CN114230790A - Polyimide powder and preparation method thereof - Google Patents
Polyimide powder and preparation method thereof Download PDFInfo
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- CN114230790A CN114230790A CN202111600048.2A CN202111600048A CN114230790A CN 114230790 A CN114230790 A CN 114230790A CN 202111600048 A CN202111600048 A CN 202111600048A CN 114230790 A CN114230790 A CN 114230790A
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- Prior art keywords
- polyimide powder
- dianhydride
- polyimide
- bis
- fluorine
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 71
- 239000004642 Polyimide Substances 0.000 title claims abstract description 56
- 239000000843 powder Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title description 18
- 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 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 238000000926 separation method Methods 0.000 claims description 19
- 239000012452 mother liquor Substances 0.000 claims description 13
- -1 4-aminophenoxyphenyl Chemical group 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 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 3
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 claims description 3
- UBRWLZBVGVNUNP-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1-trifluoropropan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C(F)(F)F)(C)C1=CC=C(N)C=C1 UBRWLZBVGVNUNP-UHFFFAOYSA-N 0.000 claims description 3
- KZSXRDLXTFEHJM-UHFFFAOYSA-N 5-(trifluoromethyl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC(C(F)(F)F)=C1 KZSXRDLXTFEHJM-UHFFFAOYSA-N 0.000 claims description 3
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 abstract description 6
- 238000005507 spraying Methods 0.000 abstract description 6
- 238000001125 extrusion Methods 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 abstract description 4
- 239000009719 polyimide resin Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BIXGISJFDUHZEB-UHFFFAOYSA-N 2-[9,9-bis(4-methylphenyl)fluoren-2-yl]-9,9-bis(4-methylphenyl)fluorene Chemical compound C1=CC(C)=CC=C1C1(C=2C=CC(C)=CC=2)C2=CC(C=3C=C4C(C5=CC=CC=C5C4=CC=3)(C=3C=CC(C)=CC=3)C=3C=CC(C)=CC=3)=CC=C2C2=CC=CC=C21 BIXGISJFDUHZEB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—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
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides polyimide powder, which is obtained by copolymerizing fluorine-containing aromatic diamine, fluorine-containing aromatic dianhydride, other aromatic dianhydride and other aromatic diamine, and is amorphous powder with the particle size of less than 0.28 mm. The powder can be prepared by processes of mould pressing, extrusion, injection molding, spraying and the like. Has wide application prospect in the fields of mould pressing, extrusion, injection molding, spraying and the like.
Description
Technical Field
The invention relates to the field of polyimide materials, in particular to polyimide powder and a preparation method thereof.
Technical Field
The polyimide material is a special high polymer material with high and low temperature resistance, flame retardance and stable size. Due to the excellent performance, the polyimide resin and the composite material are widely applied to the fields of communication electronics, aerospace, rail transit and the like, particularly to the fields of national defense equipment, electronic and electrical appliances and used as functional products with wave transmission, dielectric, high and low temperature resistance and the like, and the polyimide resin and the composite material can be used as wave-transmitting antenna materials, low-dielectric electric conduction materials, 5G communication materials and the like.
With the requirements of ultra-high-speed transmission and ultra-low delay of communication, the dielectric performance of the used dielectric material is required to be continuously improved, and a material with a lower dielectric constant is required to be adopted. In view of practical application of high frequency signal transmission, it is also required that the dielectric material has sufficient mechanical strength and good processability in a complicated environment.
The low-dielectric polyimide material used at present is a thermosetting polyimide composite material with a complex film and complex manufacturability, has a relatively high dielectric constant and large loss on transmission signals, and cannot be applied to the field with complex size requirements and higher dielectric property requirements. The low-dielectric fusible polyimide resin belongs to one of high-temperature-resistant low-dielectric high polymer materials, and has wide application prospect in the fields of aerospace, communication electronics and the like due to the low dielectric property, particularly good processing properties such as extrudability, injection molding, spraying and the like. The low dielectric polyimide materials disclosed so far are mainly films and fibers, and a large number of soluble polyimide resins have been reported.
How to prepare the polyimide resin compatible with the processes of mould pressing, extrusion, injection molding, spraying and the like is a blank in the prior art.
Disclosure of Invention
In view of the above, the present invention provides a novel polyimide powder material with low dielectric constant, melting property and easy processing, which can be used in combination with molding, extrusion, injection molding, spraying and other processes to obtain different required profiles or product products. Can also be used as a functional additive for heat resistance, toughening and the like and is used in epoxy resin, phenolic resin, bismaleimide resin and fiber reinforced resin matrix composite materials.
The polyimide powder is obtained by copolymerizing fluorine-containing aromatic diamine, fluorine-containing aromatic dianhydride, other aromatic dianhydride and other aromatic diamine, and is amorphous powder with the particle size of less than 0.28 mm.
According to the polyimide powder provided by the invention, the dielectric constant of the polyimide powder is in a range of 2.9-3.3.
According to the polyimide powder provided by the present invention, the fluorine-containing aromatic diamine is any one or more of 1, 1-bis (4-aminophenyl) -1-trifluoromethyl-ethane (3FDAM), 2-bis (4-aminophenyl) hexafluoropropane (6FDAM), 2-bis [4- (4-aminophenoxyphenyl) ] hexafluoropropane (BDAF), and 3, 5-Diaminobenzotrifluoride (DABTF).
According to the polyimide powder provided by the invention, the other aromatic diamine is any one or more of p-phenylenediamine, 4' -diaminodiphenyl sulfone (DDS), 4' -bis (3-aminophenoxy) diphenyl sulfone (m-BAPS), 2 ' -bis [4- (4-aminophenoxy phenyl) ] propane (BAPP) and m-phenylenediamine.
According to the polyimide powder provided by the invention, the fluorine-containing aromatic dianhydride is any one or more of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride (P6FDA), 3-trifluoromethyl-6-methyl pyromellitic dianhydride (P3FDA) and trifluoro dianhydride (3 FDA).
According to the polyimide powder provided by the present invention, the other aromatic dianhydride is any one or more of pyromellitic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA), and bisphenol a dianhydride (BPADA).
Another aspect of the present invention also provides a method for preparing polyimide powder, comprising the steps of:
s1, preparing polyimide mother liquor;
s2, adding the mother solution into a centrifugal device, and carrying out centrifugal solid-liquid separation to obtain initial resin;
s3, washing the initial resin with a detergent, and drying to obtain polyimide powder.
According to the method for producing a polyimide powder of the present invention, the polyimide powder has a particle diameter of less than 0.28mm and is an amorphous polyimide powder.
According to the preparation method of the polyimide powder, the rotating speed of the centrifugal equipment for solid-liquid separation is 1000-2000 rpm.
According to the preparation method of the polyimide powder provided by the invention, the detergent is ethanol, acetone or a mixture of the ethanol and the acetone.
According to the preparation method of the polyimide powder provided by the invention, the preparation method of the mother liquor comprises the following steps:
a) under the protection of inert gas, adding diamine monomer into polar solvent and xylene for full dissolution, and then heating to 110-130 ℃ to obtain a first mixed solution;
b) adding dianhydride monomer into the first mixed solution in batches, and continuously heating to 150-180 ℃ for reaction to form polyimide mother solution.
According to the preparation method of the polyimide powder provided by the invention, the inert gas is nitrogen.
According to the preparation method of the polyimide powder provided by the invention, the reaction temperature in the step b) is 170-180 ℃.
According to the method for producing the polyimide powder, at least one of the diamine monomer and the dianhydride monomer contains an aromatic fluorine-containing monomer.
According to the preparation method of the polyimide powder provided by the invention, the aromatic fluorine-containing monomer is fluorine-containing aromatic diamine or fluorine-containing aromatic dianhydride.
According to the preparation method of the polyimide powder provided by the invention, the fluorine-containing aromatic dianhydride is any one or more of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride (P6FDA), 3-trifluoromethyl-6-methyl pyromellitic dianhydride (P3FDA) and trifluoro dianhydride (3 FDA).
According to the method for producing a polyimide powder, provided by the present invention, the fluorine-containing aromatic diamine is any one or more of 1, 1-bis (4-aminophenyl) -1-trifluoromethyl-ethane (3FDAM), 2-bis (4-aminophenyl) hexafluoropropane (6FDAM), 2-bis [4- (4-aminophenoxyphenyl) ] hexafluoropropane (BDAF), and 3, 5-Diaminobenzotrifluoride (DABTF).
According to the preparation method of the polyimide powder provided by the invention, the diamine monomer and the dianhydride monomer also contain other aromatic diamine monomers and other aromatic dianhydride monomers,
according to the preparation method of the polyimide powder provided by the invention, the other aromatic diamine is any one or more of p-phenylenediamine, 4' -diaminodiphenyl sulfone (DDS), 4' -bis (3-aminophenoxy) diphenyl sulfone (m-BAPS), 2 ' -bis [4- (4-aminophenoxy phenyl) ] propane (BAPP) and m-phenylenediamine.
According to the preparation method of the polyimide powder provided by the invention, the other aromatic dianhydride is any one or more of pyromellitic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA) and bisphenol A dianhydride (BPADA).
According to the preparation method of the polyimide powder, the molar ratio of the dianhydride monomer to the diamine monomer is 0.95-1.10.
According to the preparation method of the polyimide powder, the reaction time of the step b) is 12-15 h.
According to the preparation method of the polyimide powder, the polar solvent is dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and tetrahydrofuran.
According to the preparation method of the polyimide powder provided by the invention, after the step S1 and before the step S2, no additive for promoting precipitation is required to be added.
The polyimide powder provided by the invention can be melted at high temperature, can be compatible with processes such as mould pressing, extrusion, injection molding, spraying and the like to obtain section bars or product products with different requirements, can also be used as functional modifications such as heat resistance, toughening and the like to be used in epoxy resin, phenolic resin, bismaleimide resin and fiber reinforced resin matrix composite materials, and can also be compounded with thermoplastic resins such as polyether ether ketone, polyether sulfone and the like to be used.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the present application will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
Adding 201.42g of N-methylpyrrolidone and 35.01g of dimethylbenzene into a four-neck round-bottom flask equipped with a mechanical stirrer, a water separator, a condensation reflux device and nitrogen protection, starting stirring, then adding 25.95g m-BAPS and 6.75g of m-phenylenediamine to be fully dissolved, heating to 116 ℃, adding 26.43g of pyromellitic dianhydride in three batches, heating to 160 ℃ after the addition is finished, and reacting for 12 hours to obtain polyimide resin mother liquor. Adding the mother liquor into a centrifugal separation device with the rotation number of 1000rpm for solid-liquid separation to obtain initial resin, adding the initial resin and an ethanol detergent into a self-made circulating washing device according to a certain proportion, carrying out centrifugal separation again, and carrying out vacuum drying on the washed and filtered resin to obtain the low-dielectric fusible polyimide resin, wherein the dielectric constant of the resin is 3.2, the particle size of the resin is 140 meshes, the tensile strength is 95MPa, and the impact strength is 187kJ/m 2.
Example 2
236.2g of N-methylpyrrolidone and 38.4g of dimethylbenzene are added into a four-neck round-bottom flask which is provided with a mechanical stirrer, a water separator, a condensation reflux device and nitrogen protection, stirring is started, then 25.92g of BDAF and 6.75g of p-phenylenediamine are added until the N-methylpyrrolidone and the dimethylbenzene are fully dissolved, the temperature is raised to 118 ℃, 36.44g of BPDA is added in three batches, and the temperature is raised to 163 ℃ after the addition is finished, and the reaction is carried out for 10 hours, so that the polyimide resin mother liquor is obtained. Adding the mother liquor into a centrifugal separation device with the rotation speed of 1000rpm for solid-liquid separation to obtain initial resin, adding the initial resin and an ethanol detergent into a self-made circulating washing device according to a certain proportion, carrying out centrifugal separation again, circulating for 2 times, and carrying out vacuum drying on the washed and filtered resin to obtain the low-dielectric fusible polyimide resin, wherein the dielectric constant of the resin is 3.0, the particle size of the resin is 100 meshes, the tensile strength is 102MPa, and the impact strength is 165kJ/m 2.
Example 3
Adding 217.82g of N-methylpyrrolidone and 32.02g of xylene into a four-neck round-bottom flask equipped with a mechanical stirrer, a water separator, a condensation reflux device and nitrogen protection, starting stirring, then adding 26.21g of DABTF and 5.02g of DDS until the mixture is fully dissolved, heating to 119 ℃, adding 31.49g of BPADA in three batches, heating to 165 ℃ after the addition is finished, and reacting for 14 hours to obtain a polyimide resin mother liquor. Adding the mother liquor into a centrifugal separation device with the rotation number of 1200rpm for solid-liquid separation to obtain initial resin, adding the initial resin and an ethanol detergent into a self-made circulating washing device according to a certain proportion, carrying out centrifugal separation again, and carrying out vacuum drying on the washed and filtered resin to obtain the low-dielectric fusible polyimide resin, wherein the dielectric constant of the resin is 3.0, the particle size of the resin is 160 meshes, the tensile strength is 110MPa, and the impact strength is 201kJ/m 2.
Example 4
Adding 204.03g of N-methylpyrrolidone and 29.7g of xylene into a four-neck round-bottom flask equipped with a mechanical stirrer, a water separator, a condensation reflux device and a nitrogen protection device, starting stirring, then adding 32.15g of BDAF to be fully dissolved, heating to 121 ℃, adding 17.83g P6FDA and 10.29g of BPADA in three batches, heating to 169 ℃ after adding, and reacting for 12 hours to obtain a polyimide resin mother solution. Adding the mother liquor into a centrifugal separation device with the rotation number of 1500rpm for solid-liquid separation to obtain initial resin, adding the initial resin and an ethanol detergent into a self-made circulating washing device according to a certain proportion, carrying out centrifugal separation again, circulating for 2 times, and carrying out vacuum drying on the washed and filtered resin to obtain the low-dielectric fusible polyimide resin, wherein the dielectric constant of the resin is 2.9, the particle size of the resin is 100 meshes, the tensile strength is 91MPa, and the impact strength is 137kJ/m 2.
Example 5
Adding 217.82g of N-methylpyrrolidone and 32.02g of xylene into a four-neck round-bottom flask equipped with a mechanical stirrer, a water separator, a condensation reflux device and nitrogen protection, starting stirring, then adding 26.21g of DABTF and 5.02g of DDS until the mixture is fully dissolved, heating to 119 ℃, adding 31.49g of BPADA in three batches, heating to 165 ℃ after the addition is finished, and reacting for 14 hours to obtain a polyimide resin mother liquor. Adding a settling agent methanol into the mother liquor, adding the mother liquor containing the settling agent into a centrifugal separation device with the rotation number of 1200rpm for solid-liquid separation to obtain initial resin, adding the initial resin and an ethanol detergent into a self-made circulating washing device according to a certain proportion, carrying out centrifugal separation again, and carrying out vacuum drying on the washed and filtered resin to obtain the low-dielectric fusible polyimide resin, wherein the dielectric constant of the resin is 3.1, the particle size of the resin is 180 meshes, the tensile strength is 97MPa, and the impact strength is 180kJ/m 2.
Claims (10)
1. The polyimide powder is obtained by copolymerizing fluorine-containing aromatic diamine, fluorine-containing aromatic dianhydride, other aromatic dianhydride, and other aromatic diamine, and is an amorphous powder having a particle size of less than 0.28 mm.
2. The polyimide powder according to claim 1, wherein the polyimide powder has a dielectric constant in the range of 2.9 to 3.3.
3. The polyimide powder according to claim 1, wherein the fluorine-containing aromatic diamine is any one or more of 1, 1-bis (4-aminophenyl) -1-trifluoromethyl-ethane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxyphenyl) ] hexafluoropropane, and 3, 5-diaminobenzotrifluoride.
4. The polyimide powder according to claim 1, wherein the other aromatic diamine is any one or more of p-phenylenediamine, 4' -diaminodiphenyl sulfone, 4' -bis (3-aminophenoxy) diphenyl sulfone, 2 ' -bis [4- (4-aminophenoxyphenyl) ] propane, and m-phenylenediamine.
5. The polyimide powder according to claim 1, wherein the fluorine-containing aromatic dianhydride is any one or more of 3, 6-bis (trifluoromethyl) -pyromellitic anhydride, 3-trifluoromethyl-6-methylpyromellitic anhydride, and trifluorodianhydride.
6. The polyimide powder according to claim 1, wherein the other aromatic dianhydride is any one or more of pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, and bisphenol-A dianhydride.
7. A method for preparing polyimide powder is characterized by comprising the following steps:
s1, preparing polyimide mother liquor;
s2, adding the mother solution into a centrifugal device, and carrying out centrifugal solid-liquid separation to obtain initial resin;
s3, washing the initial resin with a detergent, and drying to obtain polyimide powder.
According to the method for producing a polyimide powder of the present invention, the polyimide powder has a particle diameter of less than 0.28mm and is an amorphous polyimide powder.
8. The method for preparing polyimide powder according to claim 7, wherein the rotation speed of the centrifugal device for solid-liquid separation is 1000-2000 rpm.
9. The method for producing polyimide powder according to claim 7, wherein the polar solvent is dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, or tetrahydrofuran.
10. The method according to claim 7, wherein no precipitation-promoting additive is added after step S1 and before step S2.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1045918A (en) * | 1996-04-05 | 1998-02-17 | Ube Ind Ltd | Polyimide powder and preparation of powder molding |
| CN107881579A (en) * | 2017-09-29 | 2018-04-06 | 常州市尚科新材料有限公司 | The preparation method of solvable fusible polyimides fibrid |
| CN110028670A (en) * | 2019-04-11 | 2019-07-19 | 明士新材料有限公司 | Low-dielectric loss negative light-sensitive poly amic acid ester resin, resin combination, preparation method and application |
| CN111321480A (en) * | 2019-12-23 | 2020-06-23 | 长沙新材料产业研究院有限公司 | Low-dielectric polyimide fiber, preparation method and application |
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2021
- 2021-12-24 CN CN202111600048.2A patent/CN114230790A/en active Pending
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| JPH1045918A (en) * | 1996-04-05 | 1998-02-17 | Ube Ind Ltd | Polyimide powder and preparation of powder molding |
| CN107881579A (en) * | 2017-09-29 | 2018-04-06 | 常州市尚科新材料有限公司 | The preparation method of solvable fusible polyimides fibrid |
| CN110028670A (en) * | 2019-04-11 | 2019-07-19 | 明士新材料有限公司 | Low-dielectric loss negative light-sensitive poly amic acid ester resin, resin combination, preparation method and application |
| CN111321480A (en) * | 2019-12-23 | 2020-06-23 | 长沙新材料产业研究院有限公司 | Low-dielectric polyimide fiber, preparation method and application |
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