TITLE: Novel multicomponent fluid separation membranes.
European Patent Application EP0489418 A1

ABSTRACT:
A process for preparing multicomponent gas separation membranes is
disclosed. The process involves casting two or more solutions of
polymer, and partially removing solvent from the side of the cast
polymer that is to form the gas separation layer of the membrane. The
membrane is then quenched to freeze its structure and then the
remainder of the solvent removed to form the gas separation membrane.

INVENTORS:
Ekiner, Okan Max (US)
Hayes, Richard Allen (US)
Manos, Philip (US)

APPLICATION NUMBER: EP19910120830
PUBLICATION DATE: 06/10/1992
FILING DATE: 12/04/1991

ASSIGNEE: Pont DU. (US)
Air, Liquide (FR)
INTERNATIONAL CLASSES: B01D67/00; B01D69/08; B01D69/12; B01D71/56; B01D71/64; C08L77/00;
(IPC1-7): B01D69/12
EUROPEAN CLASSES: B01D69/08; B01D69/12; B01D71/56; B01D71/64; C08L77/00+B4K;
C08L77/00+B4N4; C08L77/00+B4N6; C08L77/00+B4P

DOMESTIC PATENT REFERENCES:
EP0087228 Polyamide membrane with controlled surface properties and
 process for its production.
EP0219878 Gas separation process and membrane.
EP0265898 Polyimide gas separation membranes.
EP0390992 Aromatic polyimide double layered hollow filamentary membrane
 and process for producing same.

FOREIGN REFERENCES:
DE3225618A1

OTHER REFERENCES:
PATENT ABSTRACTS OF JAPAN vol. 11, no. 193 (C-430)(2640) 20 June 1987 &
JP-A-62 001 925 ( NOK CORP. ) 28 January 1987

CLAIMS:
1. A process for manufacture of a multicomponent gas separation
membrane, comprising providing a solution of a film forming polymer as
a first supporting layer, applying to a surface of said first
supporting layer a second solution of a film forming polymer to provide
a separating layer to form a nascent membrane of at least two layers,
coagulating said nascent membrane, and drying said nascent membrane to
form a multicomponent gas separation membrane.
2. The process of Claim 1 wherein said providing of said first layer
and said applying of said second solution is performed by coextruding
said first solution and said second solution.
3. The process of Claim 2 wherein said coextruding yields a membrane in
the form of a hollow fiber having said separating layer on the exterior
of said fiber.
4. The process of Claim 3 wherein said separating layer is in the form
of an asymmetric membrane.
5. The process of Claim 1 wherein said nascent membrane is dried to
remove solvent from said separating layer prior to said coagulating.
6. The process of Claim 3 wherein said first layer is from about 25 to
about 300 microns in thickness.
7. The process of Claim 6 wherein said separating layer is from about
0.05 to about 150 microns in thickness, preferably from about 0.05 to
about 25 microns in thickness.
8. The process of Claim 2 wherein said second solution contains from
about 5 to about 50 weight percent film forming polymer.
9. The process of Claim 2 wherein said first solution contains from
about 15 to about 50 weight percent film forming polymer.
10. The process of Claim 6 wherein said film forming polymer of said
first solution and said polymer solution is selected from the group of
polysulfones, polyether sulfones, polyetherimides, polyimides,
polyamide, copolymers thereof, and blends thereof.
11. The process of Claim 10 wherein said film forming polymer of said
second solution is selected from the group of polyetherimide,
polyimide, polyamide, polyesters, and mixtures thereof.
12. The process of Claim 11 wherein said film forming polymer of said
first solution is selected from the group of polyether sulfones,
polysulfones, polyimides, or mixtures thereof, and said film forming
polymer of said second solution is a polyamide.
13. The process of Claim 12 wherein said polyamide has the formula:
EMI92.1 where R is one of either EMI92.2 EMI93.1 or mixtures thereof
where Z', Z'', Z''' are independently a carbon-carbon single bond, -O-,
-S-, EMI94.3 -SO2, EMI94.2 -CH2-, EMI94.1 EMI94.5 -NH-, EMI94.4 or
mixtures thereof, Ar is EMI94.6 where Z is a carbon-carbon single bond,
-O-, -S-, EMI94.9 -SO2-, EMI94.7 -CH2-, EMI94.8 EMI94.11 -NH-, EMI94.10
or mixtures thereof, n is an integer such that the polymer is of
film-forming molecular weight, -X, -X1, -X2 and -X3 are independently
hydrogen, alkyl groups of 1 to 6 carbon atoms, alkoxy groups of 1 to 5
carbon atoms, phenyl or phenoxy groups, and -Y, -Y1, -Y2, -Y3, -Y4,
-Y5, -Y6, -Y7, -Y8, -Y9, -Y10, -Y11, -Y12, -Y13, -Y14, -Y15
independently are X, X1, X2, X3, halogen, or alkyl groups of 1 to 6
carbon atoms.
14. The process of Claim 13 wherein Ar is EMI95.1 or mixtures thereof.
15. The process of Claim 14 wherein R is EMI95.2 or EMI96.1 or EMI96.2
or a mixture of EMI96.3 and EMI96.4 or a mixture of EMI96.5 and EMI97.1
or a mixture of EMI97.2 and EMI97.3 or EMI97.4 or a mixture of EMI97.5
and EMI97.6 or EMI98.1 or a mixture of EMI98.2 and EMI98.3 or a mixture
of EMI98.4 and EMI98.5 or a mixture of EMI99.1 and EMI99.2
16. The process of Claim 11 wherein said polyimide is an aromatic
polyimide comprising repeating units of the formula: EMI99.3 wherein R
and R' are selected from the group EMI99.4 EMI100.1 and EMI100.2 where
-Z- is -O-, EMI100.4 -S-, EMI100.3 a carbon-carbon single bond or
alkylene groups of 1 to 5 carbon atoms, -Ar- is one of either EMI100.5
EMI101.1 or mixtures thereof where Z', Z'', Z''' independently are a
carbon-carbon single bond, -O-, EMI101.3 -S-, EMI101.2 or alkylene
groups of 1 to 5 carbon atoms, X, X1, X2 and X3 are independently,
hydrogen, alkyl groups of 1 to 5 carbon atoms, alkoxy groups of 1 to 5
carbon atoms, phenyl or phenoxy groups, -Y, -Y1, -Y2, -Y3, -Y4, -Y5,
Y6, -Y7, -Y8, -Y9, -Y10, -Y11, -Y12, -Y13, -Y14, and -Y15 independently
are -X, -X1, -X2, -X3 or halogen, -Ar'-is EMI102.1 or mixtures thereof
where Z' has the above-defined meaning, m is 0 to 100 mole percent, n
is 0 to 100 mole percent, and (m + n) = 100%.
17. The process of Claim 16 wherein n is 0 to 20 percent and m is 0 to
80-100 percent.
18. The process of Claim 16 wherein R is EMI102.2
19. The process of Claim 18 wherein -Ar- is a mixture of EMI103.1 and
EMI103.2 or EMI103.3 or EMI103.4 or EMI103.5 or EMI104.1 or EMI104.2 or
EMI104.3 or EMI104.4 or a mixture of EMI104.5 and EMI104.6
20. The process of Claim 16 wherein R is EMI105.1
21. The process of Claim 20 wherein -Ar- is a mixture of EMI105.2 and
EMI105.3 or wherein -Ar- is EMI105.4
22. A multicomponent membrane comprising, a porous polymeric substrate
and a polyamide separating layer for separating gases, wherein said
polyamide has the formula EMI105.5 where R is one of either EMI106.1
EMI107.1 or mixtures thereof where Z', Z'', and Z''' are independently
a carbon-carbon single bond, -O-, -S-, EMI107.4 -SO2, EMI107.3 -CH2-,
EMI107.2 EMI107.6 -NH-, EMI107.5 or mixtures thereof, Ar is EMI107.7
where Z is a carbon-carbon single bond, -O-, -S-, EMI107.9 -SO2-,
EMI107.10 -CH2-, EMI107.8 EMI108.1 -NH-, EMI108.2 or mixtures thereof,
n is an integer such that the polymer is of film-forming molecular
weight, -X, -X1, -X2 and -X3 are independently hydrogen, alkyl groups
of 1 to 6 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or
phenoxy groups, and -Y, -Y1, -Y2, -Y3, -Y4, -Y5, -Y6, -Y7, -Y8, -Y9,
-Y10, -Y11, -Y12, -Y13, -Y14, -Y15 independently are X, X1, X2, X3,
halogen, or alkyl groups of 1 to 6 carbon atoms.
23. The multicomponent membrane of Claim 22 wherein said substrate is
selected from the group of polysulfones, polyether sulfones,
polyetherimide, polyimide, polyamide, polyesters, or mixtures thereof.
24. The multicomponent membrane of Claim 22 wherein Ar is EMI108.3 or
mixtures thereof.
25. The multicomponent membrane of Claim 22 wherein R is EMI108.4 or
EMI109.1 or EMI109.2 or EMI109.3 or EMI109.4 or EMI109.5 or EMI110.1 or
a mixture of EMI110.2 and EMI110.3 or a mixture of EMI110.4 and
EMI110.5 or a mixture of EMI110.6 and EMI111.1 or EMI111.2 or a mixture
of EMI111.3 and EMI111.4 or EMI111.5 or a mixture of EMI111.6 and
EMI111.7 or a mixture of EMI112.1 and EMI112.2 or a mixture of EMI112.3
and EMI112.4
26. A multicomponent membrane comprising a porous polymeric substrate
and a polyimide separating layer for separating gases wherein said
polyimide is an aromatic polyimide comprising repeating units of the
formula: EMI112.5 wherein R and R' are selected from the group EMI113.1
and EMI113.2 where -Z- is a carbon-carbon single bond, -O-, EMI113.4
-S-, EMI113.3 or alkylene groups of 1 to 5 carbon atoms, -Ar- is
EMI113.5 EMI114.1 or mixtures thereof where Z', Z'', Z''' independently
are a carbon-carbon single bond, -O-, EMI115.1 -S-, EMI115.2 or
alkylene groups of 1 to 5 carbon atoms, X, X1, X2 and X3 are
independently, hydrogen, alkyl groups of 1 to 5 carbon atoms, alkoxy
groups of 1 to 5 carbon atoms, phenyl or phenoxy groups, -Y, -Y1, -Y2,
-Y3, -Y4, -Y5, -Y6, -Y7, -Y8, -Y9, -Y10, -Y11, -Y12, -Y13, -Y14, and
-Y15 independently are -X, -X1, -X2, -X3 or halogen, -Ar'-is EMI115.3
or mixtures thereof where Z' has the above-defined meaning, m is 0 to
100 mole percent, n is 0 to 100 mole percent, and (m + n) = 100%.
27. The membrane of Claim 26 wherein m is 20 to 100 mole percent and n
is 20 to 100 mole percent.
28. The membrane of Claim 26 wherein said polymeric substrate is
selected from the group of polysulfones, polyether sulfones,
polyetherimide, polyimide, polyamide, polyesters, or mixtures thereof.
