CN105085912B - A kind of transparent polyester imide resin and preparation method thereof - Google Patents
A kind of transparent polyester imide resin and preparation method thereof Download PDFInfo
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- CN105085912B CN105085912B CN201510482834.5A CN201510482834A CN105085912B CN 105085912 B CN105085912 B CN 105085912B CN 201510482834 A CN201510482834 A CN 201510482834A CN 105085912 B CN105085912 B CN 105085912B
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Abstract
The invention discloses a kind of transparent polyester imide resin and the preparation method that passes through terephthalic acid (TPA) two (3,4 dicarboxylic acid anhydride) acrylate monomers and binary primary amine monomer polycondensation reaction.In the design of dianhydride, by reducing the electron affinity of the dianhydride, inhibits charge transfer complex in polyesterimide intramolecular and intermolecular formation, improve transparent performance.The glass transition temperature of gained polyesterimide resin is 200 DEG C~350 DEG C, light transmission rate at 400nm is 70%~90%, the water absorption rate of film is less than 0.5%, has preferable application prospect in fields such as the flexible substrate material of solar cell, flexible transparent conducting film substrate material, liquid crystal display materials.
Description
Technical field
The present invention relates to polyimides and its preparation fields, and in particular to a kind of transparent polyester imide resin and its preparation
Method.
Background technology
Polyimides is most important kind in the aromatic heterocyclic copolymer to grow up nearly half a century, and uses temperature
Highest a kind of high molecular material is spent, there is the very excellent synthesis such as high mechanical strength, high temperature resistant, chemical stabilization, creep resistant
Performance is widely used in Aeronautics and Astronautics, electrical, machinery, microelectronics, chemical industry etc..
Recently as the development of new high-tech industry, the optical fields such as light guide, waveguide and liquid crystal display are to high heat-resisting, high
The demand of the polyimides of light transmission is more and more urgent, because the transparent polyimide for having both heat-resisting quantity and high light transmittance can
To be applied to the non-serviceable field of some other transparent resin institutes, such as：Computer control display, liquid crystal display, large-scale electricity
The cover of the optical components such as sub-display, polarizer, the substrate of solar cell and plastic lens etc..But traditional polyamides is sub-
Amine film generally shows faint yellow or dark brown, greatly limits further application of the polyimides in photoelectric material, master
Want the reason is that be present in the electron attraction of carbonyl and diamines residue in the dianhydride residue being alternately present in main polymer chain to
Electronic action and the formation of intramolecular and intermolecular charge transfer complex generated.It therefore can be by changing molecule knot
Structure, exploitation can be used for flexible solar battery bottom plate, the thermostable transparent polyimides in the fields such as Flexible Displays or illumination bottom plate
Resin material.
For full aromatic polyimide, the method for reducing its color at present is mainly：(1) in polyimide molecule knot
It is introduced in structure and contains fluoro substituents, since fluorine atom has prodigious electronegativity, the conjugation of electron cloud can be cut off, inhibit electric charge transfer
The formation of complex compound.The transparent polyimide film material LaRC developed such as NASATM- CP1 and LaRCTM-CP2
All it is to use hexafluorodianhydride (6FDA) (6FDA), referring to United States Patent (USP) US 4603061 and US 4595548, but the valence of this dianhydride monomer
Lattice are expensive.(2) by reducing the electron affinity of dianhydride and diamines, inhibit the formation of charge transfer complex.Such as China is specially
Sharp CN 102911359 discloses a kind of clear polyimides prepared by two ether dianhydrides of low electron affinity, but due to this
The introducing of soft segment ehter bond in monomer causes the glass transition temperature of prepared polyimides to reduce.
In order to overcome this problem, many researchers attempt the diester two prepared using trimellitic anhydride and various diphenol
Acid anhydride synthesizes corresponding polyesterimide, such as periodical Macromol.Mater.Eng.2011, is reported in 296,1002-1017
The contrast experiment of polyetherimide and polyesterimide, it can be seen that compared to polyetherimide, polyesterimide improves poly-
The glass transition temperature of object is closed, but transparent performance substantially reduces, and needs to be further increased.
Invention content
The technical purpose of the present invention is for the above-mentioned prior art, to provide a kind of transparent polyester imide resin, is had excellent
The advantages that different optical transmittance, good heat resistance, lower water absorption rate.
A kind of transparent polyester imide resin, the transparent polyester imide resin have the following structure formula：
Wherein, Ar is binary primary amine monomer residue, and n is the integer that the quantity of repetitive unit is greater than 0.
The Ar can be selected from one or more of following groups：
Wherein, the horizontal line "-" of end two indicates the connecting key of Ar groups and nitrogen-atoms in repetitive unit, and does not indicate that first
Base.
Preferably, the Ar can be selected from one or more of following groups：
As a further preference, the Ar can be selected from one kind in following groups：
Transparence is presented in the polyesterimide resin of the present invention, and glass transition temperature can be 200 DEG C~350 DEG C,
Light transmission rate at 400nm is 70%~90%, and water absorption rate is less than 0.5%.In view of these performances, transparent polyester of the invention
Imide resin can be in the flexible substrate material of solar cell, flexible transparent conducting film substrate material, liquid crystal display material
Etc. related fields have preferable application prospect.
The present invention also provides a kind of preparation methods of the transparent polyester imide resin, have easy to operate, easy
In control the advantages that.
The preparation method of the transparent polyester imide resin, by (3, the 4- dicarboxylic acid anhydride) phenyl ester of terephthalic acid (TPA) two and
Binary primary amine monomer is obtained by polycondensation reaction.
The structural formula of described terephthalic acid (TPA) two (3,4- dicarboxylic acid anhydrides) phenyl ester is as follows：
The preparation method of the transparent polyester imide resin, specially：
(1) binary primary amine monomer is added in nitrogen or the polar non-solute of inert gas shielding, stirring keeps its complete
Terephthalic acid (TPA) two (3,4- dicarboxylic acid anhydride) phenyl ester is added after fully dissolved, is stirred to react 12 hours~48 hours, obtains transparent viscous
Thick polyesteramide acid solution；
(2) use hot imidization method or chemical imidization method that polyesteramide acid solution is prepared into polyesterimide solution,
It is dry, transparent polyester imide resin is made.
The hot imidization method includes：It is dried after polyesteramide acid solution is applied as film, transparent polyester acyl is made
Imide resin；
The chemical imidization method includes：The mixed liquor of acetic anhydride and pyridine is added in polyesteramide acid solution, after
It is continuous to be stirred to react 12 hours~48 hours, polyesterimide solution is obtained, polyesterimide solution is poured into precipitating reagent, is collected
It fully washs, dry after precipitation, transparent polyester imide resin is made.
N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl pyrroles can be selected in the polar non-solute
It is one or more in pyrrolidone etc..
Ethyl alcohol, methanol, acetone, water can be selected in the precipitating reagent.
The inert gas selects inert gas commonly used in the art, such as argon gas.
The molar ratio of (3,4- dicarboxylic acid anhydrides) phenyl ester of terephthalic acid (TPA) two and binary primary amine monomer is generally 1:0.9
~1.1.
The binary primary amine monomer can be selected from 3,3 '-diaminodiphenylsulfones, 4,4' diaminodiphenyl sulfone, 2,2 '-bis-
(trifluoromethyl) -4,4 '-benzidine, 2,2 '-two (trifluoromethyl) -4,4 '-diaminodiphenyl ether, bis- (the 4- amino of 2,2-
Phenyl) hexafluoropropane, bis- (3- aminophenyls) hexafluoropropane of 2,2-, bis- (3- amino-benzene oxygens) benzene of 1,3-, 4,4 '-bis- (3- ammonia
Phenoxyl) diphenyl sulfone, bis- [4- (3- amino-benzene oxygens) phenyl] hexafluoropropane of 2,2-, the bis- (4- amino -2- fluoroforms of 1,3-
Phenoxyl) benzene, bis- (5- amino -3- 4-trifluoromethylphenopendants) benzene of 1,3-, 4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen
Base) diphenyl sulphone (DPS), 4,4 '-bis- (3- trifluoromethyl -5- amino-benzene oxygens) diphenyl sulphone (DPS)s, the bis- [4- (2- trifluoromethyl -4- amino of 2,2-
Phenoxy group) phenyl] hexafluoropropane, bis- [4- (3- trifluoromethyl -5- amino-benzene oxygens) phenyl] hexafluoropropane of 2,2-, 9,9- be bis-
One or more of (4- aminophenyls) fluorenes, 3,3- bis- (4- aminophenyls) -3H- isobenzofuranones.
Compared with prior art, the present invention in the design of dianhydride monomer by the oxygen atom and benzene of the ester bond in diester dianhydride
Acid anhydride is connected, and changes the situation that previous carbonyl is connected with phthalic anhydride, can substantially reduce the dianhydride on the basis of retaining original ester bond
Electron affinity, inhibit charge transfer complex in polyesterimide intramolecular and intermolecular formation, improve the transparency
Can, reduce the water absorption rate of film；The reservation of ester bond makes prepared polyesterimide on glass transition temperature simultaneously
It increases than original polyetherimide.
Specific implementation mode
Below in conjunction with specific embodiment, present invention is further described in detail.
Embodiment 1
In the present embodiment, transparent polyester imide resin material has the following structure formula：
Specifically preparation method is：Under nitrogen protection, by the 4 of 1.7230g (4.0mmol), 4 '-bis- (3- amino-benzene oxygens) two
Phenylsulfone and 16 milliliters of n,N-dimethylacetamide are added in 50mL reaction bulbs, are stirred at room temperature, wait for 4,4 '-bis- (3- aminobenzene oxygen
Base) after diphenyl sulfone is completely dissolved, terephthalic acid (TPA) two (3,4- dicarboxylic acid anhydride) phenyl ester of 1.8334g (4.0mmol) is added,
Continue to be stirred at room temperature 24 hours, sticky polyesteramide acid solution is made, solution, which is then diluted to concentration expressed in percentage by weight, is
10%.Then the mixed liquor of 4mL acetic anhydrides and 2mL pyridines is added, continues to be stirred at room temperature 24 hours, it is molten to obtain polyesterimide
Liquid.Reaction solution is instilled in ethyl alcohol and obtains the polyesterimide precipitation of threadiness, drying obtains polyesterimide powder.Wherein
The glass transition temperature of polymer powder is 217 DEG C.
By obtained polyesterimide powder with DMAC N,N' dimethyl acetamide be configured to concentration expressed in percentage by weight be 10% it is molten
Its solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating thickness is 0.5 millimeter, and glass plate is put
It is placed in 80 DEG C of drying box overnight, then heats up according to following procedure：100 DEG C, 1 hour；150 DEG C, 1 hour；200
DEG C, 1 hour.It waits for that temperature is cooled to room temperature taking-up glass plate, places it in demoulding in warm water, film, which is then placed in 100 DEG C, does
Dry water removal in dry case, obtains transparent polyester imide membrane, and thickness is 26 μm.
Detection data is as follows：FT-IR (film):1780cm-1(asym C=O stretching), 1722cm-1(sym C
=O stretching), 1370cm-1(C-N stretching)；Test prepared by the above method by ultraviolet-visual spectrometer
The UV cut-off wavelength of the H103 resin of film, the film is 351nm, and the light transmission rate at 400nm is 73%；Film
Water absorption rate be 0.32%.
Comparative example 1
In this comparative example, transparent polyester imide resin material has the following structure formula：
Specific preparation process is same as Example 1, using identical diamine monomer 4,4 '-bis- (3- amino-benzene oxygens) hexichol
Base sulfone is only replaced diester dianhydride therein, makes inclined benzene into from terephthalic acid (TPA) two (3,4- dicarboxylic acid anhydride) phenyl ester
Three acid anhydrides hydroquinone esters.
The glass transition temperature of polyesterimide resin prepared by this comparative example is 220 DEG C, and the thickness of film is 20 μm,
Its UV cut-off wavelength is 360nm；Light transmission rate at 400nm is 50%；The water absorption rate of film is 0.58%.
It, can be with as it can be seen that using dianhydride monomer of (3, the 4- dicarboxylic acid anhydride) phenyl ester of terephthalic acid (TPA) two as polyesterimide
The transparent performance of polyesterimide is substantially increased, the light transmission rate at 400nm has been increased to 73% from 50%, the water suction of film
Rate is also reduced to 0.32% from original 0.58%.
Embodiment 2：
In the present embodiment, transparent polyester imide resin material has the following structure formula：
Specifically preparation method is：Under nitrogen protection, by the 2 of 1.3450g (4.0mmol), 2 '-bis- (trifluoromethyl) -4,4 ' -
Diaminodiphenyl ether and 16 milliliters of n,N-dimethylacetamide are added in 50mL reaction bulbs, are stirred at room temperature, wait for 2,2 '-bis- (trifluoros
Methyl) -4, after 4 '-diaminodiphenyl ethers are completely dissolved, add the terephthalic acid (TPA) two (3,4- bis- of 1.8333g (4.0mmol)
Formic anhydride) phenyl ester, continues to be stirred at room temperature 24 hours, sticky polyesteramide acid solution is made, solution is then diluted to weight
Percentage concentration is 10%.
Polyesteramide acid solution coating after the dilution is coated uniformly on clean glass plate, solution coating thickness is
0.5 millimeter, glass plate is positioned in drying box, is heated up according to following procedure：80 DEG C, 1 hour；150 DEG C, 1 hour；
260 DEG C, 1 hour.It waits for that temperature is cooled to room temperature taking-up glass plate, places it in demoulding in water, film, which is then placed in 100 DEG C, does
Dry water removal in dry case, obtains transparent polyester imide membrane, and thickness is 20 μm.The wherein glass transition temperature of the film
It is 243 DEG C.
Detection data is as follows：FT-IR (film):1776cm-1(asym C=O stretching), 1717cm-1(sym C
=O stretching), 1372cm-1(C-N stretching).Test prepared by the above method by ultraviolet-visual spectrometer
The UV cut-off wavelength of the H103 resin of film, the film is 365nm, and the light transmission rate at 400nm is 72%；Film
Water absorption rate be 0.38%.
Embodiment 3
In the present embodiment, transparent polyester imide resin material has the following structure formula：
Specifically preparation method is：Under nitrogen protection, by the 4 of 2.2740 (4.0mmol), 4 '-bis- (2- trifluoromethyl -4- ammonia
Phenoxyl) diphenyl sulphone (DPS) and 16 milliliters of n,N-dimethylacetamide are added in 50mL reaction bulbs, are stirred at room temperature, wait for 4,4 '-bis- (2-
Trifluoromethyl-4-aminophenoxyl) after diphenyl sulphone (DPS) is completely dissolved, add the terephthalic acid (TPA) two of 1.8333g (4.0mmol)
(3,4- dicarboxylic acid anhydride) phenyl ester continues to be stirred at room temperature 24 hours, and sticky polyesteramide acid solution is made, then dilutes solution
It is 10% to concentration expressed in percentage by weight.Then the mixed liquor of 4mL acetic anhydrides and 2mL pyridines is added, continues to be stirred at room temperature 24 hours, obtain
To polyesterimide solution.Reaction solution is instilled in ethyl alcohol and obtains the polyesterimide precipitation of threadiness, drying obtains polyester acyl
Imines powder.Wherein the glass transition temperature of polymer powder is 236 DEG C.
By obtained polyesterimide powder with DMAC N,N' dimethyl acetamide be configured to concentration expressed in percentage by weight be 10% it is molten
Its solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating thickness is 0.5 millimeter, and glass plate is put
It is placed in 80 DEG C of drying box overnight, then heats up according to following procedure：100 DEG C, 1 hour；150 DEG C, 1 hour；200
DEG C, 1 hour.It waits for that temperature is cooled to room temperature taking-up glass plate, places it in demoulding in warm water, film, which is then placed in 100 DEG C, does
Dry water removal in dry case, obtains transparent polyester imide membrane, and thickness is 22 μm.The wherein glass transition temperature of the film
It is 236 DEG C.
Detection data is as follows：FT-IR (film):1783cm-1(asym C=O stretching), 1724cm-1(sym C
=O stretching), 1371cm-1(C-N stretching)；Test prepared by the above method by ultraviolet-visual spectrometer
The UV cut-off wavelength of the H103 resin of film, the film is 343nm, and the light transmission rate at 400nm is 78%；Film
Water absorption rate be 0.28%.
Claims (4)
1. a kind of transparent polyester imide resin, which is characterized in that the transparent polyester imide resin has the following structure formula：
Wherein, Ar is binary primary amine monomer residue, and n is greater than 0 integer；
The Ar is selected from one or more of following groups：
The glass transition temperature of the transparent polyester imide resin is 200 DEG C~350 DEG C, the light transmission rate at 400nm
It is 70%~90%, water absorption rate is less than 0.5%.
2. a kind of preparation method of transparent polyester imide resin as described in claim 1, which is characterized in that including following step
Suddenly：It is obtained by polycondensation reaction by (3,4- dicarboxylic acid anhydrides) phenyl ester of terephthalic acid (TPA) two and binary primary amine monomer；
The structural formula of terephthalic acid (TPA) two (3,4- dicarboxylic acid anhydrides) phenyl ester is as follows：
The binary primary amine monomer is selected from 3,3 '-diaminodiphenylsulfones, 4,4' diaminodiphenyl sulfone, 2,2 '-bis- (fluoroforms
Base) -4,4 '-benzidine, 2,2 '-two (trifluoromethyl) -4,4 '-diaminodiphenyl ether, 2,2- bis- (4- aminophenyls) six
Bis- (3- aminophenyls) hexafluoropropane of fluoro-propane, 2,2-, bis- (3- amino-benzene oxygens) benzene of 1,3-, 4,4 '-bis- (3- aminobenzene oxygen
Base) diphenyl sulfone, bis- [4- (3- amino-benzene oxygens) phenyl] hexafluoropropane of 2,2-, the bis- (4- amino -2- trifluoromethylbenzene oxygen of 1,3-
Base) benzene, bis- (5- amino -3- 4-trifluoromethylphenopendants) benzene of 1,3-, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) hexichol
Sulfone, 4,4 '-bis- (3- trifluoromethyl -5- amino-benzene oxygens) diphenyl sulphone (DPS)s, the bis- [4- (2- trifluoromethyl-4-aminophenoxyls) of 2,2-
Phenyl] hexafluoropropane, bis- [4- (3- trifluoromethyl -5- amino-benzene oxygens) phenyl] hexafluoropropane of 2,2-, bis- (the 4- aminobenzenes of 9,9-
Base) fluorenes, one or more of 3,3- bis- (4- aminophenyls) -3H- isobenzofuranones.
3. the preparation method of transparent polyester imide resin according to claim 2, which is characterized in that including following step
Suddenly：
(1) binary primary amine monomer is added in nitrogen or the polar non-solute of inert gas shielding, stirring keeps it completely molten
Terephthalic acid (TPA) two (3,4- dicarboxylic acid anhydride) phenyl ester is added after solution, is stirred to react 12 hours~48 hours, obtains clear viscous
Polyesteramide acid solution；
(2) use hot imidization method or chemical imidization method that polyesteramide acid solution is prepared into polyesterimide solution, it is dry,
Transparent polyester imide resin is made.
4. the preparation method of transparent polyester imide resin material according to claim 3, which is characterized in that the heat
Imidization method includes：It is dried after polyesteramide acid solution is applied as film, transparent polyester imide resin is made；
The chemical imidization method includes：The mixed liquor of acetic anhydride and pyridine is added in polyesteramide acid solution, continues to stir
Reaction 12 hours~48 hours is mixed, polyesterimide solution is obtained, polyesterimide solution is poured into precipitating reagent, collects precipitation
Fully washing, drying afterwards, is made transparent polyester imide resin.
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| TWI757319B (en) * | 2016-08-03 | 2022-03-11 | 日商日產化學工業股份有限公司 | Composition for forming peeling layer |
| KR102555870B1 (en) * | 2018-02-22 | 2023-07-14 | 삼성전자주식회사 | Polymer, film including the polymer, and display device including the film |
| CN115386085B (en) * | 2022-09-21 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | Polyester imide copolymer and preparation method and application thereof |
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| JP2007314443A (en) * | 2006-05-24 | 2007-12-06 | Manac Inc | Ester group-containing tetracarboxylic acid compound, polyesterimide precursror, polyesterimide, and method for producing them |
| CN103524467B (en) * | 2009-02-12 | 2015-10-28 | 本州化学工业株式会社 | Containing ester group tetracarboxylic acid dianhydride, polyester-imide precursor, polyester-imide and manufacture method thereof |
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