CN101817926B - Phosphate side chain-containing polyimide for gasoline desulphurization and preparation method thereof - Google Patents
Phosphate side chain-containing polyimide for gasoline desulphurization and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a phosphate side chain-containing polyimide and a preparation method and application thereof. The phosphate side chain-containing polyimide is prepared by performing condensation polymerization on hydroxyl-containing aromatic diamine monomer and di-anhydride to prepare polyimide and then performing phosphate esterification and hydrolytic synthesis on the polyimide. The phosphate side chain-containing polyimide has a simple preparation process and a low cost, can be made into films used in the process of gasoline desulphurization and has high desulphurization efficiency; after the desulphurization, sulfur residues in gasoline are about 30 ppm; and simultaneously the aromatic hydrocarbon content is reduced by 5 to 10 percent and the octane value is kept unchanged.
Description
Technical field
The present invention relates to field of materials, particularly polyimide of a kind of phosphate side chain-containing and preparation method thereof.
Background technology
Modern society, vehicle exhaust has become the primary pollution source of city atmospheric environment, the oxysulfide (SO that contains in the gasoline combustion discharge tail gas
x), carbon monoxide (CO) and oxynitride (NO
x), be the major cause that forms acid rain, severe contamination urban air environment.For improving the environmental pollution that gasoline combustion brings, must reduce the content of sulfide in petrol.Along with countries in the world to the pay attention to day by day of environment protection and the increasingly stringent of environmental regulation, produce low-sulfur and super low-sulfur oil and paid close attention to by people just gradually.China's motor spirit national standard is compared with foreign advanced standard still has a certain distance; China from 2005 automobile-used content of sulfur in gasoline carry out the regulation that is not more than 500 μ g/g; Up-to-date unleaded gasoline for vehicle standard code was from December 31st, 2009; After Beijing, Shanghai and Guangzhou, nationwide white gasoline sulphur content all will be carried out EUROIII Emission Standard, reduces to 150 μ g/g.China planning quality of gasoline to 2010 year integrates with international standard, and Sinopec and CNPC are just uniting the research of carrying out Europe IV gasoline, diesel, for the gasoline, diesel standard of formulating China next stage is got ready.
Sulfide in petrol is mainly mercaptan, thioether, disulphide and thiophene-type sulfide, and wherein the mass concentration of thioether sulphur and thiophenic sulfur accounts for more than 85% of total sulfur, and gasoline desulfur is main to remove thioether sulphur and thiophenic sulfur.
Traditional gasoline desulfating method has catalytic desulfurhydrogenation, adsorption desulfurize, oxidation sweetening, biological desulphurization, SX desulfurization etc.But catalytic desulfurhydrogenation can cause gasoline octane rating to descend, and the desulfurization condition HTHP, and cost is higher; The adsorptive capacity of adsorption desulfurize is lower, and selectivity is lower; The Oil Recovery rate of oxidation sweetening is on the low side, and the cost of oxygenant and extraction solvent is higher; The stability of biological desulphurization is not high, and desulphurization reaction speed is slower; The SX desulfurization also need solve the lower problem of solvent desulfuration efficiency.
The embrane method desulfurization is a kind of novel gasoline desulfur technology, has compared remarkable advantages with traditional sulfur method.U.S. Pat 6736961 has been reported a kind of method of membrane permeation gasification desulfurization; With existing film such as Nanofiltration SR-90, Ultrafiltration G-10, Polysulfone SEP-0013 etc. petroleum naphtha is permeated gasificating desulfurization; And the pressure of keeping the other side of film is 0KPa; But its sulphur perviousness is not high, and need sweep stream with liquid in an other side of film and improve desulfuration efficiency.U.S. Pat 6702945 reported the Nafion.RTM type ionic membrane that contains perfluorinated sulfonic acid or derivatives thereof group can be from FCC and petroleum naphtha separate sulphur compound effectively, yet this film must contain the exchange ion of certain kind, like H
+, Na
+Deng.U.S. Pat 6896796 has been reported the film-forming process of several kinds of polyimide and petroleum naphtha has been permeated the gasificating desulfurization process.Chinese patent CN 1686600 has reported a kind of preparation method who permeates the gasification gasoline desulfur blend composite film, but does not relate to the variation of aromaticity content and octane value behind the gasoline desulfur, and octane value remains unchanged after not having data to show desulfurization.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide a kind of gasoline desulfur efficient high, can keep that gasoline octane rating is constant, cost is low, the polyimide of the simple phosphate side chain-containing of technology.
Another object of the present invention is to provide a kind of preparation method of polyimide of above-mentioned phosphate side chain-containing.
The object of the invention is realized through following technical proposals:
A kind of polyimide of phosphate side chain-containing, its averagemolecular wt amount is 10000～100000, structural formula is formula 1 or formula 2:
The preparation method of the polyimide of above-mentioned phosphate side chain-containing is earlier hydroxyl aryl diamine monomer and dianhydride to be carried out polycondensation to prepare polyimide, synthesizes through phosphotidic and hydrolysis then to obtain, and specifically comprises the steps:
(1) under nitrogen protection, after compound a dissolves, carried out polycondensation 3～20 hours with dianhydride in organic solvent A, add YLENE then, be warmed up to 100～200 ℃ of dehydration reactions 3～24 hours, remove organic solvent A after, obtain compound b; The structural formula of said compound a is a kind of in formula 3, formula 4, formula 5, formula 6 or the formula 7; The structural formula of said compound b is formula 8 or formula 9;
Wherein, in formula 8 and the formula 9, R
1, R
2Implication cotype 1 and formula 2 in the implication of relevant parameter;
(2) this step is a kind of in following (2-1), (2-2) step, and wherein the compound for preparing of (2-1) step does not contain alkyl, and (2-2) compound for preparing of step contains alkyl:
(2-1) compound b is dissolved in the organic solvent B under nitrogen protection, and ice bath adds triethylamine, cuprous chloride, phosphorization reagent, and normal-temperature reaction 5～24 hours is removed organic solvent B, obtains compound c 1; The structural formula of said compound c 1 is formula 10-1 or formula 11-1;
Wherein, among formula 10-1 and the formula 11-1, R
1, R
2, R
3Implication cotype 1 and formula 2 in the implication of relevant parameter, and R
3Middle n=0 representes that promptly polymer side chains phosphate group, does not contain alkyl;
(2-2) earlier weak base, Verbindung are dissolved among the organic solvent C, then under 10～100 ℃, add compound b in 1～3 hour, continue reaction 5～20 hours, filtering-depositing is removed organic solvent C, separates to obtain compound d after purifying; The structural formula of said compound d is formula 13 or formula 14; The structural formula of said Verbindung is a formula 12;
Wherein, in the formula 12, n=1～12; In formula 13 and the formula 14, R
1, R
2, R
3Implication cotype 1 and formula 2 in the implication of relevant parameter, and R
3In n=1～12, i.e. expression contains the alkyl of 1～12 carbon atom;
Then compound d is dissolved in the organic solvent B, adds phosphorization reagent,, remove organic solvent B, separate and purify, obtain compound c 2 50～200 ℃ of TR internal reactions 1～5 day; The structural formula of said compound c 2 is formula 10-2 or formula 11-2;
Wherein, among formula 10-2 and the formula 11-2, R
1, R
2, R
3Implication cotype 1 and formula 2 in the implication of relevant parameter, and R
3Middle n=1～12, i.e. expression contains the alkyl of 1～12 carbon atom;
(3) compound c 1 or c2 are dissolved in the organic solvent B, add XSi (Me)
3Hydrolysis, wherein X is Br, Cl or I, reaction finishes the back and separates purification, obtains the polyimide of phosphate side chain-containing.
In the step 1, structural formula is that the preparation method of the compound a of formula 3 is: under nitrogen protection and 100 ℃～150 ℃ temperature, PARA HYDROXY BENZALDEHYDE, aniline and aniline hydrochloride mix also and reacted 1～5 hour, and cooling also separates purifies, and obtains the compound a of formula 3.Wherein, PARA HYDROXY BENZALDEHYDE: aniline: the mol ratio of aniline hydrochloride is 1: (2～10): (0.1～1); Described separation is to filter, and described purification is a recrystallization.Structural formula is that the compound a of formula 4～7 can directly be buied in market.
In the step 1, said organic solvent A is N, a kind of in dinethylformamide, N-Methyl pyrrolidone, DMAC N,N or the meta-cresol.
In the step 1, the structural formula of said dianhydride is a kind of in the formula 15～20:
Step 1, the mol ratio of compound a and dianhydride are 1: (1～1.6).Organic solvent A and YLENE volume ratio are 2: 1.
Among the step 2-1, said organic solvent B is one or more mixtures of chloroform, THF, dioxane or DMSO 99.8MIN.; Said phosphorization reagent is diethyl chloro-phosphate, bromine diethyl phosphoric acid, iodine diethyl phosphoric acid or DFP.
Among the step 2-1, compound b: triethylamine: cuprous chloride: the mol ratio of phosphorization reagent is 1: (3～10): (0.1～1): (1～10).
