CN108602792A - Tetracarboxylic dianhydride, polyamic acid and polyimides - Google Patents
Tetracarboxylic dianhydride, polyamic acid and polyimides Download PDFInfo
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- CN108602792A CN108602792A CN201780009391.5A CN201780009391A CN108602792A CN 108602792 A CN108602792 A CN 108602792A CN 201780009391 A CN201780009391 A CN 201780009391A CN 108602792 A CN108602792 A CN 108602792A
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- PFJWDTXNMHFUPB-UHFFFAOYSA-N Oc(cc1)ccc1OC1C=CC(C2(c3ccccc3-c3ccccc23)c(cc2)ccc2Oc(cc2)ccc2O)=CC1 Chemical compound Oc(cc1)ccc1OC1C=CC(C2(c3ccccc3-c3ccccc23)c(cc2)ccc2Oc(cc2)ccc2O)=CC1 PFJWDTXNMHFUPB-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
Tetracarboxylic dianhydride and its manufacturing method shown in offer formula (1) and can be by polyamic acid and polyimides that the tetracarboxylic dianhydride obtains.
Description
Technical field
The present invention relates to the useful new tetracarboxylic acids with fluorenyl, ether and ester group of the raw material as polyimide resin etc.
Acid dianhydride and the polyamic acid and polyimides obtained by the tetracarboxylic dianhydride.
Background technology
Resin material with a high refractive index has high working property etc. compared with previous glass material, therefore has studied wide
The general lens for being used for spectacle lens, camera etc., CD lens, f θ lens, the optical system components of image display medium, optics
Film, film, substrate, various optical filters, prism, communication optical element etc., the resin of high refractive index is shown as these,
It has been presented for such as polyester, makrolon, polyimides.Wherein, polyimides as excellent heat resistance resin and widely
People knows, in such use, especially requires in the field of heat resistance, needs the polyamides of high refractive index and excellent heat resistance sub-
Amine.
But the high polyimides of heat resistance does not dissolve in organic solvent largely, to polyimides itself carry out molding plus
Work is not usually readily.Therefore, it for polyimides, needs to be shaped to film etc. with the polyamic acid solution of precursor, with 250
High temperature as~350 DEG C carries out thermal dehydration closed loop (imidizate), thus obtains polyimide film.But just with poly-
After solution molding membrane etc. of amic acid, carry out imidizate and for obtaining the method for polyimide film, from imidizate
Thermal stress caused by the process that temperature (250~350 DEG C) is cooled down to room temperature often causes curling, the stripping of film, rupture etc.
Problem, therefore there are problems that cannot get uniform polyimide film, also, 300 DEG C or more of height is needed in imidizate
Warm stove, the shortcomings that increase there is also manufacturing cost.
Therefore, polyimides that is excellent as solvent solubility and showing high refractive index, such as propose by with naphthalene
The polyimides (Japanese Unexamined Patent Publication 2010-070513 bulletins (patent document 1)) that the aromatic diamine compound of skeleton obtains.It should
Polyimides described in document dissolves in solvent, and high refractive index is of about 1.63, still, due to being rolled at present to the height of resin material
It penetrates rate requirement and needs to further increase refractive index.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-070513 bulletins
Invention content
Problems to be solved by the invention
Polyimides that is excellent the object of the present invention is to provide solvent solubility and showing high refractive index.
The means used to solve the problem
Inventors in order to solve the above-mentioned technical problem and to as polyimides raw material tetracarboxylic dianhydride and diamines
Structure has carried out various researchs, as a result, it has been found that, using shown in following formula (1), the tetracarboxylic dianhydride with fluorene skeleton manufacture
The solvent solubility of polyimides is excellent, shows high refractive index.Specifically, the present invention includes following scheme.
〔1〕
A kind of tetracarboxylic dianhydride indicates with stating formula (1),
[changing 1]
〔2〕
A kind of polyamic acid has the repetitive unit indicated with following formula (2),
[changing 2]
(in formula, Z indicates diamines residue.).
〔3〕
A kind of polyimides has the repetitive unit indicated with following formula (3),
[changing 3]
(in formula, Z indicates diamines residue.).
〔4〕
The manufacturing method of tetracarboxylic dianhydride described in a kind of (1) makes shown in trimellitic anhydride carboxylic acid halides and following formula (4)
Bisphenols reacts,
[changing 4]
Invention effect
The polyimides manufactured using the tetracarboxylic dianhydride with fluorene skeleton of the present invention it is excellent with solvent solubility and
The characteristic of high refractive index.Although in addition, with containing rigid structure as fluorene skeleton but toughness also excellent feature, therefore working as
Can so utilize the lens in spectacle lens, camera etc., CD lens, f θ lens, image display medium optical system components,
The field of optical systems such as optical film, film, various optical filters, prism, communication optical element, and can be suitable for scratching
Electronic materials or the replacement such as interlayer dielectric of property printed wiring circuit substrate, the protective film of semiconductor element, integrated circuit
The purposes of usually used flexible substrate of glass substrate etc in liquid crystal display, Electronic Paper, solar cell etc..
Description of the drawings
Fig. 1 is tetracarboxylic dianhydride shown in formula (1)1H-NMR spectrum.
Fig. 2 is tetracarboxylic dianhydride shown in formula (1)13C-NMR spectrograms.
Fig. 3 is the mass spectrogram of tetracarboxylic dianhydride shown in formula (1).
Specific implementation mode
<The manufacturing method of tetracarboxylic dianhydride shown in formula (1)>
As the method for obtaining tetracarboxylic dianhydride shown in above-mentioned formula (1), well known method can be suitably applied.It can enumerate
Such as：In the presence of deacidification agent (alkali), make above-mentioned formula (4) compound represented (9,9- bis- (4- (4- hydroxyphenoxies) benzene
Base) fluorenes, it is abbreviated as BPOPF sometimes below) method (carboxylic acid halides method) reacted with the carboxylic acid halides of trimellitic anhydride；Using BPOPF and partially
The method of the Direct Dehydration reaction of benzenetricarboxylic anhydride；The diacetate esters body of BPOPF and trimellitic anhydride is set to carry out de- second at high temperature
The method of acid reaction；Make the side of BPOPF and trimellitic anhydride progress dehydrating condensation using dehydrating agents such as dicyclohexylcarbodiimides
Method；Trimellitic anhydride is activated using toluene sulfochloride/n,N-Dimethylformamide/pyridine mixtures, to which BPOPF to be esterified
Method.Wherein, due to can inexpensively obtain the trimellitic acid carboxylic acid halides as raw material, preferred carboxylic acid halides method.Below to acyl
Halogen method is described in detail.
