USRE30351E - Aromatic polyimide, polyester and polyamide separation membranes - Google Patents

Aromatic polyimide, polyester and polyamide separation membranes Download PDF

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USRE30351E
USRE30351E US05/687,639 US68763976A USRE30351E US RE30351 E USRE30351 E US RE30351E US 68763976 A US68763976 A US 68763976A US RE30351 E USRE30351 E US RE30351E
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polymer
iadd
iaddend
gases
fluids
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Harvey H. Hoehn
John W. Richter
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/48—Polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
    • C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6826—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound

Definitions

  • This invention concerns semipermeable membranes prepared from a class of polymers whose molecular morphology renders them highly useful in chemical separations.
  • the present invention is a gas separation membrane of which at least 50% by weight consists essentially of a polymer whose main chain has a repeating unit containing at least one group selected from the group consisting of aromatic imide, aromatic ester and aromatic amide in which said repeating unit
  • (b) is sterically unable to rotate 360° around one or more of said main chain single bonds
  • polyimides from which membrane materials of this invention are selected may be represented generally as polymers in which the repeating unit is as shown in formula I: ##STR1## wherein R and R 1 are, respectively, divalent and tetravalent organic radicals, i.e., with their bonds stemming from carbon atoms. These are illustrated in more detail below.
  • polyesters from which the membrane materials of this invention are selected may be represented generally as polymers in which the repeating unit is as shown in formula II: ##STR2## wherein R 2 and R 3 , alike or different, are divalent organic radicals, i.e., with their bonds stemming from carbon atoms. These are also illustrated in more detail below.
  • polyamides from which the membrane materials of this invention are selected may be represented generally as polymers in which the repeating unit is as shown in formula III, ##STR3## wherein R and R 3 are defined as above and R 7 is hydrogen, lower alkyl, or phenyl. These are illustrated in more detail below.
  • R and R 3 are defined as above and R 7 is hydrogen, lower alkyl, or phenyl.
  • Requirement (a) specifies that the repeating unit of the polymer contain at least one rigid divalent subunit, the two main chain bonds from which are not colinear.
  • the rigid subunits in a polymer chain are those atoms, groups of atoms, or cyclic structures which are joined to other units in the main chain by single bonds between two atoms.
  • the single bond junction points in a polymer main chain are readily recognized from the structural formula of the polymer repeating unit and these points are the demarkation points between rigid subunits.
  • Such a subunit is rigid because the angle between the two single bonds extending from the subunit is fixed.
  • the two bonds from a rigid subunit are colinear (L) if they form an angle of about 180°, (particularly 170°-180°) or if they are parallel and offset not more than 2A. Otherwise, they are noncolinear (N).
  • Preferred polymers have 2-10 main-chain rigid subunits in the polymer repeating unit.
  • Requirement (b) specifies that the polymer chain contain at least one bond between rigid subunits around which bond the polymer chain is sterically prevented from rotating 360°. This determination is based on the well-known textbook rules of stereochemistry. These rules are strictly incorporated into the design of the Corey-Pauling-Koltun Models (CPK Models) described by W. L. Koltun in Biopolymers 3, 665-679 (1965) and which are available from the Ealing Corporation, 2225 Massachusetts Avenue, Cambridge, Mass., 02140.
  • CPK Models Corey-Pauling-Koltun Models
  • the determination of requirement (c) that over 50% of the atoms forming the backbone chain of the repeating unit of the polymer be in aromatic groups can readily be made from the two-dimensional representation of the polymer repeating unit noted above.
  • the main chain atoms which are counted are those in the single atom and cyclic rigid subunits. In cyclic subunits in which the two single bonds stem from different atoms, all member atoms in the basic ring of the subunit are counted, e.g., p-phenylene counts 6 atoms. Side chain atoms such as hydrogen, carbonyl oxygen, alkyl groups, haloalkyl groups, carboxyl groups, ester groups, halogen substituents and other pendant groups are not counted.
  • Aromatic rings include not only the hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, indene, and the like, but also those heterocyclic rings commonly acknowledged to have aromatic character such as furan, benzofuran, dibenzofuran, thiophene, pyrazole, indole, benzimidazle, pyrazine, carbazole, pyridine, quinoline, acridine, imidazole, isoimidazole, and the like. See, for example, R. C. Fuson, “Advanced Organic Chemistry", John Wiley & Sons, Inc., 1950, Chap.
  • the single bonds separating rigid subunits are marked by drawing dotted lines across the two-dimensional representation of the polymer repeating unit and are identified by the letters A, B, C, D, etc.
  • the rigid subunits are numbered 1, 2, 3, 4, etc.
  • the rigid subunits are then tabulated along with a notation for each whether its two main chain single bonds are colinear (L) or non-colinear (N) and a notation as to which, if any, of these bonds are restricted from rotating 360°.
  • the proportion of the main chain atoms in the repeating unit which are in aromatic structures is also shown.
  • the invention also contemplates the use of copolyimides, copolyesters and copolyamides in which the respective repeating units of the copolymer members individually satisfy criteria (a), (b), and (c), as well as physical blends of two or more of these materials meeting these criteria and also copolyimides, copolyesters, copolyamides and blends in which one or more members meet these criteria, those members constituting 50% or more of the membrane by weight.
