CA1326116C - Fluoro-oxidized polymeric membranes for gas separation and process for preparing them - Google Patents

Abstract

ABSTRACT The present invention provides a surface modified polymeric gas separation membrane having improved selectivity, particularly for oxygen/nitrogen gas mixtures, prepared by forming a membrane of a polymer having the structural formula wherein R and R" can be the same or different linear, branched or cyclic alkyl group having one to twelve carbon atoms, or R can be H, with the proviso that both R and R" cannot be methyl, and n is at least 100, and treating the surface of the membrane with a fluoro-oxidizing agent at conditions sufficient to fluoro-oxidize the membrane surface.

Description

271PUS~3835 FLUORO-OXIDI2E~ POLYMERIC MEMBRANES FOR
GAS SEPARATION AND PR30ESS FOR P~EPARING THEM
TECHNICAL FlELD OF THE INVENTION
This invention relates to polymeric membranes with fluoro-oxidized surfaces suitable for separating the components of a gas mixture and a process for producing such memb~anes.

BACKG~O~!ND OF THE INVENTICN

The separation of gases by differential gas permeation through a poly~*ric membrane is a commercially recognized technlque that contlnues to grow in importance~ Presently, membrane systelns are used to separate carbon ~ioxide/methane~ o~ygen/nitrogen, hydrogen/nitrogen, hellum/nitrogen and the lS like gas mixtures. Other ~ases that might also be separated using this technTque include helium/methane~ ethylene/ethane~ propylenelpropane~
nitrosen/methdne and the like mi~tures~
-~ Gases produ~ed by di~ferential permeatlon find many applica-ions. For example, nitrogen generated by dif-erentlal permeatlon through a membrane is 20 particularly useful for blanketing reactors and storage ~essels, for use on offshore platforms and ln marine tankers, for purglng and pres;urizing pipeline; and tanks as well as for drying r~active chemicals. Otiler uses lnclude fruit and ~egetable storage under controlled atmospheric conditions to lengthen product life, optlmally with a 95-98X nitrogen blanket at a 2S temper~ture slightly abo~e freezing~ Oxygen generated by differential permeatlon through a membrane is useful for medlcal appllcations, enrlching air streams to enhance combustlon, enriching air for organlc waste treatment, and the like~
~he polymers currently used to produce membranes for gas separatlon 30 applications are mainly those that provide membranes that need no further modification or treatment. Polymers presently employed commercially are primarily amorphous and glassy such as polysulfones, polyimides~ and cellulosics~ Crystalline, non-glassy polymers have not generally been considered optimally useful for gas separation applications because of their limited separation capabilities, particularly compared to amorphous, glassy polymers such as polysulfones and polyimides. Nevertheless, some other polymers have been observed to exhibit interesting separation characteristics. Poly(4-methyl-1- pentene), for example, has been commercialized in melt spun hollow fiber form for oxygen/nitrogen separations to produce nitrogen and oxygen useful primarily for medium purity nitrogen (95-97X) and enriched oxygen air applications, respectlvely.
A commercial system using poly~4-methyl-1- pentene~ is discussed in a review by Fritzsche et al, Gas Separations by Membrane Systems, Chemical Economy and Engineering Reviews, 19 (1,2,3), 19 (1987). This article also reviews polymeric membrane gas separation systems and gives an excellent summary of the technology, applications~ and polymeric membranes employed for such applications. Other publications describe, for example, polyolefin-based lS hollow fiber membranes used in a commerclal units to separate oxygen and n~trogen and also for other gas separations; i.e., Stannett et al, Recent Advances in Membrane Science and Technology, Adv. Polym. Scl., 32, 69 `~ (1979); Stern et al, Tests of a Free-Volume Model for the Permeation of Gas Mixtures Through Polymer Membranes C02-C2H4, C02 -C3H8, and C2 ~-C3H8 Mixtures in Polyethylene", J. Polym. Sci., Polym. Phys.
Ed., 21, 1275 ~1983); and Robeson et al, Permeation of Ethane-Butane Mixtures throuqh Polyethylene, J. Appl. Polym. Sci., 12, 2083 ~1968).
Some surface modification techniques have been proposed to provide enhanced membrane selectivity without greatly reducing the throughput of the 2S system. Such proposed treatments include W exposure, plasma treatment, plasma polymerization, and fluorination. Osterholz, in U.S. Patent 3,846,521, teaches a low energy electron beam treatment for polymerlc films, including poly(4-methyl-1-pentene). Klpplinger et al (J. Appl. Polym. Sci., 31, 2617 (1986) observed improved separation properties for fluorinated low density polyethylene, and Langsam (U.S.Patent 4,657,564) discloses that the fluorination of poly(trimethylsilylpropyne) membranes produces signlficant increases in the selectivlty for a number of gas pairs including oxygenlnitrogen, helium/methane, hydrogen/nitrogen, helium/nitrogen, hydrogenlmethane, carbon dioxide/methane, and the like. The reported ~ 326 1 1 6 treatments produce an extremely thin membrane surface layer, usually less than a micron, which determines the separation characteristics of the membrane. Consequently, surface modification can render relatively thick and easy-to-obtain dense films useful for gas separation purposes without need for applying ultra-thin coatings~
Dixon, U.S. Patent 4,020,223 teaches subjecting fiber form synthet~c resins such as polyolefins and polyacrylonitriles to a fluorination treatment along with low levels of elemental oxygen to impart stain release properties to the fibers~