Among the step 2-2, the mixture of one or more that said organic solvent C is chloroform, THF, dioxane, methyl alcohol, ethanol, acetonitrile or acetone; Said weak base is sodium hydrogencarbonate, yellow soda ash, saleratus or salt of wormwood; Said phosphorization reagent is a triethyl-phosphite; Said separation is to filter, and said purification is a solvent wash.
Among the step 2-2, compound b: Verbindung: weakly alkaline mol ratio is 1: (1～10): (1～5).
Among the step 2-2, compound d: the mol ratio of phosphorization reagent is 1: (1～10).
In the step 3, compound c 1 or c2: XSi (Me)
3Mol ratio be 1: (1～5).
In the step 3, the temperature of hydrolysis is 0～100 ℃, and the time is 1～5 day; Said separation is that rotating centrifugal separates, and said purification is the rotary evaporation solvent.
The application of the polyimide of above-mentioned phosphate side chain-containing; The polyimide (structural formula is formula 1 or formula 2) that is phosphate side chain-containing is processed flat sheet membrane; Be used for the desulfurization of gasoline; Concrete steps are: in boiling point is 50～350 ℃ solvent, process film-casting liquid, originally stable state solution becomes unstable state and produces liquid-liquid phase conversion final curing film forming, and the made film that comes out is that the top layer is fine and close, the loose porous asymmetric flat sheet membrane of bottom.The film that obtains is used for the sweetening process of high sour gasoline such as FCC gasoline, catalytic cracking gasoline, straight sulfur oil, coker gasoline, pyrolysis gasoline, thermo-cracking gas and oil or its mixing oil; Through after the desulfurization; Sulphur residual quantity in the gasoline is about 30ppm; Make the aromatic hydrocarbons amount descend 5%～10% simultaneously, octane value then remains unchanged.
The present invention compared with prior art has following advantage and effect:
(1) polyimide of phosphate side chain-containing provided by the invention can be made into film, is used for the sweetening process of gasoline, and desulfuration efficiency is high, and through after the desulfurization, the sulphur residual quantity in the gasoline makes the aromatic hydrocarbons amount descend 5%～10% about 30ppm simultaneously, and octane value then remains unchanged.
(2) preparation process of the present invention is simple, and cost is low.A kind of method of phosphoric acid side group polyimide material of synthetic similar structures is provided, and the quantity that can be through regulating phosphate group and the length of the phosphoric acid side chain infiltration gasification performance after to material filming is regulated and control.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiment of the present invention is not limited thereto.
Embodiment 1
Under the nitrogen protection, with the 0.05mol PARA HYDROXY BENZALDEHYDE, 0.10mol aniline, the 0.005mol aniline hydrochloride joins in the reaction flask; After treating that it dissolves fully, 100 ℃ of reactions 1 hour down, deposition, filtering-depositing are separated out in cooling; Obtain the bullion compound, after recrystallizing methanol operation several times, evaporation drying; Obtain purified 4,4-diamino-, 4-hydroxyl tritane (being the compound a of formula 3).
Under the nitrogen protection, with 0.02mol 4, the 4-diamino-; 4-hydroxyl tritane is dissolved in 25ml N, in the N N,N-DIMETHYLACETAMIDE, adds the 0.02mol pyromellitic acid anhydride; Normal temperature stirred 3 hours down; Add the 12.5ml xylene solution then, be warmed up to 100 ℃ of imidizations 5 hours of dewatering, obtain the compound b (R wherein of formula 8
1For
R
2For
R
3Middle n=0 representes not contain alkyl)
The compound b of 0.004mol formula 8 is dissolved under nitrogen protection in the 15ml chloroform, and ice bath adds the 0.012mol triethylamine down, the 0.0004mol cuprous chloride, and adding is dissolved in the bromine diethyl phosphoric acid 0.004mol in the 10ml chloroform in batches then.Normal-temperature reaction 8 hours reclaims filtrating, in methyl alcohol, is settled out polymkeric substance, obtains the compound c 1 (R wherein of formula 10-1 after the vacuum-drying
1For
R
2For
R
3Middle n=0 representes not contain alkyl).
The compound c 1 of 0.004mol formula 10-1 is dissolved in the chloroform; The trimethylchlorosilane that adds 0.004mol; 20 ℃ of down reactions 1 day, remove unnecessary solvent with Rotary Evaporators after, use the methanol extraction washing copolymer; (structural formula is formula 1, wherein R to obtain the polyimide of phosphate side chain-containing after the vacuum-drying
1For
R
2For
R
3Middle n=0), the averagemolecular wt amount is 35660, IR:1725,1780cm
-1About C=O stretching vibration peak in the imide bond has appearred, 1380cm
-1About C-N stretching vibration peak in the imide bond appears.