  • the membranes of this invention may be prepared by any of the known means for forming organic polymers.
  • Membranes in film form may be prepared by melt pressing, melt extrusion, solution casting, and the like.
  • Membranes in tubular or hollow form may be prepared by melt spinning and wet or dry spinning from solution.
  • soluble salt based on the polymer, i.e., a salt which is soluble (and preferably highly dissociated) in the polymer solution to the extent present and which is essentially chemically inert toward the polymer and the solvent.
  • Suitable salts include LiCl, LiBr, LiNO 3 , CaCl 2 , etc.
  • the membranes of this invention there may be incorporated up to 50% by weight of the total composition of a compatible plasticizer of the type illustrated by the phthalate esters such as dibutyl, dicyclohexyl, dioctyl and diphenyl phthalates, the aryl sulfonamides such as the N-(lower alkyl)benzenesulfonamides and N-(lower alkyl)toluenesulfonamides, the organic phosphates such as triphenyl and tricresyl phosphate, the adipates such as dioctyl adipate and diisodecyl adipate and similar compatible esters.
  • the plasticizer may be incorporated by dissolving it in the polymer solution prior to casting or spinning. Plasticizers may also be incorporated by hot blending on mixing rolls or in an extruder prior to the formation of the membrane.
  • a polymer which satisfies requirments (a), (b) and (c) is dissolved at about 20% concentration in an anhydrous organic solvent.
  • the solution is filtered to remove solids and is freed of dissolved gasses.
  • the solution is cast in film form on a support or spun through a cored spinneret to give a hollow fiber.
  • the solvent is then removed.
  • the solvent is evaporated preferably by heating at about 90° to 110° C.
  • the film or fiber structure is quenched in a liquid which is a nonsolvent for the polymer and a solvent for the organic solvent and additives already present.
  • a liquid which is a nonsolvent for the polymer and a solvent for the organic solvent and additives already present.
  • the quench liquid is water and the organic solvent is water-miscible.
  • FIG. 1 Apparatus suitable for separation of gases, as removal of hydrogen from a mixture of hydrogen and methane, by a membrane in film form is shown in the FIGURE.
  • base section 11 and upper section 12 of permeation cell 10 are machined from corrosion-resistant metal.
  • Film 13 the separation membrane, is a disk mounted against a porous support disk 14.
  • synthetic elastomer O-rings 15 seat firmly around the periphery of the membrane and against the metal.
  • Inlet 16 for feeding gases into the cell is near the membrane. By-pass of a portion of the feed gas is provided through exit 17. Gas passes through membrane 13 is collected through a metal frit 18 into exit pipe 19. Pipe 19 is connected to a metal gas receiver (not shown) which is fitted with pressure measuring devices.
  • the selectivity of a membrane in separating a two-component .[.fluid.]. .Iadd.gas .Iaddend.mixture is defined as the ratio of the rate of passage of the more readily passed component to the rate of passage of the less readily passed component.
  • Selectivity may be obtained directly by contacting a membrane with a known mixture of gases and analyzing the permeate. Alternatively, a first approximation of the selectivity is obtained by setting up the ratio of the rates of passage of the two components determined separately on the same membrane. Rates may be expressed as GTR or as cB units.
  • GTR data represents the steady state rate of gas transmission through a membrane.
  • GTR values are not normalized for membrane thickness.
  • the GTR is inversely proportional to the sample thickness.
  • the GTR is still a valid permeability characterization.
  • GTR values determine the value-in-use of the membrane in a permeation device. Derivation of the GTR equation follows.
  • the volume of gas transmitted through a membrane is directly proportional to the area, time, and pressure of the permeation test as shown in (1).
  • the units selected for volume, area, time, and pressure are cm 3 (STP), 100 in 2 , 24 hours, and atmosphere, respectively. Substituting these units in (1) gives (2): ##EQU2##
  • the standard unit for the permeability coefficient in observing the permeability of polymer films to gases is defined as the barrer which is equal to ##EQU3## in which cm 3 (STP) is the volume of permeated gas at standard temperature and pressure,
  • cm is thethickness of the film
  • cm 2 is the area of film
  • cmHg is the pressure
  • centibarrers a unit which is 1/100 of the barrer as defined above. Centibarrer values can be calculated from the relationship:
  • the polymers used in this invention are characterized by having the three elements (a), (b) and (c).
  • R, R 2 and R 3 may be any divalent organic radical and R 1 may be any tetravalent organic radical. It is to be noted it is possible to prepare polymers where all the R's are derived from compounds shown in the various tables below but would still not have elements (a), (b) and (c). Such polymeric materials are not within the scope of the invention, but may be used in combination with the polymers of this invention in amounts up to 50% by weight.
  • radicals which are used. Without any intent of limitation the radicals may be further illustrated as follows:
  • the divalent radicals R, R 2 and R 3 may be substituted or unsubstituted phenylene, naphthylene, biphenylene, anthrylene or ##STR4## where R 4 is alkylene (including alkylidene) of up to 18 carbon atoms, aralkylene of up to 18 carbon atoms, haloalkylene (including haloalkylidene) of up to 18 carbon atoms in which the haogen(s) are fluorine, chlorine, bromine or iodine, oxygen, sulfur, --SO 2 --, ##STR5## in which R 5 and R 6 are lower alkyl or phenyl.
