KR20240053115A - Novel tetracarboxylic acid anhydride, polyamic acid anc polyimide comprising the same - Google Patents

Abstract

The present invention provides a novel tetracarboxylic dianhydride, polyamic acid and polyimide polymer prepared using the same, and a polymer coating composition and film for electronic devices using the same.

Description

Novel tetracarboxylic dianhydride, polyamic acid and polyimide polymer comprising the same {NOVEL TETRACARBOXYLIC ACID ANHYDRIDE, POLYAMIC ACID ANC POLYIMIDE COMPRISING THE SAME}

The present invention relates to a novel tetracarboxylic dianhydride, polyamic acid and polyimide polymer containing the tetracarboxylic dianhydride, films using the same, and polymer coating materials for electronic devices.

As the development and distribution of various electronic devices such as smartphones accelerates, the importance of 5G communication technology, which can wirelessly transmit high-speed, large-capacity data, is increasing, and the demand for communication components and materials used in communication devices including smartphone terminals is increasing. It is also rapidly increasing.

Polyimide (PI) is a highly heat-resistant polymer material that has excellent mechanical properties, electrical insulation, low dielectric constant, and low dielectric loss. It is not only lighter than other materials, but also flexible. Because of this, its uses are diverse, including coatings, films, and adhesives, and it is used in a wide range of electronic materials such as semiconductor communication circuits and display printed wiring circuit boards.

Meanwhile, common polyimide was mainly used as the existing 4G communication material, but it has relatively high dielectric constant (Dk) and dielectric loss (Df) values to be used in the frequency band for 5G communication.

Accordingly, there is a need to develop a new polyimide that satisfies high heat resistance and has low dielectric and low dielectric loss characteristics in high frequency bands (Sub-6 and 28 GHz).

The present invention was devised to solve the above-mentioned problems, and its technical task is to provide a novel tetracarboxylic dianhydride containing a functional moiety and a triphenylmethane group and an ether group in the molecule as the basic backbone.

In addition, the present invention provides a soluble polyamic acid or polyimide having a low dielectric constant and dielectric loss rate while maintaining an appropriate level of heat resistance and mechanical properties using the above-described tetracarboxylic dianhydride, a polymer film containing the same, and a polymer coating material for electronic devices. Another technical task is to provide

Other objects and advantages of the present invention can be more clearly explained by the following detailed description and claims.

In order to achieve the above-described technical problem, the present invention provides a compound represented by the following formula (1), specifically, tetracarboxylic dianhydride for forming polyamic acid or polyimide.

[Formula 1]

In Formula 1,

R ₁ to R ₃ are the same or different from each other, and are each independently hydrogen, halogen, C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkyloxy group, C ₃ to C ₁₀ cycloalkyl group, C ₆ to Consists of an aryl group of C ₂₀ , an aryloxy group of C ₆ ~ C ₂₀ , a heterocyclic group of 5 to 20 nuclear atoms, and -(CF ₂ ) _n -CF ₃ (where n is an integer between 0 and 5) selected from the group that is,

R ₄ is selected from hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₁₀ cycloalkyl group, a C ₆ to C ₂₀ aryl group, and a trifluoromethyl group,

R ₅ and R ₆ are each independently an alkyl group of C ₁ to C ₂₀ ,

a and b are each independently integers from 0 to 4.

In addition, the present invention provides tetracarboxylic dianhydride containing the compound of formula 1 described above; It provides a polyamic acid composition containing; and diamine.

Additionally, the present invention provides a polyimide polymer obtained by imidizing the above-described polyamic acid composition.

According to one embodiment of the present invention, by using a novel tetracarboxylic dianhydride monomer containing a triphenylmethane core and an ether group, polyimide maintains the high heat resistance and excellent mechanical properties inherent in polyimide and has a low dielectric constant and dielectric loss rate. polyamic acid or polyimide; And a polymer film containing the same and a polymer coating material for electronic devices can be provided.

Accordingly, the polyimide film of the present invention is not only useful as a substrate for electronic devices and a coating material for electrical and electronic components, but can also be applied to various other fields.

The effects according to the present invention are not limited to the contents exemplified above, and more diverse effects are included in the present specification.

All terms (including technical and scientific terms) used in this specification, unless otherwise defined, may be used with meanings that can be commonly understood by those skilled in the art to which the present invention pertains. Additionally, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless clearly specifically defined.

In addition, throughout this specification, when a part is said to "include" a certain component, unless specifically stated to the contrary, this is an open term that implies the possibility of further including other components rather than excluding other components. It should be understood as (open-ended terms). In addition, throughout the specification, “above” or “on” means not only the case where it is located above or below the object part, but also the case where there is another part in the middle, and it must be in the direction of gravity. It does not mean that it is located above the standard.

As used herein, “preferred” and “preferably” refer to embodiments of the invention that may provide certain advantages under certain circumstances. However, under the same or different circumstances, other embodiments may also be preferred. Additionally, mention of one or more preferred embodiments does not mean that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

In addition, in this specification, “monomer” and “monomer” have the same meaning. Monomers in the present invention are distinguished from oligomers and polymers, and refer to compounds with a weight average molecular weight (Mw) of 1,000 g/mol or less. The term polymer also includes homopolymers, copolymers, and resins.

In general, polyimide polymers have high heat resistance, excellent mechanical properties, and low dielectric properties, and are one of the materials mainly used as communication materials. With the recent development of communication technology, there is a demand for next-generation communication materials that use high frequency bands of 10 GHz or higher. However, the problem of applying the above-described conventional polyimide polymer as a 5G communication material is that the dielectric constant (Dk) and dielectric loss (Df) values are relatively high. There is.

Accordingly, the present invention aims to develop a polyimide material that not only has low dielectric and low dielectric loss characteristics in the high frequency band, but also maintains high heat resistance and excellent mechanical properties, and includes a triphenylmethane derivative having functional moieties as pendant groups. At the same time, it is characterized by using a new tetracarboxylic dianhydride compound into which an ether group is introduced as a monomer of the polyimide polymer. The polyimide polymer not only contains an ether bond in the polymer main chain, but also has at least one functional moiety, such as a trifluoromethyl group, an alkyloxy group, or an aliphatic derivative, thereby securing low dielectric constant and low dielectric loss characteristics. In addition, by introducing a triphenylmethane derivative that exists on a different plane from the main chain of the polymer into the basic skeleton structure, free volume can be secured in the manufactured polymer, thereby ensuring improved solubility characteristics without deteriorating heat resistance and mechanical properties.

In addition, the present invention can provide a composition in the form of polyimide or polyamidoimide by presenting a polyimide or polyamidoimide polymer with improved solubility. Accordingly, instead of going through the film formation process in an unstable polyamic acid state, the advantage is that film formation is possible by adjusting the amount of solid content of the polyamidoimide composition in a stable polyimide state, applying the composition to the substrate, and simply going through the solvent volatilization process. There is.

As described above, the present invention can provide a polyimide film with improved low dielectric properties and processability properties while maintaining excellent thermal and mechanical properties through a soluble polyimide polymer, and this polymer film is made of a polyimide film known in the art. It can be usefully applied as a coating material for substrates for general electronic devices and electrical and electronic components.

<Tetracarboxylic dianhydride>

One embodiment of the present invention is tetracarboxylic acid anhydride monomer for producing polyamic acid and/or polyimide polymer. This tetracarboxylic dianhydride monomer is differentiated from conventional tetracarboxylic dianhydride in that it contains a functional moiety in the basic skeleton centered around a triphenylmethane group and ether groups connected to both sides.

For one specific example, the tetracarboxylic dianhydride monomer may be represented by the following formula (1).

In Formula 1,

R ₁ to R ₃ are the same or different from each other, and are each independently hydrogen, halogen, C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkyloxy group, C ₃ to C ₁₀ cycloalkyl group, C ₆ to Consists of an aryl group of C ₂₀ , an aryloxy group of C ₆ ~ C ₂₀ , a heterocyclic group of 5 to 20 nuclear atoms, and -(CF ₂ ) _n -CF ₃ (where n is an integer between 0 and 5) selected from the group that is,

R ₄ is selected from hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₁₀ cycloalkyl group, a C ₆ to C ₂₀ aryl group, and a trifluoromethyl group,

R ₅ and R ₆ are each independently an alkyl group of C ₁ to C ₂₀ ,

a and b are each independently integers from 0 to 4.

In one specific example of Formula 1, R ₁ to R ₃ are the same or different from each other, and are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₁₀ alkyloxy group, and C ₃ to C It may be selected from the group consisting of a ₁₀ cycloalkyl group, a C ₆ to C ₁₂ aryl group, and a C ₆ to C ₁₂ aryloxy group. More specifically, at least one of R ₁ to R ₃ does not contain hydrogen and is composed of a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₁₀ alkyloxy group, and a C ₃ to C ₁₀ cycloalkyl group. It may be selected from a group consisting of:

Additionally, R ₄ may be an alkyl group of C ₁ to C ₁₀ , or -(CF ₂ ) _n -CF ₃ (where n is an integer between 0 and 3).

The above-described alkyl group, alkyloxy group, cycloalkyl group, aryl group, aryloxy group and heterocyclic group of R ₁ to R ₄ are each independently selected from deuterium, halogen, cyano group, C ₁ to C ₁₀ alkyl group, C ₁ From the group consisting of an alkyloxy group of ~C ₁₀ , a cycloalkyl group of C ₃ ~C ₁₀ , an aryl group of C ₆ ~C ₁₂ , an aryloxy group of C ₆ ~C ₁₂ , and a heteroaryl group of 5 to 10 nuclear atoms. It may be substituted or unsubstituted with one or more selected substituents.

The novel tetracarboxylic dianhydride represented by the above-mentioned formula 1 contains an ether group in the molecular skeleton and at least one functional moiety such as a trifluoromethyl group, an alkyl group, and a cyclohexyl group with a high fluorine content as a pendant group. Includes above. Accordingly, the polyimide-based polymer using the above-described tetracarboxylic dianhydride can be expected to have low dielectric properties.

In addition, as the tetracarsylic dianhydride uses a triphenylmethane derivative as a core, it can be expected to prevent the intramolecular and/or intermolecular π-π stacking phenomenon by inhibiting the planar arrangement of aromatic rings within the molecule, and the polymer Free volume can be secured within the polyimide polymer due to specific functional moieties that exist as pendant groups on a plane different from the main chain. Accordingly, the polyimide-based polymer to which the above-described tetracarboxylic dianhydride is applied allows solvent molecules to easily enter between the polymer chains, thereby increasing the solubility of the polymer and improving the processability of polyimide, which has the disadvantage of being insoluble and infusible. Improvement can be expected.

As a preferred example, the compound represented by Formula 1 may be further specified as one of the following Formulas 2 to 6 depending on the type of R ₁ to R ₄ and their bonding positions. However, it is not limited to this.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In the above equation,

R ₁ to R ₄ are each as defined in Formula 1, except hydrogen.

The compound represented by Formula 1 of the present invention described above may be further specified as the compounds exemplified below. However, the compound represented by Formula 1 of the present invention is not limited to those exemplified below.

Hereinafter, a method for producing a novel tetracarboxylic dianhydride according to an embodiment of the present invention will be described. However, it is not limited to the following manufacturing method, and the steps of each process may be modified or selectively mixed as needed.

The tetracarboxylic dianhydride can be prepared according to common methods known in the art, and specifically according to Scheme 1 below. An example of this manufacturing method includes synthesizing a dihydroxy compound; Synthesizing a diphthalonitrile compound by reacting the dihydroxy compound with 4-nitrophthalonitrile; Synthesizing a diphthalic acid compound by oxidizing the nitrile group contained in the diphthalonitrile compound; And it may include a step of synthesizing a tetracarboxylic dianhydride compound by dehydrating and condensing the phthalic acid group contained in the diphthalic acid compound.

[Scheme 1]

The term “alkyl group” used herein refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 20 carbon atoms (specifically, 1 to 10 carbon atoms). In one embodiment, the alkyl may be selected from the group consisting of methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc., but is not limited thereto.

The term "alkenyl group" as used herein refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 20 carbon atoms (specifically, 2 to 10 carbon atoms) having one or more carbon-carbon double bonds. . In one embodiment, the alkenyl may be selected from the group consisting of vinyl, allyl, isopropenyl, 2-butenyl, etc., but is not limited thereto.

As used herein, the term “aryl group” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 20 carbon atoms (specifically, 6 to 10 carbon atoms) consisting of a single ring or a combination of two or more rings. In addition, forms in which two or more rings are simply attached or condensed to each other may also be included. In one embodiment, the aryl may be selected from the group consisting of phenyl, naphthyl, phenanthryl, anthryl, etc., but is not limited thereto.

As used herein, the term “heterocyclic group” refers to a cyclic monovalent substituent having one or more heteroatoms selected from the group consisting of N, O, S, and Se, and the remainder being C atom(s). At this time, the 'heterocyclic group' may be a single ring or a multiple ring. If the heterocyclic group is an aromatic ring, it is called a heteroaryl group, and if the heterocyclic group is an alicyclic ring, it is called a heterocycloalkyl group. The heterocyclic group may be a cyclic group containing a 4-membered, 5-membered, 6-membered, 7-membered or 8-membered ring, wherein the ring contains one or more ring atoms selected from the group consisting of N, O, Se and S, It has C as the remaining ring atom. In one embodiment, the heterocyclic group is pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholino group, thiomorpholino group, homopiperidinyl group, chromanyl group, isochromanyl group, chromenyl group, and pyrrolyl group. , furanyl group, thienyl group, pyrazolyl group, imidazolyl group, furazanyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, Pyrazinyl group, pyranyl group, indolyl group, isoindolyl group, indazolyl group, purinyl group, indolizinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, pteridinyl group, quinolizinyl group, It may be selected from the group consisting of benzoxazinyl group, carbazolyl group, phenazinyl group, phenothiazinyl group, and phenanthridinyl group, but is not limited thereto.

The term "alkyloxy group" used herein refers to a monovalent substituent represented by R'O-, where R' refers to alkyl having 1 to 20 carbon atoms (specifically, 1 to 10 carbon atoms), and is a straight chain or branched group. Alternatively, it may include a cyclic structure. In one embodiment, the alkyloxy may be selected from the group consisting of methoxy, ethoxy, n-propoxy, 1-propoxy, t -butoxy, n-butoxy, pentoxy, etc., but is not limited thereto. No.

