CN104016892B - Difluoro-sulfone monomer containing double biphenyl structure and preparation method thereof - Google Patents
Difluoro-sulfone monomer containing double biphenyl structure and preparation method thereof Download PDFInfo
- Publication number
- CN104016892B CN104016892B CN201410264880.3A CN201410264880A CN104016892B CN 104016892 B CN104016892 B CN 104016892B CN 201410264880 A CN201410264880 A CN 201410264880A CN 104016892 B CN104016892 B CN 104016892B
- Authority
- CN
- China
- Prior art keywords
- preparation
- bis
- fluorophenyl
- palladium
- sulfobenzide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a difluoro-sulfone monomer containing double biphenyl structure and a preparation method thereof and belongs to the fields of organic compounds and preparation technologies thereof. The preparation method comprises the following steps: under protection of nitrogen and stirring of magnetic force, by taking water and a polar organic solvent in volume ratio of 1: (1-2) as a mixed solvent, adding 4,4'-dichlorophenyl sulfone, 4-fluoro-substituted phenylboronic acid, anhydrous sodium bicarbonate and a palladium catalyst according to the mole ratio of 1:(2-5):(7-8):(0.005-0.1), wherein the solid content of the system is 5-25 percent; slowly heating to 60-90 DEG C, reacting for 10-50 hours, cooling to room temperature, and discharging into deionized water; at last, sequentially and repeatedly washing the obtained product by using deionized water until the obtained product is neutral, washing for 3-5 times by using ethanol, filtering by using a column chromatography column, rotatably evaporating, and performing vacuum drying to obtain light yellow powder, namely 4,4'-bis(4-fluorophenyl)diphenylsulphone. The monomer can be applied to preparation of high heat-resisting grade biphenyl polyether sulfone resins.
Description
Technical field
The invention belongs to organic compound and preparing technical field thereof, be specifically related to a kind of two fluorine sulfone monomers containing two biphenyl structural and preparation method thereof.
Background technology
Polyether sulphone (PAES) resin is a class amorphous thermoplastic special engineering plastics of the exploitation sixties in last century, its molecular backbone chain is made up of structures such as sulfuryl, aromatic ring (phenyl or xenyl) and ehter bonds, is described as the engineering plastics that first combines high heat distortion temperature, high impact and excellent processability.By the application of more than two decades, the fields such as electronics, machinery, aerospace, medical treatment are widely used in the poly (ether ketone ketone) special engineering plastics that polysulfones (PSF), polyethersulfone (PES) and biphenyl polyether sulfone (PPSU) are representative with its excellent over-all properties.
Polyaryl ether sulphone resin, primarily of nucleophilic substitution polycondensation synthesis, utilizes alkoxide or the phenates alkoxide ion of strong affinity reagent, and the halogen atom replaced in alkyl halide generates ether.Utilize the specific diversity of commercially available bis-phenol, people have developed a series of polyether sulphone resinoid (table 1) by selecting different bisphenol-type.The main two halogen monomers used have dichloro diphenyl sulfone, difluorodiphenyl sulfone etc. at present; The biphenol monomer of main use has dihydroxyphenyl propane, bisphenol S, '-biphenyl diphenol etc.
Table 1: the polyether sulphone that fluorine sulfone synthesizes from different biphenol monomer
Along with technical development, a lot of Application Areas can be had higher requirement to the mechanical property of polyether sulphone resinoid.In recent years, be incorporated into by xenyl in biphenol monomer, the biphenyl polyether sulfone (PPSU) of synthesis is paid close attention to widely with its higher temperature classification and resistance to impact shock, and e.g., BASF and Su Wei companies have developed PPSU range of commercial products kind.The document of current synthesis polyether sulphone and patented technology mainly concentrate on the design and devdlop of biphenol monomer, except above-mentioned three kinds of monomers, also have Resorcinol, phenolphthalein etc.And less to two halogen monomer research, be substantially still confined to above-mentioned dichloro diphenyl sulfone and these two kinds of monomers of difluorodiphenyl sulfone.
Summary of the invention
The present invention by molecular designing with 4,4-dichloro diphenyl sulfone and be reaction raw materials to fluorobenzoic boric acid, to have utilized SUZUKI coupling method to prepare a kind of novel two fluorine sulfone monomers containing two biphenyl structural, this monomer is the same with known two fluorine sulfone monomers, can be widely used in the preparation of high temperature classification biphenyl polyether sulphone resin.
The object of this invention is to provide a kind of novel two fluorine sulfone monomers 4,4 '-bis-(4-fluorophenyl) sulfobenzide containing two biphenyl structural and preparation method thereof.
The structure of 4,4 '-bis-(4-fluorophenyl) sulfobenzide is as follows:
4,4 '-bis-(4-fluorophenyl) sulfobenzide monomer synthesis is as follows:
Under nitrogen protection and magnetic agitation, with the water of volume ratio 1:1 ~ 2 and polar organic solvent (1, 4-dioxane, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO)) be mixed solvent, add 4 of mol ratio 1:2 ~ 5:7 ~ 8:0.005 ~ 0.1 wherein, 4'-dichloro diphenyl sulfone, 4-fluorobenzoic boric acid, anhydrous sodium bicarbonate and palladium catalyst (tetrakis triphenylphosphine palladium, two (tri-tert phosphorus) palladium, palladium/carbon, palladium, two (thricyclohexyl phosphino-) palladium chloride etc.), the solid content of system is 5% ~ 25%, slowly be warming up to 60 ~ 90 DEG C, react 10 ~ 50 hours, after being cooled to room temperature, discharging is in deionized water, finally repeatedly rinsed to neutrality with deionized water successively by products therefrom, then use alcohol flushing 3 ~ 5 times, column chromatography chromatogram post filters, and revolves steaming, obtains pale yellow powder, i.e. 4,4 '-bis-(4-fluorophenyl) sulfobenzide after vacuum drying.
Here is the building-up reactions formula of above-mentioned monomer:
Accompanying drawing explanation
The nucleus magnetic hydrogen spectrum figure of Fig. 1: 4,4 '-bis-(4-fluorophenyl) sulfobenzide;
1H NMR(500MHz,CDCl
3)δ＝8.12–7.95(d,1H),7.76–7.62(d,1H),7.59–7.47(dd,1H),7.21–7.10(t,1H)。We illustrate 4,4 '-bis-(4-fluorophenyl) sulfobenzide
1h NMR spectrogram (Fig. 1 .), and the spectrum peak in figure is pointed out and belonged to.Four kinds of hydrogen on monomer are corresponding respectively composes peak a, b, c, d, and integral area ratio is 1:1:1:1.Demonstrate our biphenyl fluorine sulfone monomer obtaining expected structure.
The infrared spectrum of Fig. 2: 4,4 '-bis-(4-fluorophenyl) sulfobenzide;
As can be seen from spectrogram, 1326 and 1154cm
-1there is the charateristic avsorption band of sulfuryl; 1005cm
-1corresponding to the vibration absorption peak of biphenyl structural; 1228cm
-1for C-F charateristic avsorption band; Further demonstrate the biphenyl fluorine wind monomer that we obtain expected structure.
The mass spectrogram of Fig. 3: 4,4 '-bis-(4-fluorophenyl) sulfobenzide;
4, the theoretical molecular of 4 '-bis-(4-fluorophenyl) sulfobenzide is 406.44, as shown in Figure 3, we can see its molecular ion peak to mass spectrometric measurement clearly: the molecular ion peak (m/e) 407 of 4,4 '-bis-(4-fluorophenyl) sulfobenzide.Measured value conforms to theoretical value, confirms us further and prepares 4,4 '-bis-(4-fluorophenyl) sulfobenzide monomer.
The DSC figure of Fig. 4: 4,4 '-bis-(4-fluorophenyl) sulfobenzide;
The fusing point of scheming this monomer visible from DSC is 224 DEG C, products pure.
Embodiment
Embodiment 1: the process (I) of synthesis 4,4 '-bis-(4-fluorophenyl) sulfobenzide
In the 1000mL two-mouth bottle that magnetic stir bar, nitrogen port, spherical condensation tube are housed, add 15 gram 4 successively, 4'-dichloro diphenyl sulfone, 21 grams of 4-fluorobenzoic boric acids, 33 grams of anhydrous sodium bicarbonates, 2.5 grams of tetrakis triphenylphosphine palladiums, 250 ml deionized water, 400 milliliters of Isosorbide-5-Nitrae-dioxane.
Subsequently, logical nitrogen, opens and stirs, be slowly warming up to 80 DEG C, and (80 DEG C) stir 10 hours at such a temperature.Now, monitor reaction process by tlc, after reacting completely, be cooled to room temperature, stop stirring also discharging in deionized water.
Product deionized water is washed repeatedly, until solution is neutral.With alcohol flushing 5 times, with column chromatography chromatogram purifying crude product, developping agent is tetrahydrofuran (THF) and sherwood oil.Revolve steaming solvent evaporated, after vacuum drying, namely obtain product 4,4 '-bis-(4-fluorophenyl) sulfobenzide light yellow crystal 18.5 grams (productive rate 91%).
Embodiment 2: the process (II) of synthesis 4,4 '-bis-(4-fluorophenyl) sulfobenzide
In the 1000mL two-mouth bottle that magnetic stir bar, nitrogen port, spherical condensation tube are housed, add 15 gram 4 successively, 4'-dichloro diphenyl sulfone, 21 grams of 4-fluorobenzoic boric acids, 33 grams of anhydrous sodium bicarbonates, 1.5 grams of tetrakis triphenylphosphine palladiums, 250 ml deionized water, 400 milliliters of Isosorbide-5-Nitrae-dioxane.
Subsequently, logical nitrogen, opens and stirs, be slowly warming up to 80 DEG C, and (80 DEG C) stir 50 hours at such a temperature.Now, monitor reaction process by tlc, after reacting completely, be cooled to room temperature, stop stirring also discharging in deionized water.
Product deionized water is washed repeatedly, until solution is neutral.With alcohol flushing 5 times, with column chromatography chromatogram purifying crude product, developping agent is tetrahydrofuran (THF) and sherwood oil.Revolve steaming solvent evaporated, after vacuum drying, namely obtain product 4,4 '-bis-(4-fluorophenyl) sulfobenzide light yellow crystal 17.4 grams (productive rate 86%).
Embodiment 3: the process (III) of synthesis 4,4 '-bis-(4-fluorophenyl) sulfobenzide
In the 1000mL two-mouth bottle that magnetic stir bar, nitrogen port, spherical condensation tube are housed, add 15 gram 4 successively, 4'-dichloro diphenyl sulfone, 21 grams of 4-fluorobenzoic boric acids, 33 grams of anhydrous sodium bicarbonates, 2.5 grams of tetrakis triphenylphosphine palladiums, 250 ml deionized water, 400 milliliters of Isosorbide-5-Nitrae-dioxane.
Subsequently, logical nitrogen, opens and stirs, be slowly warming up to 80 DEG C, and (80 DEG C) stir 20 hours at such a temperature.Now, monitor reaction process by tlc, after reacting completely, be cooled to room temperature, stop stirring also discharging in deionized water.
Product deionized water is washed repeatedly, until solution is neutral.With alcohol flushing 5 times, with column chromatography chromatogram purifying crude product, developping agent is tetrahydrofuran (THF) and sherwood oil.Revolve steaming solvent evaporated, after vacuum drying, namely obtain product 4,4 '-bis-(4-fluorophenyl) sulfobenzide light yellow crystal 19.1 grams (productive rate 94%).
Claims (3)
1. a structural formula as follows 4, the preparation method of 4 '-bis-(4-fluorophenyl) sulfobenzide, it is characterized in that: under nitrogen protection and magnetic agitation, with the water of volume ratio 1:1 ~ 2 and polar organic solvent for mixed solvent, add 4 of mol ratio 1:2 ~ 5:7 ~ 8:0.005 ~ 0.1 wherein, 4'-dichloro diphenyl sulfone, 4-fluorobenzoic boric acid, anhydrous sodium bicarbonate and palladium catalyst, the solid content of system is 5% ~ 25%, slowly be warming up to 60 ~ 90 DEG C, react 10 ~ 50 hours, after being cooled to room temperature, discharging is in deionized water; Finally repeatedly rinsed to neutrality with deionized water successively by products therefrom, then use alcohol flushing 3 ~ 5 times, column chromatography chromatogram post filters, and revolves steaming, obtains pale yellow powder, i.e. 4,4 '-bis-(4-fluorophenyl) sulfobenzide after vacuum drying;
2. the preparation method of as claimed in claim 14,4 '-bis-(4-fluorophenyl) sulfobenzide, is characterized in that: organic solvent is Isosorbide-5-Nitrae-dioxane, DMF, N,N-dimethylacetamide or dimethyl sulfoxide (DMSO).