SUMMARY OF THE INV~NTION
~he present invention provides surface modified polymeric gas separation me~branes having improved surface morphologies and selectivities.
The gas separation membranes of the invention are fluoro-oxidized membranes lS cast from a polymer having the structural formula:
`
--~CH2--R`' wherein R and R" can be the same or different linear, branched or cyclic alkyl group having one to twelve carbon atoms~ or R can be ~, with the proviso that both R and R" cannot be methyl, and n is at least 100. The fluoro-oxidized membranes have an oxygen/nitrogen selectivity of at least 2S about 5.
Surprislngly, the surface modified membranes of the present invention exhibit significantly improved gas separatlon factors or selectivities for certain gas mixtures such as 02/N2, while maintaining acceptable permeation properties.
The process for preparing the gas separation membranes of the present 1nvention comprises forming a membrane from a polymer of the above structure and treating at least one of the surfaces or faces of the membrane with a fluoro-oxidizing agent at conditions sufficient to fluoro-oxidize the membrane surface. Fluoro-oxidation is carried out by contacting the polymer surface either simultaneously or sequentially with a reactive fluorine , _ :

.
~ .

source and an oxidation source. In order to achieve sufficient fluoro-oxidation, the membrane should be treated with a fluoro-oxid~zing agent containing from about 0.01 to about 10 moleZ of available fluorine and from about 0.5 to about 99 mole~ of available oxygen, with the remainder, ~f any, inerts, Typically, employing fluorine and oxygen gases in an inert gas carrier is preferred. The fluoro-oxidation of the membrane surface increases the 02/N2 separation factor or selectivity of the membrane to at least about 5, and typically by at least one integer higher than the selectlvlty of the pre- or untreated membrane or membranes of the same general structure which ha~e been fluorinated with a gas m~xture contalning less than O.S~ by volume 2 The same or different units of the above formulae repeat to provide a polymer capable of being formed into a membrane; accordingly, any number of units which will provide a polymer in membrane form is contemplated i.e~
lS typically to be useful as a membrane n must be at least 100. Additionally, other monomer units or copolymers not having the structure of the above formula may be incorporated into the polymer structure as long a; the genera1 properties of the resultant membranes are not signific~ntly and detrimentally affected. As used herein, the term membrane lncludes supported as well as self-sustalning coherent films; membranes, e~ther dense, asymmetr~c, or thin film composite in f~ne hollow fibers; hollow tubes; spiral wound sheets; flat sheets; or combinations thereof made up of mater~als used for gas separation membranes~ including assemblies, modules, systems, or other structural configuratlons thereof. The term coherent 2S means that the membrane has a thin dense skin without defects.

BRIEF DESCRIPTION OF THE FIGURES
Figure 1 Is a secondary electron image micrograph of the surface of a membrane of poly~4-methyl-1-pentene) treated with a gas mlxture of 9X
fluorine/9X oxygen/82X nitrogen for three hours under amblent conditions at a reactive gas mixture flow rate of lOOOcc/mlnute~
Figure 2 i5 a secondary electron image mlcrograph of the surface of a membrane made from the same polymer used in Figure 1 treated with a gas mlxture of 9X fluorine and 91X nitrogen for three hours under ambient conditions at a reactive gas mlxture flow rate of lOOOcc/minute.

