CN102731782A - Polyimide containing phthalazinone structure, and preparation method thereof - Google Patents
Polyimide containing phthalazinone structure, and preparation method thereof Download PDFInfo
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 60
- 229920001721 polyimide Polymers 0.000 title claims abstract description 60
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical group C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 62
- -1 dinitro compound Chemical class 0.000 claims abstract description 48
- 150000004985 diamines Chemical class 0.000 claims abstract description 33
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 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 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 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 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 11
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 8
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical group C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 0 CC(C)CC*(C)*/C(/*C1)=C(/C)\**/*=C1/OC=CC*[C@](*(*)(C(*CCCO**)=CCO)N)C=** Chemical compound CC(C)CC*(C)*/C(/*C1)=C(/C)\**/*=C1/OC=CC*[C@](*(*)(C(*CCCO**)=CCO)N)C=** 0.000 description 3
- 125000004427 diamine group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 2
- QOHUCGWLKQHBJH-UHFFFAOYSA-N 4-(4-hydroxy-3-propan-2-ylphenyl)-2H-phthalazin-1-one Chemical compound CC(C)C1=C(O)C=CC(=C1)C1=NNC(=O)C2=CC=CC=C12 QOHUCGWLKQHBJH-UHFFFAOYSA-N 0.000 description 2
- LYLHOKOTRWUGIF-UHFFFAOYSA-N 4-(4-hydroxyphenyl)-2H-phthalazin-1-one Chemical compound C1=CC(O)=CC=C1C1=NNC(=O)C2=CC=CC=C12 LYLHOKOTRWUGIF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- BRGXONVNEKMFQY-UHFFFAOYSA-N 4-(4-hydroxy-2-methylphenyl)-2H-phthalazin-1-one Chemical group CC1=C(C=CC(O)=C1)C1=NNC(=O)C2=CC=CC=C12 BRGXONVNEKMFQY-UHFFFAOYSA-N 0.000 description 1
- HJUSOWLVKSRRGV-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)-2H-phthalazin-1-one Chemical group CC1=CC(=CC(C)=C1O)C1=NNC(=O)C2=CC=CC=C12 HJUSOWLVKSRRGV-UHFFFAOYSA-N 0.000 description 1
- YTKAUIROIYQCKN-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)-2H-phthalazin-1-one Chemical group CC1=C(O)C=CC(=C1)C1=NNC(=O)C2=CC=CC=C12 YTKAUIROIYQCKN-UHFFFAOYSA-N 0.000 description 1
- RLQUSXGTTYBZAT-UHFFFAOYSA-N CCc1cc(ccc1O)-c1n[nH]c(=O)c2ccccc12 Chemical group CCc1cc(ccc1O)-c1n[nH]c(=O)c2ccccc12 RLQUSXGTTYBZAT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
The invention discloses polyimide containing a phthalazinone structure, and a preparation method thereof. According to the invention, a bisphenol-like monomer containing a phthalazinone structure and 2-chloro-5-nitrobenzene are subjected to nucleophilic substitution, such that a dinitro compound is produced, and the compound is reduced to diamine monomer. The diamine monomer and dianhydride monomer are subjected to condensation polymerization, such that a novel type of polyimide with an intrinsic viscosity of 0.43-0.83dL/g, a glass-transition temperature above 238 DEG C, and a 5% decomposition temperature above 452 DEG C is obtained. The polyimide provided by the invention can be used for preparing high-temperature-resisting gas separation membranes.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of high polymer materials, and particularly relates to polyimide containing a phthalazinone structure and a preparation method of the polyimide.
[ background of the invention ]
Polyimide has wide application in the aspects of microelectronic technology, photoelectric information, aerospace and the like as an important structural and functional material, and overcoming the contradiction between high performance and processability becomes an important research direction for the development of advanced materials. The development of new diamine monomers for synthesizing linear polyimide starts from molecular design, and the diamine monomers have extremely important significance for expanding the application of polyimide.
Although polyimide has excellent performance, the defects of insolubility, high cost and the like still limit the application of the polyimide to a great extent. Therefore, how to overcome these disadvantages and obtain polyimide having good solubility and maintaining excellent heat resistance has become a hot problem in academia and industry.
[ summary of the invention ]
One of the technical problems to be solved by the present invention is to provide a polyimide having a phthalazinone structure, which has excellent solubility and heat resistance.
