CN108602792B - Tetracarboxylic dianhydride, polyamic acid, and polyimide - Google Patents
Tetracarboxylic dianhydride, polyamic acid, and polyimide Download PDFInfo
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- CN108602792B CN108602792B CN201780009391.5A CN201780009391A CN108602792B CN 108602792 B CN108602792 B CN 108602792B CN 201780009391 A CN201780009391 A CN 201780009391A CN 108602792 B CN108602792 B CN 108602792B
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Abstract
Provided are a tetracarboxylic dianhydride represented by formula (1), a method for producing the same, and a polyamic acid and a polyimide which can be obtained from the tetracarboxylic dianhydride.
Description
Technical Field
The present invention relates to a novel tetracarboxylic dianhydride having a fluorene group, an ether group and an ester group, which is useful as a raw material for a polyimide resin or the like, and a polyamic acid and a polyimide obtained from the tetracarboxylic dianhydride.
Background
Resin materials having a high refractive index have higher processability and the like than conventional glass materials, and therefore, have been studied to be widely used for lenses such as spectacle lenses and cameras, lenses for optical disks, f θ lenses, optical system elements for image display media, optical films, substrates, various optical filters, prisms, optical elements for communications, and the like, and as resins exhibiting high refractive indices, for example, polyesters, polycarbonates, polyimides, and the like have been proposed. Among them, polyimide is widely known as a resin having excellent heat resistance, and among the above uses, particularly in the field where heat resistance is required, polyimide having a high refractive index and excellent heat resistance is required.
However, polyimide having high heat resistance is mostly insoluble in organic solvents, and it is not easy to mold polyimide itself. Therefore, it is necessary to obtain a polyimide film by molding a polyamic acid solution as a precursor into a film or the like, and performing dehydration ring closure (imidization) by heating at a high temperature of 250 to 350 ℃. However, in the method of obtaining a polyimide film by imidization after forming a film or the like from a solution of a polyamic acid, there are problems that curling, peeling of the film, cracking, and the like are often caused by thermal stress generated in the process of cooling from the imidization temperature (250 to 350 ℃) to room temperature, and thus a uniform polyimide film cannot be obtained, and a high-temperature furnace of 300 ℃ or higher is required for imidization, and the production cost is increased.
Therefore, as a polyimide having excellent solvent solubility and exhibiting a high refractive index, for example, a polyimide obtained from an aromatic diamine compound having a naphthalene skeleton has been proposed [ japanese patent application laid-open No. 2010-070513 (patent document 1) ]. The polyimide described in this document is soluble in a solvent and has a refractive index as high as about 1.63, but the refractive index needs to be further increased due to the demand for higher refractive index of resin materials.
Documents of the prior art
Patent document
Patent document 1: japanese patent application laid-open No. 2010-070513
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a polyimide which has excellent solvent solubility and exhibits a high refractive index.
Means for solving the problems
The present inventors have made various studies on the structures of tetracarboxylic dianhydride and diamine as raw materials of polyimide in order to solve the above-mentioned problems, and as a result, have found that a polyimide produced using a tetracarboxylic dianhydride having a fluorene skeleton represented by the following formula (1) has excellent solvent solubility and exhibits a high refractive index. Specifically, the present invention includes the following aspects.
〔1〕
A tetracarboxylic dianhydride represented by the following formula (1),
[ solution 1]
〔2〕
A polyamic acid having a repeating unit represented by the following formula (2),
[ solution 2]
(wherein Z represents a diamine residue).
〔3〕
A polyimide having a repeating unit represented by the following formula (3),
[ solution 3]
(wherein Z represents a diamine residue).
〔4〕
A process for producing a tetracarboxylic dianhydride [ 1] which comprises reacting a bisphenol represented by the following formula (4) with a trimellitic acid halide,
[ solution 4]
Effects of the invention
The polyimide produced using the tetracarboxylic dianhydride having a fluorene skeleton according to the present invention has excellent solvent solubility and high refractive index. Further, since the resin composition has a characteristic of excellent toughness even though it contains a rigid structure such as a fluorene skeleton, it can be used in the field of optical systems such as lenses for spectacle lenses, cameras, and the like, lenses for optical disks, f θ lenses, optical system elements for image display media, optical films, various optical filters, prisms, optical elements for communication, and the like, and can be suitably used for electronic materials such as flexible printed circuit boards, protective films for semiconductor elements, interlayer insulating films for integrated circuits, and the like, or flexible substrates instead of glass substrates generally used in liquid crystal displays, electronic paper, solar cells, and the like.
Drawings
FIG. 1 shows a process for producing a tetracarboxylic dianhydride represented by the formula (1)1H-NMR spectrum.
FIG. 2 shows a process for producing a tetracarboxylic dianhydride represented by the formula (1)13C-NMR spectrum.
FIG. 3 is a mass spectrum of a tetracarboxylic dianhydride represented by the formula (1).
Detailed Description
< method for producing tetracarboxylic dianhydride represented by formula (1) >
As a method for obtaining the tetracarboxylic dianhydride represented by the above formula (1), a known method can be suitably applied. Examples thereof include: a method (acid halide method) in which a compound represented by the above formula (4) (9, 9-bis (4- (4-hydroxyphenoxy) phenyl) fluorene, hereinafter sometimes abbreviated as BPOPF) is reacted with an acid halide of trimellitic anhydride in the presence of a deacidification agent (base); a method utilizing a direct dehydration reaction of BPOPF with trimellitic anhydride; a method of subjecting a diacetate of BPOPF and trimellitic anhydride to a dealcoholization reaction at a high temperature; a method of dehydrating and condensing BPOPF and trimellitic anhydride using a dehydrating agent such as dicyclohexylcarbodiimide; a process for esterifying BPOPF by activating trimellitic anhydride using a tosyl chloride/N, N-dimethylformamide/pyridine mixture. Among them, the acid halide method is preferable because trimellitic acid halide as a raw material can be obtained at low cost. The acid halide method is explained in detail below.
Specifically, the acid halide method represents: a reaction in which BPOPF is reacted with an acid halide of trimellitic anhydride represented by the following formula (5) in the presence of a deacidification agent to obtain tetracarboxylic dianhydride represented by the above formula (1) (hereinafter, this reaction may be referred to as an esterification reaction).
BPOPF used as a raw material may be commercially available or may be produced by a known method (for example, International publication No. 2006/052001 and Japanese patent application laid-open No. 2015-182970). Specifically, it can be obtained by reacting fluorenone and p-phenoxyphenol in the presence of an acid.
The acid halide of trimellitic anhydride used in the esterification reaction has a structure represented by the following formula (5),
[ solution 5]
(wherein Y represents a halogen atom).
Among these acid halides of trimellitic anhydride, the acid chloride of trimellitic anhydride can be obtained at low cost, and therefore, it is desirable that Y is a chlorine atom.
The amount of the acid halide of trimellitic anhydride represented by the formula (5) used in the esterification reaction is usually 2 to 4 times by mol, preferably 2 to 3 times by mol, based on BPOPF 1. When the amount of the acid halide of trimellitic anhydride used is 2 times by mol or more, a sufficient reaction rate can be obtained, and when the amount of the acid halide used is 4 times by mol or less, the amount of unreacted acid halide of trimellitic anhydride represented by the above formula (5) can be reduced, and as a result, the purity of the obtained tetracarboxylic dianhydride represented by the above formula (1) can be improved.
Examples of the deacidification agent used in the esterification reaction include: organic tertiary amines such as pyridine, triethylamine and N, N-dimethylaniline; epoxy compounds such as propylene oxide and allyl glycidyl ether; inorganic bases such as potassium carbonate and sodium hydroxide. These deacidification agents may be used alone or in combination of two or more kinds as required. Among these deacidification agents, pyridine is preferably used because it is inexpensive and easy to separate and remove after the reaction. The amount of the deacidification agent to be used is usually 2 to 4 times by mol, preferably 2 to 3 times by mol, based on 1 mol of BPOPF. The use amount of the deacidification agent is 2 times by mol or more, whereby the reaction rate is increased, and the use amount is 4 times by mol or less, whereby the production of impurities can be suppressed.
When the esterification reaction is carried out, an organic solvent may be used as required. Examples of the organic solvent that can be used include: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as 1, 2-dimethoxyethane, tetrahydrofuran, and cyclopentyl methyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, and benzonitrile. From the viewpoint of availability and handleability, ethers, aromatic hydrocarbons, and nitriles are preferable, and these organic solvents may be used alone or in combination of two or more if necessary. The amount of the solvent used is usually 1 to 30 times, preferably 1 to 5 times, the weight of BPOPF 1.
The esterification reaction is usually carried out at-10 ℃ to 110 ℃, preferably-5 ℃ to 80 ℃, and more preferably 20 ℃ to 70 ℃. By setting the reaction temperature to 110 ℃ or lower, by-products can be reduced; by setting the reaction temperature to-10 ℃ or higher, a sufficient reaction rate can be obtained.
The esterification reaction may be carried out, for example, by the following method: to a solution obtained by mixing an acid halide of trimellitic anhydride represented by the above formula (5) with a solvent, a separately prepared solution obtained by mixing BPOPF and a deacidification agent in a solvent is intermittently or continuously added while stirring the solution, and the temperature is brought to the above temperature range, and then the reaction is further continued in the above temperature range. The following method is also possible: the deacidification agent is added to a solution obtained by mixing the acid halide of trimellitic anhydride represented by the formula (5) and BPOPF in a solvent, either directly or after mixing in a solvent, intermittently or continuously, so as to be brought into the above temperature range, and after the addition, the reaction is further continued in the above temperature range.
After the esterification reaction is completed, the reactant material (i.e., material roll マス) is cooled to 15 to 35 ℃ to precipitate crystals, the precipitated crystals are filtered off, and the obtained crystals are further washed with a solvent that can be used in the reaction, whereby the tetracarboxylic dianhydride represented by the above formula (1) can be obtained (this step is hereinafter sometimes referred to as a crystallization step). The tetracarboxylic dianhydride represented by the above formula (1) obtained may be subjected to conventional purification such as adsorption treatment and recrystallization as necessary.
After the esterification reaction is completed and before the crystallization step is performed, the following steps may be performed as necessary: the tetracarboxylic dianhydride represented by the above formula (1) is extracted into the organic solvent layer by adding water and an organic solvent separated from water to the reaction mass, stirring and separating the aqueous layer (hereinafter, sometimes referred to as a washing step), an excess amount of a deacidification agent and a hydrolysate of an acid halide of trimellitic anhydride and a halogen salt of the deacidification agent are distributed in the aqueous layer and removed, and then a ring opening body (a hydrolysate of the tetracarboxylic dianhydride represented by the above formula (1)) by-produced in the washing step is subjected to a ring closure reaction in the presence of the organic solvent and acetic anhydride to form the tetracarboxylic dianhydride represented by the above formula (1) again.