DETAILED DESCRIPTION OF THE INVENTION
In order to produce high purity oxygen and nitrogen competitively using differential gas permeation through a membrane versus other separatlon methods such as adsorption or cryogenic separation, the selectivity of a gas separation membrane should be at least 5~ Those few membranes that offer high selecti~ities~ e.g. greater than about 6, have unacceptably low oxygen permeabilities. By contrast, the membranes of the invention have significant~y higher selectivities than their non-fluorooxidized counterparts without substantial sacrifice of permeabllity or other valuable me~brane properties. Generally, the selectivity of a membrane can be impro~ed by at least one whole number, and most often by at least about 50X, o~er that of the untreated membrane.
~ he results of the present ~nvention are particularly surprising since fluorination of membranes formed from polymers ha~ing the abo~e structure produce no significant improvement in selectivity for gas mixtures such as 021N2 and produce numerous defects on the membrane surfac~.
Unexpectedly, the introduction of a source of a~ailable oxygen such as molecular oxygen into the fluorlne treatment medium produced significant increases in permselect~ve properties for 02/N2 and ~arious other gas mixtures while mainta~nlng acceptable permeation properties without adversely affecting the surface morphology of thè membrane itself. By fluoro-oxidation, it is meant that the reactive agent contalns fluorine and sufficient ~uantlties of oxygen o~er and abo~e the minor amounts of oxygen or oxygen-contalning compounds typlcally present in commercially available fluorlne sources. It has been clearly demonstrated that the amount of oxygen or oxygen-conta~ning compounds typ~cally present in commerclal fluor~ne sources ~s not suffic~ent to achie~e the lmprove~ents in selecti~ity and surface morphology whlch are achieved by the dellberate addition of an oxygen source in the reactlve mixture.
The ~mprovement in surface morphology of membranes treated in accordance with the present invention ls shown dramatlcally in Figures 1 and 2 where the surface of a membrane prepared from poly(4-methyl-1-pentene), fluoro-oxidized with a mixture of fluorine and oxygen gases (Fig.
1), is compared against the surface of the same membrane treated with a gas mixture containing fluorine but no added oxygen (Fig. 2). The membrane surface of Figure 1 is defect-free and looks as it did prior to treatment. A
membrane from the same polymer treated the same way except that the gas mixture contained no added oxygen has a marred surface full of erupt~ons and cracks.
The modified polymeric membranes of the present in~ention include those formed from polymers having the structural formula:
R
- ` (CH2--C
R"
wherein ~ and R'` are the same or different alkyl group having one to twelve linear, branched~ or cycloaliphatic carbon atoms or mixtures of any of them with the proviso that both R and R" can not be methyl. Such groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, decyl~ dodecyl, methylcyclohexyl, butylcyclohexyl, 2-methylpropyl, lS 3-methylbutyl, and the like an~ mixtures thereof. Add~tionally, R can be H. n is an integer sufficient to pro~ide a supported or self-sustainlng coherent film-forming polymer, ~e~ n is at least 100. The polymer can contain the same or different (mixed) repeating units.
Examples o~ preferred polyr~rs which are well suited for the present invention include: poly~4-methyl-1-pentene), poly(3-methyl-1-butene), poly(5-methyl-1-heptene), poly(5-methyl-1-hexene), polyt4-methyl-1-hexene), poly(5-methyl-1-pentent), poly(3-methyl-1-pentene), poly(3-methyl-1-hexene), poly(4,4-dimethyl-1-pentene), poly(4,4-d~methyl-1-hexene), polyt6-methyl-1-heptene), those hav~ng the formulae ~H3 CIH3 (CH2--~ ) (CH2-C ~
¦ ICH3 (~H2)q (~H ~ C CH CH3-CH
30CH3 ~H3 wherein n is at least 100 and q can be 0 to 9, and the like and mixtures thereof.
~he polymers described herein and mixtures of any of them used in the - 3S practlce of the present lnvention can be prepared by any suitable . .

polymerization technique known to those skilled in the art or which hereinafter may be developed. In typical membrane fabri-cation techniques, antioxidants are often added to polymers to enhance long term utility, such as if the corresponding membrane is to be utilized in an oxygen/nitrogen separation unit. Accor-dingly, any of the antioxidants known in the art can be used for this purpose in conjunction with the present invention. Addi-tionally, other additives which improve the overall performance and/or processing characteristics of the polymer such as pro-lo cessing aids, antistatic additives, nucleation additives, plas-ticizers, oil extenders, polymeric modifiers and the like, or any other additives known in the art for such purposes can be employed.
A membrane can be prepared from the polymers of the inven-tion by any suitable method known to those skilled in the art.
A preferred method is the preparation of hollow fibers by melt extrusion as described, for example, in U.S. Patent 4,664,681.
The melt extruded hollow fib~r can have any suitable dimensions including an outer diameter of from about 20 to 400 microns and a wall thickness of from about 2 to 100 microns. Preferably, the outer diameter will range from about 25 to 200 microns with a wall thickness ranging from about 3 to 50 microns. Hollow fibers can either be fluoro-oxidized as such or after being configured into a structural unit for gas separation as known in the art, for example as described in U.S. Patent 4,666,469. Alterna-tively, a melt-extruded hollow fiber can be oriented using conventional technigues to yield a more porous, hence more permeable, structure with an effective dense skin thickness down to about 0.1 micron. The oriented hollow fiber can then be fluoro-oxidized, either as such or configured for gas separation.
Thin film membranas of the invention can be prepared by any suitable method as described, for example, in U.S. Patent 4,243,701. Membrane films can have any desired dimensions but a thickness of from about 100 angstroms to about 200 microns is desirable, preferably 3-50 microns, most preferably 3-10 microns.
Thin film composites in which the membrane i9 a coherent film supported on a porous substrate can also be used. Such composites can be prepared by , ~,.

