CN103894081B - Cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as preparation and application thereof - Google Patents
Cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as preparation and application thereof Download PDFInfo
- Publication number
- CN103894081B CN103894081B CN201410107022.8A CN201410107022A CN103894081B CN 103894081 B CN103894081 B CN 103894081B CN 201410107022 A CN201410107022 A CN 201410107022A CN 103894081 B CN103894081 B CN 103894081B
- Authority
- CN
- China
- Prior art keywords
- block copolymer
- polyoxyethylene
- cross
- polycaprolactam
- polycaprolactam block
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as a preparation method and application thereof. The film is formed by cross-linking of polyoxyethylene-polycaprolactam block copolymer films. The preparation method comprises the following steps: preparing the polyoxyethylene-polycaprolactam block copolymer films; preparing a 2,4-toluene diisocynate solution; putting the polyoxyethylene-polycaprolactam block copolymer films into the 2,4-toluene diisocynate solution, and carrying out cross-linking. The preparation method has the advantages that the reaction of the cross-linked polyoxyethylene-polycaprolactam block copolymer film can be finished at the room temperature, the reaction speed is high, no catalyst needs to be added, a cross-linking effect is obvious, a formula is simple, and the operation is simple; besides, the water tolerance, mechanical stability and heat stability of the cross-linked film prepared by utilizing the preparation method are improved, and the cross-linked film is long in service life, is suitable for separating CO2 in a water-containing hygrometric state condition and presents a preferable separation effect.
Description
Technical field
The present invention relates to a kind of cross linked polyoxyethylene-polycaprolactam block copolymer film and preparation method and application, belong to gas separaion technical field of membrane.
Background technology
Economic develop rapidly brings and also brings huge pressure to environment easily simultaneously, and coal, oil and natural gas etc. are the main objects of energy resource consumption now, the CO of its combustion tail gas discharge
2, account for global CO
2more than 80% of total emission volumn, in addition, the sour gas CO contained in natural gas
2, not only can reduce the calorific value of natural gas, increase the load of gas transport equipment, also can etchant gas transport pipeline.Therefore, separation of C O from gaseous mixture
2it is the important processing processing procedure of of purification of natural gas.At present for CO
2the method be separated mainly contains chemical absorption method, pressure swing adsorption method and separation by deep refrigeration.Relative to other separation method, gaseous jet simulation method has the high and low energy consumption of separative efficiency, without phase transformation, easy to operate, equipment is simply light, easily amplifies and produces and operational reliability advantages of higher, be very applicable to CO
2the trapping of gas be separated, there is wide investigation and application prospect.
Evaluate the quality of gas separation membrane and mainly contain 3 parameters: the stability of infiltration coefficient, selective and film.In order to maintain the stability of film properties, generally speaking, all to be cross-linked polymer film.Crosslinked action is usually realize by means of chemical reaction, and chain molecule links together with covalent bond each other in the reaction, or stronger secondary key, and as hydrogen bond, they partly play and the covalently cross-linked physical crosslinking effect with similar features.In order to fundamentally solve the problem of the stability of film, the generation that controlling diaphragm is swelling, just must introduce real chemical bond and be cross-linked, and makes line polymer change spatial networks polymer into chemical bond is crosslinked.Only in this way, the stability of film could be improved significantly.For gas separation membrane, improving one of method of separating property is be cross-linked film, and be cross-linked and membrane structure molecular dimension is diminished, the permeability of gas declines to some extent, but contributes to the raising of separation selectivity.
Summary of the invention
The object of the present invention is to provide cross linked polyoxyethylene-polycaprolactam block copolymer film and preparation method and application.This cross linked polyoxyethylene-polycaprolactam block copolymer film, for separating of CO
2/ CH
4mixture, under unstripped gas and sweep gas humidified condition, have good gas separation effect, its preparation method process is simple.
The present invention is achieved through the following technical solutions, a kind of cross linked polyoxyethylene-polycaprolactam block copolymer film, it is characterized in that, this cross linked polyoxyethylene-polycaprolactam block copolymer film thickness 80-130 μm, wherein polyoxyethylene-polycaprolactam block copolymer is 55-60% polyoxyethylene segment and mass fraction by mass fraction is that the copolymerization of 40-45% polycaprolactam segment forms.
