CN108137804A - Novel tetracarboxylic acid dianhydride and polyimides and the formed body being made of the polyimides derived from the tetracarboxylic acid dianhydride - Google Patents
Novel tetracarboxylic acid dianhydride and polyimides and the formed body being made of the polyimides derived from the tetracarboxylic acid dianhydride Download PDFInfo
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- CN108137804A CN108137804A CN201680056630.8A CN201680056630A CN108137804A CN 108137804 A CN108137804 A CN 108137804A CN 201680056630 A CN201680056630 A CN 201680056630A CN 108137804 A CN108137804 A CN 108137804A
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- tetracarboxylic acid
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- acid dianhydride
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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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- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
Abstract
The issue of the present invention is to provide a kind of formed bodies of polyimides and the polyimides as derived from novel tetracarboxylic acid dianhydride, since the polyimides is excellent relative to the dissolubility of various organic solvents and has both thermoplasticity, excellent in workability and low coefficient of linear thermal expansion and high light transmittance (transparency) are had both.Can the above subject be solved by the polyimides derived from the tetracarboxylic acid dianhydride shown in following formula (1).
Description
Technical field
The present invention relates to a kind of polyimides derived from novel tetracarboxylic acid dianhydride and by the polyimides form into
Body, the excellent in workability of the polyimides and has both low coefficient of linear thermal expansion and high light transmittance (transparency).Since this is poly-
Acid imide also shows thermoplasticity other than excellent solution processability, so not only can be by solution casting method system
Film can also carry out melt molding.Compared with previous solvent-soluble polyimide or thermoplastic polyimide, further by this
The formed body that polyimides is formed transparency while low coefficient of linear thermal expansion is shown is also excellent.Come from such feature
It sees, is shown as the dimensional stability relative to heat is needed with transparent liquid crystal display (LCD), organic electroluminescent (EL)
It is transparent substrate used in device, Electronic Paper, light emitting diode (LED) device, solar cell etc., transparency protected membrane material, viscous
It is useful to connect material.
Background technology
As the previous transparent resin that processing can be formed, it is known to polyethylene terephthalate, poly- carbonic acid
Ester, polyether sulfone etc., although the solution processability of these resins or melt forming are excellent, relative to the change in size (line of heat
Coefficient of thermal expansion) it is big.When coefficient of linear thermal expansion as formed body is big, with LCD, organic el display, Electronic Paper, LED etc.
May be generated during low heat expansion inorganic material lamination used in display equipment or lighting device it is various bad, so unexcellent
Choosing.For example, due to forming above-mentioned transparent resin molding and transparent electrode (ITO；Indium Tin Oxide), copper, silver, aluminium
Deng wiring or thin film transistor (TFT) (TFT；Thin-Film Transistor) hot-working when elements, in low heat expansion
The mismatch of coefficient of linear thermal expansion is generated between inorganic material and previous high thermal expansivity resin, and generates and answers in its interface
Become, so as to there is the doubt that splitting, substrate strain and element is caused to destroy.
On the other hand, as the resin with excellent thermal dimensional stability, it is known to aromatic polyimide.By chemistry
The formed body that structure is upright and outspoken and linear aromatic polyimide is formed, such as polyimide film can be widely used in flexibility
The matrix membrane of printed circuit board or the interlayer dielectric of semiconductor etc. need high-dimensional stability (low coefficient of linear thermal expansion)
Field.However, it is consumingly coloured due to electric charge transfer interaction between intramolecular conjugation and Intramolecular, so having
The aromatic polyimide of low coefficient of linear thermal expansion is difficult to apply in above-mentioned optical applications.And then due to the molecule of polyimides
Between power it is very strong, so the dissolubility and thermoplasticity relative to solvent are not shown often, so as to lack processability.
On the other hand, it is proposed that overcome the polyimides of these shortcomings.Such as propose following method：Fluorine atom is imported poly-
In imide structure (non-patent literature 1)；Or by the diamine component for forming polyimides and tetracarboxylic acid dianhydride ingredient
Using ester ring type compound in one or both, inhibit intramolecular conjugation and electric charge transfer interaction so as to improve the transparency
(non-patent literature 2,3).By these prior arts, though the transparency and solution processability and the polyimides deposited are developed,
The report example that the polyimides of low heat expansion is also had both other than processability is still limited.
Report example as the minority, it is proposed that there is the specific polyimides (patent document 1) of ester group.The polyimides removes
Except the transparency, heat resistance, also there is the low coefficient of linear thermal expansion equal with inorganic material, but relative to various organic solvents
Dissolubility it is insufficient, still have improved space in this aspect.
And then it is still undiscovered to have both the thermoplastic polyimides with excellent processability.
Existing technical literature
Non-patent literature
Non-patent literature 1：Macromolecules,24,5001(1991)
Non-patent literature 2：J.Polym.Sci.,PartA,Polym.Chem.,51,575(2013)
Non-patent literature 3：Polymer,55,4693(2014)
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-082876 bulletins
Invention content
Technical task to be solved by this invention be to provide one kind as derived from novel tetracarboxylic acid dianhydride polyimides with
And the formed body being made of the polyimides, since the polyimides is excellent relative to the dissolubility of various organic solvents and has both
Thermoplasticity, therefore excellent in workability and have both low coefficient of linear thermal expansion and high light transmittance (transparency).
In view of aforementioned techniques background, present inventor, which has been repeated, to be studied intensively, as a result, it has been found that can be by following formula (1) Suo Shi
Tetracarboxylic acid dianhydride obtain the polyimides of excellent in workability, become material very useful in this field, thus complete this
Invention.
It is of the invention as described below.
1. a kind of tetracarboxylic acid dianhydride, which is characterized in that by following formula (1) Suo Shi,
2. a kind of polyimides, which is characterized in that there is the repetitive unit shown in following formula (2),
3. the polyimides according to 2, which is characterized in that relative to whole repetitive units in polyimides, formula (2) is shown
Repetitive unit containing ratio be more than 55mol%.
4. a kind of polyimide solution contains the polyimides and organic solvent described in 2 or 3, which is characterized in that solid constituent is dense
It spends for more than 5 weight %.
A kind of 5. polyimides formed body, which is characterized in that the formed body for the polyimides described in 2 or 3.
According to the present invention, can by using by central phenylene substitution have bulky cyclohexyl characterized by tetramethyl
Acid dianhydride is come the formed body that obtains following polyimides and be made of the polyimides：It can not be obtained with the prior art
Characteristic, i.e., since the dissolubility relative to various organic solvents is excellent and has both thermoplasticity, excellent in workability and low line
Coefficient of thermal expansion and high light transmittance (transparency) all have both.
Description of the drawings
Fig. 1 is the infrared absorption spectrum of the polyimide film of embodiment 2.
Fig. 2 is the Dynamic Viscoelastic linearity curve of the polyimide film of embodiment 2.
Fig. 3 is the infrared absorption spectrum of the polyimide film of embodiment 3.
Fig. 4 is the Dynamic Viscoelastic linearity curve of the polyimide film of embodiment 3.
Fig. 5 is the infrared absorption spectrum of the polyimide film of embodiment 4.
Fig. 6 is the Dynamic Viscoelastic linearity curve of the polyimide film of embodiment 4.
Fig. 7 is the Dynamic Viscoelastic linearity curve of the polyimide film of comparative example 2.
Specific embodiment
The tetracarboxylic acid dianhydride of the present invention has the structure shown in following formula (1).
The chemical constitution feature of tetracarboxylic acid dianhydride (hereinafter sometimes referred to simply as TACHQ) shown in formula (1) according to the present invention
The contraposition of central phenylene is bonded to via ester bond for 2 phthalic anhydride structures, and then is had in the substitution of central phenylene
Bulky cyclohexyl.
The synthetic method of TACHQ shown in the formula (1) of the present invention is not particularly limited, such as can be by following formula (3) Suo Shi
Glycol, that is, cyclohexyl hydroquinone or its diacetate esters object and the trimellitic acid shown in following formula (4) or derivatives thereof pass through
Well known esterification synthesizes.
As trimellitic acid derivative, trimellitic anhydride, trimellitic anhydride halide etc. can be enumerated.
The polyimides of the present invention has the repetitive unit shown in following formula (2).
The fisrt feature of the polyimides of repetitive unit according to the present invention with shown in formula (2) is in tetracarboxylic acid dianhydride portion
The contraposition of the central phenylene of position has the connection Asia benzene structure of para-linkage there are 2 ester bonds, and at diamines position, so poly-
Acid imide backbone structure is formed as linearity and upright and outspoken structure.Think that polyimides chain is highly along film due to this feature
In-plane orientation (being orientated in face) simultaneously shows excellent thermal dimensional stability (low coefficient of linear thermal expansion).However, due to polyamides
The cohesiveness of imines interchain is strong, so the low heat expansion polyimides with such linearity and upright and outspoken structure, usually not
It is dissolved in organic solvent and does not also melt, so as to lack processability.Therefore generally with the following method：By siloxanes key, ehter bond,
Position key is imported in polyimides main chain so as to be bent polyimides backbone structure；Or it reduces in polyimides repetitive unit
Imide concentration；And bulky substituent group imported into polyimides side chain weaken the cohesiveness of polyimides interchain from
And improve processability.However, these methods can hinder to be orientated in the face of polyimides formed body especially film, as a result make line heat swollen
Swollen coefficient increase.In other words, make processability and low heat expansion and deposit extremely difficult.
Therefore, pass through following recorded the of the polyimides of the repetitive unit according to the present invention with shown in formula (2)
Two features can solve the problems, such as this.That is, by replacing bulky cyclohexyl on the central phenylene at tetracarboxylic acid dianhydride position, and
Side chain substitution at diamines position is electron-withdrawing and bulky trifluoromethyl, in the face that can not hinder polyimides interchain
It is orientated and only weakens cohesiveness.Due to realizing the polyimides phase with the repetitive unit shown in formula (2) of the excellent balance
It is excellent for the dissolubility of various organic solvents and have both thermoplasticity, therefore excellent in workability and show and be difficult to and deposit originally
Low coefficient of linear thermal expansion in addition also be able to inhibit the electric charge transfer interaction of polyimides so as to can realize high transparency.
The polyimides of repetitive unit according to the present invention with shown in formula (2) can be by will be shown in formula (1)
TACHQ synthesizes the polyimides with above-mentioned excellent specific property as raw material.The manufacturing method of the polyimides has no special limit
It is fixed, such as can be manufactured via following process：TACHQ shown in formula (1) with as 2 shown in the following formula (5) of diamines,
2 '-bis- (trifluoromethyl) benzidine (hereinafter sometimes referred to simply as TFMB) reaction is so as to obtain having the repetitive unit shown in formula (2)
Polyimides precursor (polyamic acid)；And polyamic acid is made to carry out imidizate.
When polymerizeing polyamic acid, in the range of significantly the required characteristic of polymerisation reactivity and polyimides is not damaged,
Can and by the use of the aromatic series other than the TACHQ shown in formula (1) or aliphatic tetracarboxylic acid dianhydride as copolymer composition.
Be not particularly limited as the aromatic tetracarboxylic dianhydride that can be used at this time, for example, can enumerate pyromellitic acid anhydride,
3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, hydroquinone-bis- (trimellitic anhydrides), methyl hydroquinone-bis- (trimellitic acids
Acid anhydride), 1,4,5,8 naphthalenetetracarboxylic acid dianhydride, 2,3,6,7- naphthalenetetracarbacidic acidics dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,
The adjacent benzene of 3 ', 4,4 '-Biphenyl Ether tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic acid dianhydride, 4,4 '-(hexafluoroisopropylidenyl) two
Dicarboxylic acid anhydride, 2,2 '-bis- (3,4- dicarboxyphenyis) propionic acid dianhydrides etc..
It is not particularly limited as aliphatic tetracarboxylic acid dianhydride, for example, bicyclic [2.2.2] octyl- 7- can be enumerated for ester ring type
Alkene -2,3,5,6- tetracarboxylic acid dianhydrides, 5- (dioxotetrahydrofuryl -3- methyl -3- cyclohexene -1,2- dicarboxylic acid anhydrides, 4- (2,
5- dioxotetrahydro furans -3- bases) naphthane -1,2- dicarboxylic acid anhydrides, tetrahydrofuran -2,3,4,5- tetracarboxylic acid dianhydrides, bicyclic -3,
3 ', 4,4 '-tetracarboxylic acid dianhydride, 1,2,3,4- cyclobutanetetracarboxylics dianhydride, 1,2,3,4- cyclopentane tetracarboxylic acid dianhydrides etc..In addition,
These substances can be also used together by two or more types.
From the viewpoint of the dissolubility, heat resistance, the transparency for further improving polyimides, 4,4 '-(hexafluoroisopropylidenyl)
Diphthalic anhydrides (hereinafter sometimes referred to simply as 6FDA) are suitable as copolymer composition, from further performance polyimides formed body
Low heat expansion from the viewpoint of, there are upright and outspoken and linear structure tetracarboxylic acid dianhydride, that is, pyromellitic acid anhydride, 3,
3 ', 4,4 '-bibenzene tetracarboxylic dianhydride is suitable as copolymer composition.
When aromatic series other than TACHQ shown in formula (1) or aliphatic tetracarboxylic acid dianhydride are as copolymer composition, TACHQ
Ratio relative to whole tetracarboxylic acid dianhydrides is preferably more than 55mol%, more preferable more than 70mol%, further preferably
More than 80mol%, particularly preferred more than 90mol% are preferred.
When making polyamic acid polymerization according to the present invention, do not damaging significantly needed for polymerisation reactivity and polyimides
In the range of characteristic, can and by the use of the aromatic series other than the TFMB shown in formula (5) or aliphatic diamine as copolymer composition.
It is not particularly limited as the aromatic diamine that can be used at this time, such as p-phenylenediamine, m-phenylene diamine (MPD), 2,4- can be enumerated
Diaminotoluene, 2,5- diaminotoluenes, 2,4- diamino dimethylbenzene, 2,4- diamino durene, 4,4 '-diamino-diphenyl
Methane, 4,4 '-di-2-ethylhexylphosphine oxide (2-aminotoluene), 4,4 '-di-2-ethylhexylphosphine oxide (2- ethyl aniline), 4,4 '-di-2-ethylhexylphosphine oxide (2,6- bis-
Methylaniline), 4,4 '-di-2-ethylhexylphosphine oxide (2,6- diethylanilines), 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl
Ether, 3,3 '-diamino-diphenyl ether, 2,4 '-diamino-diphenyl ether, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino two
Phenylsulfone, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzene formailide, 4- aminobenzenes
Base -4 '-Aminobenzoate, benzidine, 3,3 '-dihydroxybiphenyl amine, 3,3 '-dimethoxy benzidine, o-tolidine (o-
Tolidine), bis- (4- amino-benzene oxygens) benzene of tolidine, 1,4-, bis- (4- amino-benzene oxygens) benzene of 1,3-, the bis- (3- of 1,3-
Amino-benzene oxygen) benzene, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, bis- (4- (3- amino-benzene oxygens) phenyl) sulfones, bis- (4- (4- ammonia
Phenoxyl) phenyl) sulfone, bis- (4- (4- amino-benzene oxygens) phenyl) propane of 2,2-, bis- (4- (4- amino-benzene oxygens) benzene of 2,2-
Base) hexafluoropropane, bis- (4- aminophenyls) hexafluoropropane of 2,2-, para-terpheny diamines (p-terphenylene diamine)
Deng.
