CN103113309B - Bipyrimidyl dibenzene/diether/diamine and synthesis method thereof - Google Patents
Bipyrimidyl dibenzene/diether/diamine and synthesis method thereof Download PDFInfo
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- 150000004985 diamines Chemical class 0.000 title abstract description 4
- 238000001308 synthesis method Methods 0.000 title description 2
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 85
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 71
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 62
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 60
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical group N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052786 argon Inorganic materials 0.000 claims description 30
- KPRAKBLCEALHKQ-UHFFFAOYSA-N 5-bromo-2-(5-bromopyrimidin-2-yl)pyrimidine Chemical compound N1=CC(Br)=CN=C1C1=NC=C(Br)C=N1 KPRAKBLCEALHKQ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- UNCQVRBWJWWJBF-UHFFFAOYSA-N 2-chloropyrimidine Chemical compound ClC1=NC=CC=N1 UNCQVRBWJWWJBF-UHFFFAOYSA-N 0.000 claims description 10
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- MMVGSPYXQMMOEL-UHFFFAOYSA-N 4-[2-[5-(4-aminophenoxy)pyrimidin-2-yl]pyrimidin-5-yl]oxyaniline Chemical compound NC1=CC=C(OC=2C=NC(=NC=2)C2=NC=C(C=N2)OC2=CC=C(C=C2)N)C=C1 MMVGSPYXQMMOEL-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- ADVGKWPZRIDURE-UHFFFAOYSA-N 2'-Hydroxyacetanilide Chemical compound CC(=O)NC1=CC=CC=C1O ADVGKWPZRIDURE-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 102100021587 Embryonic testis differentiation protein homolog A Human genes 0.000 claims description 8
- 101000898120 Homo sapiens Embryonic testis differentiation protein homolog A Proteins 0.000 claims description 8
- 239000007832 Na2SO4 Substances 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
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- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 abstract description 25
- 229920001721 polyimide Polymers 0.000 abstract description 25
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000004952 Polyamide Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 229920002647 polyamide Polymers 0.000 abstract description 5
- 125000000714 pyrimidinyl group Chemical group 0.000 abstract description 4
- -1 4-aminophenoxy Chemical group 0.000 description 24
- 238000002844 melting Methods 0.000 description 24
- 230000008018 melting Effects 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 13
- 239000008188 pellet Substances 0.000 description 12
- 238000000605 extraction Methods 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 229960005489 paracetamol Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 101150073654 dapB gene Proteins 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QLNWXBAGRTUKKI-UHFFFAOYSA-N metacetamol Chemical compound CC(=O)NC1=CC=CC(O)=C1 QLNWXBAGRTUKKI-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 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
- 241000721454 Pemphigus Species 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides an aromatic diamine containing a bipyrimidyl structure. The chemical structural formula is shown as Formula (1). The diamine can be used as a raw material for the preparation of multiple polyimides and polyamides containing pyrimidyl, can enrich the polymer variety, can enhance the heat resistance and dielectric property of the polymer, and is beneficial to improve the application processing performance of polyimides and polyamides and widen the application area thereof. The invention also provides a preparation method of the aromatic diamine containing a bipyrimidyl structure.
Description
Technical Field
The invention belongs to the technical field of organic compounds and preparation methods thereof, and particularly relates to an aromatic diamine monomer containing a bipyrimidine structure and a synthesis method thereof.
Background
Polyimide (PI) is a high polymer material which contains imide rings on a main chain, has excellent heat resistance and chemical stability resistance, and also has excellent mechanical property and electrical property, and is widely applied to the high and new technical fields of aviation, aerospace, electricity, microelectronics, automobiles and the like. The pyrimidine ring has higher thermal stability and polarity than the benzene ring, and the bipyrimidine structure has a chelating function. The bipyrimidine structure is introduced into the PI molecular structure, which is beneficial to improving the thermal stability and dielectric constant of the PI material and endowing the PI material with a chelating function to form a PI/metal chelating cross-linked functional polymer material, and the PI/metal chelating cross-linked functional polymer material has low expansion coefficient while keeping higher thermal stability and high dielectricity, so that the application field of the PI material is greatly expanded.
PI polymeric monomers having bipyrimidine structure have been reported, for example, 5 '-bis [ p- (4-aminophenoxy) phenoxy ] bipyrimidine (Pengxin, et al, novel 5, 5' -bis [ p- (4-aminophenoxy) phenoxy ] bipyrimidine, synthetic chemistry, 2011,19(3): 334-. PI obtained by polymerizing the compound as a monomer is improved in performance. However, in practice, the synthesis process of the compound has the defects of low reaction yield and the like due to post-treatment such as complexation removal by using highly toxic NaCN, and is not beneficial to production safety and environmental protection, and the performance of PI obtained after polymerization is to be further improved.
Disclosure of Invention
One of the objects of the present invention is: a novel aromatic diamine containing a bipyrimidine structure is provided, which can bring more remarkable performance improvement to PI obtained by polymerization as a monomer.
Another object of the invention is: the chemical synthesis method of the aromatic diamine containing the bipyrimidine structure has the advantages of high reaction yield, environmental friendliness and the like.
In order to realize the purpose, the technical scheme of the invention is as follows:
provides an aromatic diamine containing a bipyrimidine structure, which has a chemical structural formula shown as a formula (1):
in a preferred embodiment of the present invention, the substitution position of the amino group of the aromatic diamine containing a bipyrimidine structure represented by formula (1) on the phenoxy benzene ring is any of 2-4 positions.
In another preferred embodiment of the present invention, the positions of substitution of amino groups on the benzene rings at both ends of the aromatic diamine containing a bipyrimidine structure represented by formula (1) are the same.
The most preferred bipyrimidine structure-containing aromatic diamine of the present invention includes any one of the compounds represented by the following formulae (2) to (4):
5,5 '-bis (4-aminophenoxy) -2, 2' -bipyrimidine:
5,5 '-bis (3-aminophenoxy) -2, 2' -bipyrimidine
Or,
5,5 '-bis (2-aminophenoxy) -2, 2' -bipyrimidine
The invention also provides a preparation method of the aromatic diamine containing the bipyrimidine structure, which comprises the following steps:
1) 2-chloropyrimidine is taken as a raw material, and 2, 2' -bipyrimidine is generated through coupling reaction;
2) carrying out substitution reaction on the 2,2 ' -bipyrimidine obtained in the step 1) and bromine to obtain 5,5 ' -dibromo-2, 2 ' -bipyrimidine;
3) carrying out condensation reaction on the 5,5 '-dibromo-2, 2' -bipyrimidine obtained in the step 2) and acetaminophenol to obtain 5,5 '-bis (q-acetaminophenoxy) -2, 2' -bipyrimidine;
4) hydrolyzing the 5,5 '-bis (q-acetamidophenoxy) -2, 2' -bipyrimidine obtained in the step 3) in an acidic aqueous solution to remove acetyl, thus obtaining the bipyrimidinyl-containing aromatic diamine.
The substitution reaction in the step 2) is preferably a heating reaction of 2, 2' -bipyrimidine and liquid bromine in a hydrothermal reaction kettle.
The acetaminophen in step 3) is preferably one of 4-acetaminophen, 3-acetaminophen and 2-acetaminophen.
The acidic aqueous solution in the step 4) is preferably any one of a sulfuric acid solution, a phosphoric acid solution, a hydrochloric acid solution, a formic acid solution or an acetic acid solution.
The preferred preparation method of the invention is as follows:
the first step of reaction: deoxygenation of the N, N-dimethylformamide freed of water under argon, triphenylphosphine, NiCl2.H2Adding O and activated zinc powder into solvent, stirring for 0.5-5 hr under the protection of argon, adding 2-chloropyrimidine, reacting at 50 deg.C for 10-50 hr, vacuum filtering, washing solid with chloroform, evaporating filtrate, adding ETDA and NH into solid3.H2Stirring in solution prepared from O (7%), extracting with ethyl acetate, extracting the rest solution with chloroform, and extracting with Na2SO4Drying and evaporating chloroform to obtain a light yellow solid, and recrystallizing with ethyl acetate, methanol =19:1 to obtain a white product, 2' -bipyrimidine;
the second step of reaction: 2, 2' -bipyrimidine and bromine obtained in the first step are put into a hydrothermal reaction kettle to react for 12 hours in an oven at 150 ℃, and Na is used2CO3Washing with water solution, baking, andrecrystallizing ethyl acetate, chloroform =9:1 and a small amount of petroleum ether to obtain 5,5 '-dibromo-2, 2' -bipyrimidine;
the third step of reaction: adding 5,5 '-dibromo-2, 2' -bipyrimidine into a flask, adding dewatered DMF (dimethyl formamide), and adding anhydrous K2CO3Adding acetaminophenol, reacting for 6-12 hours at 135 ℃, pouring into distilled water after the reaction is finished, stirring and washing, filtering, and recrystallizing by using DMF and ethanol (9: 1) to obtain silver white solid bis (q-acetaminophenoxy) bipyrimidine; the acetaminophenol is any one of 4-acetaminophenol, 3-acetaminophenol or 2-acetaminophenol;
and a fourth step of reaction: adding the bis (q-acetamidophenoxy) bipyrimidine (q =2,3 or 4) obtained in the third step into a 20% sulfuric acid solution, reacting at 70 ℃ for 6-12 hours under the protection of argon, cooling to room temperature, pouring into distilled water, adjusting the pH value to be neutral by using ammonia water, and separating out an off-white solid, wherein DMF: ethanol =10:1, and recrystallizing to obtain a white solid, namely the aromatic diamine containing the bipyrimidine structure.
The aromatic diamine containing pyrimidyl prepared by the invention is a novel diamine monomer containing pyrimidyl. Compared with 5, 5' -bis [ p- (4-aminophenoxy) phenoxy ] bipyrimidine in the prior art, the structural difference is obvious, and as a monomer, the PI obtained by polymerization is provided with more obvious performance improvement, including the obvious improvement of the thermal stability and the glass transition temperature of the polymer and the obvious improvement of the dielectric property of the polymer. In conclusion, the aromatic diamine of the present invention is more useful for improving the application processability and expanding the application fields of polyimides and polyamides.
In addition, in the preferred preparation method of the aromatic diamine, NiCl is used for synthesizing 5, 5' -dibromo bipyrimidine2.H2And (3) reacting the triphenylphosphine with activated zinc powder, performing aftertreatment with EDTA (ethylene diamine tetraacetic acid), and the like, wherein the yield of the first two steps reaches 76%. Pengxin, et al, novel 5, 5' -bis [ p- (4-aminophenoxy) phenoxy ] phenoxy]Bipyrimidine, synthetic chemistry 2011,19(3):334-With highly toxic NaCN, the yield of the two-step reaction is only 42%. Therefore, the invention greatly improves the reaction yield, avoids using highly toxic nitrile compounds in the reaction and is beneficial to safe production and environmental protection.
Drawings
FIG. 1: infrared spectrum IR (KBr) of 5,5 '-bis (4-acetamidophenoxy) -2, 2' -bipyrimidine
FIG. 2: nuclear magnetic spectrum of 5,5 '-bis (4-acetamidophenoxy) -2, 2' -bipyrimidine1HMR(DMSO-d6)
FIG. 3: infrared spectrum IR (KBr) of 5,5 '-bis (4-aminophenoxy) -2, 2' -bipyrimidine
FIG. 4: nuclear magnetic spectrum of 5,5 '-bis (4-aminophenoxy) -2, 2' -bipyrimidine1HMR(DMSO-d6)
Detailed Description
The technical solution of the present invention is further described below by specific implementation. The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
850ml of dewatered N, N-dimethylformamide was deoxygenated with argon for 5 hours, 45.80 g (0.18 mol) of triphenylphosphine and NiCl2.H2O10.40 g (0.044 mol) and activated zinc dust 5.70 g (0.086 mol) were deoxygenated under vacuum for 20 minutes, added to DMF under argon and stirred at room temperature under argon. One hour later, 20.00 g (0.18 mol) of 2-chloropyrimidine was added, the reaction was carried out at room temperature for one hour, the reaction was carried out at 50 ℃ for 30 hours, suction filtration was carried out, the solid was washed with chloroform, the filtrate was evaporated to dryness, and 75 g of ETDA and NH were added to the solid3.H2O (200mL,7%) was added to the resulting solution and stirred with acetic acidEthyl ester extraction (3X 200 mL), remaining solution was extracted with chloroform (8X 150 mL), Na2SO4Drying and evaporating the chloroform to dryness to give a pale yellow solid, eluting with ethyl acetate: methanol =19:1 recrystallization afforded the white product bipyrimidine 23.87 g with a yield of 88%. Melting point: 112 ℃ and 114 ℃.
1H NMR (CDCl3) 8.95(m,4H),7.42(d,2H). IR (KBr pellet)/cm-13049w, 2979w, 1565m, sh,1557s,1403vs,1142w, 989.9w, 808.5w, 773.7w, melting point 112 ℃.
4.00 g of the bipyrimidine and 10mL of bromine are put into a hydrothermal reaction kettle, and the mixture is dried in an oven at 150 ℃ for 12 hours, taken out and added with Na2CO3The aqueous solution was washed and dried to obtain 5,5 ' -dibromo-2, 2 ' -bipyrimidine, which was recrystallized from ethyl acetate: chloroform =9:1 and a small amount of petroleum ether), to obtain 7.29 g of 5,5 ' -dibromo-bipyrimidine as a white product in 86% yield.
1HNMR(CDCl3400MHz) δ: IR (KBr pellet)/cm-1:3014m,1540w,1523vs,1411vs,1361m,1236w,1137vs,1008s,932w,758s,641s.325℃(subl.)
In a 250-neck flask, 2.00 g of the 5, 5' -dibromobipyrimidine obtained above was charged, DMF150mL with water removed was added, and anhydrous K was added2CO31.92 g, adding 2.29 g of p-acetaminophenol, performing reaction for 10 hours at 135 ℃, pouring the mixture into distilled water after the reaction is finished, stirring and washing the mixture, performing suction filtration, and recrystallizing the mixture by using DMF and ethanol (9: 1) to obtain 1.55 g of white product 5, 5' -bis (4-acetaminophenoxy) bipyrimidine, wherein the yield is 89%. The melting point is 209.5-210.3 ℃, and the infrared diagram and the nuclear magnetic diagram are shown in figure 1 and figure 2.
2g of 5,5 ' -bis (4-acetamidophenoxy) bipyrimidine obtained in the previous step was placed in a 250mL three-necked flask, 80mL of a 20% sulfuric acid solution was added, the reaction was carried out at 70 ℃ under argon atmosphere for 8 hours, the mixture was cooled to room temperature, poured into distilled water, adjusted to neutral pH with aqueous ammonia, and an off-white solid was precipitated, filtered, and recrystallized from DMF and ethanol (10: 1) to give 5,5 ' -bis (4-aminophenoxy) -2,2 ' -bipyrimidine as a white product, 1.30 g, and 85% yield. The melting point is 298.4-299.2 ℃, and the infrared diagram and the nuclear magnetic diagram are shown in figure 3 and figure 4.
Example 2
850ml of dewatered N, N-dimethylformamide was deoxygenated with argon for 5 hours, 45.80 g (0.18 mol) of triphenylphosphine and NiCl2.H2O10.40 g (0.044 mol) and activated zinc dust 5.70 g (0.086 mol) were deoxygenated under vacuum for 20 minutes, added to DMF under argon and stirred at room temperature under argon. One hour later, 20.00 g (0.18 mol) of 2-chloropyrimidine was added, the reaction was carried out at room temperature for one hour, the reaction was carried out at 50 ℃ for 30 hours, suction filtration was carried out, the solid was washed with chloroform, the filtrate was evaporated to dryness, and 75 g of ETDA and NH were added to the solid3.H2O (200mL,7%) was added to the resulting solution, followed by stirring, extraction with ethyl acetate (3X 200 mL), extraction of the remaining solution with chloroform (8X 150 mL), and Na2SO4Drying and evaporating the chloroform to dryness to give a pale yellow solid, eluting with ethyl acetate: methanol =19:1 recrystallization afforded the white product bipyrimidine 23.87 g with a yield of 88%. Melting point: 112 ℃ and 114 ℃.
1H NMR (CDCl3) 8.95(m,4H),7.42(d,2H). IR (KBr pellet)/cm-13049w, 2979w, 1565m, sh,1557s,1403vs,1142w, 989.9w, 808.5w, 773.7w, melting point 112 ℃.
4.00 g of the bipyrimidine and 10mL of bromine are put into a hydrothermal reaction kettle, and the mixture is dried in an oven at 150 ℃ for 12 hours, taken out and added with Na2CO3The aqueous solution was washed and dried to obtain 5,5 ' -dibromo-2, 2 ' -bipyrimidine, which was recrystallized from ethyl acetate: chloroform =9:1 and a small amount of petroleum ether), to obtain 7.29 g of 5,5 ' -dibromo-bipyrimidine as a white product in 86% yield.
1HNMR(CDCl3400MHz) δ: IR (KBr pellet)/cm-1:3014m,1540w,1523vs,1411vs,1361m,1236w,1137vs,1008s,932w,758s,641s.325℃(subl.)
2.00 g of the 5,5 '-dibromo-bipyrimidine obtained in the above was put into a 250-neck flask, DMAC150mL with water removed, NaOH0.56 g was added, acetaminophen 2.29 g was added, argon gas was used for protection, the reaction was carried out at 135 ℃ for 12 hours, after the completion of the reaction, the mixture was poured into distilled water and stirred for washing, filtered, and recrystallized from DMF and ethanol (9: 1) to obtain 1.53 g of 5, 5' -bis (4-acetamidophenoxy) bipyrimidine as a white product with a yield of 87%. The melting point is 209.5-210.3 ℃, and the infrared diagram and the nuclear magnetic diagram are shown in figure 1 and figure 2.
2.00 g of 5,5 ' -bis (4-acetamidophenoxy) bipyrimidine obtained in the above step was put into a 250mL three-necked flask, 80mL of a 20% sulfuric acid solution was added, the reaction was carried out at 70 ℃ under an argon atmosphere for 8 hours, the mixture was cooled to room temperature, poured into distilled water, adjusted to neutral pH with aqueous ammonia, to precipitate an off-white solid, filtered, and recrystallized from DMF and ethanol (10: 1), to obtain 5,5 ' -bis (4-aminophenoxy) -2,2 ' -bipyrimidine as a white product, 1.30 g, and 85% yield. The melting point is 298.4-299.2 ℃, and the infrared diagram and the nuclear magnetic diagram are shown in figure 3 and figure 4.
Example 3
850ml of N, N-methylformamide freed of water, which was deoxygenated with argon for 5 hours, 45.80 g (0.18 mol) of triphenylphosphine and NiCl2.H2O10.40 g (0.044 mol) and activated zinc dust 5.70 g (0.086 mol) were deoxygenated under vacuum for 20 minutes, added to DMF under argon and stirred at room temperature under argon. One hour later, 20.00 g (0.18 mol) of 2-chloropyrimidine was added, the reaction was carried out at room temperature for one hour, the reaction was carried out at 50 ℃ for 30 hours, suction filtration was carried out, the solid was washed with chloroform, the filtrate was evaporated to dryness, and 75 g of ETDA and NH were added to the solid3.H2O (200mL,7%) was added to the resulting solution, followed by stirring, extraction with ethyl acetate (3X 200 mL), extraction of the remaining solution with chloroform (8X 150 mL), and Na2SO4Drying and evaporating the chloroform to dryness to give a pale yellow solid, eluting with ethyl acetate: methanol =19:1 recrystallization afforded the white product bipyrimidine 23.87 g with a yield of 88%. Melting point: 112 ℃ and 114 ℃.
1H NMR (CDCl3) 8.95(m,4H),7.42(d,2H). IR (KBr pellet)/cm-13049w, 2979w, 1565m, sh,1557s,1403vs,1142w, 989.9w, 808.5w, 773.7w, melting point 112 ℃.
4.00 g of the bipyrimidine and 10mL of bromine are put into a hydrothermal reaction kettle, and the mixture is dried in an oven at 150 ℃ for 12 hours, taken out and added with Na2CO3The aqueous solution was washed and dried to obtain 5,5 ' -dibromo-2, 2 ' -bipyrimidine, which was recrystallized from ethyl acetate: chloroform =9:1 and a small amount of petroleum ether), to obtain 7.29 g of 5,5 ' -dibromo-bipyrimidine as a white product in 86% yield.
1HNMR(CDCl3400MHz) δ: IR (KBr pellet)/cm-1:3014m,1540w,1523vs,1411vs,1361m,1236w,1137vs,1008s,932w,758s,641s.325℃(subl.)
2.00 g of 5, 5' -dibromobipyrimidine obtained in the above step was placed in a 250-neck flask, DMF150mL was added with water removed, and anhydrous K was added2CO31.92 g, adding 2.29 g of p-acetaminophenol, performing reaction for 10 hours at 135 ℃, pouring the mixture into distilled water after the reaction is finished, stirring and washing the mixture, performing suction filtration, and recrystallizing the mixture by using DMF and ethanol (9: 1) to obtain 1.55 g of white product 5, 5' -bis (4-acetaminophenoxy) bipyrimidine, wherein the yield is 89%. The melting point is 209.5-210.3 ℃, and the infrared diagram and the nuclear magnetic diagram are shown in figure 1 and figure 2.
2.00 g of 5,5 ' -bis (4-acetamidophenoxy) bipyrimidine obtained in the above step was put into a 250mL three-necked flask, 80mL of a 20% hydrochloric acid solution was added, the reaction was carried out at 70 ℃ under an argon atmosphere for 8 hours, the mixture was cooled to room temperature, poured into distilled water, adjusted to a neutral pH with aqueous ammonia to precipitate an off-white solid, filtered, and recrystallized from DMF and ethanol (10: 1) to obtain 5,5 ' -bis (4-aminophenoxy) -2,2 ' -bipyrimidine as a white product, 1.26 g, and the yield was 83%. The melting point is 298.4-299.2 ℃, and the infrared diagram and the nuclear magnetic diagram are shown in figure 3 and figure 4.
Example 4
850ml of N, N-methylformamide freed of water, which was deoxygenated with argon for 5 hours, 45.80 g (0.18 mol) of triphenylphosphine and NiCl2.H2O10.40 g (0.044 mol) and activated zinc dust 5.70 g (0.086 mol) were deoxygenated under vacuum for 20 minutes, added to DMF under argon and stirred at room temperature under argon. One hour later, 20.00 g (0.18 mol) of 2-chloropyrimidine was added, the reaction was carried out at room temperature for one hour, the reaction was carried out at 50 ℃ for 30 hours, suction filtration was carried out, the solid was washed with chloroform, the filtrate was evaporated to dryness, and 75 g of ETDA and NH were added to the solid3.H2O (200mL,7%) was added to the resulting solution, followed by stirring, extraction with ethyl acetate (3X 200 mL), extraction of the remaining solution with chloroform (8X 150 mL), and Na2SO4Drying and evaporating the chloroform to dryness to give a pale yellow solid, eluting with ethyl acetate: methanol =19:1 recrystallization afforded the white product bipyrimidine 23.87 g with a yield of 88%. Melting point: 112 ℃ and 114 ℃.
1H NMR (CDCl3) 8.95(m,4H),7.42(d,2H). IR (KBr pellet)/cm-13049w, 2979w, 1565m, sh,1557s,1403vs,1142w, 989.9w, 808.5w, 773.7w, melting point 112 ℃.
4.00 g of the bipyrimidine and 10mL of bromine are put into a hydrothermal reaction kettle, and the mixture is dried in an oven at 150 ℃ for 12 hours, taken out and added with Na2CO3The aqueous solution was washed and dried to obtain 5,5 ' -dibromo-2, 2 ' -bipyrimidine, which was recrystallized from ethyl acetate: chloroform =9:1 and a small amount of petroleum ether), to obtain 7.29 g of 5,5 ' -dibromo-bipyrimidine as a white product in 86% yield.
1HNMR(CDCl3400MHz) δ: IR (KBr pellet)/cm-1:3014m,1540w,1523vs,1411vs,1361m,1236w,1137vs,1008s,932w,758s,641s.325℃(subl.)
2.00 g of 5, 5' -dibromobipyrimidine obtained in the above step was placed in a 250-neck flask, DMF150mL was added with water removed, and anhydrous K was added2CO31.92 g, adding 2.29 g of p-acetaminophenol, protecting with argon, reacting at 135 ℃ for 10 hours, pouring into distilled water after the reaction is finished, stirring and washing, filtering, and filtering againRecrystallization from DMF and ethanol (9: 1) gave 1.55 g of 5, 5' -bis (4-acetamidophenoxy) bipyrimidine as a white product in 89% yield. Melting point of 209.5-210.3 deg.C, Calcd for C24H20N4O4(456.462g/mol) C,63.15%, H,4.42%, N,18.41%, O,14.02%, found C,63.13%, H,4.43%, 18.39%, O,14.05%, the infrared and nuclear magnetic diagrams of which are shown in FIGS. 1 and 2.
2.00 g of 5,5 ' -bis (4-acetamidophenoxy) bipyrimidine obtained in the above step was put into a 250mL three-necked flask, 80mL of a 20% phosphoric acid solution was added, the reaction was carried out at 70 ℃ under an argon atmosphere for 8 hours, the mixture was cooled to room temperature, poured into distilled water, adjusted to a neutral pH with aqueous ammonia to precipitate an off-white solid, filtered, and recrystallized from DMF and ethanol (10: 1) to obtain 5,5 ' -bis (4-aminophenoxy) -2,2 ' -bipyrimidine as a white product, 1.28 g, and the yield was 84%. The melting point is 298.4-299.2 ℃, Calcd forC20H16N6O2(372.388g/mol) C,64.51%, H,4.33%, N,22.57%, O,8.59%, found C,64.46%, H,4.31%, N,22.58%, O,8.66%, the infrared and nuclear magnetic images of which are shown in FIGS. 3 and 4.
Example 5
850ml of dewatered N, N-dimethylformamide was deoxygenated with argon for 5 hours, 45.80 g (0.18 mol) of triphenylphosphine and NiCl2.H2O10.40 g (0.044 mol) and activated zinc dust 5.70 g (0.086 mol) were deoxygenated under vacuum for 20 minutes, added to DMF under argon and stirred at room temperature under argon. One hour later, 20.00 g (0.18 mol) of 2-chloropyrimidine was added, the reaction was carried out at room temperature for one hour, the reaction was carried out at 50 ℃ for 30 hours, suction filtration was carried out, the solid was washed with chloroform, the filtrate was evaporated to dryness, and 75 g of ETDA and NH were added to the solid3.H2O (200mL,7%) was added to the resulting solution, followed by stirring, extraction with ethyl acetate (3X 200 mL), extraction of the remaining solution with chloroform (8X 150 mL), and Na2SO4Drying and evaporating the chloroform to dryness to give a pale yellow solid, eluting with ethyl acetate: methanol =19:1 recrystallization afforded the white product bipyrimidine 23.87 g with a yield of 88%. Melting point: 112 ℃ and 114 DEG C。
1H NMR (CDCl3) 8.95(m,4H),7.42(d,2H). IR (KBr pellet)/cm-13049w, 2979w, 1565m, sh,1557s,1403vs,1142w, 989.9w, 808.5w, 773.7w, melting point 112 ℃.
4.00 g of the bipyrimidine and 10mL of bromine are put into a hydrothermal reaction kettle, and the mixture is dried in an oven at 150 ℃ for 12 hours, taken out and added with Na2CO3The aqueous solution was washed and dried to obtain 5,5 ' -dibromo-2, 2 ' -bipyrimidine, which was recrystallized from ethyl acetate: chloroform =9:1 and a small amount of petroleum ether), to obtain 7.29 g of 5,5 ' -dibromo-bipyrimidine as a white product in 86% yield.
1HNMR(CDCl3400MHz) δ: IR (KBr pellet)/cm-1:3014m,1540w,1523vs,1411vs,1361m,1236w,1137vs,1008s,932w,758s,641s.325℃(subl.)
2.00 g of 5, 5' -dibromobipyrimidine obtained in the above step was placed in a 250-neck flask, DMF150mL was added with water removed, and anhydrous K was added2CO31.92 g, adding 2.29 g of 3-acetaminophenol, reacting for 10 hours at 135 ℃ under the protection of argon, pouring into distilled water after the reaction is finished, stirring and washing, filtering, and recrystallizing by using DMF and ethanol (9: 1) to obtain 1.55 g of white product 5, 5' -bis (3-acetaminophenoxy) bipyrimidine, wherein the yield is 88%. The melting point is mp209.2-210.8 ℃.1H NMR(DMSO-d6,400MHz,ppm):δ2.0(s,6H),7.16(d，2H,J=8.1Hz),7.26（s,2H,J=8.2Hz）,7.38(t,2H,J=8.4Hz),7.59(d，2H,J=8.6Hz),8.68(s,4H),10.55(s,2H).FTIR(KBr,cm-1):3418(N-H,str.),3061(C-H,str.),1665(C=O,str.),1617,1556,1513,1414(Ar,str.).Calcd for C24H20N4O4(456.462g/mol):C,63.14%;H,4.41%;N,18.42%;O,14.03%.found:C,63.13%;H,4.43%;18.39%;O,14.05%。
2g of 5, 5' -bis (3-acetamidophenoxy) bipyrimidine obtained in the above step was charged into a 250mL three-necked flask, 80mL of a 20% sulfuric acid solution was added, reacted at 70 ℃ under an argon atmosphere for 8 hours, cooled to room temperature, poured into distilled water, and usedAdjusting pH to neutral with ammonia water to precipitate off-white solid, filtering, and recrystallizing with DMF and ethanol (10: 1) to obtain white product 5,5 '-bis (3-aminophenoxy) -2, 2' -bipyrimidine, 1.30 g, and 85% yield. The melting point is 298.0-299.1 ℃.1HNMR(DMSO-d6,400MHz,ppm):δ5.14(s,4H),6.49(s,2H,J=8.4MHz),6.52(d,2H,J=8.6MHz),6.71(t,2H,J=8.7MHz),7.21(d，2H,J=8.6MHz),8.55(s,4H).FTIR(KBr,cm-1):3440,3339(N-H,str.),1632,1579,1552,1513(Ar,str.).Calcd for C20H16N6O2(372.388g/mol):C,64.50%;H,4.33%;N,22.58%;O,8.59%.found:C,64.46%;H,4.31%;N,22.58%;O,8.66%。
Example 6
850ml of dewatered N, N-dimethylformamide was deoxygenated with argon for 5 hours, 45.80 g (0.18 mol) of triphenylphosphine and NiCl2.H2O10.40 g (0.044 mol) and activated zinc dust 5.70 g (0.086 mol) were deoxygenated under vacuum for 20 minutes, added to DMF under argon and stirred at room temperature under argon. One hour later, 20.00 g (0.18 mol) of 2-chloropyrimidine was added, the reaction was carried out at room temperature for one hour, the reaction was carried out at 50 ℃ for 30 hours, suction filtration was carried out, the solid was washed with chloroform, the filtrate was evaporated to dryness, and 75 g of ETDA and NH were added to the solid3.H2O (200mL,7%) was added to the resulting solution, followed by stirring, extraction with ethyl acetate (3X 200 mL), extraction of the remaining solution with chloroform (8X 150 mL), and Na2SO4Drying and evaporating the chloroform to dryness to give a pale yellow solid, eluting with ethyl acetate: methanol =19:1 recrystallization afforded the white product bipyrimidine 23.87 g with a yield of 88%. Melting point: 112 ℃ and 114 ℃.
1H NMR (CDCl3) 8.95(m,4H),7.42(d,2H). IR (KBr pellet)/cm-13049w, 2979w, 1565m, sh,1557s,1403vs,1142w, 989.9w, 808.5w, 773.7w, melting point 112 ℃.
4.00 g of the bipyrimidine and 10mL of bromine are put into a hydrothermal reaction kettle, and the mixture is dried in an oven at 150 ℃ for 12 hours, taken out and added with Na2CO3Aqueous solutionWashing and drying to obtain 5,5 ' -dibromo-2, 2 ' -bipyrimidine, and recrystallizing by using ethyl acetate: chloroform =9:1 and a small amount of petroleum ether), to obtain 7.29 g of white product 5,5 ' -dibromo-bipyrimidine with the yield of 86%.
1HNMR(CDCl3400MHz) δ: IR (KBr pellet)/cm-1:3014m,1540w,1523vs,1411vs,1361m,1236w,1137vs,1008s,932w,758s,641s.325℃(subl.)
2.00 g of 5, 5' -dibromobipyrimidine obtained in the above step was placed in a 250-neck flask, DMF150mL was added with water removed, and anhydrous K was added2CO31.92 g, 2.29 g of 2-acetaminophenol is added, the mixture is reacted for 10 hours at 135 ℃ under the protection of argon, after the reaction is finished, the mixture is poured into distilled water to be stirred and washed, filtered, and recrystallized by using DMF and ethanol (9: 1), so that 1.55 g of white product 5, 5' -bis (2-acetaminophenoxy) bipyrimidine is obtained, and the yield is 87%. The melting point is mp208.6-209.7 ℃.1H NMR(DMSO-d6,400MHz,ppm):δ2.0(s,6H),7.19(d，2H,J=8.3Hz),7.28（t,2H,J=8.4Hz）,7.41(t,2H,J=8.6Hz),7.71(d，2H,J=8.5Hz),8.65(s,4H),10.55(s,2H).FTIR(KBr,cm-1):3420(N-H,str.),3065(C-H,str.),1668(C=O,str.),1618,1559,1509,1418(Ar,str.).Calcd for C24H20N4O4(456.462g/mol):C,63.12%;H,4.40%;N,18.43%;O,14.04%.found:C,63.13%;H,4.43%;18.39%;O,14.05%。
2g of 5,5 ' -bis (2-acetamidophenoxy) bipyrimidine obtained in the previous step is added into a 250mL three-necked flask, 80mL of 20% sulfuric acid solution is added, reaction is carried out at 70 ℃ under the protection of argon for 8 hours, the mixture is cooled to room temperature, poured into distilled water, the pH value is adjusted to be neutral by ammonia water, an off-white solid is separated out, filtration is carried out, recrystallization is carried out by DMF and ethanol (10: 1), and a white product is 5,5 ' -bis (2-aminophenoxy) -2,2 ' -bipyrimidine, 1.30 g, and the yield is 85%. The melting point is 298.2-299.5 ℃.1H NMR(DMSO-d6,400MHz,ppm):δ5.12(s,4H),6.57(d,2H,J=8.3MHz),6.68(t,2H,J=8.5MHz),7.22(t,2H,J=8.6MHz),6.93(d，2H,J=8.7MHz),8.57(s,4H).FTIR(KBr,cm-1):3445,3333(N-H,str.),1641,1575,1558,1516(Ar,str.).Calcd for C20H16N6O2(372.388g/mol):C,64.51%;H,4.32%;N,22.59%;O,8.59%.found:C,64.46%;H,4.31%;N,22.58%;O,8.66%。
Comparative example of effects:
in a dry three-necked flask equipped with a mechanical stirrer and a thermometer, 3.44g (0.01 mol) of 5,5 '-bis (4-aminophenoxy) -2, 2' -bipyrimidine (DAPB) prepared in example 1 and 40ml of N, N-dimethylacetamide (DMAc) were charged, and 2.9421g (0.01 mol) of biphenyltetracarboxylic dianhydride (BPDA) was further added and mixed uniformly. The reaction was carried out at room temperature for 12 hours under vigorous mechanical stirring to give a viscous polyamic acid solution having a viscosity of 1.5 dL/g. And (2) preparing the polyamic acid solution on a dry and clean glass plate by a tape casting method to form a film, drying to obtain a transparent polyamic acid film, and imidizing the prepared polyamic acid film according to an imidization program of 150 ℃/1h, 200 ℃/20min, 250 ℃/20min, 300 ℃/20min, 350 ℃/20min and the heating rate of 5 ℃/min to obtain the polyimide I film.
The structure of the polyimide I is as follows:
then, a film of polyimide II was prepared by replacing DAPB prepared in example 1 of the present invention with 5, 5' -bis [ p- (4-aminophenoxy) phenoxy ] bipyrimidine in the same manner as described above.
The thermal properties of the two prepared polyimides are measured, and the measuring method comprises the following steps: differential Scanning Calorimeter (DSC) (German Nachi Co., Ltd.), under nitrogen, 10 ℃/min; thermogravimetric analysis (TGA) samples of 6-8 mg of pemphigus emoson Pyris1 were used at 10 ℃/min under nitrogen. The results are shown in Table 1:
TABLE 1
The mechanical properties of the two prepared polyimides are measured, and the measuring method comprises the following steps: the stretching test uses a Shenzhen Sansi SANS CMT8012 instrument, and the Shenzhen Sansi SANS CMT instrument is stretched at the speed of 5mm/min and is (0.5cm wide, 2cm long and 0.05mm) thick; the results are shown in Table 2:
TABLE 2
The dielectric properties of the two prepared polyimides are measured, and the measuring method comprises the following steps: dielectric constant measurement Using HP4276ALCR Instrument at frequency 102-105Measuring under Hz; the results are shown in Table 3:
TABLE 3
As can be seen from the effect comparison examples, the aromatic diamine provided by the invention, as a monomer, brings more remarkable property improvement for the polymerized PI, including remarkably improving the thermal stability and glass transition temperature of the polymer and remarkably improving the dielectric property of the polymer. The aromatic diamine is more beneficial to improving the application processability of polyimide and polyamide and expanding the application field of the polyimide and the polyamide.
Claims (5)
1. An aromatic diamine containing a bipyrimidine structure, which has a chemical name of 5,5 '-bis (4-aminophenoxy) -2, 2' -bipyrimidine and has a chemical structural formula shown in a formula (2):
2. a process for producing an aromatic diamine containing a bipyrimidine structure as claimed in claim 1, comprising the steps of:
1) 2-chloropyrimidine is taken as a raw material, and 2, 2' -bipyrimidine is generated through coupling reaction;
2) carrying out substitution reaction on the 2,2 ' -bipyrimidine obtained in the step 1) and bromine to obtain 5,5 ' -dibromo-2, 2 ' -bipyrimidine;
3) carrying out condensation reaction on the 5,5 '-dibromo-2, 2' -bipyrimidine obtained in the step 2) and 4-acetaminophenol to obtain 5,5 '-bis (q-acetaminophenoxy) -2, 2' -bipyrimidine, wherein q is 4;
4) hydrolyzing the 5,5 '-bis (q-acetamidophenoxy) -2, 2' -bipyrimidine obtained in the step 3) in an acidic aqueous solution to remove acetyl, thus obtaining the bipyrimidinyl-containing aromatic diamine.
3. The method of claim 2, wherein the substitution reaction in step 2) is a heating reaction of 2, 2' -bipyrimidine with liquid bromine in a hydrothermal reaction kettle.
4. The method of claim 2, wherein the acidic aqueous solution in step 4) is any one of a sulfuric acid solution, a phosphoric acid solution, a hydrochloric acid solution, a formic acid solution or an acetic acid solution.
5. The method of claim 2, comprising the steps of:
the first step of reaction: deoxygenation of the N, N-dimethylformamide freed of water under argon, triphenylphosphine, NiCl2.H2Adding O and activated zinc powder into solvent, stirring for 0.5-5 hr under the protection of argon, adding 2-chloropyrimidine, reacting at 50 deg.C for 10-50 hr, vacuum filtering, washing solid with chloroform, evaporating filtrate, adding ETDA and 7% NH into solid3.H2Stirring in solution prepared from O, extracting with ethyl acetate, extracting the rest solution with chloroform, and extracting with Na2SO4Drying and evaporating chloroform to obtain a light yellow solid, and recrystallizing with ethyl acetate and methanol which are 19:1 to obtain a white product, namely 2, 2' -bipyrimidine;
the second step of reaction: reversing the first stepPutting the obtained 2, 2' -bipyrimidine and bromine into a hydrothermal reaction kettle, reacting for 12 hours in an oven at 150 ℃, and reacting with Na2CO3Washing with an aqueous solution, drying, and recrystallizing ethyl acetate, chloroform-9: 1 and a small amount of petroleum ether to obtain 5,5 '-dibromo-2, 2' -bipyrimidine;
the third step of reaction: adding the 5,5 '-dibromo-2, 2' -bipyrimidine obtained in the second step into a flask, adding dewatered DMF, and adding anhydrous K2CO3Adding acetylaminophenol which is 4-acetylaminophenol, reacting for 6-12 hours at 135 ℃ under the protection of argon, pouring into distilled water after the reaction is finished, stirring and washing, filtering, and recrystallizing by using DMF and ethanol according to the proportion of 9:1 to obtain silver white solid bis (q-acetylaminophenoxy) bipyrimidine, wherein q is 4;
and a fourth step of reaction: and (3) adding 20% sulfuric acid solution into the bis (q-acetamidophenoxy) bipyrimidine obtained in the third step, reacting for 6-12 hours under the protection of argon, cooling to room temperature, pouring into distilled water, adjusting the pH value to be neutral by using ammonia water, and separating out off-white solid, wherein the DMF and the ethanol are 10:1, and recrystallizing to obtain white solid, namely the aromatic diamine containing the bipyrimidine structure.
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| CN106589372B (en) * | 2016-11-29 | 2019-12-17 | 江西师范大学 | Polyimide containing bipyrimidine ring and preparation method thereof |
| CN107056711B (en) * | 2017-05-11 | 2020-07-07 | 吉林大学 | Diamine monomer containing pyridazine group and preparation method and application thereof |
| CN108794406A (en) * | 2018-01-05 | 2018-11-13 | 吉林大学 | One kind has the active double fluorine monomers of necleophilic reaction, preparation method and its application in preparing polyarylether |
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| JPS60172971A (en) * | 1984-02-17 | 1985-09-06 | Chisso Corp | Alkyl bipyrimidine compound |
| IES78453B2 (en) * | 1997-08-12 | 1998-02-11 | Michael Hilary Burke | A process for preparing isothiocyano compounds |
| JP2000044544A (en) * | 1998-07-30 | 2000-02-15 | Daicel Chem Ind Ltd | Bipyrimidine compound, its polymer and their use |
| JP2008078040A (en) * | 2006-09-22 | 2008-04-03 | Matsushita Electric Ind Co Ltd | Secondary battery |
| CN101279948B (en) * | 2008-03-14 | 2010-08-11 | 苏州博鸿化工技术有限公司 | Synthetic method of 4,6- dichloro-5-(2-methoxyphenoxy)-2,2'-dipyridine |
| US8765271B2 (en) * | 2010-11-24 | 2014-07-01 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element material, light-emitting element, electronic device, and lighting device |
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