The preparation method of above-mentioned cross linked polyoxyethylene-polycaprolactam block copolymer film, is characterized in that comprising following process:
1. polyoxyethylene-polycaprolactam block copolymer being added mass fraction is in the ethanol water of 70%, be made into the solution that mass fraction is 2-8%, at temperature 80 DEG C, reflux heating stirs 2 h, make it dissolve completely, be poured on curtain coating on clean glass plate, dry under room temperature, then put into vacuum drying oven and remove residual solvent, obtain polyoxyethylene-polycaprolactam block copolymer film;
2. add in n-hexane by 2,4-toluene di-isocyanate(TDI), dose volume mark is the cross-linking agent solution of 1-5%;
3. the polyoxyethylene of step 1 gained-polycaprolactam block copolymer film is soaked in the cross-linking agent solution of gained in step 2, and be placed on cradle vibrate dipping, controlling cross-linking reaction time is 5-600 min, cross-linking agent-free solution to cleaning solution is repeatedly rinsed afterwards by deionized water, film is steeped after in deionized water again and take out, be put in dry 48 h in vacuum tank and obtain cross linked polyoxyethylene-polycaprolactam block copolymer film.
The application of cross linked polyoxyethylene-polycaprolactam block copolymer film prepared by said method, for separating of CO
2/ CH
4mixture, testing its flux under hygrometric state condition is 100-550 barrer(1 barrer=10
-10cm
3cm/cm
2s cmHg), CO
2/ CH
4selective is 15-35.
The invention has the advantages that: cross linked polyoxyethylene-polycaprolactam block copolymer film at room temperature reacts, reaction speed is fast, and without the need to adding catalyst, cross-linking effect is obvious, and formula is simple, is easy to operation.In addition, cross linking membrane prepared by this kind of method improves the resistance to water of film, mechanical stability and heat endurance, long service life, and is applicable to separation of C O under moisture hygrometric state condition
2, and show good separating effect.
Detailed description of the invention
Embodiment 1:
Take 0.8 g polyoxyethylene-polycaprolactam block copolymer (commodity are called Pebax 1657), 6 g deionized waters and 14 g absolute ethyl alcohols add in three mouthfuls of round-bottomed flasks of band condenser pipe, be placed in the water bath with thermostatic control that temperature is 80 DEG C, speed stirring and refluxing 2 h of 500 r/min, polyoxyethylene-polycaprolactam block copolymer is all dissolved, after being cooled to room temperature, standing and defoaming 30 min, be poured on curtain coating on clean glass plate, dry under room temperature, then put into vacuum drying oven and remove residual solvent, obtain polyoxyethylene-polycaprolactam block copolymer film, for subsequent use.Measure in the volumetric flask of 2,4-toluene di-isocyanate(TDI) to 250 mL of 5 mL with liquid-transfering gun, using n-hexane as solvent constant volume, the volume fraction of acquisition be 2, the 4-toluene di-isocyanate(TDI) solution of 2% as crosslinker solution, for subsequent use.Pipette 2 of 150 mL, 4-toluene di-isocyanate(TDI) solution is in culture dish with cover, polyoxyethylene-polycaprolactam block copolymer film is put into culture dish thorough impregnation in solution, and then culture dish with cover being placed cradle vibrate number of times speed is in 60 times/min, and crosslinked 10 min are soaked in vibration.Polyoxyethylene-polycaprolactam block copolymer film after crosslinked is taken out, three times are repeatedly rinsed to cross-linking agent-free solution by deionized water, again film bubble is taken out after 1 h in deionized water, be put in polyoxyethylene-polycaprolactam block copolymer film that dry 48 h in vacuum tank obtain being cross-linked, film thickness is 90 μm.This film is separation of C O under room temperature, 2 bar conditions
2volume fraction is the CO of 30%
2/ CH
4binary gas, under 100% humidity, tests its CO
2infiltration coefficient is 388.7 barrer, CO
2/ CH
4selective is 23.6.
Embodiment 2:
Preparation method is consistent with embodiment 1, and difference is: control cross-linking reaction time and become 60 min from 10 min.Obtained cross linking membrane is for separating of CO
2volume fraction is the CO of 30%
2/ CH
4binary gas, testing its infiltration coefficient under hygrometric state condition is 345.2 barrer, CO
2/ CH
4selective is 25.4.
Embodiment 3:
Preparation method is consistent with embodiment 1, and difference is: control cross-linking reaction time and become 120 min from 10 min.Obtained cross linking membrane is for separating of CO
2volume fraction is the CO of 30%
2/ CH
4binary gas, testing its infiltration coefficient under hygrometric state condition is 312.3 barrer, CO
2/ CH
4selective is 26.8.
Embodiment 4:
Preparation method is consistent with embodiment 1, and difference is: control cross-linking reaction time and become 240 min from 10 min.Obtained cross linking membrane is for separating of CO
2volume fraction is the CO of 30%
2/ CH
4binary gas, testing its infiltration coefficient under hygrometric state condition is 266.4 barrer, CO
2/ CH
4selective is 27.7.
Embodiment 5:
Preparation method is consistent with embodiment 1, and difference is: control cross-linking reaction time and become 360 min from 10 min.Obtained cross linking membrane is for separating of CO
2volume fraction is the CO of 30%
2/ CH
4binary gas, testing its infiltration coefficient under hygrometric state condition is 195.2 barrer, CO
2/ CH
4selective is 31.1.
Comparative example
Take 0.8 g polyoxyethylene-polycaprolactam block copolymer (commodity are called Pebax 1657), 6 g deionized waters and 14 g absolute ethyl alcohols add in three mouthfuls of round-bottomed flasks of band condenser pipe, be placed in the water bath with thermostatic control that temperature is 80 DEG C, speed stirring and refluxing 2 h of 500 r/min, polyoxyethylene-polycaprolactam block copolymer is all dissolved, after being cooled to room temperature, standing and defoaming 30 min, be poured on curtain coating on clean glass plate, dry under room temperature, then put into vacuum drying oven and remove residual solvent, obtain polyoxyethylene-polycaprolactam block copolymer film, for subsequent use.Separation of C O under room temperature, 2 bar conditions
2volume fraction is the CO of 30%
2/ CH
4binary gas, tests its CO under hygrometric state condition
2infiltration coefficient is 480.0 barrer, CO
2/ CH
4selective is 18.0.
The above embodiments and comparative example compare and can draw: cross linked polyoxyethylene-polycaprolactam block copolymer film is tested under being applicable to hygrometric state condition, can significantly improve CO
2/ CH
4separation selectivity, and crosslinked after film mechanical stability and better heat stability, long service life.
Claims (2)
1. the preparation method of cross linked polyoxyethylene-polycaprolactam block copolymer film, this cross linked polyoxyethylene-polycaprolactam block copolymer film thickness 80-130 μm, wherein polyoxyethylene-polycaprolactam block copolymer is 55-60% polyoxyethylene segment and mass fraction by mass fraction is that the copolymerization of 40-45% polycaprolactam segment forms, and it is characterized in that comprising following process:
1) polyoxyethylene-polycaprolactam block copolymer being added mass fraction is in the ethanol water of 70%, be made into the solution that mass fraction is 2-8%, at temperature 80 DEG C, reflux heating stirs 2 h, make it dissolve completely, be poured on curtain coating on clean glass plate, dry under room temperature, then put into vacuum drying oven and remove residual solvent, obtain polyoxyethylene-polycaprolactam block copolymer film;
2) add in n-hexane by 2,4-toluene di-isocyanate(TDI), dose volume mark is the cross-linking agent solution of 1-5%;
3) polyoxyethylene of step 1) gained-polycaprolactam block copolymer film is immersed in step 2) in gained cross-linking agent solution in, and be placed on cradle vibrate dipping, controlling cross-linking reaction time is 5-600 min, cross-linking agent-free solution to cleaning solution is repeatedly rinsed afterwards by deionized water, film is steeped after in deionized water again and take out, be put in dry 48 h in vacuum tank and obtain cross linked polyoxyethylene-polycaprolactam block copolymer film.
2. by an application for the cross linked polyoxyethylene-polycaprolactam block copolymer film of claim 1 preparation, for separating of CO
2/ CH
4mixture, testing its flux under hygrometric state condition is 100-550 barrer, CO
2/ CH
4selective is 15-35.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410107022.8A CN103894081B (en) | 2014-03-21 | 2014-03-21 | Cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410107022.8A CN103894081B (en) | 2014-03-21 | 2014-03-21 | Cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103894081A CN103894081A (en) | 2014-07-02 |
| CN103894081B true CN103894081B (en) | 2015-07-22 |
Family
ID=50985841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410107022.8A Expired - Fee Related CN103894081B (en) | 2014-03-21 | 2014-03-21 | Cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103894081B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10272394B2 (en) | 2017-08-30 | 2019-04-30 | Saudi Arabian Oil Company | Crosslinked polymeric blended membranes for gas separation |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525006B (en) * | 2015-01-08 | 2017-01-11 | 天津大学 | Macromolecule-carboxylic acid functional nano-hydrogel composite membrane, preparation method and application |
| CN105749769B (en) * | 2016-04-13 | 2019-01-11 | 天津大学 | A kind of preparation and application of ionic liquid blend film |
| US11148103B2 (en) | 2019-12-03 | 2021-10-19 | Saudi Arabian Oil Company | Gas separation membrane comprising crosslinked blends of rubbery polymers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500250A (en) * | 2011-11-08 | 2012-06-20 | 天津大学 | Macromolecular-inorganic hybrid membrane, and preparation method and application thereof |