The polyimide of the above-mentioned phosphate side chain-containing that makes is dissolved in N-Methyl pyrrolidone, and to process massfraction be 10% casting film solution; And fully stirred 24 hours with magnetic stirring apparatus; Treat that solute all dissolves after-filtration and removes impurity, leave standstill one day to remove the bubble in the film-casting liquid fully.Then film-casting liquid is poured on the glass plate; Smear film-casting liquid with scraper equably; Place sheet glass 80 ℃ forced convection oven 5 hours then, take out cooling after the solvent evaporates, be dipped in the water film is taken off; Drying was placed in the vacuum chamber Air drying 24 hours under the room temperature, obtained the polyimide film of phosphate side chain-containing.The polyimide film that makes is permeated gasificating desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are following: octane value 93.2 (desulfurization preceding 94.0), 20 ℃ of density are 721.3Kg/m
3(before the desulfurization is 721.9Kg/m
3), lead content 0.001g/L (0.001g/L before the desulfurization), 10% vaporization temperature is 61 ℃ (preceding 60 ℃ of desulfurization); 50% vaporization temperature is 80.5 ℃ (preceding 80.5 ℃ of desulfurization), and 90% vaporization temperature is 161 ℃ (preceding 161.5 ℃ of desulfurization), 180 ℃ of final boiling point (preceding 180 ℃ of desulfurization); Residual quantity 1.0% (desulfurization preceding 1.0%), existent gum 3mg/100mL (3mg/100mL before the desulfurization), sulphur content 29ppm (1300ppm before the desulfurization); 50 ℃, the 3h copper corrosion is 1a level (being the 1a level before the desulfurization), does not have water soluble acid or alkali (alkali-free before the desulfurization); Benzene content 1.8% (desulfurization preceding 2.5%), aromaticity content 13.8% (desulfurization preceding 17.6%), olefin(e) centent 32.1% (desulfurization preceding 38.2).
Embodiment 2:
Under the nitrogen protection, with the 0.06mol PARA HYDROXY BENZALDEHYDE, the 0.48mol aniline solution, the 0.042mol aniline hydrochloride joins in the reaction flask; After treating that it dissolves fully, 150 ℃ of reactions 5 hours down, deposition, filtering-depositing are separated out in cooling; Obtain the bullion compound, after recrystallizing methanol operation several times, evaporation drying; Obtain purified 4,4-diamino-, 4-hydroxyl tritane (being the compound a of formula 3).
" the hydroxyl tritane is dissolved in 40mlN; in the N N; add 0.030mol naphthalene tetracarboxylic dianhydride (being the compound of formula 16), and normal temperature stirred 8 hours down, added the 20ml xylene solution then; be warmed up to 130 ℃ of imidizations 10 hours of dewatering, and obtains the compound b (R wherein of formula 8 under the nitrogen protection, with 0.025mol 4,4 '-diamino--4
1For
R
2For
R
3Middle n=0 representes not contain alkyl)
The compound of 0.005mol formula 8 is dissolved under nitrogen protection in the 30ml THF, and ice bath adds the 0.025mol triethylamine down, the 0.0015mol cuprous chloride, and adding is dissolved in the diethyl chloro-phosphate 0.015mol in the 10ml chloroform in batches then.Normal-temperature reaction 8 hours reclaims filtrating, in methyl alcohol, is settled out polymkeric substance, obtains the compound c 1 (R wherein of formula 10-1 after the vacuum-drying
1For
R
2For
R
3Middle n=0 representes not contain alkyl).
The compound c 1 of 0.005mol formula 10-1 is dissolved in the chloroform; The bromotrimethylsilane that adds 0.01mol; 40 ℃ of down reactions 2 days, remove unnecessary solvent with Rotary Evaporators after, with methyl alcohol/hydrochloric acid soln washing copolymer; (structural formula is formula 1, wherein R to obtain the polyimide of phosphate side chain-containing after the vacuum-drying
1For
R
2For
R
3Middle n=0 representes not contain alkyl), the averagemolecular wt amount is 28260, IR:1725,1780cm
-1About C=O stretching vibration peak in the imide bond has appearred, 1380cm
-1About C-N stretching vibration peak in the imide bond appears.
Above-mentioned polyimide is dissolved in N-Methyl pyrrolidone, and to process massfraction be 10% casting film solution, and fully stirred 24 hours with magnetic stirring apparatus, treats that solute all dissolves after-filtration and removes impurity, leaves standstill one day to remove the bubble in the film-casting liquid fully.Then film-casting liquid is poured on the glass plate; Smear film-casting liquid with scraper equably; Place sheet glass 80 ℃ forced convection oven 5 hours then, take out cooling after the solvent evaporates, be dipped in the water film is taken off; Drying was placed in the vacuum chamber Air drying 24 hours under the room temperature, obtained polyimide film.The polyimide film that makes is permeated gasificating desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are following: octane value 93.1 (desulfurization preceding 94.0), 20 ℃ of density are 721.7Kg/m
3(before the desulfurization is 721.9Kg/m
3), lead content 0.001g/L (0.001g/L before the desulfurization), 10% vaporization temperature is 61.3 ℃ (preceding 60 ℃ of desulfurization); 50% vaporization temperature is 80.5 ℃ (preceding 80.5 ℃ of desulfurization), and 90% vaporization temperature is 161 ℃ (preceding 161.5 ℃ of desulfurization), 180 ℃ of final boiling point (preceding 180 ℃ of desulfurization); Residual quantity 1.0% (desulfurization preceding 1.0%), existent gum 3.1mg/100mL (3mg/100mL before the desulfurization), sulphur content 35ppm (1300ppm before the desulfurization); 50 ℃, the 3h copper corrosion is 1a level (being the 1a level before the desulfurization), does not have water soluble acid or alkali (alkali-free before the desulfurization); Benzene content 2.0% (desulfurization preceding 2.5%), aromaticity content 14.8% (desulfurization preceding 17.6%), olefin(e) centent 32.7% (desulfurization preceding 38.2%).
Embodiment 3:
Under the nitrogen protection, with 0.02mol 3,3 '-diamino--4; 4 '-dihydroxybiphenyl (being the compound a of formula 6) is dissolved in the 50ml N-Methyl pyrrolidone, adds 0.026mol 3,3 '; 4,4 '-diphenyl ether tetraformic dianhydride (being the compound of formula 18), normal temperature stirred 8 hours down; Add the 25ml xylene solution then, be warmed up to 150 ℃ of imidizations 12 hours of dewatering, obtain the compound b (R wherein of formula 9
1For
R
2For
R
3Middle n=0 representes not contain alkyl).
The compound b of 0.01mol formula 9 is dissolved under nitrogen protection in the 45ml dioxane, and ice bath adds the 0.06mol triethylamine down, and the 0.005mol cuprous chloride dripped in 20 minutes then and is dissolved in the diethyl chloro-phosphate 0.05mol in the 40ml dioxane.Normal-temperature reaction 12 hours reclaims filtrating, in methyl alcohol, is settled out polymkeric substance, obtains the compound c 1 (R wherein of formula 11-1 after the vacuum-drying
1For
R
2For
R
3Middle n=0 representes not contain alkyl).
The compound c 1 of 0.01mol formula 11 is dissolved in the chloroform; The trimethylchlorosilane that adds 0.03mol; 60 ℃ of down reactions 3 days, remove unnecessary solvent with Rotary Evaporators after, use the methanol solution washing copolymer; (structural formula is formula 2, wherein R to obtain the polyimide of phosphate side chain-containing after the vacuum-drying
1For
R
2For
R
3Middle n=0 representes not contain alkyl), the averagemolecular wt amount is 41430, IR:1725,1780cm
-1About C=O stretching vibration peak in the imide bond has appearred, 1380cm
-1About C-N stretching vibration peak in the imide bond appears.
Above-mentioned polyimide is dissolved in N-Methyl pyrrolidone, and to process massfraction be 10% casting film solution, and fully stirred 24 hours with magnetic stirring apparatus, treats that solute all dissolves after-filtration and removes impurity, leaves standstill one day to remove the bubble in the film-casting liquid fully.Then film-casting liquid is poured on the glass plate; Smear film-casting liquid with scraper equably; Place sheet glass 80 ℃ forced convection oven 5 hours then, take out cooling after the solvent evaporates, be dipped in the water film is taken off; Drying was placed in the vacuum chamber Air drying 24 hours under the room temperature, obtained polyimide film.The polyimide film that makes is permeated gasificating desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are following: octane value 93.8 (desulfurization preceding 94.0), 20 ℃ of density are 721.6Kg/m
3(before the desulfurization is 721.9Kg/m
3), lead content 0.001g/L (0.001g/L before the desulfurization), 10% vaporization temperature is 61.1 ℃ (preceding 60 ℃ of desulfurization); 50% vaporization temperature is 80.5 ℃ (preceding 80.5 ℃ of desulfurization), and 90% vaporization temperature is 161.2 ℃ (preceding 161.5 ℃ of desulfurization), 180 ℃ of final boiling point (preceding 180 ℃ of desulfurization); Residual quantity 1.0% (desulfurization preceding 1.0%), existent gum 3mg/100mL (3mg/100mL before the desulfurization), sulphur content 38ppm (1300ppm before the desulfurization); 50 ℃, the 3h copper corrosion is 1a level (being the 1a level before the desulfurization), does not have water soluble acid or alkali (alkali-free before the desulfurization); Benzene content 2.0% (desulfurization preceding 2.5%), aromaticity content 14.0% (desulfurization preceding 17.6) %, olefin(e) centent 35.1% (desulfurization preceding 38.2%).
Embodiment 4:
Under the nitrogen protection, with 0.02mol 2, two (3-amino-4-hydroxy the phenyl)-HFC-236fas (being the compound a of formula 7) of 2-are dissolved in the 60ml meta-cresol; Add 0.028mol 3,3 ', 4; 4 '-benzophenone tetracarboxylic acid dianhydride (being the compound of formula 20), normal temperature stirred 10 hours down, added the 30ml xylene solution then; Be warmed up to 170 ℃ of imidizations 15 hours of dewatering, obtain the compound b (R wherein of formula 9
1For
R
2For
R
3Middle n=0 representes not contain alkyl).
With 0.02mol salt of wormwood, 0.02mol 1,6-dibromo-hexane (being the Verbindung of formula 12, wherein n=6) is dissolved in the 80ml acetonitrile; Then under 40 ℃, divide the compound b that adds 0.01mol formula 9 several times in 2 hours, continue reaction 8 hours; Filtering-depositing; Filtrating is collected in washing back, concentrates the back and in normal hexane, is precipitated out, and obtains the compound d (R wherein of formula 14 after the vacuum-drying
1For
R
2For
R
3Middle n=6 representes to contain the alkyl of 6 carbon atoms).
The compound d of 0.005mol formula 14 is dissolved in the 40ml THF, adds the 0.015mol triethyl-phosphite,, after the rotary evaporation solvent, after column chromatography is purified, obtain the compound c 2 (R wherein of formula 11-2 80 ℃ of reactions 2 days down
1For
R
2For
R
3Middle n=6 representes to contain the alkyl of 6 carbon atoms).
The compound c 2 of 0.005mol formula 11-2 is dissolved in the 40ml THF; The bromotrimethylsilane that adds 0.020mol; 80 ℃ of down reactions 4 days, remove unnecessary solvent with Rotary Evaporators after, use the methanol solution washing copolymer; (structural formula is formula 2, wherein R to obtain the polyimide of phosphate side chain-containing after the vacuum-drying
1For
R
2For
R
3Middle n=6 representes to contain the alkyl of 6 carbon atoms), the averagemolecular wt amount is 57210, IR:1725,1780cm
-1About C=O stretching vibration peak in the imide bond has appearred, 1380cm
-1About C-N stretching vibration peak in the imide bond appears.
Above-mentioned polyimide is dissolved in N-Methyl pyrrolidone, and to process massfraction be 10% casting film solution, and fully stirred 24 hours with magnetic stirring apparatus, treats that solute all dissolves after-filtration and removes impurity, leaves standstill one day to remove the bubble in the film-casting liquid fully.Then film-casting liquid is poured on the glass plate; Smear film-casting liquid with scraper equably; Place sheet glass 80 ℃ forced convection oven 5 hours then, take out cooling after the solvent evaporates, be dipped in the water film is taken off; Drying was placed in the vacuum chamber Air drying 24 hours under the room temperature, obtained polyimide film.The polyimide film that makes is permeated gasificating desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are following: octane value 93.5 (desulfurization preceding 94.0), 20 ℃ of density are 721.2Kg/m
3(before the desulfurization is 721.9Kg/m
3), lead content 0.001g/L (0.001g/L before the desulfurization), 10% vaporization temperature is 61.1 ℃ (preceding 60 ℃ of desulfurization); 50% vaporization temperature is 80.5 ℃ (preceding 80.5 ℃ of desulfurization), and 90% vaporization temperature is 161.4 ℃ (preceding 161.5 ℃ of desulfurization), 180 ℃ of final boiling point (preceding 180 ℃ of desulfurization); Residual quantity 1.0% (desulfurization preceding 1.0%), existent gum 3mg/100mL (3mg/100mL before the desulfurization), sulphur content 44ppm (1300ppm before the desulfurization); 50 ℃, the 3h copper corrosion is 1a level (being the 1a level before the desulfurization), does not have water soluble acid or alkali (alkali-free before the desulfurization); Benzene content 2.1% (desulfurization preceding 2.5%), aromaticity content 14.5% (desulfurization preceding 17.6%), olefin(e) centent 32.9% (desulfurization preceding 38.2%).
Embodiment 5
Under the nitrogen protection, with 0.05mol 3,5-diaminophenol (being the compound a of formula 4) is dissolved in 70ml N; In the N-N,N-DIMETHYLACETAMIDE, add 0.08mol 3,3 '; 4,4 '-bibenzene tetracarboxylic dianhydride (being the compound of formula 17), normal temperature stirred 15 hours down; Add the 35ml xylene solution then, be warmed up to 200 ℃ of imidizations 20 hours of dewatering, obtain the compound b (R wherein of formula 9
1 
R
2 
For, R
3Middle n=0 representes not contain alkyl).
With 0.1mol sodium hydrogencarbonate, 0.1mol 1,8-two bromooctanes (being the Verbindung of formula 12, wherein n=8) are dissolved in 100ml dioxane/acetonitrile (1: 1) solution; Then under 70 ℃, divide the compound b that adds 0.025mol formula 9 several times in 3 hours, continue reaction 15 hours; Filtering-depositing; Filtrating is collected in washing back, concentrates the back and in normal hexane, is precipitated out, and obtains the compound d (R wherein of formula 13 after the vacuum-drying
1For
R
2For
R
3Middle n=8 representes to contain the alkyl of 8 carbon atoms).
The compound d of 0.05mol formula 13 is dissolved in the 80ml DMSO 99.8MIN., adds the 0.40mol triethyl-phosphite,, after the rotary evaporation solvent, after column chromatography is purified, obtain the compound c 2 (R wherein of formula 10-2 120 ℃ of reactions 3 days down
1 
For, R
2For
R
3Middle n=8 representes to contain the alkyl of 8 carbon atoms).
The compound c 2 of 0.02mol formula 10-2 is dissolved in the 90ml DMSO 99.8MIN.; The Iodotrimethylsilane that adds 0.1mol; 100 ℃ of down reactions 5 days, remove unnecessary solvent with Rotary Evaporators after, use the methanol solution washing copolymer; (structural formula is formula 1, wherein R to obtain the polyimide of phosphate side chain-containing after the vacuum-drying
1For
R
2For
R
3Middle n=8 representes to contain the alkyl of 8 carbon atoms), the averagemolecular wt amount is 53980, IR:1725,1780cm
-1About C=O stretching vibration peak in the imide bond has appearred, 1380cm
-1About C-N stretching vibration peak in the imide bond appears.
Above-mentioned polyimide is dissolved in N-Methyl pyrrolidone, and to process massfraction be 10% casting film solution, and fully stirred 24 hours with magnetic stirring apparatus, treats that solute all dissolves after-filtration and removes impurity, leaves standstill one day to remove the bubble in the film-casting liquid fully.Then film-casting liquid is poured on the glass plate; Smear film-casting liquid with scraper equably; Place sheet glass 80 ℃ forced convection oven 5 hours then, take out cooling after the solvent evaporates, be dipped in the water film is taken off; Drying was placed in the vacuum chamber Air drying 24 hours under the room temperature, obtained polyimide film.The polyimide film that makes is permeated gasificating desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are following: octane value 93.2 (desulfurization preceding 94.0), 20 ℃ of density are 721.4Kg/m
3(before the desulfurization is 721.9Kg/m
3), lead content 0.001g/L (0.001g/L before the desulfurization), 10% vaporization temperature is 61.4 ℃ (preceding 60 ℃ of desulfurization); 50% vaporization temperature is 80.7 ℃ (preceding 80.5 ℃ of desulfurization), and 90% vaporization temperature is 161.9 ℃ (preceding 161.5 ℃ of desulfurization), 180 ℃ of final boiling point (preceding 180 ℃ of desulfurization); Residual quantity 1.0% (desulfurization preceding 1.0%), existent gum 3mg/100mL (3mg/100mL before the desulfurization), sulphur content 34ppm (1300ppm before the desulfurization); 50 ℃, the 3h copper corrosion is 1a level (being the 1a level before the desulfurization), does not have water soluble acid or alkali (alkali-free before the desulfurization); Benzene content 2.2% (desulfurization preceding 2.5%), aromaticity content 15.1% (desulfurization preceding 17.6%), olefin(e) centent 33.7% (desulfurization preceding 38.2%).
Claims (7)
1. the preparation method of the polyimide of a phosphate side chain-containing, the averagemolecular wt amount of the polyimide of said phosphate side chain-containing is 10000～100000, structural formula is formula 1 or formula 2:
Wherein, R
1For
R
3＝(CH
2)
n，n＝0～12；
It is characterized in that comprising the steps:
(1) under nitrogen protection, after compound a dissolves, carried out polycondensation 3～20 hours with dianhydride in organic solvent A, add YLENE then, be warmed up to 100～200 ℃ of dehydration reactions 3～24 hours, remove organic solvent A after, obtain compound b;
Said organic solvent A is N, a kind of in dinethylformamide, N-Methyl pyrrolidone, DMAC N,N or the meta-cresol;
The structural formula of said compound a is a kind of in formula 3, formula 4, formula 5, formula 6 or the formula 7;
The structural formula of said compound b is formula 8 or formula 9;
Wherein, in formula 8 and the formula 9, R
1, R
2Implication cotype 1 and formula 2 in the implication of relevant parameter;
(2) this step is a kind of in following (2-1), (2-2) step:
(2-1) compound b is dissolved in the organic solvent B under nitrogen protection, and ice bath adds triethylamine, cuprous chloride, phosphorization reagent, and normal-temperature reaction 5～24 hours is removed organic solvent B, obtains compound c 1;
Said organic solvent B is one or more mixtures of chloroform, THF, dioxane or DMSO 99.8MIN.;
Said phosphorization reagent is diethyl chloro-phosphate, bromine diethyl phosphoric acid, iodine diethyl phosphoric acid or DFP;
The structural formula of said compound c 1 is formula 10-1 or formula 11-1;
Wherein, among formula 10-1 and the formula 11-1, R
1, R
2, R
3Implication cotype 1 and formula 2 in the implication of relevant parameter, and R
3Middle n=0 representes that promptly polymer side chains phosphate group, does not contain alkyl;
(2-2) earlier weak base, Verbindung are dissolved among the organic solvent C, then under 10～100 ℃, add compound b in 1～3 hour, continue reaction 5～20 hours, filtering-depositing is removed organic solvent C, separates to obtain compound d after purifying;
Said weak base is sodium hydrogencarbonate, yellow soda ash, saleratus or salt of wormwood;
The mixture of one or more that said organic solvent C is chloroform, THF, dioxane, methyl alcohol, ethanol, acetonitrile or acetone;
The structural formula of said compound d is formula 13 or formula 14;
The structural formula of said Verbindung is a formula 12;
Wherein, in the formula 12, n=1～12; In formula 13 and the formula 14, R
1, R
2, R
3Implication cotype 1 and formula 2 in the implication of relevant parameter, and R
3In n=1～12, i.e. expression contains the alkyl of 1～12 carbon atom;
Then compound d is dissolved in the organic solvent B, adds triethyl-phosphite,, remove organic solvent B, separate and purify, obtain compound c 2 50～200 ℃ of TR internal reactions 1～5 day; The structural formula of said compound c 2 is formula 10-2 or formula 11-2;
Wherein, among formula 10-2 and the formula 11-2, R
1, R
2, R
3Implication cotype 1 and formula 2 in the implication of relevant parameter, and R
3Middle n=1～12, i.e. expression contains the alkyl of 1～12 carbon atom;
(3) compound c 1 or c2 are dissolved in the organic solvent B, add XSi (Me)
3Hydrolysis, wherein X is Br, Cl or I, reaction finishes the back and separates purification, obtains the polyimide of phosphate side chain-containing.
2. the preparation method of the polyimide of phosphate side chain-containing according to claim 1; It is characterized in that: in the step 1; Structural formula is that the preparation method of the compound a of formula 3 is: under nitrogen protection and 100 ℃～150 ℃ temperature; PARA HYDROXY BENZALDEHYDE, aniline and aniline hydrochloride mix and reacted 1～5 hour, and wherein, PARA HYDROXY BENZALDEHYDE: aniline: the mol ratio of aniline hydrochloride is 1: (2～10): (0.1～1); Cooling also separates and purifies, and obtains the compound a of formula 3.
3. the preparation method of the polyimide of phosphate side chain-containing according to claim 1 is characterized in that: in the step 1, the structural formula of said dianhydride is a kind of in the formula 15～20:
4. the preparation method of the polyimide of phosphate side chain-containing according to claim 1, it is characterized in that: step 1, the mol ratio of compound a and dianhydride are 1: (1～1.6).
5. the preparation method of the polyimide of phosphate side chain-containing according to claim 1, it is characterized in that: among the step 2-1, compound b: triethylamine: cuprous chloride: the mol ratio of phosphorization reagent is 1: (3～10): (0.1～1): (1～10).
6. the preparation method of the polyimide of phosphate side chain-containing according to claim 1, it is characterized in that: among the step 2-2, compound b: Verbindung: weakly alkaline mol ratio is 1: (1～10): (1～5); Compound d: the mol ratio of triethyl-phosphite is 1: (1～10).
7. the preparation method of the polyimide of phosphate side chain-containing according to claim 1 is characterized in that: in the step 3, and compound c 1 or c2: XSi (Me)
3Mol ratio be 1: (1～5).
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