CN100389142C - Polyimide containing side chain of phosphate and its prepn process and film - Google Patents
Polyimide containing side chain of phosphate and its prepn process and film Download PDFInfo
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- CN100389142C CN100389142C CNB2006100349959A CN200610034995A CN100389142C CN 100389142 C CN100389142 C CN 100389142C CN B2006100349959 A CNB2006100349959 A CN B2006100349959A CN 200610034995 A CN200610034995 A CN 200610034995A CN 100389142 C CN100389142 C CN 100389142C
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Abstract
The present invention relates to a formula (1) which represents polyimide containing phosphonic acid side chains. The average molecular weight of the polyimide containing phosphonic acid side chain is 10000 to 100000, wherein R1 represents alkyl with 1 to 5 carbon atoms or halogenating alkyl; R2 represents a right formula (2). The present invention also relates to a preparation method of the polyimide and a film made of polyimide materials. The polyimide of the present invention is obtained by that after dinitrophenol which is replaced by hydroxy is reduced, phosphorylated and hydrolyzed, aryldiamine monomer containing phosphoryl side groups is synthesized and then is in polycondensation reaction with maleic anhydride. The polyimide containing phosphonic acid side chains of the present invention is made into a flat plate film by a phase conversion method, and is used for the desulfurizing process of gasoline with high sour contents, such as FCC gasoline, catalytic cracking gasoline, straight-run gasoline, coker gasoline, cracking gasoline, hot cracking gasoline or mixed gasoline. The sulfur remaining quantity in the gasoline is about 30 ppm after desulfurized, and meanwhile, an arene content reduces 5% to 10%, and octane number is unchanged.
Description
Technical field
The present invention relates to a kind of polyimide, relate to a kind of polyimide of phosphate side chain-containing specifically, and relate to the preparation method of this polyimide and the film made from this kind polyimide material.
Background technology
The oxysulfide that gasoline combustion gave off (SOx), carbon monoxide (CO), oxynitride (NOx) are the principal pollutant sources of urban air environment, the oxysulfide that produces when particularly organic compounds containing sulfur in the gasoline such as mercaptan, thiophene and thiophene derivant etc. burn, can form acid rain, the severe contamination air ambient.For reducing the environmental pollution that discharge of poisonous waste brings, countries in the world have come into effect strict control sulphur standard to fuel oil for vehicles.European Union implemented Europe-IV emission standard in 2005, required content of sulfur in gasoline less than 50ppm, will implement Europe-V discharging, and promptly require vehicle gasoline and sulfur content in vehicle gasoline is dropped to below the 10ppm in 2010.The present content of sulfur in gasoline standard of the U.S. is for being not more than 60ppm, and sulphur content will be reduced to 15ppm in 2006, and Japan requires motor spirit content to be not more than 50ppm.In China, in order to improve the low sulfuration of fuel oil quality realization, continue to increase technological development and oil refining transformation input, the fuel oil for vehicles sulphur content reduces greatly, but vehicle gasoline and sulfur content in vehicle gasoline still has big gap compared with developed countries.By 2006, it is suitable with " world's fuel oil standard " II, III class gasoline index that China Petrochemical Industry system supply Beijing, Shanghai, Guangzhou three metropolitan content of sulfur in gasoline require respectively.For market provides the gasoline products of cleaning is the common issue that is faced both at home and abroad.
Both at home and abroad the gasoline desulfur mode of research and development has a lot, and that uses always has Doctor sweetening (doctor's deodorization method), mantoquita method for refining, the desulfurization of high temperature carclazyte, a catalytic desulfurhydrogenation etc.And present industrial widespread use mainly contain oxidation sweetening, biological desulphurization, adsorption desulfurize and hydrodesulfurization etc.Though oxidation sweetening method industrialization on chemical field already, but because effective mixed problem of aqueous phase oxidation agent and sulfocompound causes desulfurization degree (about 30%) on the low side, and wait some technical problems to fail to be well solved to the reprocessing cycle and the removing of sulfide oxidation of catalyzer; Though microbial desulfurization method reaction conditions gentleness, equipment is simple, catalytic efficiency is high and the height advantages such as effect specificity, its broad spectrum is relatively poor, the speed of desulphurization reaction and the biological catalyst stability in operational process is lower; Though the caustic wash desulfuration method can be sloughed the most of sulphur in the FCC gasoline, further deep desulfuration difficulty, and make cost be difficult to reduce because of the recovery technology that consumes or increase alkali; Hydrodesulfurization is one of gasoline desulfur method the most widely at present, though can obtain the gasoline that any sulphur content requires in principle, has reduced the octane value of gasoline simultaneously, and the desulfurization condition High Temperature High Pressure, and cost is higher.Although also developed at present many other sulfur methods, all in all, there is not complete ideal sulfur method so far, each method all has relative merits, needs to continue efficient, the economic sulfur method of exploitation.
