CN101121101B - Method for preparing polyurethane-imide permeable vaporizing aromatic/alkane separating membrane - Google Patents
Method for preparing polyurethane-imide permeable vaporizing aromatic/alkane separating membrane Download PDFInfo
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Abstract
A preparation method of a polyurethane-imide infiltrated and vaporized aromatic hydrocarbon and alkane separation membrane belongs to the infiltrated and vaporized membrane separation technical field.The factors of the prior polyurethanes membrane separation is low, and a plurality of the prior polyurethanes membrane separations need a test of an infiltrated and vaporized separation performance at high temperature. The present invention includes firstly a prepolymer synthesis of polyurethane and imide is that under the conditions of a nitrogen protection, a mechanical mixing and a condensation circumfluence, a terminated prepolymer is obtained by a reaction of poly (ethylene adipate) glycol diol and diisocyanate, and pyromellitic dianhydride is added for a chain extension to obtain the polyurethane-imide prepolymer solution; secondly the preparation of a polyurethane-imide membrane is that the solution casts to form the membrane and an impregnant is volatilized under an infrared light, and the preparation of membrane can be finished after a heat treatment of 150 DEG C for 1.5 to 2 hours. The material synthesis and the membrane-preparation process of the present invention are simple, and the prepared membrane has a good thermal and chemical stability, and the prepared membrane can separate an aromatic hydrocarbon and alkane mixture under a proper temperature condition with a good separation effect as well as with a considerable practical value.
Description
Technical field:
The present invention relates to a kind of preparation method who can be used for the polyurethane-imide film of infiltration evaporation aromatic hydrocarbons/alkane separation, belong to the infiltrating and vaporizing membrane separation technology field.
Background technology:
The petrochemical industry that is separated in of aromatic hydrocarbons/paraffins mixture has great importance.Especially in the last few years, reinforcement along with people's environmental protection consciousness, countries in the world formulation standard is one after another come the content of aromatic hydrocarbons in the fuel limitation gasoline, to avoid causing the pollution of environment and the infringement of public health, require gasoline arene content≤35% among the world fuel oil standard III, China has also formulated new standard of fuel and has required arene content≤40% in the gasoline, and these standards and requirement will become strict more along with development of technology; From the Chemical Manufacture angle, in the cracking ethylene preparation process, the aromatic component in the naphtha not only can not be converted into alkene in addition, also can coking influence heat transmit, thereby has only the arene content that reduces in the naphtha, could guarantee higher production efficiency.In addition, the thick product of many important chemical is aromatic hydrocarbons/paraffins mixture, also need to reach product index by separation and purification, such as benzene and cyclohexane mixture system, the two boiling point only differs 0.6 ℃, and be can form azeotropic mixture at 50% o'clock in the mass content of benzene, so the separation of benzene/cyclohexane is a difficult problem in the chemical industry all the time.
At present, the method that industrial aromatic hydrocarbons/alkane separation is taked usually is azeotropic distillation, extracting rectifying and three kinds of technologies of liquid-liquid extraction, these traditional handicrafts all ubiquity energy consumption big, the cost of investment height, the flow process complexity must add shortcomings such as auxiliary reagent and input concentration be range limited.
Infiltration evaporation is to be used for a kind of new membrane technology that liquid (gas) body mixture separates.It is to utilize the different realization separating process of component by dense film dissolving and diffusion velocity, and its outstanding advantage is the task of separating that can be difficult to realize with low conventional methods such as energy consumption realization distillation, extraction and absorption.With respect to conventional method, the infiltration evaporation membrane separation technique has small investment, operating cost is low, separative efficiency is high, be easy to scale, expandability is good, be convenient to control, easy remarkable advantage such as replacing.
The main functional element of infiltration evaporation process is a film, and the performance of estimating infiltrating and vaporizing membrane mainly contains two indexs, the i.e. permeation flux of film and selectivity.
1) permeation flux, its definition is:
In the formula, M is the penetrating fluid quality that penetrates film; A is a membrane area, m
2T is the operating time, h; J is a permeation flux, kg/ (m
2H) or g/ (m
2H).
2) separation factor alpha, its definition is:
In the formula, A represents the penetrated preferably component; Y
AWith Y
BBe respectively the molar fraction of A and two kinds of components of B in penetrant; X
AWith X
BBe respectively the molar fraction of A and two kinds of components of B in the feed liquid.
Because infiltrating and vaporizing membrane both can be prepared into the dense film of homogeneous, also can make composite membrane, and the thickness of composite membrane was difficult to accurate mensuration, therefore, was the through performance of more different films, the transmission rates (kg/m of J=film commonly used
2H) * value of thickness (μ m) characterizes.
U.S. Exxon company has developed a series of polyester polymer and has been used for infiltration evaporation separation of methylbenzene/octane mixed system.Wherein, as crosslinked saturated polyester (U.S. Pat 5128439), when content of toluene is toluene/octane mixture of 20% during as feeding liquid, the permeation flux under 190 ℃ is 75.8kg μ mm
-2H
-1, separation factor is 6.1;
Poly-polyarylate (U.S. Pat 5012036) under 150 ℃ is toluene/isooctane mixture of 20% to content of toluene, and permeation flux is 28.1kg μ mm
-2H
-1, separation factor is 7.4;
United States Patent (USP) 5670052 has synthesized a kind of polyesters polyimides, when being used to separate trimethylbenzene/decane, under 140 ℃, is 50% feed liquid for arene content, and separation factor is 4.2, and permeation flux is 45.8kg μ mm
-2H
-1
In addition, and the polyurethane/urea material (as Muszynski J, et al, J.Appl.Polym.Sci.1999,71 (10): 1615-1625) also studied by people, its permeation flux is 25.5kg μ mm
-2H
-1, separation factor is 5.8.
Summary of the invention:
The objective of the invention is to the synthetic a kind of polyurethane-imide film that can realize the infiltration evaporation separation of aromatic hydrocarbons/paraffins mixture, and the film of the different hard segment structures of test is to the Pervaporation Separation of aromatic hydrocarbons/alkane.The polyurethane-imide film of the present invention's preparation has good mechanical strength, hear resistance and chemical stability.And membrane material has the design feature of microphase-separated, and on the one hand, soft section not only helps micromolecular seeing through, and aromatic hydrocarbons is had compatibility, can guarantee that film has differential permeability preferably, and on the other hand, hard section can suppress the swelling of film, guarantees its tolerance.Therefore in aromatic hydrocarbons/alkane infiltration evaporation separated, the polyurethane-imide film had been obtained good separating property.In addition, the cost of material that material synthesizes is cheap, and the potentiality of industrial applications are arranged.
The preparation method of polyurethane-imide film of the present invention is as follows:
1) the polyurethane-imide performed polymer is synthetic
In the there-necked flask that nitrogen protection, mechanical agitation and condensing reflux pipe are housed, add polyethylene glycol adipate two pure and mild diisocyanate monomers; the molal quantity of diisocyanate monomer is 2 times of polyethylene glycol adipate glycol; the two reacted 1.5-2 hour under the condition of vigorous stirring and 65 ℃ of-80 ℃ of water-baths heating; obtain diisocyanate terminated prepolymer; and in blocked prepolymer, adding N, dinethylformamide formation solid content is 50% pre-polymer solution.Subsequently the pyromellitic acid dianhydride with molar equivalents such as polyethylene glycol adipate glycol is mixed with N, the solution of dinethylformamide, this solution is added in the solution of terminated prepolymer, and reaction temperature is risen to 85-95 ℃ carried out chain extending reaction 2-3 hour, finally obtain the polyurethane-imide prepolymer solution of thickness.
2) preparation of polyurethane-imide film
With 1) in the polyurethane-imide prepolymer solution that obtains to be diluted to the mass concentration mark be 15%, again after filtration, after the deaeration, with this solution casting film-forming on polyfluortetraethylene plate, and under infrared lamp solvent flashing 1-1.5 hour, again it is moved to the generation of finishing imide bond in 150 ℃ of baking ovens in heat treatment 1.5-2 hour, finally obtain transparent polyurethane-imide film.
Preparation-obtained polyurethane imide membrane can reach good separating effect under the operating condition of gentleness.When operating temperature is 40-60 ℃, be that its separation factor of benzene/cyclohexane mixture of 50% is 8.3-6.5 for the mass percent of benzene, permeation flux is 12.1-41.9kg μ mm
-2H
-1
The present invention selects for use the polyethylene glycol adipate glycol as soft section, ester group in its chemical constitution has good compatibility to aromatic hydrocarbons, and four methylene can not cause soft section excessive swelling, have both guaranteed the mechanical strength of film in the infiltration evaporation test, have guaranteed the compatibility of film to aromatic hydrocarbons again; Select for use vulcabond and pyromellitic acid dianhydride as hard section, on the one hand in order to generate the firm polyimides group of polarity and structure, increased hard segment length on the other hand, made the hard section easier formation of accumulation regions, this has guaranteed that also membrane material has the structure of microphase-separated.Use difference formula scanning calorimeter that prepared membrane material is characterized and can find, membrane material has two vitrification points, and soft section vitrification point is about-45 ℃, and section is about 150 ℃ firmly, and this has fully proved the existence of micro phase separation structure.
The polyurethane imide membrane of the present invention's preparation shows good separating property when separating the benzene/cyclohexane mixture.For the mass percent of benzene is 50% benzene/cyclohexane mixture, is that separation factor can reach 6.5 under 60 ℃ the situation in operating temperature, and permeation flux can reach 41.9kg μ mm
-2H
-1Compare with other membrane materials, polyurethane imide membrane can be under comparatively gentle condition, to the mass percent of benzene is that 50% benzene/cyclohexane azeotropic mixture effectively separates, and do not need to carry out the operation of high-temperature pressurizing, greatly reduce energy consumption, and the imido cost of material of synthesis of polyurethane is cheap has industrialized potentiality.
The specific embodiment
Embodiment 1
1) the polyurethane-imide performed polymer is synthetic
In the 150ml there-necked flask that nitrogen protection, mechanical agitation and condensing reflux pipe are housed, add polyethylene glycol adipate glycol (PEA) 10g (handling through 110 ℃ of decompression dehydrations before using) and '-diphenylmethane diisocyanate (MDI) monomer (molal quantity of MDI is 2 times of PEA); it was reacted 1.5 hours under the condition of vigorous stirring and 80 ℃ of water-bath heating; obtain the prepolymer of MDI end-blocking; and in blocked prepolymer, adding 7ml N, dinethylformamide (DMF) (purifying through decompression distillation before using) is with its dilution.Subsequently being added in the solution of terminated prepolymer with 7ml DMF in addition with the 1.1g pyromellitic acid dianhydride (purifying through the decompression distillation before using) of molar equivalent such as polyethylene glycol adipate glycol, and reaction temperature is risen to 85 ℃ carried out chain extending reaction 2 hours, finally obtain the polyurethane-imide prepolymer solution of thickness.
2) preparation of polyurethane-imide film
With 1) in the polyurethane-imide prepolymer solution that obtains to be diluted to the mass concentration mark be 15%, again after filtration, after the deaeration, with this solution casting film-forming on polyfluortetraethylene plate, and under infrared lamp solvent flashing 1 hour, again it is moved to heat treatment in 150 ℃ of baking ovens and finished the generation of imide bond in 1.5 hours, finally obtain transparent polyurethane-imide film, film is peeled off from polyfluortetraethylene plate, recording thickness is 110 microns.
The polyurethane-imide film that adopts method for preparing to obtain is tested its aromatic hydrocarbons/alkane Pervaporation Separation, and the mass content of charging employing benzene is 50% benzene/cyclohexane mixture, obtains separating resulting such as table 1 under the different temperatures:
| Operating temperature (℃) | Permeation flux J (kg μ mm -2·h -1) | Separation factor alpha |
| 40 | 12.1 | 8.3 |
| 50 | 27.7 | 6.9 |
| 60 | 41.9 | 6.5 |
Table 1 polyurethane-imide film is to the separating property of benzene/cyclohexane system
Embodiment 2
1) the polyurethane-imide performed polymer is synthetic
In the 150ml there-necked flask that nitrogen protection, mechanical agitation and condensing reflux pipe are housed, add polyethylene glycol adipate glycol (PEA; molecular weight 1000g/mol) 10g (handling through 110 ℃ of decompression dehydrations before using) and 2; 4-toluene di-isocyanate(TDI) (TDI; isomery is than 80/20) monomer (molal quantity of TDI is 2 times of PEA); it was reacted 2 hours under the condition of vigorous stirring and 65 ℃ of water-bath heating; obtain the prepolymer of TDI end-blocking; and in blocked prepolymer, adding 7mlN, dinethylformamide (DMF) (purifying through decompression distillation before using) is with its dilution.Subsequently being added in the solution of terminated prepolymer with 7ml DMF in addition with the 1.1g pyromellitic acid dianhydride (purifying through the decompression distillation before using) of molar equivalent such as polyethylene glycol adipate glycol, and reaction temperature is risen to 95 ℃ carried out chain extending reaction 3 hours, finally obtain the polyurethane-imide prepolymer solution of thickness.
2) preparation of polyurethane-imide film
With 1) in the polyurethane-imide prepolymer solution that obtains to be diluted to the mass concentration mark be 15%, again after filtration, after the deaeration, with this solution casting film-forming on polyfluortetraethylene plate, and under infrared lamp solvent flashing 1.5 hours, again it is moved to heat treatment in 150 ℃ of baking ovens and finished the generation of imide bond in 2 hours, finally obtain transparent polyurethane-imide film, film is peeled off from polyfluortetraethylene plate, and the thickness that records film is 100 microns.