29. The membrane of claim 26 wherein R is EMI116.1
30. The membrane of claim 26 wherein -Ar- is a mixture of EMI116.2 and
EMI116.3 or wherein -Ar- is EMI116.4 or mixtures thereof, or wherein
-Ar- is EMI116.5 or EMI117.1 or EMI117.2 or EMI117.3 or EMI117.4 or
EMI117.5 or a mixture of EMI117.6 and EMI118.1
31. The membrane of claim 26 wherein R is EMI118.2
32. The membrane of claim 31 wherein -Ar- is a mixture of EMI118.3 and
EMI118.4 or wherein -Ar- is EMI118.5

DESCRIPTION:
Multicomponent membranes are prepared from the polymer prepared above
on top of VICTREX 600P polyethersulfone (a product of ICI). A 25%
VICTREX 600P polyethersulfone solution (based on weight) with 7.5%
polyvinyl pyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast
onto a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG
C. After drying on the plate for 0.5 minutes at 100 DEG C, a 22%
polymer solution (based on weight) of the polymer prepared above in
N-methylpyrrolidone is cast on top of the above film at 100 DEG C with
a 20-mil (5.1 x 10<-><4>m) knife gap. After drying at 100 DEG C +/- 3
DEG C for the times noted below, the membranes are coagulated in a
water bath at 25 DEG C +/- 1 DEG C. Three membranes are prepared with
dry times of 0.05 minute, 0.50 minute, and 1.00 minute, as described
above. All membranes exhibit good adhesion between the layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight at at 100 DEG C for 4 hours. All dry
membranes exhibit good adhesion between the component layers.
The procedure of this example demonstrates the applicability of the
materials described therein for fabrication into gas separation
membranes. Example 39
A stirred solution of 4,4'-[1,4-phenylenebis(1-methylethylidene)]
bisaniline (68.8g, 0.20 mol), 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)
ethylidene]-bis-1,3-isobenzofurandione (97.2g, 0.2025 mol) and
N-methylpyrrolidone (900 ml) is slowly heated to reflux under an inert
atmosphere while collecting distillates. After heating at reflux for 4
hours, a total of 346 ml distillate is collected. The viscous reaction
solution is cooled to room temperature, diluted with N-methyl
pyrrolidone, and precipitated in water. The resulting solid is
collected and washed twice with methanol. After air-drying overnight,
the solid is dried in a vacuum oven at 20 inches (0.51m) mercury and
120 DEG C for 3 hours and at 210 DEG C for 4 hours to yield 139.4g of
polymer product.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the polymer prepared above
on top of VICTREX 600P polyethersulfone (a product of ICI). A 25%
VICTREX 600P polyethersulfone solution (based on weight) with 7.5%
polyvinyl pyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast
onto a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG
C. After drying on the plate for 0.5 minutes at 100 DEG C, a 22%
polymer solution (based on weight) of the polymer prepared above in
N-methylpyrrolidone is cast on top of the above film at 100 DEG C with
a 20-mil (5.1 x 10<-><4>m) knife gap. After drying at 100 DEG C +/- 3
DEG C for the times noted below, the membranes are coagulated in a
water bath at 28 DEG C +/- 1 DEG C. Three membranes are prepared with
dry times of 0.05 minute, 0.50 minute, and 1.00 minute, as described
above. All membranes exhibit good adhesion between the layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight at 100 DEG C for 4 hours. All dry membranes
exhibit good adhesion between the component layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes. Example 40
This example illustrates the use of a polymer blend substrate
containing a small amount of the separating layer polymer to improve
the compatibility and adhesion between the separating and the substrate
layers.
ULTEM TM 1000, a commercially available polymer from GE described in
Example 18, is employed as the substrate. MATRIMID 5218, a commercially
available polymer from Ciba Geigy believed to have the following
structure EMI65.1 is employed as the separating layer.
A substrate solution containing 90:10 wt ULTEM:Matrimid ratio is
prepared according to the formulation: 30% by weight blend polymer and
6.0% by weight of tetramethylenesulfone, and 1.8% by weight of acetic
anhydride are dissolved in N-methyl-2-pyrrolidone.
A separating polymer solution is prepared according to the formulation:
27% by weight MATRIMID 5218, 5.4% by weight of tetramethylenesulfone,
and 1.6% by weight of acetic anhydride, in N-methyl-2-pyrrolidone.
The above solutions are coextruded through a composite fiber spinneret
having fiber channel dimensions as set forth in Example 4. The
separating polymer solution is extruded at a rate of 16 cm<3>/hr, and
the substrate polymer solution is extruded at a rate of 140 cm<3>/hr. A
solution of 90% by volume of N-methyl-2-pyrrolidone in water is
injected into the bore of the fiber at a rate of 60 cm<3>/hr while the
spinneret is maintained at 85 DEG C. The spun bicomponent fiber is
passed through an air-gap of 2.5 cm at room temperature into a water
coagulation bath at 27 DEG C. The composite fiber then is wound on a
drum at a rate of 100 meters/min. The composite fiber then is washed
with 50 DEG C water for about 12 hours and then solvent exchange
dehydrate by using methanol and F-113 as described in U.S. 4,080,743;
4,080,744; and 4,120,098.
The composite fiber is tested for mixed gas O2/N2 (21/79, mole) at 100
psi at 25 DEG C. The fibers exhibit the following separation
performance: O2 Productivity: 112 GPU O2/N2 Selectivity: 1.1
The composite fibers as described above then are treated to seal
defects in the separating layer as taught in U.S. 4,230,463 which is
incorporated herein by reference. The treatment involves contacting the
outer surfaces of the fibers with 2.5% by weight solution of a
polysiloxane of the tradename of SYLGARD 184, in FREON 113, decanting
the solution, and drying the fibers in a vacuum oven at 20 inches
mercury overnight. The composite fiber treated as above is retested for
mixed gas O2/N2 (21/79 mole) at 100 psi feed from 25 DEG C. The results
are reported below: O2 Productivity: 5 GPU O2/N2 Selectivity: 6.5
Examples 41-47
To a stirred solution of 1,4-bis(4-aminophenoxy)benzene (116.8g, 0.4
mol) in N-methylpyrrolidone (1000 ml) is added
5,5'-[2,2,2-trifluoro-1(trifluoromethyl)ethylidene]bis-1,3-isobenzofura
ndione (179.38g, 0.404 mol) under an inert atmosphere at room
temperature. The gold-colored reaction solution became very viscous and
is allowed to stir overnight at room temperature. A solution of acetic
anhydride (163.34g, 1.6 mol) and triethylamine (161.90g, 1.6 mol) is
added with rapid stirring at room temperature. After mixing over the
weekend at room temperature, the very viscous reaction solution is
diluted with additional N-methylpyrrolidone and precipitated in water.
The resulting solid is collected and washed three times with water,
washed twice with methanol and allowed to air dry overnight.
The solid is further dried in a vacuum oven at 20 inches (0.51m)
mercury and 130 DEG C for 5 hours an at 240 DEG C for 3 hours to yield
278.06g product. The polymer prepared above is found to be soluble in
dimethylsulfoxide, meta-cresol, N,N-dimethylacetamide and
N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the polymer prepared above
on top of VICTREX 600P polyethersulfone (a product of ICI). A 25%
VICTREX 600P polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast
onto a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG
C. After drying on the plate for 0.5 minutes at 100 DEG C, a 24%
polymer solution (based on weight) of the polymer prepared above in
N-methylpyrrolidone is cast on top of the above film at 100 DEG C with
a 20-mil (5.1 x 10<-><4>m) knife gap. After drying at 100 DEG C for the
times noted in Table 4, the membranes are coagulated in a water bath at
24 DEG C +/- 1 DEG C. All membranes exhibit good adhesion between the
layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperatures overnight at 100 DEG C for 4 hours. All dry membranes
exhibit good adhesion between the component layers.
The membranes prepared as above are tested for pure gas helium and
nitrogen permeabilities at 100 psig (689kPa), 25 DEG C. The results are
reported in Table 4.
Id=TABLE 4 Columns=4 Head Col 1: Example Head Col 2: Dry Time (min)
Head Col 3: PHe (GPU) Head Col 4: PHe/PN2 410.054683.6 420.506752.6
431.005423.8 442.003397.9 453.003022.8 464.001733.7 474.505763.3
Example 47 is further tested for mixed gas oxygen/nitrogen (21/79,
mole) permeabilities at 100 psig (689kPa), 25 DEG C. The results are
reported below: 02 Productivity: 8 GPU O2/N2 Selectivity: 3.2
The bicomponent membranes of Examples 43, 44, and 45 prepared as above
are treated as taught in U.S. 4,230,463 to seal defects in the
polyimide dense separating layer. This involves contacting the membrane
with 5.0% (weight) SYLGARD 184 solution in cyclohexane, removing the
membrane from said solution and drying the membrane in a vacuum oven at
20 inches (0.51m) mercury and 55 DEG C +/- 5 DEG C overnight.
The treated bicomponent membrane of Example 43 is tested for pure gas
helium and nitrogen permeabilities at 100 psig (689kPa), 23 DEG C. The
results are reported below: He Productivity: 141 GPU He/N2 Selectivity:
78.3
The treated bicomponent membrane of Example 44 is tested for pure gas
helium and nitrogen permeabilities at 100 psig (689kPa), 23 DEG C. The
results are reported below: He Productivity: 98 GPU He/N2 Selectivity:
54
The treated bicomponent membrane of Example 46 is tested for pure gas
helium and nitrogen permeabilities at 100 psig (689kPa), 23 DEG C. The
results are reported below: He Productivity: 66 GPU He/N2 Selectivity:
39
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes. Example 48
To a stirred solution of 4,4'-bis(4-aminophenoxy)biphenyl (25.0g, 0.068
mol) in N-methylpyrrolidone (200 ml) is added
5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]-1,3-isobenzofurand
ione (30.45g, 0.069 mol) under an inert atmosphere at room temperature.
The reaction became very viscous and additional N-methylpyrrolidone
(200 ml) is added. After stirring overnight at room temperature, a
solution of acetic anhydride (27.70g, 0.27 mol) and triethylamine
(27.4g, 0.27 mol) is added with rapid stirring at room temperature.
After stirring at room temperature for 2.5 hours, the reaction solution
is diluted with additional N-methylpyrrolidone and precipitated in
water. The resulting solid is collected and washed three times with
water, washed twice with methanol and allowed to air dry overnight.
The solid is further dried in a vacuum oven at 20 inches (0.51m)
mercury and 120 DEG C for 5 hours and at 250 DEG C for 3 hours to yield
40.8g product. The polymer prepared above is found to be soluble in
dichloromethane, m-cresol, dimethylsulfoxide, N,N-dimethylacetamide and
N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the polymer prepared above
on top of VICTREX 600P polyethersulfone (a product of ICI). A 25%
VICTREX 600P polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast
onto a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 95 DEG
C. After drying on the plate for 0.5 minutes at 95 DEG C, a 22% polymer
solution (based on weight) of the polymer prepared above in
N-methylpyrrolidone is cast on top of the above film at 95 DEG C with a
20-mil (5.1 x 10<-><4>m) knife gap. After drying at 95 DEG C for four
seconds, the membrane is coagulated in a water bath at 18 DEG C. The
membrane exhibits good adhesion between the polymer layers.
The resulting membrane is washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membrane is dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours.
Example 48 is tested for pure gas helium and nitrogen permeabilities at
100 psig (689kPa), 25 DEG C. Results are reported in Table 5.
Id=TABLE 5 Columns=4 Head Col 1: Example Head Col 2: Dry Time (min)
Head Col 3: PHe (GPU) Head Col 4: PHe/PN2 480.0641317 Example 49
To a stirred solution of 4,4'-(methylethylidene)bisaniline-A EMI71.1
(45.2g, 0.20 mol) in N-methylpyrrolidone (350 ml) is dropwise added a
melted mixture of isophthaloyl dichloride:terephthaloyl dichloride
(7:3, molar, 40.69g, 0.20 mol) under an inert atmosphere. The reaction
temperature is maintained at under 50 DEG C by control of the addition
rate. The resulting reaction solution is stirred for 4 hours. To the
resulting very viscous reaction solution is added lithium hydroxide
monohydrate (20.98g, 0.5 mol) and the resulting reaction mixture is
mixed overnight at room temperature. The reaction solution is diluted
with additional N-methylpyrrolidone and precipitated in water. The
resulting solid is collected and soaked in water overnight, washed
three times with water, washed three times with methanol and allowed to
air dry overnight.
The solid is further dried in a vacuum oven at 20 inches (0.51m)
mercury and 120 DEG C for 6 hours to yield 76.0g product. The polymer
prepared above is found to be soluble in dimethylsulfoxide,
N-methylpyrrolidone, m-cresol, and dimethylacetamide.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) (38.4 x 10 m) knife gap. After drying
on the plate at 100 DEG C +/- 2 DEG C for 0.5 hour, the films are
further dried in a vacuum oven at 20 inches (0.51m) mercury and room
temperature overnight. The films are stripped off the plate and dried
in a vacuum oven at 20 inches (0.51m) mercury and 120 DEG C for 4
hours. The films are tough and flexible and can be creased without
cracking.
Multicomponent membranes are prepared from the polymer prepared above
on top of VICTREX 600P polyethersulfone (a product of ICI). A 25%
VICTREX 600P polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast
onto a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG
C. After drying on the plate for 0.5 minutes at 100 DEG C, a 24%
polymer solution (based on weight) of the polymer prepared above in a
8.5% lithium nitrate solution (based on weight) in N-methylpyrrolidone
is cast on top of the above film at 100 DEG C with a 20-mil (5.1 x
10<-><4>m) knife gap. After drying at 100 DEG C +/- 3 DEG C for the
time noted below, the membranes are coagulated in a water bath at 27
DEG C +/- 1 DEG C Three membranes are prepared with dry times of 0.05
minute, 0.50 minute and 1.00 minute, as described above.
All water-wet membranes exhibit excellent adhesion between the polymer
layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. The membranes
exhibit excellent adhesion between layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the material described therein for gas separation
membranes. Example 50
To a stirred solution of 3,4'-aminophenylether EMI73.1 (20.02g, 0.10
mol) in N-methylpyrrolidone (200 ml) is dropwise added a melted mixture
of isophthaloyl dichloride:terephthaloyl dichloride (7:3,molar, 20.50g,
0.101 mol) under an inert atmosphere. The reaction temperature is
maintained at under 50 DEG C by control of the addition rate. The
resulting very viscous gold solution is stirred for 6.0 hours and then
lithium hydroxide monohydrate (10.5g, 0.25 mol) is added. The resulting
reaction mixture is stirred overnight and then diluted with additional
N-methylpyrrolidone and precipitated in water. The resulting solid is
washed three times with water, washed twice with methanol, and allowed
to air dry overnight. The solid is further dried in a vacuum oven at 20
inches (0.51m) mercury and 120 DEG C for 5 hours.
The polymer prepared above is found to be soluble in dimethylsulfoxide,
N,N-dimethylacetamide, and N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the polymer prepared above
on top of VICTREX 600P polyethersulfone (a product of ICI). A 25%
VICTREX 600P polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast
onto a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG
C. After drying on the plate for 0.5 minutes at 100 DEG C, a 24%
polymer solution (based on weight) of the polymer prepared above in a
8.5% lithium nitrate solution (based on weight) in N-methylpyrrolidone
is cast on top of the above film at 100 DEG C with a 20-mil (5.1 x
10<-><4>m) knife gap. After drying at 100 DEG C +/- 3 DEG C for the
time noted below, the membranes are coagulated in a water bath at 20
DEG C +/- 1 DEG C. Three membranes are prepared with dry times of 0.05
minute, 0.50 minute and 1.00 minute, as described above.
All water-wet membranes exhibit good adhesion between the polymer
layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. The membranes
exhibit good adhesion between layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the material described therein for gas separation
membranes. Examples 51-52
To a stirred solution of 2,4,6-trimethyl-1,3-phenylene diamine (15.02g,
0.10 mol) and 1,3-bis(4-aminophenoxy)benzene (29.2g, 0.10 mol) in
dimethylsulfoxide (500 ml) is added
5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)
ethylidene]-1,3-isobenzofurandione (89.69g, 0.202 mol) under an inert
atmosphere at room temperature. The very viscous,light orange reaction
solution is stirred at room temperature for 1.25 hours and then a
solution of acetic anhydride (81.67g, 0.80 mol) and triethylamine
(80.95g, 0.80 mol) is added with rapid stirring at room temperature.
After stirring at room temperature overnight, the reaction solution is
precipitated in water. The resulting solid is collected and washed
twice with water, washed twice with methanol and allowed to air dry.
The solid is further dried in a vacuum oven at 20 inches (0.51m)
mercury and 120 DEG C for 3 hours and at 250 DEG C for 5 hours to yield
122.6g product. The polymer prepared above is soluble in acetone,
dichloromethane, dimethylsulfoxide, N,N-dimethylacetamide and
N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
A film, prepared as above which is 1.1 (2.8 x 10<-><5>m) mils thick, is
tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at
499 psig (3.44 x 10<6> Pa), 25.0 DEG C. The results are reported below:
02 Productivity: 200 centiBarrers O2/N2 Selectivity: 4.6
Multicomponent membranes are prepared from the polymer prepared above
on top of VICTREX 600P polyethersulfone (a product of ICI). A 25%
VICTREX 600P polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast
onto a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG
C. After drying on the plate for 0.5 minutes at 100 DEG C, a 22%
polymer solution (based on weight) of the polymer prepared above in
N-methylpyrrolidone is cast on top of the above film at 100 DEG C with
a 20-mil (5.1 x 10<-><4>m) knife gap. After drying at 100 DEG C for the
time noted in Table 6, the membranes are coagulated in a water bath at
21 DEG C. The resulting membranes are washed in water for 24 hours,
washed in methanol for 2 hours and washed in FREON TM 113 for 2 hours.
The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury
and room temperature overnight and at 100 DEG C for 4 hours.
Examples 51 and 52 are tested for pure gas helium, nitrogen, and carbon
dioxide permeabilities at 100 psig (689kPa), room temperature. The
results are reported in Table 6. Example 51 is tested for mixed gas
oxygen/nitrogen (21/ 79, mole) permeabilities at 100 psig (689kPa), 23
DEG C. Results are reported in Table 6.
Id=TABLE 6 Columns=8 Head Col 1: Example Head Col 2: Dry Time (min)
Head Col 3: PHe (GPU) Head Col 4: PHe/PN2PCO2 (GPU) Head Col 5:
PCO2/PN2PO2 (GPU) Head Col 6: PO2/PN2 510.53233615517.3363.3
521.040013.61966.7
The membrane fabrication procedure of these examples demonstrates the
applicability of the material described therein for gas separation
membranes. Example 53
To a stirred solution of 2,4,6-trimethyl-1,3-phenylene diamine (15.02g,
0.10 mol) and 1,4-bis(4-aminophenoxy)benzene (29.2g, 0.10 mol) in
N-methylpyrrolidone (500 ml) is added
5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]-1,3-benzofurandion
e (89.69g 0.202 mol) under an inert atmosphere at room temperature. The
very viscous reaction solution is stirred at room temperature for 3.5
hours and then a solution of acetic anhydride (81.67g, 0.80 mol) and
triethylamine (80.95g, 0.80 mol) is added with rapid stirring at room
temperature. After stirring overnight at room temperature, the reaction
solution is precipitated in water. The resulting solid is collected and
washed twice with water, washed twice with methanol, and allowed to air
dry overnight.
The solid is further dried in a vacuum oven at 20 inches (0.51m)
mercury and 120 DEG C for 3 hours and at 250 DEG C for 5 hours to yield
123.1g of polymer product. The polymer prepared above is soluble in
acetone, dichloromethane, dimethylsulfoxide, N,N-dimethylacetamide, and
N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 21C for 0.5 hour, the films are further dried in a vacuum
oven at 20 inches (0.51m) mercury and room temperature overnight. The
films are stripped off the plate and dried in a vacuum oven at 20
inches (0.51m) mercury and 120 DEG C for 4 hours. The films are tough
and flexible and can be creased without cracking.
A film, prepared as above which is 1.1 mils (2.8 x 10<-><5>m) thick, is
tested for mixed gas oxygen/nitrogen (21/79,mole) permeabilities at 512
psig (3.53 x 10<6> Pa), 24.5 DEG C. The results are reported below: 02
Productivity: 400 centiBarrers O2/N2 Selectivity: 4.5
Multicomponent membranes are prepared from the above polymer on top of
VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P
polyether sulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on
a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 97.5 DEG C
+/- 3.0 DEG C. After drying on the plate for 15 seconds, a 22% polymer
solution (based on weight) of the polymer prepared above in
N-methylpyrrolidone is cast on top of the above film at 97.5 DEG C +/-
3.0 DEG C with a 20-mil (5.1 x 10<-><4>m) knife gap. After drying at
97.5 DEG C +/- 3.0 DEG C one minute, the membrane is coagulated in a
water bath at 25.0 DEG C +/- 1.O DEG C. Good adhesion between the
polymer layers is apparent.
The resulting membrane is washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membrane is dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. The membranes
exhibit good adhesion between the polymer layers.
The membrane is tested for pure gas helium, nitrogen, and carbon
dioxide permeabilities and mixed gas oxygen/nitrogen (21/79, mole)
permeabilities at 100 psig (689kPa), 24 DEG C. The results are reported
in Table 7.
Id=TABLE 7 Columns=9 Head Col 1: Example Head Col 2: Dry Time PSF (min)
Head Col 3: Dry Time PI (min) Head Col 4: PHe (GPU) Head Col 5:
PHe/PN2PCO2 (GPU) Head Col 6: PCO2/PN2PO2 (GPU) Head Col 7: PO2/PN2
530.251.04282023111603.1
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes. Example 54
To a stirred solution of 4,4'(methylethylidene)bisaniline (45.2g, 0.20
mol) in N-methylpyrrolidone (500 ml) is added
5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]-1,3-isobenzofurand
ione (89.69g, 0.202 mol) under an inert atmosphere at room temperature.
After stirring at room temperature for 5 hours, a solution of acetic
anhydride (81.67g, 0.8 mol) and triethylamine (80.95g, 0.80 mol) is
added with rapid stirring. The resulting viscous reaction solution is
stirred at room temperature overnight and then precipitated in water.
The resulting solid is collected and washed twice with water, washed
twice with methanol and allowed to air dry overnight. The solid is
further dried in a vacuum oven at 20 inches (0.51m) mercury and 120 DEG
C for 4 hours and at 250 DEG C for 4 hours to yield 130.4g product.
The polymer prepared above is soluble in acetone, dichloromethane,
m-cresol, dimethylsulfoxide, N,N-dimethylacetamide and
N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the above polymer on top of
VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P
polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. 10,000) in N-methylpyrrolidone is cast on a
glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG C.
After drying on the plate for 0.5 minutes at 100 DEG C, a 22% polymer
solution (based on weight) of the polymer prepared above in
N-methylpyrrolidone is cast on top of the above film at 100 DEG C with
a 20-mil (5.1 x 10<-><4>m) knife gap. After drying at 100 DEG C +/- 3
DEG C for the time noted below, the membranes are coagulated in a water
bath at 15 DEG C +/- 1 DEG C. Three membranes are prepared with dry
times of 0.05 minute, 0.50 minute and 1.00 minute, as described above.
All membranes exhibit excellent adhesion between the polymer layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. The membranes
exhibit excellent adhesion between the component layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes. Example 55
To a stirred solution of 4,4'-(methylethylidene) bisaniline (22.6g,
0.10 mol) and 1,4-bis(4-aminophenoxy)biphenyl (37.28g, 0.10 mol) in
N-methylpyrrolidone (350 ml) is dropwise added a melted mixture of
isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 40.69g,
0.20 mol) under an inert atmosphere. The reaction temperature is
maintained at under 50 DEG C by control of the addition rate. The
resulting very viscous light brown solution is stirred for 4.5 hours
and then lithium hydroxide monohydrate (21g, 0.5 mol) is added. The
resulting reaction mixture is stirred overnight and then diluted with
additional N-methylpyrrolidone and precipitated in water. The resulting
solid is collected and washed three times with water, washed twice with
methanol and allowed to air dry overnight.
The solid is further dried in a vacuum oven at 20 inches (0.51m)
mercury and 117 DEG C +/- 2 DEG C for 6 hours to yield 85.5g product.
The polymer prepared above is soluble in dimethylsulfoxide, m-cresol,
N,N-dimethylacetamide and N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the above polymer on top of
VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P
polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on
a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG C.
After drying on the plate for 0.5 minutes at 100 DEG C, a 20% polymer
solution (based on weight) of the polymer prepared above with 6.8%
lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top
of the above film at 100 DEG C with a 20-mil (5.1 x 10<-><4>m) knife
gap. After drying at 100 DEG C +/- 3 DEG C for the times noted below,
the membranes are coagulated in a water bath at 25 DEG C + 1 DEG C.
Three membranes are prepared with dry times of 0.05 minute, 0.50 minute
and 1.00 minute, as described above.
All membranes exhibit excellent adhesion between the polymer layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. The membranes
exhibit excellent adhesion between the component layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes. Example 56
To a stirred solution of 2,7-bis(4-aminophenoxy)naphthalene (25.0g,
0.073 mol) in N-methylpyrrolidone (200 ml) is dropwise added a melted
mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3,molar,
15.14g, 0.075 mol) under an inert atmosphere. The reaction temperature
is maintained at under 50 DEG C by control of the addition rate. The
resulting viscous solution is stirred for 1 hour after the final
addition and then lithium hydroxide monohydrate (10.50g, 0.25 mol) is
added. The resulting reaction mixture is stirred overnight at room
temperature, diluted with N-methylpyrrolidone and precipitated in
water. The resulting white solid is collected and washed three times
with water and twice with methanol. The resulting solid is air-dried
overnight and then dried in a vacuum oven at 20 inches (0.51m) mercury
and 120 DEG C for 5 h to yield 34.64g product.
The polymer prepared above is soluble in N,N-dimethylacetamide and
N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the above polymer on top of
VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P
polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on
a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG C.
After drying on the plate for 0.5 minutes at 100 DEG C, a 20% polymer
solution (based on weight) of the polymer prepared above in a 8.5%
lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top
of the above film at 100 DEG C with a 20-mil (5.1 x 10<-><4>m) knife
gap. After drying at 100 DEG C +/- 3 DEG C for the times noted below,
the membranes are coagulated in a water bath at 23 DEG C +/- 1 DEG C.
Three membranes are prepared with dry times of 0.05 minute, 0.50 minute
and 1.00 minute, as described above.
All water-wet membranes exhibit excellent adhesion between the layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. All dry
membranes exhibit excellent adhesion between the component layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes. Example 57
To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (186.4g, 0.5
mol) and 3,3'-aminophenylsulfone (124.2g, 0.5 mol) in
N,N-dimethylacetamide (2600 ml) is dropwise added a melted mixture of
isophthaloyl dichloride: terephthaloyl dichloride (7:3, molar, 203.0g,
1.0 mol) under an inert atmosphere. The reaction temperature is
maintained at under 50 DEG C by control of the addition rate. The
resulting very viscous dark solution is stirred 3.5 hours and then
lithium hydroxide (88.1g, 3.7 mol) is added. The resulting reaction
mixture is stirred overnight at room temperature. The reaction solution
is precipitated in water and the resulting solid is collected, washed
twice with water, washed twice with methanol and allowed to air dry
overnight. The solid is further dried in a vacuum oven at 20 inches
(0.51m) mercury and 120 DEG C for 5 hours to yield 457.2g product.
The polyamide prepared above is found to be soluble in
dimethylsulfoxide, N,N-dimethylacetamide, and N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 10% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 20-mil (5.1 X 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the above polymer on top of
VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P
polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on
a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG C.
After drying on the plate for 0.5 minutes at 100 DEG C, a 24% polymer
solution (based on weight) of the polymer prepared above in a 8.5%
lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top
of the above film at 100 DEG C with a 20-mil (5.1 x 10<-><4>m) knife
gap. After drying at 100 DEG C +/- 3 DEG C for the times noted below,
the membranes are coagulated in a water bath at 19 DEG C +/- 1 DEG C.
Three membranes are prepared with dry times of 0.05 minute, 0.50 minute
and 1.00 minute, as described above.
All water-wet membranes exhibit good adhesion between the layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. All dry
membranes exhibit good adhesion between the component layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes. Example 58
To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (279.57g, 0.75
mol) and 2,4,6-trimethyl-1,3-phenylene diamine (37.56g, 0.25 mol) in
N,N-dimethylacetamide (2600 ml) and pyridine (200 ml) is dropwise added
a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride
(7:3, molar, 205.05g, 1.01 mol) under an inert atmosphere. The reaction
temperature is maintained at under 50 DEG C by control of the addition
rate. The resulting very viscous reaction solution is stirred 2.5 hours
and then lithium hydroxide (88.14g, 3.7 mol) is added. The resulting
reaction mixture is mixed overnight at room temperature. The reaction
solution is diluted with N-methylpyrrolidone and precipitated in water.
The resulting solid is collected, washed twice with water, washed twice
with methanol and allowed to air dry overnight.
The solid is further dried in a vacuum oven at 20 inches (0.51m)
mercury and 120 DEG C for 5 hours to yield 448.4g product. This polymer
is found to be soluble in dimethylsulfoxide, N-methylpyrrolidone and
N,N-dimethylacetamide.
Films of the polymer prepared above are cast from a 10% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 20-mil (5.1 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the above polymer on top of
VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P
polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on
a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG C.
After drying on the plate for 0.5 minutes at 100 DEG C, a 24% polymer
solution (based on weight) of the polymer prepared above in a 8.5%
lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top
of the above film at 100 DEG C with a 20-mil (5.1 x 10<-><4>m) knife
gap. After drying at 100 DEG C +/- 3 DEG C for the times noted below,
the membranes are coagulated in a water bath at 23 DEG C +/- 1 DEG C.
Three membranes are prepared with dry times of 0.05 minute, 0.50 minute
and 1.00 minute, as described above.
All membranes exhibit excellent adhesion between the layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. The membranes
exhibit good adhesion between the component layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes. Example 59
To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (186.38g, 0.50
mol) and 2,4,6-dithiomethyltoluene-1,3-diamine (a mixture of isomers,
sold by Ethyl Corporation under the trade name ETHACURE 300, 107.25g,
0.50 mol) in a solution of pyridine (200 ml) and N,N-dimethylacetamide
(2600 m]) is dropwise added a melted mixture of isophthaloyl
dichloride:terephthaloyl dichloride (209.11g, 1.03 mol) under an inert
atmosphere. The reaction temperature is maintained at under 50 DEG C by
control of the addition rate. The resulting reaction solution is
stirred for 5.0 hours and then lithium hydroxide (88.14g, 3.7 mol) is
added. The resulting reaction mixture is stirred overnight at room
temperature and then precipitated in water. The resulting solid is
collected, washed twice with water, washed twice with methanol and
allowed to air dry overnight.
The solid is further dried in a vacuum oven at 20 inches (0.51m)
mercury and 120 DEG C for 5 hours to yield 452.6g product. The
polyamide prepared above is found to be soluble in m-cresol,
dimethylsulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.
Films of the polymer prepared above are cast from a 15% polymer
solution (based on weight) in N-methylpyrrolidone onto a glass plate
treated with Du Pont TEFLON TM dry lubricant at 100 DEG C +/- 2 DEG C
with a 15-mil (3.8 x 10<-><4>m) knife gap. After drying on the plate at
100 DEG C +/- 2 DEG C for 0.5 hour, the films are further dried in a
vacuum oven at 20 inches (0.51m) mercury and room temperature
overnight. The films are stripped off the plate and dried in a vacuum
oven at 20 inches (0.51m) mercury and 120 DEG C for 4 hours. The films
are tough and flexible and can be creased without cracking.
Multicomponent membranes are prepared from the above polymer on top of
VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P
polyethersulfone solution (based on weight) with 7.5%
polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on
a glass plate with a 15-mil (3.8 x 10<-><4>m) knife gap at 100 DEG C.
After drying on the plate for 0.5 minutes at 100 DEG C, a 24% polymer
solution (based on weight) of the polymer prepared above in a 8.5%
lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top
of the above film at 100 DEG C with a 20-mil (5.1 x 10<-><4>m) knife
gap. After drying at 100 DEG C +/- 3 DEG C for the times noted below,
the membranes are coagulated in a water bath at 17 DEG C +/- 1 DEG C.
Three membranes are prepared with dry times of 0.05 minute, 0.50 minute
and 1.00 minute, as described above.
All water-wet membranes exhibit good adhesion between the layers.
The resulting membranes are washed in water for 24 hours, washed in
methanol for 2 hours and washed in FREON TM 113 for 2 hours. The
membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and
room temperature overnight and at 100 DEG C for 4 hours. The membranes
exhibit good adhesion between the component layers.
The membrane fabrication procedure of this example demonstrates the
applicability of the materials described therein for gas separation
membranes.
From the foregoing description, one skilled in the art can easily
ascertain the essential characteristics of this invention, and without
departing from the spirit and scope thereof, can make various changes
and modifications of the invention to adapt it to various usages and
conditions.