The tetracarboxylic dianhydride represented by the formula (1) obtained by the above method can be used not only as a polyimide raw material but also as a resin raw material for polyester and the like, an additive, an epoxy resin, a curing agent for polyurethane resin, and the like. The purity of the tetracarboxylic dianhydride represented by the formula (1) is preferably 95% or more, and particularly preferably 99% or more, in terms of HPLC purity measured by a method described later, from the viewpoint of easily increasing the degree of polymerization of the polyamic acid represented by the formula (2) or the polyimide represented by the formula (3).
< Polyamic acid having repeating unit represented by the above formula (2) and Process for producing the same >
The polyamic acid having the repeating unit represented by the above formula (2) (hereinafter may be referred to as the polyamic acid of the present invention) will be described in detail.
The polyamic acid of the present invention has a repeating unit represented by the above formula (2), and the diamine residue represented by Z in the above formula (2) represents: amino group (-NH) of diamine obtained by reacting tetracarboxylic dianhydride represented by the above formula (1) with diamine described later2) And (c) other structural parts.
The molecular weight of the polyamic acid of the present invention is preferably 1 to 70 ten thousand, more preferably 2 to 60 ten thousand, in terms of a weight-average molecular weight obtained by a measurement method described later. If the molecular weight of the polyamic acid is 1 ten thousand or more, the polyamic acid can be molded and can easily maintain good mechanical properties. Further, if the molecular weight of the polyamic acid is 70 ten thousand or less, the molecular weight can be easily controlled at the time of synthesis, and a solution having an appropriate viscosity can be easily obtained and handled in many cases. The molecular weight of the polyamic acid may reflect the viscosity of the polyamic acid solution.
The polyamic acid of the present invention can be obtained, for example, as follows: the diamine described later is dissolved in a polymerization solvent described later, and then the powder of the tetracarboxylic dianhydride represented by the formula (1) is added at usually 10 to 20 ℃, and then stirred at 10 to 100 ℃, preferably 10 to 30 ℃, to obtain a polyamic acid solution (hereinafter, also referred to as polyamic acid solution).
As the diamine that can be used in the present invention, a general aromatic diamine, aliphatic diamine, alicyclic diamine, or the like used in the production of polyimide can be used. Examples of such diamines include: 1, 4-diaminobenzene, 1, 3-diaminobenzene, 2, 4-diaminotoluene, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl ether (alias 4,4 ' -oxydianiline), 3 ' -diaminodiphenyl sulfone, 3, 4 ' -diaminodiphenyl ether, 3 ' -dimethyl-4, 4 ' -diaminobiphenyl, 2 ' -bis (trifluoromethyl) -4, 4 ' -diaminobiphenyl (alias 2,2 ' -bis (trifluoromethyl) benzidine), 3, 7-diamino-dimethyldibenzothiophene-5, 5-dioxide, 4 ' -diaminobenzophenone, 2, 4 ' -diaminotoluene, 4 ' -diaminodiphenyl ether, and the like, 3, 3 '-diaminobenzophenone, 4' -bis (4-aminophenyl) sulfide, 4 '-diaminodiphenylsulfone, 4' -diaminobenzanilide, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 3-bis (4-aminophenoxy) -2, 2-dimethylpropane, 1, 2-bis [2- (4-aminophenoxy) ethoxy ] ethane, 9-bis (4-aminophenyl) fluorene, 5(6) -amino-1- (4-aminomethyl) -1, 3, 3-trimethylindane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 3 '-dicarboxyl-4, 4' -diaminodiphenylmethane, 4, 6-dihydroxy-1, 3-phenylenediamine, a salt thereof, a hydrate thereof, a crystalline solid thereof, and a crystalline solid thereof, 3, 3 ' -dihydroxy-4, 4 ' -diaminobiphenyl, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3 ', 4,4 ' -tetraaminobiphenyl, 1, 6-diaminohexane, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane, 4,4 ' -methylenebis (4-cyclohexylamine), trans-1, 4-cyclohexanediamine, bicyclo [2.2.1] heptanebis (methylamine), tricyclo [3.3.1.13, 7] decane-1, 3-diamine (alias adamantane-1, 3-diamine), 4-aminobenzoic acid-4-aminophenyl ester, 2- (4-aminophenyl) aminobenzoxazole, 9-bis [4- (4-aminophenoxy) phenyl ] fluorene, 2 ' -bis (3-sulfopropoxy) -4, 4 ' -diaminobiphenyl, 4 ' -bis (4-aminophenoxy) biphenyl-3, 3 ' -disulfonic acid, 3 ' -diaminodiphenylsulfone, and the like. Two or more of these diamines may be used in combination.
Among the above diamines, when an alicyclic diamine such as 3, 3 '-diaminodiphenyl sulfone, bicyclo [2.2.1] heptanebis (methylamine), trans-1, 4-cyclohexanediamine or the like is used, the transparency of the obtained polyimide is further improved, and when a fluorine-containing diamine such as 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane or 2, 2' -bis (trifluoromethyl) benzidine is used, the solvent solubility of the obtained polyimide can be more remarkably improved, and the low dielectric constant of the obtained polyimide can be achieved. When these diamines are used in combination with the tetracarboxylic dianhydride represented by the above formula (1) and other acid dianhydrides, 0.9 to 1.1 mol of the diamine is generally used based on 1 mol of the total acid dianhydrides including other acid dianhydrides, and 0.95 to 1.05 mol of the diamine is preferably used from the viewpoint of increasing the degree of polymerization.
Further, a general acid dianhydride may be used in combination as a copolymerization component as necessary. Examples of the acid dianhydride which can be used in combination include: pyromellitic anhydride, oxydiphthalic dianhydride, biphenyl-3, 4, 3 ', 4 ' -tetracarboxylic dianhydride, benzophenone-3, 4, 3 ', 4 ' -tetracarboxylic dianhydride, diphenylsulfone-3, 4, 3 ', 4 ' -tetracarboxylic dianhydride, 4 ' - (2, 2-hexafluoroisopropylidene) diphthalic dianhydride, m-terphenyl-3, 4, 3 ', 4 ' -tetracarboxylic dianhydride, p-terphenyl-3, 4, 3 ', 4 ' -tetracarboxylic dianhydride, cyclobutane-1, 2, 3, 4-tetracarboxylic dianhydride, 1-carboxymethyl-2, 3, 5-cyclopentanetricarboxylic acid-2, 6: 3, 5-dianhydride, cyclohexane-1, 2, 4, 5-tetracarboxylic dianhydride, pyromellitic dianhydride, Butane-1, 2, 3, 4-tetracarboxylic dianhydride, 4-phenylethynylphthalic anhydride, naphthalene-1, 4, 5, 8-tetracarboxylic dianhydride, bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylic acid) 1, 4-phenylene dianhydride, etc., and two or more of these acid dianhydrides may be used in combination. When other acid dianhydrides are used in combination, the amount of the other acid dianhydrides to be used in the total acid dianhydrides is preferably 10% by weight or more, more preferably 30% by weight or more, and on the other hand, is preferably 90% by weight or less, more preferably 70% by weight or less. By using 10% by weight or more of other acid dianhydrides, the effect of improving the physical properties by using the other acid dianhydrides in combination described later can be sufficiently obtained. On the other hand, when the amount of the other acid dianhydride is 90% by weight or less, the characteristics derived from the tetracarboxylic dianhydride structure represented by the above formula (1) can be sufficiently exhibited.
As an effect of using another acid dianhydride in combination, for example, a fluorine-containing acid dianhydride such as 4, 4' - (2, 2-hexafluoroisopropylidene) diphthalic dianhydride is used in combination, whereby the dielectric constant of the polyimide to be obtained can be reduced. In addition, when an acid dianhydride such as pyromellitic anhydride having a rigid skeleton is used in combination, the heat resistance of the polyimide obtained can be improved.
The solvent that can be used for producing the polyamic acid is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride and the diamine represented by the above formula (1) as raw material monomers and is inert to these raw materials and the produced polyamic acid. As such a solvent, for example: amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; chain ester solvents such as butyl acetate, ethyl acetate, and isobutyl acetate; cyclic ester solvents such as γ -butyrolactone, γ -caprolactone, and ε -caprolactone; carbonate solvents such as ethylene carbonate and propylene carbonate; glycol solvents such as triethylene glycol, ethyl cellosolve, butyl cellosolve, propylene glycol methyl acetate, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, dimethoxyethane, diethoxyethane, and diethylene glycol; phenol solvents such as phenol, o-cresol, m-cresol, p-cresol, 3-chlorophenol, and 4-chlorophenol; ether solvents such as tetrahydrofuran, dibutyl ether, and diethyl ether; ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, and acetophenone; alcohol solvents such as butanol and ethanol; aromatic solvents such as xylene, toluene, and chlorobenzene; sulfone solvents such as sulfolane; dimethyl sulfoxide, and the like. Preferred examples thereof include amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-pyrrolidone. These solvents may be used alone or in combination of two or more, as required.
The amount of the solvent used is such that the total concentration (monomer concentration) of the monomer components (tetracarboxylic dianhydride + diamine) in the reaction system is usually 5 to 40% by weight, preferably 8 to 25% by weight. By performing the polymerization in the above monomer concentration range, a polyamic acid solution having a uniform and high polymerization degree can be obtained. When the polymerization is carried out at a concentration lower than the above monomer concentration range, the polymerization degree of the polyamic acid is not sufficiently high, and the finally obtained polyimide film may be fragile; when the polymerization is carried out at a concentration higher than the above-mentioned monomer concentration range, the monomer may not be sufficiently dissolved, and the reaction solution may become inhomogeneous and gel. The solution of polyamic acid having the repeating unit represented by the formula (2) obtained by the above method is usually used in a solution state in a polyimide-imidization step described later.
< polyimide having repeating units represented by the above formula (3) and Process for producing the same >
The polyimide having the repeating unit represented by the above formula (3) of the present invention can be produced by subjecting the polyamic acid having the repeating unit represented by the above formula (2) obtained by the above method to a dehydration ring-closure reaction (imidization reaction). Examples of the method of the imidization reaction include a thermal imidization method and a chemical imidization method.
First, the thermal imidization method will be described in detail. The thermal imidization method is performed by casting a polymerization solution of polyamic acid on a glass plate, and heating the casting solution in vacuum, in an inert gas such as nitrogen, or in air to obtain a polyamic acid film. Specifically, for example, the film of polyamic acid can be obtained by drying the film in an oven at a temperature of usually 50 to 190 ℃, preferably 100 to 180 ℃.