| CN103055723A (en) * | 2012-12-18 | 2013-04-24 | 辽宁师范大学 | Cross-linking type polybenzimidazole porous separation membrane and preparation method and application thereof |
| CN103521100A (en) * | 2013-10-29 | 2014-01-22 | 天津大学 | High-molecular-functional mesoporous silica hybrid membrane, preparation method and applications |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101136943B1 (en) * | 2010-04-16 | 2012-04-20 | 한국과학기술연구원 | The method of preparation for hydrophilic water filtration membrane having improved antifouling and hydrophilic water filtration membrane according to the method |
| US8617395B2 (en) * | 2010-09-30 | 2013-12-31 | The United States Of America, As Represented By The Secretary Of Agriculture | Thin film composite membranes and their method of preparation and use |
-
2014
- 2014-03-21 CN CN201410107022.8A patent/CN103894081B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500250A (en) * | 2011-11-08 | 2012-06-20 | 天津大学 | Macromolecular-inorganic hybrid membrane, and preparation method and application thereof |
| CN103055723A (en) * | 2012-12-18 | 2013-04-24 | 辽宁师范大学 | Cross-linking type polybenzimidazole porous separation membrane and preparation method and application thereof |
| CN103521100A (en) * | 2013-10-29 | 2014-01-22 | 天津大学 | High-molecular-functional mesoporous silica hybrid membrane, preparation method and applications |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10272394B2 (en) | 2017-08-30 | 2019-04-30 | Saudi Arabian Oil Company | Crosslinked polymeric blended membranes for gas separation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103894081A (en) | 2014-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103894081B (en) | Cross-linked polyoxyethylene-polycaprolactam block copolymer film as well as preparation and application thereof | |
| CN106621864B (en) | MOFs- cross-linked polyethylene glycol diacrylate mixed substrate membrane containing nano-grade molecular sieve and preparation and application | |
| Petit et al. | Effect of water on the physical properties and carbon dioxide capture capacities of liquid-like Nanoparticle Organic Hybrid Materials and their corresponding polymers | |
| Liu et al. | CO2 separation by supported ionic liquid membranes and prediction of separation performance | |
| Akhmetshina et al. | Absorption behavior of acid gases in protic ionic liquid/alkanolamine binary mixtures | |
| CN105749769B (en) | A kind of preparation and application of ionic liquid blend film | |
| CN102423600B (en) | Method for improving adsorption separation efficiency of CO2-containing mixed gas | |
| Saeed et al. | CO 2 separation by supported liquid membranes synthesized with natural deep eutectic solvents | |
| Liu et al. | In situ cross‐linked‐PDMS/BPPO membrane for the recovery of butanol by pervaporation | |
| Yu et al. | Synthesis and properties of amphiprotic polyacrylamide microspheres as water shutoff and profile control | |
| CN103100313A (en) | Polyether-b-polyamide (PEBA)/polyethyleneglycol (PEG) or polyoxyethylene (PEO) blend membrane, and preparation and application thereof | |
| Chau et al. | Solubilities of CO2 and helium in an ionic liquid containing poly (amidoamine) dendrimer Gen 0 | |
| Cheng et al. | Improving CO2 permeation and separation performance of CO2-philic polymer membrane by blending CO2 absorbents | |
| Ahmadalinezhad et al. | Molecular‐level insights into the oxidative degradation of grafted amines | |
| Ansaloni et al. | Development of membrane contactors using phase change solvents for CO2 capture: material compatibility study | |
| Hu et al. | Optimization of coating solution viscosity of hollow fiber‐supported polydimethylsiloxane membrane for CO2/H2 separation | |
| Tunnat et al. | Desorption kinetics of CO2 from water and aqueous amine solutions | |
| CN104959047B (en) | Preparation method for monoamine-grafted-and-modified crosslinked polyimide solvent-resistant nanofiltration membrane | |
| CN105771683A (en) | Method for improving stability of SAPO-34(Silicoaluminophosphate-34) zeolite membrane in water vapor environment | |
| Park et al. | Preparation of water‐swollen hydrogel membranes for gas separation | |
| Fisher et al. | Cyclic Stability Testing of Aminated‐Silica Solid Sorbent for Post‐Combustion CO2 Capture | |
| CN113731198B (en) | Preparation method of high-selectivity polyimide gas separation membrane | |
| Merle et al. | An easy method for the preparation of anion exchange membranes: Graft‐polymerization of ionic liquids in porous supports | |
| Sadeghi et al. | Improved gas transport properties of polyurethane–urea membranes through incorporating a cadmium‐based metal organic framework | |
| CN114832796A (en) | Solid amine adsorbent for adsorbing carbon dioxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150722 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |