CN101704807A - Two fluoric dianhydride monomers and preparation method thereof - Google Patents
Two fluoric dianhydride monomers and preparation method thereof Download PDFInfo
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- CN101704807A CN101704807A CN200910217910A CN200910217910A CN101704807A CN 101704807 A CN101704807 A CN 101704807A CN 200910217910 A CN200910217910 A CN 200910217910A CN 200910217910 A CN200910217910 A CN 200910217910A CN 101704807 A CN101704807 A CN 101704807A
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Abstract
The invention provides two fluoric dianhydride monomers and a preparation method, belonging to the technical field of organic compound and preparation thereof. The fluoric dianhydride monomers are 4,4'-(2-(3'- trifluoromethyl-phenyl)-1,4-phenoxy)-phthalic anhydride and 4,4'-(2-(3',5'- Di(trifluoromethyl)-phenyl)-1,4-phenoxy)-phthalic anhydride. The preparation method is as follows: taking 2-(3'-trifluoromethyl-phenyl)-1,4-hydroquinone or 2-(3',5'-Di(trifluoromethyl)-phenyl)-1,4-hydroquinone as a raw material to prepare tetranitrile monomer; hydrolyzing the tetranitrile monomer under backflow of the mixed solution of potassium hydroxide, water and alcohol to prepare tetracid monomer; and refluxing, dehydrating and recrystallizing on the tetracid monomer to obtain the product. The invention has the advantages of simpler synthesis route, stable raw material monomer at room temperature, easy separation of products and lowered cost; the product can be applied in the field of preparing polyimide hyperbranched waveguide materials.
Description
Technical field
The invention belongs to organic compound and preparing technical field thereof, be specifically related to two kinds contain fluorine, big side group and ehter bond novel the time can be used for dianhydride monomer for preparing super-branched polyimide and preparation method thereof.
Background technology
Diaether dianhydride is the monomer commonly used of synthetic in the past ether acid anhydride type polyimide (PI), but the diaether dianhydride that contains fluorine, big side group and ehter bond simultaneously is the important monomer of synthetic ether acid anhydride type polyimide (PI).By introducing big side group and ehter bond, can improve the solvability of polyimide material, the introducing of trifluoromethyl can improve the light transmission of material, reduce specific inductivity, particularly be applied to optical waveguide material, can reduce the absorption loss of material, and the introducing of side group the birefringence value of polyimide material in the past can be reduced greatly, thereby the polarization loss that material in use brings can be further reduced at communication band.
The synthetic route of diaether dianhydride has three usually:
R:C wherein
6～30Aryl;
R
1: C
1～8Alkyl or C
6～13Aryl;
X: halogen atom or nitro;
M:K
+Or Na
+
Koton and Florinski propose article one synthetic route for the first time in " Zhur.Org.Kaim., 4 (5), 774 (1968) ".This method has been utilized the principle of Ulmann reaction.But raw material R (Br) in should reacting
2Extremely difficult the acquisition, and the productive rate that should react is low, and by product is many, extremely difficult separation and purification.
1976, F.J.Williams found to contain structure
Material and phenates reaction can generate various aryl oxides, utilize this reaction can produce various ether anhydride monomers (" J.Org.chem.42 (21) 1977 ").
The second synthetic route is referring to US3879428, US4017511, US3957826, US4202993, US4247464, United States Patent (USP)s such as US6008374, all disclose in aprotic solvent such as dimethyl sulfoxide (DMSO) (DMSO), used the reactant aqueous solution of diphenol and sodium hydroxide among the N, N '-dimethyl formamide (DMF), generate phenates, after phenates is separated again with raw material
Reaction makes condensation product.But in fact the separation of phenates is an extremely difficult process, because it is very easily oxidized, so need special equipment when dry and preservation phenates, is unfavorable for the realization of industrialization.When temperature of reaction when being lower than 75 ℃, need 5% quantity of solvent just can make the solid dissolving, reaction system is carried out in mutually at solution.And when temperature of reaction is higher than 100 ℃, because reaction system is alkalescence, raw material
Self condensation reaction very easily takes place.When the reaction times less than 12 hours, material content is high in the product, is difficult to separate.Because solvent load is bigger in this reaction process, solid content is low, if reaction solution is directly poured into when in acid or other solution product being separated out, causes great solvent waste.
Article three, using very easily oxidized pyrocatechol, Resorcinol etc. in the synthetic route is raw material, must strict control reaction conditions be anhydrous and oxygen-free, and higher to the sealing requirements of device, nitrogen will pass through processed earlier, therefore, also needs further to improve.
Summary of the invention
The technical problem to be solved in the present invention is, simple more, the segregative synthetic route of product are provided, the processing condition of routine are carried out preferably, prepare the dianhydride monomer of two kinds of brand news---4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride and 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1, the 4-phenoxy group)-Tetra hydro Phthalic anhydride, to satisfy the requirement that polyimide material is used in the field of superbranched light wave conductive material.
A kind of fluorine-containing dianhydride monomer of the present invention is 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride, and its structure is as follows:
The fluorine-containing dianhydride monomer of another kind of the present invention is 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride, and its structure is as follows:
Two kinds of dianhydride monomer synthetic methods of the present invention are as follows:
With 2-(3 '-trifluoromethyl-phenyl)-1,4-Resorcinol or 2-(3 ', 5 '-two trifluoromethyls-phenyl)-1, the 4-Resorcinol is a raw material, divides three-step reaction to carry out;
The first step reaction, raw material and 4-nitro phthalic nitrile, salt of wormwood 1: 2 in molar ratio～3: 2～3 are put into container, with N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) are solvent, and the solid content that makes system is 30～60%; Logical nitrogen starts stirring, reacts 45～50 hours, slowly is warmed up to 50～80 ℃ afterwards, reacts 2 hours, stops heating and continues to be stirred to room temperature, finishes reaction; Discharging in deionized water, with product with deionized water be washed till repeatedly deionized water colourless till, suction filtration, vacuum drying gets four nitrile monomers of yellow powder, i.e. 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1, the 4-phenoxy group)-1,1 ', 2,2 '-adjacent pyromellitonitrile or 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1, the 4-phenoxy group)-1,1 ', 2,2 '-adjacent pyromellitonitrile.
The second step reaction is put into container with four nitrile monomers and potassium hydroxide, is that 1: 1 second alcohol and water is a mixed solvent with mol ratio, and reflux 2 hours splashes into H again
2O
2Dropwise the sealing back flow reaction 48 hours, and be cooled to 40～50 ℃, suction filtration, clear liquid is poured in the concentrated hydrochloric acid on the rocks, constantly stir and regulate pH to 2～3 with concentrated hydrochloric acid, water is poured out, and with ether solid is dissolved, pour separating funnel after the dissolving into, extract 4～5 times, revolve and steam the back oven dry, obtain the tetracid monomer; Four nitrile monomers in molar ratio wherein: potassium hydroxide: H
2O
2=1: 20～25: 15～20.
Three-step reaction, the tetracid monomer was joined in the mixing solutions of acetate and diacetyl oxide reflux 8～10 hours, the recrystallization after-filtration 160～200 ℃ of oven dry down, obtains fluorine-containing dianhydride monomer, promptly 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride or 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride.
In three-step reaction, the recrystallization after the reflux is important, and recrystallization can obtain more purified product, helps the application of synthesis of polyimides optical waveguide material.
The solid content of the system in the first step reaction is 30～60%, is meant that the quality that adds solid (raw material and 4-nitro phthalic nitrile, salt of wormwood) in the reaction vessel accounts for the massfraction of the total mass that adds reactant and solvent.