In addition, being chain fatty race or ester ring type diamines as aliphatic diamine, it is not particularly limited as ester ring type diamines, example
4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine), isophorone diamine, anti-form-1,4- diaminocyclohexanes, cis- -1,4- can such as be enumerated
Diaminocyclohexane, 1,4- hexamethylenes bis- (methyl amines), bicyclic [2.2.1] heptane of 2,5- bis- (amino methyls), the bis- (amino of 2,6-
Methyl) bicyclic [2.2.1] heptane, bis- (amino methyl) tricyclic [5.2.1.0] decane of 3,8-, 1,3- diamino adamantane, 2,2-
Bis- (4- aminocyclohexyls) hexafluoropropane of bis- (4- aminocyclohexyls) propane, 2,2-；It is had no especially as chain fatty race diamines
It limits, such as 1,3- propanediamines, Putriscine, 1,5- pentanediamines, 1,6- hexamethylene diamines, 1,7- heptamethylene diamines, 1,8- can be enumerated
Octamethylenediamine, 1,9-nonamethylene diamine, diamino radical siloxane etc..In addition, it can also be used together by two or more types these substances.
Used solvent during as polymerisation, preferably n,N-Dimethylformamide, n,N-dimethylacetamide, N- first
The non-protonic solvents such as base -2-Pyrrolidone, dimethyl sulfoxide (DMSO), but as long as dissolving starting monomer and the polyamic acid that is generated with
And the polyimides through imidizate, then arbitrary solvent can use without problems, the structure of the solvent is not particularly limited.Tool
For body, such as it can be used the amides such as n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone molten
Agent；Gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, Alpha-Methyl-gamma-butyrolacton, butyl acetate,
The ester solvents such as ethyl acetate, isobutyl acetate；The carbonate solvents such as ethylene carbonate, propylene carbonate；Diethylene glycol dimethyl ether,
The di-alcohols solvent such as triethylene glycol, triethylene glycol dimethyl ether；Phenol, metacresol, paracresol, o-cresol, 3- chlorophenols, 4- chlorophenols etc.
Phenol solvent；The ketones solvents such as cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl iso-butyl ketone (MIBK)；Tetrahydrochysene
The ether solvents such as furans, 1,4- dioxanes, dimethoxy-ethane, diethoxyethane, dibutyl ethers；Other common solvents, example
Acetophenone, 1,3- dimethyl -2- imidazolidines ketone, sulfolane, dimethyl sulfoxide (DMSO), propylene glycol methyl acetic acid esters, ethyl such as can be used
Cellosolve (ethylcellosolve), butyl cellosolve, 2- methylcellosolve acetates, ethyl cellosolve acetate, butyl are molten
Fine agent acetic acid esters, butanol, ethyl alcohol, dimethylbenzene, toluene, chlorobenzene, turpentine oil, Mineral spirits, naphthas solvent etc., can mix 2 kinds
The above substance uses.
After polyamic acid being obtained by the TFMB progress sudden reactions shown in the TACHQ shown in formula (1) and formula (5),
Then by its imidizate, it can obtain the polyimides of the extremely useful present invention in the industry.
Feature from the linearity of high polymer main chain, outspoken nature, the chemical constitution on side chain there are bulky substituent group
From the point of view of, since the polyimides of the present invention is when forming polyimide resin, the dissolubility relative to various organic solvents is excellent
And thermoplasticity is had both, therefore excellent in workability, and then the formed body of the polyimides especially film can be swollen as low line heat is had both
The material of swollen coefficient and high transparency.
In general, the polymerisation reactivity of tetracarboxylic acid dianhydride and diamines can cause the toughness of finally obtained polyimides formed body
Larger impact.Polymerisation reactivity can not obtain high polymer when being not high enough to, and the as a result mutual winding of polymer chain reduces, so as to
There is polyimides formed body to become fragile doubt.Since the TACHQ and the TFMB of formula (5) of formula used in the present invention (1) are shown
Sufficiently high polymerisation reactivity is shown, so without this doubt.
The method for manufacturing the polyimides of the present invention is not particularly limited, and can suitably apply well known method.It is specific and
Speech, such as can synthesize by the following method.The TFMB of formula (5) is dissolved in polymer solvent first, and will be with the TFMB of formula (5)
The TACHQ powder of substantial equimolar formula (1) is added slowly in the solution, using mechanical agitator etc. at 0~100 DEG C
Range, preferably 20~60 DEG C of range stir 0.5~150 hour, preferably 1~48 hour.At this point, monomer concentration is usually 5
The range of the range of~50 weight %, preferably 10~40 weight %.It, can by being polymerize in such monomer concentration range
Obtain uniform and high polymerization degree polyamic acid.When being difficult to stir polymeric solution when the excessive increase of the degree of polymerization of polyamic acid,
Also it can suitably be diluted with same solvent.From the viewpoint of the toughness of polyimides formed body, preferred polyamide acid gathers
It is right high as much as possible.By being polymerize in above-mentioned monomer concentration range, the degree of polymerization of polymer is sufficiently high, can also fully really
The dissolubility of declaration form body and polymer.When being polymerize with the concentration for being less than above range, the degree of polymerization of polyamic acid is sometimes not
Enough height, when being polymerize in addition with being higher than the concentration of above-mentioned monomer concentration range, monomer or the polymer that is generated are dissolved with
When can be insufficient.In addition, during using aliphatic diamine, salt is often caused to be formed in polymerization initial stage and interfere polymerization, in order to press down
Salt manufacturing forms and improves the degree of polymerization as far as possible, is above-mentioned suitable concentration range preferably by monomer concentration management when polymerizeing.
Then explanation makes the method that polyamic acid carries out imidizate.The polyimides of the present invention can pass through well known method
Carry out imidizate.Such as it can enumerate：Make the chemical imidization of polyamic acid progress imidizate by cyclodehydration reagent
Method；After polyamic acid is made to polymerize in high boiling solvent, 150 DEG C or more are then heated in the presence of the entrainers such as dimethylbenzene
And secondary raw water is removed out of system, so as to obtain the solution hot-imide of the polyimides of high polymerization degree with solution state
Method；It either polyamic acid solution is cast on the supporters such as glass substrate is dried, and by obtained polyamic acid
Film-like formed body carry out the hot-imide of imidizate with equal to 250 DEG C or more, preferably 300 DEG C or more heating of heating furnace
Method.Transparent high polyimides formed body in order to obtain, preferably can be in the mild condition of stabilization in these imidizate methods
The lower chemical imidization method for carrying out imidizate.