Then, the film of the obtained polyamic acid is heated on a glass plate at a temperature of usually 200 to 400 ℃, preferably 250 to 350 ℃. This causes an imidization reaction, and a polyimide film can be obtained. The heating temperature is preferably 200 ℃ or higher from the viewpoint of sufficiently proceeding the imidization reaction, and is preferably 400 ℃ or lower from the viewpoint of thermal stability of the polyimide film to be formed.
It is desirable that the imidization reaction is carried out in vacuum or in an inert gas, but if the imidization reaction temperature is not too high, it does not affect the imidization reaction even in air.
Next, the chemical imidization method will be described in detail. In the chemical imidization method, first, the same solvent as used in the polymerization is added to the polyamic acid solution having the repeating unit represented by the above formula (2) of the present invention obtained by the above method to have an appropriate solution viscosity for easy stirring, the organic acid anhydride and the dehydration ring-closing agent (these two are sometimes referred to as a chemical imidizing agent in combination) are added while stirring, and the mixture is stirred at a temperature of 0 to 100 ℃, preferably 10 to 50 ℃ for 1 to 72 hours, whereby the imidization can be chemically completed.
Examples of the organic acid anhydride that can be used for the chemical imidization include acetic anhydride and propionic anhydride. Among these organic acid anhydrides, acetic anhydride is preferable from the viewpoint of easy handling and separation. As the dehydration ring-closing agent, pyridine, triethylamine, quinoline, or the like can be used. Among these dehydration ring-closing agents, pyridine is preferable in view of easy handling and separation. The amount of the organic acid anhydride in the chemical imidizing agent is preferably in the range of 1 to 10 times by mol, and more preferably 2 to 10 times by mol, based on the theoretical dehydration amount of the polyamic acid. The amount of the dehydration ring-closing agent is preferably in the range of 0.1 to 5 times by mol, more preferably 1 to 5 times by mol, based on the amount of the organic acid anhydride.
The reaction solution obtained by the chemical imidization method may be mixed with unreacted chemical imidizing agent, organic acid, and other by-products (hereinafter referred to as impurities), and these may be removed to separate and purify the polyimide. The purification can be carried out by a known method. For example, the following methods may be applied: the reaction solution after imidization is dropped into a poor solvent to precipitate polyimide, and then the polyimide powder is recovered, washed repeatedly until impurities are removed, and dried to obtain polyimide powder. The solvent that can be used as the poor solvent is not particularly limited as long as it can precipitate the polyimide, remove impurities efficiently, and is easy to dry, and for example, water, alcohols such as methanol, ethanol, and isopropyl alcohol are preferable, and these solvents may be used in combination.
When the concentration of the polyimide solution to be precipitated by dropping the polyimide solution into the poor solvent is too high, the precipitated polyimide forms a cake, and impurities may remain in the cake, and a long time may be required to redissolve the obtained polyimide powder in the solvent. Therefore, the concentration of the polyimide solution when added dropwise to the poor solvent is preferably 20 wt% or less, and more preferably 10 wt% or less. The amount of the poor solvent used is preferably 1 time by weight or more, and more preferably 1.5 to 10 times by weight, based on the polyimide solution.
The temperature at which the obtained polyimide powder is recovered and the residual solvent is removed by vacuum drying, hot air drying, or the like is not limited as long as the temperature is a temperature at which the polyimide does not deteriorate, and is, for example, 30 to 150 ℃.
When the polyimide powder having the repeating unit represented by the above formula (3) thus obtained is formed into a polyimide film, it is necessary to prepare a polyimide solution by temporarily dissolving the polyimide powder having the repeating unit represented by the above formula (3) in a solvent. As the solvent that can be used, any solvent that dissolves the polyimide powder may be used as appropriate depending on the use and processing conditions, and specifically, for example, other than the following solvents: amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; ester solvents such as gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, epsilon-caprolactone, alpha-methyl-gamma-butyrolactone, butyl acetate, ethyl acetate, isobutyl acetate and the like; carbonate solvents such as ethylene carbonate and propylene carbonate; glycol solvents such as diethylene glycol dimethyl ether, triethylene glycol, and triethylene glycol dimethyl ether; phenol solvents such as phenol, m-cresol, p-cresol, o-cresol, 3-chlorophenol, and 4-chlorophenol; ketone solvents such as cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone; ether solvents such as tetrahydrofuran, 1, 4-dioxane, dimethoxyethane, diethoxyethane and dibutyl ether, general-purpose solvents such as acetophenone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, petroleum spirit and naphtha, and one or two or more of these solvents may be used. The polyimide powder can be dissolved in air or an inert gas at a temperature ranging from room temperature to the boiling point of the solvent or less to prepare a polyimide solution.
The polyimide solution thus obtained is cast on a glass plate, for example, and heated in vacuum, an inert gas such as nitrogen, or air to remove the solvent, whereby a polyimide film can be obtained. For example, the polyimide film can be obtained by drying the film in an oven at a temperature of usually 200 to 400 ℃, preferably 250 to 350 ℃. The polyimide film is preferably produced in vacuum or in an inert gas, but if the temperature is not excessively high, the production in air is not affected.
The molecular weight of the polyimide having a repeating unit represented by the formula (3) obtained by the above method is preferably 1 to 60 ten thousand, more preferably 2 to 50 ten thousand, and further preferably 4 to 40 ten thousand, based on the weight average molecular weight obtained by a measurement method described later. If the molecular weight of the polyimide is 1 ten thousand or more, the polyimide can be molded and can easily maintain good mechanical properties. Further, if the molecular weight of the polyimide is 40 ten thousand or less, the molecular weight can be easily controlled at the time of synthesis, and a solution having an appropriate viscosity can be easily obtained and handled in many cases. The molecular weight of the polyimide may reflect the viscosity of the polyimide solution.
The polyimide having the repeating unit represented by the formula (3) of the present invention obtained by the above method has excellent solvent solubility, a refractive index of 1.65 or more and a high refractive index, and a glass transition temperature of 260 ℃ or more and excellent heat resistance. In addition, by combining with the diamine used, a polyimide having characteristics such as low dielectric constant and high transparency is obtained.
Examples
The following examples are illustrative of the present invention, and the present invention is not limited to these examples. The physical property values shown in the examples and comparative examples were measured by the following measuring apparatus and conditions.
[ 1] NMR measurement
1H-NMR、13C-NMR was recorded using a JEOL-ESC400 spectrometer using tetramethylsilane as an internal standard and deuterated DMSO as a solvent.
[ 2] LC-MS measurement
The target was identified by separation and mass spectrometry under the following measurement conditions.
An apparatus: "Xevo G2Q-Tof" manufactured by Waters,
Column: ACQUITY UPLC BEHC18,
(1.7μm、
)、
Column temperature: at 40 deg.C,
Detection wavelength: UV 220 + 500nm,
The mobile phase: 0.1% formic acid solution A, acetonitrile solution B,
Mobile phase flow rate: 0.3 mL/min,
Mobile phase gradient: concentration of the solution B: 80% (0 min) → 80% (after 10 min) → 100% (after 15 min) →,
Detection method: Q-Tof,
Ionization method: APCI (-) method,
Ion Source (Ion Source): the temperature is 120℃,
Sampling Cone (Sampling Cone): voltage of 50V, gas flow rate of 50L/h,
Desolventizing Gas (Desolvation Gas): the temperature is 500 ℃, and the gas flow is 1000L/h.
(3) HPLC purity
The purity of each compound was determined as an area percentage value measured by High Performance Liquid Chromatography (HPLC) under the following measurement conditions.
An apparatus: l-2130 manufactured by Hitachi Ltd,
Column: ZORBAX CN (5 μm,
)、
Column temperature: at 40 deg.C,
Detection wavelength: UV 254nm,
The mobile phase: hexane in liquid A, tetrahydrofuran in liquid B,
Mobile phase flow rate: 1.0 ml/min,
Mobile phase gradient: concentration of the solution A: 85% (0 min) → 60% (after 35 min) → 0% (after 40 min).
(4) weight average molecular weight of Polyamic acid
The weight average molecular weight was measured under the following measurement conditions. (conversion of polystyrene)
An apparatus: HLC-8320GPC made by Tosoh corporation,
Column: TSK-GEL Super AWM-H (6.0mm I.D.. times.15 cm),
The mobile phase: n, N-dimethylformamide, flow rate: 0.6 ml/min,
Column temperature: at 40 ℃.
Measurement of melting Point [ 5]
The melting point was determined as the maximum temperature of the melting endotherm detected when the temperature was measured at a temperature increase rate of 10 ℃ per minute using a differential scanning calorimeter (EXSTAR DSC 7020C manufactured by SII Nano Techno1 gy).
[ 6] measurement of glass transition temperature (Tg)
The temperature was measured at a temperature rise rate of 30 ℃ per minute using a differential scanning calorimeter ("EXSTAR DSC 7020" manufactured by SII Nano Technology), and the intersection of tangents to the inflection point was defined as the glass transition temperature.
[ 7] measurement of cut-off wavelength
The transmittance of the polyimide film was measured by a spectrophotometer ("UV-2450" manufactured by Shimadzu corporation) at 200 to 800 nm. The wavelength at which the transmittance is 0.5% or less is set as the cutoff wavelength. The shorter the cutoff wavelength, the better the transparency of the polyimide film.
[ 8] light transmittance (T)400) Measurement of (2)
The transmittance of the polyimide film at 400nm was measured by a spectrophotometer ("UV-2450" manufactured by Shimadzu corporation). The higher the transmittance, the better the transparency of the polyimide film.
[ 9] refractive index (n)in) Measurement of dielectric constant (. epsilon.)
The direction parallel to the polyimide film (n) was measured using an Abbe refractometer (a "multiwavelength Abbe refractometer DR-M2" manufactured by ATAGO Ltd.)in) And the vertical direction (n)out) Refractive index (wavelength: 589nm), the average refractive index (n) of the polyimide film was determined by the following equationav)。
nav＝(2nin+nout)/3
Based on the average refractive index (n)av) The dielectric constant (. epsilon.) of the polyimide film at 1MHz was calculated by the following equation.
ε＝1.1×nav 2
[ 10] measurement of tensile elongation
A tensile test (tensile rate 10 mm/min) was carried out on a test piece (dumbbell type test piece parallel portion 5 mm. times.20 mm) of a polyimide film using a tensile tester ("autographa-X" manufactured by Shimadzu corporation), and the tensile elongation (%) of the film was found to be higher.
Solubility in solvent [ 11]
The polyimide film or powder thus obtained (20 mg) was put in 1mL of N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), Tetrahydrofuran (THF), Cyclopentanone (CPN), and gamma-butyrolactone (GBL) to test the solubility. The solvent solubility was evaluated according to the following criteria.
O: dissolved at room temperature.
And (delta): the solution dissolved when heated, and did not precipitate even when cooled to room temperature.
X: insoluble.
1. Preparation example of acid dianhydride represented by the formula (1)
< example 1>
Into a 1L four-necked flask equipped with a thermometer, a dropping funnel and a stirring rod, 11.0g (52.2mmol) of trimellitic anhydride acid chloride, 20.0g of acetonitrile, 10.0g of toluene and 10.0g (18.7mmol) of 9, 9-bis (4- (4-hydroxyphenoxy) phenyl) fluorene (BPOPF) were charged, and the mixture was stirred and cooled to 2 ℃. After cooling, 4.1g (51.8mm0l) of pyridine was further added dropwise at 2 ℃ to 7 ℃. After the dropwise addition, the temperature was raised to 25 ℃ and then stirred at the temperature, and since crystals began to precipitate when the stirring was performed for 1 hour, 10.0g of acetonitrile and 5.0g of toluene were added and further stirred for 1 hour.
After completion of the stirring, the crystals were filtered off at 25 ℃ and further washed with acetonitrile, whereby yellow crystals were obtained. The yellow crystals were vacuum-dried at 80 ℃ to obtain 11.6g of the tetracarboxylic dianhydride of the above formula (1) (yield 70.2%, purity 99.4%).
By means of what is shown in FIG. 11H-NMR spectrum shown in FIG. 213The C-NMR spectrum and the mass spectrum shown in FIG. 3 confirmed that the obtained product was tetracarboxylic dianhydride represented by the above formula (1). The tetracarboxylic dianhydride represented by the formula (1) was obtained1H-NMR and13C-NMR is described in detail.
The tetracarboxylic dianhydride represented by the formula (1) is obtained1H-NMR(DMSO-d6) This is illustrated in FIG. 1. Herein, 8.26 to 8.64ppm of a peak is ascribed to hydrogen on the benzene ring of trimellitic acid source, 7.35 to 7.96ppm of a peak is ascribed to hydrogen on the benzene ring of fluorenone skeleton, and 6.95 to 7.43ppm of a peak is ascribed to hydrogen on the benzene ring of 4- (4-hydroxyphenoxy) phenyl. The peak observed at 2.5ppm was derived from DMSO as a solvent, and the peak observed at 3.3ppm was derived from water contained in DMSO.
Will be provided with13C-NMR (DMSO-d6) is schematically shown in FIG. 2. Here, 164.0 to 168.9ppm and 139.95 to 156.02ppm are assigned to the carbon derived from the trimellitic anhydride skeleton, 118.8 to 138.83ppm are assigned to the carbon derived from the benzene ring of 9, 9-bis (4- (4-hydroxyphenoxy) phenyl) fluorene, and 64.4ppm of the peak is assigned to the carbon at the 9-position of fluorenone. To say thatIt is clear that the peaks observed at 39.2-40.5 ppm are from the solvent DMSO.
The mass spectrum value and melting point of the obtained tetracarboxylic dianhydride represented by the formula (1) are as follows.
Mass spectrum value (M- ·): 882.17,
Melting point (DSC): 193 ℃.
2. Examples of production of polyamic acid having repeating unit represented by the above formula (2) and polyimide having repeating unit represented by the above formula (3)
< example 2>
(in the polyamic acid represented by the above formula (2), a polyamic acid (referred to as a polyamic acid having a repeating unit represented by the following formula (2-A)) obtained by reacting a tetracarboxylic dianhydride represented by the above formula (1) with 9, 9-bis (4-aminophenyl) fluorene (hereinafter, may be referred to as FDA) is produced by the following method)
[ solution 6]
A tetracarboxylic dianhydride represented by the above formula (1) obtained in example 1 (5.0 g, 5.66mmol) and FDA2.0g, 5.66mmol) were dissolved in N, N-dimethylacetamide (80.2 g) at room temperature, and after the temperature was raised to 100 ℃, it was confirmed that the solution was homogeneous, and after cooling, the reaction was carried out at room temperature for 24 hours, whereby a polyamic acid having a repeating unit represented by the above formula (2-A) was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 335,368.
< example 3>
(production of polyimide having repeating units represented by the following formula (3-A) based on chemical imidization of polyamic acid having repeating units represented by the following formula (2-A) among polyimides represented by the following formula (3))
[ solution 7]
To 87.2g of the N, N-dimethylacetamide solution of a polyamic acid having a repeating unit represented by the formula (2-A) obtained in example 2, 5.8g of acetic anhydride and 2.2g of pyridine were added, and the mixture was stirred at room temperature for 24 hours to obtain an N, N-dimethylacetamide solution of a polyimide having a repeating unit represented by the formula (3-A).
The obtained polyimide having the repeating unit represented by the above formula (3-A) was dissolved in N, N-dimethylacetamide by dropwise adding 250g of methanol to precipitate a polyimide having the repeating unit represented by the above formula (3-A). The precipitated polyimide was filtered off, washed with methanol, and dried to obtain 7.2g of pale yellow polyimide powder.
To 5.0g of the obtained polyimide powder, 28.3g of N, N-dimethylacetamide was added and stirred until uniform, thereby obtaining an N, N-dimethylacetamide solution of a polyimide having a repeating unit represented by the above formula (3-A). After this solution was coated on a glass plate, it was heated at 150 ℃ for 1 hour and at 250 ℃ for 1 hour to obtain a polyimide film having a repeating unit represented by the above formula (3-A). The thickness of the thin film was about 19 μm.