The term “aryloxy group” used herein refers to a monovalent substituent represented by RO-, where R refers to aryl having 5 to 20 carbon atoms (specifically, 6 to 10 carbon atoms). In one embodiment, the aryloxy may be selected from the group consisting of phenyloxy, naphthyloxy, diphenyloxy, etc., but is not limited thereto.

<Polyamic acid composition>

Another embodiment of the present invention is a polyamic acid composition containing the novel tetracarboxylic dianhydride described above, which corresponds to a precursor solution for forming polyamic acid and/or polyimide (co)polymer.

For one specific example, the polyamic acid composition includes at least one type of diamine; At least one type of dianhydride; and at least one of the tetracarboxylic dianhydrides includes tetracarboxylic dianhydride represented by Chemical Formula 1. If necessary, at least one type of curing agent, latent curing agent, and/or conventional additives known in the art may be further included.

Hereinafter, the composition of the polyamic acid composition will be examined in detail as follows.

Tetracarboxylic dianhydride

The polyamic acid composition according to the present invention includes at least one tetracarboxylic dianhydride compound, and includes tetracarboxylic dianhydride represented by Formula 1 above.

Here, since the tetracarboxylic dianhydride of Formula 1 is the same as described above, separate description is omitted.

In the polyamic acid composition according to the present invention, the amount of the tetracarboxylic dianhydride compound represented by Formula 1 is not particularly limited and can be appropriately adjusted within the content range known in the art. For example, the compound of Formula 1 may be included in the range of 1 to 100 mol%, specifically in the range of 10 to 100 mol%, based on 100 mol% of the total tetracarboxylic dianhydride.

The polyamic acid composition according to the present invention may further include conventional tetracarboxylic dianhydride known in the art in addition to the novel tetracarboxylic dianhydride compound described above.

Such tetracarboxylic dianhydride can be used without particular limitation as long as it is a compound having a tetracarboxylic dianhydride structure within the molecule. Examples include aromatic, alicyclic, or aliphatic compounds having a tetracarboxylic dianhydride structure. Specifically, tetracarboxylic dianhydride compounds include non-fluorinated aromatic, fluorinated aromatic with fluorine substituent introduced, sulfone-based, hydroxy-based, ether-based, and alicyclic tetracarboxylic dianhydrides known in the art, respectively, individually or in combination of two or more types. Can be used interchangeably.

The fluorinated aromatic tetracarboxylic dianhydride monomer is not particularly limited as long as it is an aromatic dianhydride into which a fluorine substituent is introduced. An example of a usable fluorinated aromatic tetracarboxylic dianhydride is 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 6 -FDA), 4-(trifluoromethyl)pyromellitic dianhydride (4-(trifluoromethyl)pyromellitic dianhydride, 4-TFPMDA), etc. These may be used alone or in combination of two or more types.

Additionally, alicyclic tetracarboxylic dianhydride is not particularly limited as long as it is a compound that has a dianhydride structure and has an alicyclic ring rather than an aromatic ring in the compound. Examples of alicyclic tetracarboxylic dianhydrides that can be used include cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride (CPDA), and bicyclo[2. ,2,2]-7-octene-2,3,5,6-tetracarboxylic acid dianhydride (BCDA), etc., but is not particularly limited thereto. The above-described dianhydrides can be used individually or in a mixture of two or more types.

Additionally, the non-fluorinated aromatic tetracarboxylic dianhydride monomer is not particularly limited as long as it is a non-fluorinated aromatic dianhydride in which a fluorine substituent is not introduced. Non-limiting examples of non-fluorinated aromatic tetracarboxylic dianhydride monomers that can be used include Pyromellitic Dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (3) ,3′,4,4′-Biphenyl tetracarboxylic acid dianhydride (BPDA), benzophenone tetracarboxylic dianhydride (BTDA), and oxydiphthalic dianhydride (ODPA). These may be used alone, or two or more types thereof may be mixed.

Non-limiting examples of acid dianhydrides that can be used include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,5,6-anthracenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl Tetracarboxylic acid dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, Bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3, 3-Hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2 ,3,4,5-Pyridine tetracarboxylic dianhydride, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,4 ,9,10-Perylene tetracarboxylic dianhydride, 1,3-diphenyl- 1,2,3,4-cyclobutane tetracarboxylic dianhydride, oxydiphthalate tetracarboxylic dianhydride, 1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1, 2,3,4-Cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride , 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, bicyclo[3,3,0]octane -2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2 ,4,7,9-Tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[6.3.0.0＜2,6＞]undecane -3,5,9,11-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2, 3,4-Tetrahydrinaphthalene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexane-1,2-dicarboxylic dianhydride, tetracyclo[6,2,1,1,0,2,7]dodeca -4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2:3, 5:6 dicarboxylic dianhydride, 1,2,4,5-cyclohexane Tetracarboxylic dianhydride, etc. can be mentioned.

diamine

The polyamic acid composition according to the present invention can use, without limitation, conventional diamine compounds known in the art having a diamine structure in the molecule.

The diamine is not particularly limited as long as it is a typical diamine compound that reacts with tetracarboxylic dianhydride, and specifically includes non-fluorinated aromatic diamine, fluorinated aromatic diamine with a fluorine substituent introduced, sulfone diamine, hydroxy diamine, ether diamine, Alicyclic diamines, etc. can be used individually or in combination of two or more types.

Non-limiting examples of diamines that can be used include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene. Diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5- Diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3' -Difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamino Biphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline , bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodi Phenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl( 3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-dia Minobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzo Phenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4- Aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5- Diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene , 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4 -phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline , 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3 -phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3 -Phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1, 4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl) Terephthalate, bis(3-aminophenyl) terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4- Aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N ,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide , N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4' -bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl ]Hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino -4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4) -Methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4 -Bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy) )hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis( 4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy) ) undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane. Bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminoctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, 12-diaminododecane, or mixtures thereof. Moreover, as the diamine side chain, a diamine compound having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, and a cyclic substituent formed from these can be used.

The amount of diamine used is not particularly limited and can be appropriately adjusted within the content range known in the art. For example, at least one type of diamine may be included in the range of 1 to 100 mol%, specifically 10 to 100 mol%, based on 100 mol% of the total diamine.

In the polyamic acid composition of the present invention, the ratio (a/b) of the number of moles of the diamine component (a) and the number of moles of the tetracarboxylic dianhydride component (b) may be 0.7 to 1.3, preferably 0.8 to 1.2. and, more preferably, may be in the range of 0.9 to 1.1. However, it is not particularly limited thereto.

menstruum

The polyamic acid composition according to the present invention is a solvent for the solution polymerization reaction of the above-described diamine and tetracarboxylic dianhydride monomers, and organic solvents known in the art can be used without limitation.

The organic solvent is not particularly limited as long as the polymer is soluble, and examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, and dimethylsulfoxide. Side, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoa Milketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoiso. Propyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, ethylene glycol monoacetate, diethylene glycol Dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether , 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butylate, Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate. , ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, Examples include 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropyl propionate, butyl 3-methoxypropionate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. These may be used individually or mixed.

The content of the solvent is not particularly limited as long as the remaining amount makes the total amount of the composition 100 parts by weight. In order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, it may be 50 to 95 parts by weight, specifically 70 to 90 parts by weight, based on the total weight of the composition for producing polyamic acid.

additive

In addition to the above-mentioned components, the polyamic acid composition of the present invention may contain at least one type of conventional curing agent, latent curing agent, and/or other additives known in the art, within the range that does not impair the effect of the invention. .

The curing agent and latent curing agent are not particularly limited, and components known in the art can be used without limitation. For example, epoxy curing agents, amine adduct series, dicyandiamide, urea series [e.g., 3-(3,4-dichlorophenyl)-1,1-dimethylurea], imidazole series curing agents, or one or more types thereof. Mixtures, etc. can be used.

Additionally, examples of additives that can be used include plasticizers, antioxidants, flame retardants, dispersants, viscosity modifiers, leveling agents, inorganic fillers, and curing accelerators. These can be used alone or two or more types can be used together. The content of the additive is not particularly limited and can be appropriately adjusted within the usage range known in the art. For example, at least one type of additive may be included in an amount of 0.01 to 10 parts by weight, specifically 0.1 to 5 parts by weight, based on the total weight of the polyamic acid composition.

The polyamic acid composition according to the present invention is prepared by adding at least one tetracarboxylic dianhydride containing the tetracarboxylic acid dianhydride of the above-described formula (1), at least one diamine, and, if necessary, a curing agent according to a common method known in the art. , can be prepared by adding a latent hardener and/or additive to a solvent and then reacting.

When reacting tetracarboxylic dianhydride and diamine in an organic solvent, a solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and tetracarboxylic dianhydride is added as is or as dispersed or dissolved in the organic solvent. Conversely, A method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of adding tetracarboxylic dianhydride and diamine components alternately, etc. can be used. Any of these methods may be used. In addition, when tetracarboxylic dianhydride or diamine consists of multiple types of compounds, the reaction may be performed in a pre-mixed state, the reaction may be performed individually sequentially, or the individually reacted low molecular weight substances may be mixed and reacted.

The polyamic acid composition constituted as described above is not particularly limited in composition or viscosity, etc., as long as it contains tetracarboxylic dianhydride represented by Chemical Formula 1. For example, the polyamic acid composition may have a viscosity (based on 25°C) ranging from about 1,000 to 400,000 cps, specifically about 5,000 to 100,000 cps. When the viscosity of the polyamic acid solution falls within the above-mentioned range, it is easy to control the thickness when coating the polyamic acid solution, and the coating surface can be uniform.

<Polyamic acid>

Another embodiment of the present invention is a polyamic acid formed using the above-described polyamic acid composition, and is a polyimide precursor (poly(amic acid), PAA) polymer for producing a polyimide polymer.

For one specific example, the polyamic acid includes a repeating unit represented by any one of Formulas 7 to 9 below.

[Formula 7]

[Formula 8]

[Formula 9]

In the above equation,

A of Formula 7; At least one of A ₁ and A ₂ of Formula 8; At least one of A ₃ to A ₅ of Formula 9 is a group derived from the compound of Formula 1,

The B is a group derived from diamine,

In Formula 8, x and y are rational numbers that satisfy x+y=1,

In Formula 9, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1.

Here, the degree of polymerization of each repeating unit represented by Formulas 7 to 9 is not particularly limited and can be appropriately adjusted within a range known in the art. For example, it may be an integer between 1 and 10,000.

In Formulas 8 and 9, A ₁ to A ₅ may include a group derived from another tetracarboxylic dianhydride that is different from the tetracarboxylic dianhydride of Formula 1 described above. Since this tetracarboxylic dianhydride is the same as the additional tetracarboxylic dianhydride component described in the polyamic acid composition described above, further details are omitted. In addition, in Formulas 7 to 9, B is a group derived from diamine, and since the diamine component is the same as the specific diamine component described in the polyamic acid composition described above, further details are omitted. And in Formula 9, A ₁ to A ₅ may be the same as or different from each other, and specifically, A ₄ or A ₅ may be the same as or different from A ₃ .

<Polyimide polymer>

In addition, another embodiment of the present invention is a polyamic acid obtained by reacting a polyamic acid composition containing tetracarboxylic dianhydride represented by the above-described formula (1), or a polymer or copolymer obtained by dehydrating and ring-closing the polyamic acid.

The polyimide polymer is not particularly limited and may be in the form of a common random copolymer or block copolymer known in the art. For one specific example, the polymer includes a polyimide-based structural unit (repeating unit) represented by any one of the following formulas 10 to 12.

[Formula 10]

[Formula 11]

[Formula 12]

In the above equation,

A of Formula 10; At least one of A ₁ and A ₂ of Formula 11; At least one of A ₃ to A ₅ of Formula 12 is a group derived from the compound of Formula 1,

The B is a group derived from diamine,

In Formula 11, x and y are rational numbers that satisfy x+y=1,

In Formula 12, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1.

Here, the degree of polymerization of each repeating unit represented by Formulas 10 to 12 is not particularly limited and can be appropriately adjusted within a range known in the art. For example, it may be an integer between 1 and 10,000.

In Formulas 11 and 12, A ₁ to A ₅ may include a group derived from another tetracarboxylic dianhydride that is different from the tetracarboxylic dianhydride of Formula 1 described above. Since this tetracarboxylic dianhydride is the same as the additional tetracarboxylic dianhydride component described in the polyamic acid composition described above, further details are omitted. In addition, in Formulas 10 to 12, B is a group derived from diamine, and since the diamine component is the same as the specific diamine component described in the polyamic acid composition described above, further details are omitted. And in Formula 12, A ₁ to A ₅ may be the same as or different from each other, and specifically, A ₄ or A ₅ may be the same as or different from A ₃ .

The polyimide polymer according to the present invention can be obtained by dehydrating and ring-closing a polyamic acid solution (eg, polyamic acid composition) or the polyamic acid according to a conventional method known in the art. For example, the polyamic acid solution can be prepared by inducing an imide ring closure reaction (Imidazation) for 0.5 to 8 hours while gradually increasing the temperature in the range of 30 to 350 ° C.

At this time, the imidization rate does not necessarily have to be 100% and can be arbitrarily adjusted depending on the use or purpose. Additionally, the polymerization temperature may be selected at any temperature from -20°C to 150°C, and preferably ranges from -5°C to 100°C. The reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, so tetra The total concentration of carboxylic dianhydride and diamine may be 1 to 50% by weight, preferably 5 to 30% by weight.

The method of imidizing the polyamic acid polymerized with exothermic solution according to the present invention is not particularly limited, and examples include thermal imidization method of heating the polyamic acid solution as is, catalyst imidization (or It can be applied by combining the chemical imidization method, or the thermal imidization method and the catalytic imidization method.

The thermal imidization method is a method of imidizing a polyamic acid solution by heating it for 1 to 10 hours while slowly raising the temperature in the temperature range of 30 to 400 ° C. At this time, the temperature may be 100°C to 400°C, preferably 120°C to 250°C, and it is preferably carried out while removing water generated by the imidization reaction.

In addition, the catalytic imidization method is a method of imidizing by adding a basic catalyst and an acid anhydride and stirring at -20°C to 250°C, preferably 0°C to 180°C.

The basic catalyst may be one known in the art, and examples include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and amines such as isoquinoline, β-picoline, and pyridine. Imidation catalysts such as these can also be used. Among these, pyridine is preferable because it has an appropriate basicity to proceed with the reaction. The amount of this basic catalyst is not particularly limited, and may be, for example, 0.5 to 30 mole times the amount of the amic acid group, preferably 2 to 20 mole times the amount of the amic acid group.

Additionally, as the acid anhydride, dehydrating agents represented by acid anhydrides such as acetic anhydride, trimellitic anhydride, and pyromellitic anhydride can be used. Among them, the use of acetic anhydride is preferable because it facilitates purification after completion of the reaction. The amount of this acid anhydride is not particularly limited and may be, for example, 1 to 50 mole times the amount of the amic acid group, and preferably 3 to 30 mole times the amount of the amic acid group. The imidization rate by catalyst imidization can be freely controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

In addition, when the thermal imidization method and the chemical imidization method are used together, the heating conditions of the polyamic acid solution may change depending on the type of polyamic acid solution, the thickness of the polyimide film to be produced, etc. To explain the above production example, acid dianhydride and basic catalyst are added to a polyamic acid solution, and then heated at 80 to 400°C, preferably 150 to 250°C to activate the dehydrating agent and imidization catalyst, thereby partially curing and drying. It can be implemented.

The method for recovering the polyamic acid or polyimide produced from the reaction solution of the above-described polyamic acid or polyimide is not particularly limited, and for example, the reaction solution may be added to a poor solvent to cause precipitation. Poor solvents used for precipitation include, but are not particularly limited to, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.

The polymer precipitated by adding it to a poor solvent can be recovered by filtration and then dried at room temperature or by heating under normal or reduced pressure.

The molecular weight of the polyamic acid and polyimide polymer of the present invention obtained as described above is not particularly limited and may have a typical molecular weight range known in the art. For example, the weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography may be 5,000 to 1,000,000 g/mol, and preferably 10,000 to 150,000 g/mol.

The polyimide polymer of the present invention described above is manufactured by applying a novel tetracarboxylic dianhydride containing functional moieties while having a basic skeleton containing triphenylmethane and ether groups in the molecule, thereby ensuring excellent heat resistance and mechanical properties. Since the dielectric properties and solubility are improved, it can be usefully applied as conventional films, compositions, substrates for electronic devices, and coating materials for electrical and electronic components known in the art. At this time, in the case of a composition containing the polymer, there is no particular limitation on components, content, composition, and/or its use.

<Polyimide film>

In addition, another embodiment of the present invention is a polyimide film containing the above-described polyimide polymer.

The manufacturing method of the polyimide film is not particularly limited and can be manufactured according to conventional methods known in the art.

For example, the above-described polyamic acid solution, that is, the polyamic acid composition, is applied (cast) on a support (e.g., a substrate), and then the imide is added for 0.5 to 8 hours while gradually increasing the temperature in the range of 30 to 350 ° C. It can be manufactured by inducing a ring closure reaction (Imidization). At this time, the reaction may occur under an inert atmosphere such as argon or nitrogen.

As another example, it can be manufactured by applying a polyimide composition (eg, polymer-containing solution) on a support (eg, substrate) and then curing it.

The application method can be used without limitation to conventional methods known in the art, such as spin coating, dip coating, solvent casting, slot die coating, and It can be achieved by at least one method selected from the group consisting of spray coating.

Meanwhile, conventionally, it was common to apply a polyamic acid composition to a substrate and then manufacture it through a two-step thermal curing process of pre-curing and main-curing. At this time, pre-curing is a process to volatilize the solvent at a temperature of 100 to 150°C, and main-curing is a process to polymerize polyamic acid into polyimide through ring-closure dehydration reaction at a temperature of 300 to 550°C. In other words, due to the insoluble and infusible characteristics of polyimide, the film forming process had to be performed in a relatively unstable polyamic acid state.

In contrast, the present invention can provide a composition in a polyimide state by presenting a polyimide polymer with improved solubility. Accordingly, there is an advantage that film formation is possible by applying a polyamide composition in a stable polyimide state to a substrate and then only going through a solvent volatilization process, without going through a film formation process in an unstable polyamic acid state.

The thickness of the polyimide film of the present invention formed in this way is not particularly limited and can be appropriately adjusted depending on the field to which it is applied. For example, it may be in the range of 1 to 150 ㎛, specifically 5 to 100 ㎛, and more specifically 10 to 80 ㎛.

For example, the polyimide film may satisfy at least two of the following physical properties (i) to (iii), and preferably all of them. (i) The 5% weight loss temperature (Td, 5%) measured by thermogravimetric analysis (TGA) exceeds 300°C, and may specifically be 350°C or higher, preferably 400°C or higher. (ii) At a frequency of 10 GHz, the dielectric constant (Dk) is less than 3.5 and the dielectric loss (Df) is less than 0.006. Preferably, the dielectric constant (Dk) is less than 3.0 and the dielectric loss (Df) is less than 0.004. (iii) Moisture absorption rate is less than 1%.

The polyimide polymer, polyimide composition, and film of the present invention having the above-described physical properties can be applied to all fields where conventional polyimide is used, and specifically, to various technical fields that require heat resistance, excellent mechanical properties, low dielectric constant, etc. It can be usefully applied. For example, flexible display substrates such as displays for organic EL devices (OLED), displays for liquid crystal devices, TFT substrates, flexible printed circuit boards, flexible OLED surface lighting substrates, and substrate materials for electronic paper, and/ Alternatively, it can be used as a protective shield. However, it is not limited to this.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Examples 1 to 3: Synthesis of tetracarboxylic dianhydride monomer]

Synthesis Example 1: 4,4'-(((1-(3,5-bis(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy) )Synthesis of diphthalic anhydride

1-1: Synthesis of 4,4'-(1-(3,5-bis(trifluoromethyl)phenyl)ethane-1,1-diyl)diphenol

139.65 g (0.545 mol) of 3',5'-bis(trifluoromethyl)acetphenone and 108.77 g (1.156 mol) of phenol were added to the reactor, stirred in a nitrogen atmosphere, and the reactor was heated to 50°C. 20.46 g (0.136 mol) of triflic acid was slowly injected in small amounts and stirred for 22 hours. When the reaction was completed, the reactant was added to stirred distilled water at 80°C, precipitated, and filtered. The precipitate was dried and recrystallized from dichloromethane, and the purified crystals were filtered and dried in vacuum. The yield rate was 40%.

^1H NMR (DMSO-d ₆ , 400MHz, ppm): 9.06(d, 2H), 8.02(s, 1H), 7.75(s, 2H), 7.01(d, 4H), 6.67(d, 4H), 2.28 (s, 3H)

1-2: 4,4'-(((1-(3,5-bis(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy) ) Synthesis of diphthalonitrile

4,4'-(1-(3,5-bis(trifluoromethyl)phenyl)ethane-1,1-diyl)diphenol 23.63 g (0.055 mol), 4-nitrophthalonitrile 19.67 g (0.114 mol) ), 22.98 g (0.166 mol) of potassium carbonate, and 200 mL of anhydrous dimethylformamide were added to the reactor and stirred in a nitrogen atmosphere. The reactor was heated to 120°C and stirred for 16 hours. When the reaction was completed, the reactant was added to stirring distilled water, precipitated, and filtered. Dissolve the precipitate in ethyl acetate, place it in a separatory funnel with distilled water, extract, and remove impurities. The organic layer was separated, concentrated under reduced pressure, recrystallized with ethyl acetate and normal-hexane, and the purified crystals were filtered and dried in vacuum. The yield rate was 97%.

^1H NMR (DMSO-d ₆ , 400MHz, ppm): 8.16(d, 2H), 8.08(s, 1H), 7.94(s, 1H), 7.70(s, 2H), 7.58(d, 2H), 7.33 (m, 8H), 2.29(s, 3H)

1-3: 4,4'-(((1-(3,5-bis(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy) )Synthesis of diphthalic acid

4,4'-(((1-(3,5-bis(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthalonitrile 36.0 g (0.053 mol), 84.88 g (2.122 mol) of sodium hydroxide, 200 mL of methanol, and 300 mL of distilled water were added to the reactor, then the reactor was heated to 100°C and stirred for 52 hours. When the reaction is completed, the heated reactant is filtered to remove solid impurities. Cool the filtrate to 0~10℃ and add HCl (35%) while stirring until the pH of the filtrate reaches 1. When a precipitate formed, it was filtered and vacuum dried. The yield rate was 88%.

¹ H NMR (DMSO-d ₆ , 400 MHz, ppm): 13.17 (s, 4H), 8.05 (s, 1H), 7.78 (d, 2H), 7.68 (s, 2H), 7.14 (m, 12H), 2.30 (s, 3H)

1-4: 4,4'-(((1-(3,5-bis(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy) )Synthesis of diphthalic anhydride

4,4'-(((1-(3,5-bis(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthalic acid 30 g (0.040 mol) and 90 mL of acetic anhydride were added to the reactor, heated to 140°C, and stirred for 8 hours. When the reaction was completed, the reactor was cooled to room temperature. The resulting crystals were filtered, washed with a small amount of acetic acid, and dried under vacuum to prepare the final compound (yield: 86%) represented by the following chemical formula.

¹ H NMR (DMSO-d ₆ , 400 MHz, ppm): 8.09 (m, 3H), 7.71 (s, 2H), 7.58 (d, 2H), 7.47 (s, 2H), 7.23 (m, 8H), 2.34 (s, 3H)

Synthesis Example 2: 4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene) )Synthesis of bis(oxy))diphthalic anhydride

2-1: Synthesis of 4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)diphenol

50 g (0.207 mol) of 2,2,2-trifluoro-4'-methylacetophenone and 41.20 g (0.438 mol) of phenol were added to the reactor, stirred in a nitrogen atmosphere, and the reactor was heated to 50°C. Slowly inject 7.75 g (0.052 mol) of triflic acid in small amounts and stir for 22 hours. When the reaction was completed, the reactant was added to stirred distilled water at 80°C, precipitated, and filtered. The precipitate was dried and recrystallized from dichloromethane, and the purified crystals were filtered and dried in vacuum. The yield rate was 51%.

¹ H NMR (DMSO-d ₆ , 400MHz, ppm): 9.01(d, 2H), 7.50(d, 2H), 7.09(m, 6H), 6.67(d, 4H)

2-2: 4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene) )Synthesis of bis(oxy))dipthalonitrile

4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)diphenol 30.0 g (0.073 mol), 4-nitrope 25.82 g (0.149 mol) of talonitrile, 30.17 g (0.218 mol) of potassium carbonate, and 200 mL of anhydrous dimethylformamide were added to the reactor and stirred in a nitrogen atmosphere. The reactor was heated to 120°C and stirred for 16 hours. When the reaction was completed, the reactant was added to stirring distilled water, precipitated, and filtered. Dissolve the precipitate in ethyl acetate, place it in a separatory funnel with distilled water, and extract to remove impurities. The organic layer was separated, concentrated under reduced pressure, recrystallized with ethyl acetate and normal-hexane, and the purified crystals were filtered and dried in vacuum. The yield rate was 88%.

¹ H NMR (DMSO-d ₆ , 400 MHz, ppm): 8.01 (d, 2H), 7.99 (s, 2H), 7.55 (m, 4H), 7.32 (d, 4H), 7.13 (m, 6H)

2-3: 4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene) )Synthesis of bis(oxy))diphthalic acid

4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy )) 35.0 g (0.0527 mol) of diphthalonitrile, 84.27 g (2.107 mol) of sodium hydroxide, 200 mL of methanol, and 300 mL of distilled water were added to the reactor, then the reactor was heated to 100°C and stirred for 52 hours. When the reaction is completed, the heated reactant is filtered to remove solid impurities. Cool the filtrate to 0~10℃ and add HCl (35%) while stirring until the pH of the filtrate reaches 1. When a precipitate formed, it was filtered and vacuum dried. The yield rate was 91%.

¹ H NMR (DMSO-d ₆ , 400 MHz, ppm): 13.21 (s, 4H), 7.85 (d, 2H), 7.61 (d, 2H), 7.41 (m, 6H), 7.11 (m, 8H)

2-4: 4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene) )Synthesis of bis(oxy))diphthalic anhydride

4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy )) 30.0 g (0.041 mol) of diphthalic acid and 90 mL of acetic anhydride were added to the reactor, then heated to 140°C and stirred for 8 hours. When the reaction was completed, the reactor was cooled to room temperature. The resulting crystals were filtered, washed with a small amount of acetic acid, and dried under vacuum to prepare the final compound (yield: 91%) represented by the following formula.

¹ H NMR (DMSO-d ₆ , 400MHz, ppm): 8.01(d, 2H), 7.62(d, 2H), 7.47(d, 2H), 7.32(s, 2H), 7.19(d, 2H), 7.05 (m, 8H)

Synthesis Example 3:

3-1: Synthesis of 4,4'-(1-(4-hexylphenyl)ethane-1,1-diyl)diphenol

50 g (0.193 mol) of 4'-hexylacetophenone and 38.58 g (0.410 mol) of phenol were added to the reactor, stirred in a nitrogen atmosphere, and the reactor was heated to 50°C. Slowly inject 7.26 g (0.048 mol) of triflic acid in small amounts and stir for 22 hours. When the reaction was completed, the reactant was added to stirred distilled water at 80°C, precipitated, and filtered. The precipitate was dried and recrystallized from dichloromethane, and the purified crystals were filtered and dried in vacuum. The yield rate was 52%.

¹ H NMR (DMSO-d ₆ , 400MHz, ppm): 8.95(d, 2H), 7.18(d, 2H), 7.03(m, 6H), 6.61(d, 4H), 2.59(t, 2H), 2.25 (s, 3H), 1.58(m, 2H), 1.30(m, 6H), 0.88(t, 3H)

3-2: Synthesis of 4,4'-(((1-(4-hexylphenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthalonitrile

4,4'-(1-(4-hexylphenyl)ethane-1,1-diyl)diphenol 30.0 g (0.080 mol), 4-nitrophthalonitrile 28.43 g (0.164 mol), potassium carbonate 33.21 g (0.240 mol) mol) Then, 200 mL of anhydrous dimethylformamide was added to the reactor and stirred in a nitrogen atmosphere. The reactor was heated to 120°C and stirred for 16 hours. When the reaction was completed, the reactant was added to stirring distilled water, precipitated, and filtered. Dissolve the precipitate in ethyl acetate, place it in a separatory funnel with distilled water, and extract to remove impurities. The organic layer was separated, concentrated under reduced pressure, recrystallized with ethyl acet and n-hexane, and the purified crystals were filtered and dried in vacuum. The yield rate was 93%.

¹ H NMR (DMSO-d ₆ , 400 MHz, ppm): 8.08 (d, 2H), 7.94 (s, 2H), 7.58 (d, 2H), 7.25 (d, 4H), 7.14 (m, 6H), 7.04 (d, 2H), 2.59(t, 2H), 2.28(s, 3H), 1.58(m, 2H), 1.30(m, 6H), 0.88(t, 3H)

3-3: Synthesis of 4,4'-(((1-(4-hexylphenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthaloic acid

4,4'-(2,2,2-trifluoro-1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy )) 35.0 g (0.056 mol) of diphthalonitrile, 89.35 g (0.223 mol) of sodium hydroxide, 200 mL of methanol, and 300 mL of distilled water were added to the reactor, then the reactor was heated to 100°C and stirred for 52 hours. When the reaction is completed, the heated reactant is filtered to remove solid impurities. Cool the filtrate to 0~10℃ and add HCl (35%) while stirring until the pH of the filtrate reaches 1. When a precipitate formed, it was filtered and vacuum dried. The yield rate was 94%.

¹ H NMR (DMSO-d ₆ , 400 MHz, ppm): 13.10 (s, 4H), 7.87 (d, 2H), 7.41 (m, 6H), 7.08 (m, 10H), 2.59 (t, 2H), 2.28 (s, 3H), 1.58(m, 2H), 1.30(m, 6H), 0.88(t, 3H)

3-4: Synthesis of 4,4'-(((1-(4-hexylphenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthaloic anhydride

30.0 g (0.043 mol) of 4,4'-(((1-(4-hexylphenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy))diphthaloic acid and acetic acid After adding 90 mL of anhydride to the reactor, the temperature was raised to 140°C and stirred for 8 hours. When the reaction was completed, the reactor was cooled to room temperature. The resulting crystals were filtered, washed with a small amount of acetic acid, and dried under vacuum to prepare the final compound (yield: 87%) represented by the following chemical formula.

¹ H NMR (DMSO-d ₆ , 400MHz, ppm): 7.89(d, 2H), 7.40(m, 6H), 7.07(m, 10H), 2.59(t, 2H), 2.28(s, 3H), 1.58 (m, 2H), 1.30(m, 6H), 0.88(t, 3H)

[Example 1: Preparation of polyimide polymer and film]

A polyimide composition and film were prepared using the tetracarboxylic dianhydride monomer synthesized in Synthesis Example 1.

Specifically, 24.97 mmol of tetracarboxylic dianhydride monomer (Synthesis Example 1), 5 g (24.97 mmol) of ODA, and 11.47 g of isoquinoline were dissolved in 206 g of meta-cresol and then incubated at 70°C for 2 hours under a nitrogen atmosphere at 150°C. It was stirred for 3 hours. After the reaction was completed, the temperature was cooled to room temperature, the viscous solution was precipitated in methanol, filtered, and the precipitate was washed several times with water and methanol. Afterwards, it was dried under reduced pressure at a temperature of 80°C to obtain a polyimide polymer.

A portion of the synthesized polyimide polymer was made into a polyimide composition that was a 10% by weight DMAc solution, applied to a glass plate, and then the solvent was removed at a temperature of 200°C and under vacuum conditions to prepare a polyimide film.

[Example 2: Polyimide polymer and film production]

A polyimide composition and film were prepared using the tetracarboxylic dianhydride monomer synthesized in Synthesis Example 2.

Specifically, 24.97 mmol of tetracarboxylic dianhydride monomer (Synthesis Example 2), 5 g (24.97 mmol) of ODA, and 11.30 g of isoquinoline were dissolved in 203 g of meta-cresol and then incubated at 70°C for 2 hours and 150°C under a nitrogen atmosphere. It was stirred for 3 hours. After the reaction was completed, the temperature was cooled to room temperature, the viscous solution was precipitated in methanol, filtered, and the precipitate was washed several times with water and methanol. Afterwards, it was dried under reduced pressure at a temperature of 80°C to obtain a polyimide polymer.

A portion of the synthesized polyimide polymer was made into a polyimide composition that was a 10% by weight DMAc solution, applied to a glass plate, and then the solvent was removed at a temperature of 200°C and under vacuum conditions to prepare a polyimide film.

[Example 3: Preparation of polyimide polymer and film]

A polyimide composition and film were prepared using the tetracarboxylic dianhydride monomer synthesized in Synthesis Example 3.

Specifically, 24.97 mmol of tetracarboxylic dianhydride monomer (Synthesis Example 3), 5 g (24.97 mmol) of ODA, and 10.82 g of isoquinoline were dissolved in 195 g of meta-cresol and then incubated at 70°C for 2 hours and 150°C under a nitrogen atmosphere. It was stirred for 3 hours. After the reaction was completed, the temperature was cooled to room temperature, the viscous solution was precipitated in methanol, filtered, and the precipitate was washed several times with water and methanol. Afterwards, it was dried under reduced pressure at a temperature of 80°C to obtain a polyimide polymer.

A portion of the synthesized polyimide polymer was made into a polyimide composition that was a 10% by weight DMAc solution, applied to a glass plate, and then the solvent was removed at a temperature of 200°C and under vacuum conditions to prepare a polyimide film.

[Comparative Example 1: Preparation of polyamic acid composition and polyimide film]

24.97 mmol of 3,3,4,4-Biphenyltetracarboxylic dianhydride (BPDA) and 5 g (24.97 mmol) of ODA were dissolved in 111 g of meta-cresol and stirred for 2 hours while maintaining the reactor temperature at 25°C under a nitrogen atmosphere. . From the above reaction, a polyamic acid composition with a solid content concentration of 10% by weight was prepared.

The polyamic acid composition was spin-coated on a glass substrate to a thickness of 55㎛. The glass substrate coated with the polyamic acid composition was placed in an oven and heated at a rate of 5°C/min, and maintained at 80°C for 30 minutes and 450°C for 1 hour to proceed with the imide ring closure reaction (Imidization). After the ring closure reaction was completed, the glass substrate was immersed in water, the film formed on the glass substrate was removed, and it was dried in an oven at 120° C. to prepare a polyimide film.

[Comparative Example 2: Preparation of polyamic acid composition and polyimide film]

24.97 mmol of 4,4'-Oxydiphthalic Anhydride (ODPA) and 5 g (24.97 mmol) of ODA were dissolved in 115 g of meta-cresol and stirred for 2 hours while maintaining the reactor temperature at 25°C under a nitrogen atmosphere. From the above reaction, a polyamic acid composition with a solid content concentration of 10% by weight was prepared.

The polyamic acid composition was spin-coated on a glass substrate to a thickness of 55㎛. The glass substrate coated with the polyamic acid composition was placed in an oven and heated at a rate of 5°C/min, and maintained at 80°C for 30 minutes and 450°C for 1 hour to proceed with the imide ring closure reaction (Imidization). After the ring closure reaction was completed, the glass substrate was immersed in water, the film formed on the glass substrate was removed, and it was dried in an oven at 120° C. to prepare a polyimide film.

[Comparative Example 3: Preparation of polyamic acid composition and polyimide film]

24.97 mmol of 4,4′-(Hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 5 g (24.97 mmol) of ODA were dissolved in 111 g of meta-cresol and stirred for 2 hours while maintaining the reactor temperature at 25°C under a nitrogen atmosphere. . From the above reaction, a polyamic acid composition with a solid content concentration of 10% by weight was prepared.

The polyamic acid composition was spin-coated on a glass substrate to a thickness of 55㎛. The glass substrate coated with the polyamic acid composition was placed in an oven and heated at a rate of 5°C/min, and maintained at 80°C for 30 minutes and 450°C for 1 hour to proceed with the imide ring closure reaction (Imidization). After the ring closure reaction was completed, the glass substrate was immersed in water, the film formed on the glass substrate was removed, and it was dried in an oven at 120° C. to prepare a polyimide film.

[Experimental example. Physical property evaluation]

The physical properties of the polyimide films prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated in the following manner, and the results are shown in Table 1 below.

(1) Solubility (polyimide)

While maintaining the temperature at 20°C, a small amount of the sample was added dropwise to 100 g of the solvent being stirred until it no longer dissolved and left for 23 hours. Solubility was measured according to Equation 1 below.

[Equation 1]

Solubility (%) = dissolved sample amount (g)/solvent (100g) ×100

(2) Film thickness

The thickness of the film was measured using a thickness measuring device (KG601B Electric Micro meter (Anritsu)).

(3) Heat resistance

Measurements were made using a thermogravimetric analyzer (TGA) under a nitrogen atmosphere. At this time, the heat resistance measurement range was 25 to 700°C, and the temperature increase rate was 10°C/min. To remove moisture absorbed from the atmosphere, the weight was calculated as 100% after constant temperature at 105°C for 30 minutes, and the temperature at which 5% weight loss occurs (Td, 5%) was measured.

(4) Dielectric constant

The size of the specimen was 5 × 5 cm or more, and the thickness of the specimen was 50㎛. Each specimen was placed into the resonator and measured at room temperature/pressure.

(5) Dielectric loss

The size of the specimen was 5 × 5 cm or more, and the thickness of the specimen was 50㎛. Each specimen was placed in the resonator and measured at room temperature/pressure.

(6) Moisture absorption rate

The prepared polyimide film was made into a specimen with a size of 10 x 10 mm, and the initial weight (W1) was measured. Next, each specimen was left in a purified water bath for 24 hours under the conditions of temperature 25 ± 2℃ and relative humidity 30% to absorb moisture. Then, the specimen was taken out, wiped with a cloth, and the weight (W2) was measured after moisture absorption treatment. The moisture absorption rate was calculated by substituting the measured values into Equation 2 below.

[Equation 2]

Moisture absorption rate (%) = [(W2-W1)/W1] ×100

Composition (mol%) thickness
(㎛) Properties diamine acid dianhydride Td _5% (℃) Dielectric constant (@10GHz) moisture absorption rate
(%) solubility powder film permittivity
(Dk) oil field loss
(Df) Example 1 O.D.A. Synthesis example 1 50 ++ ++ ++ ++ ++ ++ Example 2 O.D.A. Synthesis example 2 50 ++ ++ ++ ++ ++ ++ Example 3 O.D.A. Synthesis example 3 50 ++ + ++ + ++ + Comparative Example 1 O.D.A. BPDA 50 - ++ + + ++ - Comparative Example 1 O.D.A. ODPA 50 - ++ + + + - Comparative example 2 O.D.A. 6FDA 50 - + ++ + + +

Properties Judgment criteria Heat resistance (Td _5%) powder + (>150℃), ++ (>170℃) Film (@50 ㎛) + (> 350℃), ++ (> 400℃) permittivity permittivity + (< 3.5), ++ (< 3.0) oil field loss + (< 0.006), ++ (< 0.004) moisture absorption rate + (> 1.0), ++ (< 0.8) solubility + NMP, DMF, THF / ++ MC, CHCl ₃ , AcOH

As shown in Table 1, it was found that the polyimide film containing the novel tetracarboxylic dianhydride monomer according to the present invention exhibits low dielectric constant and low moisture absorption, making it possible to produce a film with excellent processability and heat resistance. .

Claims (13)

Compound for forming polyamic acid or polyimide represented by the following formula (1):
[Formula 1]

R ₁ to R ₃ are the same or different from each other, and are each independently hydrogen, halogen, C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkyloxy group, C ₃ to C ₁₀ cycloalkyl group, C ₆ to Consists of an aryl group of C ₂₀ , an aryloxy group of C ₆ ~ C ₂₀ , a heterocyclic group of 5 to 20 nuclear atoms, and -(CF ₂ ) _n -CF ₃ (where n is an integer between 0 and 5) selected from the group that is,
R ₄ is selected from hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₁₀ cycloalkyl group, a C ₆ to C ₂₀ aryl group, and a trifluoromethyl group,
R ₅ and R ₆ are each independently an alkyl group of C ₁ to C ₂₀ ,
a and b are each independently integers from 0 to 4. According to paragraph 1,
The compound of Formula 1 is a compound represented by any one of the following Formulas 2 to 6:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In the above equation,
R ₁ to R ₄ are each as defined in clause 1, except hydrogen. According to paragraph 1,
R ₁ to R ₃ are the same or different from each other, and each independently represents hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₁₀ alkyloxy group, a C ₃ to C ₁₀ cycloalkyl group, and C ₆ to C ₁₂ is selected from the group consisting of an aryl group, and an aryloxy group of C ₆ to C ₁₂ ,
R ₄ is a compound selected from the group consisting of a C ₁ to C ₁₀ alkyl group, and a trifluoromethyl group. The compound represented by Formula 1 is a compound selected from the group of compounds represented by the following formula.
Tetracarboxylic dianhydride containing the compound of formula 1 according to any one of claims 1 to 4; and
diamine;
A polyamic acid composition containing. According to clause 5,
A polyamic acid composition in which the compound represented by Formula 1 is contained in the range of 1 to 100 mol% based on 100 mol% of the total tetracarboxylic dianhydride. According to clause 5,
The diamine is a fluorinated aromatic primary diamine; A polyamic acid composition comprising at least one member selected from the group consisting of sulfone-based aromatic secondary diamine, hydroxy-based aromatic tertiary diamine, ether-based aromatic quaternary diamine, and cycloaliphatic fifth diamine. A polyamic acid formed from the polyamic acid composition of claim 5. According to clause 8,
The polyamic acid includes a repeating unit represented by any one of the following formulas 7 to 9:
[Formula 7]

[Formula 8]

[Formula 9]

In the above equation,
A of Formula 7; At least one of A ₁ and A ₂ of Formula 8; At least one of A ₃ to A ₅ of Formula 9 is a group derived from the compound of Formula 1,
The B is a group derived from diamine,
In Formula 8, x and y are rational numbers that satisfy x+y=1,
In Formula 9, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1. A polyimide polymer formed by imidizing the polyamic acid of claim 8. According to clause 10,
The polyimide polymer includes a repeating unit represented by any one of the following formulas 10 to 12.
[Formula 10]

[Formula 11]

[Formula 12]

In the above equation,
A of Formula 10; At least one of A ₁ and A ₂ of Formula 11; At least one of A ₃ to A ₅ of Formula 12 is a group derived from the compound of Formula 1,
The B is a group derived from diamine,
In Formula 11, x and y are rational numbers that satisfy x+y=1,
In Formula 12, x, y, and z are rational numbers that satisfy x + y + z = 1, 0 < y + z ≤ 0.7, and 0.3 ≤ x + y < 1. A polyimide composition comprising the polyimide polymer of claim 10. A polyimide film comprising the polyimide polymer of claim 10.