CN115232093A - Method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester - Google Patents
Method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester Download PDFInfo
- Publication number
- CN115232093A CN115232093A CN202211007969.2A CN202211007969A CN115232093A CN 115232093 A CN115232093 A CN 115232093A CN 202211007969 A CN202211007969 A CN 202211007969A CN 115232093 A CN115232093 A CN 115232093A
- Authority
- CN
- China
- Prior art keywords
- formyloxy
- phthalic anhydride
- purity
- catalyst
- anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000001914 filtration Methods 0.000 claims abstract description 39
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 230000007062 hydrolysis Effects 0.000 claims abstract description 32
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000012043 crude product Substances 0.000 claims abstract description 26
- 150000002148 esters Chemical class 0.000 claims abstract description 24
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- -1 trimellitic anhydride acyl chloride Chemical class 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 238000005580 one pot reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 11
- AQBFKBMMIDHCFS-UHFFFAOYSA-N 4-bromo-2-benzofuran-1,3-dione Chemical compound BrC1=CC=CC2=C1C(=O)OC2=O AQBFKBMMIDHCFS-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical group ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- 238000002834 transmittance Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester, which uses a novel catalyst and comprises the following steps: preparing a hydrolysis intermediate of the halogenated phthalic anhydride; mixing trimellitic anhydride acyl chloride, a hydrolysis intermediate, a catalyst and a solvent, heating until the reaction is complete, filtering to remove the catalyst, cooling the filtrate, acidifying, filtering, washing and drying in vacuum to obtain an ester tetra-acid intermediate; and dehydrating the ester tetra-acid intermediate to obtain a crude product containing the required product, wherein the catalyst is prepared from formaldehyde, dialkyl amine and ionic resin by a one-pot method. The method for preparing the high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester has the advantages of short reaction steps, mild conditions, simple post-treatment operation, high yield and the like, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester.
Background
Polyimide is a polymer containing polyimide cyclic repeating units in a main chain, and is one of organic high polymer materials with the best comprehensive performance. Polyimide is used as a special engineering material, has good mechanical property, high temperature resistance, dimensional stability, solvent resistance, excellent electrical property and the like, and is widely applied to the fields of aviation, aerospace, electronic and electrical products, mechanical and chemical engineering, microelectronics, nano-scale, liquid crystal, separation membranes, laser and the like.
The polyester imide has important prospect in improving the defects of low transparency and insufficient flexibility of the polyimide film, particularly the high-frequency stability.
The synthesis control difficulty and purification difficulty of (4-phthalic anhydride) formyloxy-4-phthalic acid ester are high, and the literature on (4-phthalic anhydride) formyloxy-4-phthalic acid ester in the prior art is less reported, and the literature is only documented in the following documents:
1) The invention patent with publication number WO 2021085329 A1;
2) The invention patent with publication number CN 112194792A;
3) The invention patent with publication number CN 112194790A;
4) The invention patent with publication number CN 106478968A;
5)Journal of Polymer Materials(2001),18(4),449-458；
6)Eur.Pat.Appl.(1998),EP 827986A2 19980311；
7)Ger.Offen.(1970),DE 1901028 A 19700806。
the above documents do not describe a method for synthesizing (4-phthalic anhydride) formyloxy-4-phthalate which is suitable for industrial production, and therefore, it is important to develop a novel method for producing (4-phthalic anhydride) formyloxy-4-phthalate.
Disclosure of Invention
In view of the above, the present invention is directed to a catalyst for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate, thereby increasing the conversion rate during the reaction and facilitating the purification.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a catalyst for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate, which is prepared from formaldehyde, dialkyl amine and ionic resin by a one-pot method, and has the following structural formula:
the preparation method comprises the following steps:
dissolving formaldehyde and dialkyl amine in toluene, adding ionic resin in batches, stirring at room temperature, slowly heating until reflux reaction is finished, separating water and refluxing until no water is separated out, cooling, filtering, and drying at low temperature to obtain the target catalyst.
