CN115386085A - Polyester imide copolymer and preparation method and application thereof - Google Patents
Polyester imide copolymer and preparation method and application thereof Download PDFInfo
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- CN115386085A CN115386085A CN202211153469.XA CN202211153469A CN115386085A CN 115386085 A CN115386085 A CN 115386085A CN 202211153469 A CN202211153469 A CN 202211153469A CN 115386085 A CN115386085 A CN 115386085A
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- polyester imide
- anhydride
- polyesterimide
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- 229920003055 poly(ester-imide) Polymers 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 18
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000009477 glass transition Effects 0.000 claims abstract description 11
- -1 aromatic acyl chloride Chemical class 0.000 claims abstract description 8
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims abstract description 8
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 6
- 238000002834 transmittance Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000012024 dehydrating agents Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 2
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- NKYXYJFTTIPZDE-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F NKYXYJFTTIPZDE-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C08G73/16—Polyester-imides
-
- 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
-
- 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
Abstract
The invention discloses a polyester imide copolymer and a preparation method and application thereof, belonging to the technical field of macromolecules, wherein the structural formula of the polyester imide copolymer is shown as a formula (I), wherein x, y and z are integers of 1-100; r 1 Is the residue of an aromatic diamine monomer, R 2 Is an aromatic acyl chloride monomer residue; the preparation method comprises the following steps: under the protection of inert gas, carrying out polymerization reaction in an organic solvent by taking tert-butyl hydroquinone bis (trimellitic anhydride), 4' - (hexafluoro-isopropenyl) diphthalic anhydride, an aromatic diamine monomer and an aromatic acyl chloride monomer as polymerization monomers to obtain a polyamic acid solution; and imidizing the polyamic acid solution, and performing post-treatment to obtain the polyester imide copolymer. The film prepared by the polyester imide copolymer has a glass transition temperature of more than or equal to 300 ℃ and a thermal expansion coefficient of less than or equal to 30ppmThe transmittance at 400nm of the material is more than or equal to 70 percent, and the material has potential application in the field of optics.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a polyesterimide copolymer, and a preparation method and application thereof.
Background
Polyimide has been widely used in aerospace, electronic and electrical appliances, automobiles, chemical and mechanical industries and other fields due to its excellent thermal stability, chemical stability and dielectric properties. In the traditional polyimide film, an electron transfer complex is generated in the polymerization process of a dianhydride monomer and a diamine monomer, so that the optical performance of the product film is influenced, and the application of the polyimide in the optical field is further limited.
The polyester imide is a polymer with ester bonds introduced into a polyimide main chain, and the repeating units take the ester groups and the imide groups as structural characteristic groups, so that the polyester imide is beneficial to coordinating and coordinating the advantages of the traditional polyester and polyimide due to the unique molecular structure, and has excellent thermal stability, insulativity, electromagnetic shielding property, solvent resistance and excellent mechanical property. The transmittance at 400nm of a polyesterimide film prepared from T-butylhydroquinone bis (trimellitic anhydride) reported in the prior art is only 58.7%, the glass transition temperature is 234 ℃, and the thermal and optical properties need to be further improved (Hasegawa M, ishigami T, ishii J. Optical transport aromatic poly (ester imide) s with low coefficients of thermal expansion (1). Self-orientation glass fiber reinforced plastic molding process and substrate impact [ J ] Polymer,2015, 74.
Further, chinese patent publication No. CN114656636A discloses a polyesterimide obtained by mixing an acid monomer, an alcohol monomer, an acid anhydride monomer and an amine monomer under a protective atmosphere, and adjusting the molar ratio of the alcohol monomer to the acid monomer to 2.5 to 4.0:1, reacting under the action of a catalyst, and preparing to obtain polyesterimide without adding a solvent, wherein the glass transition temperature of the polyesterimide is 117-178 ℃, and the thermal property needs to be improved; chinese patent publication No. CN106810695A discloses an aromatic polyesterimide, which is characterized in that in the process of melt processing, an asymmetric aromatic diphenol monomer containing imide bonds prepared in advance is condensed with a meta-position wholly aromatic diacid monomer to form a polyesterimide molecular chain which is not easy to crystallize, a polyester molecular chain formed by an AB-type wholly aromatic monomer is easy to crystallize, the two are connected through meta-position wholly aromatic dicarbonyl, and a dynamic ester exchange reaction exists between the molecular chains, which is beneficial to establishing a strong chemical bond acting force between the molecular chains; in the subsequent cooling process, the polyester molecular chain is rapidly crystallized and uniformly dispersed in the polyester-imide-containing molecular chain which is not easy to crystallize, so that the aromatic polyester imide with self-enhanced tensile strength and Tg is obtained. However, the method is complex and has high requirements on parameters.
Disclosure of Invention
In order to improve the thermal property and the optical property of the polyester imide film in the prior art, the invention provides the polyester imide copolymer, and the film prepared by utilizing the polyester imide copolymer has high glass transition temperature, low thermal expansion coefficient and good optical property.
The technical scheme is as follows:
a polyesterimide copolymer having the structural formula (I):
wherein x, y and z are integers from 1 to 100;
R 1 any one selected from the group represented by formula (II):
R 2 any one selected from the group represented by the formula (III):
preferably, R 1 Is composed of
R 2 Is composed of
According to the invention, an amide structure is introduced into a main chain of the polyester imide, hydrogen bonds are formed among molecular chains, the rigidity and linearity of the chains are enhanced, and the acting force among the molecular chains is enhanced, so that the glass transition temperature of the polyester imide is increased, and the thermal expansion coefficient of the polyester imide is reduced; in addition, a strong electron-withdrawing group, namely trifluoromethyl, and a large-volume side group, namely tert-butyl, are introduced, so that the optical performance of the material can be improved.
Preferably, the ratio of x to z is 0.1 to 7:1; when the ratio of the amide segment to the polyester segment is within the above range, the resulting polyesterimide exhibits more excellent thermal and optical properties.
The invention also provides a preparation method of the polyester imide copolymer, which comprises the following steps:
(1) Under the protection of inert gas, taking tert-butyl hydroquinone bis (trimellitic anhydride), 4' - (hexafluoro isopropyl) diphthalic anhydride, an aromatic diamine monomer and an aromatic acyl chloride monomer as polymerization monomers, and carrying out polymerization reaction in an organic solvent to obtain a polyamic acid solution;
(2) And (2) imidizing the polyamic acid solution in the step (1) under the action of a dehydrating agent and a catalyst, and performing post-treatment to obtain the polyester imide copolymer.
The ratio of the molar quantity of the aromatic diamine monomer to the total molar quantity of the aromatic acyl chloride monomer, the tert-butyl hydroquinone bis (trimellitic anhydride) and the 4,4' - (hexafluoroisopropylidene) diphthalic anhydride is 1:1-1.05.
Preferably, the molar ratio of the aromatic acyl chloride monomer to the tert-butyl hydroquinone bis (trimellitic anhydride) is 0.1 to 7:1; within the above preferred range, the thermal expansion coefficient of the polyesterimide copolymer decreases and the glass transition temperature increases as the content of the aromatic acid chloride increases.
The organic solvent comprises N, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethyl sulfoxide, N-methylpyrrolidone or m-cresol.
The dehydrating agent is at least one of acetic anhydride, propionic anhydride, n-butyric anhydride, valeric anhydride and benzoic anhydride; the catalyst is at least one of pyridine, isoquinoline and triethylamine; the molar ratio of the dehydrating agent to the catalyst is 1:0.5 to 1; the molar ratio of the dehydrating agent to the diamine monomer is 1-3:1.
in the step (2), the temperature of the imidization reaction is 25-100 ℃ and the time is 2-24h.
Preferably, the temperature of the imidization reaction is 70-90 ℃ and the time is 2-3 h. This reaction condition is advantageous for achieving complete imidization in a short time.
The invention also provides a polyester imide film which is prepared from the polyester imide copolymer, preferably, the polyester imide copolymer is dissolved to obtain a polyester imide solution, and the polyester imide solution is cast or coated to form a film and then cured to obtain the polyester imide film.
Preferably, the temperature programming is adopted during curing, and the temperature programming steps are curing for 1 to 2 hours at 60 to 100 ℃, curing for 1 to 2 hours at 100 to 160 ℃, curing for 1 to 2 hours at 180 to 250 ℃ and curing for 1 to 2 hours at 300 to 350 ℃.
Further preferably, the temperature programming step is curing at 80 ℃ for 1-2 hours, at 100 ℃ for 1-2 hours, at 150 ℃ for 1-2 hours, at 200 ℃ for 1-2 hours, and at 250 ℃ for 1-2 hours.
The glass transition temperature of the polyester imide film is more than or equal to 300 ℃, the thermal expansion coefficient is less than or equal to 30ppm/K, and the optical transmittance at 400nm is more than or equal to 70%.
Preferably, the glass transition temperature of the polyester imide film is 300-350 ℃, and the thermal expansion coefficient is 10-26ppm/K; the optical transmittance at 400nm is more than or equal to 74 percent.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, an amide structure is introduced into a polyesterimide system, hydrogen bonds are formed among molecular chains, and the rigidity and linearity of the chains are enhanced, so that the thermal expansion coefficient of the polyesterimide film is less than or equal to 30ppm/K, and the glass transition temperature is greater than or equal to 300 ℃;
(2) The proportion of imide groups can be relatively reduced due to the existence of amide groups, and the polyester imide disclosed by the invention introduces a strong electron-withdrawing group, namely trifluoromethyl, and a large-volume side group, namely tert-butyl, so that the transmittance of a product polyester imide film at a 400nm position is more than or equal to 70%, and the product polyester imide film has potential application in the field of optics.
Drawings
FIG. 1 is an infrared spectrum of the polyesterimide copolymers of examples 1 to 4 and comparative example 1.
Detailed Description
The invention will be further elucidated with reference to the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
(1) Under nitrogen protection, 1.6015g (5.001 mmol) of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 1.3247g (2.575 mmol) of t-butylhydroquinone bis (trimellitic anhydride), 0.3137g (1.545 mmol) of terephthaloyl chloride and 0.4576g (1.030 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 20.6233g of N, N-dimethylacetamide were charged into a 100mL reaction flask and stirred at room temperature for 10 hours to obtain a transparent polyamic acid solution;
(2) Diluting the transparent polyamic acid solution to a solid content of 10%, adding 1.2759g (12.498 mmol) of acetic anhydride and 0.9884g (12.496 mmol) of pyridine, carrying out imidization reaction at 80 ℃ for 2.5h, cooling to room temperature after the reaction is finished, precipitating in ethanol/water to obtain a fibrous polyester imide copolymer, and boiling, washing and drying to obtain the polyester imide copolymer;
(3) Adding the polyester imide copolymer powder into N, N-dimethylacetamide, completely dissolving to obtain a polyester imide solution with solid content of 10%, coating the solution on a glass substrate, placing the glass substrate in an oven for heating and curing, specifically 80 ℃/2 h, 100 ℃/1 h, 150 ℃/1 h, 200 ℃/1 h and 250 ℃/1 h, cooling to room temperature, taking out the glass plate from the oven, soaking the glass plate in water, automatically stripping a polyester imide film, and placing the polyester imide film in the oven for drying for later use.
The FT-IR spectrum of the polyesterimide copolymer of this example is shown in FIG. 1, 1788, 1722, 1367cm -1 The appearance of characteristic peaks can prove the successful synthesis of the polyesterimide copolymer.
Example 2
(1) Under nitrogen protection, 1.6013g (5.000 mmol) of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 1.0597g (2.060 mmol) of tert-butylhydroquinone bis (trimellitic anhydride), 0.4182g (2.060 mmol) of terephthaloyl chloride and 0.4578g (1.030 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 19.7209g of N, N-dimethylacetamide were put into a 100mL reaction flask and stirred at room temperature for 10 hours to obtain a transparent polyamic acid solution;
(2) Diluting the transparent polyamic acid solution to a solid content of 10%, adding 1.2764g (12.503 mmol) of acetic anhydride and 0.9890g (12.503 mmol) of pyridine, imidizing for 2h at 90 ℃, cooling to room temperature after the reaction is finished, precipitating in ethanol/water to obtain a fibrous polyesterimide copolymer, boiling, washing and drying to obtain the polyesterimide copolymer;
(3) Adding the polyester imide copolymer powder into N, N-dimethylacetamide, completely dissolving to obtain a polyester imide solution with solid content of 10%, coating the solution on a glass substrate, placing the glass substrate in an oven for heating and curing, specifically 80 ℃/2 h, 100 ℃/1 h, 150 ℃/1 h, 200 ℃/1 h and 250 ℃/1 h, cooling to room temperature, taking out the glass plate from the oven, soaking the glass plate in water, automatically stripping a polyester imide film, and placing the polyester imide film in the oven for drying for later use.
The FT-IR spectrum of the polyesterimide copolymer of this example is shown in FIG. 1, 1784, 1722, 1369cm -1 The appearance of characteristic peaks can prove the successful synthesis of the polyesterimide copolymer.
Example 3
(1) Under nitrogen protection, 1.6012g (4.999 mmol) of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 0.7794g (1.515 mmol) of t-butylhydroquinone bis (trimellitic anhydride), 0.5127g (2.525 mmol) of terephthaloyl chloride and 0.4487g (1.010 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 29.9219g of N, N-dimethylacetamide were added to a 100mL reaction flask and stirred at room temperature for 10 hours to obtain a transparent polyamic acid solution;
(2) Diluting the transparent polyamic acid solution to a solid content of 10%, adding 1.2762g (12.500 mmol) of acetic anhydride and 0.9885g (12.497 mmol) of pyridine, carrying out imidization reaction at 80 ℃ for 2.5h, cooling to room temperature after the reaction is finished, precipitating in ethanol/water to obtain a fibrous polyester imide copolymer, and boiling, washing and drying to obtain the polyester imide copolymer;
(3) Adding the polyester imide copolymer powder into N, N-dimethylacetamide, completely dissolving to obtain a polyester imide solution with a solid content of 10%, coating the solution on a glass substrate, placing the glass substrate in an oven for heating and curing, specifically 80 ℃/2 h, 100 ℃/1 h, 150 ℃/1 h, 200 ℃/1 h and 250 ℃/1 h, cooling to room temperature, taking out the glass plate from the oven, soaking the glass plate in water, automatically stripping a polyester imide film, and placing the polyester imide film in the oven for drying for later use.
The FT-IR spectrum of the polyesterimide copolymer of this example is shown in FIG. 1, 1786, 1726, 1369cm -1 The appearance of characteristic peaks can prove the successful synthesis of the polyesterimide copolymer.
Example 4
(1) Under nitrogen protection, 1.6015g (5.001 mmol) of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 0.5299g (1.030 mmol) of t-butylhydroquinone bis (trimellitic anhydride), 0.6273g (3.090 mmol) of terephthaloyl chloride and 0.4576g (1.030 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 28.5461g of N, N-dimethylacetamide were put into a 100mL reaction flask and stirred at room temperature for 10 hours to obtain a transparent polyamic acid solution;
(2) Diluting the transparent polyamic acid solution to a solid content of 10%, adding 1.2766g (12.505 mmol) of acetic anhydride and 0.9890g (12.503 mmol) of pyridine, carrying out imidization reaction at 70 ℃ for 3h, cooling to room temperature after the reaction is finished, precipitating in ethanol/water to obtain a fibrous polyesterimide copolymer, and boiling, washing and drying to obtain the polyesterimide copolymer;
(3) Adding the polyester imide copolymer powder into N, N-dimethylacetamide, completely dissolving to obtain a polyester imide solution with a solid content of 10%, coating the solution on a glass substrate, placing the glass substrate in an oven for heating and curing, specifically 80 ℃/2 h, 100 ℃/1 h, 150 ℃/1 h, 200 ℃/1 h and 250 ℃/2 h, cooling to room temperature, taking out the glass plate from the oven, soaking the glass plate in water, automatically stripping a polyester imide film, and placing the polyester imide film in the oven for drying for later use.
The FT-IR spectrum of the polyesterimide copolymer of this example is shown in FIG. 1, 1788, 1724, 1369cm -1 The appearance of characteristic peaks can prove the successful synthesis of the polyesterimide copolymer.
Example 5
(1) Under the protection of nitrogen, 1.6812g (5.000 mmol) of 2,2' -bis (trifluoromethyl) -4,4' -diaminodiphenyl ether, 2.0583g (4.001 mmol) of tert-butylhydroquinone bis (trimellitic anhydride), 0.1015g (0.500 mmol) of isophthaloyl chloride and 0.2230g (0.502 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 16.2564g of N, N-dimethylacetamide were put into a 100mL reaction flask and stirred at room temperature for 10 hours to obtain a transparent polyamic acid solution;
(2) Diluting the transparent polyamic acid solution to a solid content of 10%, adding 1.2762g (12.500 mmol) of acetic anhydride and 0.9888g (12.500 mmol) of pyridine, carrying out imidization reaction at 80 ℃ for 2.5h, cooling to room temperature after the reaction is finished, precipitating in ethanol/water to obtain a fibrous polyester imide copolymer, and boiling, washing and drying to obtain the polyester imide copolymer;
(3) Adding the polyester imide copolymer powder into N, N-dimethylacetamide, completely dissolving to obtain a polyester imide solution with a solid content of 10%, coating the solution on a glass substrate, placing the glass substrate in an oven for heating and curing, specifically 80 ℃/2 h, 100 ℃/1 h, 150 ℃/1 h, 200 ℃/1 h and 250 ℃/2 h, cooling to room temperature, taking out the glass plate from the oven, soaking the glass plate in water, automatically stripping a polyester imide film, and placing the polyester imide film in the oven for drying for later use
Comparative example 1
(1) Under nitrogen protection, 1.6011g (5.000 mmol) of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2.0583g (4.001 mmol) of tert-butylhydroquinone bis (trimellitic anhydride), 0.4442g (1.000 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, and 10.1482g of N, N-dimethylacetamide were put into a 50mL reaction flask and stirred at room temperature for 10 hours to obtain a transparent polyamic acid solution;
(2) Diluting the transparent polyamic acid solution to a solid content of 10%, adding 1.2769g (12.508 mmol) of acetic anhydride and 0.9894g (12.508 mmol) of pyridine, imidizing at 80 ℃ for 2.5h, cooling to room temperature after the reaction is finished, precipitating in ethanol/water to obtain a fibrous polyesterimide copolymer, and boiling, washing and drying to obtain the polyesterimide copolymer;
(3) Adding the polyester imide copolymer powder into N, N-dimethylacetamide, completely dissolving to obtain a polyester imide solution with solid content of 10%, coating the solution on a glass substrate, placing the glass substrate in an oven for heating and curing, specifically 80 ℃/2 h, 100 ℃/1 h, 150 ℃/1 h, 200 ℃/1 h and 250 ℃/1 h, cooling to room temperature, taking out the glass plate from the oven, soaking the glass plate in water, automatically stripping a polyester imide film, and placing the polyester imide film in the oven for drying for later use.
The FT-IR spectrum of the polyesterimide copolymer of this comparative example is shown in FIG. 1, 1788, 1724, 1367cm -1 The appearance of characteristic peaks can prove the successful synthesis of the polyesterimide copolymer.
Sample analysis
The structural formula of the polyesterimide copolymers obtained in examples 1 to 4 is shown below,
wherein R is 1 Is composed of
R 2 Is composed of
The structural formula of the polyesterimide copolymer prepared in comparative example 1 is shown in the following formula,
wherein R is 1 Is composed of
The main properties of the polyesterimide films obtained in examples 1 to 4 are shown in Table 1, the glass transition temperatures and T of the examples are shown in comparison with the comparative examples 400nm All are improved, and the thermal expansion coefficient is obviously reduced.
TABLE 1 Main Properties of the polyesterimide films prepared in examples 1 to 4
The technical solutions of the present invention have been described in detail with reference to the above embodiments, it should be understood that the above embodiments are only specific examples of the present invention and should not be construed as limiting the present invention, and any modifications, additions or similar substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A polyester imide copolymer having the structural formula (I):
wherein x, y and z are integers from 1 to 100;
R 1 any one selected from the group represented by formula (II):
R 2 any one selected from the group represented by the formula (III):
2. the method for producing a polyesterimide copolymer according to claim 1, comprising the steps of:
(1) Under the protection of inert gas, taking tert-butyl hydroquinone bis (trimellitic anhydride), 4' - (hexafluoro-isopropyl) diphthalic anhydride, an aromatic diamine monomer and an aromatic acyl chloride monomer as polymerization monomers, and carrying out polymerization reaction in an organic solvent to obtain a polyamic acid solution;
(2) And (2) imidizing the polyamic acid solution in the step (1) under the action of a dehydrating agent and a catalyst, and performing post-treatment to obtain the polyester imide copolymer.
3. The method of claim 2, wherein the ratio of the molar amount of the aromatic diamine monomer to the total molar amount of the aromatic acid chloride monomer, t-butylhydroquinone bis (trimellitic anhydride), and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride is 1:1-1.05.
4. The method of preparing polyesterimide copolymer according to claim 2, wherein the molar ratio of aromatic acid chloride monomer to t-butylhydroquinone bis (trimellitic anhydride) is 0.1 to 7:1.
5. the method of claim 2, wherein the organic solvent used in the step (1) comprises N, N-dimethylformamide, N-dimethylacetamide, sulfolane, dimethylsulfoxide, N-methylpyrrolidone, or m-cresol.
6. The method for preparing polyesterimide copolymer according to claim 2, wherein said dehydrating agent is at least one of acetic anhydride, propionic anhydride, n-butyric anhydride, valeric anhydride and benzoic anhydride; the catalyst is at least one of pyridine, isoquinoline and triethylamine; the molar ratio of the dehydrating agent to the catalyst is 1:0.5 to 1; the molar ratio of the dehydrating agent to the diamine monomer is 1-3:1.
7. the method of preparing a polyesterimide copolymer as claimed in claim 2, wherein the imidization temperature in step (2) is 25 to 100 ℃ and the time is 2 to 24 hours.
8. A polyester imide film which is obtained from the polyester imide copolymer described in claim 1.
9. The polyesterimide film of claim 8, wherein said polyesterimide film has a glass transition temperature of not less than 300 ℃, a thermal expansion coefficient of not more than 30ppm/K, and an optical transmittance at 400nm of not less than 70%.
10. Use of the polyesterimide film of claim 8 or 9 in the optical field.
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| WO2024060583A1 (en) * | 2022-09-21 | 2024-03-28 | 中国科学院宁波材料技术与工程研究所 | Polyester imide copolymer, preparation method therefor, and use thereof |
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| KR102075739B1 (en) * | 2017-02-03 | 2020-02-10 | 주식회사 엘지화학 | Polyamideimide copolymers and polyamideimide film comprising the same |
| TWI773937B (en) * | 2019-10-29 | 2022-08-11 | 達興材料股份有限公司 | Poly(imide-ester-amide) copolymer and optical 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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