Chemical imidization method is described in detail.Pass through it for identical solvent to dilute with the solvent used during polymerization
The obtained polyamic acid solution of method of preceding record.The polyamides of the solution viscosity of appropriateness easily stirred will be diluted on one side
The acid anhydride by organic acid and the tertiary amine structure as basic catalyst is added dropwise in the stirrings such as amino acid solution mechanical agitator wherein on one side
Into dehydration closed-loop agent (chemical imidization agent), and in 0~100 DEG C, preferably 10~50 DEG C stirring 1~72 hour come completion
Learn imidizate.The organic acid anhydride that can be used at this time is not particularly limited, and can enumerate acetic anhydride, propionic andydride etc..From reagent
From the point of view of processing or purifying easness, it is suitble to use acetic anhydride.In addition, pyridine, triethylamine, quinoline can be used in basic catalyst
(Quinoline) etc., from the point of view of the processing of reagent or separation easness, it is suitble to using pyridine, but it's not limited to that.Chemical acyl
1~10 times mole of range of the organic acid anhydride amount for the theoretical dehydrating amount of polyamic acid in imines agent, more preferable 1~5 times
Mole.In addition, relative to organic acid anhydride amount, the amount of basic catalyst is 0.1~2 times mole of range, more preferable 0.1~1 times
Mole range.
As mentioned above due to chemical imidization agent or carboxylic acid etc. have been mixed into it in reaction solution after chemical imidization
By-product (hereinafter referred to as impurity), therefore these need to be removed and purify polyimides.Purifying can utilize well known method.Such as make
It can should be with the following method for most easy method：It is added dropwise while the reaction solution for stirring imidizate in a large amount of lean solvent
In and after polyimides is precipitated, recycling polyimide powder and repeated washing is to impurity is removed until, be dried under reduced pressure thus
Obtain polyimide powder.As the lean solvent that can be used at this time, as long as polyimides can be precipitated and efficiently remove miscellaneous
Matter and easily dry solvent, then be not particularly limited, such as the alcohols such as preferred water, methanol, ethyl alcohol, isopropanol, can mix this
A little substances use.Be added dropwise the polyimides that is precipitated during the excessive concentration of polyimide solution when being precipitated in lean solvent into
For grain block, make obtained polyimide powder so as to have in the coarse particle possibility of residual impurity or exist
Longer doubt the time required to dissolving in a solvent.On the other hand, it is needed when the concentration of polyimide solution is too low a large amount of poor
Solvent, carrying capacity of environment increase, manufacture cost caused by solvent slop processing improve, so not preferably.Therefore, it is added dropwise in lean solvent
In polyimide solution a concentration of 20 weight % hereinafter, more preferable below 10 weight %.Used lean solvent at this time
Amount is preferably more than the isodose of polyimide solution, and 5~100 times of amount is suitble to.Recycle obtained polyimide powder simultaneously
Residual solvent is removed by vacuum drying or heated-air drying etc..As long as drying temperature and time for do not make polyimides go bad and
The temperature for evaporating residual solvent, then it is not restricted, it is less than 48 hours dry preferably in 30~200 DEG C of temperature range.
For the polyimides of the present invention, come from the viewpoint of the treatability of the toughness and solution of polyimides formed body
It sees, the intrinsic viscosity of polyimides is preferably the range of 0.1~10.0dL/g, the range of further preferred 0.3~5.0dL/g.
Due to the present invention polyimides dissolve in various organic solvents, so can according to usage or processing conditions come
Select solvent.Such as during continuous coating for a long time, the solvent in polyimide solution can absorb the moisture in air so as to there is analysis
Go out the doubt of polyimides, so it is preferable to use the agent of low hygroscopicity solvents such as triethylene glycol dimethyl ether, gamma-butyrolacton or cyclopentanone.
Therefore, the various solvents or mixed solvent of display agent of low hygroscopicity may be selected in polyimides of the invention.Used agent of low hygroscopicity
Solvent is not particularly limited, such as usable gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, α-
The ester solvents such as methyl-gamma-butyrolactone, butyl acetate, ethyl acetate, isobutyl acetate；The carbon such as ethylene carbonate, propylene carbonate
Acid esters solvent；The di-alcohols solvent such as diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether；Phenol, metacresol, to first
The phenol solvents such as phenol, o-cresol, 3- chlorophenols, 4- chlorophenols；Cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, first
The ketones solvents such as base isobutyl ketone；Tetrahydrofuran, 1,4- dioxanes, dimethoxy-ethane, diethoxyethane, dibutyl ethers etc.
Ether solvent；As other common solvents, acetophenone, 1,3-Dimethyl-2-imidazolidinone, sulfolane, dimethyl also can be used
Sulfoxide, propylene glycol methyl acetic acid esters, ethyl cellosolve, butyl cellosolve, 2- methylcellosolve acetates, ethyl cellosolve acetic acid
Ester, butyl cellosolve acetate, chloroform, butanol, ethyl alcohol, dimethylbenzene, toluene, chlorobenzene, turpentine oil, Mineral spirits, naphtha
Class solvent etc. can mix two or more these substance to use.Even in addition, the n,N-Dimethylformamide of hygroscopicity solvent,
The amide solvents such as n,N-dimethylacetamide, n-methyl-2-pyrrolidone, also can by mixed with above-mentioned agent of low hygroscopicity solvent come
Inhibit the precipitation of the polyimides caused by moisture absorption.
As the polyimides of the present invention being dissolved in solvent and solid component concentration when forming solution, also depend on poly-
The thickness of imido molecular weight, manufacturing method or manufactured film, but preferably more than 5 weight %.Solid component concentration mistake
When low, it is difficult to form the sufficient film of film thickness.As the method when polyimides of the present invention is dissolved in solvent, such as can be on one side
The polyimide powder that solvent adds in the present invention on one side is stirred, and in room temperature~solvent boiling point in air or in non-active gas
Following temperature range was dissolved through 1~48 hour, so as to form polyimide solution.
In addition, remover, filling material, dyestuff, pigment, silane coupled can be added in the polyimides of the present invention as needed
The additives such as agent, crosslinking agent, endcapped agent, antioxidant, antifoaming agent, levelling agent.
Obtained polyimide solution can be film-made to form polyimides formed body or film by well known method.It is for example, logical
It crosses and is cast in polyimide solution on the supporters such as glass substrate using scraper (doctor blade) etc., and use hot air drying
The range usually at 40~300 DEG C such as dry device, infrared drying stove, vacuum desiccator, inert atmosphere stove, preferably 50~250
DEG C range be dried and can form polyimide film.
Embodiment
The present invention is illustrated, but be not limited to these embodiments by the following examples.
And the physics value in example below can measure by the following method.
＜ infrared absorption spectrums ＞
Using fourier-transform infrared spectrophotometer FT/IR4100 (Japan's light splitting corporation), measured by KBr transmission beam methods
The infrared absorption spectrum of tetracarboxylic acid dianhydride.In addition, the infrared absorption spectrum of Kapton can be measured by transmission beam method.
〈1H-NMR spectrum ＞
Using fourier transform NMR spectrophotometer JNM-ECP400 (JEOL systems), measured in deuterated dimethyl sulfoxide
Tetracarboxylic acid dianhydride and polyimide powder through chemical imidization1H-NMR spectrum.
＜ Differential Scanning Calorimetries analyze (fusing point) ＞
The fusing point of tetracarboxylic acid dianhydride is using Differential Scanning Calorimetry analyzer DSC3100 (NETZSCH corporations) in nitrogen atmosphere
It is measured with 5 DEG C/min of heating rate.Fusing point is higher and melting peakss are more sharp, represents that purity is higher.