3. as claimed in claim 14, the preparation method of 4 '-bis-(4-fluorophenyl) sulfobenzide, is characterized in that: palladium catalyst is tetrakis triphenylphosphine palladium, two (tri-tert phosphorus) palladium, palladium/carbon, palladium or two (thricyclohexyl phosphino-) palladium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410264880.3A CN104016892B (en) | 2014-06-13 | 2014-06-13 | Difluoro-sulfone monomer containing double biphenyl structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410264880.3A CN104016892B (en) | 2014-06-13 | 2014-06-13 | Difluoro-sulfone monomer containing double biphenyl structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104016892A CN104016892A (en) | 2014-09-03 |
| CN104016892B true CN104016892B (en) | 2015-03-25 |
Family
ID=51433946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410264880.3A Active CN104016892B (en) | 2014-06-13 | 2014-06-13 | Difluoro-sulfone monomer containing double biphenyl structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104016892B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016096081A1 (en) * | 2014-12-19 | 2016-06-23 | Merck Patent Gmbh | Bimesogenic compounds and mesogenic media |
| CN104629038B (en) * | 2015-02-16 | 2017-05-17 | 吉林大学 | Crystalline polyethersulfone containing double biphenyl structure and preparation method thereof |
| CN105295024A (en) * | 2015-11-24 | 2016-02-03 | 吉林大学 | Di(biphenyl) structure-containing polyethersulfones with high heat resistance class and preparation method thereof |
| EP3784463A4 (en) * | 2018-04-26 | 2022-01-19 | 3M Innovative Properties Company | Fluorosulfones |
| CN112645855A (en) * | 2020-12-24 | 2021-04-13 | 中国科学院过程工程研究所 | Purification method and application of 4, 4-dichlorodiphenyl sulfone |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59155431A (en) * | 1983-02-23 | 1984-09-04 | Showa Denko Kk | Separation and recovery of polysulfone resin |
| JP2602100B2 (en) * | 1989-09-08 | 1997-04-23 | 宇部興産株式会社 | Method for producing polyether sulfone |
| CN101332415A (en) * | 2008-07-31 | 2008-12-31 | 中国科学院长春应用化学研究所 | Polyamide reverse osmosis composite membrane containing biphenyl structure and production method thereof |
-
2014
- 2014-06-13 CN CN201410264880.3A patent/CN104016892B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104016892A (en) | 2014-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104016892B (en) | Difluoro-sulfone monomer containing double biphenyl structure and preparation method thereof | |
| CN101602853B (en) | Purification process of crude product of poly(aryl ether ketone)s | |
| CN107108895B (en) | Process for the manufacture of poly (aryl ether) s using at least one organic base | |
| CN101565503A (en) | Polyarylether with phosphaphenanthrene structure and method for synthesizing the same | |
| CN106589348A (en) | Polyarylether with main chain containing bisbenzofiurene and triaryl-s-triazine structure and preparation method of polyarylether | |
| WO2019176855A1 (en) | Method for producing poly(vinylbenzyl)ether compound | |
| CN105295024A (en) | Di(biphenyl) structure-containing polyethersulfones with high heat resistance class and preparation method thereof | |
| CN105754089B (en) | A kind of synthetic method of high temperature resistant poly (arylene ether nitrile) resin | |
| CN103275015B (en) | Bisphenol monomer containing bipyridine structure, as well as preparation method and application thereof | |
| CN101955586A (en) | Epoxy terminated polyarylether resins with phthalonitrile side group and curing materials and preparation methods thereof | |
| CN108779252A (en) | By fused-extracting to polyaryl ether desalination | |
| CN106750257B (en) | A kind of heat-resisting polyarylether resin of high fluorinated volume and preparation method thereof | |
| Botvay et al. | Nitration of polyethersulfone by ammonium nitrate and trifluoroacetic anhydride | |
| CN104311828A (en) | Polyarylether containing adamantine structure and preparation method | |
| CN104003861B (en) | Hexaphenyl terminated monomer and preparation method and application thereof in preparation of hexa-benzene ring terminated polyether ketone | |
| CN111788252B (en) | Polyether sulfone-ether imide copolymer and preparation method thereof | |
| CN101381307B (en) | 4-ethyl benzoate phenyl p-dihydroxy benzene and preparation method and application thereof | |
| CN102775609A (en) | Polyphenyl ether thioether sulfoxide and preparation method thereof | |
| CN102492132A (en) | Polyaryletherketone copolymers containing cyano group and preparation method for polyaryletherketone copolymers | |
| CN102093190B (en) | Method for synthesizing hydroxybenzophenone compound | |
| CN105837814B (en) | A kind of lateral group polyarylether containing pyridine and preparation method thereof | |
| CN101186579B (en) | Method for preparing 4,4'-di(4-aminophenoxy)-3,3',5,5'-tetramethylbiphenyl | |
| RU2529030C2 (en) | Fireproof unsaturated polyetherketone | |
| CN105461613A (en) | Carbazole derivative graft monomer, preparing method and application of carbazole derivative graft monomer to polyarylether polymer | |
| CN101157623B (en) | Method for preparing 1,4-di(4-amino-benzene oxygen) benzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |