatic temperature controller. After cooling to room temperature, the reaction mixture was diluted to 4 times the original volume with acetone. The solid polymer was precipitated via a separatory funnel by slowly dropping the diluted solution into 200mL of stirred, room temperature deionized water. The resulting cloudy suspension of solid polymer was vacuum filtered to provide a wet solid polymer which was washed with 500mL room temperature deionized water in a 1L beaker by magnetic stirring for 1 hour. The solid was vacuum filtered, placed in a vacuum oven heated at 60 ℃ and dried under high vacuum for 48 hours. The dried polymer (3.742g) was used in the next step for formulation and solubility impact testing. Polymer molecular weight was determined using GPC.

Comparative example Synthesis 3

This example illustrates the preparation of a comparative bis-imide compound (compound B).

4, 4' - (Hexafluoroisopropylidene) diphthalic anhydride (6FDA) (5.000g, 20.935 mmol, 1 equiv.) and 3-ethynylaniline (5.000g, 41.869mmol, 2 equiv.) were combined in glacial acetic acid (84mL) under a nitrogen atmosphere in a 250-mL round bottom flask equipped with a magnetic stir bar. The round bottom flask was equipped with a claisen adapter equipped with a thermometer probe extending into the reaction mixture and a water cooled condenser mounted on a side arm. The mixture temperature was raised to 118 ℃ (reflux) using a thermostatic temperature controller under magnetic stirring for 6 hours. After cooling to room temperature, the product was precipitated via a separatory funnel by slowly dropping the reaction mixture into 200-mL of stirred, room temperature deionized water. The solid was vacuum filtered to provide a wet product (white solid). The solid precipitate was washed in a 500-mL beaker with 200-mL room temperature deionized water for 1 hour with stirring. The solid was vacuum filtered, placed in a room temperature vacuum chamber, and dried under high vacuum for 48 hours. Use of¹H and¹³c NMR confirmed the solid monomer product (12.50g, 19.455mmol, 92.9%) as product. If any residual acetic acid is detected, the solid is further washed with deionized water and dried until undetectable.

Comparative example Synthesis 4

This example shows the preparation of a polymer based on a bis-imide compound B and DPO-CPD (comparative polymer B).

The monomer prepared in comparative example 3 (10.000g, 15.564mmol, 1.025 equiv.) and compound M2-1(11.888g, 15.184mmol, 1 equiv.) were combined under nitrogen in 75mL of gamma-butyrolactone (GBL) in a 250-mL round-bottomed flask equipped with a magnetic stir bar. The round bottom flask was equipped with a claisen adapter equipped with a thermometer probe extending into the reaction mixture and a water cooled condenser mounted on a side arm. The temperature of the mixture was raised to 165 ℃ for 24hr under magnetic stirring using a thermostatic temperature controller. After cooling to room temperature, the reaction mixture was diluted to 4 times the original volume with acetone. The solid polymer was precipitated via a separatory funnel by slowly dropping the diluted solution into 1L of stirred, room temperature deionized water. The resulting cloudy suspension of solid polymer was vacuum filtered to provide a wet solid polymer which was washed in a 1L beaker by magnetic stirring with 500mL of room temperature deionized water for 1 hour. The solid was vacuum filtered, placed in a vacuum oven heated at 60 ℃ and dried under high vacuum for 48 hours. The dried polymer (18.665g) was used in the next step for formulation and solubility impact testing. Polymer molecular weight was determined using GPC.

Solubility examples

Polymer solubility was evaluated by subjecting the formulations to impact testing to determine their compatibility with solvent systems commonly used in the electronics and display industry. The polymer was first formulated at a solid polymer concentration of 12 wt% or 30 wt% in a solvent system of methyl 3-methoxypropionate (MMP), anisole and gamma-butyrolactone (GBL) at a ratio of 61.75:33.25:5, and then filtered through a 0.2 μm PTFE filter. The more viscous solution was filtered through a 0.45 μm PTFE or 5 μm nylon filter. The test solvent system consisted of Propylene Glycol Monomethyl Ether (PGME) and Propylene Glycol Monomethyl Ether Acetate (PGMEA) in a 70:30 ratio. Impact testing was performed by attempting to dissolve and dilute small amounts of polymer formulation at 30:1 and 200:1 with the test solvent system. The mixture was then rotated to mix. Next, solubility grades were designated based on the following criteria in table 1 below for visual inspection of the two diluted solutions. In some embodiments, the requirement in use sets the acceptability threshold to 4.5 in the impact test rating.

TABLE 1 rating system for assigned impact test solubility values based on visual inspection.

Table 2 summarizes representative results for the polymers disclosed herein.

TABLE 2 comparison of the impact test values of the polymers disclosed herein with the previous (para) -FPL polymers. Molecular weight data for each impact test rating and formulated solid polymer concentration were included for reference.

In the solvent systems disclosed herein, it was found that both polymer 1 and polymer 2 exhibited improved solubility compared to comparative polymer a and comparative polymer B. In addition, the higher molecular weight versions of these polymers retain favorable solubility characteristics in the solvents of interest.

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

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

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

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