any suitable method known for forming a film in situ on a porous substrate such as a hollow fiber, flat sheet, or the like, or the film can be prepared and thereafter disposed on a porous substrate.
One method for forming a thin film composite includes dissolut~on of a polymer in a medlum which is a solvent for the polymer but a non-solvent for a porous substrate such as a polysulfone, polyethersulfone, polyimide, cellulosic, polyacrylonitrile, polypropylene or any other suitable substrate material. With a preferred polymer of the invention, such as poly(4-methy1-1-pentene), the sol~ent can be cyclohexene, carbon tetrachloride or a cyclohexene/carbon tetrachloride mixture, or the like.
The polymer can then be cast on the substrate and the surface of the membrane thus formed is then treated with a fluoro-oxidizing agent such as a fluorine/oxygen-containing gas mixture to si nificantly improve its selectivity~ Alternatively, the composite membrane can be assembled into a lS module, for example a hollow fiber or spiral wound membrane module, and fluoro-ox~d~zed thereafter, or fluoro-ox~dation can be carried out during the formation of the polymer me~brane itself~
St~ll another ~ethod for preparing a separatlon membrane of the ~nvention ~ molves producing a thin f~lm by spreading a dilute solution of the polymer onto an approprlate non-solvent for the polymer such as, for example, water. Th~s techn~que provides very thin membranes and is preferred where very high permeation rates are des~red~ The thin film thus produced can then be p1aced on a porous substrate such as a flat sheet or hollow f~ber and fluorc~oxld~zed as such or after assembly ~nto a module.
2S Surface modif~cat~on of the membrane~ either as such or in configurat~on, ~s achieved by exposing the surface of the membrane to any organlc or lnorganic fluoro-oxid~zlng agent, particularly in a fluld mixture. The available reactlve fluor~ne content, however generated, of the flu~d mixture, preferably in the form of a gas, desirably ranges from 3~ about 0.01 to about 10 mole~. The available oxygen content of the mixture, however generated, desirably ranges from about 0.5 to about 99 mole~, with the remainder inert components.
The fluid mixture can be a gas containing fluorine or other fluorinatlon agents such as, for example, HF, NF3, SF4 , ClF3, CF4, and the like and mixtures thereof in the presence of an activation source ' . ' :' when free F2 iS unavailable. In addition to the fluorinating agent and the oxygen source, there may be other components present which react with the membrane without adversely affecting the desired properties. Such components can be present or added without deviating from the spirit of the present invention. The remainder of the gas mixture can be any gas inert with respect to the other components of the gas and the membrane such as, for example, nitrogen, argon, and the like, with nitrogen being preferred.
Fluoro-oxidation may also be carried out in liquid phase where the fluorine and oxygen sources are dissol~edtbubbled through a sol~ent such as a halocarbon fluid. The polymer surface to be treated is then contacted with the dissolved reactive gases for a specified time. The fluoro-oxidation may also be achieved by reactions w~th liquids that y~eld such chemical functionalities and make them available to treat or modlfy the surface. ~hen employing liquid phase fluorination, any suitable technique lS for contacting the membrane with the treatment medium may be used.
~ hen treating the membrane with a fluoro-oxidizing gas mixture, the mixture can contact the surface of the membrane at any desirable flow rate, - typically 200L2000 cc/m~nute, to prov~de the surface with an effective modif~ed layer up to about 2 microns thick. Any suitable temperatures and pressures may be employed during the surface treatment. Preferably, ambient conditions are used but temperatures ranging from -200C. to the softening point of the polymer may be employed. The reaction need not be carried by flowing reactive flu~ds such as gases over the polymer surface. Static treatment works ~ust as ~ell and a fluid-filled reactor can be used to pro~ide the same results.
The fluoro-ox~dation may also be carried out in a low pressure or cold plasma which may conta~n gas mixtures of F2102, CF4/02, NF3/02, other fluorocarbons mixed with oxygen/air, or fluorine-containing compounds or the~r mixtures that yield fluorine and oxygen radicals or other active species ~n the plasma. ~he excitation/decomposition of the gas/gases may also be carr~ed out us~ng low pressure, atmospheric, or higher pressure plasmas generated by radio frequency, audio frequency, microwave, DC sources and the like. Acti~ation using an electron beam, x-rays, UV radiation sources, corona discharge, ultrasonic devices, lasers and the like would also be poss~ble.