Further experiment shows, preferred feed ratio is in the first step reaction, in molar ratio raw material [be 2-(3 '-trifluoromethyl-phenyl)-1,4-Resorcinol or 2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-Resorcinol]: 4-nitro phthalic nitrile: salt of wormwood=1: 2.5: 3; Preferred solvent is a N,N-dimethylacetamide; Preferred feed ratio, four nitrile monomers in molar ratio in the reaction of second step: potassium hydroxide: H
2O
2=1: 20: 15.
Be fluorine-containing dianhydride monomer building-up reactions formula of the present invention below:
In the building-up reactions: DMAc is a N,N-dimethylacetamide;
Compare with background technology, dianhydride of the present invention is a kind of brand-new compound.In addition, synthetic route of the present invention is simpler, as long as just can obtain two monomers through three-step reaction, used two kinds of diphenol monomers are at ambient-temp-stable, the product separate easily, and easy handling has reduced cost.In two kinds of fluorine-containing dianhydride monomers of the present invention flexible ehter bond, trifluoromethyl group and big benzene lateral group are arranged all, dianhydride monomer with these characteristics can improve the transmittance of material equally in the preparation polymer materials, increase the solvability of material, reduce the specific inductivity and the water-intake rate of material, therefore can in the field of preparation polyimide superbranched light wave conductive material, use.
Description of drawings
Fig. 1 is the DSC figure of 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride of making of embodiment 1;
Fig. 2 is the DSC figure of 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride of making of embodiment 2;
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride of making of embodiment 1;
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride of making of embodiment 2;
Fig. 5 is the infrared spectrum of 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride of making of embodiment 1;
Fig. 6 is the infrared spectrum of 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride of making of embodiment 2.
Embodiment
Embodiment 1: the process of synthetic 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride
In the 500ml there-necked flask of being furnished with mechanical stirring, band thermometer nitrogen port, spherical condensation tube, add 30.30 gram (0.12mol) 2-(3 '-trifluoromethyl-phenyl)-1, the 4-Resorcinol, 42.56 gram (0.30mol) 4-nitro phthalic nitrile, 49.68 gram (0.36mol) salt of wormwood, 240ml N,N-dimethylacetamide (solid content is 51.1%), logical nitrogen, start stirring, reacted two days, and slowly be warmed up to 50～80 ℃ afterwards, reacted 2 hours, stop heating, continue to stir for some time, room temperature to be returned to stops to stir, and finishes reaction again.Discharging is in deionized water; Then product is washed repeatedly with deionized water, till water colorless, suction filtration, vacuum drying gets yellow powder, i.e. 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-1,1 ', 2,2 '-adjacent pyromellitonitrile 55.86g.
With above-mentioned 55.86g (0.11mol) four nitrile monomers and 123.65g potassium hydroxide, ethanol, each 450mL of water put into the 1500mL there-necked flask reflux 2 hours that mechanical stirring, dropping funnel and spherical condensation tube are housed, and splash into 27.0mL H lentamente
2O
2(massfraction is 30%) after dripping off, changes dropping funnel into glass stopper again, reaction refluxed 48 hours, was cooled to 40～50 ℃, suction filtration, obtain clear liquid, this clear liquid is poured in the concentrated hydrochloric acid on the rocks, constantly stir and regulate pH to 2～3 with concentrated hydrochloric acid, water is poured out, and with ether solid is dissolved, and pours separating funnel after the dissolving into, extract 4～5 times, after revolving steaming, solid is put into about 100 ℃ oven dry of baking oven, obtain the tetracid monomer.
The tetracid monomer was joined in acetate and the solution of acetic anhydride reflux 8～10 hours, the recrystallization after-filtration, 160～200 ℃ of oven dry in vacuum drying oven obtain 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride.144 ℃ of DSC test melting temperatures.
Fig. 1,3,5 that DSC figure, the nucleus magnetic hydrogen spectrum figure of final product, infrared spectrum are seen accompanying drawing respectively.
Use N, it is solvent that dinethylformamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) substitute N,N-dimethylacetamide, and effect is more or less the same.The solid content of system all can be realized the preparation of 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride in 30～60% scope.
Embodiment 2:
Method is with embodiment 1, with 2-(3 ', 5 '-two trifluoromethyls-phenyl)-1, the amount of 4-Resorcinol changes 38.40 grams (0.12mol) into, 42.56 gram (0.3mol) 4-nitro phthalic nitriles, 49.68 gram (0.36mol) salt of wormwood, 240ml N,N-dimethylacetamide (solid content is 54.4%) is packed into and is furnished with the nitrogen port of band thermometer, mechanical stirring, in the 500ml there-necked flask of spherical condensating tube, logical nitrogen starts stirring, reacts two days, slowly be warmed up to 50～80 ℃ afterwards, reacted 2 hours, and stopped heating, continue again to stir for some time, room temperature to be recovered stops to stir, and finishes reaction.Discharging is in deionized water; Then product is washed repeatedly with deionized water, till water colorless, suction filtration, vacuum drying gets yellow powder, i.e. 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-phenoxy group)-1,1 ', 2,2 '-adjacent pyromellitonitrile 62.40g.
With above-mentioned 62.40g (0.109mol) four nitrile monomers and 122.08g potassium hydroxide, ethanol, each 450mL of water put into the 1500mL there-necked flask that mechanical stirring, dropping funnel and spherical condensation tube are housed, and reflux 2 hours splashes into 26.4mL H lentamente
2O
2(massfraction is 30%) after dripping off, changes dropping funnel into glass stopper again, reaction refluxed 48 hours, was cooled to 40～50 ℃, suction filtration, obtain clear liquid, this clear liquid is poured in the concentrated hydrochloric acid on the rocks, constantly stir and regulate pH to 2～3 with concentrated hydrochloric acid, water is poured out, with ether solid is dissolved, pour separating funnel after the dissolving into, extract 4～5 times, after revolving steaming, solid is put into about 100 ℃ oven dry of baking oven obtain the tetracid monomer.
The tetracid monomer was joined in acetate and the solution of acetic anhydride reflux 8～10 hours, recrystallization after-filtration, 160～200 ℃ of oven dry in vacuum drying oven, obtain 4,159 ℃ of 4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride .DSC test melting temperatures.
Fig. 2,4,6 that DSC figure, the nucleus magnetic hydrogen spectrum figure of final product, infrared spectrum are seen accompanying drawing respectively.
Use N, it is solvent that dinethylformamide, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) substitute N,N-dimethylacetamide, and effect is more or less the same.The solid content of system all can be realized the preparation of 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1,4-phenoxy group)-Tetra hydro Phthalic anhydride in 30～60% scope.
Claims (3)
1. fluorine-containing dianhydride monomer, it is characterized in that, fluorine-containing dianhydride monomer is 4,4 '-(2-(3 '-trifluoromethyl-phenyl)-1, the 4-phenoxy group)-and Tetra hydro Phthalic anhydride or 4,4 '-(2-(3 ', 5 '-two trifluoromethyls-phenyl)-1, the 4-phenoxy group)-and Tetra hydro Phthalic anhydride, the structure of fluorine-containing dianhydride monomer is respectively:
2. the preparation method of the fluorine-containing dianhydride monomer of a claim 1, with 2-(3 '-trifluoromethyl-phenyl)-1,4-Resorcinol or 2-(3 ', 5 '-two trifluoromethyls-phenyl)-1, the 4-Resorcinol is a raw material, divides three-step reaction to carry out;
The first step reaction, raw material and 4-nitro phthalic nitrile, salt of wormwood 1: 2 in molar ratio～3: 2～3 are put into container, with N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) are solvent, and the solid content that makes system is 30～60%; Logical nitrogen, stirring reaction 45～50 hours slowly is warmed up to 50～80 ℃ afterwards, reacts 2 hours, stops heating and continues to be stirred to room temperature, finishes reaction; Discharging in deionized water, with product with deionized water be washed till repeatedly deionized water colourless till, suction filtration, vacuum drying get four nitrile monomers of yellow powder;
The second step reaction is put into container with four nitrile monomers and potassium hydroxide, is that 1: 1 second alcohol and water is a mixed solvent with mol ratio, and reflux 2 hours splashes into H again
2O
2Dropwise the sealing back flow reaction 48 hours, and be cooled to 40～50 ℃, suction filtration, clear liquid is poured in the concentrated hydrochloric acid on the rocks, constantly stir and regulate pH to 2～3 with concentrated hydrochloric acid, water is poured out, and with ether solid is dissolved, pour separating funnel after the dissolving into, extract 4～5 times, revolve and steam the back oven dry, obtain the tetracid monomer; Four nitrile monomers in molar ratio wherein: potassium hydroxide: H
2O
2=1: 20～25: 15～20;
Three-step reaction joined the tetracid monomer in the mixing solutions of acetate and diacetyl oxide reflux 8～10 hours, and the recrystallization after-filtration 160～200 ℃ of oven dry down, obtains fluorine-containing dianhydride monomer.
3. according to the preparation method of the described fluorine-containing dianhydride monomer of claim 2, it is characterized in that, described the first step reaction, feeding intake is raw material in molar ratio: 4-nitro phthalic nitrile: salt of wormwood=1: 2.5: 3, solvent are N,N-dimethylacetamide; Described second step reaction, feeding intake is four nitrile monomers in molar ratio: potassium hydroxide: H
2O
2=1: 20: 15.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267940A (en) * | 2011-05-31 | 2011-12-07 | 湖北大学 | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof |
| CN103980158A (en) * | 2014-05-21 | 2014-08-13 | 中国科学院上海有机化学研究所 | Method of synthesizing phthalonitrile aryl ether by phase-transfer catalysis |
| US9074051B2 (en) | 2013-03-18 | 2015-07-07 | Unimicron Technology Corp. | Dianhydride monomer having side chain, polyimide compound having side chain and manufacturing method thereof |
| CN106496557A (en) * | 2016-11-02 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of high transparency high temperature resistant fluorinated polyimide resin |
| CN106543438A (en) * | 2016-11-07 | 2017-03-29 | 沈阳化工大学 | A kind of preparation method of chlorinated and fluorinated polyamide-imide resin |
| CN109678826A (en) * | 2019-02-21 | 2019-04-26 | 浙江诺诚技术发展有限公司 | A kind of method that temperate condition prepares hexafluorodianhydride (6FDA) |
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2009
- 2009-11-24 CN CN200910217910A patent/CN101704807A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267940A (en) * | 2011-05-31 | 2011-12-07 | 湖北大学 | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof |
| US9074051B2 (en) | 2013-03-18 | 2015-07-07 | Unimicron Technology Corp. | Dianhydride monomer having side chain, polyimide compound having side chain and manufacturing method thereof |
| CN103980158A (en) * | 2014-05-21 | 2014-08-13 | 中国科学院上海有机化学研究所 | Method of synthesizing phthalonitrile aryl ether by phase-transfer catalysis |
| CN106496557A (en) * | 2016-11-02 | 2017-03-15 | 沈阳化工大学 | A kind of preparation method of high transparency high temperature resistant fluorinated polyimide resin |
| CN106543438A (en) * | 2016-11-07 | 2017-03-29 | 沈阳化工大学 | A kind of preparation method of chlorinated and fluorinated polyamide-imide resin |
| CN109678826A (en) * | 2019-02-21 | 2019-04-26 | 浙江诺诚技术发展有限公司 | A kind of method that temperate condition prepares hexafluorodianhydride (6FDA) |
| CN109678826B (en) * | 2019-02-21 | 2023-03-14 | 浙江诺诚技术发展有限公司 | Method for preparing hexafluoro dianhydride under mild condition |
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Application publication date: 20100512 |