CN112592475A - Preparation method and application of polyimide micropowder - Google Patents
Preparation method and application of polyimide micropowder Download PDFInfo
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- CN112592475A CN112592475A CN202011512603.1A CN202011512603A CN112592475A CN 112592475 A CN112592475 A CN 112592475A CN 202011512603 A CN202011512603 A CN 202011512603A CN 112592475 A CN112592475 A CN 112592475A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 61
- 239000004642 Polyimide Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 claims abstract description 27
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000000889 atomisation Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 11
- 150000004985 diamines Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 50
- 239000002245 particle Substances 0.000 claims description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 20
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000000969 carrier Substances 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
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- -1 4,4 ' -bis (2, 2 ' -bis trifluoromethyl-4-aminophenoxy) biphenyl Chemical group 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 claims description 2
- HBWBFCWUNUNGAQ-UHFFFAOYSA-N FC(C1(C(OC2=CC=CC=C2)C=CC(=C1)N)C(F)(F)F)(F)F Chemical compound FC(C1(C(OC2=CC=CC=C2)C=CC(=C1)N)C(F)(F)F)(F)F HBWBFCWUNUNGAQ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 238000009826 distribution Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 150000001263 acyl chlorides Chemical class 0.000 description 12
- 210000003298 dental enamel Anatomy 0.000 description 12
- 239000004005 microsphere Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 102220042174 rs141655687 Human genes 0.000 description 6
- 102220043159 rs587780996 Human genes 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229940031826 phenolate Drugs 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VETKABGDXXVERL-UHFFFAOYSA-N 4-[2-[2-[4-amino-2-(trifluoromethyl)phenoxy]phenyl]phenoxy]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1OC1=CC=C(N)C=C1C(F)(F)F VETKABGDXXVERL-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08G73/1075—Partially aromatic polyimides
Abstract
The invention discloses a preparation method and application of polyimide micro powder. Firstly, dissolving aromatic organic dianhydride and a catalyst in an organic alcohol solvent, carrying out esterification reaction for several hours at a certain temperature, and then dripping thionyl chloride at a low temperature to obtain acyl halide; then adding acyl halide into the solution in which diamine and catalyst are dissolved to obtain polyamic acid ester; spraying the polyamic acid ester into a precipitator solution rotating at a high speed through a high-pressure atomization device, centrifuging, washing with water, and drying to obtain the polyimide micro powder.
Description
Technical Field
The invention belongs to the technical field of polyimide, and particularly relates to a preparation method and application of polyimide micro powder.
Background
The polyimide micropowder is a high-performance polymer material containing imide functional groups in a series of molecular structures, not only has the characteristics of excellent high temperature resistance, high strength and toughness, corrosion resistance, low dielectric constant and the like, but also has the characteristics of large specific surface area, strong adsorbability, large condensation effect, active surface reaction capacity and the like, shows good application prospects in the fields of interlayer toughening, resin modification, catalyst carriers, photosensitive materials, pressure-sensitive materials, powder metallurgy and the like of composite materials, can also be widely used as substitutes and other effects of automobile parts, electronic components, metals and ceramics, and has been successfully applied to a part of products in the high and new technical fields of aerospace, microelectronics, solar energy, advanced electronic display and the like at present. However, there is still a great technical difficulty in processing polyimide into micron or even nanometer level powder in industrial mass production.
The main methods for preparing the polyimide micropowder at present include emulsion reprecipitation, liquid-liquid phase separation, ultrasonic precipitation, suspension polymerization, physical auxiliary methods and the like, which can prepare a small amount of microspheres, but have defects. Although the emulsion reprecipitation method can prepare polyimide microspheres with the particle size of less than 1 micron, the preparation efficiency of the microspheres is low, and only micro-upgraded dispersion liquid can be prepared once; the liquid-liquid phase separation method realizes the preparation of polyimide micro powder particles by controlling the phase separation of crystalline polyimide, and the polyimide micro powder particles are generally obtained by crystallization of oligomers, so the prepared micro powder particles have smaller molecular weight and poorer mechanical property; the micro powder prepared by suspension polymerization is generally 100-1000 um, but the dispersibility is poor; although a certain amount of polyimide micropowder can be obtained by physical assistance methods such as microwave assistance, the preparation method has low preparation efficiency and high requirements on equipment, and other methods have some defects in the aspects of controlling the particle size and particle size distribution of the polyimide micropowder.