The invention solves the technical problems through the following technical scheme: a polyimide containing a phthalazinone structure has the following structural formula:
wherein Ar is
The viscosity of the polyimide in chloroform as a solvent is 0.43 dL/g-0.83 dL/g, the glass transition temperature of the polyimide is more than or equal to 238 ℃, and the 5% decomposition temperature of the polyimide is more than or equal to 452 ℃.
The second technical problem to be solved by the present invention is to provide a preparation method of the polyimide containing a phthalazinone structure, which is low in cost.
The invention solves the technical problems through the following technical scheme: a preparation method of the polyimide containing the phthalazinone structure comprises the following steps:
(1) preparation of diamine monomer: reacting a bisphenol-like monomer containing a phthalazinone structure with 2-chloro-5-nitrobenzene, wherein a solvent is N, N-dimethylacetamide, potassium carbonate is used as a catalyst, and the mass ratio of the bisphenol-like monomer to the 2-chloro-5-nitrobenzene is 1: 2; firstly, reacting for 5 hours at the temperature of 138 ℃, then increasing the temperature to 145 ℃, and reacting for 2 hours; raising the temperature to 164 ℃ for reaction for 2h to obtain a dinitro compound solution; the dinitro compound solution is settled in ice water, filtered and washed with warm water, and then vacuum-dried at 60 ℃ to obtain a dinitro compound; dissolving a dinitro compound in ethylene glycol monomethyl ether, taking Pd/C as a catalyst, dropwise adding excessive hydrazine hydrate in the stirring, heating and refluxing process, reacting for 5 hours after dropwise adding, filtering to remove Pd/C while hot, standing until crystals are completely separated out, filtering, discarding filtrate, washing the crystals with diethyl ether for multiple times, and finally drying the washed crystals at the vacuum temperature of 60 ℃ to obtain a diamine monomer;
(2) preparation of polyimide: completely dissolving the diamine monomer obtained by the treatment of the step (1) in N-methyl pyrrolidone, adding a dianhydride monomer with the same amount as the diamine monomer, and stirring and reacting for 12 hours at room temperature or in an ice bath in a nitrogen atmosphere; then raising the reaction temperature to 120 ℃, and stirring and reacting for 12 hours by taking acetic anhydride as a dehydrating agent and pyridine as a catalyst to obtain a polymer solution; the polymer solution was poured into a 50% volume fraction aqueous ethanol solution, and vigorously stirred, and then filtered to obtain a solid, and finally the solid was dried under vacuum at 100 ℃ for 4 hours to obtain polyimide.
Further, the structural formula of the bisphenol monomer is as follows:
wherein Ar is
Any of the above.
Further, the dianhydride monomer is bisphenol A type dianhydride, and the structural formula is as follows:
further, the diamine monomer has the following structural formula:
wherein Ar is
Any one of the above.
The invention has the beneficial effects that: utilizing bisphenol-like monomers containing a phthalazinone structure and 2-chloro-5-nitrobenzene to produce dinitro compounds through nucleophilic substitution, and reducing the dinitro compounds into diamine monomers; then, the diamine monomer and the dianhydride monomer are subjected to polycondensation to obtain the novel polyimide with excellent solubility and heat resistance, and the preparation method is low in cost.
[ description of the drawings ]
The invention will be further described with reference to the following examples with reference to the accompanying drawings.
FIG. 1 shows IR spectra of IP-DA and IP-PI in the present invention.
FIG. 2 shows IP-PI of the present invention1H NMR spectrum.
FIG. 3 shows a synthesis reaction formula in the preparation of polyimide.
[ detailed description ] embodiments
A polyimide containing a phthalazinone structure has the following structural formula:
wherein Ar is
The viscosity of the polyimide in chloroform as a solvent is 0.43 dL/g-0.83 dL/g, the glass transition temperature of the polyimide is more than or equal to 238 ℃, and the 5% decomposition temperature of the polyimide is more than or equal to 452 ℃.
The polyimide can be prepared by the following steps:
(1) preparation of diamine monomer: reacting a bisphenol-like monomer containing a phthalazinone structure with 2-chloro-5-nitrobenzene, wherein a solvent is N, N-dimethylacetamide, potassium carbonate is used as a catalyst, 20ml of toluene can be added, so that trace water generated in the reaction process and the toluene can form an azeotrope to be removed, and the mass ratio of the bisphenol-like monomer to the 2-chloro-5-nitrobenzene is 1: 2; firstly, reacting for 5 hours at the temperature of 138 ℃, then increasing the temperature to 145 ℃, reacting for 2 hours, and separating out toluene from a water separator so as to avoid that the toluene and a diamine monomer are separated out and crystallized together after the reaction is finished and the yield of the diamine monomer is influenced; raising the temperature to 164 ℃ for reaction for 2h to obtain a dinitro compound solution; the dinitro compound solution is settled in ice water, filtered and washed with warm water, and then vacuum-dried at 60 ℃ to obtain a dinitro compound; dissolving a dinitro compound in ethylene glycol monomethyl ether, taking Pd/C as a catalyst, dropwise adding excessive hydrazine hydrate in the stirring, heating and refluxing process, reacting for 5 hours after dropwise adding, filtering to remove Pd/C while hot, standing until crystals are completely separated out, filtering, discarding filtrate, washing the crystals with diethyl ether for multiple times, and finally drying the washed crystals at the vacuum temperature of 60 ℃ to obtain a diamine monomer; wherein the structural formula of the bisphenol monomer is as follows:
the structural formula of the dinitro compound is:
the structural formula of the diamine monomer is as follows:
ar may be 
Any one of (a);
the synthesis reaction formula of the step (1) is as follows:
(2) preparation of polyimide: completely dissolving the diamine monomer obtained by the treatment in the step (1) in N-methylpyrrolidone, then adding dianhydride monomer with the amount equal to that of the diamine monomer, wherein the solid content of the reaction system is 10%, and stirring and reacting for 12 hours at room temperature or in an ice bath under the nitrogen atmosphere; then raising the reaction temperature to 120 ℃, and stirring and reacting for 12 hours by taking acetic anhydride as a dehydrating agent and pyridine as a catalyst to obtain a polymer solution; the polymer solution was poured into a 50% volume fraction aqueous ethanol solution, and vigorously stirred, and then filtered to obtain a solid, and finally the solid was dried under vacuum at 100 ℃ for 4 hours to obtain polyimide.
Wherein the dianhydride monomer is bisphenol A dianhydride (BPADA), and the structural formula is as follows:
the synthesis reaction formula of the step (2) is shown in figure 3.
The following provides representative examples of the invention, which are intended to be illustrative only and not to limit the scope of the invention described herein, and which are intended to be merely illustrative of the practice of the invention:
example one
(1) Preparation of diamine monomer: sequentially adding bisphenol-like monomer 4- (3-isopropyl-4-hydroxyphenyl) phthalazinone 30 multiplied by 10 into a three-neck flask provided with a mechanical stirrer, a condenser pipe, a thermometer and a water separator-3mol (i.e. 8.41g), 2-chloro-5-nitrobenzene 60X 10-3mol (i.e. 9.45g), anhydrous potassium carbonate 66X 10-360ml of N, N-dimethylacetamide (DMAc) and 20ml of toluene are dehydrated under reflux at 138 ℃ for 5 hours under the protection of nitrogen; then heating to 145 ℃ and reacting for 2 h; then, toluene is separated from the water separator and continuously reacts for 2 hours at 164 ℃ to obtain a dinitro compound solution; the dinitro compound solution is poured rapidly into a large amount of ice water and allowed to settle in the ice water with vigorous stirring. Standing, filtering, washing with warm water several times, and vacuum drying at 60 deg.C to obtain light yellow solid 12.5g, i.e. dinitro compound 2- (4-nitrophenyl) -4- [ 3-isopropyl-4- (4-nitrophenoxy) phenyl]Naphthyridin-1-one (IP-DN).
Adding dinitro compound 2- (4-nitrophenyl) -4- [ 3-isopropyl-4- (4-nitrophenoxy) phenyl into a three-neck flask with a mechanical stirrer, a condenser tube and a constant pressure dropping funnel]Naphthyridin-1-one (IP-DN)12g (i.e. 23X 10)-3mol), 120ml of ethylene glycol monomethyl ether and 0.3g of Pd/C (5 percent), then heating the mixture until the reaction system generates reflux, and dropwise adding 40ml of hydrazine hydrate; after adding hydrazine hydrate, carrying out reflux reaction for 5h, stopping the reaction, filtering Pd/C while the reaction is hot, standing until crystals are completely separated out, filtering, discarding filtrate, repeatedly washing with diethyl ether, and finally washing the crystalsThe resulting mixture was dried under vacuum at 60 ℃ to give 9.7g of pale yellow crystals, i.e., 2- (4-aminophenyl) -4- [ 3-isopropyl-4- (4-aminophenoxy) phenyl diamine monomer]Naphthyridin-1-one (IP-DA) in 90.7% yield and a melting point of 249-250 ℃.
The structural formula of the bisphenol monomer 4- (3-isopropyl-4-hydroxyphenyl) phthalazinone is as follows:
The structural formula of the dinitro compound 2- (4-nitrophenyl) -4- [ 3-isopropyl-4- (4-nitrophenoxy) phenyl ] naphthyridin-1-one is as follows:
The structural formula of the diamine monomer 2- (4-aminophenyl) -4- [ 3-isopropyl-4- (4-aminophenoxy) phenyl ] naphthyridin-1-one (IP-DA) is as follows:
(2) Preparation of polyimide:
is equipped with N2A three-neck flask with a protection device, a magnetic stirring device and a condenser pipe is added with 1 multiplied by 10-3mol of diamine monomer 2- (4-aminophenyl) -4- [ 3-isopropyl-4- (4-aminophenoxy) phenyl]Naphthyridin-1-one (IP-DA), 4mL N-methylpyrrolidone (i.e., NMP), added in equimolar amounts (i.e., 1X 10) once more after the diamine monomer is completely dissolved-3mol) of dianhydride monomer bisphenol A dianhydride (BPADA), the reaction system having a solids content of about 10%. After the addition is finished, stirring for 12h at room temperature, wherein the yellow color of the solution is deepened, and the system is kept in a homogeneous phase state; then, a water separator and a condenser pipe are assembled on the device, 1mL of acetic anhydride and 0.5mL of pyridine are added into the system, the temperature is raised to 120 ℃, and the mixture is stirred and reacts for 12 hours at the temperature to obtain a polymer solution, at the moment, a small amount of liquid appears on the wall of the water separator, the system is changed from yellow to brown, and the viscosity is increased; finally, the polymer solution was poured into 200mL of 50% by volume aqueous ethanol solution, vigorously stirred while settling, and filtered to give a flaky or fibrous solid, and finally the solid was dried under vacuum at 100 ℃ for 4 hours to give polyimide in a yield of 92.8%.
The structural formula of the polyimide is as follows:
wherein Ar is
Example two
The difference between the present part and the first embodiment is that: bisphenol monomer 4- (4-hydroxyphenyl) phthalazinone 30X 10-3The structural formula of the 4- (4-hydroxyphenyl) phthalazinone is shown as follows:
The structural formula of the dinitro compound is 2- (4-nitrophenyl) -4- [4- (4-nitrophenoxy) phenyl ] naphthyridin-1-one as follows:
ar is
The diamine monomer is 2- (4-aminophenyl) -4- [4- (4-aminophenoxy) phenyl ] naphthyridin-1-one, and the structural formula is as follows:
The structural formula of the polyimide is as follows:
ar is
EXAMPLE III
The difference between the present part and the second embodiment is that:
the structural formula of the bisphenol monomer is 4- (2-methyl-4-hydroxyphenyl) phthalazinone is as follows:
The structural formula of the dinitro compound is 2- (4-nitrophenyl) -4- [ 2-methyl-4- (4-nitrophenoxy) phenyl ] naphthyridin-1-ketone is as follows:
The diamine monomer is 2- (4-aminophenyl) -4- [ 2-methyl-4- (4-aminophenoxy) phenyl ] naphthyridine-1-ketone, and the structural formula is as follows:
The structural formula of the polyimide is as follows:
ar is
Example four
The difference between the present part and the first embodiment is that:
the structural formula of the bisphenol monomer is 4- (3-methyl-4-hydroxyphenyl) phthalazinone is as follows:
The structural formula of the dinitro compound is 2- (4-nitrophenyl) -4- [ 3-methyl-4- (4-nitrophenoxy) phenyl ] naphthyridin-1-ketone is as follows:
The structural formula of the diamine monomer which is 2- (4-aminophenyl) -4- [ 3-methyl-4- (4-aminophenoxy) phenyl ] naphthyridine-1-ketone is as follows:
The structural formula of the polyimide is as follows:
ar is
EXAMPLE five
The difference between the present part and the first embodiment is that:
the structural formula of the bisphenol monomer is 4- (3-ethyl-4-hydroxyphenyl) phthalazinone is as follows:
wherein Ar is
The structural formula of the dinitro compound is 2- (4-nitrophenyl) -4- [ 3-ethyl-4- (4-nitrophenoxy) phenyl ] naphthyridin-1-one as follows:
The diamine monomer is 2- (4-aminophenyl) -4- [ 3-ethyl-4- (4-aminophenoxy) phenyl ] naphthyridine-1-ketone, and the structural formula is as follows:
The structural formula of the polyimide is as follows:
ar is
EXAMPLE six
The difference between the present part and the first embodiment is that:
the structural formula of the bisphenol monomer is 4- (3, 5-dimethyl-4-hydroxyphenyl) phthalazinone is as follows:
The structural formula of the dinitro compound is 2- (4-nitrophenyl) -4- [3, 5-dimethyl-4- (4-nitrophenoxy) phenyl ] naphthyridin-1-ketone is as follows:
The diamine monomer is 2- (4-aminophenyl) -4- [3, 5-dimethyl-4- (4-aminophenoxy) phenyl ] naphthyridine-1-ketone, and the structural formula is as follows:
The structural formula of the polyimide is as follows:
diamine substituted with o-isopropyl (i.e., 2- (4-aminophenyl) -4- [ 3-isopropyl-4- (4-aminophenoxy) phenyl as described in example one)]Naphthyridin-1-one (IP-DA)) as an example, for convenience of description, the 2- (4-aminophenyl) -4- [ 3-isopropyl-4- (4-aminophenoxy) phenyl group will be described hereinafter]The naphthyridin-1-one is called IP-DA, and the polyimide obtained by condensation polymerization of IP-DA and bisphenol A dianhydride is called IP-PI. The infrared spectrum characterization results of IP-DA and IP-PI thereof are shown in FIG. 1, and IP-DA (i.e. IPDA in FIG. 1) is 3400cm-1A typical amino group vibration absorption peak appears nearby, namely at 3451cm-1And 3348cm-1Exhibits a characteristic double peak of 1655cm of primary amine-1Is the N-H bending vibration peak.
The characteristic peak of the imide ring appears in the figure of polyimide IP-PI corresponding to IP-DA (namely IP-PI in figure 1): 1780cm-1The left and right sides are carbonyl asymmetric stretching vibration absorption peak, 1723cm-1Is a carbonyl symmetric telescopic vibration absorption peak, and is 1375cm-1C-N bond stretching vibration; in addition, at 1680cm-1There was no absorption peak characteristic of polyamic acid and disappearance of the amino characteristic peak, indicating completion of imidization during polymerization.
Diamine substituted with o-isopropyl (i.e., 2- (4-aminophenyl) -4- [ 3-isopropyl-4- (4-aminophenoxy) phenyl as described in example one)]Naphthyridin-1-one (IP-DA)) and bisphenolsFor example, as shown in fig. 2, the polyimide synthesized by condensation polymerization of type a dianhydride, i.e., IP-PI, has no characteristic peak of amino group of diamine monomer and no characteristic peak of amide group in polyamic acid in fig. 2, indicating that the obtained polyamic acid is completely imidized; 8.61-8.63 ppm of H-d, 7.00-7.93 ppm of Ar-H, 3.70-3.74 ppm and 1.24ppm of H-b and H-c in isopropyl, 1.75ppm of methyl in bisphenol A dianhydride, 7.26ppm of residual proton in CDCl3, and 1.63ppm of H2Absorption peak of O. Of other polyimides1The H NMR spectrum data is similar to that of FIG. 2, the integral ratio of various hydrogen absorption peaks is consistent with the structure, as can be seen from the close integral values of the methyl hydrogen H-a in the bisphenol A dianhydride structure and the methyl hydrogen H-b in the o-isopropyl in the phthalazinone diamine structure, the numbers of the dianhydride and diamine structures in the polymer are approximately equal, the polymer structure is consistent with the strict equivalent ratio of the monomers, and the sum of the integral of H-c and the integral of each peak except the chloroform peak between 7 ppm and 9ppm is close to 1: 28.
The total of 6 polyimides prepared in the above examples were tested in N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, pyridine, m-cresol, chloroform, tetrahydrofuran, and all of the polyimides were found to be soluble at room temperature, and colorless, transparent, tough films could be prepared in chloroform solution, demonstrating that they have very excellent solubility. The intrinsic viscosity of the polyimide is measured to be between 0.43 and 0.83dL/g by taking chloroform as a solvent. The polyimide has a glass transition temperature of 238 ℃ or higher and a 5% decomposition temperature of 452 ℃ or higher. The polyimide prepared by the method can be used for preparing a high-temperature resistant membrane and a gas separation membrane.
The invention introduces the distorted non-coplanar asymmetric structure of the phthalazinone on the main chain of the polymer to reduce the acting force between chains and reduce the close packing between chains to improve the solubility of the polyimide, and simultaneously, the rigidity of the molecular chain can be kept, thereby keeping good heat resistance.
Claims (5)
1. A polyimide containing a phthalazinone structure is characterized in that: the structural formula of the polyimide is as follows:
wherein Ar is
The viscosity of the polyimide in chloroform as a solvent is 0.43 dL/g-0.83 dL/g, the glass transition temperature of the polyimide is more than or equal to 238 ℃, and the 5% decomposition temperature of the polyimide is more than or equal to 452 ℃.
2. A method for preparing a polyimide containing a phthalazinone structure as claimed in claim 1, wherein: the method comprises the following steps:
(1) preparation of diamine monomer: reacting a bisphenol-like monomer containing a phthalazinone structure with 2-chloro-5-nitrobenzene, wherein a solvent is N, N-dimethylacetamide, potassium carbonate is used as a catalyst, and the mass ratio of the bisphenol-like monomer to the 2-chloro-5-nitrobenzene is 1: 2; firstly, reacting for 5 hours at the temperature of 138 ℃, then increasing the temperature to 145 ℃, and reacting for 2 hours; raising the temperature to 164 ℃ for reaction for 2h to obtain a dinitro compound solution; the dinitro compound solution is settled in ice water, filtered and washed with warm water, and then vacuum-dried at 60 ℃ to obtain a dinitro compound; dissolving a dinitro compound in ethylene glycol monomethyl ether, taking Pd/C as a catalyst, dropwise adding excessive hydrazine hydrate in the stirring, heating and refluxing process, reacting for 5 hours after dropwise adding, filtering to remove Pd/C while hot, standing until crystals are completely separated out, filtering, discarding filtrate, washing the crystals with diethyl ether for multiple times, and finally drying the washed crystals at the vacuum temperature of 60 ℃ to obtain a diamine monomer;
(2) preparation of polyimide: completely dissolving the diamine monomer obtained by the treatment of the step (1) in N-methyl pyrrolidone, adding a dianhydride monomer with the same amount as the diamine monomer, and stirring and reacting for 12 hours at room temperature or in an ice bath in a nitrogen atmosphere; then raising the reaction temperature to 120 ℃, and stirring and reacting for 12 hours by taking acetic anhydride as a dehydrating agent and pyridine as a catalyst to obtain a polymer solution; the polymer solution was poured into a 50% volume fraction aqueous ethanol solution, and vigorously stirred, and then filtered to obtain a solid, and finally the solid was dried under vacuum at 100 ℃ for 4 hours to obtain polyimide.
3. The method for producing a polyimide containing a phthalazinone structure as claimed in claim 2, wherein: the structural formula of the bisphenol monomer is as follows:
wherein Ar is
Any of the above.
4. The method for producing a polyimide containing a phthalazinone structure as claimed in claim 2, wherein: the dianhydride monomer is bisphenol A type dianhydride, and the structural formula is as follows:
5. the method for producing a polyimide containing a phthalazinone structure as claimed in claim 2, wherein: the diamine monomer has the following structural formula:
wherein Ar is
Any one of the above.
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| CN111233842A (en) * | 2020-03-20 | 2020-06-05 | 吉林大学 | Phthalazinone diamine monomer and preparation method thereof, polyimide and preparation method thereof, and polyimide film |
| CN114920933A (en) * | 2022-06-10 | 2022-08-19 | 大连理工大学 | Polyimide with main chain containing fluorine ether atom and phthalazinone structure as well as preparation method and application thereof |
| CN115160567A (en) * | 2022-07-22 | 2022-10-11 | 大连理工大学 | Polyimide containing carbon chain phthalazinone structure and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233842A (en) * | 2020-03-20 | 2020-06-05 | 吉林大学 | Phthalazinone diamine monomer and preparation method thereof, polyimide and preparation method thereof, and polyimide film |
| CN114920933A (en) * | 2022-06-10 | 2022-08-19 | 大连理工大学 | Polyimide with main chain containing fluorine ether atom and phthalazinone structure as well as preparation method and application thereof |
| CN114920933B (en) * | 2022-06-10 | 2023-09-15 | 大连理工大学 | Polyimide with main chain containing fluoroether atom and phthalazinone structure, and preparation method and application thereof |
| CN115160567A (en) * | 2022-07-22 | 2022-10-11 | 大连理工大学 | Polyimide containing carbon chain phthalazinone structure and preparation method thereof |
| CN115160567B (en) * | 2022-07-22 | 2024-04-26 | 大连理工大学 | Polyimide containing carbon chain naphthyridine ketone structure and preparation method thereof |
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