JPS63283718A - Gas permeable conjugated film - Google Patents

Abstract

PURPOSE:To improve both the permeability and selectivity of gases by using for gas separation a conjugated film having an active layer of a glassy compolymer which incorporates therein at least one of metallic phthalocyanines and at least one of phthalic acid derivative, amine or the like. CONSTITUTION:An active layer of a gas permeable conjugated film consists of a glassy polymer such as 1,2-disubstituted-polyacetylene and polyphenylene oxide incorporating therein at least one of metallic phthalocyanines and at least one of the tertiary substances (such as phthalic acid derivative, pyromellitic anhydride, amide, imide and amine). This gas separation film is excellent in both the permeability and selectivity of gases and, in the case of destitute of either metallic phthalocyanine or a third substance, it does not exert its effect. For example: PO2=9.00X10<-8>cc.cm/cm<2>.sec.cmHg,alphaN2O<2>=4.8.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a gas permeable composite membrane used to separate and concentrate a specific gas from a gas mixture.

Conventional technology In recent years, specific gases have been separated and concentrated from mixed gases.

Methods using selectively permeable polymer membranes are being actively researched and put into practical use. Examples include helium extraction from natural gas and recovery of hydrogen gas from factory exhaust, but the technology to selectively permeate oxygen from the atmosphere to create oxygen-enriched air has a wide range of applications and various The impact on industries such as chemical processes, sludge treatment, combustion systems, and medicine is extremely large. The characteristics required of polymer membranes used in such technology are high selectivity for the gases to be separated and gas permeability, and stable performance during long-term operation. be.

Problems to be Solved by the Invention Among currently known polymers, polytrimethylsilylpropyne (PM) has particularly excellent gas permeability.
SP), the oxygen permeability coefficient Po2 is 1.60 x 10-
'cc -am/cm2・sec-cmHg, i/Po2 for silicone rubber is ~6.0×110-8CC-C
/Cm2・seC-CmHg, etc., but these have a separation coefficient a (f'o2 / P N2 '
is only about 1.4 for the former and about 2.0 for the latter. On the other hand, there are many polymeric materials with large separation coefficients, but all of them have poor gas permeability.For example, polyphenylene oxide has a large α of about 4.0, but Po2 is 2.8 x 10
-9cc-cn1/cm2・SeC-cmHg, which is extremely small. In general, the relationship between gas permeability and gas selectivity in polymer membranes is such that as one increases, the other decreases, and selective gas permeable membranes that can separate large amounts of specific gases at high concentrations have not yet been developed. I wasn't getting it.

The present invention solves the above-mentioned problems, and aims to provide a gas permeable composite membrane having excellent characteristics in both gas permeability and gas selectivity.

Means for Solving the Problems The present invention provides that at least one layer of a membrane having selective gas permeability is made of a glassy polymer containing at least one metal cap and at least one third substance. The above objective is achieved by a gas permeable composite membrane.

Function The present invention can improve gas permeability and gas separation property at the same time by incorporating a metal phthalocyanine and a third substance into a glassy polymer.

Suitable glassy polymer membrane materials used in the present invention include polyphenylene oxide, 1,2-disubstituted polyacetylene, polysulfone, polyfumaric acid ester, etc., and the central metal of the metal phthalocyanine contained in this polymer is Fe. .

Cu, Ni, Co, etc. are good, and as a third substance,
Preferred examples include phthalimide, phthalonitrile, phthalic acid derivatives of phthalic anhydride, mellitic acid derivatives such as pyromellitic anhydride, and compounds having an amino group such as amides, imides, amines, and heterocyclic amines.

As a method for incorporating the metal butalocyanine and the third substance into the glassy polymer layer (composite method), the metal butalocyanine and the third substance may be dissolved together with the polymer in a film forming solution during the production of the glassy polymer film; The polymer film may be dissolved in a suitable solvent and immersed in it, or it may be applied to the surface of the film. The treatment to contain the substance may be carried out simultaneously or in two separate steps, and in this case, a different treatment method may be used.In addition, metal phthalocyanines are generally poorly soluble or insoluble in solvents, so when a solution is made as described above. is -CHs e
You can change the solubility by adding an appropriate substituent such as C2Hs.

The above-mentioned compounding method is ineffective or ineffective if only the metal phthalocyanine or the above third substance is used, and the effect of improving the gas permeability of the polymer membrane can only be obtained by compounding using both. It is.

Example Examples of the present invention will be described in detail below.

<Example-1> Polytrimethylsilylpropyne (
-PMSP) to prepare a 2 wt % toluene solution, and cast this onto a glass plate to produce a 40 μm thick film. This film was heated at 120°C in a vacuum of 10-5 Torr using phthalimide as a third substance.
4 minutes in a vacuum of 10-5 Torr using iron phthalocyanine as the metal phthalocyanine.
Vapor deposition was carried out at 20°C (heated twice for 3 minutes. When the gas permeability of this composite film was measured by a low vacuum method, the oxygen permeability coefficient P
o2 is 9.00 x 100-8CC-C/Cm2Cm
At 2-8 eC-C, an oxygen/nitrogen separation coefficient α of about 4.8 was obtained. Compared to untreated PMSP membrane, Po2 is 10
However, α can be increased by 3.5 times, and this can be compared to the silicone rubber (Po
276, OX 10-8cc・cm/cm2-sec
-cmHg, α22.0), 1 for Po2
．． The characteristics are 5 times better and 2.4 times better at α.

Comparative Example-1> In Example-IC=, when only iron phthalocyanine was used as the metal phthalocyanine and was heated to 420°C for 3 minutes in a vacuum of 10-5 Torr, Po2 was 1.0.
2×110-6CCIIC/Cm2・SeCjCmHg
, α was 1.5. In addition, using only phthalimide as the third substance, the temperature was 120°C in a vacuum of 10-5 Torr.
When heated for 3 minutes, Po2 is 1.05 x 1
0""'cc·cm/cm2·sec-cmHg, α was 1.5. In this way, in the composite treatment, it is not possible to improve α with either the metal phthalocyanine or the third substance, and this tendency is reflected in the above-mentioned iron phthalocyanine,
Similar findings were observed not only with phthalimide but also with the other substances mentioned above. To obtain the effects of the present invention, both the metal phthalocyanine and the third substance are required.

<Example-2> In Example-1, the thickness of the PMSP film was 19 μm.
A mixture of iron phthalocyanine and phthalimide (weight ratio 7:3) was added to it at a vacuum level of 10-5 Torr.
Pre-coating was carried out at 120-200°C for 1 minute and at 200-400°C for 4 minutes. The T'o2 of this composite membrane is 1.10X
10-'cc#cm/cm2asec#cmHg1α
was approximately 4.6, and Po2 was reduced to one-tenth of that of the untreated PMSP film, but α was able to be increased by 3.3 times.

<Example-3> When composited in the same manner as in Example-1 using polyphenylene oxide (PPO) as the glassy polymer, Po2 was 1.32 x 10-9cc-cm/a.
m2·seC-cmHg, α obtained a value of 6.9, and untreated pp.

Compared to , α was 1.7 times larger.

<Example-4> A 2 wt % benzene solution was prepared using PMSP as the glassy polymer, and this was cast on a Teflon plate.
A 2 μm film was produced. Pyromellitic anhydride was used as the third substance, heated to 2800C in a vacuum of 1O-5 Torr, and pre-deposited for 5 minutes, then Alcian blue was used as the soluble metal phthalocyanine, and 1wt.
% methanol solution was prepared, and the above film was immersed therein for 1 hour.

Further, it was heated and dried at 80°C for 30 minutes to form a composite film. The gas permeability of this composite membrane is 2.8×10
″′″8CC@Cm/Cm2·seC@CmHg, α was approximately 3.2.

In the above example, PMsp, p was used as the glassy polymer.
po, iron phthalocyanine as metal phthalocyanine,
Although only phthalimide and pyromellitic anhydride have been described as Alcian blue and tertiary substances, the present invention is not limited thereto.

Effects of the Invention The present invention provides a gas permeable composite membrane in which at least one layer of the membrane having selective gas permeability contains at least one metal phthalocyanine and at least one third substance in a glassy polymer. Compared to conventional gas permeable membranes, this method has the advantage of providing a high-performance gas permeable membrane with excellent gas permeability and gas separation properties.

Claims (3)

[Claims] (1) A gas permeable composite membrane characterized in that at least one layer of the membrane having selective gas permeability is made of a glassy polymer containing at least one metal phthalocyanine and at least one third substance. (2) The third substance is a phthalic acid derivative, a mellitic acid derivative,
The gas permeable composite membrane according to claim 1, which is selected from the group consisting of amines and heterocyclic amines. (3) The gas permeable composite membrane according to claim 1, wherein the glassy polymer is 1,2-disubstituted polyacetylene or polyphenylene oxide.