Membrane separating method is the hi-tech of an emerging multiple subject crossing, the embrane method desulfurization of foreign latest development demonstrates than remarkable advantages, mainly show following some: (1) equipment is simple, floor space is little, (2) simple to operate, separation efficiency is high, maintenance is simple, can produce for a long time, (3) service temperature low (about 90-120 ℃), energy consumption is low, (4) sepn process does not have chemical reaction, do not produce hydrogen sulfide, (5) remove aromatic hydrocarbons, and (6) loss of octane number is less.U.S. Pat 6,736,961 have 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 film opposite side is 0KPa, finds that the film that (1) contains solubilising glycerine has higher sulphur perviousness; When (2) the film opposite side had liquid to sweep stream, desulfuration efficiency was better; (3) pressure difference at reduction Polysulfone SEP-0013 film two ends can increase the sulphur transmitance; (4) with diesel oil do the film opposite side sweep the flow liquid body time, sweetening effectiveness is better.U.S. Pat 6,702,945 reported the Nafion.RTM type ionic membrane that contains perfluorinated sulfonic acid or derivatives thereof group can be from FCC and petroleum naphtha effective separate sulphur compound, contain exchangable ion and carry out the Nafion.RTM film that base material treatment crosses and higher sweetening effectiveness is arranged than general Nafion.RTM film, adopting Nafion.RTM film that trolamine handled is after FCC gasoline that the methyl alcohol of 950ppm dilutes permeates gasificating desulfurization to sulphur content, sulphur content in the film opposite side penetrating fluid has reached 5000ppm, yet this film must contain the exchange ion of certain kind, as H
+, Na+ etc., Cu
+, Ag
+Plasma is inapplicable.U.S. Pat 6,896,796 have reported the film-forming process of several polyimide and petroleum naphtha have been permeated the gasificating desulfurization process.Matrimid 5218 polyimide are according to USP 5,264, and 166 methods that provided make that the enrichment factor to thiophene is 1.68 behind the film; The method that Lenzing P84 polyimide is provided according to USP 09/126,261 makes that the enrichment factor to thiophene and mercaptan is respectively 4.69 and 3.45 behind the film; After Matrimid 5218 polyimide and nylon base are made composite membrane, the enrichment factor of thiophene and mercaptan is respectively 2.68 and 1.41.But octane value does not remain unchanged after having these polyimide of data representation can keep desulfurizing oil.Chinese patent CN 1686600 has reported a kind of preparation method who permeates the gasification gasoline desulfur blend composite film, this film basic composition is 30%～70% dimethyl silicone rubber and 70%～30% trifluoro propyl silicon rubber, after being used for gasoline infiltration gasificating desulfurization, the permeation flux of film is 600g/ (m
2.h
-1), be 2.65 to the enrichment factor of thiophene.But wherein do not relate to the variation of aromaticity content and octane value behind the gasoline desulfur.But octane value does not remain unchanged after having the data representation desulfurizing oil yet.
Summary of the invention
The objective of the invention is to develop a kind of desulfurization degree height to gasoline, and can keep the constant mould material of its octane value, another purpose provides out this preparation method of film material; Further purpose provides the film that this material is made.
The dinitrophenol reduction of the present invention by hydroxyl is replaced, synthesize the aryl diamine monomer that contains the phosphinylidyne side group after phosphorylation and the hydrolysis, carry out the polyimide that solubility phosphoric acid side group is prepared in polycondensation with dianhydride again, film with this polyimide can make high sour gasoline slough most sulfide, and octane value remains unchanged, thereby realized purpose of the present invention.
The polyimide of phosphate side chain-containing of the present invention, its structure is represented by formula (1):
Formula (1)
Its average molecular mass is 10000～100000, R
1Expression contains the alkyl or the halo alkyl of 1～5 carbon atom,
Group is represented
R
2Expression
In the compound of formula (1),
On other position of the phenyl ring of group hydrocarbyl substituent can also be arranged.
The preparation method of the polyimide of phosphate side chain-containing of the present invention is characterized in that comprising the steps:
A kind of in the dinitrophenol that the hydroxyl of a. following formula (2)～formula (5) expression replaces
Formula (2) formula (3) formula (4) formula (5)
React salify with alkali down in normal temperature, add organic solvent then and reflux, the compound that adds formula (6) again separates purification 100～120 ℃ of reactions down, obtains the compound of formula (7),
Formula (6) formula (7)
R in its Chinese style (6) and the formula (7)
1Implication cotype (1) described, group in the formula (7)
In substituent position cotype (1) described;
B. the compound of formula (7) reacts down at 60～90 ℃ with reductive agent under protection of nitrogen gas, separates the compound that obtains formula (8) after purifying, wherein R
1Implication cotype (1) described ,-NH
2In the dinitrophenol that the described hydroxyl of the position of group and step a replaces-the NO position is identical;
Formula (8)
C. behind the compound dissolution of formula (8) under strong acidic condition back hydrolysis, separate to purify, obtain the compound of formula (9), wherein R
1Implication cotype (1) described ,-NH
2In the dinitrophenol that the described hydroxyl of the position of group and step a replaces-the NO position is identical;
Formula (9)
D. the compound of formula (9) and dianhydride are at middle N, carry out polycondensation under the normal temperature of dissolving back in N '-dimethyl formamide, remove the compound that obtains formula (1) after desolvating, described dianhydride is represented with formula (10), formula (11), formula (12), formula (13) or formula (14).
Formula (10) formula (11) formula (12)
Formula (13) formula (14)
Alkali described in the step a can be sodium hydroxide or potassium hydroxide etc., described organic solvent can be a toluene, dimethylbenzene, the mixture of one or more in the benzene, on other position on the phenyl ring of the dinitrophenol that described hydroxyl replaces hydrocarbyl substituent can also be arranged, for example 2, the 4-dinitrophenol, 2, the 5-dinitrophenol, 2, the 6-dinitrophenol, 3,5-dinitrophenol or 3 methyl-2,6 dinitrophenols etc., the compound of described formula (6) can be the brooethyl diethyl phosphonate, the phosphonic acid ethyl bromide diethyl ester, difluoro brooethyl diethyl phosphonate, 1,1-two fluoro-21-phosphonic acid ethyl bromide diethyl esters or trisbromomethyl diethyl phosphonate etc., group in the formula (7)
In other position of phenyl ring on hydrocarbyl substituent is arranged, the dinitrophenol that hydroxyl replaces and the time of alkali reaction can be 0.5～1h, reflux time can be 2～5h, with the reaction times of the compound of formula (6) can be 20～60h, described separation can be adopted usual method such as solvent extraction, and described purification can be adopted for example recrystallization of conventional method.
The described reductive agent of step b can be Pd/C and hydrazine hydrate, transition metal and hydrazine hydrate, LiAlH
4, Fe and HCl, Sn and HCl or Zn and HCl etc., described transition metal can be Pd etc., the reduction reaction time can be 20～50h, and described separation can be adopted usual method such as centrifugation, and described purification can be adopted for example recrystallization of conventional method.
Strong acid described in the step c can be sulfuric acid, hydrochloric acid or nitric acid etc., and hydrolysis time can be 2～5h, and described separation can adopt usual method such as rotating centrifugal to separate, and described purification can be adopted for example recrystallization of conventional method.
The compound of steps d Chinese style (9) and the mol ratio of dianhydride are 1: 1～1.6.
The film that the polyimide of phosphate side chain-containing of the present invention is made, be by phase inversion method the compound of above-mentioned formula (1) to be made flat sheet membrane to obtain, concrete preparation method makes film-casting liquid earlier in boiling point is 50～350 ℃ solvent, carry out solvent, the exchange of non-solvent mass transfer with surrounding environment, 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 the loose porous asymmetric flat sheet membrane of top layer densification, bottom.The film that obtains is used for the sweetening process of high sour gasoline such as FCC gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pyrolysis gasoline or its mixing oil, through after the desulfurization, the residual amount of sulphur in the gasoline is about 30ppm, make the aromatic hydrocarbons amount descend 5%～10% simultaneously, octane value then remains unchanged.
Embodiment
Embodiment 1:
3.42g sodium hydroxide is dissolved in the 15mL distilled water, add 50mL dimethyl formamide and 13.791g 2 then, 2, 4-dinitrophenol (being the compound of formula (2)), stir under the room temperature and add 50mL toluene after 40 minutes, reflux was divided water 3 hours, be cooled to that to add 13.32mL brooethyl diethyl phosphite after the room temperature in reactant (be the compound of formula (6), wherein R
1For-CH
3), be warming up to 110 ℃ of reactions 48 hours again.Reactant obtains 2 behind solvent extraction, evaporation drying, recrystallization, 4-dinitro methyl diethyl phosphite (is the compound of formula (7), wherein R
1For-CH
2).
Adding 60mL ethanol and 20mL water make its dissolving in past 12g 2, the 4 dinitrobenzene methyl diethyl phosphites, add the 1.11gPd/C mixture again, N
2Drip the 27mL hydrazine hydrate after being heated to 70 ℃ under the protection, continue reaction 24 hours.Centrifugal reactant takes out precipitation, and oven dry back recrystallization obtains 2, and 4-diamines methyl diethyl phosphite (is the compound of formula (8), wherein R
1=-CH
2).
With 2,4-diamines phenmethyl diethyl phosphite dissolving back adds an amount of concentrated hydrochloric acid, and back hydrolysis 4 hours obtains 2 behind rotary evaporation, the recrystallization, and 4-diamines methyl phosphite hydrochlorate (is the compound of formula (9), wherein R
1=-CH
2).
With 2 of equimolar amount, 4-diamines phenmethyl phosphite hydrochlorate and 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (being the compound of formula (10)) is dissolved in N, carry out the cryogenic fluid polycondensation in N '-dimethyl formamide, obtain polyamic acid solution, DMF is removed in underpressure distillation after high temperature dehydration, obtain the compound of formula (1), average molecular mass is 45000, IR:1779,1725cm
-1About C=0 stretching vibration peak in the imide bond has appearred, 1370cm
-1About C-N stretching vibration peak in the imide bond has appearred.
The polyimide that obtains is dissolved in N-Methyl pyrrolidone is mixed with massfraction 10% casting film solution, and fully stirred 24 hours, treat that solute all dissolves after-filtration and removes impurity, leave standstill one day to remove the bubble in the casting film solution fully with magnetic stirring apparatus.Then film-casting liquid is poured on the glass plate, smear film-casting liquid with scraper uniformly, then sheet glass is placed 80 ℃ forced convection oven 5 hours, take out cooling after the solvent evaporates, be dipped in the water film is taken off, dry back obtains polyimide film as for Air drying in the vacuum chamber 24 hours under the room temperature.The film that makes is carried out the pervaporation desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are as follows: 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), 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 (a 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:
2.277g sodium hydroxide is dissolved in the 10mL distilled water, add 40mL dimethyl formamide and 9.194g 2 then, 5-dinitrophenol(DNP) (being the compound of formula (3)), stir under the room temperature and add 50mL toluene after 30 minutes, reflux was divided water 2 hours, be cooled to that to add 9.42mL 2-bromotrifluoromethane diethyl phosphite after the room temperature in reactant (be the compound of formula (6), wherein R
1=-(CH
2)
2), be warming up to 100 ℃ of reactions 20 hours again.Reactant obtains 2 behind solvent extraction, evaporation drying, recrystallization, 5-dinitrobenzene ethyl phosphorous acid diethyl ester (is the compound of formula (7), wherein R
1For-(CH
2)
2).
Toward 10g2, adding 60ml ethanol and 20ml water make its dissolving in the 5-dinitrobenzene ethyl phosphorous acid diethyl ester, add 1.2gFe, N again
2Drip 40mLHCl after being heated to 60 ℃ under the protection, continue reaction 20 hours.Centrifugal reactant takes out precipitation, and oven dry back recrystallization obtains 2, and 5-diamines styroyl diethyl phosphite (is the compound of formula (8), wherein R
1=-(CH
2)
2).
With 2,5-diamines styroyl diethyl phosphite dissolving back adds an amount of sulfuric acid, and back hydrolysis 5 hours obtains 2 behind rotary evaporation, the recrystallization, and 5-diamines styroyl phosphite hydrochlorate (is the compound of formula (9), wherein R
1=-(CH
2)
2).
With 2,5-diamines styroyl phosphite hydrochlorate and 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (being the compound of formula (10)) was dissolved in and carries out the cryogenic fluid polycondensation among the DMF in 1: 1.2 in molar ratio, obtain polyamic acid solution, high temperature dehydration imidization behind the DMF is removed in underpressure distillation, obtains the compound of formula (1), and average molecular mass is 17800, IR:1779,1725cm
-1About C=0 stretching vibration peak in the imide bond has appearred, 1370cm
-1About C-N stretching vibration peak in the imide bond has appearred.
Above-mentioned polyimide is dissolved in N-Methyl pyrrolidone makes massfraction 10% casting film solution, and fully stirred 24 hours, treat that solute all dissolves after-filtration and removes impurity, leave standstill one day to remove the bubble in the casting film solution fully with magnetic stirring apparatus.Then film-casting liquid is poured on the glass plate, smear film-casting liquid with scraper uniformly, then sheet glass is placed 80 ℃ forced convection oven 5 hours, take out cooling after the solvent evaporates, be dipped in the water film is taken off, dry back obtains polyimide film as for Air drying in the vacuum chamber 24 hours under the room temperature.The polyimide film that makes is carried out the pervaporation desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are as follows: octane value 93.1 (desulfurization preceding 94.0), 20 ℃ of density are 721.8Kg/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 61.5 ℃ (preceding 60 ℃ of desulfurization), 50% vaporization temperature is 80.5 ℃ (preceding 80.5 ℃ of desulfurization), 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 50ppm (1300ppm before the desulfurization), 50 ℃, the 3h copper corrosion is 1a level (a 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 14.3% (desulfurization preceding 17.6%), olefin(e) centent 33.2% (desulfurization preceding 38.2%).
Embodiment 3:
2.4g potassium hydroxide is dissolved in the 10mL distilled water, add 40mL dimethyl formamide and 9.217g 4-methyl-3 then, the 5-dinitrophenol(DNP), the mixed solvent that adds 60mL toluene and benzene under the room temperature behind the stirring 1h, reflux was divided water 5 hours, be cooled to that to add 9.44mL 2-bromotrifluoromethane diethyl phosphite after the room temperature in reactant (be the compound of formula (6), wherein R
1=-(CH
2)
2), be warming up to 120 ℃ of reactions 60 hours again.Reactant obtains purified 4-methyl-3 behind solvent extraction, evaporation drying, recrystallization, 5-dinitrobenzene ethyl phosphorous acid diethyl ester (is the compound of formula (7), wherein R
1For-(CH
2)
2).
Toward 8g4-methyl-3, adding 50mL ethanol and 16mL water make its dissolving in the 5-dinitrobenzene ethyl phosphorous acid diethyl ester, add 0.812g Pd/C mixture again, N
2Drip the 18ml hydrazine hydrate after being heated to 90 ℃ under the protection, continue reaction 50 hours.Centrifugal reactant takes out precipitation, and oven dry back recrystallization obtains purified 4-methyl-3, and 5-diamines styroyl diethyl phosphite (is the compound of formula (8), wherein R
1=-(CH
2)
2).
With 2,5-diamines styroyl diethyl phosphite dissolving back adds an amount of concentrated hydrochloric acid, and back hydrolysis 2 hours obtains 4-methyl-3 behind rotary evaporation, the recrystallization, and 5-diamines styroyl phosphite hydrochlorate (is the compound of formula (9), wherein R
1=-(CH
2)
2).
4-methyl-3 with equimolar amount, 5-diamines styroyl phosphite hydrochlorate and pyromellitic dianhydride (being the compound of formula (11)) are dissolved in and carry out the cryogenic fluid polycondensation among the DMF, obtain polyamic acid solution, high temperature dehydration imidization behind the DMF is removed in underpressure distillation, obtain the compound of formula (1), average molecular mass is 59210, IR:1779,1725cm
-1About C=0 stretching vibration peak in the imide bond has appearred, 1370cm
-1About C-N stretching vibration peak in the imide bond has appearred.
Above-mentioned polyimide is dissolved in N-Methyl pyrrolidone makes massfraction 10% casting film solution, and fully stirred 24 hours, treat that solute all dissolves after-filtration and removes impurity, leave standstill one day to remove the bubble in the casting film solution fully with magnetic stirring apparatus.Then film-casting liquid is poured on the glass plate, smear film-casting liquid with scraper uniformly, then sheet glass is placed 80 ℃ forced convection oven 5 hours, take out cooling after the solvent evaporates, be dipped in the water film is taken off, dry back obtains polyimide film as for Air drying in the vacuum chamber 24 hours under the room temperature.The polyimide film that makes is carried out the pervaporation desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are as follows: octane value 93.0 (desulfurization preceding 94.0), 20 ℃ of density are 721.5Kg/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), 90% vaporization temperature is 161.1 ℃ (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 36ppm (1300ppm before the desulfurization), 50 ℃, the 3h copper corrosion is 1a level (a 1a level before the desulfurization), does not have water soluble acid or alkali (alkali-free before the desulfurization), benzene content 1.9% (desulfurization preceding 2.5%), aromaticity content 13.9% (desulfurization preceding 17.6%), olefin(e) centent 35.2% (desulfurization preceding 38.2%).
Embodiment 4:
1.242g sodium hydroxide is dissolved in the 5ml distilled water, add 20mL dimethyl formamide and 3.678g 2 then, 5-dinitrophenol(DNP) (being the compound of formula (3)), stir under the room temperature and add 50mL toluene after 40 minutes, reflux was divided water 3 hours, be cooled to that to add 3.768mL 2-bromotrifluoromethane diethyl phosphite after the room temperature in reactant (be the compound of formula (6), wherein R
1=-(CH
2)
2), be warming up to 110 ℃ of reactions 48 hours again.It is purified 2 that reactant obtains behind solvent extraction, evaporation drying, recrystallization, and 5-dinitrobenzene ethyl phosphorous acid diethyl ester (is the compound of formula (7), wherein R
1For-(CH
2)
2).
Toward 8g 2, adding 50ml ethanol and 16ml water make its dissolving in the 5-dinitrobenzene ethyl phosphorous acid diethyl ester, add the 0.825gPd/C mixture again, N
2Drip the 18ml hydrazine hydrate after being heated to 70 ℃ under the atmosphere, continue reaction 24 hours.Centrifugal reactant takes out precipitation, and oven dry back recrystallization obtains purifiedly 2, and 5-diamines styroyl diethyl phosphite (is the compound of formula (8), wherein R
1=-(CH
2)
2).
With 2,5-diamines styroyl diethyl phosphite dissolving back adds an amount of nitric acid, and back hydrolysis 4 hours obtains 2 behind rotary evaporation, the recrystallization, and 5-diamines styroyl phosphite hydrochlorate (is the compound of formula (9), wherein R
1=-(CH
2)
2).
With 2,5-diamines styroyl phosphite hydrochlorate and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (being the compound of formula (10)) was dissolved in and carries out the cryogenic fluid polycondensation among the DMF in 1: 1.5 in molar ratio, obtain polyamic acid solution, high temperature dehydration imidization behind the DMF is removed in underpressure distillation, obtains the compound of formula (1), and average molecular mass is 86100, IR:1779,1725cm
-1About C=0 stretching vibration peak in the imide bond has appearred, 1370cm
-1About C-N stretching vibration peak in the imide bond has appearred.
Above-mentioned polyimide is dissolved in N-Methyl pyrrolidone makes massfraction 10% casting film solution, and fully stirred 24 hours, treat that solute all dissolves after-filtration and removes impurity, leave standstill one day to remove the bubble in the casting film solution fully with magnetic stirring apparatus.Then film-casting liquid is poured on the glass plate, smear film-casting liquid with scraper uniformly, then sheet glass is placed 80 ℃ forced convection oven 5 hours, take out cooling after the solvent evaporates, be dipped in the water film is taken off, dry back obtains polyimide film as for Air drying in the vacuum chamber 24 hours under the room temperature.The polyimide film that makes is carried out the pervaporation desulfurization to FCC gasoline, the gasoline sampling analysis after the desulfurization, data are as follows: 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 61.2 ℃ (preceding 60 ℃ of desulfurization), 50% vaporization temperature is 80.5 ℃ (preceding 80.5 ℃ of desulfurization), 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 50ppm (1300ppm before the desulfurization), 50 ℃, the 3h copper corrosion is 1a level (a 1a level before the desulfurization), does not have water soluble acid or alkali (alkali-free before the desulfurization), benzene content 2.3% (desulfurization preceding 2.5%), aromaticity content 14.8% (desulfurization preceding 17.6%), olefin(e) centent 36.1% (desulfurization preceding 38.2%).
Embodiment 5 (Comparative Examples):
With the mphenylenediamine and 3 of equimolar amount, 3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride is dissolved in and carries out the cryogenic fluid polycondensation among the DMF, obtains polyamic acid solution, and DMF is removed in underpressure distillation after the high-temperature sub amination obtains corresponding polyimide.
Above-mentioned polyimide is dissolved in N-Methyl pyrrolidone makes massfraction 10% casting film solution, and fully stirred 24 hours, treat that solute all dissolves after-filtration and removes impurity, leave standstill one day to remove the bubble in the casting film solution fully with magnetic stirring apparatus.Then film-casting liquid is poured on the glass plate, smear film-casting liquid with scraper uniformly, then sheet glass is placed 80 ℃ forced convection oven 5 hours, take out cooling after the solvent evaporates, be dipped in the water film is taken off, dry back obtains polyimide film as for Air drying in the vacuum chamber 24 hours under the room temperature.
The polyimide film that makes is carried out the pervaporation desulfurization to FCC gasoline.70 ℃ of feed gasoline temperature, film left side pressure 600KPa, right atrial pressure 5KPa.Gasoline sampling analysis after the desulfurization, data are as follows: octane value 92.0 (desulfurization preceding 94.0), 20 ℃ of density are 721.8kg/m
3(before the desulfurization is 721.9kg/m
3), lead content 0.01g/L (0.001g/L before the desulfurization), 10% vaporization temperature is 60 ℃ (preceding 60 ℃ of desulfurization), 50% vaporization temperature is 80.5 ℃ (preceding 80.5 ℃ of desulfurization), 90% vaporization temperature is 161.5 ℃ (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 1100ppm (1300ppm before the desulfurization), 50 ℃, the 3h copper corrosion is 1a level (a 1a level before the desulfurization), does not have water soluble acid or alkali (alkali-free before the desulfurization), benzene content 2.4% (desulfurization preceding 2.5%), aromaticity content 17.3% (desulfurization preceding 17.6%), olefin(e) centent 37.9% (desulfurization preceding 38.2%).
Claims (10)
1. the compound of following formula (1):
Formula (1)
Its average molecular mass is 10000～100000, R
1Expression contains the alkyl or the halo alkyl of 1～5 carbon atom,
Group is represented
Or
Or
Or
R
2Expression
Or
Or
Or
Or
2. compound according to claim 1 is characterized in that it
On other position of the phenyl ring of group hydrocarbyl substituent is arranged.
3. the preparation method of claim 1 compound is characterized in that comprising the steps:
A kind of in the dinitrophenol that the hydroxyl of a. following formula (2)～formula (5) expression replaces
Formula (2) formula (3) formula (4) formula (5)
React salify with alkali down in normal temperature, add organic solvent then and reflux, the compound that adds formula (6) again separates purification 100～120 ℃ of reactions down, obtains the compound of formula (7)
Formula (6) formula (7)
R in its Chinese style (6) and the formula (7)
1Implication cotype (1) described, group in the formula (7)
In substituent position cotype (1) described;
B. the compound of formula (7) reacts down at 60～90 ℃ with reductive agent under protection of nitrogen gas, separates the compound that obtains formula (8) after purifying
Formula (8)
R wherein
1Implication cotype (1) described ,-NH
2In the dinitrophenol that the described hydroxyl of the position of group and step a replaces-the NO position is identical;
C. behind the compound dissolution of formula (8) under strong acidic condition back hydrolysis, separate to purify, obtain the compound of formula (9)
Formula (9)
R wherein
1Implication cotype (1) described ,-NH
2In the dinitrophenol that the described hydroxyl of the position of group and step a replaces-the NO position is identical;
D. the compound of formula (9) and dianhydride carry out polycondensation under the normal temperature of dissolving back at N in N '-dimethyl formamide, remove the compound that obtains formula (1) after desolvating, and described dianhydride is represented with formula (10), formula (11), formula (12), formula (13) or formula (14)
Formula (10) formula (11) formula (12)
Formula (13) formula (14)
4. according to the preparation method of the compound of claim 3, it is characterized in that hydrocarbyl substituent being arranged, group in the formula (7) on other position on the phenyl ring of the dinitrophenol that the hydroxyl described in the step a replaces
In other position of phenyl ring on hydrocarbyl substituent is arranged.
5. according to the preparation method of the compound of claim 3 or 4, it is characterized in that the alkali described in the step a is sodium hydroxide or potassium hydroxide, described organic solvent is a toluene, dimethylbenzene, the mixture of one or more in the benzene, the compound of described formula (6) is the brooethyl diethyl phosphonate, the phosphonic acid ethyl bromide diethyl ester, difluoro brooethyl diethyl phosphonate, 1,1-two fluoro-, 21 phosphonic acid ethyl bromide diethyl esters or trisbromomethyl diethyl phosphonate, the dinitrophenol that hydroxyl replaces and the time of alkali reaction are 0.5～1h, reflux time is 2～5h, with the reaction times of the compound of formula (6) be 20～60h, described separation is solvent extraction, and described purification is a recrystallization.
6. according to the preparation method of the compound of claim 3 or 4, it is characterized in that the described reductive agent of step b is Pd/C and hydrazine hydrate, transition metal and hydrazine hydrate, LiAlH
4, Fe and HCl, Sn and HCl or Zn and HCl, the reduction reaction time is 20～50h, described separation is centrifugation, described purification is a recrystallization.
7. according to the preparation method of the compound of claim 6, it is characterized in that described transition metal is Pd.
8. according to the preparation method of the compound of claim 3 or 4, it is characterized in that the strong acid described in the step c is sulfuric acid, hydrochloric acid or nitric acid, hydrolysis time is 2～5h, and described separation is that rotating centrifugal separates, and described purification is a recrystallization.
9. according to the preparation method of the compound of claim 3 or 4, it is characterized in that the compound of steps d Chinese style (9) and the mol ratio of dianhydride are 1: 1～1.6.
10. the film made of claim 1 or 2 compounds is made flat sheet membrane by phase inversion method with claim 1 or 2 described compounds and is obtained.
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| CN1974729B (en) * | 2006-11-23 | 2010-12-08 | 中国石油化工股份有限公司 | Prepn process of membrane material for desulfurizing FCC gasoline |
| CN101817926B (en) * | 2010-04-07 | 2012-03-07 | 中科院广州化学有限公司 | Phosphate side chain-containing polyimide for gasoline desulphurization and preparation method thereof |
| CN102108113B (en) * | 2011-01-20 | 2012-08-22 | 中科院广州化学有限公司 | Polyimide with phosphoric acid side chain-containing long chain and preparation method and application thereof |
| CN104497310B (en) * | 2014-12-16 | 2017-03-08 | 武汉理工大学 | A kind of phosphonic-acid grafted polyimides high temperature proton exchange film and preparation method thereof |
| CN105111489B (en) * | 2015-08-31 | 2018-06-29 | 重庆大学 | In the method that Kapton surface introduces phosphorus-containing groups |
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| CN1490345A (en) * | 2002-07-06 | 2004-04-21 | 三星Sdi株式会社 | Proton conductive polymer and producing method thereof, membrane therewith and fuel cell with the membrane |
| CN1603354A (en) * | 2004-11-05 | 2005-04-06 | 中国科学院长春应用化学研究所 | Process for synthesis of sulfonated polyimide proton transmission film |
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| CN1603354A (en) * | 2004-11-05 | 2005-04-06 | 中国科学院长春应用化学研究所 | Process for synthesis of sulfonated polyimide proton transmission film |
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