JPS5855006A - Polysulfone ether amide membrane - Google Patents

Abstract

PURPOSE:To obtain a membrane having high sepn. performance in a membrane for separating gaseous mixtures to each other by using poly(acyl sulfone ether amide) as a material. CONSTITUTION:Poly(acryl sulfone ether amide) of about 1,000-100,000 number average mol.wts. is dissolved in a solvent such as dimethyl formamide and the soln. is cast on a glass sheet and is dried, whereby a membrane with 0.01- 1,000mu thickness is prepd. The membrane of this invention is usable for sepn. of liquid mixtures to each other. The coeff. of permeation (CC.cm/cm<2>.sec.cm Hg) of a membrane with 26mu thickness produced by using the DMF soln. of the polysulfone ether amide from the p-aminophenol 4,4'-dichlorodiphenyl sulfone and the isophthalic chloride in one embodiment is N2(1.9X10<-12>), O2(1.9X10<-11>).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to poly(arylsulfone ether amide) membranes for use in the separation of substances.

Although various polymeric membranes have been tested in the past for the purpose of separating gas mixtures, they have not exhibited acceptable permeation rates and gas selectivity, making them unsuitable for commercial separation.

Furthermore, although some conventional membranes have a high permeation rate, they have low gas selectivity, so they can be used to separate a specific gas from a gas temperature mixture to a higher concentration. This separation does not lead to obtaining a highly concentrated gas, and requires multiple stages of separation, which increases the cost of compressing the gas, resulting in an economical disadvantage.

Especially in gas! It is difficult to separate element and nitrogen by imparting permselectivity tmK because the molecular sizes of nitrogen and oxygen are similar.

Therefore, if there is a membrane with excellent permselectivity in the separation of oxygen and nitrogen, it can generally be expected to have excellent permselectivity in the separation of other gas mixtures as well.

In addition, excellent permselectivity can be expected in the separation of not only gases but also other substance mixtures.

The present inventors also investigated the separation performance (!l) in the separation of oxygen and nitrogen.
! As a result of studying membranes with large permeability coefficients (expressed as the ratio of the permeability coefficients of carbon dioxide and nitrogen), the present inventors discovered that membranes made of polyallylsulfone etheramide exhibit high separation performance for oxygen and nitrogen, and arrived at the present invention. .

Various poly(arylsulfone etheramides) can be used as the membrane material of the present invention, but
For example, it can be synthesized by reacting at least one of the diamine compounds shown in the following Table 1 with iso7thal acid tetralide and/or terephthalyl chloride according to the method normally used when synthesizing polyamide. The molecular weight is not particularly limited, but a number average molecular weight of 7,000 to 100,000 is usually preferred.

Table 7 For forming a film of polysulfone ether amide, any material can be used as long as it can dissolve the polymer, but dimethylformamide is suitable.

Anisotropic 4!1 also has a dense, non-porous surface layer and a porous layer.
The belly is dimethylformamide, pyridine-n
- a non-volatile solvent such as hexanol - a volatile solvent, - a poor solvent combination system,
1゜The thickness of the polysulfone ether amide in the present invention is not particularly limited, but 0.0/p-1000ts is preferable.
.

The present invention uses gases such as cellulose, nitrogen, carbon dioxide-carbon oxide, water, wood, helium, methane, albo, etc. Separation of s1 element and oxygen in the production of l-phoneme air, separation of methane and helium in the recovery of helium from natural gas,
Separation of argon and hydrogen, methane and hydrogen, nitrogen and hydrogen in the recovery of hydrogen from hydrogenation reaction exhaust gas, separation of carbon monoxide and hydrogen in the recovery of hydrogen from cracking gas, carbon dioxide from combustion gas It can be applied to the separation of carbon dioxide and nitrogen in the recovery of carbon dioxide.

It can also be applied to mutual separation from liquid mixtures.

Next, the scope of this patent will be explained using examples.

Reference example 1 ah・m5try 1aition vol/2. J
Various sulfone ether diamines were synthesized according to the method described in d j ~4θl(/?7&).

As an example of the synthesis method, a four-hole flask equipped with a sulfomine stirrer is prepared from dobuminophenol and hedadic 0-rodiphenyl sulfone.

Heat up to 10° C. and add gastric soda as an approximately 10% aqueous solution.

/10 to 1 σtK to azeotrope the water with toluene and remove it.

After removing the water for about 1 hour, the remaining toluene was distilled off while increasing the temperature to 160°C.The reaction temperature was cooled to 1/θ°C, and 24 tons of dichlorodiphenyl sulfone was added. /l/ (0.01 μmol) was added, heated to /40 to 761°C, and reacted for 1 hour.

The reaction mixture was cooled to room temperature and treated with 2% MaOH-/% Ma,
Add to an aqueous solution of N-80, solidify, separate F and 7% N-80
3 solution and washed with isoprono(Nol).

Dry under vacuum at 21°C.

Reference example - Table - Polysulfonated /I from sulfone ether diamine (I) and isophthaloyl chloride of /lee Sulfo/ether diamine (1) /-2 in a three-necked flask
, Rij J9 (0, O7 mol), Water J 701111
Add 1° caustic soda t, o 11 (θ, /j mol) t-.

While stirring vigorously, cyclohexanone=! 0ymlK dissolved isophthaloyl chloride O, 09g (o, ox
mol) at once and react for 10 minutes. - Tanol j 00 mj k210t was used to precipitate the polymer, washed with water, washed with water, and dried under reduced pressure to obtain a polymer of /l.

The polysulfonamide/g synthesized in Example/Reference Example was dissolved in itg dimethylformamide, cast onto a glass plate using a doctor knife, and dried with slight heating to a thickness of 26 mm.
A transparent film 1 of μ was obtained.

The permeability coefficients of @ element and nitrogen were measured for this film using a Seikaken type gas permeability measuring device.

The following ratio of oxygen permeability coefficient to nitrogen permeability coefficient Po, /
Bi! The value of t/
``2*/<7 is large compared to the values of other polymers that have been previously reported.

N! Transmission coefficient (PH = Hewa x IO'''''12Co
(flTP), cx/Cll5ec, cmHJFO8 p (Po2)=/, riX/ 0-”
Po, / PN, =/θ Patent applicant: Mitsubishi Chemical Industries, Ltd., agent: Patent attorney Chokashu - 1 other person

Claims (2)

[Claims] (1) Substance separation membrane 0 made of poly(arylsulfone ether amide) that allows multiple types of substances to permeate and separates the substances from each other based on the difference in permeation rate. (2) A polymer in which poly(arylsulfone ether amide) has a plurality of chemical structures represented by the formula - sulfone ether amide 'F)! .