＜ intrinsic viscosities ＞
The polyamic acid solution of 0.5 weight % or the reduced viscosity of polyimide solution using Ovshinsky (Ostwald) viscosimeter in
30 DEG C measure.The value is considered as intrinsic viscosity.
The dissolubility test ＞ of ＜ polyimide powders in organic solvent
Relative to polyimides 10mg, the organic solvent 1g that table 1 is recorded (1 weight % of solid component concentration) is packed into sample tube
In, it is stirred 5 minutes using test tube mixer and carrys out visual confirmation dissolved state.Solvent uses chloroform (CF), acetone, tetrahydrochysene furan
It mutters (THF), 1,4- dioxanes (DOX), ethyl acetate, cyclopentanone (CPN), cyclohexanone (CHN), N,N-dimethylformamide
(DMF), DMAC N,N' dimethyl acetamide (DMAc), n-methyl-2-pyrrolidone (NMP), metacresol, dimethyl sulfoxide (DMSO) (DMSO),
Gamma-butyrolacton (GBL), triethylene glycol dimethyl ether (Tri-GL).
Evaluation result is is expressed as in room-temperature dissolution ++, when still keeping uniformity after dissolving and let cool to room temperature by heating
Be expressed as+, when swelling/part dissolving is expressed as ±, be expressed as when insoluble-.
＜ glass transition temperatures：Tg, thermoplasticity ＞
Using TA Instruments corporations measurement of dynamic viscoelasticity device (Q800), from frequency 0.1Hz, amplitude 0.1%, rise
The loss peak of warm 5 DEG C/min of speed acquires the glass transition temperature of polyimide film.In addition, after and then glass transition temperature
The sharpness that declines of storage modulus curve evaluate thermoplasticity.
＜ coefficients of linear thermal expansion：CTE〉
The coefficient of linear thermal expansion of polyimide film uses NETZSCH corporations TMA4000 (sample size width 5mm, length
15mm), load is set as film thickness (μm) × 0.5g, after 150 DEG C (the 1st heatings) are first temporarily warming up to 5 DEG C/min, be cooled to
It 20 DEG C, further with 5 DEG C/min heatings (the 2nd heating), and is calculated from TMA curves during the 2nd heating.Coefficient of linear thermal expansion
Acquire the average value between 100~200 DEG C.
The transmissivity of ＜ polyimide films：T400〉
Polyimide film (20 μ m-thick) is measured using Japan's light splitting corporation UV, visible light near infrared spectrometer (V-650) to exist
Light transmission at 200-700nm, and use index of the light transmission as the transparency at 400nm wavelength.In addition, it also acquires
Transmissivity is less than 0.5% wavelength (cutoff wavelength).
＜ yellow chromaticities (yellowness index)：YI〉
Using ultraviolet-visible spectrophotometer V-530 (Japan's light splitting corporation), the polyimides at 380~780nm of wavelength
The light transmission (T%) of film is calculated by VWCT-615 types color diagnostic program (Japan's light splitting corporation) according to JISK77373
Go out yellow chromaticity (YI).
＜ total light transmittances and mist degree ＞
Using Haze Meter NDH4000 (Japan's electricity color industry system) the total of polyimide film is acquired according to JISK7361
Light rate, and mist degree (turbidity) is acquired according to JISK7136.
＜ birefringences：Δn〉
Using Atago corporations Abbe refractometer (Abbe 1T), measured with Abbe refractometer (using sodium vapor lamp, wavelength 589nm)
Direction (the n parallel with polyimides film surfacein) and vertical direction (film thickness direction) (nout) refractive index, and from these folding
The difference of rate is penetrated to acquire birefringence (Δ n=nin-nout).The degree of orientation is higher in the higher face for meaning polymer chain of birefringence value.
1 ＞ of ＜ synthesis examples
The synthesis of A.TAHQ
Tetracarboxylic acid dianhydride (TAHQ) shown in following formula (6) synthesizes as follows.By trimellitic anhydride chloride 12.6751g
(60.1940mmol) carries out diaphragm in eggplant type flask, and in room-temperature dissolution in tetrahydrofuran (THF) 33mL is dehydrated
(septum) it seals to prepare solution A.It further will dehydration THF 8.2mL, pyridine 9.7mL (120mmol) in another flask
It is added in hydroquinone (HQ) 2.2209g (20.1700mmol), carries out diaphragm seal to prepare solution B.On one side in ice bath
It cools down and stirs, solution B is slowly added dropwise in solution A through about 5 minutes by syringe on one side, is then stirred at room temperature 24
Hour.White precipitate is filtered after reaction, is cleaned with THF and ion exchange water.Pyridine hydrochloride is gone divided by by silver nitrate
Aqueous solution addition is in washing lotion and does not observe white precipitate to confirm.It recycles cleaned product and carries out 12 in 100 DEG C
The vacuum drying of hour.Obtained product be white powder, yield 8.0287g, yield 87.6%.
The identification of B.TAHQ
Product is by fourier-transform infrared spectrophotometer FT/IR4100 (Japan's light splitting corporation), in 3082cm-1Really
Aromatic series C-H stretching vibration absorption bands are recognized, in 1847cm-1And 1781cm-1Confirm anhydride group C=O stretching vibrations absorption
Band, in 1742cm-1Confirm ester group C=O stretching vibration absorption bands.
In addition, it is carried out using fourier transform NMR spectrophotometer JNM-ECP400 (JEOL systems)1H-NMR is measured, knot
Fruit can belong to (DMSO-d6,δ,ppm)：7.54 (s, 4H), 8.30 (d, J=7.9Hz, 2H), 8.65 (sd, J=0.72Hz,
2H), 8.67 (dd, J=8.0Hz, 1.3Hz, 2H), elemental analysis value are guess value C：62.89%th, H：2.20%, measured value C：
62.69%th, H：2.42%, it is TAHQ that can confirm product.
And fusing point is measured by Differential Scanning Calorimetry analyzer DSC3100 (NETZSCH corporations), it is as a result aobvious in 272.4 DEG C
Show sharp melting peakss, it is high-purity thus to prompt the product.
2 ＞ of ＜ synthesis examples
A. the synthesis of tetracarboxylic acid dianhydride TAPh
Tetracarboxylic acid dianhydride (TAPh) shown in following formula (7) synthesizes as follows.By trimellitic anhydride chloride 15.1116g
(71.8mmol) in room-temperature dissolution in tetrahydrofuran (THF) 16.5mL is dehydrated, carries out diaphragm seal in eggplant type flask
Prepare solution A.Dehydration THF 23.5mL, pyridine 8.7mL (108mmol) are further added to 2- phenyl pair in another flask
In benzenediol 6.2721g (34mmol), diaphragm seal is carried out to prepare solution B.It cools down and stirs in ice bath on one side, it is logical on one side
It crosses syringe solution B is slowly added dropwise in solution A through about 5 minutes, then be stirred at room temperature 24 hours.It crosses after reaction
White precipitate is filtered, is cleaned with THF and ion exchange water.Pyridine hydrochloride going divided by adding silver nitrate aqueous solution in washing lotion
And white precipitate is not observed to confirm.Cleaned product is recycled, the vacuum drying for carrying out 1 hour in 80 DEG C is simultaneously further
The vacuum drying of 12 hours is carried out in 100 DEG C.Obtained product is white powder, and yield 17.93g, yield is
98.7%.
The identification of B.TAPh
Product by fourier-transform infrared spectrophotometer FT/IR4100 (Japan light splitting corporation), in 3092,
3065cm-1Aromatic series C-H stretching vibration absorption bands are confirmed, in 1847cm-1And 1775cm-1Anhydride group C=O is confirmed to stretch
Absorption of vibrations band, in 1752cm-1Confirm ester group C=O stretching vibration absorption bands.
