CN101816899A - Molecular sieve/polyimide composite film for adsorption separation and preparation method thereof - Google Patents
Molecular sieve/polyimide composite film for adsorption separation and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a molecular sieve/polyimide composite film for adsorption separation and a preparation method thereof. The preparation method comprises the following steps: firstly, preparing a molecular sieve solution; then, adding diamine into the mixed solution; after the diamine is dissolved, adding dianhydride, and continuously stirring to form a polyamic acid (PAA) composite solution in which the molecular sieve is uniformly dispersed; dipping and coating the PAA molecular sieve composite solution on non-porous carriers such as a glass plate and the like; putting the non-porous carriers into a baking oven for gradually heating; and carrying out dehydration and cyclization to obtain the molecular sieve/PI composite film. In the composite film, the polyimide is used as a basal body, and the molecular sieve padding is inserted into the polyimide basal body, wherein the mass ratio of the molecular sieve to the polyimide is 0.05-0.5. The preparation process of the invention has the advantages of simplicity, easy control, convenient operation and good uniformity. Compared with the traditional powdered, spherical and strip-shaped molecular sieves, the molecular sieve composite film is more convenient in storage during engineering, is more beneficial to construction, can be recovered more easily, has reduced production cost, stable thermal properties, high mechanical properties and good abrasion resistance.
Description
Technical field
The present invention relates to a kind of adsorbing separation molecular sieve/polyimide (PI) laminated film and preparation thereof.Relating in particular to a kind of is that matrix, molecular sieve are adsorbing separation laminated film and preparation method thereof of filler with PI.
Background technology
Polyimides (PI) is the aromatic heterocycle polymer material that contains imide group on the class main chain, it is one of present engineering plastics with general high-performance material, and being easy to machine-shaping, its goods such as film, adhesive, coating, laminate etc. are widely used in high-tech areas such as Aero-Space, machinery, electronics.Because contain aromatic rings on the main chain, the PI film has outstanding advantage: (1) heat resistance: can the low temperature of anti-the utmost point, as can embrittlement in-269 ℃ liquid helium; High temperature resistant, decomposition starting temperature is generally all about 500 ℃; (2) thermal coefficient of expansion of PI is 2 * 10
-5～3 * 10
-5℃; (3) solvent resistance: have good oil resistant and organic solvent resistance, stable to diluted acid; (4) mechanical performance: all more than 100MPa, elastic modelling quantity is generally 3GPa～4GPa to the hot strength of unfilled PI plastics; (5) PI is nontoxic, can be used to make tableware and medical appliance, packaging material etc.
In addition, choose suitable molecular structure and select for use suitable film technique can obtain allowing little molecule, as permeable PI films such as hydrones.Be mixed with the molecular sieve of nothing in conjunction with water in the PI matrix, hydrone can pass the PI strand by molecular sieve adsorption, and adsorption moisture in the molecular sieve pore passage is the adsorbing separation laminated film of matrix, the molecular sieve filler that is with the high molecular polymer thereby can prepare a kind of.In the commercial Application, generally need add the adhesive moulding in molecular screen primary powder and make the particle with certain mechanical strength and shape at present, commercially available molecular sieve shape mainly contains sphere and bar shaped.That traditional sphere, bar shaped molecular sieve store on engineering is inconvenient, be unfavorable for construction, and is difficult for reclaiming, and wearability remains to be improved, and can produce dust, has limited the use of molecular sieve.
CN101380565 mixes molecular sieve, binding agent by a certain percentage, calcines after the moulding, again formed body is carried out Li
+Exchange makes active low silicon lithium dimer sieve air system oxygen absorbent after drying, the activation.Though this invention has improved selectivity and the adsorption capacity of adsorbent to nitrogen, the molecular sieve of moulding (sphere or bar shaped) stores inconvenient, needs the vessel splendid attire; Sphere or bar shaped molecular sieve are unfavorable for construction on engineering, and are difficult for reclaiming, and cause the raising of production cost.
US6918948 has prepared a kind of attapulgite fiber binder of high degree of dispersion, it mixes with zeolite powder, make a kind of adsorbent of molecular sieve blend that improves Performance Characteristics behind the shaping and roasting, and and zeolite be tending towards occupying space between the zeolite crystal when mixing, be difficult for mixing with the zeolite interface, but the attapulgite specific area is big, and adsorption capacity is stronger, may influence the selection adsorbing separation effect of zeolite to a certain extent.
RU2337064 is the mixed raw material grain with starch (or carboxymethyl cellulose) suspension, the synthesis of molecular sieve of acidifying aluminum sulfate, 350 ℃ are disperseed dry, calcining finally makes sieve particle and has anti-wear performance and adsorption capacity preferably after alkaline sodium aluminate crystallization obtains the A type molecular sieve crystal.Though the molecular sieve in this invention increases aspect anti-wear performance, but still can there be dry linting to a certain degree in the granulin molecule sieve, in fixed bed uses, can result in blockage, cause absorption property to descend, and the molecular sieve dry linting also can cause the mechanical strength of molecular sieve to reduce gradually.
The Turk
Prepare laminated film Deng natural zeolite that utilizes surface modification and polypropylene material, though the zeolite addition is that 2% o'clock composite water vapor permeation is very little, but 4% zeolite is filled laminated film and is had quite high permeability, and very close with the vapor permeability of natural leather, this laminated film can be used to prepare the packaging material of high water vapor permeability.But the polypropylene/zeolite laminated film mechanical performance of extruding that makes in this invention descends very fast, the laminated film yield stress of adding 4% zeolite descends 21.1%, yield strain descends 14.3%, so can only add a spot of zeolite under the future that guarantees substrate performance, this zeolite molecular sieve to preparation laminated film form is very unfavorable; Can become fragile when polypropylene is low temperature resistant, cause impact poor, not wear-resisting, more aging, need by modification and add antioxidant to be overcome.
It is the food air conditioned packing PE composite fresh-keeping film of raw material with polymeric matrix, molecular sieve (coupling agent modified), plasticizer that CN101205306 has prepared a kind of.This laminated film utilizes molecular sieve as active inorganic particulate, makes film have air permeability and good, poisture-penetrability, the porosity, thereby regulates the package interior gas componant.But the modified molecular screen mass percent of using in this invention only is 1.5～20%, and the content of molecular sieve has limited maximum permeability, the water vapour permeability of laminated film; Need be during the molecular sieve surface modification room temperature reaction under the nitrogen protection 24 hours, process conditions are comparatively strict.
Summary of the invention
The objective of the invention is on engineering, to store inconvenience in order to improve traditional sphere, bar shaped molecular sieve, be unfavorable for construction, be difficult for deficiencies such as recovery, thereby a kind of molecular sieve/polyimide composite film for adsorption separation is provided, and another object of the present invention provides the preparation method of above-mentioned laminated film.
Technical scheme of the present invention is: a kind of molecular sieve/polyimide composite film for adsorption separation, it is characterized in that with the polyimides being matrix, and the molecular sieve filling intercalation is in polyimide matrix, and wherein the mass ratio of molecular sieve and polyimides is 0.05～0.5.
The present invention also provides the method for preparing above-mentioned molecular sieve/polyimide composite film for adsorption separation, and concrete steps are as follows:
The preparation of A, molecular sieve solution
Molecular sieve is added in the aprotic polar solvent, and the control temperature-time stirs, to disperseing fully;
The preparation of B, molecular sieve/polyamic acid PAA composite solution
Add diamines in the mixed solution that in steps A, makes, the control temperature stirs, treat to add after it dissolves fully the dianhydride with the diamines equimolar amounts, continuous stirring becomes molecule screening uniform polyamic acid (PAA, the condensation polymer of diamines and the dianhydride) composite solution that looses in batches again;
The preparation of C, molecular sieve/polyimide (PI) laminated film
The dip-coating of PAA molecular sieve composite solution on non-porous support such as glass plate, is put into the baking oven ladder-elevating temperature, and cyclodehydration makes molecular sieve/polyimide (PI) laminated film.
Molecular sieve adds in the aprotic polar solvent among the above-mentioned steps A, and temperature is controlled at 20～30 ℃; Stir 20～30min after adding molecular sieve; Wherein molecular sieve is 0.005～0.25 with the solvent quality ratio.
Among above-mentioned few rapid B, make mixed solution in the diamines adding steps A, temperature is controlled at 20～30 ℃; Stir 4～8h behind the dianhydride of 2～4 batches of addings of branch and diamines equimolar amounts; Wherein molecular sieve and PAA mass ratio are 0.05～0.5.
In the above-mentioned steps C ladder-elevating temperature process, heating rate is 2～5 ℃/min; Be warmed up to 80～120 ℃ of constant temperature 30～90min; Be warmed up to 180～220 ℃ of constant temperature 30～90min; Be warmed up to 280～350 ℃ of constant temperature 30～90min.
Molecular sieve addition sequence among the above-mentioned steps A can be following several: before making PAA solution, directly add in the solvent, diamines is dissolved in fully that the back adds in the solvent, dianhydride be dissolved in fully in the solvent back add or making PAA solution after add, wherein preferred addition sequence is to be first kind.
Used PAA is by predecessor dianhydride and diamines reactive polymeric and obtaining in described solvent among the present invention.
Used dianhydride is preferably pyromellitic acid anhydride (PMDA) among the present invention, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4, the two phthalic anhydrides (ODPA) of 4 '-oxygen, isomery diphenyl sulfide dianhydride (TDPA), triphen diether tetracarboxylic dianhydride (HQDPA), benzophenone tetracarboxylic acid dianhydride (BTDA), benzophenone tetracarboxylic dianhydride (BDPA), bisphenol-A dianhydride (BPADA), hexafluoro isopropylidene two phthalandione dianhydrides (6-FDA), 3,3 ', a kind of or two kinds of blend in 4,4 ' the diphenyl sulfone tetracarboxylic anhydride (DSDA).
Diamines among the present invention is preferably selected for use: 4, and 4 '-diaminodiphenyl ether (ODA), dimethyl diphenyl methane diamines (DMMDA), 1, two (3-amino-benzene oxygen) benzene (BAPB) of 3-, 4,4 '-bisphenol-A diphenyl ether diamines (BAPP), perfluor isopropylidene diamine (4-BDAF), 4,4 '-two (4-amino-benzene oxygen) diphenyl sulphone (DPS)s (BAPS), 4,4 '-two (4-amino-benzene oxygen) diphenyl ether (BAPE), diaminourea hexichol (first) ketone (DABP), 4,4 '-diaminourea triphenylamine (DATPA), 4,4 '-MDA (MDA), diamino diphenyl sulfone (DDS), phenylenediamine (PDA), 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, 4,4 '-diaminourea-hexichol Oxy-1 ", 4 "-benzene, 4,4 '-diaminourea-hexichol Oxy-1 "; 3 "-benzene, 3,3 '-diaminourea-hexichol Oxy-1 "; 3 "-benzene, 4,4 '-diaminourea-two phenoxy group-4 ", a kind of or two kinds of blend in the different propane of 4-diphenyl.
Molecular sieve among the present invention is any in zeolite molecular sieve (comprise activation after activating zeolite powder), mesopore molecular sieve or the former powder of carbon molecular sieve.
Aprotic polar solvent among the present invention is N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO) or oxolane.
Beneficial effect:
1, the molecular sieve good uniformity of the PI laminated film form that makes of the present invention, the molecular sieve laminated film than traditional Powdered, spherical, bar shaped molecular sieve on engineering, store more convenient, be more conducive to construction, and easier recovery reduces production costs; Hot property is stable, can add the thermal desorption adsorbate, and renewable repeated use; Chemical property is stablized nontoxic, and molecular sieve is difficult for running off, and the scope of application is wide; Forming preferably between the PI matrix parcel molecular sieve, PI and molecular sieve, the interface combines; The mechanical performance height does not chap, long service life, and importantly anti-wear performance is good, can not produce dust, can not only satisfy fixed bed and use, and can also satisfy the demand of fixed bed various application scenarios in addition, separates or reaction as packing, film.
Typical PI (ODA/PMDA) film performance of the present invention's preparation sees Table 1.
The key property of the typical PI film of table 1
| Project | Unit | ??PI | Remarks |
| Outward appearance | ??- | Transparent, homogeneous | Perusal |
| Thermal coefficient of expansion | ??10 -6·K -1 | ??26.63 | ??GB/T?1036-1989 |
| Peak load | ??N | ??49.13 | ??GB/T?1040-1992 |
| Hot strength | ??MPa | ??196.5 | ??GB/T?1040-1992 |
| Elastic modelling quantity | ??GPa | ??3.25 | ??GB/T?1040-1992 |
| Elongation at break | ??％ | ??12.94 | ??GB/T?1040-1992 |
2, technical process is convenient: the requirement to device is lower, and operating process is easy, and course of reaction is easily controlled, and has certain using value.
Description of drawings
Fig. 1 is the SEM figure of example 1 laminated film;
Fig. 2 desorption rate figure that is water on the prepared 3A/PI of 3A and example 1.
The specific embodiment
To help to understand the present invention by following example, but not limit content of the present invention.
Example 1
Take by weighing 2.25g3A activating zeolite powder, be dissolved in 40.25gDMF, stir 20min, add 3.04g4,4 '-diaminodiphenyl ether (ODA), treat that it dissolves fully after, divide 2 batches to add 4.46g pyromellitic acid anhydride (PMDA), stir 4h, make 50g 3A activating zeolite powder and PAA composite solution.
3A activating zeolite powder/PAA composite solution dip-coating on glass plate, is put into the baking oven ladder-elevating temperature, control heating rate be 3 ℃/min (90 ℃ * 0.8h, 190 ℃ * 0.8h, 320 ℃ * 1h), make the 3A active zeolite laminated film of cyclodehydration.
The internal structure of laminated film of the present invention as shown in Figure 1, as can be seen from Figure, the molecular sieve intercalation is in polyimide matrix, forming preferably between polyimide matrix and the molecular sieve filling, the interface combines.
Adopting STA 409 PC simultaneous thermal analysis instrument is nitrogen at reaction atmosphere, and heating rate is under the 10 ℃/min condition, measures temperature programmed desorption (TG/DTG) curve of laminated film, calculates temperature～dehydrating amount graph of a relation.Desorption rate figure of the present invention as shown in Figure 2, as can be seen from Figure, water is consistent with desorption by heating curvilinear trend on the laminated film at molecular sieve, and maximum dehydrating amount differs very little.
Example 2
Take by weighing 3.38g5A activating zeolite powder, be dissolved in 31.62gDMF, stir 20min, add 6.08g4,4 '-diaminodiphenyl ether (ODA), after treating that it dissolves fully, divide 2 batches to add 8.92g3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) stirs 4h, makes 50g 5A activating zeolite powder and PAA composite solution.
5A activating zeolite powder/PAA composite solution dip-coating on glass plate, is put into the baking oven ladder-elevating temperature, control heating rate be 4 ℃/min (100 ℃ * 1h, 190 ℃ * 0.5h, 300 ℃ * 0.6h), make the 5A active zeolite laminated film of cyclodehydration.
Example 3
Take by weighing the 1.00g5A molecular sieve, be dissolved in 44.00gDMAc, stir 30min, add 2.85g4,4 '-bisphenol-A diphenyl ether diamines (BAPP), treat that it dissolves fully after, divide 3 batches to add 2.15g4, the two phthalic anhydrides (ODPA) of 4 '-oxygen stir 5h, make 50g5A molecular sieve and PAA composite solution.
5A molecular sieve/PAA composite solution dip-coating on glass plate, is put into the baking oven ladder-elevating temperature, control heating rate be 5 ℃/min (110 ℃ * 0.5h, 200 ℃ * 1h, 280 ℃ * 0.9h), make the 5A active zeolite laminated film form of cyclodehydration.
Example 4
Take by weighing 1.5gX type molecular sieve, be dissolved in 42.5gDMF, stir 30min, add 3.02g perfluor isopropylidene diamine (4-BDAF), treat that it dissolves fully after, divides 4 batches of adding 2.98g triphen diether tetracarboxylic dianhydrides (HQDPA), stir 8h, make 50gX type molecular sieve and PAA composite solution.
X type molecular sieve/PAA composite solution dip-coating on glass plate, is put into the baking oven ladder-elevating temperature, control heating rate be 3 ℃/min (120 ℃ * 1.1h, 200 ℃ * 0.8h, 290 ℃ * 1.1h), make the X type molecular sieve laminated film of cyclodehydration.
Example 5
Take by weighing 0.4gY type molecular sieve, be dissolved in 45.6gDMAc, stir 25min, add 1.97g4,4 '-two (4-amino-benzene oxygen) diphenyl sulphone (DPS)s (BAPS), treat that it dissolves fully after, divide 4 batches to add 2.03g hexafluoro isopropylidene two phthalandione dianhydrides (6-FDA), stir 6h, make 50gY type molecular sieve and PAA composite solution.
Y zeolite/PAA composite solution dip-coating on glass plate, is put into the baking oven ladder-elevating temperature, and the control heating rate is 3 ℃/min, (110 ℃ * 1h, 210 ℃ * 1.2h, 300 ℃ * 1h), make the Y zeolite laminated film of cyclodehydration.
Maximum dehydrating amount sees Table 2 under 30～420 ℃ among the example 1-5.
The maximum dehydrating amount of table 2 example 1-5
Claims (8)
1. a molecular sieve/polyimide composite film for adsorption separation is characterized in that with the polyimides being matrix, and the molecular sieve filling intercalation is in polyimide matrix, and wherein the mass ratio of molecular sieve and polyimides is 0.05～0.5.
2. film according to claim 1 is characterized in that described molecular sieve is any in the former powder of zeolite molecular sieve, mesopore molecular sieve or carbon molecular sieve.
3. method for preparing molecular sieve/polyimide composite film for adsorption separation as claimed in claim 1, concrete steps are as follows:
The preparation of A, molecular sieve solution
Molecular sieve is added in the aprotic polar solvent, and the control temperature-time stirs, to disperseing fully;
The preparation of B, molecular sieve/polyamic acid PAA composite solution
Add diamines in the mixed solution that makes in steps A, the control temperature stirs, and treats to add after it dissolves fully the dianhydride with the diamines equimolar amounts in batches again, and continuous stirring becomes the molecule screening uniform polyamic acid PAA composite solution that looses;
The preparation of C, molecular sieve/polyimide composite film
The dip-coating of PAA molecular sieve composite solution on non-porous support such as glass plate, is put into the baking oven ladder-elevating temperature, and cyclodehydration makes molecular sieve/polyimide composite film.
4. method according to claim 3 is characterized in that molecular sieve adds in the aprotic polar solvent among the above-mentioned steps A, and temperature is controlled at 20～30 ℃; Mixing time is 20～30min; Wherein molecular sieve and aprotic polar solvent mass ratio are 0.005～0.25.
5. method according to claim 3 is characterized in that among the above-mentioned steps B that temperature is controlled at 20～30 ℃; Stir 4～8h behind the dianhydride of 2～4 batches of addings of branch and diamines equimolar amounts; Wherein molecular sieve and PAA mass ratio are 0.05～0.5.
6. method according to claim 3 is characterized in that the speed of ladder-elevating temperature among the above-mentioned steps C is 2～5 ℃/min, is warmed up to 80～120 ℃ of constant temperature 30～90min; Be warmed up to 180～220 ℃ of constant temperature 30～90min; Be warmed up to 280～350 ℃ of constant temperature 30～90min.
7. method according to claim 3, it is characterized in that described dianhydride is a pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 4, the two phthalic anhydrides of 4 '-oxygen, isomery diphenyl sulfide dianhydride, triphen diether tetracarboxylic dianhydride, benzophenone tetracarboxylic acid dianhydride, benzophenone tetracarboxylic dianhydride, bisphenol-A dianhydride, hexafluoro isopropylidene two phthalandione dianhydrides or 3,3 ', 4, one or both blend in 4 '-diphenyl sulfone tetracarboxylic anhydride; Described diamines is 4,4 '-diaminodiphenyl ether, the dimethyl diphenyl methane diamines, 1, two (3-amino-benzene oxygen) benzene of 3-, 4,4 '-bisphenol-A diphenyl ether diamines, perfluor isopropylidene diamine, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulphone (DPS), 4,4 ' two (4-amino-benzene oxygen) diphenyl ether, diaminourea hexichol (first) ketone, 4,4 '-diaminourea triphenylamine, 4,4 '-MDA, diamino diphenyl sulfone, phenylenediamine, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,3 ' dimethyl-4,4 '-diaminodiphenyl-methane, 4,4 '-diaminourea-hexichol Oxy-1 "; 4 "-benzene, 4,4 ' diaminourea-hexichol Oxy-1 ", 3 "-benzene, 3,3 '-diaminourea-hexichol Oxy-1 "; 3 "-benzene or 4,4 '-diaminourea-two phenoxy group-4 ", one or both blend in the different propane of 4-diphenyl.
8. method according to claim 3 is characterized in that described aprotic polar solvent is N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO) or oxolane.
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| CN102716680A (en) * | 2012-06-05 | 2012-10-10 | 中国科学院化学研究所 | Polyamide microporous membrane and preparation method thereof |
| CN109126727A (en) * | 2018-10-12 | 2019-01-04 | 淮阴工学院 | The preparation method of the mesoporous molecular sieve membrane of amino functional |
| CN109937084A (en) * | 2016-11-10 | 2019-06-25 | 陶氏环球技术有限责任公司 | The improved method for preparing carbon molecular sieve hollow-fibre membrane |
| CN113354816A (en) * | 2021-05-28 | 2021-09-07 | 无锡高拓新材料股份有限公司 | Method for synthesizing polyamic acid solution and film prepared by method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102716680A (en) * | 2012-06-05 | 2012-10-10 | 中国科学院化学研究所 | Polyamide microporous membrane and preparation method thereof |
| CN109937084A (en) * | 2016-11-10 | 2019-06-25 | 陶氏环球技术有限责任公司 | The improved method for preparing carbon molecular sieve hollow-fibre membrane |
| CN109937084B (en) * | 2016-11-10 | 2022-05-24 | 陶氏环球技术有限责任公司 | Improved method for preparing carbon molecular sieve hollow fiber membrane |
| CN109126727A (en) * | 2018-10-12 | 2019-01-04 | 淮阴工学院 | The preparation method of the mesoporous molecular sieve membrane of amino functional |
| CN109126727B (en) * | 2018-10-12 | 2021-02-19 | 淮阴工学院 | Preparation method of amino functionalized mesoporous molecular sieve membrane |
| CN113354816A (en) * | 2021-05-28 | 2021-09-07 | 无锡高拓新材料股份有限公司 | Method for synthesizing polyamic acid solution and film prepared by method |
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| CN101816899B (en) | 2012-03-21 |
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