CN115304579B - Preparation method of 4,4' -biphenyl dithioanhydride - Google Patents
Preparation method of 4,4' -biphenyl dithioanhydride Download PDFInfo
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- CN115304579B CN115304579B CN202210847745.6A CN202210847745A CN115304579B CN 115304579 B CN115304579 B CN 115304579B CN 202210847745 A CN202210847745 A CN 202210847745A CN 115304579 B CN115304579 B CN 115304579B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 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 30
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 20
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims abstract description 15
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 239000012065 filter cake Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical group [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims 3
- 150000003568 thioethers Chemical class 0.000 abstract description 12
- UYPMEGMZCYYSAH-UHFFFAOYSA-N 7-oxatricyclo[7.2.2.22,5]pentadeca-1(12),2(15),3,5(14),9(13),10-hexaene-6,8-dione Chemical compound C1=CC2=CC=C1C(=O)OC(=O)C1=CC=C2C=C1 UYPMEGMZCYYSAH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- -1 derivative of 4,4' -biphenyl tetracarboxylic dianhydride Chemical class 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- XWKIXFQOFAVHQI-UHFFFAOYSA-N disodium;sulfide;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[S-2] XWKIXFQOFAVHQI-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/72—Benzo[c]thiophenes; Hydrogenated benzo[c]thiophenes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention belongs to the technical field of preparation of fine chemical organic materials, and provides a preparation method of 4,4' -biphenyl dithioanhydride. The preparation method provided by the invention comprises the following steps: dissolving 3,3', 4' -biphenyl tetracarboxylic dianhydride, a phase transfer catalyst and alkali metal sulfide salt, and performing a thio reaction to obtain the 4,4' -biphenyl dithioanhydride. The preparation method provided by the invention takes 3,3', 4' -biphenyl tetracarboxylic dianhydride and alkali metal sulfide salt as preparation raw materials, and the preparation method generates a thio reaction under the action of a phase transfer catalyst, so that the molar ratio yield of the 4,4' -biphenyl dicarboxylic anhydride is improved. Meanwhile, 3', 4' -biphenyl tetracarboxylic dianhydride has low price and is suitable for industrialization. The molar yield of 4,4' -biphenyldithioanhydride was 90-98.5% as demonstrated in the examples.
Description
Technical Field
The invention relates to the technical field of preparation of fine chemical organic materials, in particular to a preparation method of 4,4' -biphenyl dithioanhydride.
Background
4,4 '-biphenyl dithioanhydride is also an important polyimide monomer as a derivative of 4,4' -biphenyl tetracarboxylic dianhydride, and can be polycondensed with various amines to generate polyimide. When 4,4 '-biphenyl dithioanhydride is used as a raw material to prepare polyimide, compared with 4,4' -biphenyl tetracarboxylic dianhydride, the temperature of complete imidization is much lower, and the prepared polyimide has lighter color, more excellent performance, more excellent insulating performance and more excellent processability, can be used for preparing liquid crystal display, heat-sensitive resin, crosslinking adhesive and the like, and is widely applied to the fields of aviation, aerospace, electronics and the like.
The existing preparation process of the 4,4 '-biphenyl dicarboxylic anhydride is that the 4,4' -biphenyl tetracarboxylic dianhydride and sodium sulfide pentahydrate are subjected to solid-state reaction, and the molar yield is only 30 percent.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for producing 4,4' -biphenyldithioic anhydride. The preparation method provided by the invention has high molar yield.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of 4,4' -biphenyl dithioanhydride, which comprises the following steps:
dissolving 3,3', 4' -biphenyl tetracarboxylic dianhydride, a phase transfer catalyst and alkali metal sulfide salt, and performing a thio reaction to obtain the 4,4' -biphenyl dithioanhydride.
Preferably, the phase transfer catalyst comprises one or more of tetrabutylammonium bromide, tetrabutylammonium chloride and tetraphenylphosphonium bromide; the mass ratio of the 3,3', 4' -biphenyl tetracarboxylic dianhydride to the phase transfer catalyst is 1: 0.005-0.03.
Preferably, the alkali metal sulphide salt is potassium sulphide and/or sodium sulphide.
Preferably, the molar ratio of 3,3', 4' -biphenyltetracarboxylic dianhydride to alkali metal sulfide salt is 1:2.2 to 2.6.
Preferably, the dissolved reagent is a polar aprotic solvent, which is N, N-dimethylformamide and/or dimethylsulfoxide; the mass ratio of the 3,3', 4' -biphenyl tetracarboxylic dianhydride to the dissolved reagent is 1:1.5 to 4.5.
Preferably, the temperature of the thio reaction is 150-170 ℃ and the time is 12-18 h.
Preferably, after the thio reaction, the method further comprises: filtering the obtained reaction liquid while the reaction liquid is hot to obtain a filter cake and a filtrate; washing the filter cake, mixing the obtained washing liquid and the filtrate, cooling to 20-30 ℃, mixing with chloralkane, crystallizing, carrying out solid-liquid separation on the obtained crystallized feed liquid, and washing and drying the obtained solid in sequence.
Preferably, the temperature of the hot filtration is 80-100 ℃.
Preferably, the chlorinated alkane comprises one or more of dichloromethane, chloroform and carbon tetrachloride; the weight ratio of the dissolved reagent to the chloralkane is 1:1 to 4.
Preferably, the crystallization includes sequentially performing a first crystallization and a second crystallization; the temperature of the first crystallization is 20-30 ℃, and the heat preservation time is 0.5h; the temperature of the second crystallization is-10-0 ℃, and the heat preservation time is 2-6 h;
the rate of the temperature decrease from the first crystallization to the second crystallization was 0.15 c/min.
The invention provides a preparation method of 4,4' -biphenyl dithioanhydride, which comprises the following steps: dissolving 3,3', 4' -biphenyl tetracarboxylic dianhydride, a phase transfer catalyst and alkali metal sulfide salt, and performing a thio reaction to obtain the 4,4' -biphenyl dithioanhydride. The preparation method provided by the invention takes the 4,4 '-biphenyl tetracarboxylic dianhydride and the alkali metal sulfide salt as preparation raw materials, and the thioreaction is carried out under the action of the phase transfer catalyst, so that the molar yield of the 4,4' -biphenyl dicarboxylic anhydride is improved. Meanwhile, 3', 4' -biphenyl tetracarboxylic dianhydride has low price and is suitable for industrialization. The data of the examples show that the molar yield of 4,4' -biphenyldithioanhydride is 90-98.5%.
Further, after the thio reaction, the method further comprises: filtering the obtained reaction liquid while the reaction liquid is hot to obtain a filter cake and a filtrate; washing the filter cake, mixing the obtained washing liquid and the filtrate, cooling to 20-30 ℃, mixing with chloralkane, crystallizing, carrying out solid-liquid separation on the obtained crystallized feed liquid, and washing and drying the obtained solid in sequence. The post-treatment step provided by the invention improves the purity of the 4,4' -biphenyl dithioanhydride. The data of the examples show that: the purity of the obtained 4,4' -biphenyl dithioanhydride is 98.7-99.6 percent.
Detailed Description
The invention provides a preparation method of 4,4' -biphenyl dithioanhydride, which comprises the following steps:
dissolving 3,3', 4' -biphenyl tetracarboxylic dianhydride, a phase transfer catalyst and alkali metal sulfide salt, and performing a thio reaction to obtain the 4,4' -biphenyl dithioanhydride.
In the present invention, the phase transfer catalyst preferably includes one or more of tetrabutylammonium bromide, tetrabutylammonium chloride and tetraphenylphosphonium bromide, and further preferably tetrabutylammonium bromide. In the present invention, the mass ratio of the 3,3', 4' -biphenyltetracarboxylic dianhydride to the phase transfer catalyst is preferably 1: 0.005-0.03.
In the present invention, the alkali metal sulfide salt is preferably potassium sulfide and/or sodium sulfide, and more preferably potassium sulfide. In the present invention, the molar ratio of the 3,3', 4' -biphenyltetracarboxylic dianhydride and the alkali metal sulfide salt is preferably 1:2.2 to 2.6, more preferably 1:2.3 to 2.5.
In the present invention, the dissolving agent is preferably a polar aprotic solvent, which is preferably N, N-dimethylformamide and/or dimethylsulfoxide, and more preferably N, N-dimethylformamide. In the present invention, the mass ratio of the 3,3', 4' -biphenyltetracarboxylic dianhydride and the dissolved reagent is preferably 1:1.5 to 4.5, more preferably 1:2 to 4, more preferably 1:2.5 to 3.5.
In the present invention, the dissolving and mixing of 3,3', 4' -biphenyltetracarboxylic dianhydride, phase transfer catalyst and alkali metal sulfide salt preferably comprises: dissolving 3,3', 4' -biphenyl tetracarboxylic dianhydride to obtain a 3,3', 4' -biphenyl tetracarboxylic dianhydride solution; adding a phase transfer catalyst and an alkali metal sulfide salt into the 3,3', 4' -biphenyl tetracarboxylic dianhydride solution.
In the present invention, the temperature of the thio reaction is preferably 150 to 170 ℃, and more preferably 155 to 165 ℃; the time for the above-mentioned thio reaction is preferably 12 to 18 hours, more preferably 14 to 16 hours.
After the thio reaction, the present invention preferably further comprises: filtering the obtained reaction liquid while the reaction liquid is hot to obtain a filter cake and a filtrate; washing the filter cake, mixing the obtained washing liquid and the filtrate, cooling to 20-30 ℃, mixing with chloralkane, crystallizing, carrying out solid-liquid separation on the obtained crystallized feed liquid, and washing and drying the obtained solid in sequence.
In the present invention, the temperature of the hot filtration is preferably 80 to 100 ℃. In the invention, the mode of reducing the reaction feed liquid to the temperature of hot filtration is preferably natural temperature reduction.
In the present invention, the agent for washing the filter cake preferably includes a polar aprotic solvent, the kind of which is consistent with the above-mentioned dissolved agent, and will not be described herein. In the present invention, the temperature of the reagent for washing the filter cake is preferably consistent with the temperature of the hot filtration, and will not be described herein. In the invention, the mass ratio of the reagent for washing the filter cake to the alkali metal sulfide salt is preferably 0.2-1: 1.
in the present invention, the chlorinated alkane preferably includes one or more of dichloromethane, chloroform and carbon tetrachloride, and further preferably dichloromethane. In the present invention, the mass ratio of the dissolved reagent to the chlorinated alkane is preferably 1:1 to 4, more preferably 1:2 to 3.
In the present invention, the crystallization preferably includes sequentially performing a first crystallization and a second crystallization; the temperature of the first crystallization is preferably 20-30 ℃, and the heat preservation time is preferably 0.5h; the temperature of the second crystallization is preferably-10 to 0 ℃, and more preferably-5 ℃; the holding time is preferably 2 to 6 hours, more preferably 3 to 5 hours. In the present invention, the rate of lowering the temperature from the first crystallization to the temperature of the second crystallization is preferably 0.15 ℃/min.
In the present invention, the solid-liquid separation is preferably filtration. In the present invention, the reagent for washing the solid preferably includes a chlorinated alkane, and the chlorinated alkane is preferably of a type consistent with the chlorinated alkane described above, and will not be described in detail herein. In the present invention, the mass ratio of the reagent for washing the solid to 3,3', 4' -biphenyltetracarboxylic dianhydride is preferably 0.5 to 2:1.
in the present invention, the drying temperature is preferably 35 to 60℃and the pressure is preferably atmospheric pressure.
In the invention, the reaction formula of the thio reaction is shown as a formula I:
the following is a detailed description of the preparation method of 4,4' -biphenyldithioic anhydride provided by the present invention in connection with examples, but they should not be construed as limiting the scope of the present invention.
Example 1
29.4g (0.1 mol) of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 44.1g of N, N-dimethylformamide are put into a 250mL four-port reaction flask, and the mixture is stirred and heated to 150 ℃; adding 0.15g of tetrabutylammonium bromide serving as a phase transfer catalyst and 24.2g (0.22 mol) of potassium sulfide into the reaction solution, and carrying out reflux heat preservation for 12h at 150-155 ℃ to finish the reaction; cooling to 80 ℃, performing hot filtration to obtain a filter cake and a filtrate, washing the filter cake with 7.3g of N, N-dimethylformamide at 80 ℃, combining the obtained washing liquid and the filtrate, continuously cooling to 20-30 ℃, adding the mixture into 176.4g of dichloromethane, preserving heat for 0.5h, then continuously cooling to-10 ℃ at the speed of 0.15 ℃/min, and preserving heat for 2h; the resulting solid was filtered, washed with 14.7g of methylene chloride and then dried at 35℃under normal pressure to obtain 30.7g (94.2% molar yield) of 4,4' -biphenyldithioic anhydride as a white crystalline powder with an HPLC purity of 98.7%.
