CN108034049A - A kind of polyimide resin and preparation method thereof - Google Patents
A kind of polyimide resin and preparation method thereof Download PDFInfo
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- CN108034049A CN108034049A CN201711373126.3A CN201711373126A CN108034049A CN 108034049 A CN108034049 A CN 108034049A CN 201711373126 A CN201711373126 A CN 201711373126A CN 108034049 A CN108034049 A CN 108034049A
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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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to a kind of polyimide resin and preparation method thereof, the structural formula such as following formula (I) of polyimide resin is shown：Wherein, n is greater than 0 integer；Ar1ForAny one in structural formula；Ar2For any one in the residue of fragrant diphenol monomer of the structural formula as shown in following formula (II) or following formula (III),R1, R2, R3, R4For any one in hydrogen atom, alkyl, phenyl or substituted-phenyl, the horizontal line "-" for being connected in phenyl ring represents Ar2With the connecting key of oxygen atom.Its preparation method comprises the following steps：Under protective atmosphere; by structural formula such as formula (II) or the fragrant diphenol monomer of formula (III) and 1; 4 pairs of (4 fluoro acid imide) hexamethylenes mix in solvent, heating reaction are carried out under basic catalyst, obtains polyimide solution；By polyimide solution and precipitant mix, drying after precipitation is collected, obtains the polyimide resin with excellent heat resistance and optical transmittance.
Description
Technical field
The present invention relates to polyimides and its preparation field, more particularly to a kind of polyimide resin and its preparation side
Method.
Background technology
In recent years, as the optical field such as the development of new high-tech industry, light guide, waveguide and liquid crystal display is to high resistance to
The demand of the polyimides of hot, high printing opacity is more and more urgent.But traditional polyimides generally shows yellow, the big day of one's doom
Polyimides further applying in photoelectric material is made.Therefore, exploitation is aobvious available for flexible solar battery bottom plate, flexibility
Show or illuminate the high temperature resistant in the fields such as bottom plate, clear polyimides resin material has very important application value.
At present, it is to be obtained to have fat with the dianhydride or diamine monomer of full lipid structure to reduce the most effective method of its color
The polyimides of unit, fundamentally suppresses the formation of charge transfer complex.But (1), the dianhydride of lipid structure are due to list
The reduction of precursor reactant activity, leads to not the polyimides for obtaining high molecular weight, as Publication No. CN101084254A,
The Chinese invention patent of CN101831074A, CN1034707A are all reported with alicyclic dianhydride monomer synthesis of polyimides；
(2), the diamines of lipid structure, such as common Isosorbide-5-Nitrae-cyclohexane diamine, due to its alkalescence it is too strong, during preparation easily into
Salt out, it is necessary to be regulated and controled to pH value (Macromolecules, 2007,40,3527), or use the method for heating
(High Performance Polymers, 2001,13, S93.), but heating easily allows polyamic acid to degrade, and causes to prepare
Complicated condition is harsh.Meanwhile the above method is suitable only for trans Isosorbide-5-Nitrae-cyclohexane diamine, for the Isosorbide-5-Nitrae-hexamethylene closed along back mixing
Alkane diamines, can not all prepare flexible film.In this regard, the Chinese invention patent of Publication No. CN105754097A reports use
Phenolphthalein series and phenol red series diphenol monomer are prepared soluble clear polyimides, but its resistance to elevated temperatures (glass
Change transition temperature (Tg) and heat endurance (Td5%) needs to be further improved, especially because the wherein presence of ester bond, sulfuryl,
Cause thermal polymer degradation temperature relatively low.
The content of the invention
Based on this, it is necessary in view of the above-mentioned problems, providing a kind of excellent with excellent heat resistance and optical transmittance etc.
Polyimides of point and preparation method thereof, the preparation method is easy to operate, easily controllable.
A kind of clear polyimides resin, shown in the structural formula such as following formula (I) of the polyimide resin：
Wherein, n is greater than 0 integer；
Ar1ForAny one in structural formula；
Ar2For any one in the residue of fragrant diphenol monomer of the structural formula as shown in following formula (II) or following formula (III),
R1, R2, R3, R4It is former for hydrogen
Any one in son, alkyl, phenyl or substituted-phenyl, the horizontal line "-" for being connected in phenyl ring represents Ar2With the connection of oxygen atom
Key.
Structure aboveRepresent trans cvclohexvl groups, structural formulaRepresent cis
Cyclohexane group, structural formulaRepresent the trans cvclohexvl groups of arbitrary proportion mixing and cis cyclohexyl
Group.
The more preferable amido link (- CO-NH-) of heat endurance or carbon-carbon bond (- C=are introduced in above-mentioned polyimide resin
C-), amido link (- CO-NH-) or carbon-carbon bond (- C=C-) are used to substitute in the prior art using phenolphthalein series and phenol red series
Ester bond (- COO-) in the polyimides that diphenol monomer is prepared, therefore, polyimide resin of the present invention have higher
Thermal degradation temperature (Td5%).Meanwhile in preparation method, using fragrant diphenol monomer as raw material, since fragrant diphenol monomer has
The rotation steric hindrance of bigger, can suppress charge transfer complex in polyimide molecule and intermolecular formation, so can carry
The transparent performance and glass transition temperature (Tg) of high polyimides.Specifically, white, glass is presented in the polyesterimide resin
Glass transition temperature is 300 DEG C~400 DEG C, and 5% thermal weight loss temperature is more than 400 DEG C under nitrogen environment, and the light at 400nm is saturating
Rate is crossed more than 80%.The polyimide resin can be served as a contrast as the flexible substrate material of solar cell, flexible transparent conducting film
Bottom material, liquid crystal display material etc. are further applied.
In one of the embodiments, the Ar1ForIt is any in structural formula
It is a kind of.
In one of the embodiments, the Ar2For appointing in the residue of structural formula fragrant diphenol monomer as follows
Meaning is a kind of：
Wherein, the horizontal line "-" for being connected in phenyl ring represents Ar2With the connecting key of oxygen atom.
The present invention also provides a kind of preparation method of polyimide resin, the preparation method comprises the following steps：
Under protective atmosphere, fragrant diphenol monomer is mixed with Isosorbide-5-Nitrae-bis- (4- fluoro acid imides) hexamethylene in solvent,
Heating reaction is carried out under basic catalyst, obtains polyimide solution；
By the polyimide solution and precipitant mix, drying after precipitation is collected, obtains polyimide resin.
The preparation method of above-mentioned polyimide resin, traditional two are substituted using the method for aromatic nucleophilic substitution reaction
Acid anhydride diamines polycondensation method, overcome causes when prepared by traditional dianhydride diamines polycondensation since Isosorbide-5-Nitrae-cyclohexane diamine alkalescence is too strong
Into the problem of salting out.The preparation method also has the advantages that easy to operate, easily controllable.
In one of the embodiments, shown in the structural formula such as following formula (IV) or following formula (V) of the fragrant diphenol monomer：
Wherein, R1, R2, R3, R4For any one in hydrogen atom, alkyl, phenyl or substituted-phenyl.
Above-mentioned Ar2In fragrant diphenol monomer in, the fragrant diphenol monomer of structural formula shown in formula (IV) passes through corresponding
Phenolphthalein and primary amine are prepared, and the fragrant diphenol monomer of structural formula shown in formula (V) can be directly commercially available.
In one of the embodiments, the Isosorbide-5-Nitrae-bis- (4- fluoro acid imides) hexamethylene is Isosorbide-5-Nitrae-bis- (4- fluoro acyl Asias
Amine) cis hexamethylene, one or both of double (4- fluoro acid imide) trans cyclohexanes of 1,4-；
The structural formula of double (the 4- fluoro acid imide) trans cyclohexanes of the 1,4- is as follows：
The structural formula of double (4- fluoro acid imide) the cis hexamethylenes of the 1,4- is as follows：
Double (the 4- fluoro acid imide) trans cyclohexanes of double (4- fluoro acid imide) the cis hexamethylenes and 1,4- of the 1,4- are mixed
The structural formula of compound is as follows：
In one of the embodiments, mole of the fragrant diphenol monomer and Isosorbide-5-Nitrae-bis- (4- fluoro acid imides) hexamethylene
Than 1：(0.95-1.05).
In one of the embodiments, the basic catalyst is carbonate, in bicarbonate, hydroxide, organic base
At least one, the mole of the basic catalyst is the 100%~150% of the mole of the fragrant diphenol monomer.Its
In, carbonate is stable and the polymer viscosity of preparation is high, therefore basic catalyst is more preferably carbonate.
In one of the embodiments, the temperature of the heating reaction is 180 DEG C~230 DEG C, and the solvent is non-for polarity
Proton solvent.
In one of the embodiments, the polar non-solute is selected from n,N-Dimethylformamide, N, N- diformazans
At least one of yl acetamide, 1-methyl-2-pyrrolidinone.
In one of the embodiments, the precipitating reagent is selected from least one of ethanol, methanol, acetone, water.
In one of the embodiments, the described and temperature of the polyimide solution of precipitant mix is 70 DEG C~90 DEG C,
Preferably 80 DEG C.
In one of the embodiments, the protective atmosphere is nitrogen or inert gas, and the inert gas selects this
The common inert gas in field, such as argon gas.
In one of the embodiments, further, by the step of the polyimide solution and the precipitant mix
It is further comprising the steps of before rapid：The polyimides in the polyimide solution is blocked by end-capping reagent, the envelope
Shown in the structure such as following formula (VI) for holding agent：
In one of the embodiments, the mole of the end-capping reagent is the 1% of the mole of the fragrant diphenol monomer
~5%.After end-capping reagent, the heat endurance and processability of obtained polyimide resin further improve.
Compared with prior art, the invention has the advantages that：
White is presented in polyimide resin, obtained Kapton to be transparent, glass transition temperature for 300 DEG C~
400 DEG C, 5% thermal weight loss temperature is more than 400 DEG C under nitrogen environment, and the light transmission rate at 400nm is more than 80%, can be too
It is positive can the association area such as the flexible substrate material of battery, flexible transparent conducting film substrate material, liquid crystal display material have it is preferable
Application prospect.
The preparation method of polyimide resin has the advantages that easy to operate, easily controllable.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1：
In the present embodiment, the structural formula of raw material fragrance diphenol monomer is as follows：
Obtained polyimide resin has following structural formula：
Specifically preparation method is：It is under nitrogen protection, the Isosorbide-5-Nitrae of 2.0544 (5.0mmol)-bis- (4- fluoro acid imides) is trans
Hexamethylene, the fragrant diphenol monomer of 1.65684g (5.0mmol), the potassium carbonate of 0.7614g (5.5mmol), 10 milliliters of N, N- bis-
Methylacetamide and 15 milliliters of dimethylbenzene (effect of dimethylbenzene is water entrainer) are added in 100mL reaction bulbs, are warming up to 180 DEG C
Stir 5 it is small when, be then progressively warming up to 220 DEG C of reaction 6h, sticky polyimide solution be made.Polyimide solution is cooled down
To 80 DEG C, n,N-dimethylacetamide dilution is added, is then added in ethanol and precipitates, the filtered polyamides for obtaining threadiness is sub-
Amine, boils and washes drying, obtain polyimide powder.The glass transition temperature of obtained polyimide powder is 316 DEG C, nitrogen
5% thermal weight loss temperature is 434 DEG C under environment.
Obtained polyimide powder is configured to the solution that concentration expressed in percentage by weight is 10% with n,N-dimethylacetamide,
Its solution is coated uniformly on the glass plate of cleaning with the tape casting, glass plate is positioned in 80 DEG C of drying box overnight, so
Heat up afterwards according to following procedure：100 DEG C, 1 it is small when；150 DEG C, 1 it is small when；200 DEG C, 1 it is small when.Treat that temperature is cooled to room temperature to take
Go out glass plate, be placed on demoulding in warm water, film is then placed in 100 DEG C of drying boxes dry water removal, obtains polyimides
Film, its thickness are 20 μm.
It is as follows to detect data：FT-IR (film):1776,1710,1373,1238,749cm-1；Pass through uv-vis spectra
The H103 resin of film prepared by the instrument test above method, the UV cut-off wavelength of the film is 350nm, at 400nm
Light transmission rate be 83%.
Embodiment 2：
In the present embodiment, the structural formula of raw material fragrance diphenol monomer is as follows：
Obtained polyimide resin has following structural formula：
Specifically preparation method is：It is under nitrogen protection, the Isosorbide-5-Nitrae of 4.1004 (10.0mmol)-bis- (4- fluoro acid imides) is anti-
Formula hexamethylene, the fragrant diphenol monomer of 3.5947g (10.0mmol), the potassium carbonate of 1.5230g (11.0mmol), 40 milliliters of N, N-
The dimethylbenzene of dimethylacetylamide and 30 milliliters is added in 150mL reaction bulbs, be warming up to 190 DEG C of stirrings 5 it is small when, then progressively rise
Sticky polyimide solution is made to 210 DEG C of reaction 8h in temperature.Polyimide solution is cooled to 80 DEG C, adds N, N- diformazans
Yl acetamide dilutes, and is then added in ethanol and precipitates, filtered to obtain the polyimides of threadiness, boils and washes drying, is gathered
Acid imide powder.The glass transition temperature of obtained polyimide powder is 306 DEG C, 5% thermal weight loss under nitrogen environment
Temperature is 421 DEG C.
Obtained polyimide powder is configured to the solution that concentration expressed in percentage by weight is 10% with n,N-dimethylacetamide,
Its solution is coated uniformly on the glass plate of cleaning with the tape casting, glass plate is positioned in 80 DEG C of drying box overnight, so
Heat up afterwards according to following procedure：100 DEG C, 1 it is small when；150 DEG C, 1 it is small when；200 DEG C, 1 it is small when.Treat that temperature is cooled to room temperature to take
Go out glass plate, be placed on demoulding in warm water, film is then placed in 100 DEG C of drying boxes dry water removal, obtains polyimides
Film, its thickness are 20 μm.
It is as follows to detect data：FT-IR (film):1771,1706,1369,1238,749cm-1；Pass through uv-vis spectra
The H103 resin of film prepared by the instrument test above method, the UV cut-off wavelength of the film is 345nm, at 400nm
Light transmission rate be 87%.
Embodiment 3：
In the present embodiment, the structural formula of raw material fragrance diphenol monomer is as follows：
Obtained polyimide resin has following structural formula：
Specifically preparation method is：It is under nitrogen protection, the Isosorbide-5-Nitrae of 2.0515 (5.0mmol)-bis- (4- fluoro acid imides) is trans
Hexamethylene, the fragrant diphenol monomer of 1.8923g (5.0mmol), the potassium carbonate of 0.7612g (5.5mmol), 10 milliliters of N, N- diformazans
Yl acetamide and 15 milliliters of dimethylbenzene are added in 100mL reaction bulbs, are warming up to 200 DEG C of reaction 8h, and the polyamides for being made sticky is sub-
Amine aqueous solution.Polyimide solution is cooled to 80 DEG C, n,N-dimethylacetamide dilution is added, is then added in ethanol and sinks
Form sediment, it is filtered to obtain the polyimides of threadiness, boil and wash drying, obtain polyimide powder.Obtained polyimide powder
Glass transition temperature be 310 DEG C, under nitrogen environment 5% thermal weight loss temperature be 432 DEG C.
Obtained polyimide powder is configured to the solution that concentration expressed in percentage by weight is 10% with n,N-dimethylacetamide,
Its solution is coated uniformly on the glass plate of cleaning with the tape casting, glass plate is positioned in 80 DEG C of drying box overnight, so
Heat up afterwards according to following procedure：100 DEG C, 1 it is small when；150 DEG C, 1 it is small when；200 DEG C, 1 it is small when.Treat that temperature is cooled to room temperature to take
Go out glass plate, be placed on demoulding in warm water, film is then placed in 100 DEG C of drying boxes dry water removal, obtains polyimides
Film, its thickness are 20 μm.
The H103 resin of film prepared by the above method is tested by ultraviolet-visual spectrometer, the UV absorption of the film is cut
Only wavelength is 347nm, and the light transmission rate at 400nm is 80%.
Embodiment 4：
In the present embodiment, the structural formula of raw material fragrance diphenol monomer is as follows：
Obtained polyimide resin material has following structural formula：
Specifically preparation method is：It is under nitrogen protection, the Isosorbide-5-Nitrae of 2.0515 (5.0mmol)-bis- (4- fluoro acid imides) is trans
Hexamethylene, the fragrant diphenol monomer of 2.0326g (5.0mmol), the potassium carbonate of 0.7612g (5.5mmol), 10 milliliters of N, N- diformazans
Yl acetamide and 15 milliliters of dimethylbenzene are added in 100mL reaction bulbs, are warming up to 200 DEG C of reaction 8h, and the polyamides for being made sticky is sub-
Amine aqueous solution.Polyimide solution is cooled to 80 DEG C, n,N-dimethylacetamide dilution is added, is then added in ethanol and sinks
Form sediment, it is filtered to obtain the polyimides of threadiness, boil and wash drying, obtain polyimide powder.Obtained polyimide powder
Glass transition temperature be 360 DEG C, under nitrogen environment 5% thermal weight loss temperature be 431 DEG C.
Obtained polyimide powder is configured to the solution that concentration expressed in percentage by weight is 10% with n,N-dimethylacetamide,
Its solution is coated uniformly on the glass plate of cleaning with the tape casting, glass plate is positioned in 80 DEG C of drying box overnight, so
Heat up afterwards according to following procedure：100 DEG C, 1 it is small when；150 DEG C, 1 it is small when；200 DEG C, 1 it is small when.Treat that temperature is cooled to room temperature to take
Go out glass plate, be placed on demoulding in warm water, film is then placed in 100 DEG C of drying boxes dry water removal, obtains polyimides
Film, its thickness are 20 μm.
The H103 resin of film prepared by the above method is tested by ultraviolet-visual spectrometer, the UV absorption of the film is cut
Only wavelength is 323nm, and the light transmission rate at 400nm is 86%.
Embodiment 5：
In the present embodiment, the structural formula of raw material fragrance diphenol monomer is as follows：
Obtained polyimide resin material has following structural formula：
Wherein trans/cis=5/1 in cyclohexane structure
Specifically preparation method is：It is under nitrogen protection, the Isosorbide-5-Nitrae of 2.0515 (5.0mmol)-bis- (4- fluoro acid imides) is cis
Mixture, the fragrant diphenol list of 2.0326g (5.0mmol) of hexamethylene and double (the 4- fluoro acid imide) trans cyclohexanes of 1,4-
It is anti-that body, the potassium carbonate of 0.7612g (5.5mmol), 10 milliliters of DMAC N,N' dimethyl acetamides and 15 milliliters of dimethylbenzene add 100mL
Answer in bottle, be warming up to 200 DEG C of reaction 8h, sticky polyimide solution is made.Polyimide solution is cooled to 80 DEG C, is added
N,N-dimethylacetamide dilutes, and is then added in ethanol and precipitates, filtered to obtain the polyimides of threadiness, boils and washes baking
It is dry, obtain polyimide powder.The glass transition temperature of obtained polyimide powder is 344 DEG C, 5% under nitrogen environment
Thermal weight loss temperature be 426 DEG C.
Obtained polyimide powder is configured to the solution that concentration expressed in percentage by weight is 10% with n,N-dimethylacetamide,
Its solution is coated uniformly on the glass plate of cleaning with the tape casting, glass plate is positioned in 80 DEG C of drying box overnight, so
Heat up afterwards according to following procedure：100 DEG C, 1 it is small when；150 DEG C, 1 it is small when；200 DEG C, 1 it is small when.Treat that temperature is cooled to room temperature to take
Go out glass plate, be placed on demoulding in warm water, film is then placed in 100 DEG C of drying boxes dry water removal, obtains polyimides
Film, its thickness are 18 μm.
The H103 resin of film prepared by the above method is tested by ultraviolet-visual spectrometer, the UV absorption of the film is cut
Only wavelength is 345nm, and the light transmission rate at 400nm is 83%.
Embodiment 6：
In the present embodiment, the structural formula of raw material fragrance diphenol monomer is as follows：
The structural formula of end-capping reagent is as follows：
Obtained polyimide resin material has following structural formula：
Wherein trans/cis=5/1 in cyclohexane structure
Specifically preparation method is：It is under nitrogen protection, the Isosorbide-5-Nitrae of 2.0515 (5.0mmol)-bis- (4- fluoro acid imides) is cis
Mixture, the fragrant diphenol list of 2.0326g (5.0mmol) of hexamethylene and double (the 4- fluoro acid imide) trans cyclohexanes of 1,4-
It is anti-that body, the potassium carbonate of 0.7612g (5.5mmol), 10 milliliters of DMAC N,N' dimethyl acetamides and 15 milliliters of dimethylbenzene add 100mL
Answer in bottle, be warming up to 230 DEG C of reaction 8h, then add end-capping reagent 0.1mmol, sticky polyimide solution is made.By polyamides
Imide liquor is cooled to 80 DEG C, adds n,N-dimethylacetamide dilution, is then added in ethanol and precipitates, filtered to obtain fibre
The polyimides of shape is tieed up, boils and washes drying, obtain polyimide powder.The glass transition temperature of obtained polyimide powder
For 347 DEG C, 5% thermal weight loss temperature is 436 DEG C under nitrogen environment.
Obtained polyimide powder is configured to the solution that concentration expressed in percentage by weight is 10% with n,N-dimethylacetamide,
Its solution is coated uniformly on the glass plate of cleaning with the tape casting, glass plate is positioned in 80 DEG C of drying box overnight, so
Heat up afterwards according to following procedure：100 DEG C, 1 it is small when；150 DEG C, 1 it is small when；200 DEG C, 1 it is small when.Treat that temperature is cooled to room temperature to take
Go out glass plate, be placed on demoulding in warm water, film is then placed in 100 DEG C of drying boxes dry water removal, obtains polyimides
Film, its thickness are 18 μm.
The H103 resin of film prepared by the above method is tested by ultraviolet-visual spectrometer, the UV absorption of the film is cut
Only wavelength is 345nm, and the light transmission rate at 400nm is 85%.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of polyimide resin, it is characterised in that shown in the structural formula such as following formula (I) of the clear polyimides resin：
Wherein, n is greater than 0 integer；
Ar1ForAny one in structural formula；
Ar2For any one in the residue of fragrant diphenol monomer of the structural formula as shown in following formula (II) or following formula (III),R1, R2, R3, R4For hydrogen atom, alkyl, benzene
Any one in base or substituted-phenyl, the horizontal line "-" for being connected in phenyl ring represents Ar2With the connecting key of oxygen atom.
2. polyimide resin according to claim 1, it is characterised in that the Ar1ForAny one in structural formula.
3. polyimide resin according to claim 1, it is characterised in that the Ar2For structural formula fragrance as follows
Any one in the residue of diphenol monomer：
Wherein, the horizontal line "-" for being connected in phenyl ring represents Ar2With the connecting key of oxygen atom.
It is 4. a kind of such as the preparation method of claims 1 to 3 any one of them polyimide resin, it is characterised in that described
Preparation method comprises the following steps：
Under protective atmosphere, fragrant diphenol monomer is mixed with Isosorbide-5-Nitrae-bis- (4- fluoro acid imides) hexamethylene in solvent, in alkalescence
Heating reaction is carried out under catalyst, obtains polyimide solution；
By the polyimide solution and precipitant mix, drying after precipitation is collected, obtains polyimide resin.
5. the preparation method of polyimide resin according to claim 4, it is characterised in that the fragrance diphenol monomer
Shown in structural formula such as following formula (IV) or following formula (V)：
Wherein, R1, R2, R3, R4For any one in hydrogen atom, alkyl, phenyl or substituted-phenyl.
6. the preparation method of polyimide resin according to claim 4, it is characterised in that the Isosorbide-5-Nitrae-bis- (4- fluoro
Acid imide) hexamethylene is double (4- fluoro acid imide) the cis hexamethylenes of 1,4-, double (the 4- fluoro acid imide) trans cyclohexanes of 1,4-
One or both of.
7. the preparation method of polyimide resin according to claim 4, it is characterised in that the basic catalyst is carbon
At least one of hydrochlorate, bicarbonate, hydroxide, organic base, the mole of the basic catalyst is described fragrant two
The 100%~150% of the mole of phenol monomer.
8. the preparation method of polyimide resin according to claim 4, it is characterised in that the temperature of the heating reaction
For 180 DEG C~230 DEG C, the solvent is polar non-solute.
9. the preparation method of polyimide resin according to claim 4, it is characterised in that it is further, by described in
It is further comprising the steps of before the step of polyimide solution and the precipitant mix：It is sub- to the polyamides by end-capping reagent
Polyimides in amine aqueous solution is blocked, shown in the structure such as following formula (VI) of the end-capping reagent：
10. the preparation method of polyimide resin according to claim 9, it is characterised in that mole of the end-capping reagent
Measure 1%~5% of the mole for the fragrant diphenol monomer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503835A (en) * | 2018-09-20 | 2019-03-22 | 中国科学院宁波材料技术与工程研究所 | A kind of polyetherimide and preparation method thereof |
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| US4870155A (en) * | 1987-12-02 | 1989-09-26 | Amoco Corporation | Novel poly (etherimide) compositions |
| CN105754097A (en) * | 2016-03-17 | 2016-07-13 | 中国科学院宁波材料技术与工程研究所 | Transparent polyimide resin and preparation method thereof |
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| US4870155A (en) * | 1987-12-02 | 1989-09-26 | Amoco Corporation | Novel poly (etherimide) compositions |
| CN105754097A (en) * | 2016-03-17 | 2016-07-13 | 中国科学院宁波材料技术与工程研究所 | Transparent polyimide resin and preparation method thereof |
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| NAFEESA MUSHTAQ ET AL.: "Synthesis of cardo containing asymmetric poly(ether-naphthalimide-phthalimide)s", 《POLYMINT.》 * |
| 唐咏梅 等: "芳香亲核取代反应合成cardo型透明聚酰亚胺", 《中国化学会2017全国高分子学术论文报告会摘要集-主题K:高性能高分子》 * |
| 李兰: "芳香亲核取代法合成基于1,4-环己烷二胺的透明聚酰亚胺及其性能研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503835A (en) * | 2018-09-20 | 2019-03-22 | 中国科学院宁波材料技术与工程研究所 | A kind of polyetherimide and preparation method thereof |
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| CN108034049B (en) | 2020-11-06 |
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