The ionic resin is resin with the model number of XR935J produced by Shanghai Sener chemical engineering Co., ltd, and the catalyst is CT-06A when R is hydrogen, CT-06B when R is methyl, CT-06C when R is ethyl, CT-06D when R is n-propyl, and CT-06E when R is isopropyl.
Another object of the present invention is to provide a method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate, so as to reduce the process steps, reduce the operation difficulty, and improve the product yield and purity.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a process for preparing high purity (4-phthalic anhydride) formyloxy-4-phthalate using the catalyst of claim 1, comprising the steps of:
s1: preparing a hydrolysis intermediate of the halogenated phthalic anhydride;
s2: mixing trimellitic anhydride acyl chloride, a hydrolysis intermediate, a catalyst and a solvent, heating to perform acyl chloride reaction, filtering to remove the catalyst when the reaction is complete, cooling the filtrate, acidifying, filtering, washing a filter cake, and performing vacuum drying to obtain an ester tetracid intermediate;
s3: the estertetracarboxylic acid intermediate is dehydrated to obtain a crude product containing the desired product.
Further, the specific operation method of step S1 is:
mixing halogenated phthalic anhydride with water and alkali, heating to a certain temperature for reaction, cooling by ice water to separate out solid after the raw materials completely react, filtering, and drying to obtain a required hydrolysis intermediate; preferably, the halogenated phthalic anhydride is chlorophthalic anhydride or bromophthalic anhydride, and the base is sodium hydroxide or potassium hydroxide.
Further, the reaction temperature in step S1 is 110 to 130 ℃.
Further, the mixing method of the trimellitic anhydride chloride, the hydrolysis intermediate, the catalyst and the solvent in the step S2 is as follows:
dropping trimellitic anhydride chloride into solvent to form trimellitic anhydride chloride solution, adding catalyst at low temperature, adding hydrolysis intermediate in batches, and slowly heating to certain temperature for reaction.
Preferably, the acid used for acidification is hydrochloric acid, the concentration of hydrochloric acid is 1M, and the pH of the reaction solution after acidification is about 1.
Further, the molar ratio of the trimellitic anhydride chloride to the hydrolysis intermediate in the step S2 is 1:1-1.5; preferably 1.
Further, in the step S2, the mass ratio of the trimellitic anhydride acid chloride to the catalyst is 1:0.2 to 3, preferably 1:0.7.
further, the solvent in step S2 is one of ultrapure water, tetrahydrofuran, acetonitrile, dichloromethane, toluene, dioxane, N-dimethylformamide, and N, N-dimethylacetamide; preferably ultrapure water or tetrahydrofuran.
Further, the specific operation method of step S3 is as follows:
and mixing the estertetracarboxylic acid intermediate with acetic anhydride, heating to reflux, cooling after complete reaction, and filtering to obtain a crude product containing the required product.
Further, the method also comprises the following steps:
s4: mixing the crude product with a solvent and then recrystallizing to obtain high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester; preferably, the mixed solution of the crude product and the solvent is decolorized for more than 3 times by activated carbon.
Further, the method also comprises the following steps:
s5: and (3) soaking the catalyst filtered in the step (S2) in alkali liquor for regeneration.
Further, the main component in the alkali liquor comprises one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium tert-butoxide and sodium tert-butoxide; preferably, the concentration of the lye is 2M; further preferably, the main component in the alkali liquor is potassium carbonate.
The total yield of the product prepared by the preparation method of the invention reaches 85 percent, the purity reaches more than 99.5 percent, the polymerization viscosity of the product and diamines such as p-phenylenediamine, biphenyldiamine, TFMB,6FODA, m-toidine, APAB, ABHQ and the like reaches 9-78 ten thousand, the average light transmittance at the wavelength of 380-780 nm is 76-89 percent based on the thickness of a film of 50 mu m measured by a UV spectrometer, the Coefficient of Thermal Expansion (CTE) at 50-300 ℃ is 5-15 ppm/DEG C, the tensile strength is 120-230 MPa, and the modulus is more than 3.5-6.0 Gpa.