Table 1 shows the glass transition temperature (Tg), the cutoff wavelength, and the transmittance at 400nm (T) of the obtained polyimide film400) Refractive index (n)in) The dielectric constant (. epsilon.) and the tensile elongation were measured. In addition, table 2 shows the solubility in various solvents.
< example 4>
(production of Polyamic acid (hereinafter referred to as "polyamic acid having a repeating unit represented by formula (2-B)") obtained by reacting tetracarboxylic dianhydride represented by formula (1) with 2,2 ' -bis (trifluoromethyl) -4, 4 ' -diaminobiphenyl (also referred to as "2, 2 ' -bis (trifluoromethyl) benzidine") (hereinafter referred to as "TFMB" in some cases) among the polyamic acids represented by formula (2))
[ solution 8]
5.0g (5.66mmol) of the tetracarboxylic dianhydride represented by the above formula (1) obtained in example 1 and 5.8g (5.66mmol) of TFMB1 were dissolved in 16.8g of N, N-dimethylacetamide at room temperature, and then stirred at room temperature. The viscosity gradually increased with the progress of the reaction, and thus, N-dimethylacetamide solution of polyamic acid having a repeating unit represented by the above formula (2-B) was synthesized by stirring at room temperature for 25 hours while appropriately adding N, N-dimethylacetamide (total added amount: 52.0 g). The weight average molecular weight (Mw) of the polyamic acid was 537,315.
< example 5>
(production of polyimide having repeating units represented by the following formula (3-B) based on chemical imidization of polyamic acid having repeating units represented by the following formula (2-B) among polyimides represented by the following formula (3))
[ solution 9]
To 92.3g of the N, N-dimethylacetamide solution of a polyamic acid having a repeating unit represented by the formula (2-B) obtained in example 4, 5.8g of acetic anhydride and 2.2g of pyridine were added, and the mixture was stirred at room temperature for 24 hours, thereby obtaining an N, N-dimethylacetamide solution of a polyimide having a repeating unit represented by the formula (3-B).
The obtained polyimide solution having the repeating unit represented by the above formula (3-B) was added dropwise to 250g of methanol to precipitate a polyimide having the repeating unit represented by the above formula (3-B). The precipitated polyimide was filtered off, washed with methanol, and dried to obtain 6.8g of a white polyimide powder.
To 5.0g of the obtained polyimide powder, 45.0g of N, N-dimethylacetamide was added and stirred until uniform, thereby obtaining an N, N-dimethylacetamide solution of a polyimide having a repeating unit represented by the above formula (3-B). After the obtained solution was coated on a glass plate, it was heated at 150 ℃ for 1 hour and at 250 ℃ for 1 hour to obtain a polyimide film having a repeating unit represented by the above formula (3-B). The thickness of the thin film was about 14 μm.
Table 1 showsThe obtained polyimide film had a glass transition temperature (Tg), a cut-off wavelength, and a transmittance (T) at 400nm400) Refractive index (n)in) Dielectric constant (. epsilon.) and tensile elongation. In addition, table 2 shows the solubility in various solvents.
3. Examples of production of polyimides derived from other acid dianhydrides having a fluorene skeleton, and physical properties of the polyimides
< reference example 1>
(example of production of polyimide having repeating units represented by the following formula (7) and obtained from acid dianhydride represented by the following formula (6) and TFMB)
[ solution 10]
5.0g (6.88mmol) of tetracarboxylic dianhydride represented by the following formula (6) and 2.2g (6.88mmol) of TFMB were dissolved in 17.8g of N, N-dimethylacetamide at room temperature, and reacted at room temperature for 24 hours to synthesize an N, N-dimethylacetamide solution of polyamic acid. The weight average molecular weight (Mw) of the polyamic acid was 66,029.
[ solution 11]
To 25.0g of the N, N-dimethylacetamide solution of the obtained polyamic acid, 11.0g of N, N-dimethylacetamide, 7.0g of acetic anhydride, and 2.7g of pyridine were added, and the mixture was stirred at room temperature for 22 hours, thereby obtaining an N, N-dimethylacetamide solution of a polyimide having a repeating unit represented by the above formula (7).
The obtained polyimide solution having the repeating unit represented by the above formula (7) was added dropwise to 250g of methanol to precipitate a polyimide having the repeating unit represented by the above formula (7). The precipitated polyimide was filtered, washed with methanol, and dried to obtain 6.6g of a white polyimide powder.
To 5.0g of the obtained polyimide powder, 20.0g of N, N-dimethylacetamide was added and stirred until uniform, thereby obtaining an N, N-dimethylacetamide solution of a polyimide having a repeating unit represented by the above formula (7). After the obtained solution was coated on a glass plate, it was heated at 150 ℃ for 1 hour and at 250 ℃ for 1 hour to obtain a polyimide film having a repeating unit represented by the above formula (7). The film thickness of the thin film was about 25 μm.
Table 1 shows the glass transition temperature (Tg), the cutoff wavelength, and the transmittance at 400nm (T) of the obtained polyimide film400) Refractive index (n)in) Dielectric constant (. epsilon.) and tensile elongation.
[ Table 1]
[ Table 2]
Claims (3)
1. A tetracarboxylic dianhydride represented by the following formula (1),
2. a polyimide having a repeating unit represented by the following formula (3),
wherein Z represents-NH, which is an amino group-removed residue of 9, 9-bis (4-aminophenyl) fluorene or 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl2And (c) other structural parts.
3. A process for producing a tetracarboxylic dianhydride according to claim 1, which comprises reacting a bisphenol represented by the following formula (4) with a trimellitic acid halide,
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