The polyurethane-imide film that adopts method for preparing to obtain is tested its aromatic hydrocarbons/alkane Pervaporation Separation, and the mass content of charging employing benzene is 50% benzene/cyclohexane mixture, obtains separating resulting such as table 2 under the different temperatures:
Table 2 polyurethane-imide film is to the separating property of benzene/cyclohexane system
| Operating temperature (℃) | Permeation flux J (kg μ mm -2·h -1) | Separation factor alpha |
| 40 | 4.6 | 5.8 |
| 50 | 5.6 | 5.4 |
| 60 | 11.3 | 5.2 |
Claims (2)
1. the preparation method of polyurethane-imide permeable vaporizing aromatic hydrocarbons/alkane separation film is characterized in that, may further comprise the steps:
1) the imide-urethane performed polymer is synthetic
In the there-necked flask that nitrogen protection, mechanical agitation and condensing reflux pipe are housed, add polyethylene glycol adipate two pure and mild diisocyanate monomers, the molal quantity of diisocyanate monomer is 2 times of polyethylene glycol adipate glycol, the two reacted 1.5-2 hour under the condition of vigorous stirring and 65 ℃ of-80 ℃ of water-baths heating, obtain diisocyanate terminated performed polymer, and in terminated prepolymer, adding N, dinethylformamide formation solid content is 50% prepolymer solution; Subsequently the pyromellitic acid dianhydride with molar equivalents such as polyethylene glycol adipate glycol is mixed with N, the solution of dinethylformamide, this solution is added in the solution of terminated prepolymer, and reaction temperature is risen to 85-95 ℃ carried out chain extending reaction 2-3 hour, finally obtain the imide-urethane prepolymer solution of thickness;
2) preparation of polyurethane-imide film
It is 15% that the polyurethane-imide prepolymer solution that obtains in the step 1) is diluted to the mass concentration mark, again after filtration, after the deaeration, with this solution casting film-forming on polyfluortetraethylene plate, and under infrared lamp solvent flashing 1-1.5 hour, again it is moved to the generation of finishing imide bond in 150 ℃ of baking ovens in heat treatment 1.5-2 hour, finally obtain transparent polyurethane-imide film.
2. according to the preparation method of claim 1, it is characterized in that: in described step 1) polyurethane-imide performed polymer synthetic, the weight average molecular weight of the polyethylene glycol adipate glycol that is adopted is 1000-2000g/mol, and diisocyanate monomer is any one in toluene di-isocyanate(TDI) and the '-diphenylmethane diisocyanate.
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|---|---|---|---|
| CN2007101184801A CN101121101B (en) | 2007-07-06 | 2007-07-06 | Method for preparing polyurethane-imide permeable vaporizing aromatic/alkane separating membrane |
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| CN2007101184801A CN101121101B (en) | 2007-07-06 | 2007-07-06 | Method for preparing polyurethane-imide permeable vaporizing aromatic/alkane separating membrane |
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| CN101121101B true CN101121101B (en) | 2010-06-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017004492A1 (en) | 2015-07-01 | 2017-01-05 | 3M Innovative Properties Company | Pvp- and/or pvl-containing composite membranes and methods of use |
| JP6838819B2 (en) | 2015-07-01 | 2021-03-03 | スリーエム イノベイティブ プロパティズ カンパニー | Composite membranes with improved performance and / or durability and usage |
| KR20180023971A (en) | 2015-07-01 | 2018-03-07 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Polymeric ionomer membranes and methods of use |
| CN105367733B (en) * | 2015-12-16 | 2018-02-06 | 合肥工业大学 | A kind of preparation method and purposes based on benzoic anhydride polyester polyol aqueous polyurethane film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1637034A (en) * | 2004-01-08 | 2005-07-13 | 日立化成工业株式会社 | Polyurethane-imide resin,adhesive composition and adhesive composition for circuit connection |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1637034A (en) * | 2004-01-08 | 2005-07-13 | 日立化成工业株式会社 | Polyurethane-imide resin,adhesive composition and adhesive composition for circuit connection |
Non-Patent Citations (4)
| Title |
|---|
| Hossein Behniafar et al..Direct synthesis of soluble and thermally stablepoly(urethane-imide)s from a new triimide-dicarbonylazide.Polymer46.2005,464628-4629. * |
| Min Zuo et al..Preparation and characterization of poly(urethane-imide) filmsprepared from reactive polyimide and polyurethane prepolymer.Polymer40.1999,405144-5155. * |
| T.Philip Gnanarajan et al..Preparation and properties of poly(urethane-imide)s derivedfrom amine-blocked-polyurethane prepolymer and pyromelliticdianhydride.European Polymer Journal38.2002,38488. * |
| Tsutomu Takeichi et al..High performance poly(urethane-imide)prepared byintroducingimide blocks into the polyurethane backbone.polymer46.2005,4611226. * |
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