Compared with the prior art, the method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester has the following advantages:
the method for preparing the high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester has the advantages of mild reaction conditions, simple post-treatment operation, high yield, good quality, good performance of polymerized film formation and the like, and is suitable for industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of the reaction principle of the method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate according to the embodiment of the present invention, wherein the structural formula of halogenated phthalic anhydride is shown in formula I, X = Cl, br, the structural formula of hydrolysis intermediate is shown in formula II, M = Na, K, the structural formula of trimellitic anhydride acyl chloride is shown in formula III, the structural formula of catalyst is shown in formula IV, R = H, CH 3 、C 2 H 5 、C 3 H 8 The structural formula of the ester tetra-acid intermediate is shown as a formula V, (4-phthalic anhydride) formyloxy-4-phthalic acidThe structural formula of the ester is shown as a formula VI;
FIG. 2 is a liquid chromatogram of the (4-phthalic anhydride) formyloxy-4-phthalate product obtained in example 9 according to the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents; the experimental methods are all conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Catalyst preparation examples
Dissolving formaldehyde (1.0 mol) and dialkylamine (1.0 mol) in toluene, adding 120g of ionic resin in batches, stirring for 2h at room temperature, slowly heating to reflux reaction, separating water and refluxing until no water is separated out, cooling, filtering, and drying at low temperature to obtain the target catalyst.
The products prepared in examples 1-9 were tested as follows:
dissolving the product in N-methyl pyrrolidone, polymerizing with diamines (p-phenylenediamine, biphenyldiamine, TFMB,6FODA, m-Tolidine, APAB, ABHQ) with different structures to form 15% of viscous slurry with the film thickness of about 50 micrometers, coating the viscous slurry on a glass substrate, gradually heating the viscous slurry in an oven to 200 ℃, cooling the viscous slurry after 8 hours, and stripping the viscous slurry in water to obtain a transparent polyimide film, wherein the transparency, the thermal expansion coefficient and the mechanical property of the transparent polyimide film are analyzed by the following instruments and conditions:
(1) and (3) tensile test: an electronic universal tester with a stretching speed of 5mm/min.
(2) Rotational viscosity: digital viscometer, room temperature.
(3) Optical transmittance: an ultraviolet visible spectrum tester, and average light transmittance at 380-780 nm wavelength.
(4) Coefficient of Thermal Expansion (CTE): testing by using a thermal mechanical analyzer; and (3) testing conditions are as follows: 10 ℃/min, 100-300 ℃.
(5) The contents are as follows: agilent 1260 liquid chromatograph.
Example 1
Adding bromo-phthalic anhydride (1.0 mol), water (5 mol) and sodium hydroxide (6.0 mol) into a reaction bottle, heating to 120 ℃, cooling with ice water to separate out a solid after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of a mixed solution of trimellitic anhydride acyl chloride (1.0 mol) and acetonitrile (10 mol) to be 5 ℃ (+/-3 ℃), adding 147g of catalyst CT-06A, adding hydrolysis intermediates in batches, slowly heating to 85 ℃ (+/-3 ℃) to react until raw materials disappear, removing the catalyst by heat filtration, cooling reaction liquid to 4 ℃ (+/-2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH value to be about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester tetracid intermediate;
refluxing the ester tetra-acid intermediate and 6 times volume of acetic anhydride for 6 hours, cooling and separating out solid to obtain a (4-phthalic anhydride) formyloxy-4-phthalic acid ester crude product. Decolorizing the crude product with toluene/DMF mixed solvent active carbon for 3 times, and recrystallizing to obtain 257.05g of high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester product, white powder with yield of 75.0% and content of 99.56%. The viscosity of the polymerized product and biphenyldiamine was 21.9 ten thousand, and the light transmittance of the prepared 50-micron thick PI film was 81.5%. The Coefficient of Thermal Expansion (CTE) at 50 to 300 ℃ is 13 ppm/DEG C, the tensile strength is 158MPa, and the modulus is 4.4GPa.
