DE4241302A1 - Aromatic polyamide(s) - derived from aromatic di:amine(s) contg. phenyl:indane gp. and aromatic di:carboxylic acid(s) - Google Patents

Abstract

New aromatic polyamides have the formula (I) (where X = CO or SO2; R1 = Me and R2 = R3 = R4 = H; or R1 = R2 = R4 = Me and R3 = H; or R1 = R4 = Me and R2 = R3 = 1-6C alkyl or aryl; or R1 = Me, R3 = H and R2 = R4 = 1-16C alkyl or aryl; and Ar = 6-30C aromatic residue). USE/ADVANTAGE - The polyamides are useful e.g. in the prodn. of gas sepn. membranes and semipermeable membranes such as ultrafiltration or microfiltration membranes with good selectivity and permeability; also for prodn. of moulded articles. The polyamides are soluble in solvents such as NMP, DMAc, DMSO, THF and CHCl3 which facilitates processing, and they are completely amorphous and have Tgs of 200-300 deg. C so that they are processable as thermoplastics. Membranes and other prods. made from the polyamides are resistant to high temps. and aggressive media.

Description

The present invention relates to polyamides derived from an aromatic Diamine with a phenylindane moiety and aromatic dicarboxylic acids derive their production and use.

Polyamides are used for the production of membranes for the separation of gases and Liquids, especially at high temperatures and in aggressive media suitable. They generally show good selectivity with limited Permeability. From US 4,765,897 it is known that aromatic polyamides (for example, the condensation product of phenylenediamine and 1,3,5- Benzene tricarboxylic acid) a layer of a membrane for reverse osmosis can be produced.

It was therefore the task of creating a new polyamide, which is too process a membrane with good selectivity and permeability. The The present invention solves this problem.

The invention relates to a polyamide of the general formula V

in which
X = CO or SO ₂ ,
R ¹ = CH ₃ , R ² = R ³ = H or
R ¹ = R ² = CH ₃ , R ³ = H or
R ¹ = CH ₃ , R ² = R ³ = C ₁ -C ₁₆ alkyl or aryl or
R ¹ = CH ₃ , R ³ = H, R ² = C ₁ -C ₁₆ alkyl or aryl and
Ar = an aromatic radical having 6 to 30 carbon atoms.

Preferably, the aryl radical R ^{1 is} a phenyl radical.

The polyamides of the invention are soluble in common organic Solvents such as N-methylpyrrolidone (NMP), N, N-dimethyl-acetamide (DMAc), Dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and chloroform Room temperature or slightly elevated temperature. They are completely amorphous. Their glass transition temperature is 200 to 300 ° C, so they too are thermoplastically processable.

A process for the preparation of the polyamide according to the invention is based on an aromatic diamine and an aromatic activated dicarboxylic acid. The process is characterized in that about equimolar amounts a diamine of the general formula

wherein
X = CO or SO ₂ ,
R ¹ = CH ₃ , R ² = R ³ = H or
R ¹ = R ² = CH ₃ , R ³ = H or
R ¹ = CH ₃ , R ² = R ³ = C ₁ -C ₁₆ alkyl or aryl or
R ¹ = CH ₃ , R ³ = H, R ² = C ₁ -C ₁₆ alkyl or aryl, and an activated derivative of an aromatic dicarboxylic acid of the general formula Ar (COOH) ₂ , wherein Ar is a bivalent aromatic radical having 6 to 30 C atoms is allowed to react in an aprotic-dipolar solvent at elevated temperature and the polyamide is isolated.

The diamine can be prepared by reacting a bis-halogen compound of the formula (VI)

where Hal is chlorine or fluorine and X, R ¹ , R ² and R ^{3 have} the abovementioned meaning, with at least 2 moles of 4-aminophenol at elevated temperature in the presence of a base and in the presence of a solvent. As the solvent, aprotic solvents such as. B. N-methylpyrrolidone use. The preparation of the diamine I is the subject of a German patent application of the same filing date, to which reference is hereby expressly made.

The bis-halogen compound used as the starting material can be divided into two Make steps from a styrene derivative. This way is schematic on Example of a 1,1,3-trimethyl-3-phenylindane derivative of α-methylstyrene shown.

Friedel-Crafts acylation or sulfonation of the obtained phenylindane Derivatives with 4-halobenzoic acid chloride or 4-halosulfonyl chloride according to the scheme

provides the desired bishalum compound.

The preparation of the bis-halogen compound is also not described in the previously published German patent application P 42 05 811.2, to the hereby express reference is made.

Another process for producing 1 proceeds as follows scheme

The reaction proceeds analogously with p-Chlorphenylsulfochlorid and analogously with phenylindanes having other substituents R ¹ , R ² and R ³ .

The dicarboxylic acid Ar (COOH) _{2 used} preferably has the formulas HOOC-Ar ¹ -COOH or HOOH-Ar ¹ -X-Ar ² -COOH in which Ar ¹ and Ar ² independently of one another are 1,3-phenylene- or 1, 4-phenylene radicals represented by (C ₁ -C ₆ ) -alkyl, in particular t-butyl, (C ₁ -C ₆ ) -alkoxy, preferably each having up to 4 C atoms in the alkyl group, -CF ₃ or halogen, For example, fluorine, chlorine or bromine, and the radical X may be substituted

• a) a direct bond or one of the bivalent radicals -O-, -SO ₂ -, -SO-, -C (R ¹ ) ₂ -, in which R ^{1 is} hydrogen, (C ₁ -C ₆ ) -alkyl, C ₃ C ₆ -Cycloalkyl or fluoroalkyl having 1-4 C atoms in the alkyl group, such as -CH ₂ -, -C (CH ₃ ) ₂ - or -C (CF ₃ ) ₂ - or
• b) one of the radicals -O-Ar ¹ -O- or -C (CH ₃ ) ₂ -Ar ¹ -C (CH ₃ ) ₂ - or
• c) a radical -O-Ar ¹ -Y-Ar ² -O-, in which Y is O, SO ₂ or CO.

For the preparation of the aromatic polyamides of the general formula (V) according to the invention, the following acid derivatives are suitable, for example:
Aromatic dicarboxylic acid derivatives of the formula Cl-CO-Ar ¹ -CO-Cl as
4,4'-Diphenylsulfondicarbonsäuredichlorid,
4,4'-Diphenyletherdicarbonsäurechlorid,
4,4'-diphenyldicarboxylic acid dichloride, 2,6-naphthalenedicarboxylic acid dichloride,
Isophthalic acid dichloride, but especially Terephthalsäuredichlorid and
substituted terephthalic acid dichloride, e.g. B. 2-chloro-terephthalic acid dichloride.

The preparation of polyaramids can generally in a known manner Solution, interfacial or melt condensation take place. Hereby determined the method of carrying out the polycondensation, whether random copolymers, Block or graft copolymers are formed.

The solution condensation of the aromatic dicarboxylic acid dichlorides with the aromatic diamines are obtained in aprotic, polar solvents from Amide type such as N, N-dimethylacetamide or in particular N-methyl-2-pyrrolidone carried out. Optionally, these solvents can be prepared in a known manner to increase the solubility or to stabilize the polyamide solutions Halide salts of the first and / or second group of the periodic system be added. Preferred additives are calcium chloride and / or Lithium chloride. The amount of dicarboxylic acid dichloride is chosen so that the desired solution viscosity is achieved.

The polycondensation temperatures are usually between -20 and + 120 ° C preferably between +10 and + 100 ° C. Especially good results  are achieved at reaction temperatures between +10 and + 80 ° C. The Polycondensation reactions are generally carried out so that Conclusion of the reaction 2 to 30%, preferably 3.5 to 20 wt .-% of Polycondensate in the solution.

The polycondensation can be carried out in the usual manner, for. B. by adding monofunctional compounds such as benzoyl chloride are stopped.

After completion of the polycondensation, d. H. when the polymer solution to the Processing has reached required viscosity, the resulting and loosely bound to the amide solvent hydrogen chloride by addition neutralizes basic substances. Suitable for example Lithium hydroxide, calcium hydroxide, but especially calcium oxide.

To prepare a membrane of the polyamide according to the invention can be prepare a solution of the polyamide in an aprotic-polar solvent and produce thin liquid films on supports with it, e.g. By spin coating. Often the polycondensation solution can be applied directly. To Evaporation of the solvent remain on the substrate polyamide films with a thickness of at least 0.1 microns back.

When the activated derivatives of the aromatic dicarboxylic acid replaced by a derivative of an aromatic Tricarboxylic acid with anhydride, so you get to poly (amide-imides). When using benzene-1,2,4-tricarboxylic acid-1,2-anhydro-4-chloride is this Reaction represented by the following equation

The reaction takes place in solution, for. In N-methyl-2-pyrrolidone. The accumulating Polymer solutions can be processed into films or baked enamels.

For the preparation of poly (amide-imides) from the diamine of general formula I. you can also at least two polyvalent aromatic carboxylic acids use different valence. For example, you can first enter aromatic bis-dicarboxylic anhydride of the general formula II or III

wherein
Y is a direct bond or -O-, -S-, -CO-, -SO ₂ -, -CH ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -,
in an aprotic dipolar solvent, then react with an excess of the diamine of Formula I until a polyamic acid is formed, then thermally or chemically cleave water until an intermediate molecular weight imide and amino end groups are present.

The imidization in solution can be carried out by dissolving the Polyamic acid is a water entrainer, especially an aromatic Connection such. For example, benzene, toluene or chlorobenzene, adding the solution heated to boiling and until boiling for the imide cyclization calculated amount of water with the help of the water drag as an azeotrope is deposited. The imidization is in the presence of a base as a catalyst accelerated. After completion of the imide cyclization, the imide is released from the solution isolated, for example by precipitation in a solvent in which the imide is not soluble, such. For example methanol.

Another method of imidization in solutions is to Solution of the polyamic acid a molar excess of a dehydrating water To give, for example, acetic anhydride, and after the completion of the Formation of the polyimide the excess of the dehydrating agent distill.

The obtained as an intermediate imide with amino end groups can be with an activated derivative of an aromatic dicarboxylic acid as above described further condensed. This results in a poly (amide-imide). The polyamides of the general formula V according to the invention can be according to known methods to gas separation membranes or to semipermeable membranes, for example to ultrafiltration or microfiltration membranes. In addition, can be through Thermoplastic processing also produce moldings.

The invention is further illustrated by the following examples.

example 1 (Terephthalic acid derivative)

26.34 g (40 mmol) of 1,6-bis [4- (4-aminophenoxy) benzoyl] -1,3,3-trimethylindane were dissolved under nitrogen in 243 ml of N-methyl-pyrrolidone. At 6 ° C., initially 7.72 g (38 mmol = 95 mol%) of terephthaloyl chloride (TPC) were added with stirring. The mixture was then heated to 70 ° C., and 0.56 g of TPC (in total 40.8 mmol = 102 mol%) were added in portions. 30 min later, the addition of 2.24 g (40 mmol) of CaO, which dissolves almost completely with heating within a few minutes. The viscous solution was stirred for 60 min, filtered and precipitated by dropping in water. After repeated washing with hot water (4 × 1 h) was stirred twice with acetone and the polymer dried to constant weight, finally at 100 ° C and 1 mbar.
Staudinger index in NMP + 0.06% LiBr: [n] _o = 1.04 dl / g
GPC in NMP + 0.06% LiBr (polystyrene calibration):
M _w = 158,000, M _n = 54,000, D = 2,9.

Example 2

For the production of an ultrafiltration membrane, the solution prepared in Example 1 was used. This solution was applied in a layer thickness of 200 microns on a polypropylene carrier fleece and coagulated in water at 20 ° C. An asymmetric ultrafiltration membrane was obtained, which was characterized as follows: The hydraulic permeability (ultrafiltration) and the retention capacity of the membrane with respect to dissolved macromolecules were determined at pressures of 3.0 bar at 20 ° C. in a stirred cylindrical cell (500 rpm, 250 ml, membrane area 38 cm ² ). The retention is by definition
R [%] = 100 * (C ₁ -C ₂ ) / C ₁
C ₁ is the concentration of the aqueous test solution,
C ₂ is the concentration in the permeate.

As a test solution, a 2% poly (N-vinylpyrrolidone) solution (PVP) was used, available under the trade name "®Kollidon K30" from BASF (PVP K30). The molecular weight was 47,000 g / mol. The concentration of the test solutions and the permeates were determined by measuring the density of the aqueous solutions. The density measurements were carried out with a density meter DA 210 from Kyoto Electronics. The hydraulic permeability was determined to be 2700 l / m ² h. The retention capacity for PVP K30 was R = 75%.

Example 3

4.74 g of the polymer powder prepared according to Example 1 was in a Vacuum press, in the middle of a square, 10 cm × 10 cm large, 0.5 mm thick aluminum frame given. There was first a print of 50 mbar, then the sample within 10 minutes 360 ° C. heated and then 2 minutes at 360 ° C and a pressure of 150 bar pressed.

In this process, a 0.5 mm thick, stable plastic plate was created. Mechanical measurements on 1 cm wide strips from this plate were cut, yielded the following property values:

E-modulus (MPa): 2900 Tear stress (MPa): 69 Elongation at break (%): 42 Yield voltage (MPa): 73 Yield stretch (%): 123

Example 4 Preparation of Bisfluoro Compound VI (X = CO, Hal = F)

20 g (84.6 mmol) of 1,1,3-trimethyl-3-phenylindane are treated with 27 g (170 mmol) of 4-fluorobenzoic acid chloride in the presence of 29.3 g (220 mmol) of AlCl ₃ in 100 ml of nitrobenzene as solvent for 12 h heated to boiling. Then the solvent is removed in vacuo and slowly added to the residue 500 ml of 10% HCl. This mixture is extracted several times with a total of 500 ml of chloroform to take up the crude product. The organic phase is washed with water, concentrated in vacuo, and pre-purified by double column chromatography (silica gel, eluent hexane / ethyl acetate 4: 1).

Recrystallization from ethanol / water (10: 1) further purifies the monomer.
Mp: 45-48 ° C.

This product contains the following two isomers in the ratio 1: 1.

By repeated recrystallization, the 5-isomer can be obtained pure.

Example 5 Preparation of bischloro compound VI (X = SO ₂ , Hal = Cl)

The representation is completely analogous to Example 1 from 1,1,3-trimethyl-3-phenylindan and 4-chlorobenzenesulfonyl chloride, but here falls after a single recrystallization of the 5-isomer purely.
Yield: 35%, mp: 200-202 ° C

Example 6 Preparation of a bisfluoro compound VI (X = 502, Hal = F)

The preparation is carried out completely analogously to Example 4 from 1,1,3-trimethyl-3-phenylindane and 4-fluorobenzenesulfonyl chloride, but falls here after only one recrystallization of the 5-isomer purely.
Yield: 35%, mp: 168-170 ° C

Example 7 (diamine)

A mixture of 36.3 g (0.062 mol) of 1,1,3-trimethyl-3-phenyl-4 ', 5 (6) -bis (4 "-chlorophenylsulfonyl) indan (VI), 15.2 g (0.139 g) mol) 4-aminophenol, 20.0 g (0.145 mol) of potassium carbonate, 200 ml of N-methylpyrrolidone and 100 ml of toluene is heated for 8 hours on a water to reflux. After cooling to room temperature, the mixture is added in a separating funnel with 200 ml of chloroform. The water-soluble components are extracted with 200 ml of water (1 ×) and 200 ml of 5% sodium bicarbonate solution (2 ×) each time. Then it is extracted again with 200 ml of water. The aqueous phases are discarded. The organic phase is dried over anhydrous sodium sulfate and the solvent removed in vacuo. The residue is taken up in 100 ml of THF. The product is precipitated by pouring into 100 ml of an ethanol / water mixture (1: 1). It is filtered off and dried for 20 hours at 80 ° C vacuum.
Yield: 39.8 g (88% of theory) of I (X = SO ₂ , R ¹ = R ³ = CH ₃ , R ² -H)
Melting point 110 ° C (isomer mixture).

Example 8 (Synthesis of 1,1,3-trimethyl-3-phenyl-4 ', 5 (6) -bis [4' '(4' '' -] aminophenoxy) benzoyl] indan)

A mixture of 29.8 g (0.062 mol) of 1,1,3-trimethyl-3-phenyl-4 ', 5 (6) -bis (4 "-fluorobenzoyl) indan (VI), 15.2 g ( 0.139 mol) of 4-aminophenol, 20.0 g (0.145 mol) of potassium carbonate, 200 ml of N-methylpyrrolidone and 100 ml of toluene is heated to reflux for 8 hours on a water. After cooling to room temperature, 200 ml of chloroform are added to the reaction mixture in a separating funnel and extracted with 200 ml of water (1 ×) and 200 ml of 5% sodium bicarbonate solution (2 ×) to remove the water-soluble constituents. Then it is extracted again with 200 ml of water. The aqueous phases are discarded. The organic phase is dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure, the residue is taken up in 100 THF and precipitated by pouring into 100 ml of an ethanol / water mixture (1: 1). The product is filtered off and dried at 80 ° C in vacuo for 20 hours.
Yield: 36.8 g (90% of theory) of I (X = CO, R ¹ = R ³ = CH ₃ , R ² = H)
Melting point: 145 ° C (isomer mixture).

Claims (4)

1. polyamide of the general formula V wherein
X = CO or SO ₂ ,
R ¹ = CH ₃ , R ² = R ³ = R ⁴ = H or
R ¹ = R ² = R ⁴ = CH₃, R ³ = H or
R ¹ = R ⁴ = CH ₃ , R ² = R ³ = C ₁ -C ₁₆ alkyl or aryl or
R ¹ = CH ₃ , R ³ = H, R ² = R ⁴ = C ₁ -C ₁₆ -alkyl or aryl and
Ar is an aromatic radical having 6 to 30 carbon atoms. 2. A process for preparing a polyamide of an aromatic diamine and an aromatic activated dicarboxylic acid, characterized in that about equimolar amounts of a diamine of the general formula (I), wherein X, R ¹ , R ² and R ^{3 have} the meaning given in claim 1 with an activated derivative of an aromatic dicarboxylic acid of the general formula Ar (COOH) ₂ , wherein Ar is a bivalent aromatic radical having 6 to 30 carbon atoms, in react an aprotic-dipolar solvent at elevated temperature and the polyamide is isolated. 3. Use of a polyamide of the general formula (V) for the preparation a semipermeable membrane. 4. molding of a polyamide of the general formula (V).