U.S. Pat. No. 4, 6084000,78,78,78,78 provides a method for preparing hollow polyimide microspheres, which comprises adding dianhydride into methanol and ether solvent to synthesize diester diacid, adding diamine, heating to evaporate solvent to obtain polyamic acid, mechanically pulverizing, and treating at high temperature to obtain polyimide micropowder, wherein the size of the polyimide microsphere is 100-1500 μm, and the large particle size limits the difficulty in uniform dispersion during the mixing process of the composite material, thereby affecting the mechanical properties and the consistency of acoustic transmission.
Chai et al (j.polym.sci., PartB: polym.phys.,2003,41:159 to 165) prepared a polyimide resin using diaminodiphenyl ether and diphenyl ether tetracarboxylic dianhydride, and then dissolved in an organic solvent with a dispersant added thereto, can obtain a polyimide fine powder, but since the solubility of the resin is only 2wt%, it is difficult to realize large-scale industrial production.
Chinese patent CN 101089030a discloses a method for preparing polyimide microspheres, which comprises dissolving diamine and dianhydride in an organic solvent to synthesize polyamic acid, adding an imidization accelerator to the polyamic acid to synthesize polyimide, and adding an aqueous solution containing a dispersant dropwise into the polyimide solution. In the method, the dropwise added dispersion liquid cannot be in full contact with all polyimide structures in time, so that the obtained polyimide micro powder has wide particle size distribution and the particle size is difficult to control.
Chinese patent CN103570946 discloses a "method for preparing polyimide microspheres", which comprises synthesizing a polyamic acid solution with a solid content of 10wt% from dianhydride and diamine, diluting the polyamic acid solution to 1wt%, then dripping distilled water to obtain a polyamic acid microsphere solution, and dripping the microsphere solution into a mixed solution containing pyridine and acetic anhydride to obtain polyimide microspheres.
Based on the defects of the prior art, the invention develops a simple method for synthesizing the polyimide micro powder, and the method has simple operation and low requirement on equipment and is suitable for large-scale production.
Disclosure of Invention
The invention discloses a preparation method and application of polyimide micropowder, which is characterized in that the polyimide micropowder with specific particle size and distribution can be obtained by changing the molecular structure and the powder preparation conditions of resin.
The method disclosed by the invention is suitable for preparing various polyimide structures such as thermoplastic polyimide, thermosetting polyimide, photosensitive polyimide, pressure-sensitive polyimide and the like, and industrial application materials such as interlaminar toughening, resin modification, catalyst carriers and the like used as composite materials.
The technical scheme of the invention is as follows: the preparation method and the application of the polyimide micro powder comprise the following specific steps:
adding aromatic dianhydride, organic alcohol, catalyst and solvent into a reaction kettle provided with a stirring sleeve set, a temperature control sleeve set, an inert gas inlet and an inert gas outlet and a condensation reflux tower, and heating and refluxing for reaction for hours; then, reducing the temperature in the reaction kettle to 0 ℃, dropwise adding thionyl chloride at the temperature of 0-5 ℃, and reacting at room temperature for several hours after dropwise adding to obtain acyl halide; adding diamine, a catalyst and a solvent into the other reaction kettle with a stirring sleeve set, a temperature control sleeve set and an inert gas inlet and outlet, controlling the temperature in the kettle to be 0-5 ℃, dripping the prepared acyl halide, stirring for several hours after dripping is finished, and then heating to 25-30 ℃ to react for several hours to obtain a polyamic acid ester solution; injecting the polyamic acid ester solution into high-pressure atomization equipment, and spraying the resin into distilled water containing a precipitator by controlling the atomization pressure and the caliber of a nozzle; and centrifuging, washing and drying the obtained solution to obtain the polyimide micro powder.
The aromatic dianhydride used in the invention is one or a mixture of two of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4' -diphenyl ether tetracarboxylic dianhydride, 2, 2-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic dianhydride, 1,2,4, 5-tetracarboxylic dianhydride, 3,3 ', 4, 4' -diphenyl sulfide tetracarboxylic dianhydride, 2,3,3 ', 4' -biphenyl tetracarboxylic dianhydride and 2, 2-bis (3, 4-dicarboxylic acid) isopropane dianhydride.
The diamine used in the present invention is one or a mixture of two of 2,2 ' -bis (3-amino-4-phenolate) hexafluoropropane, 4,4 ' -bis (2, 2 ' -bis trifluoromethyl-4-aminophenoxy) benzene, 2,2 ' -bis (3-amino-4-phenolate) isopropane, 4,4 ' -bis (2, 2 ' -bis trifluoromethyl-4-aminophenoxy) biphenyl, 2,2 ' -bis (4-amino-3-phenolate) hexafluoropropane, and 3,3 ' -diamino-4, 4 ' -dihydroxybiphenyl sulfide.
The organic alcohol used in the invention is one or a mixture of two of n-butyl alcohol, ethanol and methanol.
The catalyst used in the invention is one or a mixture of two of triethylamine, pyridine, sodium acetate and isoquinoline.
The precipitant used in the invention is one or a mixture of two of polyacrylic acid, polyvinyl alcohol and polymethacrylate.
The solvent used in the invention is one or a mixture of two of tetrahydrofuran, N, N-dimethylacetamide, DMSO, m-cresol and methyl pyrrolidone.
The heating reflux time in the invention is 2-24 hours; after the thionyl chloride is added, the reaction time at room temperature is 3-5 hours; dropwise adding acyl halide and stirring for 2-24 hours; the reaction time after the temperature is raised to 25-30 ℃ is 3-5 hours.
The feeding molar ratio of the aromatic dianhydride, the organic alcohol, the catalyst, the solvent and the thionyl chloride is as follows: (1.00) (2.05-2.10), (0.01-0.05), (6-10), (2.05-2.1).
The feeding molar ratio of the diamine, the catalyst, the solvent and the acyl halide used in the invention is as follows: (1.05-1.10), (0.01-0.05), (10-15), (1.00).
The pressure range of the high-pressure atomization adopted by the invention is as follows: 0.5 to 0.7 MPa; the nozzle size is: 0.02-0.1 mm.
The drying process adopted by the invention comprises the following steps: 80 ℃/1-2 hours; 120 ℃/1-2 hours; 150 ℃/2-4 hours; 180 ℃/2-4 hours; 220 ℃/4-6 hours; 260 ℃/6-8 hours; 300 ℃/1-2 hours.
The particle size range of the polyimide micropowder prepared by the invention is as follows: d10 (1.718-17.846 um), D50 (2.881-35.216 um), and D90 (4.729-59.575 um).
The invention is suitable for preparing polyimide materials with different molecular structures, such as thermoplastic polyimide, thermosetting polyimide, photosensitive polyimide, pressure-sensitive polyimide and the like, and has wide application prospect in the industrial fields of interlayer toughening of composite materials, resin modification, catalyst carriers and the like.
Drawings
FIG. 1 is a particle size distribution diagram of the polyimide micropowder prepared in the first example.
FIG. 2 is a particle size distribution diagram of the polyimide micropowder prepared in example two.
FIG. 3 is a particle size distribution diagram of the polyimide micropowder prepared in example III.
FIG. 4 is a particle size distribution diagram of the polyimide micropowder prepared in example four.
FIG. 5 is a particle size distribution diagram of a polyimide micropowder prepared in example V.
FIG. 6 is a particle size distribution diagram of a polyimide micropowder prepared in example six.
Detailed Description
The first embodiment is as follows: adding 515.6g of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 237.2g of N-butanol, 8g of triethylamine and 1200g of N-methylpyrrolidone into a 5L enamel reaction kettle provided with a stirring sleeve set, a temperature control sleeve set, an inert gas protection device and a condensation reflux device, heating to 75-80 ℃, stirring and refluxing for 12 hours, and then reducing the temperature of the solution to 0 ℃; keeping the temperature of the solution within the range of 0-5 ℃, starting to dropwise add 384.4g of thionyl chloride, and stirring and reacting at normal temperature for 3 hours after dropwise addition is finished to obtain an acyl chloride compound; adding 2100g of N-methylpyrrolidone, 585.3g of 2,2 '-bis (3-amino-4-phenolic) hexafluoropropane and 455.6g of pyridine into another 5L enamel reaction kettle provided with a stirring sleeve, a temperature control sleeve and an inert gas protection device, stirring until the N-methylpyrrolidone, the 2, 2' -bis (3-amino-4-phenolic) hexafluoropropane and the pyridine are completely dissolved, cooling the solution to 0-5 ℃ by adopting an ice water bath, then dripping acyl chloride compounds into the solution, keeping stirring at a low temperature for reacting for 4 hours after dripping is finished, and then heating to room temperature and stirring for 3 hours to obtain a polyamic acid ester resin; injecting the resin into high-pressure atomization equipment, adjusting the atomization pressure to be 0.5MPa, spraying the resin into polyacrylic acid aqueous solution which is stirred at high speed by adopting a nozzle with the caliber of 0.1mm, then centrifugally desolventizing, washing for multiple times, and drying by controlling the temperature in stages to obtain the polyimide micropowder. The particle size data of the micro powder is as follows: d10=17.846um, D50=35.216um, D90=59.575um, and the specific particle size distribution is shown in figure 1.
Example two: adding 497g of 2,3,3 ', 4' -diphenyl ether tetracarboxylic dianhydride, 75g of ethanol, 119g of butanol, 8g (0.08 mol) of triethylamine and 1200g of N-methylpyrrolidone into a 5L enamel reaction kettle provided with a stirring sleeve set, a temperature control sleeve set, an inert gas protection device and a condensation reflux device, heating to 75-80 ℃, and cooling the solution to 0 ℃ after stirring reflux reaction for 12 hours; keeping the temperature of the solution within the range of 0-5 ℃, starting to dropwise add 384.4g of thionyl chloride, and stirring and reacting at normal temperature for 3 hours after dropwise addition is finished to obtain an acyl chloride compound; adding 2100g of N-methylpyrrolidone, 585.3g of 2,2 '-bis (3-amino-4-phenolic) hexafluoropropane and 455.6g of pyridine into another 5L enamel reaction kettle provided with a stirring sleeve, a temperature control sleeve and an inert gas protection device, stirring until the N-methylpyrrolidone, the 2, 2' -bis (3-amino-4-phenolic) hexafluoropropane and the pyridine are completely dissolved, cooling the solution to 0-5 ℃ by adopting an ice water bath, then dripping acyl chloride compounds into the solution, keeping stirring at a low temperature for reacting for 4 hours after dripping is finished, and then heating to room temperature and stirring for 3 hours to obtain a polyamic acid ester resin; injecting the resin into high-pressure atomization equipment, adjusting the atomization pressure to be 0.5MPa, spraying the resin into polyacrylic acid aqueous solution which is stirred at high speed by adopting a nozzle with the caliber of 0.1mm, then centrifugally desolventizing, washing for multiple times, and drying by controlling the temperature in stages to obtain the polyimide micropowder. The particle size data of the micro powder is as follows: d10=7.667um, D50=16.363um, D90=42.327um, and the specific particle size distribution is shown in figure 2.
Example three: adding 344g of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 807.3g of 2, 2-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 237.2g of N-butanol, 8g of triethylamine and 1000g of N-methylpyrrolidone into a 5L enamel reaction kettle provided with a stirring sleeve set, a temperature control sleeve set, an inert gas protection device and a condensing reflux device, heating to 75-80 ℃, and carrying out stirring reflux reaction for 12 hours to reduce the temperature of the solution to 0 ℃; keeping the temperature of the solution within the range of 0-5 ℃, starting to dropwise add 384.4g of thionyl chloride, and stirring and reacting at normal temperature for 3 hours after dropwise addition is finished to obtain an acyl chloride compound; adding 2100g of N-methylpyrrolidone, 585.3g of 2,2 '-bis (3-amino-4-phenolic) hexafluoropropane and 455.6g of pyridine into another 5L enamel reaction kettle provided with a stirring sleeve, a temperature control sleeve and an inert gas protection device, stirring until the N-methylpyrrolidone, the 2, 2' -bis (3-amino-4-phenolic) hexafluoropropane and the pyridine are completely dissolved, cooling the solution to 0-5 ℃ by adopting an ice water bath, then dripping acyl chloride compounds into the solution, keeping stirring at a low temperature for reacting for 4 hours after dripping is finished, and then heating to room temperature and stirring for 3 hours to obtain a polyamic acid ester resin; injecting the resin into high-pressure atomization equipment, adjusting the atomization pressure to be 0.55MPa, spraying the resin into polyacrylic acid aqueous solution which is stirred at high speed by adopting a nozzle with the caliber of 0.1mm, then centrifugally desolventizing, washing for multiple times, and drying by controlling the temperature in stages to obtain the polyimide micropowder. The particle size data of the micro powder is as follows: d10=7.741um, D50=11.011um, D90=15.577um, and the specific particle size distribution is shown in figure 3.
Example four: adding 3,3 ', 4' -diphenyl sulfone tetracarboxylic dianhydride 573.3, N-butyl alcohol 119.6g, ethanol 73.7g, triethylamine 8g and N-methyl pyrrolidone 1200g into a 5L enamel reaction kettle provided with a stirring sleeve set, a temperature control sleeve set, an inert gas protection device and a condensation reflux device, heating to 75-80 ℃, stirring and refluxing for 12 hours, and then cooling the solution to 0 ℃; keeping the temperature of the solution within the range of 0-5 ℃, starting to dropwise add 384.4g of thionyl chloride, and stirring and reacting at normal temperature for 3 hours after dropwise addition is finished to obtain an acyl chloride compound; adding 2100g of N-methylpyrrolidone, 585.3g of 2,2 '-bis (3-amino-4-phenolic) hexafluoropropane and 455.6g of pyridine into another 5L enamel reaction kettle provided with a stirring sleeve, a temperature control sleeve and an inert gas protection device, stirring until the N-methylpyrrolidone, the 2, 2' -bis (3-amino-4-phenolic) hexafluoropropane and the pyridine are completely dissolved, cooling the solution to 0-5 ℃ by adopting an ice water bath, then dripping acyl chloride compounds into the solution, keeping stirring at a low temperature for reacting for 4 hours after dripping is finished, and then heating to room temperature and stirring for 3 hours to obtain a polyamic acid ester resin; injecting the resin into high-pressure atomization equipment, adjusting the atomization pressure to be 0.55MPa, spraying the resin into polyacrylic acid aqueous solution which is stirred at high speed by adopting a nozzle with the caliber of 0.04mm, then centrifugally desolventizing, washing for multiple times, and drying by controlling the temperature in stages to obtain the polyimide micropowder. The particle size data of the micro powder is as follows: d10=4.807um, D50=6.926um, D90=9.932um, and the specific particle size distribution is shown in figure 4.
Example five: adding 807.3g of 2, 2-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 286.6g of 3,3 ', 4' -diphenylsulfone tetracarboxylic dianhydride, 147g of ethanol, 8g of triethylamine and 1200g of N-methylpyrrolidone into a 5L enamel reaction kettle provided with a stirring sleeve set, a temperature control sleeve set, an inert gas protection device and a condensation reflux device, heating to 75-80 ℃, and carrying out stirring reflux reaction for 12 hours to reduce the temperature of the solution to 0 ℃; keeping the temperature of the solution within the range of 0-5 ℃, starting to dropwise add 384.4g of thionyl chloride, and stirring and reacting at normal temperature for 3 hours after dropwise addition is finished to obtain an acyl chloride compound; adding 2100g of N-methylpyrrolidone, 585.3g of 2,2 '-bis (3-amino-4-phenolic) hexafluoropropane and 455.6g of pyridine into another 5L enamel reaction kettle provided with a stirring sleeve, a temperature control sleeve and an inert gas protection device, stirring until the N-methylpyrrolidone, the 2, 2' -bis (3-amino-4-phenolic) hexafluoropropane and the pyridine are completely dissolved, cooling the solution to 0-5 ℃ by adopting an ice water bath, then dripping acyl chloride compounds into the solution, keeping stirring at a low temperature for reacting for 4 hours after dripping is finished, and then heating to room temperature and stirring for 3 hours to obtain a polyamic acid ester resin; injecting the resin into high-pressure atomization equipment, adjusting the atomization pressure to be 0.6MPa, adopting a nozzle with the caliber of 0.04mm, spraying the resin into a polyvinyl alcohol aqueous solution stirred at a high speed, then centrifugally desolventizing, washing for multiple times, and drying by controlling the temperature in stages to obtain the polyimide micropowder. The particle size data of the micro powder is as follows: d10=1.796um, D50=4.049um, D90=8.655um, and the specific particle size distribution is shown in figure 5.
Example six: adding 515.6g (1.6 mol) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 237.2g (3.2mol) of butanol, 8g (0.08 mol) of triethylamine and 1200g of N-methylpyrrolidone into a 5L enamel reaction kettle provided with a stirring sleeve set, a temperature control sleeve set, an inert gas protection device and a condensation reflux device, heating to 75-80 ℃, and carrying out stirring reflux reaction for 12 hours to reduce the temperature of the solution to 0 ℃; keeping the temperature of the solution within the range of 0-5 ℃, starting to dropwise add 384.4g (3.232 mol) of thionyl chloride, and stirring and reacting at normal temperature for 3 hours after dropwise addition to obtain an acyl chloride compound; adding 1000g of tetrahydrofuran, 1000g of N-methylpyrrolidone, 256.2g of 4,4 ' -bis (2, 2 ' -bis (trifluoromethyl-4-aminophenoxy) biphenyl, 293.0g of 2,2 ' -bis (4-amino-3-phenol) hexafluoropropane and 455.6g of pyridine into another 5L enamel reaction kettle provided with a stirring sleeve set, a temperature control sleeve set and an inert gas protection device, stirring until the mixture is completely dissolved, cooling the solution to 0-5 ℃ by adopting an ice water bath, then dripping an acyl chloride compound into the solution, keeping stirring at a low temperature for reaction for 4 hours after dripping is finished, and then heating to room temperature and stirring for 3 hours to obtain a polyamide ester resin; injecting the resin into high-pressure atomization equipment, adjusting the atomization pressure to be 0.65MPa, adopting a nozzle with the caliber of 0.04mm, spraying the resin into a polyvinyl alcohol aqueous solution stirred at a high speed, then centrifugally desolventizing, washing for multiple times, and drying by controlling the temperature in stages to obtain the polyimide micropowder. The particle size data of the micro powder is as follows: d10=1.718um, D50=2.881um, D90=4.729um, and the specific particle size distribution is shown in figure 6.
Claims (9)
1. The preparation of the polyimide micro powder comprises the following steps: adding aromatic dianhydride, organic alcohol, catalyst and solvent into a reaction kettle provided with a stirring sleeve set, a temperature controller, an inert gas inlet and an inert gas outlet and a condensation reflux tower, and heating and refluxing for reaction for hours; then, reducing the temperature in the reaction kettle to 0 ℃, dropwise adding thionyl chloride at the temperature of 0-5 ℃, and reacting at room temperature for several hours after dropwise adding to obtain acyl halide; adding diamine, a catalyst and a solvent into the other reaction kettle with a stirring sleeve set, a temperature controller and an inert gas inlet and outlet, controlling the temperature in the kettle to be 0-5 ℃, dripping the prepared acyl halide, stirring for several hours after dripping is finished, and then heating to 25-30 ℃ to react for several hours to obtain a polyamic acid ester solution; injecting the polyamic acid ester solution into high-pressure atomization equipment, and spraying the resin into distilled water containing a precipitator by controlling the atomization pressure and the caliber of a nozzle; and centrifuging, washing and drying the obtained solution to obtain the polyimide micro powder.
2. The aromatic dianhydride according to claim 1, which is one or a mixture of two of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4' -diphenyl ether tetracarboxylic dianhydride, 2, 2-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic dianhydride, 1,2,4, 5-tetracarboxylic dianhydride, 3,3 ', 4, 4' -diphenyl sulfide tetracarboxylic dianhydride, 2,3,3 ', 4' -biphenyl tetracarboxylic dianhydride, 2, 2-bis (3, 4-dicarboxylic acid) isopropane dianhydride; the diamine is one or a mixture of two of 2,2 ' -bis (3-amino-4-phenolic) hexafluoropropane, 4,4 ' -bis (2, 2 ' -bis trifluoromethyl-4-aminophenoxy) benzene, 2,2 ' -bis (3-amino-4-phenolic) isopropane, 4,4 ' -bis (2, 2 ' -bis trifluoromethyl-4-aminophenoxy) biphenyl, 2,2 ' -bis (4-amino-3-phenolic) hexafluoropropane and 3,3 ' -diamino-4, 4 ' -dihydroxydiphenyl sulfide; the organic alcohol is one or a mixture of n-butanol, ethanol and methanol; the catalyst is one or a mixture of two of triethylamine, pyridine, sodium acetate and isoquinoline; the precipitator is one or a mixture of two of polyacrylic acid, polyvinyl alcohol and polymethacrylate; the solvent is one or a mixture of two of tetrahydrofuran, N, N-dimethylacetamide, DMSO and methyl pyrrolidone.
3. The heating reflux time of claim 1 is 2 to 24 hours; after the thionyl chloride is added, reacting at room temperature for 3-5 hours; dropwise adding acyl halide and stirring for 2-24 hours; heating to 25-30 ℃ and reacting for 3-5 hours.
4. The aromatic dianhydride according to claim 1, wherein the molar ratio of the aromatic dianhydride to the organic alcohol to the catalyst to the solvent to the thionyl chloride is as follows: (1.00) (2.05-2.10), (0.01-0.05), (6-10), (2.05-2.1).
5. The diamine, catalyst, solvent and acyl halide of claim 1, wherein the molar ratio of the diamine, catalyst, solvent and acyl halide is as follows: (1.05-1.10), (0.01-0.05), (10-15), (1.00).
6. The pressure range for high pressure atomization according to claim 1 is: 0.5 to 0.7 MPa; the nozzle size is: 0.02-0.1 mm.
7. The drying process according to claim 1 is: 80 ℃/1-2 hours; 120 ℃/1-2 hours; 150 ℃/2-4 hours; 180 ℃/2-4 hours; 220 ℃/4-6 hours; 260 ℃/6-8 hours; 300 ℃/1-2 hours.
8. The particle size range of the polyimide micropowder produced according to claim 1: d10 (1.718-17.846 um), D50 (2.881-35.216 um), and D90 (4.729-59.575 um).
9. The polyimide material with different molecular structures, such as thermoplastic polyimide, thermosetting polyimide, photosensitive polyimide, pressure-sensitive polyimide and the like, containing the polyimide micropowder of claim 1, and industrial applications of interlaminar toughening, resin modification, catalyst carriers and the like of composite materials.
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