In addition, it is carried out using Fourier nuclear magnetic resonance spectrophotometer JNM-ECP400 (JEOL systems)1H-NMR is measured, and as a result may be used
Belong to (DMSO-d6,δ,ppm)：7.30-7.40 (m, 3H), 7.55-7.66 (m, 5H), 8.23 (d, J=7.8Hz, 1H),
8.29-8.32 (m, 1H), 8.50-8.56 (m, 2H), 8.66-8.70 (m, 2H), elemental analysis value are guess value C：67.42%th,
H：2.64%, measured value C：67.49%th, H：2.82%, it is TAPh that can confirm product.
In addition, fusing point is measured by Differential Scanning Calorimetry analyzer DSC3100 (NETZSCH corporations), as a result in 198.4 DEG C
Show sharp melting peakss, it is high-purity thus to prompt the product.
1 ＞ of ＜ embodiments
A. the synthesis of the tetracarboxylic acid dianhydride TACHQ shown in formula (1)
TACHQ shown in formula (1) is synthesized as follows.By trimellitic anhydride chloride 12.7003g (60.3137mmol) mounted in eggplant
In shape flask, in room-temperature dissolution in tetrahydrofuran (THF) 33mL is dehydrated, diaphragm seal is carried out to prepare solution A.Further exist
Dehydration THF 6.5mL, pyridine 9.7mL (120mmol) are added to 2- cyclohexyl hydroquinone (CHQ) in another flask
In 3.8551g (20.0661mmol), diaphragm seal is carried out to prepare solution B.
It cools down and stirs in ice bath on one side, solution B is slowly added dropwise in solution A through about 5 minutes by syringe on one side,
Then it is stirred at room temperature 24 hours.White precipitate is filtered after reaction, is cleaned with THF and ion exchange water.Pyridine hydrochloride
Go divided by silver nitrate aqueous solution added in washing lotion and do not observe white precipitate confirm.Recycle cleaned thick generation
Object carries out the vacuum drying of 12 hours in 100 DEG C.Obtained thick product is white powder, and yield 6.54g, yield is
87.6%.
(purifying)
Obtained thick product 2.5526g is made to be dissolved in acetic anhydride and toluene (volume ratio 1 in 90 DEG C：10) after mixed solvent,
Naturally it places and cools down and stand 72 hours.Filtering white powder be precipitated carries out the vacuum drying of 12 hours in 160 DEG C.Institute
The yield of obtained white powder is 1.3602g, and recrystallization yield is 53.3%.
The identification of B.TACHQ
Fourier-transform infrared spectrophotometer FT/IR4100 (Japanese light splitting companies are passed through by the product of recrystallization purifying
System), in 2928cm-1Aliphatic C-H stretching vibration absorption bands are confirmed, in 1861cm-1And 1778cm-1Confirm anhydride group C=
O stretching vibration absorption bands, in 1745cm-1Confirm ester group C=O stretching vibration absorption bands.
In addition, it is carried out using fourier transform NMR spectrophotometer JNM-ECP400 (JEOL systems)1H-NMR is measured, knot
Fruit can belong to (DMSO-d6,δ,ppm)：1.80-1.23 (m, 10H), 2.69 (t, J=12Hz, 1H), 7.50-7.18 (m,
3H), 8.33-8.29 (m, 2H), 8.71-8.65 (m, 4H), elemental analysis value are theoretical value C：66.67%th, H：3.73%, actual measurement
Value C：66.27%th, H：3.78%, it is TACHQ that can confirm product.
In addition, fusing point is measured by Differential Scanning Calorimetry analyzer DSC3100 (NETZSCH corporations), as a result in 229.1 DEG C
Show sharp melting peakss, it is high-purity thus to prompt the product.
2 ＞ of ＜ embodiments
A. the synthesis of the polyimides of the repetitive unit shown in formula (8)
(polymerization of polyamic acid) TACHQ/TFMB
Making 2,2 '-bis- (trifluoromethyl) benzidine (TFMB) 3mmol are dissolved in dehydration DMAC N,N' dimethyl acetamide (DMAc).At it
In be slowly added into embodiment 1 record TACHQ powder 3mmol, be stirred at room temperature 72 hours, be properly joined into DMAc to obtain
Polyamic acid (16.7 weight % of solid component concentration) as polyimide precursor.The intrinsic viscosity of obtained polyamic acid
For 1.72dL/g.
(chemical imidization reaction)
After obtained polyamic acid solution is diluted to about 10.0 weight % of solid component concentration with dehydration DMAc, on one side by it
It is stirred, 2.8mL (30mmol) acetic anhydrides is slowly added dropwise in room temperature on one side and the mixing of 1.2mL (15mmol) pyridine is molten
Liquid futher stirs 24 hours after completion of dropwise addition.Obtained polyimide solution is slowly added dropwise in a large amount of methanol
In precipitate polyimides.Obtained white depositions with methanol are fully cleaned, the vacuum of 12 hours is carried out in 100 DEG C
It is dry.Obtained fibrous polyimide powder is carried out1H-NMR is measured, and does not as a result observe that polyamic acid is distinctive
COOH protons (near δ=13ppm) and NHCO protons (near δ=11ppm) thus prompt chemical imidization to react
Into.The intrinsic viscosity of obtained polyimides is 2.55dL/g, is high molecular weight body.In addition, polyimide powder relative to
The dissolubility of solvent is as shown in table 1.Excellent solvent solubility is shown as can be known from Table 1.
B. the film of the preparation of polyimide solution and polyimide film
Above-mentioned polyimide powder is re-dissolved in gamma-butyrolacton (GBL) to prepare the uniform of 6.0 weight % while heating
Solution.By polyimide solution casting on the glass substrate, it is and 2 hours dry in 80 DEG C in hot-air drier.Then, even
With substrate in a vacuum, after 200 DEG C of dryings 1 hour and placing are cooled to room temperature, polyimide film is removed from glass substrate.It will
The polyimide film again in a vacuum, 200 DEG C of heat treatments 1 hour remove residual strain.
The infrared absorption spectrum of obtained polyimide film as shown in Figure 1, Dynamic Viscoelastic linearity curve as shown in Fig. 2, heat is special
Property optical characteristics is as shown in table 2.The polyimides of target can be accredited as according to Fig. 1.It is nearby seen in 225 DEG C as can be seen from FIG. 2
The drastically decline of storage modulus is measured, so as to show high thermoplasticity.According to table 2 coefficient of linear thermal expansion (CTE) down to
11.9ppm/K is colourless transparent film.These excellent characteristics are the effect as caused by the structure of formula (2).
3 ＞ of ＜ embodiments
A. the synthesis of the polyimides of the repetitive unit shown in following formula (9)
(polymerization of polyamic acid) TACHQ (80) 6FDA (20)/TFMB
By 2,2 '-bis- (trifluoromethyl) benzidine (TFMB) 3mmol are dissolved in dehydration DMAC N,N' dimethyl acetamide (DMAc).At it
In be slowly added into embodiment 1 record TACHQ powder 2.4mmol and 4,4 '-(hexafluoroisopropylidenyl) diphthalic anhydrides
(6FDA) powder 0.6mmol is stirred at room temperature 72 hours, is properly joined into DMAc and obtains the polyamides as polyimide precursor
Amino acid (22.7 weight % of solid component concentration).The intrinsic viscosity of obtained polyamic acid is 0.91dL/g.
(chemical imidization reaction)
After obtained polyamic acid solution is diluted to about 10.0 weight % of solid component concentration with dehydration DMAc, on one side by it
The mixed solution of 2.8mL (30mmol) acetic anhydrides and 1.2mL (15mmol) pyridine is slowly added dropwise in stirring in room temperature on one side,
It is stirred for after completion of dropwise addition 24 hours.Obtained polyimide solution is slowly added dropwise makes polyamides sub- in a large amount of methanol
Amine precipitates.Obtained white depositions with methanol are fully cleaned, the vacuum drying of 12 hours is carried out in 100 DEG C.To institute
Obtained fibrous polyimide powder carries out1H-NMR is measured, and does not as a result observe the distinctive COOH protons (δ of polyamic acid
Near=13ppm) and NHCO protons (near δ=11ppm), chemical imidization reaction is thus prompted to complete.It is obtained
The intrinsic viscosity of polyimides is 1.75dL/g, is high molecular weight body.In addition, dissolubility of the polyimide powder relative to solvent
As shown in table 1.Excellent solvent solubility is shown as can be known from Table 1.
B. the film of the preparation of polyimide solution and polyimide film
Above-mentioned polyimide powder is re-dissolved in cyclopentanone (CPN) to prepare the uniform molten of 8.0 weight % while heating
Liquid.By polyimide solution casting on the glass substrate, it is and 2 hours dry in 60 DEG C in hot-air drier.Then, together with
After substrate is in a vacuum, 200 DEG C of dryings 1 hour and placing are cooled to room temperature, polyimide film is removed from glass substrate.It should
Polyimide film again in a vacuum, 200 DEG C of heat treatment 1 hour to be to remove residual strain.Obtained polyimide film it is red
Outer absorption spectrum as shown in figure 3, Dynamic Viscoelastic linearity curve as shown in figure 4, thermal characteristics optical characteristics is as shown in table 2.According to fig. 3
The polyimides of target can be accredited as.The decline of storage modulus drastically, display are nearby observed in 225 DEG C as can be seen from FIG. 4
High thermoplasticity.Coefficient of linear thermal expansion (CTE) is colourless transparent film down to 24.7ppm/K according to table 2.These excellent specific properties
For effect caused by the structure as formula (2).
4 ＞ of ＜ embodiments
A. the synthesis of the polyimides of the repetitive unit shown in following formula (10)
(polymerization of polyamic acid) TACHQ (50) 6FDA (50)/TFMB
By 2,2 '-bis- (trifluoromethyl) benzidine (TFMB) 2mmol are dissolved in dehydration DMAC N,N' dimethyl acetamide (DMAc).At it
In be slowly added into embodiment 1 record TACHQ powder 1.0mmol and 4,4 '-(hexafluoroisopropylidenyl) diphthalic anhydrides
(6FDA) powder 1.0mmol is stirred at room temperature 72 hours, is properly joined into DMAc and obtains the polyamides as polyimide precursor
Amino acid (30 weight % of solid component concentration).
The intrinsic viscosity of obtained polyamic acid is 0.56dL/g.
(chemical imidization reaction)
After obtained polyamic acid solution is diluted to about 10.0 weight % of solid component concentration with dehydration DMAc, on one side by it
The mixed solution of 1.9mL (20mmol) acetic anhydrides and 0.8mL (10mmol) pyridine is slowly added dropwise in stirring in room temperature on one side,
It is futher stirred after completion of dropwise addition 24 hours.Obtained polyimide solution is slowly added dropwise to be made to gather in a large amount of methanol
Acid imide precipitates.Obtained white depositions with methanol are fully cleaned, the vacuum drying of 12 hours is carried out in 100 DEG C.
Obtained fibrous polyimide powder is carried out1H-NMR is measured, and does not as a result observe the distinctive COOH matter of polyamic acid
Sub (near δ=13ppm) and NHCO protons (near δ=11ppm) thus prompt chemical imidization reaction to complete.Gained
The intrinsic viscosity of the polyimides arrived is 0.76dL/g.In addition, dissolubility such as table 1 institute of the polyimide powder relative to solvent
Show.Excellent solvent solubility is shown according to table 1.
B. the film of the preparation of polyimide solution and polyimide film
Above-mentioned polyimide powder is re-dissolved in cyclopentanone (CPN) in room temperature to prepare the homogeneous solution of 23 weight %.It should
Polyimide solution is cast on the glass substrate, and 2 hours dry in 60 DEG C in hot-air drier.Then, exist together with substrate
In vacuum, after 200 DEG C of dryings 1 hour and placing are cooled to room temperature, polyimide film is removed from glass substrate.By polyamides Asia
Amine film again in a vacuum, 200 DEG C of heat treatment 1 hour to be to remove residual strain.
The infrared absorption spectrum of obtained polyimide film as shown in figure 5, Dynamic Viscoelastic linearity curve as shown in fig. 6, thermal characteristics/
Optical characteristics is as shown in table 2.The polyimides of target can be accredited as according to Fig. 5.Energy storage is nearby observed at 230 DEG C according to Fig. 6
The drastically decline of modulus, it is known that display high thermoplasticity is further colourless transparent film according to table 2.
1 ＞ of ＜ comparative examples
A. the synthesis of the polyimides of the repetitive unit shown in following formula (11)
(polymerization of polyamic acid) TAPh (100)/TFMB
By 2,2 '-bis- (trifluoromethyl) benzidine (TFMB) 3mmol are dissolved in dehydration n-methyl-2-pyrrolidone (NMP).At it
In be slowly added into synthesis example 2 record TAPh powder 3mmol, be stirred at room temperature 72 hours to obtain as polyimide precursor
Polyamic acid (20 weight % of solid component concentration).The intrinsic viscosity of obtained polyamic acid is 1.6dL/g.
B. the film of polyimide film
By polyamic acid solution casting on the glass substrate, it is and 3 hours dry in 80 DEG C in hot-air drier.Then, together with
Hot-imide that substrate carries out 1 hour in 250 DEG C in a vacuum and after 350 DEG C carry out the hot-imide of 1 hour, will
Polyimide film is removed from glass substrate.By the polyimide film again in a vacuum, 200 DEG C heat treatment 1 hour it is residual to remove
Stay strain.
Thermal characteristics/optical characteristics of obtained polyimide film is as shown in table 2.It is poor light transmission according to table 2, and
There are fierce xanthochromia and muddiness.Think since the cyclohexyl in the polyimides of the repetitive unit of formula (8) is changed into phenyl, so
The optical characteristics of the polyimide film of the repetitive unit of formula (11) is significantly deteriorated.I.e., it is known that even similary bulky structure,
The structure of cyclohexyl is extremely useful.
2 ＞ of ＜ comparative examples
A. the synthesis of the polyimides of the repetitive unit shown in formula (12)
(polymerization of polyamic acid) TAHQ/TFMB
By 2,2 '-bis- (trifluoromethyl) benzidine (TFMB) 2mmol are dissolved in dehydration DMAC N,N' dimethyl acetamide (DMAc).At it
In be slowly added into TAHQ powder 2mmol recorded in synthesis example 1, be stirred at room temperature 72 hours, be properly joined into DMAc and come
To the polyamic acid (11.4 weight % of solid component concentration) as polyimide precursor.The intrinsic viscosity of obtained polyamic acid
It spends for 4.45dL/g.
(chemical imidization reaction)
After obtained polyamic acid solution is diluted to about 10.0 weight % of solid component concentration with dehydration DMAc, on one side by it
It is stirred, 1.9mL (20mmol) acetic anhydrides is slowly added dropwise in room temperature on one side and the mixing of 0.8mL (10mmol) pyridine is molten
Liquid, further loses flowability through 3 hours solution and gelation after completion of dropwise addition.From the repetitive unit of formula (8) and formula (12)
The comparison of polyimides, it is known that bulky cyclohexyl greatly improves the dissolubility relative to solvent.
B. the film of polyimide film
By the casting of above-mentioned polyamic acid solution on the glass substrate, it is and 2 hours dry in 60 DEG C in hot-air drier.Then,
The hot-imide and the hot acid imide in 250 DEG C of progress 2 hours for carrying out 0.5 hour in 200 DEG C in a vacuum together with substrate
After change, polyimide film is removed from glass substrate.By the polyimide film again in a vacuum, 300 DEG C heat treatment 1 hour with
Remove residual strain.
The Dynamic Viscoelastic linearity curve of obtained polyimide film is as shown in fig. 7, thermal characteristics optical characteristics is as shown in table 2.Root
Understand that the temperature that storage modulus is begun to decline is up to 375 DEG C according to Fig. 7, so compared with the polyimides of the repetitive unit of formula (8)
Hot-workability is poor.In addition, yellow chromaticity and mist degree are also high, optical characteristics is also poor.
I.e., it is known that the cyclohexyl of formula (2) plays epochmaking effect.
The dissolubility test result of 1 polyimide powder of table
The thermal characteristics and optical characteristics of 2 polyimide film of table
Number in () is the thickness of polyimide film
Claims (5)
1. a kind of tetracarboxylic acid dianhydride, which is characterized in that by following formula (1) Suo Shi,
2. a kind of polyimides, which is characterized in that there is the repetitive unit shown in following formula (2),
3. polyimides according to claim 2, which is characterized in that relative to whole repetitive units in polyimides,
The containing ratio of repetitive unit shown in formula (2) is more than 55mol%.
4. a kind of polyimide solution contains the polyimides and organic solvent described in Claims 2 or 3, which is characterized in that Gu
Body constituent concentration is more than 5 weight %.
A kind of 5. polyimides formed body, which is characterized in that the formed body for the polyimides described in Claims 2 or 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-192377 | 2015-09-30 | ||
| JP2015192377 | 2015-09-30 | ||
| PCT/JP2016/078448 WO2017057360A1 (en) | 2015-09-30 | 2016-09-27 | Novel tetracarboxylic dianhydride, polyimide derived from said tetracarboxylic dianhydride, and molded article produced from said polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108137804A true CN108137804A (en) | 2018-06-08 |
| CN108137804B CN108137804B (en) | 2021-01-19 |
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| CN201680056630.8A Active CN108137804B (en) | 2015-09-30 | 2016-09-27 | Novel tetracarboxylic dianhydride, polyimide derived from the tetracarboxylic dianhydride, and molded article comprising the polyimide |
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| JP (1) | JP6715496B2 (en) |
| KR (2) | KR102591070B1 (en) |
| CN (1) | CN108137804B (en) |
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| WO (1) | WO2017057360A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229331A (en) * | 2019-04-28 | 2019-09-13 | 南京岳子化工有限公司 | A kind of thermoplastic polyimide resin powder and preparation method thereof |
| CN112194792A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | High-strength low-thermal-expansion transparent polyimide and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021063212A (en) * | 2019-10-15 | 2021-04-22 | 住友化学株式会社 | Optical film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09258229A (en) * | 1996-03-25 | 1997-10-03 | Japan Synthetic Rubber Co Ltd | Liquid crystal orienting agent |
| JP2004182757A (en) * | 2002-11-29 | 2004-07-02 | Kanegafuchi Chem Ind Co Ltd | Polyimide resin and its production method |
| CN101195711A (en) * | 2006-12-06 | 2008-06-11 | 大立高分子工业股份有限公司 | Polyamic acid component and alignment film produced by the same |
| WO2008091011A1 (en) * | 2007-01-26 | 2008-07-31 | Honshu Chemical Industry Co., Ltd. | Novel ester group-containing tetracarboxylic acid dianhydride, novel polyesterimide precursor derived therefrom, and polyesterimide |
| JP2013082876A (en) * | 2011-03-16 | 2013-05-09 | Kaneka Corp | Polyimide solution and polyimide film obtained from the solution |
| CN102317352B (en) * | 2009-02-12 | 2014-04-09 | 本州化学工业株式会社 | Ester group-containing tetracarboxylic acid dianhydride, polyester polyimide precursor, polyesterimide, and methods for producing same |
| CN104151823A (en) * | 2014-09-02 | 2014-11-19 | 长春聚明光电材料有限公司 | Polyimide film and preparation methods thereof |
-
2016
- 2016-09-27 CN CN201680056630.8A patent/CN108137804B/en active Active
- 2016-09-27 KR KR1020187011187A patent/KR102591070B1/en active IP Right Grant
- 2016-09-27 WO PCT/JP2016/078448 patent/WO2017057360A1/en active Application Filing
- 2016-09-27 KR KR1020237015346A patent/KR102619074B1/en active IP Right Grant
- 2016-09-27 JP JP2017543430A patent/JP6715496B2/en active Active
- 2016-09-30 TW TW105131577A patent/TWI708769B/en active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09258229A (en) * | 1996-03-25 | 1997-10-03 | Japan Synthetic Rubber Co Ltd | Liquid crystal orienting agent |
| JP2004182757A (en) * | 2002-11-29 | 2004-07-02 | Kanegafuchi Chem Ind Co Ltd | Polyimide resin and its production method |
| CN101195711A (en) * | 2006-12-06 | 2008-06-11 | 大立高分子工业股份有限公司 | Polyamic acid component and alignment film produced by the same |
| WO2008091011A1 (en) * | 2007-01-26 | 2008-07-31 | Honshu Chemical Industry Co., Ltd. | Novel ester group-containing tetracarboxylic acid dianhydride, novel polyesterimide precursor derived therefrom, and polyesterimide |
| CN102317352B (en) * | 2009-02-12 | 2014-04-09 | 本州化学工业株式会社 | Ester group-containing tetracarboxylic acid dianhydride, polyester polyimide precursor, polyesterimide, and methods for producing same |
| JP2013082876A (en) * | 2011-03-16 | 2013-05-09 | Kaneka Corp | Polyimide solution and polyimide film obtained from the solution |
| CN104151823A (en) * | 2014-09-02 | 2014-11-19 | 长春聚明光电材料有限公司 | Polyimide film and preparation methods thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229331A (en) * | 2019-04-28 | 2019-09-13 | 南京岳子化工有限公司 | A kind of thermoplastic polyimide resin powder and preparation method thereof |
| CN112194792A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | High-strength low-thermal-expansion transparent polyimide and preparation method thereof |
| CN112194792B (en) * | 2020-06-16 | 2022-03-29 | 中国科学院长春应用化学研究所 | High-strength low-thermal-expansion transparent polyimide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017057360A1 (en) | 2017-04-06 |
| KR102591070B1 (en) | 2023-10-17 |
| JPWO2017057360A1 (en) | 2018-08-30 |
| KR20180061248A (en) | 2018-06-07 |
| TWI708769B (en) | 2020-11-01 |
| CN108137804B (en) | 2021-01-19 |
| JP6715496B2 (en) | 2020-07-01 |
| TW201730172A (en) | 2017-09-01 |
| KR20230066490A (en) | 2023-05-15 |
| KR102619074B1 (en) | 2023-12-27 |
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