Example 2
Adding chlorophthalic anhydride (1.0 mol), water (8 mol) and potassium hydroxide (5.0 mol) into a reaction bottle, heating to 130 ℃, cooling with ice water to separate out solids after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of a mixed solution of trimellitic anhydride acyl chloride (1 mol) and THF (10 mol), adding 150g of CT-06B as a catalyst, adding hydrolysis intermediates in batches, slowly heating to 65 ℃ (± 3 ℃) to react until the raw materials disappear, removing the catalyst by thermal filtration, cooling the reaction solution to 4 ℃ (± 2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH to about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester-based tetraacid intermediate;
refluxing the ester tetra-acid intermediate and 6 times volume of acetic anhydride for 6 hours, cooling and separating out solid to obtain a (4-phthalic anhydride) formyloxy-4-phthalic acid ester crude product. Decolorizing the crude product with toluene/DMF mixed solvent active carbon for 3 times, and recrystallizing to obtain 275g of high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester product, white powder, yield 81.3% and content 99.65%. The viscosity of the product after polymerization with biphenyldiamine was measured to be 15.4 ten thousand, and the light transmittance of the prepared 50-micron thick PI film was 88.2%. The Coefficient of Thermal Expansion (CTE) at 50 to 300 ℃ is 13 ppm/DEG C, the tensile strength is 163MPa, and the modulus is 4.1GPa.
Example 3
Adding bromophthalic anhydride (1.2 mol), water (5 mol) and sodium hydroxide (6.0 mol) into a reaction bottle, heating to 120 ℃, cooling with ice water to separate out a solid after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of a mixed solution of trimellitic anhydride acyl chloride (1 mol) and DMAc (5 mol), controlling the temperature to be 25 ℃ (± 3 ℃), adding 147g of catalyst CT-06C, adding hydrolysis intermediates in batches, reacting until the raw materials disappear, thermally filtering to remove the catalyst, cooling the reaction solution to 4 ℃ (± 2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH to be about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester-based tetraacid intermediate;
refluxing the ester tetra-acid intermediate and 10 times volume of acetic anhydride for 5 hours, cooling and separating out solid to obtain a crude product of (4-phthalic anhydride) formyloxy-4-phthalic acid ester. Decolorizing the crude product with toluene/DMF mixed solvent active carbon for 3 times, and recrystallizing to obtain 291.2g of high-purity (4-phthalic anhydride) formyloxy-4-phthalate product as white powder with yield of 86.1% and content of 99.71%. The viscosity of the product after polymerization with TFMB was measured to be 21.8 ten thousand, and the light transmittance of the prepared 50 micron thick PI film was 89.5%. The Coefficient of Thermal Expansion (CTE) at 50-300 ℃ is 12 ppm/DEG C, the tensile strength is 183MPa, and the modulus is 5.2GPa.
Example 4
Adding bromo-phthalic anhydride (1.2 mol), water (5 mol) and potassium hydroxide (6.0 mol) into a reaction bottle, heating to 110 ℃, cooling with ice water to separate out a solid after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of a mixed solution of trimellitic anhydride acyl chloride (1 mol) and dichloromethane (8 mol), adding 148g of CT-06D as a catalyst, adding hydrolysis intermediates in batches, slowly heating to 35 ℃ (± 3 ℃) to react until the raw materials disappear, removing the catalyst by thermal filtration, cooling the reaction solution to 4 ℃ (± 2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH to about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester-based tetraacid intermediate;
refluxing the ester tetra-acid intermediate and 5 times volume of acetic anhydride for 6 hours, cooling and separating out solid to obtain a crude product of (4-phthalic anhydride) formyloxy-4-phthalic acid ester. The crude product is decolorized for 3 times by using toluene/DMF mixed solvent active carbon, and is recrystallized to obtain 284.5g of high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester product, white powder, yield 84.1 percent and content 99.76 percent. The viscosity of the product after polymerization with 6FODA was measured to be 61.8 ten thousand, and the light transmittance of the prepared 50-micron thick PI film was 88.6%. The Coefficient of Thermal Expansion (CTE) at 50 to 300 ℃ is 11 ppm/DEG C, the tensile strength is 177MPa, and the modulus is 5.0GPa.
Example 5
Adding bromo-phthalic anhydride (1.2 mol), water (5 mol) and sodium hydroxide (6.0 mol) into a reaction bottle, heating to 120 ℃, cooling with ice water to separate out a solid after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of a mixed solution of trimellitic anhydride acyl chloride (1 mol) and dioxane (10 mol), controlling the temperature to be 25 ℃ (± 3 ℃), adding 150g of CT-06E catalyst, adding hydrolysis intermediates in batches, slowly heating to 80 ℃ (± 3 ℃) to react until raw materials disappear, removing the catalyst by thermal filtration, cooling reaction liquid to be 5 ℃ (± 2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH to be about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester tetracid intermediate;
refluxing the ester tetra-acid intermediate and 6 times volume of acetic anhydride for 6 hours, cooling and separating out solid to obtain a (4-phthalic anhydride) formyloxy-4-phthalic acid ester crude product. Decolorizing the crude product with dioxane/DMF mixed solvent active carbon for 3 times, and recrystallizing to obtain high purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester product 278g, white powder, yield 82.2%, content 99.35%. The viscosity of the product after polymerization with 6FODA was measured to be 60.9 ten thousand, and the light transmittance of the prepared PI film with the thickness of 50 micrometers was 88.8%. The Coefficient of Thermal Expansion (CTE) at 50 to 300 ℃ is 10 ppm/DEG C, the tensile strength is 179MPa, and the modulus is 5.0GPa.
Example 6
Adding bromo-phthalic anhydride (1.2 mol), water (8 mol) and sodium hydroxide (6.0 mol) into a reaction bottle, heating to 120 ℃, cooling with ice water to separate out a solid after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of a mixed solution of trimellitic anhydride acyl chloride (1 mol) and acetonitrile (10 mol), controlling the temperature to be 5 ℃ (± 3 ℃), adding 140g of CT-06D catalyst, adding hydrolysis intermediates in batches, slowly heating to 85 ℃ (± 3 ℃) to react until raw materials disappear, removing the catalyst by thermal filtration, cooling reaction liquid to 4 ℃ (± 2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH to be about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester-based tetraacid intermediate;
refluxing the ester tetra-acid intermediate and 6 times volume of acetic anhydride for 6 hours, cooling and separating out solid to obtain a (4-phthalic anhydride) formyloxy-4-phthalic acid ester crude product. Decolorizing the crude product with toluene/DMF mixed solvent active carbon for 3 times, recrystallizing to obtain high purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester product 287.2g, white powder, yield 84.9%, content 99.28%. The viscosity of the product after polymerization with ABHQ was measured to be 32.1 ten thousand and the light transmittance of the prepared 50 micron thick PI film was 81.6%. The Coefficient of Thermal Expansion (CTE) at 50-300 ℃ is 9 ppm/DEG C, the tensile strength is 156MPa, and the modulus is 5.8GPa.