Example 2
29.4g (0.1 mol) of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 88.2g of N, N-dimethylformamide are put into a 250mL four-port reaction flask, and the mixture is stirred and heated to 150 ℃; adding 0.4g of tetrabutylammonium bromide serving as a phase transfer catalyst and 26.4g (0.24 mol) of potassium sulfide into the reaction solution, and carrying out reflux heat preservation for 15h at 150-155 ℃ to finish the reaction; cooling to 90 ℃, performing hot filtration to obtain a filter cake and a filtrate, washing the filter cake with 18.5g of N, N-dimethylformamide at 80 ℃, combining the obtained washing liquid and the filtrate, continuously cooling to 20-30 ℃, adding the mixture into 220.5g of dichloromethane, preserving heat for 0.5h, continuously cooling to-5 ℃ at a speed of 0.15 ℃/min, and maintaining for 2h; the resulting solid was filtered, washed with 30g of methylene chloride and then dried at 45℃under normal pressure to obtain 32.1g (molar yield 98.5%) of 4,4' -biphenyldithioic anhydride as a white crystalline powder, with an HPLC purity of 99.6%.
Example 3
29.4g (0.1 mol) of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 132.3g of N, N-dimethylformamide are put into a 250mL four-port reaction flask, and the mixture is stirred and heated to 150 ℃; adding 0.88g of tetrabutylammonium bromide serving as a phase transfer catalyst and 28.6g (0.26 mol) of potassium sulfide into the reaction solution, and carrying out reflux heat preservation reaction for 18h at 150-155 ℃ to finish the reaction; cooling to 100 ℃, performing hot filtration to obtain a filter cake and a filtrate, washing the filter cake with 28.6g of N, N-dimethylformamide at 100 ℃, combining the obtained washing liquid and the filtrate, continuously cooling to 20-30 ℃, adding the mixture into 529.2g of dichloromethane, preserving heat for 0.5h, then continuously cooling to 0 ℃ at the speed of 0.15 ℃/min, and preserving heat for 2h; the resulting solid was filtered, washed with 59g of methylene chloride and then dried at 60℃under normal pressure to obtain 31.7g (97.2% molar yield) of 4,4' -biphenyldithioic anhydride as a white crystalline powder, with an HPLC purity of 99.3%.
Example 4
29.4g (0.1 mol) of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 132.3g of N, N-dimethylacetamide are put into a 250mL four-port reaction flask, and stirred and heated to 160 ℃; adding 0.88g of tetrabutylammonium chloride serving as a phase transfer catalyst and 10.1g (0.26 mol) of anhydrous sodium sulfide into the reaction solution, and carrying out reflux heat preservation reaction for 12 hours at 165-170 ℃ to finish the reaction; cooling to 90 ℃, performing hot filtration to obtain a filter cake and filtrate, washing the filter cake with 3g of N, N-dimethylacetamide at 90 ℃, combining the obtained washing liquid and filtrate, continuously cooling to 20-30 ℃, adding the mixture into 198g of chloroform, preserving heat for 0.5h, then continuously cooling to 0 ℃ at the speed of 0.15 ℃/min, and maintaining for 6h; the solid obtained was filtered, washed with 29.4g of chloroform and dried at 60℃under normal pressure to obtain 30.3g (92.9% molar yield) of 4,4' -biphenyldisulfide anhydride as a white crystalline powder with an HPLC purity of 99.1%.
Example 5
29.4g (0.1 mol) of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 44.1g of dimethyl sulfoxide are put into a 250mL four-port reaction flask, and the mixture is stirred and heated to 160 ℃; adding 0.15g of tetraphenyl phosphonium bromide serving as a phase transfer catalyst and 24.2g (0.22 mol) of potassium sulfide into the reaction solution, and preserving the temperature at 165-170 ℃ for 18h to finish the reaction; cooling to 100 ℃, performing hot filtration to obtain a filter cake and filtrate, washing the filter cake with 17g of dimethyl sulfoxide at 100 ℃, combining the obtained washing liquid and filtrate, continuously cooling to 20-30 ℃, adding the mixture into 176.4g of carbon tetrachloride, preserving heat for 0.5h, continuously cooling to-10 ℃ at a speed of 0.15 ℃/min, maintaining for 2h, and filtering; the obtained solid was washed with 59.8g of carbon tetrachloride and then dried at 50℃under normal pressure to obtain 29.5g (molar yield: 90.5%) of 4,4' -biphenyldisulfide anhydride as a white crystalline powder, with an HPLC purity of 98.7%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The preparation method of the 4,4' -biphenyl dithioanhydride is characterized by comprising the following steps:
dissolving 3,3', 4' -biphenyl tetracarboxylic dianhydride, a phase transfer catalyst and alkali metal sulfide salt, and performing a thio reaction to obtain the 4,4' -biphenyl dithioanhydride;
the phase transfer catalyst comprises one or more of tetrabutylammonium bromide, tetrabutylammonium chloride and tetraphenylphosphonium bromide; the mass ratio of the 3,3', 4' -biphenyl tetracarboxylic dianhydride to the phase transfer catalyst is 1: 0.005-0.03;
the temperature of the thio reaction is 150-170 ℃ and the time is 12-18 h.
2. The method of claim 1, wherein the alkali metal sulfide salt is potassium sulfide and/or sodium sulfide.
3. The preparation method according to claim 1 or 2, wherein the molar ratio of 3,3', 4' -biphenyltetracarboxylic dianhydride to alkali metal sulfide salt is 1:2.2 to 2.6.
4. The method of claim 1, wherein the dissolved reagent is a polar aprotic solvent, which is N, N-dimethylformamide and/or dimethylsulfoxide; the mass ratio of the 3,3', 4' -biphenyl tetracarboxylic dianhydride to the dissolved reagent is 1:1.5 to 4.5.
5. The method according to claim 1, characterized by further comprising, after the thio reaction: filtering the obtained reaction liquid while the reaction liquid is hot to obtain a filter cake and a filtrate; washing the filter cake, combining the obtained washing liquid and the filtrate, and then reducing
Mixing with chloralkane after reaching 20-30 ℃ for crystallization, carrying out solid-liquid separation on the obtained crystallization feed liquid, and washing and drying the obtained solid in sequence.
6. The process according to claim 5, wherein the hot filtration is carried out at a temperature of 80 to 100 ℃.
7. The method of claim 5, wherein the chlorinated alkane is one or more of dichloromethane, chloroform and carbon tetrachloride; the weight ratio of the dissolved reagent to the chloralkane is 1:1 to 4.
8. The method according to claim 5, wherein the crystallization comprises sequentially performing a first crystallization and a second crystallization; the temperature of the first crystallization is 20-30 ℃, and the heat preservation time is 0.5h; the temperature of the second crystallization is-10-0 ℃, and the heat preservation time is 2-6 h;
the rate of the temperature decrease from the first crystallization to the second crystallization was 0.15 c/min.
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Citations (7)
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|---|---|---|---|---|
| JP2003146964A (en) * | 2001-11-15 | 2003-05-21 | New Japan Chem Co Ltd | Method for producing diarylsulfone polycarboxylic acid or its anhydride |
| CN1845930A (en) * | 2003-07-03 | 2006-10-11 | 通用电气公司 | Process for the preparation of thiocarboxylate silane |
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| US20090163697A1 (en) * | 2007-12-20 | 2009-06-25 | David Crich | Multicomponent coupling and glycopeptide synthesis with cyclic thioanhydrides |
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| JP2003146964A (en) * | 2001-11-15 | 2003-05-21 | New Japan Chem Co Ltd | Method for producing diarylsulfone polycarboxylic acid or its anhydride |
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| CN106478968A (en) * | 2016-10-11 | 2017-03-08 | 陕西科技大学 | A kind of preparation method of nanometer of Kapton |
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