  • R 4 are alkylidene, haloalkylidene, aralkylidene, oxy and iminocarbonyl (--NH--CO--).
  • Preferred alkylene and haloalkylene moieties in R 4 are those of 1-3 carbon atoms.
  • the tetravalent radical R 1 may be a substituted or unsubstituted grouping: ##STR6## where R 4 is defined as above.
  • Substituents on the above divalent and tetravalent radicals may be alkyl of up to 18 carbon atoms such as methyl, ethyl, isopropyl, butyl, tert.-butyl, hexyl, and octadecyl, phenyl, halogen such as fluorine, chlorine, bromine and iodine, lower alkoxy, carboxyl, lower alkoxycarbonyl, carbacyl of up to 6 carbon atoms such as acetyl and hexanoyl, sulfo and sulfo salt of an alkali or alkaline earth metal.
  • Preferred embodiments of R, R 1 , R 2 and R 3 are those in which the aromatic portions are of the benzene or naphthalene series.
  • Suitable polyimides for use in this invention can be obtained when equivalent amounts of the dianhydrides shown in Table I are substituted, for example, for pyromelletic dianhydride in the procedure of Example 13, Part A.
  • Suitable polyimides can be obtained when equivalent amounts of the diamines shown in Table II are substituted, for example, for 1,5-diaminonaphthalene in the procedure of Example 15, Part A.
  • Polyesters suitable for use in this invention are obtained when, as in the procedure of Example 1, Part A, 4,4'-diphenylbis(trifluoromethyl)methane dicarboxylic acid dichloride is substituted for example for isophthaloyl chloride and the diols shown in Table III are substituted for example for 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane.
  • a preferred group of polyesters and polyamides are copolyesters and copolyamides formed by reacting a glycol or a diamine with an equivalent amount of a mixture of isophthaloyl and terephthaloyl chlorides where the molar and weight proportions of the acid chlorides may vary from 99/1 to 1/99 respectively.
  • Particularly preferred are copolyesters and copolyamides in which isophthaloyl chloride is used in excess of terephthaloyl chloride, especially where the ratio is 70/30.
  • Preferred diamines are items 1-3, 5-10, 14, 15, 19, 20 and 30 of Table II.
  • Preferred diols are items 1-3, 5-10, 19, 24, 25, 31 and 50 of Table III.
  • Preferred dicarboxylic acids are items 1-6, 13 and 16 of Table IV.
  • Polyester from isophthaloyl chloride and 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane.
  • the repeating unit of the polyester prepared as above was checked against requirements (a), (b), and (c) as follows:
  • the repeating unit has 2 L and 6 N rigid subunits, 2 bonds with restricted rotation, 2 of the N subunits have at least one bond with restricted rotation, and18/23 (78%) of the atoms in the chain are aromatic. This polymer thus satisfies the requirements set out above.
  • the polyester of Part A was dissolved in tetrachloroethane in an amount to give a 16% solution.
  • the solution was filtered through a 5.0 ⁇ silver membrane.
  • the filtrate was degassed to remove bubbles.
  • the filtrate was cast on a glass plate which had been coated with a low molecular weight polytetrafluoroethylene wax dispersion (Vydax®) and heated to 110° C. A 15 mil doctor knife was used to spread the solution.
  • the film was then covered to protect the solution or the partially dried tacky film from dust.
  • the cover was equipped with vents. After allowing the film to dry for 5 minutes at 110° C. vents in the cover were opened and the film was allowed to dry another 10 minutes.
  • the 1.5 mil film was then stripped from the glass plate and tested as a permeation membrane for a mixture of oxygen and nitrogen using the apparatus of the Figure.
  • the film permeated O 2 at 140 GTR and 126 cB.
  • the film permeated nitrogen at 25 GTR and 22 cB.
  • Example 1 Part B was repeated using a 15 mil doctor knife. The film was covered and dried at 100° C. for 5 minutes after which vents were opened and drying continued for 10 minutes. The clear, bluish, smooth, crisp, 2.4 mil film was stripped from the plate and tested for oxygen and nitrogen permeability. The film permeated O 2 at 115 GTR and 166 cB and N 2 at 21 GTR and 30 cB. The S O .sbsb.2 /N .sbsb.2 was 5.5.
  • Example 1 Part B was repeated, using a 10 mil knife in place of the 15 mil knife and under otherwise similar conditions except that the plate was allowed to cool at room temperature for 15 min before stripping the film. A film of 1.35 mil thickness was obtained. It permeated O 2 at 221 GTR and 179 cB and N 2 at 40 GTR and 32 cB. S O .sbsb.2 /N .sbsb.2 was 5.5.
  • Example 1 The procedure of Example 1, Part B was repeated four times with the exception that casting and drying temperatures of 50°, 55°, 60° and 70° C. were used respectively in place of 110° C.
  • the S H .sbsb.2 /CH .sbsb.4 was 31.
  • the S H .sbsb.2 /CH .sbsb.4 was 27.
  • the S H .sbsb.2 /CH .sbsb.4 was 27.
  • the S H .sbsb.2 /CH .sbsb.4 was 28.
  • the polyamide from m-phenylenediamine and a 70/30 mixture of isophthalic and terephthalic acid chlorides was prepared using the procedure shown by Richter and Hoehn in U.S. Pat. No. 3,567,632, col. 28, line 61 to col. 29, line 12. This polyamide is referred to as MPD-I/T (100-70/30).
  • This example concerns a semipermeable membrane made from a blend of a polyester which satisfies requirements (a), (b), and (c) with a polyamide.
  • a casting solution was prepared using 10 parts of a solution containing 15 wt % MPD-I/T (100-70/30) in tetrahydrofuran, 10 parts of a solution containing 15 wt % of the polyester of Example 1, Part A, in dimethylacetamide, and 1.2 parts Santicizer 8. This solution was cast on a Vydax® coated glass plate at room temperature with a 15 mil knife. The file was dried for 15 min at 110° C. The 1.55 mil film permeated H 2 at 572 GTR and 532 cB, and CH 4 at 6 GTR and 6 cB. The S H .sbsb.2 /CH .sbsb.4 was 95.
  • the combined solution was filtered through a 0.8 ⁇ silver membrane.
  • the filtrate was cast on a Vydax® coated glass plate at room temperature in a dust-free cabinet with a 15 mil doctor knife.
  • the film was allowed to dry for 15 min at room temperature in the dust-free cabinet and was then transferred to a hot plate maintained at 110° C. and allowed to dry for 5 min.
  • the film was stripped, air dried, and then dried in a vacuum at room temperature.
  • the S H .sbsb.2 /CH .sbsb.4 was 6.2.
  • Example 6 Part B The procedure of Example 6, Part B was repeated except that the plasticizer (Santicizer 8) was omitted.
  • the S H .sbsb.2 /CH .sbsb.4 was 67.
  • Polyester from isophthaloyl chloride and 2,2-bis(3,5-dichloro-4-hydroxyphenyl)hexafluoropropane.
  • Example 1 Part A was repeated except that the 2,2-bis(3,5-dichloro-4-hydroxyphenyl) propane was replaced by a chemically equivalent amount of 2,2-bis(3,5-dichloro-4-hydroxyphenyl)hexafluoropropane.
  • the polymer was isolated as before.
  • the polyester prepared as above was checked against requirements (a), (b) and (c) as follows:
  • the repeating unit has 6 N and 2 L subunits, 4 bonds with restricted rotation, 3 of the N subunits have at least one bond with restricted rotation, and 18/23 of the chain atoms are aromatic.
  • a solution was prepared from 5.4 g of the polyester of Part A and 30.6 g of chloroform.
  • the solution was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at room temperature in a dust-free cabinet using a 15 mil doctor knife.
  • the film was allowed to dry for 15 minutes at room temperature, stripped, and dried in a vacuum at room temperature.
  • the S H .sbsb.2 /CH .sbsb.4 was 45.
  • Polyester from a 1:1 mixture of isophthaloyl chloride and terephthaloyl chloride and 2,2-bis(4-hydroxyphenyl)hexafluoropropane.
  • Example 9 Part A was repeated except that half of the isophthaloyl chloride was replaced with terephthaloyl chloride. The polymer was isolated as before.
  • the polyester prepared as above was checked against requirements (a), (b) and (c) as follows:
  • the repeating unit (I) has 2 L and 6 N subunits.
  • the repeating unit (T) has 3 L and 5 N subunits. In both (I) and (T) there are 2 restricted bonds and one of the N subunits has two bonds with restricted rotation. In both (I) and (T) 18/23 of the chain atoms are aromatic.
  • a solution prepared from 6 g of the polyester shown in Part A and 34 g of chloroform was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate using a 15 mil doctor knife at room temperature in a dust-free box. The film was allowed to dry for 15 min at room temperature and was then stripped. The clear, 1.6 mil film permeated H 2 at 2627 GTR and 2522 cB and CH 4 at 70 GTR and 67 cB.
  • the S H .sbsb.2 /CH .sbsb.4 was 38.
  • Example 11 The procedure of Example 11 was repeated except that a 15 mil knife was used in place of a 25 mil knife.
  • the S H .sbsb.2 /CH .sbsb.4 was 30.
  • the repeating unit has 1 L and 1 N subunit, one bond with restricted rotation and 12/18 chain atoms are aromatic.
  • a solution of 15 g of the polyimide of Example 13, Part A, 0.75 g of lithium nitrate and 85 g of dimethylacetamide was filtered through 0.45 ⁇ silver membrane, degassed, and cast on an Inconel plate at 110° C. with a 15 mil knife and dried for 5 min.
  • the Inconel plate was then taken from the hot plate directly into a bath of methanol, cooled to 0° C., and allowed to remain there for 30 min.
  • the 1.05 mil film was stripped from the plate and allowed to air dry.
  • the S H .sbsb.2 /CH .sbsb.4 was 18.
  • the repeating unit contains 4 N subunits, 4 bonds with restricted rotation, all of the N subunits have at least one bond having restricted rotation, and 22/29 of the chain atoms are aromatic.
  • a solution of 20 g of the polyimide of Part A in 80 g of dimethylacetamide was filtered through a 0.8 ⁇ silver membrane, degassed, cast on a Vydax® coated glass plate at 100° C. using a 25 mil doctor knife.
  • the film was covered, dried at 100° C. for 5 min. with the cover vents closed and 10 min. with the vents open. The film was then stripped.
  • the S H .sbsb.2 /CH .sbsb.4 was 39.
  • the polyimide was precipitated by drowning in a large excess of methanol under vigorous agitation, recovered by filtration, washed with methanol and dried under vacuum, first for 4 hours at 170° C. and then for 3 hours at 260° C.
  • the repeating unit has 4 N and 2 L subunits, 2 bonds with restricted rotation, 3 of the N subunits have at least one bond with restricted rotation, 24/32 of the atoms in the chain are aromatic.
  • a solution of 30 g of the polyimide of Part A and 170 g of dichloromethane was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated Inconel sheet at room temperature in a dust-free cabinet with a 15 mil doctor knife. The solution was dried for 15 min and the film stripped. The clear, yellow film, 1.42 mils thick, permeated H 2 at 3197 GTR and 2724 cB and CH 4 at 106 GTR and 90 cB.
  • the S H .sbsb.2 /CH .sbsb.4 was 30.
  • a solution of 20 g of the polyimide of Example 16, Part A in 80 g of dimethylacetamide was filtered through a 0.8 ⁇ silver membrane, degassed, and cast on a Vydax® coated glass plate at 100° C. with a 25 mil doctor knife. The film was covered, dried at 100° C. for 5 min after which the vents on the cover were opened and drying continued 10 min.
  • the S H .sbsb.2 /CH .sbsb.4 was 29.
  • Polyimide from 3,4,3',4'-diphenylhexafluoroisopropylidene tetracarboxylic dianhydride and 4-isopropyl-1,3-diaminobenzene.
  • the polyimide was precipitated from the cooled solution by drowning it in a large excess of methanol under vigorous agitation.
  • the polyimide was recovered by filtration, washed 3 times with methanol and dried under vacuum, first for 4 hours at 100° C. and then for 4 hours at 260° C.
  • the repeating unit has 4 N subunits, 3 restricted bonds, all of the N subunits have at least one bond with restricted rotation, 18/25 of the chain atoms are aromatic.
  • a solution of 85 g of the polymide of Part A in 340 g of dimethylacetamide was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 100° C. using a 15 mil doctor knife.
  • the film was .Iadd.then .Iaddend.covered and allowed to dry for 5 min after which the vents in the cover were opened and film allowed to dry another 10 min.
  • the S H .sbsb.2 /CH .sbsb.4 was 13.
  • Repeating unit has 4 N subunits, 2 bonds with restricted rotation, 3 of the N subunits have at least one bond with restricted rotation, and 18/25 of the atoms in the chain are aromatic.
  • the 15% solution of the polyimide in dimethylacetamide from Part A was filtered, degassed, and cast on a Vydax® coated glass plate at 100° l C. with a 25 mil doctor knife. The film was covered and allowed to dry for 5 minutes at 100° C. The vents in the cover were then opened and drying was continued for 10 minutes.
  • the S H .sbsb.2 /CH .sbsb.4 was 44.
  • the polyimide was precipitated by drowning the solution in a large excess of methanol under vigorous agitation.
  • the polyimide was recovered by filtration, washed twice with methanol and dried under vacuum, first for 16 hours at room temperature and then for 3 hours at 260° C.
  • Repeating unit has 1 L and 3 N subunits, 2 restricted bonds, all of the N subunits have at least one bond with restricted rotation, and 18/25 of the atoms in the chain are aromatic.
  • Polyimide from 3,4,3',4'-diphenylhexafluoroisopropylidene tetracarboxylic dianhydride and the bisamide from metaphenylenediamine and metaaminobenzoic acid.
  • the polyimide was precipitated by drowning the solution in excess methanol under vigorous agitation.
  • the polyimide was recovered by filtration, washed twice with methanol and dried under vacuum, first for about 18 hours at room temperature and then for 3 hours at 260° C.
  • the repeating unit has 10 N subunits, 2 bonds with restricted rotation, 3 of the N subunits have at least one bond with restricted rotation, and 30/41 of the atoms in the chain are aromatic.
  • a solution of 12 g of the polyimide of Part A in 68 g of dimethylacetamide was filtered through 0.45 ⁇ silver membrane, degassed, and cast on a Vydax® coated glass plate at 100° C. with a 25 mil doctor knife. The film was covered and dried for 5 min. THe vents in the cover were then opened and drying continued for 10 min.
  • the S H .sbsb.2 /CH .sbsb.4 was 53.
  • a solution of 9 g of the polyester of Example 9, Part A, and 51 g of dimethylacetamide was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 100° C. with a 25 mil doctor knife.
  • the film was covered, dried at 100° C. for 5 min. with the cover vents closed, and for 10 minutes with the cover vents open.
  • the film was stripped and tested without further treatment.
  • the S O .sbsb.2 /N .sbsb.2 was 8.7.
  • Polyimide from 3,4,3',4'-diphenylhexafluoroisopropylidene tetracarboxylic dianhydride and 3,5-diaminobenzoic acid.
  • the repeating unit has 4 N subunits, 2 bonds with restricted rotation, 3 of the N subunits have at least one bond with restricted rotation, and 18/27 of the atoms in the chain are aromatic.
  • the polyimide was recovered by filtration, washed twice with methanol and dried under vacuum, first for about 16 hours at room temperature and then for 3 hours at 260° C. At 0.1% concentration in dimethylacetamide at 25° C. the polyimide had an inherent viscosity of 1.15.
  • the repeating unit has 7 N subunits, 2 bonds with restricted rotation, 3 of the N subunits have at least one bond with restricted rotation, and 24/33 of the atoms in the chain are aromatic.
  • a solution of 15 g of the polyimide-amide of Part A in 85 g of dimethylacetamide was filtered through a 0.45 ⁇ silver membrane, degassed, and cast on a Vydax® coated glass plate at 100° C. with a 25 mil doctor knife. The film was covered, dried for 5 min, after which the vents in the cover were opened and drying was continued for 10 minutes.
  • the S H .sbsb.2 /CH .sbsb.4 was 83.
  • Example 15 A series of five polymers and copolymers were prepared, the first by repeating the procedure of Example 15, Part A.
  • the second, third, fourth and fifth were prepared by the same procedure except that 25%, 50%, 75% and 100% respectively of the 1,5-diaminonaphthalene (1,5-ND) was replaced by a molecular equivalent amount of 4,4'-diaminodiphenyl ether (ODA).
  • ODA 4,4'-diaminodiphenyl ether
  • Films were prepared from the five polyimides of Part A by preparing 20% solutions in dimethylacetamide and casting on a Vydax® coated glass plate at 100° C. with a 25 mil doctor knife. The films were covered and dried for 5 min after which the vents on the cover were opened and drying was continued for 10 min. The films were then stripped from the plate and placed in a vacuum chamber and heat treated at 260° C. for 6 hrs under a vacuum of 2 ⁇ . The films were then tested for permeation of hydrogen and methane as shown in Table V.
  • a polyamide was prepared using the procedure of the Richter and Hoehn patent mentioned above as shown in Example 6, Part A, with the exception that 11.5 mole percent (20 weight percent) of the m-phenylenediamine was replaced by a molecular equivalent amount of calcium sulfometaphenylenediamine of the formula ##STR70## to obtain the corresponding copolyamide, referred to as MPD/CaSMPD-I/T (88.5/11.5-70/30).
  • Polyimide/polyamide blends were prepared by dissolving together in varying proportions the polyimide of Example 16, Part A and the polyamide of Part A above, the amounts of the two polymers being selected to give a total of 15% polymer weight in solution in dimethylacetamide.
  • the resulting solutions were cast on Vydax® coated glass at 100° C. using a 25 mil doctor knife. The films were first dried for 5 minutes at 100° C. with the cover vents closed and then for 10 minutes with the vents open. The films were tested for permeation of hydrogen and methane as shown in Table VI.
  • Polyimide/polyamide blends were prepared by dissolving together in varying proportions the polyimide of Example 15, Part A and the polyamide of Example 26, Part A. Amounts of the two polymers were selected to give a total of 15% polymer weight in solution in dimethylacetamide. The resulting solutions were cast on Vydax® coated glass at 100° C. using a 25 mil doctor knife. The films were first dried for 5 minutes at 100° C. with the covers vents closed and then for 10 minutes with the vents open. The films were then tested for permeation of hydrogen and methane as shown in Table VII.
  • Example 19 The procedure of Example 19, Part B, was repeated except that the doctor knife thickness was varied in order to observe the effect of varying film thickness on the permeation of hydrogen and methane. Details of this study are shown in Table VIII.
  • Example 20 The procedure of Example 20 was repeated except that the doctor knife thickness was varied in order to observe the effect of varying film thickness on the permeation of hydrogen and methane. Details of this study are shown in Table IX.
  • the repeating unit has six N subunits, one bond with restricted rotation, two of the N subunits have one bond with restricted rotation, and 12/16 of the main chain atoms are aromatic.
  • a solution of 40 g of the polyamide from Part A in 160 g of dimethylacetamide was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 110° C. with a 15-mil doctor knife.
  • the film was covered and dried for 5 minutes at 110° C. with the cover vents closed and 10 minutes with the vents open.
  • the film was stripped from the plate and air-dried.
  • the S H .sbsb.2 /CH .sbsb.4 was 58.
  • Example 30 Part B The procedure of Example 30, Part B was repeated up to the stripping of the film from the plate.
  • the stripped film was immersed in distilled water at room temperature for 20 hours and then in acetone for 1 hour. The film was then air-dried.
  • the S H .sbsb.2 /CH .sbsb.4 was 136.
  • Example 30 Part B The procedure of Example 30, Part B was repeated up to the stripping of the film from the plate.
  • the stripped film was dried overnight under vaccum at room temperature. It was then immersed in distilled water for 2 hours, air-dried, and further dried under vacuum overnight at room temperature.
  • the S H .sbsb.2 /CH .sbsb.4 was 103.
  • Example 30 Part B The procedure of Example 30, Part B was repeated up to the stripping of the film from the plate.
  • the stripped film was dried overnight under vaccum at room temperature.
  • the film was then immersed first in distilled water at room temperature for 1 hour and then in acetone for 1 hour, after which it was air-dried and further dried under vacuum at room temperature overnight.
  • the S H .sbsb.2 /CH .sbsb.4 was 118.
  • Example 30 Part A Using the procedure of Example 30, Part A, a solution of 64.12 g (0.427 mole) of 4-isopropylmetaphenylenediamine in 678 g of dimethylacetamide was treated slowly with 86.65 g (0.427 mole) of terephthaloyl chloride during a period of 2.5 hours, keeping the reaction temperature in the range of 35° to 55° C. After the indicated recovery, there was obtained 111 g of polyamide of inherent viscosity 0.41.
  • the repeating unit has five N and one L subunits, one bond with restricted rotation, two of the N subunits have one bond with restricted rotation and 12/16 of the main chain atoms are aromatic.
  • a solution of 15 g of the polyamide from Part A in 85 g of dimethylacetamide was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 110° C. with a 15-mil doctor knife.
  • the film was covered and dried for 5 minutes at 110° C. with the cover vents closed and 10 minutes with the vents open.
  • the film was stripped from the plate and air-dried.
  • the S H .sbsb.2 /CH .sbsb.4 was 62.
  • Example 30 Part A Using the procedure of Example 30, Part A, a solution of 47.37 g (0.35 mole) of 4-isopropylmetaphenylenediamine in 501 g of dimethylacetamide was treated slowly with 64.12 g (0.315 mole) of a 70/30 mixture of isophthaloyl chloride/terephthaloyl chloride during a period of 5 hours, keeping the reaction temperature in the range of 45° to 50° C. After the indicated recovery, there was obtained 86 g of copolyamide of inherent viscosity 0.53.
  • the repeating unit (I) has six N subunits.
  • the repeating unit (T) has five N and one L subunits. In both (I) and (T), two of the N subunits have one bond with restricted rotation and 12/16 of the main chain atoms are aromatic.
  • Example 30 Part A Using the procedure of Example 30, Part A, a solution of 18.89 g (0.119 mole) of 1,5-naphthalenediamine in 195 g of dimethylacetamide was treated slowly with 24.24 g (0.119 mole) of a 70/30 mixture of isophthaloyl chloride/terephthaloyl chloride during a period of 2 hours, keeping the reaction temperature in the range of 40° to 43° C. After the indicated recovery, there was obtained 28 g of copolyamide of inherent viscosity 0.74.
  • the repeating unit (I) has six N subunits.
  • the repeating unit (T) has five N and one L subunits. In both (I) and (T) three N subunits have at least one bond with restricted rotation and 16/20 of the main chain atoms are aromatic.
  • Example 30 Part A Using the procedure of Example 30, Part A, a solution of 24.463 g of 3,3'-dimethoxybenzidine in 212 g of dimethylacetamide was treated slowly with 20.333 g of a 70/30 mixture of isophthaloyl chloride/terephthaloyl chloride during a period of 2.5 hours, keeping the reaction temperature in the range of 36° to 50° C. After the indicated recovery, there was obtained 35 g of copolyamide of inherent viscosity 1.80.
  • the repeating unit (I) has five N and two L subunits.
  • the repeating unit (T) has four N and three L subunits. In both (I) and (T), two of the N subunits have one bond with restricted rotation and 18/22 of the main chain atoms are aromatic.
  • a solution of 15 g of the copolyamide of Part A in 85 g of dimethylacetamide was filtered through a 0.5 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 110° C. with a 25-mil doctor knife. The film was covered, dried 5 minutes at 110° C. with the cover vents closed and 10 minutes with the vents open.
  • the S H .sbsb.2 /CH .sbsb.4 was 72.
  • Example 30 Using the procedure of Example 30, Part A, a solution of 30.142 g of 4,4'-diaminodiphenylbis(trifluoromethyl)methane in 426 g of dimethylacetamide was treated slowly with 30.455 g of a 70/30 mixture of isophthaloyl chloride/terephthaloyl chloride during a period of 4.5 hours, keeping the reaction temperature in the range of 40° to 47° C. After the indicated recovery, there was obtained 68 g of copolyamide of inherent viscosity 1.37.
  • the repeating unit (I) has six N and two L subunits.
  • the repeating unit (T) has five N and three L subunits. In both (I) and (T), one of the N subunits has two bonds with restricted rotation and 18/23 of the main chain atoms are aromatic.
  • a solution of 15 g of the copolyamide of Part A in 85 g of dimethylacetamide was filtered through a 0.8 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 110° C. with a 15-mil doctor knife. The film was covered, dried 5 minutes at 110° C. with the cover vents closed and 10 minutes with the vents open.
  • the 1.43-mil air-dried film permeated H 2 at 2304 GTR and 1977 cB and CH 4 at 41 GTR and 35 cB.
  • the S H .sbsb.2 /CH .sbsb.4 was 56.
  • Example 30 Part A Using the procedure of Example 30, Part A, a solution of 18.475 g of 4,4'-diamino-2,5,2',5 ⁇ -tetraethoxytriphenylmethane in 135 g of dimethylacetamide was treated slowly with 8.324 g of a 70/30 mixture of isophthaloyl chloride/terephthaloyl chloride during a period of 7 hours, keeping the reaction temperature in the range of 40° to 50° C. After the indicated recovery, there was obtained 23 g of copolyamide of inherent viscosity 0.81.
  • the repeating unit I has six N and two L subunits.
  • the repeating unit (T) has five N and three L subunits. In both (I) and (T), three of the N subunits have at least one restricted bond and 18/23 of the main chain atoms are aromatic.
  • a solution of 15 g of the copolyamide of Part A in 60 g of dimethylacetamide was filtered through a 0.8 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 110° C. with a 15-mil doctor knife.
  • the film was covered, dried 5 minutes at 110° C. with the cover vents closed and 10 minutes with the vents open.
  • the 1.59-mil air-dried film permeated H 2 at 3641 GTR and 3474 cB and CH 4 at 226 GTR and 216 cB.
  • the S H .sbsb.2 /CH .sbsb.4 was 16.
  • a polyamide was prepared from 32.203 g of 2,5,2',5'-tetrachlorobenzidine and 20.302 g of isophthaloyl chloride in 170 ml of N-methylpyrrolidone solvent at 20° to 45° C.
  • the recovered polyamide had an inherent viscosity of 0.81.
  • the repeating unit of the polyamide prepared as shown above checked against requirements (a), (b), and (c) as follows:
  • the repeating unit has five N and two L subunits and three bonds with restricted rotation. Two of the N subunits each have one bond with restricted rotation and 18/22 of the main chain atoms are aromatic.
  • a polyamide was prepared from 161.01 g of 2,5,2',5'-tetrachlorobenzidene and 147.56 g of the dichloride of oxydibenzoic acid in 1200 ml of dimethylacetamide solvent at 5° to 50° C.
  • the recovered polyamide had an inherent viscosity 0.76.
  • the repeating unit has five N and four L subunits and three bonds with restricted rotation. Two of the N subunits each have one bond with restricted rotation and 24/29 of the main chain atoms are aromatic.
  • a solution of 15 g of the polyamide of Part A in 85 g of dimethylacetamide was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 110° C. with a 25-mil doctor knife.
  • the film was covered, dried 5 minutes at 110° C. with the cover vents closed and 10 minutes with the vents open.
  • the film was stripped from the plate and dried under a vacuum of 2 ⁇ at room temperature overnight.
  • the S H .sbsb.2 /CH .sbsb.4 was 55.
  • Example 41 Part A, a copolyamide was prepared from equimolar quantites of 4,6-dichlorometaphenylenediamine and a 70/30 mixture of isophthaloyl chloride/terephthaloyl chloride.
  • the repeating unit (I) has six N subunits.
  • the repeating unit (T) has five N subunits and one L subunit. In both (I) and (T), three of the N subunits have at least one bond with restricted rotation and 12/16 of the main chain atoms are aromatic.
  • a solution of 20 g of the copolyamide of Part A in 80 g of dimethylacetamide was filtered through a 0.45 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 90° C. with a 15-mil doctor knife. The film was covered, dried 5 minutes at 90° C. with the cover vents closed and 10 minutes with the vents open. The air-dried 1.17-mil film permeated H 2 at 574 GTR and 403 cB and CH 4 at 7.4 GTR and 5.2 cB.
  • the S H .sbsb.2 /CH .sbsb.4 was 78.
  • Example 41 Part A, a copolyamide was prepared from equimolar quantities of 2,6-dichloroparaphenylenediamine and a 70/30 mixture of isophthaloyl chloride/terephthaloyl chloride.
  • the repeating unit (I) has five N and one L subunits.
  • the repeating unit (T) has four N and two L subunits. In both (I) and (T), one N unit has one bond with restricted rotation and 12/16 of the main chain atoms are aromatic.
  • Example 41 Part A, a copolyamide was prepared from equimolar quantites of isophthaloyl chloride and a 50/50 (molar) mixture of metaphenylenediamine and 3,3'-dichlorobenzidine.
  • the repeating unit (DClPP) which constitutes 50% of the polymer has five N and two L subunits and two bonds with restricted rotation. Two of the N units each have one bond with restricted rotation and 18/22 of the main chain atoms are aromatic.
  • a solution of 10 g of the copolyamide of Part A in 90 g of hexamethylphosphoramide was filtered through a 0.5 ⁇ silver membrane, degassed and cast on a Vydax® coated glass plate at 110° C. with a 25-mil doctor knife.
  • the film was covered, dried 5 minutes at 110° C. with the cover vents closed, 10 minutes with the vents open and 10 minutes with the cover removed.
  • the film was cooled on the plate for 10 minutes, stripped and dried under a vacuum of 2 ⁇ at room temperature overnight.
  • the S H .sbsb.2 /CH .sbsb.4 was 27.

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