Example 7
Adding bromo-phthalic anhydride (1.2 mol), dioxane (5 mol) and sodium hydroxide (6.0 mol) into a reaction bottle, heating to 120 ℃, cooling with ice water to separate out a solid after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of a mixed solution of trimellitic anhydride acyl chloride (1 mol) and acetonitrile (10 mol) at 5 ℃ (± 3 ℃), adding 150g of CT-06C as a catalyst, adding a hydrolysis intermediate in batches, slowly heating to 85 ℃ (± 3 ℃) to react until the raw materials disappear, removing the catalyst by thermal filtration, cooling the reaction solution to 4 ℃ (± 2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH to about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester-based tetraacid intermediate;
refluxing the ester tetra-acid intermediate and 6 times volume of acetic anhydride for 6 hours, cooling and separating out solid to obtain a (4-phthalic anhydride) formyloxy-4-phthalic acid ester crude product. Decolorizing the crude product with toluene/DMF mixed solvent active carbon for 3 times, recrystallizing to obtain high purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester product, 257.7g, white powder, yield 76.2%, content 99.15%. The viscosity of the product after polymerization with p-phenylenediamine was measured to be 16.9 ten thousand, and the light transmittance of the prepared 50-micron-thick PI film was 80.6%. The Coefficient of Thermal Expansion (CTE) at 50-300 ℃ is 14 ppm/DEG C, the tensile strength is 121MPa, and the modulus is 3.2GPa.
Example 8
Adding bromo-phthalic anhydride (1.3 mol), water (5 mol) and sodium hydroxide (9.0 mol) into a reaction bottle, heating to 120 ℃, cooling with ice water to separate out a solid after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of mixed solution of trimellitic anhydride acyl chloride (1 mol) and DMF (10 mol), adding 148g of CT-06C as a catalyst, adding hydrolysis intermediates in batches, slowly heating to 85 ℃ (± 3 ℃) to react until the raw materials disappear, removing the catalyst by thermal filtration, cooling reaction liquid to 4 ℃ (± 2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH to about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester-based tetraacid intermediate;
refluxing the ester tetra-acid intermediate and 6 times volume of acetic anhydride for 6 hours, cooling and separating out solid to obtain a (4-phthalic anhydride) formyloxy-4-phthalic acid ester crude product. Decolorizing the crude product with toluene/DMF mixed solvent active carbon for 3 times, recrystallizing to obtain high purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester product 270.9g, white powder with yield 80.1% and content 99.32%. The viscosity of the product after polymerization with biphenyldiamine was measured to be 33.6 ten thousand, and the light transmittance of the prepared 50-micron-thick PI film was 86.1%. The Coefficient of Thermal Expansion (CTE) at 50-300 ℃ is 14 ppm/DEG C, the tensile strength is 116MPa, and the modulus is 3.8GPa.
Example 9
Adding bromo-phthalic anhydride (1.2 mol), water (9 mol) and potassium hydroxide (5.0 mol) into a reaction bottle, heating to 120 ℃, cooling with ice water to separate out a solid after the raw materials completely react, filtering and drying to obtain a hydrolysis intermediate;
controlling the temperature of a mixed solution of 1mol of trimellitic anhydride acyl chloride and 10mol of DMF (dimethyl formamide), controlling the temperature to be 5 ℃ (± 3 ℃), adding 148g of CT-06C as a catalyst, adding hydrolysis intermediates in batches, slowly heating to 45 ℃ (± 3 ℃) after the addition is finished, reacting until raw materials disappear, removing the catalyst by heat filtration, cooling reaction liquid to 4 ℃ (± 2 ℃), dropwise adding 1.0M hydrochloric acid, adjusting the pH to be about 1, filtering, washing a filter cake, and performing vacuum drying to obtain an ester tetracid intermediate;
refluxing the ester tetra-acid intermediate and 5 times volume of acetic anhydride for 6 hours, cooling and separating out solid to obtain a crude product of (4-phthalic anhydride) formyloxy-4-phthalic acid ester. Decolorizing the crude product with THF/DMF mixed solvent active carbon for 3 times, recrystallizing to obtain high purity (4-phthalic anhydride) formyloxy-4-phthalate product 289.5g, white powder with yield 85.6%, content 99.98%, as shown in FIG. 2. The viscosity of the product after polymerization with 6FODA was measured to be 82.1 ten thousand, and the light transmittance of the prepared PI film with the thickness of 50 micrometers was 90.6%. The Coefficient of Thermal Expansion (CTE) at 50-300 ℃ is 8 ppm/DEG C, the tensile strength is 201MPa, and the modulus is 5.6GPa.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A catalyst for preparing high purity (4-phthalic anhydride) formyloxy-4-phthalate, characterized by: the catalyst is prepared from formaldehyde, dialkyl amine and ionic resin by a one-pot method.
2. A process for preparing high purity (4-phthalic anhydride) formyloxy-4-phthalate using the catalyst of claim 1, comprising the steps of:
s1: preparing a hydrolysis intermediate of the halogenated phthalic anhydride;
s2: mixing trimellitic anhydride acyl chloride, a hydrolysis intermediate, a catalyst and a solvent, heating until the reaction is complete, filtering to remove the catalyst, cooling the filtrate, acidifying, filtering, washing and drying in vacuum to obtain an ester tetra-acid intermediate;
s3: the estertetracarboxylic acid intermediate is dehydrated to obtain a crude product containing the desired product.
3. The method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate according to claim 2, wherein the specific operation method of step S1 is:
mixing halogenated phthalic anhydride with water and alkali, heating until the reaction is complete, cooling with ice water, filtering, and drying to obtain a required hydrolysis intermediate; preferably, the halogenated phthalic anhydride is chlorophthalic anhydride or bromophthalic anhydride, and the base is sodium hydroxide or potassium hydroxide.
4. The method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate according to claim 3, wherein the reaction temperature is 110 to 130 ℃.
5. The method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate according to claim 2, wherein: in the step S2, the molar ratio of the trimellitic anhydride chloride to the hydrolysis intermediate is 1:1-1.5, and the mass ratio of the trimellitic anhydride chloride to the catalyst is 1:0.2 to 3; preferably, the molar ratio of the trimellitic anhydride chloride to the hydrolysis intermediate is 1.1, and the mass ratio of the trimellitic anhydride chloride to the catalyst is 1:0.7.
6. the method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate according to claim 2, wherein the solvent in step S2 is one of ultrapure water, tetrahydrofuran, acetonitrile, dichloromethane, toluene, dioxane, N-dimethylformamide, N-dimethylacetamide; preferably ultrapure water or tetrahydrofuran.
7. The method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate according to claim 2, wherein the specific operation of step S3 is as follows:
and (3) mixing the estertetracarboxylic acid intermediate with acetic anhydride, heating to reflux, cooling after complete reaction, and filtering to obtain a crude product containing the required product.
8. The method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate according to claim 2, which further comprises the steps of:
s4: and mixing the crude product with a solvent, and recrystallizing to obtain the high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester.
9. The method for preparing high purity (4-phthalic anhydride) formyloxy-4-phthalate according to claim 2, further comprising the steps of:
s5: and (3) soaking the catalyst filtered in the step (S2) in alkali liquor for regeneration.
10. The method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate according to claim 9, wherein the main component in the lye comprises one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide; preferably, the main component in the alkali liquor is potassium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211007969.2A CN115232093B (en) | 2022-08-22 | 2022-08-22 | Method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211007969.2A CN115232093B (en) | 2022-08-22 | 2022-08-22 | Method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115232093A true CN115232093A (en) | 2022-10-25 |
| CN115232093B CN115232093B (en) | 2023-10-27 |
Family
ID=83680733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211007969.2A Active CN115232093B (en) | 2022-08-22 | 2022-08-22 | Method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115232093B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115301287A (en) * | 2022-08-22 | 2022-11-08 | 天津众泰材料科技有限公司 | Preparation method of high-purity p-phenylene-ditrimellitic dianhydride |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1901028A1 (en) * | 1969-01-10 | 1970-08-06 | Bayer Ag | Polyimides |
| CN101402625A (en) * | 2008-10-15 | 2009-04-08 | 南京工业大学 | Process for producing aromatic diaether dianhydride monomer |
| CN108727319A (en) * | 2018-09-05 | 2018-11-02 | 常州大学 | A kind of preparation method of 3- nitrophthalic acids acid anhydride |
| CN110878012A (en) * | 2019-10-16 | 2020-03-13 | 南京大学 | Synthetic method of E-type methyl styrene compound |
| CN115301287A (en) * | 2022-08-22 | 2022-11-08 | 天津众泰材料科技有限公司 | Preparation method of high-purity p-phenylene-ditrimellitic dianhydride |
-
2022
- 2022-08-22 CN CN202211007969.2A patent/CN115232093B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1901028A1 (en) * | 1969-01-10 | 1970-08-06 | Bayer Ag | Polyimides |
| CN101402625A (en) * | 2008-10-15 | 2009-04-08 | 南京工业大学 | Process for producing aromatic diaether dianhydride monomer |
| CN108727319A (en) * | 2018-09-05 | 2018-11-02 | 常州大学 | A kind of preparation method of 3- nitrophthalic acids acid anhydride |
| CN110878012A (en) * | 2019-10-16 | 2020-03-13 | 南京大学 | Synthetic method of E-type methyl styrene compound |
| CN115301287A (en) * | 2022-08-22 | 2022-11-08 | 天津众泰材料科技有限公司 | Preparation method of high-purity p-phenylene-ditrimellitic dianhydride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115301287A (en) * | 2022-08-22 | 2022-11-08 | 天津众泰材料科技有限公司 | Preparation method of high-purity p-phenylene-ditrimellitic dianhydride |
| CN115301287B (en) * | 2022-08-22 | 2023-11-10 | 天津众泰材料科技有限公司 | Preparation method of high-purity p-phenylene-bis (trimellitate) dianhydride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115232093B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115232093B (en) | Method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate | |
| JP2006206825A (en) | Aromatic polyimide resin precursor and aromatic polyimide resin | |
| JP2005187768A (en) | Method for producing polyimide/inorganic composite material | |
| CN112029099B (en) | Preparation method of polyamide acid solution and polyimide film | |
| CN112375010B (en) | Novel diamine, polyimide and polyimide film | |
| CN115400793B (en) | Method for preparing high-purity bis [ (3, 4-dianhydride) phenyl ] terephthalate | |
| CN107936248A (en) | A kind of preparation method of polyimide resin | |
| CN115301287B (en) | Preparation method of high-purity p-phenylene-bis (trimellitate) dianhydride | |
| CN109666143B (en) | Preparation method of polyamic acid solution | |
| CN111087632B (en) | Preparation method of block type colorless transparent polyimide film, film and transparent substrate | |
| CN108997578B (en) | High-heat-resistance hyperbranched polyimide and preparation method and application thereof | |
| RU2644152C1 (en) | Method for producing polyimide copolymers containing crown-ethical and polysyloxane fragments | |
| CN111793009B (en) | Phthalonitrile monomer containing spiro structure and resin thereof | |
| WO2007034716A1 (en) | Soluble transparent polybenzoxazole precursor, polybenzoxazole and methods for producing those | |
| CN112062962B (en) | Polyimide and high heat-resistant low-expansion transparent polyimide film | |
| CN109054017B (en) | Hyperbranched polyimide containing phenanthrene ring structure and preparation method and application thereof | |
| CN101560166B (en) | Method for preparing 1,3-di(2-trifluoromethyl-4-aminophenoxy) benzene | |
| WO2008007629A1 (en) | Polyamic acid and polyimide | |
| CN113667119B (en) | Polyacetamide-imide film and preparation method thereof | |
| JP3475754B2 (en) | Novel polyimide precursor, polyimide and method for producing the same | |
| CN115477629B (en) | Preparation method and application of tetrafluoroethyl bis (phthalic anhydride) derivative | |
| CN111944147B (en) | Preparation method of thermosetting polyimide prepolymer | |
| CN101560163B (en) | Preparation method of 4,4'-bi(2-trifluoromethyl-4-aminophenoxyl)biphenyl | |
| KR100277161B1 (en) | Novel aromatic polyimide resin powder with improved processability and preparation method thereof | |
| CN116444394A (en) | Diamine monomer for preparing polyimide film, preparation method thereof and polyimide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |