CN112979582A - Preparation method of diamine containing phenothiazine structure and synthetic polyimide - Google Patents
Preparation method of diamine containing phenothiazine structure and synthetic polyimide Download PDFInfo
- Publication number
- CN112979582A CN112979582A CN201911288082.3A CN201911288082A CN112979582A CN 112979582 A CN112979582 A CN 112979582A CN 201911288082 A CN201911288082 A CN 201911288082A CN 112979582 A CN112979582 A CN 112979582A
- Authority
- CN
- China
- Prior art keywords
- monomer
- phenothiazine
- diamine
- polyimide
- phenothiazine structure
- 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
- 229920001721 polyimide Polymers 0.000 title claims abstract description 46
- 239000004642 Polyimide Substances 0.000 title claims abstract description 45
- 150000004985 diamines Chemical class 0.000 title claims abstract description 42
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title description 8
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- 238000006887 Ullmann reaction Methods 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004377 microelectronic Methods 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- 229930192474 thiophene Natural products 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 20
- 229920000642 polymer Polymers 0.000 abstract description 12
- 238000002425 crystallisation Methods 0.000 abstract description 9
- 230000008025 crystallization Effects 0.000 abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 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 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 229950000688 phenothiazine Drugs 0.000 abstract description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000001939 inductive effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 18
- -1 N2,N8-bis(4-nitrophenyl)-10H-phenothiazine-2,8-diamine Chemical compound 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YZJQLAFOMUQCAW-UHFFFAOYSA-N 10h-phenothiazine-2,7-diamine Chemical compound NC1=CC=C2NC3=CC(N)=CC=C3SC2=C1 YZJQLAFOMUQCAW-UHFFFAOYSA-N 0.000 description 3
- JGUXTMBWMUVGIF-UHFFFAOYSA-N 10h-phenothiazine-2,8-diamine Chemical compound C1=C(N)C=C2NC3=CC(N)=CC=C3SC2=C1 JGUXTMBWMUVGIF-UHFFFAOYSA-N 0.000 description 3
- LZILOGCFZJDPTG-UHFFFAOYSA-N 10h-phenothiazine-3,7-diamine Chemical compound C1=C(N)C=C2SC3=CC(N)=CC=C3NC2=C1 LZILOGCFZJDPTG-UHFFFAOYSA-N 0.000 description 3
- 230000005526 G1 to G0 transition Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 125000001821 azanediyl group Chemical group [H]N(*)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- GTTFJYUWPUKXJH-UHFFFAOYSA-N n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=CC=C1 GTTFJYUWPUKXJH-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- WMASLRCNNKMRFP-UHFFFAOYSA-N 1-fluoro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(F)=C1 WMASLRCNNKMRFP-UHFFFAOYSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- ZULYCUDVOSSRCO-UHFFFAOYSA-N 2,7-dibromo-10h-phenothiazine Chemical compound BrC1=CC=C2NC3=CC(Br)=CC=C3SC2=C1 ZULYCUDVOSSRCO-UHFFFAOYSA-N 0.000 description 1
- BXAGHOQNWNDDFA-UHFFFAOYSA-N 2,8-dibromo-10H-phenothiazine Chemical compound BrC1=CC=2NC3=CC(=CC=C3SC2C=C1)Br BXAGHOQNWNDDFA-UHFFFAOYSA-N 0.000 description 1
- XOZAJNLUAODXSP-UHFFFAOYSA-N 2-fluoro-5-nitropyridine Chemical compound [O-][N+](=O)C1=CC=C(F)N=C1 XOZAJNLUAODXSP-UHFFFAOYSA-N 0.000 description 1
- VQYAEJWTLQMEFS-UHFFFAOYSA-N 2-fluoro-6-nitronaphthalene Chemical compound C1=C(F)C=CC2=CC([N+](=O)[O-])=CC=C21 VQYAEJWTLQMEFS-UHFFFAOYSA-N 0.000 description 1
- NVORBAXCWWFMSA-UHFFFAOYSA-N 3,7-dibromo-10h-phenothiazine Chemical compound C1=C(Br)C=C2SC3=CC(Br)=CC=C3NC2=C1 NVORBAXCWWFMSA-UHFFFAOYSA-N 0.000 description 1
- GSRATABOOOOTDV-UHFFFAOYSA-N 4-fluoro-n-(4-nitrophenyl)benzamide Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC(=O)C1=CC=C(F)C=C1 GSRATABOOOOTDV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- WZAJDEVHFCARMK-UHFFFAOYSA-N n-(4-fluorophenyl)-4-nitroaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=C(F)C=C1 WZAJDEVHFCARMK-UHFFFAOYSA-N 0.000 description 1
- GMGQGZYFQSCZCW-UHFFFAOYSA-N n-(4-nitrophenyl)benzamide Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC(=O)C1=CC=CC=C1 GMGQGZYFQSCZCW-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/20—[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- 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
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Abstract
The invention discloses diamine containing a phenothiazine structure and polyimide prepared from the diamine. The invention utilizes the intermediate containing phenothiazine substituted by two halogen atoms to react with ammonia water, and converts the halogen atoms into amino; grafting a nitro-containing group through Ullmann coupling reaction and reducing to obtain a diamine monomer containing a phenothiazine structure, and polymerizing the prepared diamine monomer and dianhydride to obtain polyimide with a phenothiazine structure in a main chain. The invention creatively introduces the plane rigid structure and the polar group of the phenothiazine into the polyimide main chain, the plane rigid structure is beneficial to regular stacking of molecular chains and inducing polymer crystallization, and the polar group can enhance the hydrogen bond action of the molecular chains and promote the tight stacking of the molecular chains, so that the polyimide has excellent barrier property, higher glass transition temperature and thermal stability, lower thermal expansion coefficient and antibacterial property.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a preparation method of diamine containing a phenothiazine structure and synthetic polyimide.
Background
An Organic light-emitting diode (OLED) is a flexible Organic electroluminescent device (FOLED) made of flexible polymer materials and packaged into an OLED, has the characteristics of light weight, convenience in carrying, bending, folding, and even being wearable, and is an important development direction of future display technologies. However, FOLED suffers from the inherent instability, low lifetime and sensitivity to water and oxygen of OLED devices, limiting their popularization and application. Most FOLED adopts plastics as the substrate, and the plastics substrate exists not high temperature resistant, the barrier properties is poor, and the surface smoothness is not as good as glass etc. not enough to cause very big difficulty to the preparation of device, the FOLED device of preparation produces the problem that the material drops or follow-up performance and life-span are reduced easily, consequently, needs to provide a roughness height, the substrate material that heat resistance is strong and barrier properties is good.
Polyimide has extremely strong heat resistance, good mechanical property and dimensional stability, and is one of the best choices of flexible OLED substrates or packaging materials. The barrier property of the current commercial polyimide can not meet the packaging requirement of an FOLED device, and the barrier property can be obviously improved by adopting means such as multilayer film compounding, film surface plating or flaky nano modification and the like, but in application, a high-barrier layer film used in multilayer compounding has poor heat resistance and low stability; the flexibility of the coating film is influenced, and the surface is not smooth and easy to break and fall off; inorganic nano-modification is the most commonly used method, and effectively prolongs the diffusion path of water vapor and oxygen molecules in the base material through the sheet-shaped nano layer, so as to improve the barrier property of the base material, however, the method is based on the property difference of the base body, the improvement of the barrier property is limited, and the barrier property of polyimide still cannot meet the high requirement of the OLED on the substrate or the packaging material.
The polyimide can increase the planarity of a polymer chain through reasonable molecular structure design and chemical synthesis, improve the stacking density of the molecular chain and reduce the free volume of the polymer, thereby obtaining the polyimide with high barrier property, which fundamentally solves the problem of insufficient barrier property of the polyimide and has important significance for promoting the development of FOLED. Compared with the molecular design and synthesis of dianhydride monomers, the design and synthesis of diamine monomers are more diverse. Thus, providing a structure with high electron density and good rigidity can improve the barrier properties of the polyimide.
Disclosure of Invention
The invention aims to solve the technical problem of providing a diamine monomer containing a phenothiazine structure, which has good planarity and antibacterial property, aiming at the defect of barrier property of the existing polyimide.
The invention also aims to solve the technical problem of preparing polyimide with high barrier property, good thermal stability and high planarity by using the diamine monomer.
The purpose of the invention is realized by the following technical scheme:
a diamine containing a phenothiazine structure has a structural general formula as follows:
Ar1any one selected from the following structural formulas:
Further, said Ar2And Ar3Any one selected from the following structural formulas:
further, said Ar2Preferably, it is
Ar3 is one or more of
One or more of (a).
The preparation method of the diamine containing the phenothiazine structure comprises the following preparation steps:
s1, phenothiazine monomer substituted by two halogen atoms
Reacting with ammonia water under a protective atmosphere to obtain a monomer 1, a monomer 2 or a monomer 3;
s2, adding the monomer 1, the monomer 2 or the monomer 3 in the step S1, an Ar1 monomer containing a halogen atom and a nitro substituent into a solvent, adding alkali in a protective gas atmosphere, and performing Ullmann coupling reaction to obtain a monomer 4, a monomer 5 or a monomer 6 containing two nitro groups;
s3, adding the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding a reducing agent, and carrying out reduction reaction in a protective gas atmosphere to obtain a diamine monomer containing a phenothiazine structure shown in a structural general formula I, II or III;
the monomer 1, the monomer 2 and the monomer 3 in the step S1, and the monomer 4, the monomer 5 and the monomer 6 in the step S2 respectively have the following structural characteristics:
further, in S2, the ratio of the amount of the monomer 1, the monomer 2 or the monomer 3 to the amount of the substance containing a halogen atom and a nitro-substituted Ar1 monomer is 1: 2-4, and the ratio of the amount of the added alkali to the amount of the substance containing the monomer 1, the monomer 2 or the monomer 3 is 1: 0.5-2.
Further, the ratio of the amount of the monomer 4, the monomer 5, or the monomer 6 to the amount of the reducing agent in S3 is 1:2 to 32.
Further, the protective gas from S1 to S3 is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon.
Further, the base in S2 is one or more of sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-butyl lithium, potassium tert-butoxide, sodium tert-butoxide, and lithium hexamethyldisilazide.
Further, in S3, the reducing agent is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder, and zinc powder.
Further, the solvent in S1 is one or more of dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene, and xylene.
Further, the solvent in S2 is one or more selected from dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1,4 dioxane, toluene, xylene, acetone, acetonitrile, and diphenyl ether.
Further, the solvent in S3 is one or more selected from ethanol, methanol, N-propanol, tert-butanol, tert-amyl alcohol, ethanol, hexanol, tetrahydrofuran, 1,4 dioxane, dimethyl sulfoxide, N-dimethylformamide, ethyl acetate, and toluene.
Further, the reaction temperature of S1-S3 is 50-170 ℃, the reaction time is 10-48 h, the drying temperature is 40-120 ℃, and the drying time is 6-30 h. Preferably, in the step S1, the reaction temperature is 100 ℃, the reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in the S2, the reaction temperature is 150 ℃, the reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 24 hours; in S3, the reaction temperature is 80 ℃, the reaction time is 24h, the drying temperature is 80 ℃, and the drying time is 24 h.
The diamine prepared by the method is used for synthesizing polyamide, polyimide, polyamide-imide or polyester-imide polymers.
Further, the diamine obtained by the method is used for preparing polyimide suitable for microelectronics, military industry, aerospace, packaging and protection and electronic device packaging, and the polyimide has a structural general formula as follows:
wherein y is 1-10000, and X is selected from any one of the following components:
the preparation method of the polyimide containing the phenothiazine structure comprises the following steps: in an argon protective atmosphere, diamine containing a phenothiazine structure and dianhydride containing an X structure are dissolved in a strong-polarity aprotic solvent according to a molar ratio of 1: 0.95-1.05, the mixture is stirred and reacted for 2-48 hours at a temperature of-15-30 ℃ to obtain a homogeneous polyamic acid glue solution, and then the polyamic acid glue solution is subjected to thermal imidization or chemical imidization dehydration to obtain polyimide.
Compared with the prior art, the beneficial effects are:
the invention designs and synthesizes an angle through a molecular structure, creatively introduces a phenothiazine structure and a polar group into a diamine monomer at the same time, and prepares the high-planarity diamine monomer containing the polar group. Phenothiazine is a good electron donor with aromaticity, is easy to form a D-pi-D or A-pi-A system, and has high electron density and good rigid structure. Meanwhile, part of the medicines containing phenothiazine have certain antibacterial effect, and the diamine disclosed by the invention takes a phenothiazine structure as a core, so that the prepared diamine has certain antibacterial performance, and the functional diversity of diamine monomers is enriched to a great extent.
The invention introduces phenothiazine structure into diamine monomer, and then prepares polymer through copolymerization. The large-volume plane rigid phenothiazine structure is introduced into the polyimide main chain, so that polyimide molecular chains can be stacked more tightly, the free volume of the polymer is reduced, and the barrier property of the polyimide is effectively improved; the rigidity of the polyimide molecular chain can be increased, the movement of the molecular chain is limited, the polymer is difficult to form a gas channel, and the barrier property of the polyimide is effectively improved.
The polyimide prepared by the invention contains a phenothiazine structure and a secondary amine bond, the rigidity of the phenothiazine structure can also improve the glass transition temperature of the polymer and improve the heat resistance of the polymer, and the conjugated structure of the phenothiazine structure can improve the heat resistance and the oxidation resistance stability of the polymer and improve the stability of the polymer in extreme environments. The introduction of secondary amine groups can generate hydrogen bonds in and among polyimide molecular chains, and the stacking efficiency of the polyimide molecular chains can be improved through the action of the hydrogen bonds; hydrogen bonding can also induce crystallization of the polyimide, and tight packing and crystallization can also improve the barrier properties of the polyimide. The method has very wide application prospect in the fields of high-performance separation membranes, high-temperature-resistant high-performance structural materials, composite materials, paint, coatings and the like which need high-temperature-resistant high-performance materials with chemical resistance. And because of having certain antibacterial property, the packaging film can also be suitable for packaging materials with high requirements.
Detailed Description
The following examples are further explained and illustrated, but the present invention is not limited in any way by the specific examples. Unless otherwise indicated, the methods and equipment used in the examples are conventional in the art and all materials used are conventional commercially available materials.
Example 1
This example provides N1,N1' - (10H-phenathiazine-2, 8-diyl) bis (bezene-1, 4-diamine):
s1, synthesizing an intermediate 10H-phenothiazine-2, 8-diamine:
adding 3.57g (0.01mol) of 2,8-dibromo-10H-phenothiazine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29 percent and 0.2mol) into a 200ml pressure bottle, carrying out argon protection, carrying out reaction at 100 ℃, pouring the reaction solution into ice water after the reaction is finished, extracting with dichloromethane, removing the solvent under reduced pressure, and adding dichloromethane: and (3) purifying the mixture by column chromatography with mobile phase silica gel serving as a stationary phase and normal hexane being 2: 1 (volume ratio), collecting and spin-drying a product, and drying the product for 24 hours in vacuum at 80 ℃ to obtain an intermediate. The intermediate has the following structure:
s2, synthesizing an intermediate N2,N8-bis(4-nitrophenyl)-10H-phenothiazine-2,8-diamine：
2.29g (0.01mol) of 10H-phenothiazine-2,8-diamine, 7.50g (0.05mol) of p-fluoronitrobenzene and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the reaction solution was heated to 150 ℃ to react for 12 hours, and then poured into cold water, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
s3, synthesizing N1,N1'-(10H-phenothiazine-2,8-diyl)bis(benzene-1,4-diamine)：
4.71g (0.01mol) of N2,N8Adding bis (4-nitrophenyl) -10H-phenothiazine-2,8-diamine into a 500ml three-necked bottle, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating the mixture to 70 ℃ in an oil bath, adding 0.1g of 10% wt palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing and reacting for 24 hours, filtering the reaction liquid by using a funnel, placing the filtrate in a refrigerator for 24 hours for crystallization, collecting an off-white solid after suction filtration, and drying the off-white solid in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 2
The present embodiment provides
N2-(5-aminopyridin-2-yl)-N7Synthesis of- (6-aminopyridin-3-yl) -10H-phenothiazine-2, 7-diamine:
s1, synthesizing an intermediate 10H-phenothiazine-2, 7-diamine:
adding 3.57g (0.01mol) of 2,7-dibromo-10H-phenothiazine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29 percent and 0.2mol) into a 200ml pressure bottle, carrying out argon protection, carrying out reaction at 100 ℃, pouring the reaction solution into ice water after the reaction is finished, extracting with dichloromethane, removing the solvent under reduced pressure, and adding dichloromethane: and (3) purifying the mixture by column chromatography with mobile phase silica gel serving as a stationary phase and normal hexane being 2: 1 (volume ratio), collecting and spin-drying a product, and drying the product for 24 hours in vacuum at 80 ℃ to obtain an intermediate. The intermediate has the following structure:
s2, synthesizing an intermediate
N2-(5-nitropyridin-2-yl)-N7-(6-nitropyridin-3-yl)-10H-phenothiazine-2,7-diamine ：
2.29g (0.01mol) of 10H-phenothiazine-2,7-diamine, 7.105g (0.05mol) of 2-fluoro-5-nitropyridine and 13.8g (0.1mol) of potassium carbonate were charged into a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the temperature was raised to 150 ℃ to react for 12 hours, the reaction solution was poured into cold water, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
s3. synthesis
N2-(5-aminopyridin-2-yl)-N7-(6-aminopyridin-3-yl)-10H-phenothiazine-2,7-diami ne:
4.73g (0.01mol)
N2-(5-nitropyridin-2-yl)-N7- (6-nitropyridin-3-yl) -10H-phenothiazine-2,7-diamine is added into a 500ml three-necked flask, 450ml of absolute ethyl alcohol is added, the mixture is magnetically stirred and is aerated with argon, after the mixture is heated to 70 ℃ in an oil bath, 0.1g of 10 percent wt palladium carbon is added, 10ml of hydrazine hydrate is gradually dripped, after the mixture is refluxed for 24 hours, the reaction solution is pumped out by a funnelAnd (4) filtering, placing the filtrate in a refrigerator for 24 hours for crystallization, filtering, collecting off-white solid, and drying in a vacuum drying oven at the temperature of 80 ℃ for 24 hours to obtain the product.
Example 3
This example provides N1,N1'-(dibenzo[b,d]Synthesis of furan-2,8-diyl) bis (bezene-1, 3-diamine):
s1, synthesizing an intermediate 10H-phenothiazine-3, 7-diamine:
adding 3.57g (0.01mol) of 3,7-dibromo-10H-phenothiazine, a proper amount of cuprous oxide, 50ml of NMP and 13ml of ammonia water (29 percent and 0.2mol) into a 200ml pressure bottle, carrying out argon protection, carrying out reaction at 100 ℃, pouring the reaction solution into ice water after the reaction is finished, extracting with dichloromethane, removing the solvent under reduced pressure, and adding dichloromethane: and (3) purifying the mixture by column chromatography with mobile phase silica gel serving as a stationary phase and normal hexane being 2: 1 (volume ratio), collecting and spin-drying a product, and drying the product for 24 hours in vacuum at 80 ℃ to obtain an intermediate. The intermediate has the following structure:
s2, synthesizing an intermediate N3,N7-bis(3-nitrophenyl)-10H-phenothiazine-3,7-diamine：
2.29g (0.01mol) of 10H-phenothiazine-3,7-diamine, 7.50g (0.05mol) of m-fluoronitrobenzene and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the reaction solution was heated to 150 ℃ to react for 12 hours, and then poured into cold water, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
s3, synthesizing N1,N1'-(10H-phenothiazine-3,7-diyl)bis(benzene-1,3-diamine)：
4.71g (0.01mol) of N3,N7Adding bis (3-nitrophenyl) -10H-phenothiazine-3,7-diamine into a 500ml three-necked bottle, adding 450ml of absolute ethyl alcohol, magnetically stirring and introducing argon, heating in an oil bath to 70 ℃, adding 0.1g of 10% wt palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing for 24 hours, filtering the reaction liquid by using a funnel, placing the filtrate in a refrigerator for 24 hours for crystallization, collecting an off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 4
The present embodiment provides
N2,N2'-(10H-phenothiazine-2,7-diyl)bis(naphthalene-2,6-diamine)：
S1, synthesizing an intermediate
N2,N7-bis(6-nitronaphthalen-2-yl)-10H-phenothiazine-2,7-diamine：
2.29g (0.01mol) of 10H-phenothiazine-2,7-diamine, 9.56g (0.05mol) of 2-fluoro-6-nitro-naphthalene and 13.8g (0.1mol) of potassium carbonate were added to a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the reaction solution was poured into cold water after warming to 150 ℃ for 12 hours, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
s2. Synthesis of N2,N2'-(10H-phenothiazine-2,7-diyl)bis(naphthalene-2,6-diamine)：
5.72g (0.01mol)
N2,N7-bis (6-nitrilophthalen-2-yl) -10H-phenothiazine-2,7-diamine was added to a 500ml three-necked flask and added450ml of absolute ethyl alcohol, magnetic stirring and argon introduction, heating in oil bath to 70 ℃, adding 0.1g of 10 wt% palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, refluxing and reacting for 24 hours, filtering the reaction solution by using a funnel, placing the filtrate in a refrigerator for 24 hours for crystallization, collecting off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 5
The present embodiment provides
N1,N1'-(10H-phenothiazine-3,7-diyl)bis(N4Synthesis of- (4-aminophenyl) bezene-1, 4-diamine):
s1, synthesizing an intermediate
N1,N1'-(10H-phenothiazine-3,7-diyl)bis(N4-(4-nitrophenyl)benzene-1,4-diamine)：
2.29g (0.01mol) of 10H-phenothiazine-3,7-diamine, 11.61g (0.05mol) of 4-fluoro-N- (4-nitrophenyl) aniline and 13.8g (0.1mol) of potassium carbonate were put into a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was carried out while introducing argon gas, the reaction solution was poured into cold water after heating to 150 ℃ for 12 hours, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
s2. synthesis
N1,N1'-(10H-phenothiazine-3,7-diyl)bis(N4-(4-aminophenyl)benzene-1,4-diamine) ：
Mixing 6.54g (0.01mol)
N1,N1'-(10H-phenothiazine-3,7-diyl)bis(N4- (4-nitrophenyl) bezene-1, 4-diamine) was charged into a 500ml three-necked flask, 450ml of absolute ethanol was added, magnetic stirring was conducted while introducing argon gas, oil bath was heated to 70 ℃ and then the mixture was added0.1g of 10 wt% palladium carbon, gradually dropwise adding 10ml of hydrazine hydrate, performing reflux reaction for 24 hours, filtering the reaction liquid by using a funnel, placing the filtrate in a refrigerator for 24 hours for crystallization, collecting off-white solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24 hours to obtain the product.
Example 6
The present embodiment provides
Synthesis of 4,4' - ((10H-phenyliazine-2, 8-diyl) bis (azanediyl)) bis (N- (4-aminophenyl) benzamide):
s1, synthesizing an intermediate
4,4'-((10H-phenothiazine-2,8-diyl)bis(azanediyl))bis(N-(4-nitrophenyl)benzamide) ：
2.29g (0.01mol) of 10H-phenothiazine-2,8-diamine, 13.01g (0.05mol) of 4-fluoro-N- (4-nitrophenyl) benzamide and 13.8g (0.1mol) of potassium carbonate were put into a 250ml three-necked flask, 150ml of dimethyl sulfoxide was added, magnetic stirring was conducted while introducing argon gas, the reaction solution was heated to 150 ℃ to react for 12 hours, and then poured into cold water, the precipitate was filtered off, and washed with hydrochloric acid and water to obtain an intermediate. The intermediate has the following structure:
s2. synthesis
4,4'-((10H-phenothiazine-2,8-diyl)bis(azanediyl))bis(N-(4-aminophenyl)benzamid e)：
7.10g (0.01mol)
4,4' - ((10H-phenyliazine-2, 8-diyl) bis (azanediyl)) bis (N- (4-nitrophenyl) benzamide) is added into a 500ml three-necked bottle, 450ml of absolute ethyl alcohol is added, magnetic stirring is carried out, argon is introduced, after the oil bath is heated to 70 ℃, 10% wt of palladium-carbon 0.1g is added, 10ml of hydrazine hydrate is gradually dripped, after refluxing reaction is carried out for 24H, reaction liquid is filtered by a funnel, filtrate is placed in a refrigerator for 24H to crystallize, after suction filtration, off-white solid is collected, and the off-white solid is dried in a vacuum drying oven at 80 ℃ for 24H to obtain the product.
Example 7
This example provides a process for preparing a polyimide by a thermal imidization process, comprising the steps of:
dissolving diamine containing a phenothiazine structure and dianhydride containing an X structure in a strong-polarity aprotic solvent according to a molar ratio of 1: 0.95-1.05 in an argon protective atmosphere, stirring and reacting at-10-30 ℃ for 1-48 h to obtain a homogeneous polyamic acid glue solution, scraping and coating the polyamic acid glue solution on a glass plate to form a thin layer with the thickness of 1-3 mm, placing the glass plate in a vacuum oven, vacuumizing, heating, and performing the heating process: and heating to 100 ℃ and keeping the temperature constant for 0.5-1 h, heating from 100 ℃ to 200 ℃ and keeping the temperature constant for 0.5-1 h, heating from 200 ℃ to 300 ℃ and keeping the temperature constant for 0.5-1 h, finally heating from 300 ℃ to 420 ℃ and keeping the temperature constant for 1.0-2.0 h, and cooling to obtain the high-planarity polyimide film containing the phenothiazine structure.
Polyimide was prepared by the method of example 7 using the phenothiazine-structured high-plane diamine prepared in examples 1 to 4, and pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, 4 '-diphenyl ether dianhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, 4' - (hexafluoroisopropylene) diphthalic anhydride and 3,3', 4' -benzophenonetetracarboxylic dianhydride, respectively, and the diamine prepared in examples 1 to 6 was classified into examples 8 to 43, and the barrier properties, glass transition temperature, thermal stability and thermal expansion coefficient of the polyimide were measured to calculate the average value of each set of polyimide test, and the results of the measurements are shown in tables 1 to 6:
wherein the dianhydrides are all commercially available on the commercial scale from the reagent Aladdin. The barrier property is detected according to GB/T1038-2000 differential pressure method for testing gas permeability of plastic films and sheets and GB/T19789-2005 coulometer detection method for testing oxygen permeability of plastic films and sheets of packaging materials, and the thermal expansion coefficient and the proud transition temperature are detected according to GB/T36800.2-2018 thermo-mechanical analysis method for plastics.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
The diamine monomers prepared in examples 1 to 6 and the polyimide prepared from the diamine and the dianhydride of the examples were tested for antibacterial performance of escherichia coli according to QB/T25912003, and p-phenylenediamine and the polyimide synthesized with p-phenylenediamine were selected as blank control groups, and the test results are shown in tables 7 to 8:
TABLE 7
TABLE 8
As shown in Table 1, the invention introduces phenothiazine structure and polar group into diamine monomer at the same time to prepare the polar group-containing diamine monomer with high planarity, high electron density and good rigid structure. A plane rigid structure and a polar group are introduced into a polyimide main chain, the plane rigid structure is beneficial to regular stacking of molecular chains and induces polymer crystallization, and the polar group can enhance the hydrogen bond effect of molecular chain bonds and promote the tight stacking of the molecular chains. The synergy of the effects can ensure that molecular chains are regularly arranged and tightly stacked, and the barrier property of the polyimide is obviously improved, so that the polyimide has excellent barrier property, higher glass transition temperature and thermal stability and lower thermal expansion coefficient. As is apparent from Table 2, the phenothiazine structure-containing diamine monomer obtained in the present invention has a good antibacterial activity against Escherichia coli, and it is also apparent from Table 3 that a polyimide prepared using the diamine has a good antibacterial activity.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. Diamine containing phenothiazine structure is characterized in that the structural general formula is as follows:
Ar1any one selected from the following structural formulas:
wherein n is 0-6, m is 0-6, and n and m in the same structural formula are not 0 at the same time.
2. The phenothiazine structure-containing diamine of claim 1, wherein Ar is selected from the group consisting of2And Ar3Any one selected from the following structural formulas:
3. the phenothiazine structure-containing diamine of claim 1, wherein Ar is selected from the group consisting of2Is composed of
One or more of, Ar3Is composed of
One or more of (a).
4. The phenothiazine-structure-containing diamine according to claim 1 or 2, characterized in that the phenothiazine-structure-containing diamine is produced by a method comprising:
s1, using thiophene containing two halogen atoms for substitutionThiazine monomer
Reacting with ammonia water under a protective atmosphere to obtain a monomer 1, a monomer 2 or a monomer 3;
s2, adding the monomer 1, the monomer 2 or the monomer 3 in the step S1, an Ar1 monomer containing a halogen atom and a nitro substituent into a solvent, adding alkali in a protective gas atmosphere, and performing Ullmann coupling reaction to obtain a monomer 4, a monomer 5 or a monomer 6 containing two nitro groups;
s3, adding the monomer 4, the monomer 5 or the monomer 6 in the step S2 into a solvent, adding a reducing agent, and carrying out reduction reaction in a protective gas atmosphere to obtain a diamine monomer containing a phenothiazine structure shown in a structural general formula I, II or III;
the monomer 1, the monomer 2 and the monomer 3 in the step S1, and the monomer 4, the monomer 5 and the monomer 6 in the step S2 respectively have the following structural characteristics:
5. the phenothiazine structure-containing diamine of claim 3, wherein a ratio of the amount of the monomer 1, the monomer 2, or the monomer 3 to the amount of a substance containing a halogen atom and a nitro group-substituted Ar1 monomer in S2 is 1:2 to 4, and a ratio of the amount of the added base to the amount of the substance containing the monomer 1, the monomer 2, or the monomer 3 is 1: 0.5 to 2; the mass ratio of the monomer 4, the monomer 5 or the monomer 6 to the reducing agent in S3 is 1: 2-32.
6. The phenothiazine structure-containing diamine of claim 3, wherein the base in S2 is one or more selected from the group consisting of sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-butyl lithium, potassium tert-butoxide, sodium tert-butoxide, and lithium hexamethyldisilazide; the reducing agent in S3 is one or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder and zinc powder.
7. The phenothiazine structure-containing diamine of claim 3, wherein the solvent in S1 is one or more selected from dimethyl sulfoxide, N-dimethylformamide, pyrrolidone, N-dimethylacetamide, toluene, and xylene; the solvent in S2 is one or more of dimethyl sulfoxide, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, toluene, xylene, acetone, acetonitrile and diphenyl ether; the solvent in S3 is one or more of ethanol, methanol, N-propanol, tert-butanol, tert-amyl alcohol, ethanol, hexanol, tetrahydrofuran, 1,4 dioxane, dimethyl sulfoxide, N-dimethylformamide, ethyl acetate and toluene.
8. A diamine containing a phenothiazine structure according to claim 3, wherein the reaction temperature in S1-S3 is 50 ℃ to 170 ℃, the reaction time is 10 to 48 hours, the drying temperature is 40 ℃ to 120 ℃, and the drying time is 6 to 30 hours.
9. The method for synthesizing polyimide by using diamine containing phenothiazine structure as claimed in any one of claims 1 to 8, wherein the structural formula of the polyimide is as follows:
wherein y is 1-10000, and X is selected from any one of the following structures:
10. the phenothiazine structure-containing polyimide of claim 9, wherein the polyimide is used in microelectronics, military, aerospace, packaging and protection, and electronics packaging.
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| CN115521456A (en) * | 2022-06-29 | 2022-12-27 | 江西有泽新材料科技有限公司 | Polyimide for glue-free flexible copper clad laminate and preparation method thereof |
| CN115612099A (en) * | 2022-09-05 | 2023-01-17 | 江西有泽新材料科技有限公司 | Low-expansion transparent copolymerized polyimide material, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115521456A (en) * | 2022-06-29 | 2022-12-27 | 江西有泽新材料科技有限公司 | Polyimide for glue-free flexible copper clad laminate and preparation method thereof |
| CN115521456B (en) * | 2022-06-29 | 2023-07-21 | 江西有泽新材料科技有限公司 | Polyimide for glue-free flexible copper-clad plate and preparation method thereof |
| CN115612099A (en) * | 2022-09-05 | 2023-01-17 | 江西有泽新材料科技有限公司 | Low-expansion transparent copolymerized polyimide material, preparation method and application |
| CN115612099B (en) * | 2022-09-05 | 2023-10-03 | 江西有泽新材料科技有限公司 | Low-expansion transparent copolyimide material and preparation method and application thereof |
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