_ 10 -Contact times are generally determined by the degree of membrane surface modification desired. Generally, exposure times will range from about one minute to about 48 hours, preferably five minutes to 8 hours, as desired. Generally, it is commercially preferable to treat the membranes from about 15 to about 60 minutes. Typlcally, permeability remains quite good e~en after ext~nded treatment times. The composition of the fluoro-oxidation mixture does not have to be held constant throughout the treatment, for example, the polymer can initially be treated with F2 gas (plus inerts) followed by treatment with an 02/F2 gas mixture, balance 10 ~nerts, Optionally, the membrane can be heat treated either before or after fluoro-oxidation. Prel~minary surface treatments to clean or etch the surface before fluoro-oxidation are also contemplated as are post fluoro-oxidation treatments such as surface coat~ng (e.g., with a permeable protective layer such as a silicone rubber or poly(trimethylsilylpropyne) to pre~ent erosior, of the separat~ng layer. Preferably, the membranes are post-purged, preferably ~ith nitrogen or oxygen or air, typically for from about 5 to about 15 minutes followlng the fluoro-oxldizing treatment.
~he membranes of the present in~entlon can be used for separating the components of gas mixtures by differentlal gas permeatlon techniques, and are particularly suitable for separating oxygen/ nltrogen mixtures. Other gas mixtures can also be separated effectl~ely uslng the membranes of the in~entlon lncluding, but not limited to those containlng carbon dioxide, methane, hydrogen, nitrogen, helium, and mixtures thereof such as carbon d~oxide/methane, carbon dloxide/nitrogen, hellum/methane, hydrogen/methane, hydrogen/ n~trogen, helium/ nitrogen, helium/air and so on.
Although the exact mechanism by which fluoro-oxidation of the polymers of the present ~n~ention takes place, or the mechanism by whlch both 02/N2 selecti~ity and surface morphology are improved, have not been totally ascertained, without belng bound by theory, lt is believed that fluoro-oxidation reaction occurs readily with polymeric substrates containing functionalities or bonds which are labile towards creation of free radicals. Polymers, such as poly(4-methyl-1-pentene~ contain hydrogen atoms which are especially reacti~e with fluoro-oxidation agents. It is hypothesized that the hydrogen atoms are abstracted by fluorine radicals yielding stable tertiary carbon radicals. Accordingly, other polymers may also be susceptible to fluoro-oxidation and yield membranes with ~mpro~ed surface morphology and selectivity; for example, fluoro-oxdation of substituted poly~acetylenes) should be easily fluoro-oxidized to yield impro~ed me~branes.
In ~ preferred embodiment, the fluoro-oxidized membrane of the invention is used to separate gas mixtures after being assembled in a module such that the feed stream is separated from the permeate stream by the membrane te.g. hollow fiber or spiral wound flat sheet). The feed stream, lS such as air, ~s pressurized ~generally 40-500 ps~) and the permeate streamis generally at or sl~ghtly abo~e atmospherlc pressure. The air stream contacts the membrane whereby the oxygen select~vely permeates through the membrane leaving the feed stream enriched ln nitrogen and the permeate stream enriched in oxygen. Alternati~ely, the permeate stream can be maintained at less than atmospheric pressure, by applying a vacuum to the permeate side of the membrane, with the feed stream maintained at or above atmospheric pressure. ~here hollow fibers are used, the feed stream can be introduced e~ther into the bore of the fibers or to their exterior. Feed `- configurations can be ~aried to maximize productivity or selectivity, for example by co-current or counter-current flow. Details of module design and operatlon are ~ell w~thin the skill of the art but modules as described, for example, in U.S~ Patent 4,2~3,701 are preferred.
The inventlon is further illustrated but is not intended to be limited by the follo~ng examples in which all percentages are by volume. The 3~ fluoro-oxidized membranes of the examples were all post-purged with oxygenor nitrogen for ten minutes following the fluoro-oxidation treatment. All permeability (F) measureMents are gi~en in units of 8arrers, and all - permeances (PIQ) are given in Barrers/cm.

A 50 micron thick film of poly~4-methyl-1-pentene) (melting polnt 240C, density 0.834 glcc, Grade TPX-44) which is available commercially from Mitsui Chemical ~ompany was obtained and mounted on a glass plate with the edges secured by transparent tape. The mounted film was placed ln a batch reactor and purged at ambient temperature and pressure for ten minutes with nitrogen at a flow rate of 1000 cc/minute to remove ambient alr.
Preset ratios of fluorineloxygenlnitrogen were flowed through the reactor at a rate of 1000 cc/minute for`predetermined periods of time, as shown in Table 1. The films were removed from the reactor and measured for total thickness with a micrometer.
The films thus surface modified were mounted in a CSC-13S Permeation Cell (Custom Scientific) where the permeability and selectivity of the treated membranes ~ere measured. In this type cell, pressurized gas mixtures ~ere passed over the membrane surface and the permeate stream was measured on the permeate side using a volumetric flow device according to ASTM test procedure D-1434.
~ he fluoro-oxidized membrane can be considered a composite of the unmodifled base material and the modlfied or fluoro-oxidized layer. The permeability (F02 and ~N2) and selectiv~ty (~), defined as P021FN2, measured for the composite membrane are tabulated below (~ABLE 1) . The ~ntrinsic properties of the modified layer can be calculated from the permeability data of the untreated and treated (composite) membranes using the series-resistance model~ The expression for5 fluoro-oxidi2ed membranes is:

t fl ut ~here P/Q ~s the permeability to film thickness 30 membrane, fl = fluoro-oxidized layer, and ut = untreate~ membrane. The the thickness of the fluoro-oxidized layer is very small compared to the total thickness of the membrane. The intrlnsic selectivity of the fluoro-oxidized layer (a fast gas to a slow gas) is given by:

':. : , . . .

~, . .
. , .

rl 1- _1 f L( )t ( )ut fast gas =
s _ 1 1 -1 ( ~ t( )ut slow gas QOMPOSITE PER~EATION INTRINSIC
DATA PROPERTIES OF
MODIFIED LAYER
SAMPLE XF XO TIME PO2 ~N2 P2~Q X 10 (Barrers) ~Barrers) (Barrerslcm) 1 1 10 4 hr 5.4 0.71 7.6 0.015 8.9

2 2 10 4 hr 3.8 0.59 6.4 0.0087 7.0

3 0.1 10 4 hr 16.4 0.30 5.5 0.14 11.2

4 1 20 4 hr 5.1 0.73 7.0 0.013 7.8 1 1 4 hr 7.0 0~87 7.6 0.019 10.0 6 1 10 8 hr 4.4 0.67 6.6 0.010 6.9 7 1 10 0.5 hr 12.9 2.1 6.1 0.064 10.1 8 2 20 8 hr 1.3 0.24 5.4 0.0089 5.5 9 2 20 0.5 hr 13.0 2.3 5.7 0.060 8.3 . 10 2 10 0.5 hr 12.0 2.0 6.0 0.055 8.7 ; 11 0.1 20 8 hr 11.6 1.7 6.8 0.055 10.9 12 0.1 1 8 hr 11.7 2.2 5.3 0.059 7.4 ~- 13 0.5 15 30m 8.4 1.4 6.1 0.026 9.7 14 0.132.5 30m 17.0 3.2 5.3 0.15 23.1 0.5 50 30m 13.0 2.4 5.3 0.060 12.5 16 1 32.5 30m 11.0 1.8 5.9 0.040 11.0 17 0.532.5 30m 13.5 2.3 5.9 0.070 10.3 18 No Treatment 2.2 .57 3.9 ... . .
.
... . .

The foregoing results indicate that fluoro-oxidized membranes show a significant increase in selectivity for 02lN2 compared to similar untreated membr~nes. The increased selectivity is a direct result of the fluoro-oxidation treatment since the control (no fluoro-oxidation) has a select'vity of 3.9. The unique permselective properties of the fluoro-oxidized ~embranes are attributed to the chemistry and morphology of the fluoro-oxidized layer. The extremely high select3vity factor calculated for sample 14 is believed to be artificially high due to the similarities in Fo2 of the treated material and the base poly(4-methyl-1-pentene).
In an alternate method a 50 micron thick film of this examplP was treated statically by evacuating the reactor to 10 torr and f~lled with a mixture containing lXF2 lOX 2- and 90X N ~at atmospheric pressure) for 240 minutes. At the end of the react~on perlod the reaction mixture was evacuated and the reactor purged with nitrogen for 10 minutes. The lS permeability ~as measured as described above. ~he values determined are:
P02 = 3.7~ Barrers; FN2 = 0.60 Barrers; selectivity was 6.2.
For comparative purposes~ samples treated with preset quantities of fluorine alone (i.e. no added oxygen~ in nitrogen for predetermined times as sho~n in Table 2 exhibited selectivities very similar to the control sample ~n ~able 1 above. ~able 2 lists only composite permeat~on data for these samples.

~ABLE 2 SANPLE XF2 in N2REAC~ION ~IMEF2 FN2 ~02/FN2 2S (Barrers) (Barrers~

19 0.05 60 min 23.0 5.i 4.1 0.1 60 min 21.2 S.l 4.2 21 0.1 30 m~n 23.0 5.6 4.1 22 0.1 10 min 21.0 5.2 4.0 23 0.1 2 min 32.1 5.7 4.0 24 0.5 8 hrs 22.0 5.6 4.1 1.0 8 hrs 22.0 4.7 4.6 :`

.
.:

EXAMYLE 2 (Comparatlve) Dense wall hollow fiber poly(4-methyl-1-pentene) membranes made by spinning a solution of the homogeneous polymer of Table 1 were assembled ln a membrane module as described belov. A correspondlng ~0 micron thick dense f~lm of this polymer has an oxygen and nitrogen permeabil~ty of 22 and 5.7 Barrers, respecti~ely, and a selectivity of 3.9.
The outer diameter of the hol10w fibers was about 126 microns, the inner diameter was about 99 microns, and the wall thickness was about 13.5 microns.
Bundles of 24 or 48 twelve, 20 cm long fibers were potted on one end in a 24 hour cur~ng epoxy and heat sealed on the other end. The potted end was placed in a stainless steel shell and secured with the required fittings and valves.
This design ensured that the feed gas and permeate gas chambers were segregated~
A gas containing oxygen and nitrogen was introduced lnto the shell side of the module at a pressure of 10 psig and oxygen and n~trogen gas permeatlon rates were measured~ Oxygen and nitrogen permeances of 1.26 x 10 and 3.4 x ; 10~ Barrers/cm were obta~n`ed, respect~vely, y~eld~ng a selectivity of 3.7.
The experimentally determ~ned selectl~lty was strikingly similar to the selectivity for the corresponding dense film reported herein. Furthermore, the ` 20 oxygen permeation, deflned as the product of the oxygen permeance and the - membrane wall thickness, was 17 Barrers whlch agrees fairly closely with the value for the correspond~ng dense fllm~ Such results con~lrm that the hollow flber membrane walls are defect-free~

EXAMPLE 3 (Comparatlve) - Asymmetr~c hollow fiber poly(4-methyl-1-pentene) membranes were ` prepared. The membrane f~bers had an outer diameter of 136~3 mlcrons, an ~nner dlameter of 198.4 mlcrons and a wall thlckness of 17~2 mlcrons~ Both ends of the f~ber bundle wer~ potted in a 0~5 inch diameter stalnless steel tube with 5 m~nute epoxy~ The approprlate valves and flttings were added to c~mplete a shell and tube conflguration and a gas containlng oxygen and n~trogen was fed to the shell side of the module as in Example 2~ Permeation rates measured at 10~50 psig were summarized in Table 3. Average oxygen and n~trogen permeances for these me~branes is 6.78 x 104 and 1.87 x 104 3S Barrers/cm, respectlvely~ yieldlng an average selectlvlty of 3.6.

NON-TREATED ASYMMETRIC HOLLO~ FI3ER MEMBRANE PERMEANCE RATES

Pl02lQ x 10 4 P/N2lQ x 10 4 ~ 02/N2 dule Barrers/cm Barrers/cm 126 6.98 1.90 3.67 127 8~36 2.49 3.36 128 4.35 l.lg 3.66 A~e 6~78 1~87 3.64 The h~llow fiber membrane module of Example 2 was flushed with nltrogen lS at room te~perature for thirty mlnutes at a flow rate of 1000 cc/minute. A
reaction qas mixture containing 1~ fluor~ne, lOX oxygen, and 89X nitrogen was introduced at a flow rate of 1000 cc/mlnute for thirty m~nutes. The shell side of the module was then flushed with nltrogen at a flow rate of 1000 cc/
m~nute for thirty minutes. Oxygen and nitrogen permeance rates of 3.11 x 103 and 3~39 ~ 102 Barrerslcm, respectively, are obtalned wlth thls module, - yielding a selectiv~ty of 9~2.

2S ~he three modules of Example 3 were treated as described ln Example 4 using the reactlve gases for the reaction tlmes set out in Table 4 below.
Table 4 also contains permeation data for each module.

` 30 ~`

~: ' . . ' ,' ' . - ' . .:

. : ' . ~ - .

Permeance~
Fo /Q FN jQ aO /N

5 Module Reactl e GaN Treatment 2 3 2 -2 2 2 Number 2 2 2 Time (min.) x 10- x 10 126 20 2 78 30 3.50 3.2 10.9 127 10 1 89 30 7.93 1.13 7.0 128 10 1 89 15 6.52 9.95 6.55 ` 10 ~Barrers k m A film of poly~4-methyl-1-pentene) was treated in accordance with the lS procedure described in Example 1 abo~e using 0~2~ by volume F2, 2~ by volume 2' balance N2 for a reaction time of 8 hours. The permeabil~ty for various gases ~as measured for both the treated film and a corresponding sample of untreated film. ~he results are reported in Table 5 below.

PERMEABILITY (BARRERS) Gas Untreated Film Treated Film ` Hydrogen 108.3 13.7 Helium 30.2 9.6 Oxygen 19.8 10.5 Nitrogen 5.7 1~8 - 30 Methane 13.3 2.3 Carbon dloxide 84.1 10.4 .
The results reported in Table 5 above clearly indicate that the permeability of all the gases tested is lower for the treated film. These .

.

lo~er permeability values are sufficient, however, for separating various mixtures containing these gases. In some instances the separation factor (selectivity) for various gas mixtures is higher for the untreated film, however, for the case of 02/N2, the selectivity of the treated membrane was measured at about 5.8 compared to only about 3.5 for the untreated membrane, making the membranes of the present invention especially useful in air separation and similar processes.
Although the invention has been described in considerable detail in the foregoing description, it is to be understood that such detail is solely for the purpose of illustration. Variations can be made by those skilled in the art ~ithout departing from the spirit and scope of the invention except as set fort~ in the claims.

2~46K

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Claims (43)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A treated, semi-permeable, polymeric membrane comprising a polymer, cast into membrane form having general structural formula:

wherein R and R" can be the same or different linear, branched or cyclic alkyl group having one to twelve carbon atoms, or R can be H, with the proviso that both R and R" cannot be methyl, and n is at least 100, which has been treated with a fluoro-oxidizing agent at conditions sufficient to fluoro-oxidize the membrane surface.

2. The membrane of Claim 1 which has been treated with a fluoro-oxidizing agent containing from about 0.01 to about 10 mole% available fluorine and from about 0.5 to about 99 mole % available oxygen, balance inerts.

3. The membrane of Claim 1 wherein the polymer is poly(4-methyl-1-pentene).

4. The membrane of Claim 1 having an oxygen/nitrogen selectivity of at least 5.

5. The membrane of Claim 1 in the form of a hollow fiber.

6. The membrane of Claim 5 wherein the exterior surface of the hollow fiber has been fluoro-oxidized.

7. The membranes of Claim 5 wherein the interior surface of the hollow fiber has been fluoro-oxidized.

8. The membrane of Claim 5 wherein the hollow fiber has an outer diameter from 20 to 400 microns and a wall thickness from 2 to 100 microns.

9. The membranes of Claim 5 wherein the hollow fiber has an outer diameter of 25 to 200 microns and a wall thickness of 3 to 50 microns.

10. The membrane of Claim 1 in the form of a flat sheet.

11. The membrane of Claim 1 wherein the polymer is cast into the form of an asymmetric membrane having a thin dense layer over a microporous layer.

12. The membrane of Claim 1 wherein the polymer is coated nto the surface of a microporous substrate.

13. The membrane of Claim 12 wherein the polymer which is coated onto the surface of a microporous substrated has a thickness of from about 100 angstroms to 200 microns.

14. The membrane of Claim 1 which has been treated with a gas mixture comprising oxygen and a fluorinating agent selected from the group consisting of F2, NF3, SF4, ClF3, CF4 and mixtures thereof, with the balance inerts.

15. The membrane of Claim 1 which has been fluoro-oxidized in the liquid phase.

16. The membrane of Claim 1 which has been fluoro-oxidized using a low pressure or cold plasma containing a source of fluorine and oxygen.

17. The membrane of Claim 5 which has been fluoro-oxidized on both the inner and outer surfaces.

18. The membrane of Claim 1 having a fluoro-oxidized surface layer up to 2 microns thick.

19. A process for separating a feed gas mixture containing at least two components, said process comprising bringing said feed gas mixture into contact with a treated, semi-permeable, polymeric membrane comprising a polymer, cast into membrane form, having the structural formula:

wherein R and R" can be the same or different linear, branched or cyclic alkyl group having one to twelve carbon atoms, or R can be H, with the proviso that both R and R" cannot be methyl, and n is at least 100, which has been treated with a fluoro-oxidizing agent at conditions sufficient to fluoro-oxidize the membrane surface.

20. A process in accordance with Claim 19 wherein said polymer, cast into membrane form has been treated with a fluoro-oxidizing agent containing from about 0.01 to about 10 moleX available fluorine and from about 0.5 to about 99 moleX available oxygen, balance inerts.

21. A process in accordance with Claim 20 wherein the membrane is treated with a gas mixture containing an oxygen source and a fluorine source.

22. A process in accordance with Claim 21 wherein the fluorine source is selected from the group consisting of F2, HF3 NF3, SF4, ClF3, CF4 and mixtures thereof.

23. A process in accordance with Claim 19 wherein the membrane is treated with a fluoro-oxidizing agent in the liquid phase.

24. A process in accordance with Claim 19 wherein said feed gas mixture is brought into contact with a treated semi-permeable membrane cast from poly(4-methyl-l-pentene).

25. A process in accordance with Claim 19 wherein the feed gas mixture is selected from the group consisting of: O2/N2 CO2/N2 He/CH4, H2/CH4, H2/N2, He/N2, and He/air.

26. A process in accordance with Claim 19 wherein the feed gas is pressurized to about 40 to 500 psi.

27. A process in accordance with Claim 19 wherein the feed gas is at a pressure between atmospheric and 40 psi.

28. A process in accordance with Claim 19 wherein the feed gas is at atmospheric pressure and vacuum is applied to the permeate side of the membrane.

29. A process in accordance with Claim 19 wherein said treated semi-permeable membrane is in hollow fiber form and the feed stream is introduced into the bores of the hollow fiber.

30. A process in accordance with Claim 19 wherein said treated semi-permeable membrane is in hollow fiber form and the feed stream is contacted with the exterior of the hollow fiber.

31. A process in accordance with Claim 19 wherein said membrane has been contacted with a fluoro-oxidizing agent for a period of time form 1 minute to 48 hours.

32. A process for preparing a gas separation membrane comprising;
casting into membrane form a polymer having the structural formula:

wherein R and R" can be the same or different linear, branched or cyclic alkyl group having one to twelve carbon atoms, or R can be H, with the proviso that both R and R" cannot be methyl, and n is at least 100; and treating a surface of said polymer by contacting said polymer with a fluoro-oxidizing agent at conditions sufficient to fluoro-oxidize the membrane surface.

33. A process in accordance with Claim 32 wherein said fluoro-oxidizing agent contains from about 0.01 to about 10 mole% available fluorine and from about 0.5 to 99 mole% available oxygen, with the balance inerts.

34. The membrane of Claim 33 which has been treated with a gas mixture comprising oxygen and a fluorinating agent selected from the group consisting of F2, HF, NF3, SF4, ClF3, CF4 and mixtures thereof, with the balance inerts.

35. The membrane of Claim 32 which has been fluoro-oxidized in the liquid phase.

36. The membrane of Claim 32 which has been fluoro-oxidized using a low pressure or cold plasma coating a source of fluorine and oxygen.

37. A process in accordance with Claim 32 wherein one or more antioxidants are added to the polymer.

38. A process in accordance with Claim 32 wherein an additive selected from the group consisting of: processing aids, antistatic additives, nucleation additives, plasticizers, oil extenders, polymeric modifiers, and mixtures thereof are added to the polymer.

39. A process in accordance with Claim 32 wherein said polymer is coated onto a porous support.

40. A process in accordance with Claim 32 wherein the surface of said polymer is fluoro-oxidized prior to being cast into membrane form.

41. A process in accordance with Claim 32 wherein the surface of said polymer is fluoro-oxidized after being cast into membrane form.

42. A process in accordance with Claim 32 wherein a surface of said polymer to be treated is first contacted with a reactive source of fluorine and subsequently contacted with a source of available oxygen.

43. A process in accordance with Claim 32 wherein a surface of said polymer to be treated is simultaneously contacted with a reactive source of fluorine and a source of available oxygen.