Specifically, carboxylic acid halides method indicates：In the presence of deacidification agent, make BPOPF and trimellitic anhydride shown in following formula (5)
Carboxylic acid halides reaction, to obtain the reaction of tetracarboxylic dianhydride shown in above-mentioned formula (1) (hereinafter, the reaction is also known as ester sometimes
Change reaction).
BPOPF as raw material can both use commercially available product, can also pass through known method (such as International Publication No. 2006/
No. 052001, Japanese Unexamined Patent Publication 2015-182970 bulletins) it manufactures.Specifically, can be by making Fluorenone and right in presence of an acid
Phenoxy phenyl reaction obtains.
The carboxylic acid halides of trimellitic anhydride used in esterification has structure shown in following formula (5),
[changing 5]
(in formula, Y indicates halogen atom.).
In the carboxylic acid halides of these trimellitic anhydrides, the acyl chlorides of trimellitic anhydride can be obtained inexpensively, it is therefore desirable for Y is that chlorine is former
Son.
The usage amount of the carboxylic acid halides of trimellitic anhydride shown in above-mentioned formula (5) used in esterification usually relative to
1 mole of BPOPF is 2~4 times moles, preferably 2~3 times moles.By making the usage amount of the carboxylic acid halides of trimellitic anhydride be 2 times
Mole or more, sufficient reaction speed can be obtained, by making usage amount for 4 times moles hereinafter, can reduce on unreacted
The carboxylic acid halides of trimellitic anhydride shown in formula (5) is stated, as a result, tetrabasic carboxylic acid two shown in obtained above-mentioned formula (1) can be improved
The purity of acid anhydride.
As the deacidification agent used in esterification, it can be mentioned, for example：Pyridine, triethylamine, n,N-Dimethylaniline etc. have
Machine tertiary amines；The epoxies such as propylene oxide, allyl glycidyl ether；The inorganic bases such as potassium carbonate, sodium hydroxide.These deacidification agents
It can use a kind of or be used in combination of two or more as needed.In these deacidification agents, pyridine after cheap and reaction due to holding
It is easily separated removing and it is preferable to use.The usage amount of deacidification agent is usually 2~4 times moles relative to 1 mole of BPOPF, and preferably 2
~3 times moles.By make deacidification agent usage amount be 2 times moles or more, to reaction speed improve, by for 4 times moles with
Under, the generation of impurity can be inhibited.
When implementing esterification, organic solvent can be used as needed.As the organic solvent that can be used, can illustrate
Such as：The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；1,2- dimethoxy-ethane, tetrahydrofuran, cyclopentyl-methyl
The ethers such as ether；Benzene,toluene,xylene etc. is aromatic hydrocarbon；The halogenated aromatics hydrocarbon such as chlorobenzene, dichloro-benzenes；Acetonitrile, propionitrile, butyronitrile,
The nitriles such as isobutyronitrile, valeronitrile, isobutyl cyanide, benzonitrile.From the viewpoint of acquired and treatability, preferably ethers, it is aromatic hydrocarbon,
Nitrile, these organic solvents can be used a kind of or are use mixing two or more as needed.Make when using these solvents
Dosage is 1~30 times of weight, preferably 1~5 times of weight usually relative to 1 times of weight of BPOPF.
Esterification usually -10 DEG C~110 DEG C, preferably -5 DEG C~80 DEG C, it is 20 DEG C~70 DEG C further preferred at implement.
By making reaction temperature for 110 DEG C hereinafter, by-product can be reduced；By making reaction temperature be -10 DEG C or more, can be filled
The reaction speed divided.
As esterification, such as there are as below methods：By the carboxylic acid halides and solvent of trimellitic anhydride shown in above-mentioned formula (5)
In the solution being obtained by mixing, the solution is stirred on one side, intermittently or continuously add being mixed in a solvent of separately preparing on one side
The solution of BPOPF and deacidification agent, and above-mentioned temperature range is reached, then continue to carry out in above-mentioned temperature range
Reaction.In addition can also be following method：To be mixed in a solvent the carboxylic acid halides of trimellitic anhydride shown in above-mentioned formula (5) and
In the solution of BPOPF, deacidification agent directly or is mixed in after solvent and is intermittently or continuously added, and reaches above-mentioned temperature
Range is spent, after addition, continues to be reacted in above-mentioned temperature range.
After esterification, by reaction substance (Japanese：Anti- ying マ ス) it is cooled to 15 DEG C~35 DEG C and crystallization is made to be precipitated, it will
The crystallization being precipitated filters out, and obtained crystallization is further washed with workable solvent in above-mentioned reaction, thus, it is possible to obtain
Tetracarboxylic dianhydride's (hereinafter, the process is also known as partial crystallization process sometimes) shown in above-mentioned formula (1).It can also be on obtained
It states tetracarboxylic dianhydride shown in formula (1) as needed and carries out the purifying of adsorption treatment, the routine such as partial crystallization again.
In addition, after esterification, before implementing above-mentioned partial crystallization process, following work can be implemented as needed
Sequence：After water and the organic solvent being separated from water are added into reaction substance, stirring, separation water layer (hereinafter sometimes referred to washes work
Sequence), thus tetracarboxylic dianhydride shown in above-mentioned formula (1) is extracted into organic solvent layer, by excessive deacidification agent and inclined benzene three
After the hydrolysate of the carboxylic acid halides of acid anhydrides and the halogen of deacidification agent are assigned in water layer and remove, further make by-product in washing step
Open loop body (hydrolysate of tetracarboxylic dianhydride shown in above-mentioned formula (1)) that closed loop is carried out in the presence of organic solvent and acetic anhydride is anti-
It answers, forms tetracarboxylic dianhydride shown in above-mentioned formula (1) once again.
Acting not only as polyimides raw material by tetracarboxylic dianhydride shown in above-mentioned formula (1) obtained by the above method makes
With, and the curing agent etc. for the resin raw material, additive, epoxy resin, polyurethane resin that can be used for polyester etc..In addition, from
From the perspective of being easy to improve the degree of polymerization of polyimides shown in polyamic acid or above-mentioned formula (3) shown in above-mentioned formula (2), on
The HPLC purity meters that the purity of tetracarboxylic dianhydride shown in formula (1) is stated to be measured by aftermentioned method, preferably 95% or more, it is special
It You Xuanwei 99% or more.
<Polyamic acid and its manufacturing method with repetitive unit shown in above-mentioned formula (2)>
To the polyamic acid (polyamide of the following otherwise referred to as present invention with repetitive unit shown in above-mentioned formula (2)
Acid) it is described in detail.
The polyamic acid of the present invention has repetitive unit shown in above-mentioned formula (2), diamines shown in the Z in above-mentioned formula (2)
Residue indicates：It is obtained, diamines when tetracarboxylic dianhydride shown in above-mentioned formula (1) being made to be reacted with aftermentioned Diamines to remove amino
(-NH2) other than structure division.
The molecular weight of the polyamic acid of the present invention is preferably 10,000 with the Weight-average molecular gauge obtained by aftermentioned assay method
~70 ten thousand, more preferably 20,000~600,000.It can be molded if the molecular weight of polyamic acid is 10,000 or more, and be easy to maintain
Good mechanical characteristic.In addition, if the molecular weight of polyamic acid be 700,000 hereinafter, if synthesis when be easy to control molecular weight,
And it is easy to get the suitable solution of viscosity in most cases, is easily handled.It should be noted that the molecular weight of polyamic acid can
To reflect the viscosity of polyamic acid solution.
The polyamic acid of the present invention can for example obtain as follows：Aftermentioned Diamines are dissolved in aftermentioned polymer solvent
Afterwards, after the powder of tetracarboxylic dianhydride shown in above-mentioned formula (1) usually being added at 10~20 DEG C, 10~100 DEG C, preferably 10~
It is stirred at 30 DEG C, to be obtained in the form of polyamic acid solution (being otherwise referred to as polyamic acid solution below).
As the Diamines that can be used in the present invention, the common fragrance used in polyimides manufacture can be used
Race's Diamines, aliphatic diamine class, ester ring type Diamines etc..As such Diamines, it can be mentioned, for example：Isosorbide-5-Nitrae-diamino
Benzene, 1,3- diaminobenzenes, 2,4- diaminotoluenes, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl ether (alias
4,4 '-oxygen diphenylamines), 3,3 '-diamino diphenyl sulfones, 3,4 '-diamino-diphenyl ethers, 3,3 '-dimethyl -4,4 '-diaminos
Base biphenyl, 2,2 '-dimethyl -4,4 '-benzidines, 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines (alias 2,
2 '-bis- (trifluoromethyl) benzidine), 3,7- diamino-dimethyl Dibenzothiophene -5,5- dioxide, 4,4 '-diamino two
Benzophenone, 3,3 '-diaminobenzophenones, 4,4 '-bis- (4- aminophenyls) thioethers, 4,4 '-diamino diphenyl sulfones, 4,4 '-
Bis- (4- amino-benzene oxygens) propane of diaminobenzene anilid, 1,3-, bis- (4- amino-benzene oxygens) butane of Isosorbide-5-Nitrae-, the bis- (4- of 1,5-
Amino-benzene oxygen) pentane, bis- (4- amino-benzene oxygens) -2, the 2- dimethylpropanes of 1,3-, bis- [2- (4- amino-benzene oxygens) second of 1,2-
Oxygroup] ethane, bis- (4- aminophenyls) fluorenes of 9,9-, 5 (6)-amino -1- (4- amino methyls) -1,3,3- trimethyl indanes, Isosorbide-5-Nitrae -
Bis- (4- amino-benzene oxygens) benzene of bis- (4- amino-benzene oxygens) benzene, 1,3-, bis- (3- amino-benzene oxygens) benzene of 1,3-, 4,4 '-bis- (4- ammonia
Phenoxyl) it is biphenyl, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl, bis- [4- (4- amino-benzene oxygens) phenyl] propane of 2,2-, double
[4- (4- amino-benzene oxygens) phenyl] sulfone, bis- [4- (3- amino-benzene oxygens) phenyl] sulfones, bis- [4- (4- amino-benzene oxygens) benzene of 2,2-
Base] hexafluoropropane, 3,3 '-dicarboxyl -4,4 '-diaminodiphenyl-methanes, 4,6- dihydroxy -1,3- phenylenediamine, 3,3 '-dihydroxies
Bis- (3- amino-4-hydroxylphenyls) hexafluoropropane of 4,4 '-benzidine of base-, 2,2-, 3,3 ', 4,4 '-tetra-amino-biphenyls, 1,
Bis- (3- aminopropyls) tetramethyl disiloxanes of 6- diamino hexanes, 1,3-, 1- amino -3- amino methyls -3,5,5- trimethyls
Hexamethylene, 4,4 '-di-2-ethylhexylphosphine oxides (4- cyclo-hexylamines), anti-form-1,4- cyclohexanediamine, bicyclic [2.2.1] heptane bis- (methyl amines),
Tricyclic [3.3.1.13,7] decane -1,3- diamines (alias adamantane -1,3- diamines), 4-aminobenzoic acid -4- aminobenzenes base ester,
Bis- [4- (4- amino-benzene oxygens) phenyl] fluorenes of 2- (4- aminophenyls) An bases benzoxazole, 9,9-, 2,2 '-bis- (the third oxygen of 3- sulphurs
Base) -4,4 '-benzidines, 4,4 '-bis- 3,3 '-disulfonic acid of (4- amino-benzene oxygens) biphenyl -, 3,3 '-diamino diphenyl sulfones
Deng.In addition, these Diamines can also be used in combination of two or more.
In above-mentioned Diamines, 3,3 '-diamino diphenyl sulfones, bicyclic [2.2.1] heptane bis- (methyl amines), anti-are being used
In the case of the ester ring types diamines such as formula-Isosorbide-5-Nitrae-cyclohexanediamine, the transparency of obtained polyimides further increases, in addition,
Using the fluorinated diamines such as bis- [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane of 2,2-, 2,2 '-bis- (trifluoromethyl) benzidine
It in the case of class, can significantly more improve the solvent solubility of obtained polyimides, and can realize obtained
The low dielectric of polyimides.These Diamines make being combined with tetracarboxylic dianhydride and other acid dianhydrides shown in above-mentioned formula (1)
In the case of, relative to comprising 1 mole of whole acid dianhydrides including other acid dianhydrides usually using 0.9~1.1 mole, from carrying
, it is preferable to use 0.95~1.05 mole from the perspective of high polymerization degree.
Furthermore it is possible to which common acid dianhydride is applied in combination as needed as copolymer composition.As what can be applied in combination
Acid dianhydride can illustrate for example：Pyromellitic dianhydride, two O-phthalic acid dianhydride of oxygen, biphenyl -3,4,3 ', 4 '-tetracarboxylic dianhydrides, two
Benzophenone -3,4,3 ', 4 '-tetracarboxylic dianhydrides, diphenyl sulfone -3,4,3 ', 4 '-tetracarboxylic dianhydrides, 4,4 '-(the different Asias of 2,2- hexafluoros
Propyl) two O-phthalic acid dianhydrides, meta-terphenyl base -3,4,3 ', 4 '-tetracarboxylic dianhydrides, para-terpheny base -3,4,3 ', 4 '-four
Carboxylic acid dianhydride, cyclobutane -1,2,3,4- tetracarboxylic dianhydrides, 1- carboxymethyl groups -2,3,5- pentamethylene tricarboxylic acids -2,6: 3,5- diacid
Acid anhydride, hexamethylene -1,2,4,5- tetracarboxylic dianhydrides, butane -1,2,3,4- tetracarboxylic dianhydrides, 4- phenylene-ethynylene phthalic acids
Acid anhydride, naphthalene-Isosorbide-5-Nitrae, 5,8- tetracarboxylic dianhydrides, bis- (1,3- dioxo -1,3- dihydroisobenzofuran -5- carboxylic acids) Isosorbide-5-Nitraes-Asia phenyl ester
Deng these acid dianhydrides can also be used in combination of two or more.When other acid dianhydrides are applied in combination, its in whole acid dianhydrides
The usage amount of its acid dianhydride is preferably 10 weight % or more, more preferably 30 weight % or more, on the other hand, preferably 90 weights
% is measured hereinafter, more preferably 70 weight % or less.By using other acid dianhydrides of 10 weight % or more, after can fully obtain
That states is applied in combination physical property improvement effect caused by other acid dianhydrides.On the other hand, by making the usage amounts of other acid dianhydrides
For 90 weight % hereinafter, so as to give full play to the characteristic for coming from tetracarboxylic dianhydride's structure shown in above-mentioned formula (1).
As the effect that other acid dianhydrides are applied in combination, for example, by the way that 4,4 '-(2,2- hexafluoroisopropylidenyls) are applied in combination
The fluorine-containing acid dianhydrides such as two O-phthalic acid dianhydrides, so as to realize the low-k of obtained polyimides.In addition,
In the case where the acid dianhydrides such as the pyromellitic dianhydride with rigid backbone are applied in combination, obtained polyimides can be improved
Heat resistance.
The solvent that can be used when as manufacture polyamic acid, as long as starting monomer, above-mentioned formula (1) can be dissolved
Shown in tetracarboxylic dianhydride and Diamines, and relative to these raw materials and the polyamic acid torpescence generated then without special
It limits.As such solvent, can use for example：N,N-Dimethylformamide, n,N-dimethylacetamide, N- methyl -2-
The amide solvents such as pyrrolidones；The chains ester series solvent such as butyl acetate, ethyl acetate, isobutyl acetate；Gamma-butyrolacton, γ-oneself
The ring-type ester solvent such as lactone, 6-caprolactone；The carbonate solvents such as ethylene carbonate, propylene carbonate；The molten fibre of triethylene glycol, ethyl
Agent, butyl cellosolve, propylene glycol methyl acetic acid esters, 2- methylcellosolve acetates, ethyl cellosolve acetate, butyl cellosolve
Two alcohol series solvent such as acetic acid esters, dimethoxy-ethane, diethoxyethane, diethylene glycol；Phenol, o-cresol, metacresol, to first
The phenol systems solvents such as phenol, 3- chlorophenols, 4- chlorophenols；The ether series solvents such as tetrahydrofuran, dibutyl ethers, ether；Methyl iso-butyl ketone (MIBK),
The ketone series solvents such as diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, acetophenone；The alcohol series solvents such as butanol, ethyl alcohol；Diformazan
The aromatic systems solvent such as benzene, toluene, chlorobenzene；The sulfones series solvent such as sulfolane；Dimethyl sulfoxide (DMSO) etc..It is preferred that N is illustrated, N- dimethyl methyls
The amide solvents such as amide, n,N-dimethylacetamide, N- methyl-pyrrolidons.These solvents can use it is a kind of or according to
It needs to be used in mixed way two or more.
For the usage amount of solvent, make the total concentration of the monomer component (tetracarboxylic dianhydride+Diamines) in reaction system
(monomer concentration) generally reaches 5~40 weight %, preferably 8~25 weight %.By being polymerize with above-mentioned monomer concentration range,
So as to obtain the polyamic acid solution of uniform and high polymerization degree.It should be noted that if to be less than above-mentioned monomer concentration model
The concentration enclosed is polymerize, then the degree of polymerization of polyamic acid is not high enough to, and finally obtained polyimide film becomes fragile sometimes；
If being polymerize with the concentration higher than above-mentioned monomer concentration range, there is a situation where that monomer is not sufficiently dissolved, reaction solution becomes
It obtains uneven and there is a situation where gelations.By obtained by the above method with the poly- of repetitive unit shown in above-mentioned formula (2)
The solution of amic acid is usually used for aftermentioned polyimides chemical industry sequence with solution state.
<Polyimides and its manufacturing method with repetitive unit shown in above-mentioned formula (3)>
The polyimides with repetitive unit shown in above-mentioned formula (3) of the present invention can be by that will obtain in aforementioned manners
The polyamic acid with repetitive unit shown in above-mentioned formula (2) manufactured for dehydration closed-loop reaction (imidization reaction).
As the method for imidization reaction, such as hot-imide method, chemical imidization method can be illustrated.
First, hot-imide method is described in detail.About hot-imide method, first, make the poly- of polyamic acid
It closes solution to be cast on a glass, is heated in a vacuum or in the inactive gas such as nitrogen or in air, obtain polyamides
Amino acid film, thus implements.Specifically, for example, can be carried out in an oven with usual 50~190 DEG C, preferably 100~180 DEG C
It is dry, thus obtain the film of polyamic acid.
Next, by by the film of obtained polyamic acid on a glass with usual 200~400 DEG C, preferably 250~
350 DEG C are heated.Cause imidization reaction as a result, polyimide film can be obtained.From make imidization reaction fully into
From the perspective of row, heating temperature is preferably 200 DEG C or more, from the viewpoint of the thermal stability of the polyimide film of generation,
Preferably 400 DEG C or less.
Preferably imidization reaction carries out in a vacuum or in inactive gas, but as long as imidization reaction temperature
It is not excessively high, then it is not influenced carrying out in air.
Next, chemical imidization method is described in detail.About chemical imidization method, first, to by upper
Having in the polyamic acid solution of repetitive unit shown in above-mentioned formula (2) for the present invention that the method for stating obtains is added and polymerize phase
Same solvent reaches the suitable solution viscosity for being easy stirring, stirs on one side, adds organic acid anhydride and dehydration closed-loop on one side
Both merging (are known as chemical imidization agent) by agent sometimes, and 1~72 is stirred at 0~100 DEG C of temperature, preferably 10~50 DEG C
Hour, so as to chemically complete imidizate.
As the organic acid anhydride that chemical imidization can use, acetic anhydride, propionic andydride etc. can be enumerated.These organic acids
In acid anhydride, from the angle for being easily processed and detaching, preferably acetic anhydride.In addition, as dehydration closed-loop agent, can use pyridine,
Triethylamine, quinoline etc..In these dehydration closed-loop agent, from the angle for being easily processed and detaching, preferably pyridine.Chemical acid imide
Organic acid anhydride amount in agent is preferably 1~10 times mole of range of the theoretical dehydrating amount of polyamic acid, and more preferably 2~10
Times mole.In addition, the amount of dehydration closed-loop agent is relative to the range that organic acid anhydride amount is preferably 0.1~5 times mole, more preferably 1
~5 times moles of range.
Be mixed into the reaction solution obtained by above-mentioned chemical imidization method unreacted chemical imidization agent,
The by-products such as organic acid (hereinafter referred to as impurity), therefore these can be removed, polyimides is detached, is purified.Purifying
Known method can be utilized.For example, following methods can be applied：Reaction solution after progress imidizate is added drop-wise to poor solvent
In and make polyimides be precipitated after, recycle polyimide powder, repeatedly washing until removing impurity, be dried, obtain
Polyimide powder.For can be as the solvent that poor solvent uses, as long as polyimides can be made to be precipitated, expeditiously
It removes impurity and is easy dry solvent, the preferably alcohols such as water, methanol, ethyl alcohol, isopropanol, these can also be mixed
It closes and uses.
When being added drop-wise to the excessive concentration of the polyimide solution in poor solvent and when being precipitated, the polyimides of precipitation forms grain
Block, to remain impurity in this block sometimes, obtained polyimide powder be re-dissolved in solvent sometimes when need compared with
For a long time.Therefore, the concentration of polyimide solution when being added drop-wise in poor solvent is preferably 20 weight % hereinafter, more preferably 10
Weight % or less.In addition, the usage amount of poor solvent is preferably 1 times of weight or more, more preferably 1.5 relative to polyimide solution
~10 times of weight.
Obtained polyimide powder is recycled, when about by residual solvent by removings such as vacuum drying, heated-air dryings
Temperature, there is no limit for example, 30~150 DEG C as long as the temperature to undergo no deterioration for polyimides.
Polyimide film is formed making the obtained polyimide powder with repetitive unit shown in above-mentioned formula (3)
When, it needs temporarily to make to have the polyimide powder of repetitive unit shown in above-mentioned formula (3) to be dissolved in solvent and polyamides Asia is made
Amine aqueous solution.As the solvent that can be used, as long as according to usage, processing conditions suitably using dissolving polyimide powder
Solvent, specifically, for example, in addition to that can use：N,N-Dimethylformamide, n,N-dimethylacetamide, N- first
The amide solvents such as base -2-Pyrrolidone；Gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, α-first
The ester solvents such as base-gamma-butyrolacton, butyl acetate, ethyl acetate, isobutyl acetate；The carbonic acid such as ethylene carbonate, propylene carbonate
Ester solvent；Two alcohol series solvents such as diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether；It is phenol, metacresol, right
The phenol systems solvents such as cresols, o-cresol, 3- chlorophenols, 4- chlorophenols；Cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, two isobutyls
The ketone series solvents such as base ketone, methyl iso-butyl ketone (MIBK)；Tetrahydrofuran ,-dioxane of Isosorbide-5-Nitrae, dimethoxy-ethane, diethoxyethane, two
Except the ether series solvents such as butyl ether, acetophenone, 1,3-Dimethyl-2-imidazolidinone, sulfolane, dimethyl can also be used sub-
Sulfone, propylene glycol methyl acetic acid esters, ethyl cellosolve, butyl cellosolve, 2- methylcellosolve acetates, ethyl cellosolve acetic acid
Ester, butyl cellosolve acetate, butanol, ethyl alcohol, dimethylbenzene, toluene, chlorobenzene, turpentine oil, benzin, naphtha system etc lead to
With solvent etc., these solvents can be used alone, or mixing two or more.With regard to polyimide powder dissolving method and
Speech can make it dissolve in air or within the scope of the temperature in inactive gas, below the boiling point of room temperature~solvent and make
At polyimide solution.
By making the obtained polyimide solution for example be cast on a glass, in a vacuum or nitrogen etc. is not lived
It sprinkles in gas or heats in air and remove solvent, it is hereby achieved that polyimide film.For example, by an oven to lead to
Normal 200~400 DEG C, preferably 250~350 DEG C are dried, so as to obtain polyimide film.The making of polyimide film is managed
What is thought is to carry out in a vacuum or in inactive gas, but as long as temperature is not excessively high, is not then had carrying out in air
It influences.
By the molecular weight obtained by the above method with the polyimides of repetitive unit shown in above-mentioned formula (3) to pass through
The Weight-average molecular gauge that aftermentioned assay method obtains is preferably 10,000~600,000, more preferably 20,000~500,000, further preferably 4
Ten thousand~400,000.It can be molded if the molecular weight of polyimides is 10,000 or more, and be easy to maintain good mechanical characteristic.
In addition, if the molecular weight of polyimides be 400,000 hereinafter, if in synthesis when be easy to control molecular weight, and hold in most cases
It is easy to get to the suitable solution of viscosity, is easily handled.It should be noted that the molecular weight of polyimides can reflect that polyimides is molten
The viscosity of liquid.
Pass through the solvent with the polyimides of repetitive unit shown in above-mentioned formula (3) of the present invention obtained by the above method
Dissolubility is excellent, and refractive index also reaches 1.65 or more and shows high refractive index, and glass transition temperature also reaches 260 DEG C or more
And excellent heat resistance.In addition, by being combined with used diamines, to as also have both low-k, high transparency it
The polyimides of category feature.
Embodiment
The embodiment of the present invention described below, the present invention are not limited by these examples.It is each shown in each embodiment, comparative example
Physics value is the result determined using following measurement device, condition.
(1) NMR is measured
1H-NMR、13C-NMR uses tetramethylsilane to utilize JEOL- using deuterated DMSO as solvent as internal standard
ESC400 spectrometers are recorded.
(2) LC-MS is measured
It is detached according to following determination condition, mass spectrum, to identify object.
Device：(strain) Waters systems " Xevo G2Q-Tof ",
Column：ACQUITY UPLC BEHC18、
(1.7μm、)、
Column temperature：40℃、
Detection wavelength：UV 220-500nm、
Mobile phase：The aqueous formic acid of A liquid=0.1%, B liquid=acetonitrile,
Mobile phase flow rate：0.3mL/ minutes,
Eluent gradient：B liquid concentration：80% (after ten minutes) → 100% of (0 minute) → 80% (after 15 minutes),
Detection method：Q-Tof、
Ionization method：APCI (-) method,
Ion source (Ion Source)：120 DEG C of temperature,
Sampling spiroid (Sampling Cone)：Voltage 50V, gas flow 50L/h,
Desolvation gas (Desolvation Gas)：500 DEG C of temperature, gas flow 1000L/h.
(3) HPLC purity
Area percentage value when high performance liquid chromatography (HPLC) measures will be carried out according to following determination condition as eachization
Close the purity of object.
Device：Hitachi corporation L-2130,
Column：ZORBAX CN(5μm、)、
Column temperature：40℃、
Detection wavelength：UV 254nm、
Mobile phase：A liquid=hexane, B liquid=tetrahydrofuran,
Mobile phase flow rate：1.0ml/ minutes,
Eluent gradient：A liquid concentration：85% (0 minute) → 60% (after 35 minutes) → 0% (after forty minutes).
(4) weight average molecular weight of polyamic acid
Weight average molecular weight is measured according to following determination condition.(polystyrene conversion)
Device：Tosoh (strain) HLC-8320GPC processed,
Column：TSK-GEL Super AWM-H(6.0mmI.D.×15cm)、
Mobile phase：N,N-Dimethylformamide, flow：0.6ml/ minutes,
Column temperature：40℃.
(5) measurement of fusing point
It, will be with heating using differential scanning calorimetry (DSC) (SII Nano Techno1ogy systems " EXSTAR DSC 7020C ")
The melting that 10 DEG C/min of speed detects when being measured absorbs heat maximum temperature as fusing point.
(6) measurement of glass transition temperature (Tg)
Using differential scanning calorimetry (DSC) (SII Nano Technology systems " EXSTAR DSC 7020 ") with heating rate
30 DEG C/min are measured, using the intersection point of the tangent line of inflection point as glass transition temperature.
(7) measurement of cutoff wavelength
Using spectrophotometer ((strain) Shimadzu Seisakusho Ltd. system " UV-2450 ") to the saturating of 200~800nm of polyimide film
The rate of penetrating is measured.Transmissivity is reached into 0.5% wavelength below as cutoff wavelength.The more short then polyimide film of cutoff wavelength
The transparency it is the better.
(8) light transmission (T400) measurement
The transmission of the 400nm of polyimide film is measured using spectrophotometer ((strain) Shimadzu Seisakusho Ltd. system " UV-2450 ")
Rate.The transparency of the more high then polyimide film of transmissivity is the better.
(9) refractive index (nin), the measurement of dielectric constant (ε)
It is measured using Abbe refractometer ((strain) ATAGO systems " multi-wavelength Abbe refractometer DR-M2 ") flat with polyimide film
Capable direction (nin) and vertical direction (nout) refractive index (wavelength：589nm), the flat of polyimide film is found out with following formula
Equal refractive index (nav)。
nav=(2nin+nout)/3
Based on the mean refractive index (nav) normal by the dielectric of following formula, the polyimide film being calculate by the following formula out under 1MHz
Number (ε).
ε=1.1 × nav 2
(10) measurement of tensile elongation
Use cupping machine (test film of (strain) Shimadzu Seisakusho Ltd. system " AutographAGS-X " to polyimide film
(dumbbell shape test film parallel portion 5mm × 20mm) implements tension test (tensile speed 10mm/ minutes), finds out the tensile elongation of film
Rate (%).The tensile elongation the high, means that the toughness of film is higher.
(11) solvent solubility
Obtained polyimide film or powder 20mg are put into n,N-dimethylacetamide (DMAc), N- methyl -2- pyrroles
In alkanone (NMP), tetrahydrofuran (THF), cyclopentanone (CPN), gamma-butyrolacton (GBL) 1mL, dissolubility is tested.According to
Following benchmark evaluation solvent solubilities.
○：It dissolves at room temperature.
△：Heating is then dissolved, and is not also precipitated even if cooled to room temperature.
×：It is insoluble.
1. the Production Example of acid dianhydride shown in above-mentioned formula (1)
<Embodiment 1>
To have thermometer, dropping funel, stirring rod 1L four-hole boiling flask in Trimellitic Anhydride Chloride 11.0g is added
Bis- (4- (4- hydroxyphenoxies) phenyl) fluorenes (BPOPF) 10.0g of (52.2mmol), acetonitrile 20.0g, toluene 10.0g, 9,9-
(18.7mmol), stirring postcooling is to 2 DEG C.After cooling, pyridine 4.1g (51.8mm0l) is further added dropwise at 2 DEG C~7 DEG C.Drop
It is warming up to 25 DEG C after adding, is stirred at such a temperature after heating, starts that crystallization is precipitated at the time of stirring has carried out 1 hour, therefore
Acetonitrile 10.0g, toluene 5.0g is added, futher stirs 1 hour.
After stirring, crystallization is filtered out at 25 DEG C, acetonitrile wash crystallization is further used, thus obtains yellow crystal.It will be yellow
Color crystallization is dried in vacuo at 80 DEG C, obtains tetracarboxylic dianhydride 11.6g (yield 70.2%, the purity of above-mentioned formula (1)
99.4%).
By shown in FIG. 11It is H-NMR spectrum, shown in Fig. 213C-NMR spectrograms and mass spectrogram shown in Fig. 3 confirmation, gained
The product arrived is tetracarboxylic dianhydride shown in above-mentioned formula (1).Hereinafter, to tetracarboxylic dianhydride shown in obtained above-mentioned formula (1)1H-NMR and13C-NMR is described in detail.
By tetracarboxylic dianhydride shown in obtained above-mentioned formula (1)1H-NMR(DMSO-d6) it is illustrated in Fig. 1.Here, 8.26
The peak of~8.64ppm belongs to the benzene ring hydrogen in trimellitic acid source, the peak of 7.35~7.96ppm belongs to Fluorenone skeleton
The hydrogen of phenyl ring, the peak of 6.95~7.43ppm belong to the benzene ring hydrogen of 4- (4- hydroxyphenoxies) phenyl.It needs to illustrate
It is the peak that is observed at 2.5ppm from the DMSO as solvent, the peak observed at 3.3ppm comes from contained in DMSO
Water.
It will13C-NMR (DMSO-d6) is illustrated in Fig. 2.Here, 164.0~168.9ppm and 139.95~156.02ppm return
Belong to the carbon from trimellitic anhydride skeleton, 118.8~138.83ppm belongs to 9,9- bis- (4- (4- hydroxyphenoxies) phenyl)
The peak of the carbon in the phenyl ring source of fluorenes, 64.4ppm belongs to 9 carbon of Fluorenone.It should be noted that in 39.2~40.5ppm
The peak that place observes carrys out solvent DMSO.
The mass spectrum map values of tetracarboxylic dianhydride and fusing point shown in obtained above-mentioned formula (1) are as follows.
Mass spectrum map values (M-)：882.17、
Fusing point (DSC)：193℃.
2. with the polyamic acid of repetitive unit shown in above-mentioned formula (2) and with repetitive unit shown in above-mentioned formula (3)
Polyimides Production Example
<Embodiment 2>
(in polyamic acid shown in above-mentioned formula (2), the tetracarboxylic dianhydride shown in above-mentioned formula (1) and bis- (the 4- amino of 9,9-
Phenyl) fluorenes (below be otherwise referred to as FDA) reaction obtained from polyamic acid (referred to as there is weight shown in following formula (2-A)
The polyamic acid of multiple unit) Production Example)
[changing 6]
By tetracarboxylic dianhydride 5.0g (5.66mmol) and FDA2.0g shown in the above-mentioned formula (1) obtained in embodiment 1
(5.66mmol) is dissolved in n,N-dimethylacetamide 80.2g at room temperature, after being warming up to 100 DEG C, confirms that solution is uniform,
After letting cool, react at room temperature 24 hours, thus synthesis has the polyamic acid of repetitive unit shown in above-mentioned formula (2-A).It is poly-
The weight average molecular weight (Mw) of amic acid is 335,368.
<Embodiment 3>
(in polyimides shown in above-mentioned formula (3), based on the polyamide with repetitive unit shown in above-mentioned formula (2-A)
The chemical imidization of acid, polyimides with repetitive unit shown in following formula (3-A) manufacture)
[changing 7]
N being obtained into embodiment 2, with the polyamic acid of repetitive unit shown in above-mentioned formula (2-A), N- dimethyl
Acetic anhydride 5.8g and pyridine 2.2g is added in acetamide solution 87.2g, is stirred at room temperature 24 hours, thus obtains having above-mentioned
The n,N-dimethylacetamide solution of the polyimides of repetitive unit shown in formula (3-A).
The n,N-dimethylacetamide solution with the polyimides of repetitive unit shown in above-mentioned formula (3-A) that will be obtained
It is added drop-wise in methanol 250g, thus makes to have the polyimides of repetitive unit shown in above-mentioned formula (3-A) to be precipitated.By the poly- of precipitation
Acid imide filters out, and is dried after being washed with methanol, obtains flaxen polyimide powder 7.2g.
N,N-dimethylacetamide 28.3g is added into obtained polyimide powder 5.0g and is stirred until homogeneous, thus
Obtain the n,N-dimethylacetamide solution with the polyimides of repetitive unit shown in above-mentioned formula (3-A).The solution is applied
Cloth on a glass after, heated 1 hour with 150 DEG C, heated 1 hour with 250 DEG C, obtain having weight shown in above-mentioned formula (3-A)
The film of the polyimides of multiple unit.The film thickness of film is about 19 μm.
Table 1 shows saturating under the glass transition temperature (Tg) of obtained Kapton, cutoff wavelength, 400nm
Penetrate rate (T400), refractive index (nin), the measurement result of dielectric constant (ε), tensile elongation.In addition, table 2 is shown in various solvents
In dissolubility.
<Embodiment 4>
(in polyamic acid shown in above-mentioned formula (2), the tetracarboxylic dianhydride and 2 shown in above-mentioned formula (1), 2 '-bis- (trifluoros
Methyl) -4,4 '-benzidines (alias 2,2 '-bis- (trifluoromethyl) benzidine) (hereinafter sometimes referred to TFMB) react
The manufacture of the polyamic acid (polyamic acid hereinafter referred to as with repetitive unit shown in formula (2-B)) arrived)
[changing 8]
By tetracarboxylic dianhydride 5.0g (5.66mmol) and TFMB1.8g shown in the above-mentioned formula (1) obtained in embodiment 1
After (5.66mmol) is dissolved in n,N-dimethylacetamide 16.8g at room temperature, it is stirred at room temperature.Due to viscosity with
The progress of reaction and be gradually increasing, therefore, suitably additional n,N-dimethylacetamide (the total additional quantity in side：52.0g) side is in room temperature
Lower stirring 25 hours, thus synthesis have the N of the polyamic acid of repetitive unit shown in above-mentioned formula (2-B), N- dimethylacetamides
Amine aqueous solution.The weight average molecular weight (Mw) of polyamic acid is 537,315.
<Embodiment 5>
(in polyimides shown in above-mentioned formula (3), based on the polyamide with repetitive unit shown in above-mentioned formula (2-B)
The chemical imidization of acid, polyimides with repetitive unit shown in following formula (3-B) manufacture)
[changing 9]
The N with the polyamic acid of repetitive unit shown in above-mentioned formula (2-B) obtained into embodiment 4, N- dimethyl
Acetic anhydride 5.8g and pyridine 2.2g is added in acetamide solution 92.3g, is stirred at room temperature 24 hours, thus obtains having above-mentioned
The n,N-dimethylacetamide solution of the polyimides of repetitive unit shown in formula (3-B).
The n,N-dimethylacetamide solution with the polyimides of repetitive unit shown in above-mentioned formula (3-B) that will be obtained
It is added drop-wise in methanol 250g, thus makes to have the polyimides of repetitive unit shown in above-mentioned formula (3-B) to be precipitated.By the poly- of precipitation
Acid imide filters out, and is dried after being washed with methanol, obtains the polyimide powder 6.8g of white.
N,N-dimethylacetamide 45.0g is added into obtained polyimide powder 5.0g and is stirred until homogeneous, thus
Obtain the n,N-dimethylacetamide solution with the polyimides of repetitive unit shown in above-mentioned formula (3-B).It is molten by what is obtained
It after liquid coating on a glass, is heated 1 hour with 150 DEG C, is heated 1 hour with 250 DEG C, obtain having shown in above-mentioned formula (3-B)
Repetitive unit polyimides film.The film thickness of film is about 14 μm.
Table 1 shows saturating under the glass transition temperature (Tg) of obtained Kapton, cutoff wavelength, 400nm
Penetrate rate (T400), refractive index (nin) dielectric constant (ε), tensile elongation measurement result.In addition, table 2 is shown in various solvents
Dissolubility.
3. about the Production Example of polyimides and the object of the polyimides derived from other acid dianhydrides with fluorene skeleton
Property
<Reference example 1>
(acid dianhydride and TFMB shown in following formula (6) obtain, with the poly- of repetitive unit shown in following formula (7)
Imido Production Example)
[changing 10]
By tetracarboxylic dianhydride 5.0g (6.88mmol) shown in following formula (6) and TFMB 2.2g (6.88mmol) in room temperature
Under be dissolved in n,N-dimethylacetamide 17.8g, at room temperature react 24 hours, the N of synthesizing polyamides acid, N- dimethylacetamides
Amine aqueous solution.The weight average molecular weight (Mw) of polyamic acid is 66,029.
[changing 11]
N,N-dimethylacetamide is added into the n,N-dimethylacetamide solution 25.0g of obtained polyamic acid
11.0g, acetic anhydride 7.0g and pyridine 2.7g are stirred at room temperature 22 hours, thus obtain having shown in above-mentioned formula (7) repeatedly
The n,N-dimethylacetamide solution of the polyimides of unit.
The n,N-dimethylacetamide solution drop with the polyimides of repetitive unit shown in above-mentioned formula (7) that will be obtained
It is added in methanol 250g, thus makes to have the polyimides of repetitive unit shown in above-mentioned formula (7) to be precipitated.The polyamides of precipitation is sub-
Amine filters, and is dried after being washed with methanol, obtains the polyimide powder 6.6g of white.
N,N-dimethylacetamide 20.0g is added into obtained polyimide powder 5.0g and is stirred until homogeneous, thus
Obtain the n,N-dimethylacetamide solution with the polyimides of repetitive unit shown in above-mentioned formula (7).The solution that will be obtained
It after coating on a glass, is heated 1 hour with 150 DEG C, is heated 1 hour with 250 DEG C, obtain that there is weight shown in above-mentioned formula (7)
The film of the polyimides of multiple unit.The film thickness of film is about 25 μm.
Table 1 shows saturating under the glass transition temperature (Tg) of obtained Kapton, cutoff wavelength, 400nm
Penetrate rate (T400), refractive index (nin) dielectric constant (ε), tensile elongation measurement result.
[table 1]
[table 2]
Claims (4)
1. a kind of tetracarboxylic dianhydride is indicated with following formula (1),
2. a kind of polyamic acid has the repetitive unit indicated with following formula (2),
In formula, Z indicates diamines residue.
3. a kind of polyimides has the repetitive unit indicated with following formula (3),
In formula, Z indicates diamines residue.
4. a kind of manufacturing method of tetracarboxylic dianhydride described in claim 1 makes trimellitic anhydride carboxylic acid halides and with following formula (4)
The bisphenols of expression reacts,
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