CN116023657A - Silicon-boron synergistic modified atomic oxygen resistant polyimide composite film and preparation method and application thereof - Google Patents
Silicon-boron synergistic modified atomic oxygen resistant polyimide composite film and preparation method and application thereof Download PDFInfo
- Publication number
- CN116023657A CN116023657A CN202310147801.XA CN202310147801A CN116023657A CN 116023657 A CN116023657 A CN 116023657A CN 202310147801 A CN202310147801 A CN 202310147801A CN 116023657 A CN116023657 A CN 116023657A
- Authority
- CN
- China
- Prior art keywords
- composite film
- film
- polyimide composite
- poss
- mixture
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- 239000004642 Polyimide Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical class [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 72
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 title abstract description 8
- 230000002195 synergetic effect Effects 0.000 title abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical group [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 90
- 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 description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 21
- 239000002313 adhesive film Substances 0.000 claims description 17
- -1 hexafluoroisopropyl Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010292 electrical insulation Methods 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
- 239000002798 polar solvent Substances 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004377 microelectronic Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- JTWJUVSLJRLZFF-UHFFFAOYSA-N 2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},11$l^{2},12$l^{2}-decaborabicyclo[8.1.1]dodecane Chemical compound [B]1C2[B]C1[B][B][B][B][B][B][B][B]2 JTWJUVSLJRLZFF-UHFFFAOYSA-N 0.000 claims description 2
- UFTJOJZFWHQVDD-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C.CC1=CC=CN=C1C UFTJOJZFWHQVDD-UHFFFAOYSA-N 0.000 claims description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 2
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 125000005591 trimellitate group Chemical group 0.000 claims description 2
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims 1
- CFNUZRMHHJZBOM-UHFFFAOYSA-N [B]1C2[B][B]C1[B][B][B][B][B][B][B]2 Chemical compound [B]1C2[B][B]C1[B][B][B][B][B][B][B]2 CFNUZRMHHJZBOM-UHFFFAOYSA-N 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 238000010438 heat treatment Methods 0.000 description 27
- 239000002904 solvent Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 23
- 239000012456 homogeneous solution Substances 0.000 description 22
- 229920005575 poly(amic acid) Polymers 0.000 description 21
- 230000003628 erosive effect Effects 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 230000009471 action Effects 0.000 description 12
- 230000004907 flux Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 10
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 9
- 239000000523 sample Substances 0.000 description 7
- 238000007790 scraping Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001709 polysilazane Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- MDRTVGIFNOFHMV-UHFFFAOYSA-N B.[C] Chemical group B.[C] MDRTVGIFNOFHMV-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Images
Abstract
The invention discloses a silicon-boron synergistic modified atomic oxygen resistant polyimide composite film, and a preparation method and application thereof. The preparation method of the polyimide composite film provided by the invention comprises the following steps: adding an aromatic diamine (BACB) containing a borane group and an imidizing reagent into a polyimide precursor resin solution containing a siloxane group at a side chain, mixing and defoaming, forming a wet film on a substrate, and performing high-temperature imidization treatment to obtain the polyimide composite film. The composite film has excellent atomic oxygen resistance due to the addition of POSS and BACB, and the composite film maintains excellent thermal performance and mechanical performance of the PI substrate film due to the molecular level composition formed between the BACB and the PI substrate. The polyimide composite film can be used for the outer surface of a near-earth orbit (LEO) space vehicle, and can effectively improve the atomic oxygen tolerance and long-term service performance of the aircraft.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a silicon-boron synergistic modified atomic oxygen resistant polyimide composite film, and a preparation method and application thereof.
Background
The aromatic polyimide film has excellent comprehensive performances of high temperature resistance, low temperature resistance, high strength and toughness, high dimensional stability, high electrical insulation, low dielectric loss, radiation resistance, high flame retardance, low vacuum volatile matters and the like due to the special rigid aromatic heterocyclic resin main chain structure, and has wide application prospects in the high technical fields of aerospace, electrical insulation, microelectronic manufacturing and packaging, plane display and the like. The polyimide film also has important application value in the space field, and is mainly used for manufacturing solar cell wings of space stations, multi-layer heat insulation blankets of satellites, solar sails of deep space probes and the like, wherein the running Orbit of a Low Earth Orbit (LEO) aircraft is usually 200-800 km from the ground, the space environment is extremely complex, and the atmospheric components of the polyimide film change along with the Orbit height and the solar activity condition.
Spatial factors of LEO orbit, including thermal cycling (-100 ℃), ultraviolet (UV), vacuum Ultraviolet (VUV), atomic Oxygen (AO), ionizing radiation, micro-fluid stars and space debris, can have significant impact on the service performance of polyimide films. Wherein AO produced by dissociation of oxygen molecules under ultraviolet radiation is a major component of LEO space environment, has high flux (10 14 ～10 15 atoms·cm -2 ·s -1 ) And high energy (4.5-5 eV). AO can oxidize and degrade the surface of the polyimide film, and further continuously diffuse into the material, thereby seriously damaging the service performance and service life of the material. For example, commercialized
After the H film is corroded by AO, the quality is greatly lost, the surface presents a characteristic carpet-like shape, and the corrosion rate is up to 3.0x10 -24 cm 3 ·atom -1 . For a thickness of 25 μm +.>
The H film can be completely eroded by AO after 6 months of on-orbit service time, and becomes a key factor for limiting the service life of the spacecraft.
In order to meet the long-term on-orbit service requirement of a spacecraft, scientific and technological staff are subjected to a great deal of research and study, and two methods for improving the atomic oxygen resistance of a polyimide film are developed, namely an outer layer protection method for coating a protective coating on the surface of the polyimide film, and an in-vivo enhancement method for introducing specific groups or fillers into a polyimide film matrix.
The outer protective coating adopted by the outer protective method mainly comprises SiO 2 、Al 2 O 3 、TiO 2 、SnO 2 Inorganic coatings such as ITO. The inorganic oxide coating has high AO tolerance and does not influence the performance of the film material; however, the coating has defects such as poor toughness, mismatching with the thermal expansion coefficient of the PI film, and easy occurrence of defects, holes, cracks, interfacial peeling (AIP Conference Proceedings,2009,1087 (1), 75-82). The outer layer protection method can also adopt polysiloxane, polysilazane (PSZ), polytetrafluoroethylene (PTFE) and other flexible organic coatings. The organic coating can be gradually converted into an inorganic coating under the action of AO and thermal decomposition; because of the poor stability of the organic coating itself, it has a high atomic oxygen erosion resistance, micro-cracks can form during the aging degradation process, and the generated volatiles can deposit on the surface of the optical device causing secondary pollution (Journal of Spacecraft and Rockets,2006,43 (2), 393-401;Applied Mechanics and Materials,2014,651-653,65-68).
The in vivo enhancement method comprises introducing organic group containing phosphorus (or silicon) into main chain structure of film precursor resin to form precursor resin solution, or adding inorganic oxide micro-nano particles (such as SiO 2 、Al 2 O 3 、TiO 2 、ZrO 2 Etc.) are uniformly dispersed in the film precursor resin solution; and coating the resin precursor resin solution into a film and aminating the film by high Wen Ya to form the atomic oxygen resistant polyimide film. The in-vivo modified film has the capability of self-repairing, and the polyimide film resin can generate an inorganic protective layer in situ in the AO erosion process, and can still form a new protective layer at the defect after being damaged. However, phosphorus-containing PI films have high brittleness and poor fracture toughness (Macromolecules 2002,35, (13), 4968-4974), and silicone-containing block PI films have low modulus and high thermal expansion coefficient; siO (SiO) 2 、TiO 2 The inorganic particles reduce the thicknessMechanical and light transmission properties of the films (Journal of Applied Polymer Science 2010,115, (6), 3256-3264,Journal of Applied Polymer Science 2012,123, (1), 143-151).
In summary, new methods and techniques are needed to address the above performance deficiencies of existing PI films.
Disclosure of Invention
The invention aims to provide a silicon-boron synergistic modified atomic oxygen resistant polyimide composite film, and a preparation method and application thereof, wherein the polyimide composite film not only has excellent atomic oxygen resistant property, but also keeps excellent heat resistance and mechanical property, so that the polyimide composite film can be used for manufacturing a near-earth orbit space vehicle.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the present invention provides a method for preparing a polyimide composite film, comprising the steps of:
adding aromatic diamine containing a borane group and an imidizing reagent into polyimide precursor resin solution containing a siloxane group at a side chain, mixing and defoaming to form a wet film on a substrate, and performing high-temperature imidization treatment to obtain the polyimide composite film;
wherein:
the structure of the polyimide precursor resin with the side chain containing the siloxane group is shown as a formula I:
in formula I:
Ar 1 one or more selected from the following groups:
Ar 2 one or more selected from the following groups:
r is selected from one or more of isobutyl, phenyl, epoxy, hydroxyl and carboxyl; m and n represent the degree of polymerization, m: n=1, (1 to 9);
the structure of the aromatic diamine containing the carborane group is shown as a formula II:
in the preparation method, the polyimide precursor resin with the side chain containing the siloxane group is prepared by taking aromatic diamine, siloxane-containing aromatic diamine POSS and aromatic dianhydride as raw materials through polycondensation reaction in an aprotic polar solvent.
Wherein the aromatic diamine is one or more of 1, 4-p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -biphenyl diamine, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, bisphenol A-type diether diamine and 1, 4-bis (4-aminophenoxy) benzene;
specifically, the aromatic diamine may be selected from one or more of the following compounds:
wherein the siloxane-containing aromatic diamine POSS is one or more of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide, N- [ (heptaphenyl POSS) propyl ] -3, 5-diaminobenzamide, N- [ (heptaepoxy POSS) propyl ] -3, 5-diaminobenzamide, N- [ (heptahydroxy POSS) propyl ] -3, 5-diaminobenzamide and N- [ (heptacarboxy POSS) propyl ] -3, 5-diaminobenzamide.
Wherein the aromatic dianhydride is 1,2,4, 5-pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4 '-oxydiphthalic anhydride, 3',4 '-benzophenone tetracarboxylic dianhydride, 3', one or more of 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 4' - (hexafluoroisopropyl) diphthalic anhydride, bisphenol a-type diether dianhydride, and p-phenyl bis (trimellitate) dianhydride;
specifically, the aromatic dianhydride may be selected from one or more of the following compounds:
wherein the molar ratio of the aromatic diamine to the aromatic dianhydride is 1: (0.98 to 1.02), preferably 1:1.
the mass fraction of the siloxane-containing aromatic diamine POSS in the raw material is 5-30%, preferably 10-20%.
The raw materials account for 12 to 25 percent, preferably 15 to 20 percent of the total mass of the reaction system.
The conditions of the polycondensation reaction are as follows:
the temperature is 0-35 ℃, preferably 25-35 ℃;
the time is 3 to 48 hours, preferably 6 to 24 hours, and particularly 6 hours, 12 hours, 18 hours and 24 hours.
In the above preparation method, the aromatic diamine BACB containing carbon borane groups is one or more of 1, 7-di (aminophenylene) meta-carborane, 1, 7-di (aminophenylene) para-carborane and 1, 7-di (aminophenylene) ortho-carborane.
The imidizing agent is one or more of acetic anhydride/pyridine mixture, acetic anhydride/2-methylpyridine mixture, acetic anhydride/3-methylpyridine mixture, acetic anhydride/4-methylpyridine mixture, acetic anhydride/2, 3-dimethylpyridine mixture, acetic anhydride/2, 4-dimethylpyridine mixture, acetic anhydride/2, 6-dimethylpyridine mixture, acetic anhydride/quinoline mixture, acetic anhydride/isoquinoline mixture and acetic anhydride/pyrrole mixture.
The addition amount of the imidizing agent is 1-100% of the mass of the polyimide precursor resin with the side chain containing siloxane groups, preferably 20-50%.
The high-temperature imidization treatment process comprises the following steps:
treating the wet film for 0.5-1 h at 60-80 ℃ and then for 5-15 min at 100-120 ℃ to form a semi-cured adhesive film; and stripping the semi-cured adhesive film from the substrate, and treating for 10-30 min at the temperature of 350-450 ℃ to obtain the polyimide composite film.
The substrate is glass, stainless steel, ceramic, aluminum foil or the like.
In a second aspect, the invention further provides a polyimide composite film obtained by the preparation method.
In the polyimide composite film, the content of the aromatic diamine BACB containing the boron alkyl group is 1-30%, preferably 5-20%.
In a third aspect, the invention further provides application of the polyimide composite film in the fields of aerospace, electrical insulation, microelectronic manufacturing and packaging and flat panel display.
In a fourth aspect, the present invention further provides a near-earth orbit spacecraft outer surface material, which contains the polyimide composite film.
Compared with the prior art, the invention has the following beneficial effects:
the polyimide film synergistically modified by the silicon and the boron not only has excellent atomic oxygen resistance, but also has excellent heat resistance and mechanical property, and can be used for manufacturing long-life flexible solar cell substrates, satellite multilayer heat insulation felts, solar sails and the like of near-earth orbit space vehicles.
Drawings
FIG. 1 is a dynamic mechanical thermal analysis (DMA) curve of the polyimide films obtained in examples 1 to 3 of the present invention and comparative example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the surface of a polyimide film obtained in example 4 of the present invention after atomic oxygen irradiation, at 10000 times magnification.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the surface of the polyimide film obtained in comparative example 1 after atomic oxygen irradiation, at 10000 times magnification.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the surface of the polyimide film obtained in comparative example 4 after atomic oxygen irradiation, at 10000 times magnification.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials are available from published commercial sources unless otherwise specified.
The invention specifically provides a preparation method of a polyimide composite film, which comprises the following steps:
the first step: dissolving N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide and aromatic diamine powder in an aprotic polar solvent in a nitrogen atmosphere, and mechanically stirring to form a homogeneous solution;
and a second step of: adding aromatic dianhydride powder into the homogeneous solution obtained in the first step, performing polycondensation reaction to obtain polyamic acid resin solution, and sealing and preserving the obtained polyamic acid resin solution at low temperature;
and a third step of: the BACB solution is obtained by dissolving BACB with the mass fraction of 1-60% in aprotic polar solvent;
fourth step: mixing a certain amount of the resin prepared in the second step with the BACB solution prepared in the third step to prepare a composite resin solution; the mixing method includes mechanical stirring method and ultrasonic dispersing method, and preferably mechanical stirring method.
Fifth step: uniformly mixing the composite resin solution prepared in the fourth step with an imidizing reagent, defoaming, uniformly scraping and coating a wet film on a substrate, treating the wet film in a clean oven until a semi-cured adhesive film is obtained, stripping the semi-cured adhesive film from the substrate, fixing the periphery of the semi-cured adhesive film or completing high-temperature imidization under the action of biaxial stretching, and cooling to room temperature to obtain the silicon-boron synergistic modified atomic oxygen resistant polyimide film.
The reagents in the following examples were purchased from the following sources:
1, 4-p-phenylenediamine: purchased from the company of the solar pharmaceutical company, inc.
4,4' -diaminodiphenyl ether: purchased from the company of the solar pharmaceutical company, inc.
N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide: purchased from hybrid plastics, U.S.A.
3,3', 4' -biphenyltetracarboxylic dianhydride: purchased from Tianjin Zhongtai materials science and technology Co.
1, 7-bis (aminophenylene) m-carborane: purchased from wegian new chemical industry limited.
Example 1 preparation of BACB/PI-1 composite film
(1) In a 500mL three-necked flask equipped with mechanical stirring, nitrogen blanket and thermometer, 180.00g of N, N '-dimethylacetamide solvent, 7.10g (0.0656 mol) of 1, 4-p-phenylenediamine, 5.63g (0.0281 mol) of 4,4' -diaminodiphenyl ether and 7.50g (0.0074 mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide (POSS) were charged, and the mixture was stirred under nitrogen blanket to dissolve the solids all to form a homogeneous solution;
29.77g (0.1012 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride and the remaining 20.00g of N, N ' -dimethylacetamide solvent were added to the homogeneous solution in portions, and POSS was about 15% of the total mass of each raw material; after the solid is completely dissolved, carrying out polycondensation reaction for 12 hours at 25 ℃ to obtain a viscous homogeneous polyamide acid resin solution;
(2) 1.05g of 1, 7-bis (aminophenylene) meta-carborane was dissolved in 10.00g of N, N' -dimethylacetamide solvent to prepare a BACB solution;
(3) Taking 100.00g of the polyamic acid resin solution, adding the BACB solution and a mixture of 20.00g of acetic anhydride and pyridine (2/1 mol ratio) into a 200mL beaker under stirring, uniformly mixing, defoaming, uniformly scraping and coating the substrate into a wet film, placing the wet film in a 60 ℃ environment for heat treatment for 1h, and then treating the wet film at 120 ℃ for 10min to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or performing heat treatment for 0.5h under the action of biaxial stretching at 350 ℃, and cooling to room temperature to obtain the BACB/PI-1 composite film.
The BACB content in the BACB/PI-1 composite film is about 5%.
The thickness of the BACB/PI-1 composite film is 50+/-2 mu m, and the glass transition temperature T g 292.5 ℃ and a tensile modulus of 4.5GPa; using 2X 2cm 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 0.70X10 -24 cm 3 ·atom -1 。
Example 2 preparation of BACB/PI-1 composite film
(1) In a 500mL three-necked flask equipped with mechanical stirring, nitrogen blanket and thermometer, 180.00g of N, N '-dimethylacetamide solvent, 7.10g (0.0656 mol) of 1, 4-p-phenylenediamine, 5.63g (0.0281 mol) of 4,4' -diaminodiphenyl ether and 7.50g (0.0074 mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide (POSS) were charged, and the mixture was stirred under nitrogen blanket to dissolve the solids all to form a homogeneous solution; 29.77g (0.1012 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride and the remaining 20.00g of solvent were added to the homogeneous solution in portions, with POSS accounting for approximately 15% of the total mass of each raw material; after the solid is completely dissolved, the reaction is continued for 12 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution.
(2) 2.22g of 1, 7-bis (aminophenylene) meta-carborane was dissolved in 10.00g of N, N' -dimethylacetamide solvent to prepare a BACB solution;
(3) Taking 100.00g of the polyamic acid resin solution in a 200mL beaker, adding a BACB solution and a mixture of 20.00g of acetic anhydride and pyridine (2/1 mol ratio) under stirring, uniformly mixing, defoaming, uniformly scraping and coating the mixture on a substrate to form a wet film, performing heat treatment at 60 ℃ for 1h, and performing heat treatment at 120 ℃ for 10min to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or performing heat treatment for 0.5h under the action of biaxial stretching at 350 ℃, and cooling to room temperature to obtain the BACB/PI-1 composite film.
The BACB content in the BACB/PI-1 composite film is about 10%.
The thickness of the BACB/PI-1 composite film is 50+/-2 mu m, and the glass transition temperature T g At 290.0deg.C, a tensile modulus of 4.3GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 0.59X10 -24 cm 3 ·atom -1 。
Example 3 preparation of BACB/PI-1 composite film
(1) In a 500mL three-necked flask equipped with mechanical stirring, nitrogen blanket and thermometer, 180.00g of N, N '-dimethylacetamide solvent, 7.10g (0.0656 mol) of 1, 4-p-phenylenediamine, 5.63g (0.0281 mol) of 4,4' -diaminodiphenyl ether and 7.50g (0.0074 mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide (POSS) were charged, and the mixture was stirred under nitrogen blanket to dissolve the solids all to form a homogeneous solution; 29.77g (0.1012 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride and the remaining 20.00g of solvent were added to the homogeneous solution in portions, with POSS accounting for approximately 15% of the total mass of each raw material; after the solid is completely dissolved, the reaction is continued for 12 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution.
(2) 3.53g of 1, 7-bis (aminophenylene) meta-carborane was dissolved in 10.00g of N, N' -dimethylacetamide solvent to prepare a BACB solution;
(3) Taking 100.00g of the polyamic acid resin solution in a 200mL beaker, adding a BACB solution and a mixture of 20.00g of acetic anhydride and pyridine (2/1 mol ratio) under stirring, uniformly mixing, defoaming, uniformly scraping and coating the mixture on a substrate to form a wet film, performing heat treatment at 60 ℃ for 1h, and performing heat treatment at 120 ℃ for 10min to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or performing heat treatment for 0.5h under the action of biaxial stretching at 350 ℃, and cooling to room temperature to obtain the BACB/PI-1 composite film.
The BACB content in the BACB/PI-1 composite film is about 15%.
The film thickness of the BACB/PI-1 composite film is 50+/-2 mu m, and the glass transition temperature T g At 287.6deg.C, tensile modulus of 4.2GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 0.44×10 -24 cm 3 ·atom -1 。
Example 4 preparation of BACB/PI-1 composite film
(1) In a 500mL three-necked flask equipped with mechanical stirring, nitrogen blanket and thermometer, 180.00g of N, N '-dimethylacetamide solvent, 7.10g (0.0656 mol) of 1, 4-p-phenylenediamine, 5.63g (0.0281 mol) of 4,4' -diaminodiphenyl ether and 7.50g (0.0074 mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide (POSS) were charged, and the mixture was stirred under nitrogen blanket to dissolve the solids all to form a homogeneous solution; 29.77g (0.1012 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride and the remaining 20.00g of solvent were added to the homogeneous solution in portions, with POSS accounting for approximately 15% of the total mass of each raw material; after the solid is completely dissolved, the reaction is continued for 12 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution.
(2) 5.00g of 1, 7-bis (aminophenylene) meta-carborane was dissolved in 10.00g of N, N' -dimethylacetamide solvent to prepare a BACB solution;
(3) Taking 100.00g of the polyamic acid resin solution in a 200mL beaker, adding a BACB solution and a mixture of 20.00g of acetic anhydride and pyridine (2/1 mol ratio) under stirring, uniformly mixing, defoaming, uniformly scraping and coating the mixture on a substrate to form a wet film, performing heat treatment at 60 ℃ for 1h, and performing heat treatment at 120 ℃ for 10min to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or performing heat treatment for 0.5h under the action of biaxial stretching at 350 ℃, and cooling to room temperature to obtain the BACB/PI-1 composite film.
The BACB content in the BACB/PI-1 composite film is about 20%.
The film thickness of the BACB/PI-1 composite film is 50+/-2 mu m, and the glass transition temperature T g At 285.3 ℃and a tensile modulus of 4.0GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 0.30X10 -24 cm 3 ·atom -1 。
Example 5 preparation of BACB/PI-2 composite film
(1) In a 500mL three-necked flask equipped with mechanical stirring, nitrogen blanket and thermometer, 180.00g of N, N' -dimethylformamide solvent, 10.83g (0.0100 mol) of 1, 4-p-phenylenediamine and 7.50g (0.0074 mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide (POSS) were charged, and the solids were stirred under nitrogen blanket to completely dissolve to form a homogeneous solution; 27.29g (0.0927 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride and the remaining 20.00g of solvent were added to the homogeneous solution in portions, with POSS accounting for about 15% of the total mass of each raw material; after the solid is completely dissolved, the reaction is continued for 24 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution.
(2) 5.00g of 1, 7-bis (aminophenylene) meta-carborane was dissolved in 10.00g of N, N' -dimethylformamide solvent to prepare a BACB solution;
(3) Taking 100.00g of the polyamic acid resin solution, adding a BACB solution and a mixture of 20.00g of acetic anhydride and pyridine (2/1 mol ratio) into a 200mL beaker under stirring, uniformly scraping the mixture on a substrate to form a wet film, performing heat treatment for 1h at 60 ℃, and performing heat treatment for 10min at 120 ℃ to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or carrying out heat treatment for 0.5h under the action of biaxial stretching at 450 ℃, and cooling to room temperature to obtain the BACB/PI-2 composite film.
The BACB content in the BACB/PI-2 composite film is about 20%.
The film thickness of the BACB/PI-2 composite film is 50+/-2 mu m, and the glass transition temperature T g At 420.2℃and a tensile modulus of 8.5GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 0.32X10 -24 cm 3 ·atom -1 。
Example 6 preparation of BACB/PI-3 composite film
(1) In a 500mL three-necked flask equipped with mechanical stirring, nitrogen blanket and thermometer, 180.00g of N-methylpyrrolidone solvent, 19.57g (0.0977 mol) of 4,4' -diaminodiphenyl ether and 7.50g (0.0074 mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide (POSS) were charged, and the solid was completely dissolved by stirring under nitrogen blanket to form a homogeneous solution; to the homogeneous solution, 22.93g (0.1052 mol) of 1,2,4, 5-pyromellitic dianhydride and the remaining 20.00g of solvent were added in portions, with POSS accounting for about 15% of the total mass of each raw material; the solids content of the solution was adjusted to 20%. After the solid is completely dissolved, the reaction is continued for 6 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution.
(2) 5.00g of 1, 7-bis (aminophenylene) meta-carborane was dissolved in 10.00g of N-methylpyrrolidone solvent to prepare a BACB solution;
(3) Taking 100.00g of the polyamic acid resin solution, adding a BACB solution and a mixture of 20.00g of acetic anhydride and pyridine (2/1 mol ratio) into a 200mL beaker under stirring, uniformly scraping the mixture on a substrate to form a wet film, performing heat treatment for 1h at 60 ℃, and performing heat treatment for 10min at 120 ℃ to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or performing heat treatment for 20min at 450 ℃ under the action of biaxial stretching, and cooling to room temperature to obtain the BACB/PI-3 composite film.
The BACB content in the BACB/PI-3 composite film is about 20%.
The film thickness of the BACB/PI-3 composite film is 50+/-2 mu m, and the glass transition temperature T g At 398.5 ℃and a tensile modulus of 2.1GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 0.36×10 -24 cm 3 ·atom -1 。
Comparative example 1 preparation of POSS modified PI-1 film
(1) In a 500mL three-necked flask equipped with mechanical stirring, nitrogen blanket and thermometer, 180.00g of N, N '-dimethylacetamide solvent, 7.10g (0.0656 mol) of 1, 4-p-phenylenediamine, 5.63g (0.0281 mol) of 4,4' -diaminodiphenyl ether and 7.50g (0.0074 mol) of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide (POSS) were charged, and the mixture was stirred under nitrogen blanket to dissolve the solids all to form a homogeneous solution; 29.77g (0.1012 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride and the remaining 20.00g of solvent were added to the homogeneous solution in portions, with POSS accounting for approximately 15% of the total mass of each raw material; after the solid is completely dissolved, the reaction is continued for 12 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution.
(2) Taking 100.00g of the polyamic acid resin solution in a 200mL beaker, adding 20.00g of a mixture of acetic anhydride and pyridine (2/1 molar ratio) under stirring, uniformly mixing and defoaming; uniformly doctor-blading a wet film on a substrate, performing heat treatment for 1h at 60 ℃ and performing heat treatment for 10min at 120 ℃ to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or performing heat treatment for 0.5h under the action of biaxial stretching at 350 ℃, and cooling to room temperature to obtain the PI-1 film.
The film thickness of the PI-1 film is 50+ -2 μm, the glass transition temperature T g At 304.4deg.C, tensile modulus of 4.1GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 0.86×10 -24 cm 3 ·atom -1 。
Comparative example 2 preparation of PI-1 film
(1) 180.00g of N, N '-dimethylacetamide solvent, 8.80g (0.0814 mol) of 1, 4-p-phenylenediamine and 6.99g (0.0349 mol) of 4,4' -diaminodiphenyl ether were charged into a 500mL three-necked flask equipped with a mechanical stirrer, a nitrogen-protecting device and a thermometer, and the solid was completely dissolved by stirring under nitrogen protection to form a homogeneous solution; 29.77g (0.1012 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride and the remaining 20.00g of solvent were added in portions to the homogeneous solution; after the solid is completely dissolved, the reaction is continued for 12 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution.
(2) Taking 100.00g of the polyamic acid resin solution in a 200mL beaker, adding 20.00g of a mixture of acetic anhydride and pyridine (2/1 molar ratio) under stirring, uniformly mixing and defoaming; uniformly doctor-blading a wet film on a substrate, performing heat treatment for 1h at 60 ℃ and performing heat treatment for 10min at 120 ℃ to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or performing heat treatment for 0.5h under the action of biaxial stretching at 350 ℃, and cooling to room temperature to obtain the PI-1 film.
The film thickness of the PI-1 film is 50+ -2 μm, the glass transition temperature T g At 317.6deg.C, tensile modulus of 5.8GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 3.86×10 -24 cm 3 ·atom -1 。
Comparative example 3 preparation of PI-2 film
(1) 180.00g of N, N' -dimethylformamide solvent and 13.44g (0.1243 mol) of 1, 4-p-phenylenediamine were put into a 500mL three-necked flask equipped with a mechanical stirrer, a nitrogen protection device and a thermometer, and the mixture was stirred under nitrogen to completely dissolve the solid to form a homogeneous solution; 36.5618g (0.1243 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride and the remaining 20.00g of solvent were added in portions to the homogeneous solution so that the solid content of the solution was adjusted to 20%. After the solid is completely dissolved, the reaction is continued for 24 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution.
(2) Taking 100.00g of the polyamic acid resin solution in a 200mL beaker, adding 20.00g of a mixture of acetic anhydride and pyridine (2/1 molar ratio) under stirring, uniformly mixing and defoaming; uniformly doctor-blading a wet film on a substrate, performing heat treatment for 1h at 60 ℃ and performing heat treatment for 10min at 120 ℃ to obtain a semi-cured adhesive film; stripping from the substrate, fixing the periphery of the substrate or performing heat treatment for 0.5h under the action of biaxial stretching at 450 ℃, and cooling to room temperature to obtain the PI-2 film.
The film thickness of the PI-2 film is 50+/-2 mu m, and the glass transition temperature T g At 448.8 ℃and a tensile modulus of 8.9GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 3.77×10 -24 cm 3 ·atom -1 。
Comparative example 4 preparation of PI-3 film
(1) 180.00g of N-methylpyrrolidone solvent and 23.93g (0.1195 mol) of 4,4' -diaminodiphenyl ether were put into a 500mL three-necked flask equipped with a mechanical stirrer, a nitrogen gas protector and a thermometer, and the mixture was stirred under nitrogen gas to dissolve the whole solid to form a homogeneous solution; 26.07g (0.1195 mol) of 1,2,4, 5-pyromellitic dianhydride and the remaining 20.00g of solvent were added in portions to the above homogeneous solution, so that the solid content of the solution was adjusted to 20%. After the solid is completely dissolved, the reaction is continued for 6 hours at 25 ℃ to obtain a viscous homogeneous polyamic acid resin solution. Wherein the mass fraction of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide (POSS) is 0%.
(2) Taking 100.00g of the polyamic acid resin solution, adding 20.00g of a mixture of acetic anhydride and pyridine (2/1 mol ratio) into a 200mL beaker under stirring, uniformly mixing, defoaming, uniformly doctor-coating the resin solution on a substrate into a wet film, and obtaining a semi-cured adhesive film at the temperature of 60 ℃ for 1h and at the temperature of 120 ℃ for 10 min; stripping from the substrate, fixing the periphery of the substrate or under the action of biaxial stretching, cooling to room temperature at 450 ℃ for 20min to obtain the PI-3 film.
The film thickness of the PI-3 film is 50+/-2 mu m, and the glass transition temperature T g At 424.6deg.C, tensile modulus of 2.3GPa, 2X 2cm was used 2 Atomic oxygen floor simulated exposure test was performed on samples of the size at an AO flux of 6.79×10 20 atoms·cm -2 ·s -1 At an AO erosion rate of 4.22×10 -24 cm 3 ·atom -1 。
And (3) effect verification:
1. performance of polyimide film
The main properties of the polyimide films prepared in each example and comparative example were compared, and the results are shown in table 1.
T g Is characterized by comprising the following steps: the test frequency was measured by a Q800 dynamic thermo-mechanical analyzer (DMA) from TA company of America under nitrogen atmosphere and was constant at 1Hz, and the heating rate was 5 ℃/min. Wherein the temperature corresponding to the peak value of the Tan Delta curve is taken as T of the film g 。
Tensile modulus test method: the dimensions of the sample were 80mm x 10mm x d (μm) as determined by an Instron 5567 universal tensile machine in the United states according to national standard GB/T13022-91, where d is the film thickness as determined by a contact film thickness gauge to an accuracy of 0.5 μm and the draw rate was controlled at 2mm/min. Each spline was tested in 7 groups and averaged.
Test method of AO erosion rate: the measurement is carried out by filament discharge magnetic field constraint atomic oxygen effect ground simulation equipment, the sample size is 2cm multiplied by 2cm, and the reference sample is the same size
H-type PIThe film (25 μm), AO flux and erosion rate of the sample were calculated from the mass loss of the film after different irradiation cycles. The mass of the film is weighed by a DT-2000 type electronic balance to be accurate to 10 -5 mg, 5 times per sample, and average.
TABLE 1 principal Properties of polyimide film
Note that: 1. the addition amount of POSS refers to the addition amount of POSS in the raw material for preparing the homogeneous polyamide acid resin.
2. The BACB content refers to the content of BACB in the final product composite film.
As can be seen from Table 1, in comparison with the unmodified PI substrate films prepared in comparative examples 2 to 4, in comparative example 1, an aromatic diamine (N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide) containing cage-type oligomeric silsesquioxane (POSS) and an aromatic dianhydride are subjected to polycondensation reaction to form a precursor resin solution, and then the resin solution is coated into a film and aminated by high Wen Ya to form an intrinsically modified atomic oxygen resistant polyimide film, so that the intrinsically modified atomic oxygen resistant polyimide film has excellent atomic oxygen resistant performance.
Compared with comparative example 1, examples 1 to 6, the addition of the aromatic diamine BACB containing the carborane group on the basis of the addition of POSS, the AO erosion rate of the obtained polyimide composite film is further reduced, and the atomic oxygen resistance of the composite film is better along with the increase of the BACB content.
It should be noted that, as the groups with large steric hindrance effect such as POSS and BACB are introduced into the system, the close packing between the polymer molecular chains is affected, the free volume of the molecular chain segments is increased, so that the T of the film g And the tensile modulus gradually decreased as in examples 1 to 3. At the same time, T of the film g And the tensile modulus can also be controlled by changing the stiffness and flexibility of the molecular main chain structure, as in examples 4 to 6 and comparative examples 2 to 4, the degree of stiffness of the main chain structure PI-2 > PI-1 > PI-3, and thus T of the film g And tensile modulus, and can be rootedSelecting proper T according to the technical requirements of practical application g And tensile modulus.
2. Dynamic mechanical thermal analysis
The dynamic mechanical thermal analysis (DMA) curve of the film sample is shown in fig. 1, and the composite films obtained in examples 1-3 maintain the excellent thermal performance and mechanical performance of the PI matrix film due to the molecular level composite formed between the BACB and the PI matrix.
3. AO irradiation results
SEM images of the surface of the film sample after AO irradiation are shown in figures 2-4, and the BACB/PI composite film obtained in the embodiment 4 forms a denser protective layer on the surface of the film under atomic oxygen corrosion, as shown in figure 2, so that the atomic oxygen irradiation weightlessness and corrosion rate of the film are further effectively reduced, and an obvious silicon-boron synergistic enhancement effect is exerted; comparative example 1 the surface of the PI substrate film was converted from POSS to SiO x The inert protective layer is in a honeycomb structure, as shown in fig. 3, and still fails to prevent AO from further eroding the underlying substrate under long-term irradiation conditions; the PI substrate film without POSS obtained in comparative example 4, after AO irradiation, showed severe oxidative attack on the film surface, as shown in fig. 4, and exhibited a typical "carpet" morphology.
Therefore, the silicon-boron synergistic modified atomic oxygen resistant polyimide film provided by the invention has excellent atomic oxygen resistant performance, thermal performance, mechanical performance and other basic performances, and is a film with excellent performance in the application aspect of the aerospace field.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a polyimide composite film comprises the following steps:
adding aromatic diamine containing a borane group and an imidizing reagent into polyimide precursor resin solution containing a siloxane group at a side chain, mixing and defoaming to form a wet film on a substrate, and performing high-temperature imidization treatment to obtain the polyimide composite film;
wherein:
the structure of the polyimide precursor resin with the side chain containing the siloxane group is shown as a formula I:
in formula I:
Ar 1 one or more selected from the following groups:
Ar 2 one or more selected from the following groups:
r is selected from one or more of isobutyl, phenyl, epoxy, hydroxyl and carboxyl;
m and n represent the degree of polymerization, m: n=1, (1 to 9);
the structure of the aromatic diamine containing the carborane group is shown as a formula II:
2. the method for producing a polyimide composite film according to claim 1, characterized in that: the polyimide precursor resin with the side chain containing the siloxane group is prepared by taking aromatic diamine, siloxane-containing aromatic diamine POSS and aromatic dianhydride as raw materials through polycondensation reaction in an aprotic polar solvent;
the aromatic diamine is one or more of 1, 4-p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -biphenyl diamine, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, bisphenol A type diether diamine and 1, 4-bis (4-aminophenoxy) benzene;
the siloxane-containing aromatic diamine POSS is one or more of N- [ (heptaisobutyl POSS) propyl ] -3, 5-diaminobenzamide, N- [ (heptaphenyl POSS) propyl ] -3, 5-diaminobenzamide, N- [ (heptaepoxy POSS) propyl ] -3, 5-diaminobenzamide, N- [ (heptahydroxy POSS) propyl ] -3, 5-diaminobenzamide and N- [ (heptacarboxy POSS) propyl ] -3, 5-diaminobenzamide;
the aromatic dianhydride is 1,2,4, 5-pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 4 '-oxydiphthalic anhydride, 3',4 '-benzophenone tetracarboxylic dianhydride, 3', one or more of 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 4' - (hexafluoroisopropyl) diphthalic anhydride, bisphenol a-type diether dianhydride, and p-phenyl bis (trimellitate) dianhydride.
3. The method for producing a polyimide composite film according to claim 2, characterized in that: the molar ratio of the aromatic diamine to the aromatic dianhydride is 1: (0.98-1.02);
the mass fraction of the siloxane-containing aromatic diamine POSS in the raw materials is 5-30%;
the raw materials account for 12 to 25 percent of the total mass of the reaction system.
4. The method for producing a polyimide composite film according to claim 2 or 3, characterized in that: the conditions of the polycondensation reaction are as follows:
the temperature is 0-35 ℃;
the time is 3-48 h.
5. The method for producing a polyimide composite film according to any one of claims 1 to 4, characterized in that: the aromatic diamine containing the carborane group is one or more of 1, 7-di (amino phenylene) m-carborane, 1, 7-di (amino phenylene) p-carborane and 1, 7-di (amino phenylene) o-carborane;
the imidizing agent is one or more of acetic anhydride/pyridine mixture, acetic anhydride/2-methylpyridine mixture, acetic anhydride/3-methylpyridine mixture, acetic anhydride/4-methylpyridine mixture, acetic anhydride/2, 3-dimethylpyridine mixture, acetic anhydride/2, 4-dimethylpyridine mixture, acetic anhydride/2, 6-dimethylpyridine mixture, acetic anhydride/quinoline mixture, acetic anhydride/isoquinoline mixture and acetic anhydride/pyrrole mixture;
the addition amount of the imidizing reagent is 1-100% of the mass of the polyimide precursor resin with the side chain containing siloxane groups.
6. The method for producing a polyimide composite film according to any one of claims 1 to 5, characterized in that: the high-temperature imidization treatment process comprises the following steps:
treating the wet film for 0.5-1 h at 60-80 ℃ and then for 5-15 min at 100-120 ℃ to form a semi-cured adhesive film; and stripping the semi-cured adhesive film from the substrate, and treating for 10-30 min at the temperature of 350-450 ℃ to obtain the polyimide composite film.
7. The polyimide composite film obtained by the production method according to any one of claims 1 to 6.
8. The polyimide composite film according to claim 7, wherein: in the polyimide composite film, the mass fraction of the aromatic diamine containing the carborane group is not more than 30%.
9. Use of the polyimide composite film according to claim 7 or 8 in the fields of aerospace, electrical insulation, microelectronic fabrication and packaging, flat panel display.
10. A near earth orbit spacecraft exterior surface material comprising the polyimide composite film of claim 7 or 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310147801.XA CN116023657A (en) | 2023-02-10 | 2023-02-10 | Silicon-boron synergistic modified atomic oxygen resistant polyimide composite film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310147801.XA CN116023657A (en) | 2023-02-10 | 2023-02-10 | Silicon-boron synergistic modified atomic oxygen resistant polyimide composite film and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116023657A true CN116023657A (en) | 2023-04-28 |
Family
ID=86081397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310147801.XA Pending CN116023657A (en) | 2023-02-10 | 2023-02-10 | Silicon-boron synergistic modified atomic oxygen resistant polyimide composite film and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116023657A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4208492A (en) * | 1977-12-30 | 1980-06-17 | Union Carbide Corporation | High molecular weight carborane-siloxane block copolymers and method for their preparation |
| CN101412847A (en) * | 2007-10-18 | 2009-04-22 | 东丽纤维研究所（中国）有限公司 | Heat resisting polyimides / polyhedral oligomeric silsesquioxane nano hybridization material |
| EP2188330A1 (en) * | 2007-09-07 | 2010-05-26 | Mantech Srs Technologies, Inc. | Polyimide polymer with oligomeric silsesquioxane |
| CN103881091A (en) * | 2014-03-15 | 2014-06-25 | 西南石油大学 | Preparation method of polyimide containing carborane structure |
| CN107759478A (en) * | 2016-08-16 | 2018-03-06 | 北京航空航天大学 | A kind of Thermocurable polyimide material and preparation method and application containing double carboranes |
| CN108250748A (en) * | 2018-01-19 | 2018-07-06 | 吉林大学 | A kind of cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material and preparation method thereof |
| CN110698670A (en) * | 2019-10-31 | 2020-01-17 | 中国科学院化学研究所 | Carborane modified polyimide film and preparation method thereof |
| CN110746449A (en) * | 2018-07-23 | 2020-02-04 | 中国科学院化学研究所 | Aromatic amine functionalized carborane compound containing flexible silica chain link and preparation method and application thereof |
-
2023
- 2023-02-10 CN CN202310147801.XA patent/CN116023657A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4208492A (en) * | 1977-12-30 | 1980-06-17 | Union Carbide Corporation | High molecular weight carborane-siloxane block copolymers and method for their preparation |
| EP2188330A1 (en) * | 2007-09-07 | 2010-05-26 | Mantech Srs Technologies, Inc. | Polyimide polymer with oligomeric silsesquioxane |
| CN101412847A (en) * | 2007-10-18 | 2009-04-22 | 东丽纤维研究所（中国）有限公司 | Heat resisting polyimides / polyhedral oligomeric silsesquioxane nano hybridization material |
| CN103881091A (en) * | 2014-03-15 | 2014-06-25 | 西南石油大学 | Preparation method of polyimide containing carborane structure |
| CN107759478A (en) * | 2016-08-16 | 2018-03-06 | 北京航空航天大学 | A kind of Thermocurable polyimide material and preparation method and application containing double carboranes |
| CN108250748A (en) * | 2018-01-19 | 2018-07-06 | 吉林大学 | A kind of cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material and preparation method thereof |
| CN110746449A (en) * | 2018-07-23 | 2020-02-04 | 中国科学院化学研究所 | Aromatic amine functionalized carborane compound containing flexible silica chain link and preparation method and application thereof |
| CN110698670A (en) * | 2019-10-31 | 2020-01-17 | 中国科学院化学研究所 | Carborane modified polyimide film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| GUANGQIANG FANG等: "Intrinsically Atomic-oxygen-resistant POSS-containing Polyimide Aerogels:Synthesis and Characterization", CHEM. LETT., no. 44, 20 May 2015 (2015-05-20), pages 1083 * |
| ZIYU WU等: "Long-term atomic oxygen resistant polyimide films containing carborane nanocage structure in the main chains", POLYMER DEGRADATION AND STABILITY, no. 210, 3 February 2023 (2023-02-03), pages 110280 - 110290 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7037534B2 (en) | Polyimide film with voids and its manufacturing method | |
| KR102312462B1 (en) | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same | |
| US20110091732A1 (en) | Polyamic acid resin composition and polyimide film prepared therefrom | |
| Lei et al. | Evolution of surface chemistry and morphology of hyperbranched polysiloxane polyimides in simulated atomic oxygen environment | |
| WO2012173204A1 (en) | Method for producing polyimide laminate, and polyimide laminate | |
| CN110698670B (en) | Carborane modified polyimide film and preparation method thereof | |
| EP1167423B1 (en) | Polyimide silicone resin, solution containing it, and polyimide silicone resin film | |
| CN112831071B (en) | Method for preparing polyimide film from polyamide acid slurry | |
| CN114015233B (en) | Polyimide material and preparation method and application thereof | |
| EP0621888B1 (en) | Laminate on the basis of a strengthened polyimide film containing organometallic compounds for improving adhesion | |
| CN112500569B (en) | Polyimide precursor composition, polyimide film, laminated film, and display device | |
| EP1803762A1 (en) | Heat-resistant resin | |
| CN116023657A (en) | Silicon-boron synergistic modified atomic oxygen resistant polyimide composite film and preparation method and application thereof | |
| CN113861481B (en) | High-transmittance hydrophobic optical polyimide composite film material and preparation method thereof | |
| CN113061338B (en) | Polyamide acid composition, polyimide film and polyimide copper-clad plate | |
| US4528216A (en) | Process for forming heat-resistant resin films of polyimide and organosilicic reactants | |
| Zhao et al. | Factors influencing thermal, mechanical, optical, and adhesive properties of segmented poly (imide siloxane) copolymers films | |
| Moon et al. | Dynamics of solvent diffusion in an aromatic polyimide | |
| JPS61111182A (en) | Manufacture of polyimide-metallic foil composite film | |
| CN115960353A (en) | Polymer for preparing polyimide film, polyimide film and preparation method thereof | |
| EP2787024B1 (en) | Thermosetting composition, hardened film and electronic component | |
| CN113667164B (en) | Polyimide multilayer structure and method for producing same | |
| CN115315462A (en) | Resin film, method for producing same, resin composition, display, and method for producing same | |
| KR20090022937A (en) | Polyimide film | |
| CN116462630A (en) | Quinoline low-temperature curing agent, polyimide and photosensitive resin |
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 |