CA1047718A - Microporous polyester membranes and polymer assisted phase inversion process for making same - Google Patents
Microporous polyester membranes and polymer assisted phase inversion process for making sameInfo
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- CA1047718A CA1047718A CA290,213A CA290213A CA1047718A CA 1047718 A CA1047718 A CA 1047718A CA 290213 A CA290213 A CA 290213A CA 1047718 A CA1047718 A CA 1047718A
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Abstract
ABSTRACT OF THE DISCLOSURE
A microporous membrane is disclosed which is suitable as a membrane filler in liquid permeation, microfiltration and ultra filtration in reverse osmosis, as a porous support substrate or for another reverse osmosis membrane, in electrophoresis, curtain electrophoresis, thin layer, gas or liquid chromatography or as a substrate for enzyme attachment.
The membrane consists essentially of a polyester resin of the general formula
A microporous membrane is disclosed which is suitable as a membrane filler in liquid permeation, microfiltration and ultra filtration in reverse osmosis, as a porous support substrate or for another reverse osmosis membrane, in electrophoresis, curtain electrophoresis, thin layer, gas or liquid chromatography or as a substrate for enzyme attachment.
The membrane consists essentially of a polyester resin of the general formula
Description
- ~\
10~7718 This invention relates to microporous membrane filters composed of polyesters derived from aromatic dibasic acids, especially polytetra-methylene terephthalate and to a new process for forming microporous poly-meric membrane filters. The new process, referred to as a polymer assisted phase inversion, obviates the necessity for a surfactant in the membrane and represents a new approach to the formation of microporous membrane filters.
The technology of synthetic polymeric membranes is quite well developed in many areas and the literature on the subject is profuse. Probably the best and most comprehensive treatment of this subject is the recent work 10 by the present inventor, Dr. Robert Kesting, entitled SYNTHETIC POLY-- MERIC MEMBRANES, McGraw-Hill Book Company, 1971, Library of Congress catalog card No. 72-132345. The reader is referred in particular to Chapter 5 of this work entitled "Porous Phase-Inversion Membranes" for a discussion of the principles of membrane formation.
Polyester resins and the terephthalate polymers are, in general, well known. Polyesters were described by Carothers and Arvin, Journal of the American Chemical Society, Volume 51, pages 2560-70 in 1929. See also collected papers of W.H. Carothers on High Polymeric Substances, Volume I
Hl~H POLYMERS, INTERSCIENCE PUBLISHERS INC., New York 1940. - -20 Polyethylene terephthalate films have been marketed for several years under the trademark MYLAR by DuPont and other polyester materials in various - forms have been available for several years. ~ -Until now, however, microporous membrane filters of the polyesters -~
have not been available. One of the principle features of this invention involves microporous membrane filters composed of polyesters derived from ~ -aromatic dibasic acids. One of the more specific features of the invention is - ~ the discovery and preparation of microporous membrane filters composed of polytetramethylene terephthalate.
Another principle feature of the present invention is the provision of 30 a dry process for forming microporous membrane filters of aromatic dibasic .. . .
~ acid polyesters in which membrane formation is accomplished without the ~- -.
~ necessity of the usual low molecular weight swelling agents and wetting agents, , :."
.. ~' - 1 -. ,.
. . . - - . , ~ . . : . .
1~477~8 the membrane ~ormation being assisted by the inclusion of a separate and distant polymeric compound. This dry process is called a polymer assisted phase inversion process for forming microporous membrane filters of aromatic dibasic acid poly-esters and is particularly applicable to polytetramethylene terephthalate and equivalent polyester resins.
Thus, in accordance with the present teachings, a polymer assisted phase inversion process is provided for forming microporous polyester membranes. The process 10- comprises casting a solution containing a polyester derived ; from an aromatic dibasic acid and an alkyl diol of the formula O O
wherein a is an integer of at least 3 and not greater than 7 and n is an integer greater than about 45, and an assisting polymer, in concentrations-of between about 2% and about 20%
by weight total polymer in a mutual solvent for the polymers into a large surface area configuration. The mutual solvent is extracted from the polymers from the configuration to thereby form a membrane with the membrane having inchoate -pores filled with the assisting polymer.
Within these broad and unique principle features of the invention lie other significant features which will be discussed in detail in the specification hereinafter.
Polyesters Derived from Aromatic Dibasic Acids ~ .
Polyesters which are derived from aromatic diabasic acids, especially those derived from terephthalic acid, have excellent chemical resistance, including resistance to acid and base hydrolysis and resistance to a great number of organic solvents.
In addition, these resins exhibit other outstanding . . , . , . , :
1()477~8 properties, such as high tensile strength, flexibility, and thermal stability. For these reasons, this class of resins represents an excellent a priori candidate for the formation of microporous membrane filters. Until the present invention, however, membranes of these materials which exhibit the structure of the "typical" microporous membrane filters, such as those prepared from nitrate and acetate esters of cellulose, and certain polycarbonates (see Canadian Patent 991,776), etc., have eluded workers in the field.
Polyesters prepared from the condensation of dibasic acids and diols are well known as resins and possess the follow-ing general formula:
O O
.. .. .
~ RC-O-R'-O-C-~-wherein R is aryl and R' is typically alkyl, wherein n is an integer which may be as low as a few hundred to as high as several thousand. --The only polyesters of interest in the present ~ -invention are those in which the dibasic acid moiety is aromatic, e.g. the benzene nucleus. The specific dibasic acid of the -;
greatest interest in the present invention is terephthalic acid.
, :
.
.
- 2a -, ` ~ 1047718 Ortho- and Isophthalic acid derived polymers are regarded as equivalent only in the very broadest sense and only marginally suitable as membrane formers in the present invention.
Polyesters of the class under consideration derived from tere-phthalic acid have, within the context of the present invention, such unique properties as to set terephthalate resins apart from other resins of this class, Diols which are suitable for the present invention are the aLkyl diols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, etc. Ethylene glycol derived polyesters of the class under consideration are regarded as only very marginally suitable, and equivalent to tetramethylene :-glycol derived polymers only in a broad sense, which would include usable, but much less satisfactory membrane forming systems.
Generally, then, the most suitable polyesters are those having the formula:
O O .
10~7718 This invention relates to microporous membrane filters composed of polyesters derived from aromatic dibasic acids, especially polytetra-methylene terephthalate and to a new process for forming microporous poly-meric membrane filters. The new process, referred to as a polymer assisted phase inversion, obviates the necessity for a surfactant in the membrane and represents a new approach to the formation of microporous membrane filters.
The technology of synthetic polymeric membranes is quite well developed in many areas and the literature on the subject is profuse. Probably the best and most comprehensive treatment of this subject is the recent work 10 by the present inventor, Dr. Robert Kesting, entitled SYNTHETIC POLY-- MERIC MEMBRANES, McGraw-Hill Book Company, 1971, Library of Congress catalog card No. 72-132345. The reader is referred in particular to Chapter 5 of this work entitled "Porous Phase-Inversion Membranes" for a discussion of the principles of membrane formation.
Polyester resins and the terephthalate polymers are, in general, well known. Polyesters were described by Carothers and Arvin, Journal of the American Chemical Society, Volume 51, pages 2560-70 in 1929. See also collected papers of W.H. Carothers on High Polymeric Substances, Volume I
Hl~H POLYMERS, INTERSCIENCE PUBLISHERS INC., New York 1940. - -20 Polyethylene terephthalate films have been marketed for several years under the trademark MYLAR by DuPont and other polyester materials in various - forms have been available for several years. ~ -Until now, however, microporous membrane filters of the polyesters -~
have not been available. One of the principle features of this invention involves microporous membrane filters composed of polyesters derived from ~ -aromatic dibasic acids. One of the more specific features of the invention is - ~ the discovery and preparation of microporous membrane filters composed of polytetramethylene terephthalate.
Another principle feature of the present invention is the provision of 30 a dry process for forming microporous membrane filters of aromatic dibasic .. . .
~ acid polyesters in which membrane formation is accomplished without the ~- -.
~ necessity of the usual low molecular weight swelling agents and wetting agents, , :."
.. ~' - 1 -. ,.
. . . - - . , ~ . . : . .
1~477~8 the membrane ~ormation being assisted by the inclusion of a separate and distant polymeric compound. This dry process is called a polymer assisted phase inversion process for forming microporous membrane filters of aromatic dibasic acid poly-esters and is particularly applicable to polytetramethylene terephthalate and equivalent polyester resins.
Thus, in accordance with the present teachings, a polymer assisted phase inversion process is provided for forming microporous polyester membranes. The process 10- comprises casting a solution containing a polyester derived ; from an aromatic dibasic acid and an alkyl diol of the formula O O
wherein a is an integer of at least 3 and not greater than 7 and n is an integer greater than about 45, and an assisting polymer, in concentrations-of between about 2% and about 20%
by weight total polymer in a mutual solvent for the polymers into a large surface area configuration. The mutual solvent is extracted from the polymers from the configuration to thereby form a membrane with the membrane having inchoate -pores filled with the assisting polymer.
Within these broad and unique principle features of the invention lie other significant features which will be discussed in detail in the specification hereinafter.
Polyesters Derived from Aromatic Dibasic Acids ~ .
Polyesters which are derived from aromatic diabasic acids, especially those derived from terephthalic acid, have excellent chemical resistance, including resistance to acid and base hydrolysis and resistance to a great number of organic solvents.
In addition, these resins exhibit other outstanding . . , . , . , :
1()477~8 properties, such as high tensile strength, flexibility, and thermal stability. For these reasons, this class of resins represents an excellent a priori candidate for the formation of microporous membrane filters. Until the present invention, however, membranes of these materials which exhibit the structure of the "typical" microporous membrane filters, such as those prepared from nitrate and acetate esters of cellulose, and certain polycarbonates (see Canadian Patent 991,776), etc., have eluded workers in the field.
Polyesters prepared from the condensation of dibasic acids and diols are well known as resins and possess the follow-ing general formula:
O O
.. .. .
~ RC-O-R'-O-C-~-wherein R is aryl and R' is typically alkyl, wherein n is an integer which may be as low as a few hundred to as high as several thousand. --The only polyesters of interest in the present ~ -invention are those in which the dibasic acid moiety is aromatic, e.g. the benzene nucleus. The specific dibasic acid of the -;
greatest interest in the present invention is terephthalic acid.
, :
.
.
- 2a -, ` ~ 1047718 Ortho- and Isophthalic acid derived polymers are regarded as equivalent only in the very broadest sense and only marginally suitable as membrane formers in the present invention.
Polyesters of the class under consideration derived from tere-phthalic acid have, within the context of the present invention, such unique properties as to set terephthalate resins apart from other resins of this class, Diols which are suitable for the present invention are the aLkyl diols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, etc. Ethylene glycol derived polyesters of the class under consideration are regarded as only very marginally suitable, and equivalent to tetramethylene :-glycol derived polymers only in a broad sense, which would include usable, but much less satisfactory membrane forming systems.
Generally, then, the most suitable polyesters are those having the formula:
O O .
(2) ~--o-(cH2)a -O-C
wherein a is an integer from 3 to 5, most preferably 4, and marginally as low as 2 or as high as 6 or 7, and wherein _ is an integer greater than about 45 (MW-- 10,000) and preferably greater than 90 (MW -- 20,000). The most - --suitable available range of polymers of this class thus far proved have an n value within n = 90 (MW-- 20,000) to n = 225 (MW-- 50,000), but the use of such polymers having an n value of up to 450 (MW 100,000) or higher will predictably permit preparation of High Void Volume membranes by the dry process here disclosed, as well as by the process described in my co-pending patent application referred to previously.
The range of effective equivalents, for purposes of this invention, must, to some degree, be determined empirically, since a full range of potential equivalents is not now available for evaluation and may not become available soon enough to avoid undue delay in making this technology available to the industry. ~ -Some guidlines to potential equivalents are possible, however.
These are outlined briefly below.
Polyesters derived from ortho- or isophthalic acid are regarded as potential, but significantly inferior, marginal equivalents suitable for some applications if the solvating power of the casting solution solvent is reduced and carefully controlled. (For use in the dry process herein disclosed, the solvent must also dissolve the assisting polymer, thus making solvent selection critical and unpredictable).
Polyesters of the class under consideration having the general 10 formula:
s O -: . - -
wherein a is an integer from 3 to 5, most preferably 4, and marginally as low as 2 or as high as 6 or 7, and wherein _ is an integer greater than about 45 (MW-- 10,000) and preferably greater than 90 (MW -- 20,000). The most - --suitable available range of polymers of this class thus far proved have an n value within n = 90 (MW-- 20,000) to n = 225 (MW-- 50,000), but the use of such polymers having an n value of up to 450 (MW 100,000) or higher will predictably permit preparation of High Void Volume membranes by the dry process here disclosed, as well as by the process described in my co-pending patent application referred to previously.
The range of effective equivalents, for purposes of this invention, must, to some degree, be determined empirically, since a full range of potential equivalents is not now available for evaluation and may not become available soon enough to avoid undue delay in making this technology available to the industry. ~ -Some guidlines to potential equivalents are possible, however.
These are outlined briefly below.
Polyesters derived from ortho- or isophthalic acid are regarded as potential, but significantly inferior, marginal equivalents suitable for some applications if the solvating power of the casting solution solvent is reduced and carefully controlled. (For use in the dry process herein disclosed, the solvent must also dissolve the assisting polymer, thus making solvent selection critical and unpredictable).
Polyesters of the class under consideration having the general 10 formula:
s O -: . - -
(3) ~-C-O-(CH2)a-0-C }n -- ~
wherein a and n are the integers as previously defined and wherein s is a ~ -substituent which does not prevent polymerization of the polyester, e. g. a - ~
methyl or other lower alkyl group (1-4 carbon atoms), are also potential -equivalents and should permit the more effective use of diols having 2 carbon ~ -atoms. Selection of a solvent having a lower solvating power, as discussed previously is indicated for casting solutions of such polyesters, especially where larger, or plural, aLkyl substituents occupy one or more positions on -~-20 the aromatic dibasic acid nucleus. ~ ` ~
Polyesters derived from fused polycyclic dibasic acids, for example - ~ -01 :
wherein a and n are the integers as previously defined and wherein s is a ~ -substituent which does not prevent polymerization of the polyester, e. g. a - ~
methyl or other lower alkyl group (1-4 carbon atoms), are also potential -equivalents and should permit the more effective use of diols having 2 carbon ~ -atoms. Selection of a solvent having a lower solvating power, as discussed previously is indicated for casting solutions of such polyesters, especially where larger, or plural, aLkyl substituents occupy one or more positions on -~-20 the aromatic dibasic acid nucleus. ~ ` ~
Polyesters derived from fused polycyclic dibasic acids, for example - ~ -01 :
(4) HOC ~COH
are not good candidates as equivalents, although the dry process described herein could be used if a suitable solvent could be found.
Polyesters of the class under consideration derived from diols con- --taining etheric linkage, for example
are not good candidates as equivalents, although the dry process described herein could be used if a suitable solvent could be found.
Polyesters of the class under consideration derived from diols con- --taining etheric linkage, for example
(5) HO- CH2CH2-0-CHZCH2-OH
and
and
(6) Ho-cHzcH2-o~o-cH2cH
., :,-- .
..
.
.- iO47718 and from diols of high molecular weight, for example
., :,-- .
..
.
.- iO47718 and from diols of high molecular weight, for example
(7) HO-(CH2) a' -OH
wherein a' is an integer of 7 or 8 or higher, are also not good candidates as equivalents to the extent that membranes formed from such materials would be less stable, less resistant and generally inferior and would require a different solvent system. The dry process disclosed herein could be used, however, if a suitable solvent could be found.
Obviously, not all criteria for equivalence are set forth, and not all 10 parameters are known. I do not, however, wish to be limited to those materials specifically set forth in the examples, nor do I wish to ignore the ~
fact that one particular combination of materials (polytetramethylene tere- ;
phthalate polyester, polyvinyl alcohol assisting polymer, and hexafluoro- -isopropanol) possesses such unexpected advantages as to be a distinct discovery within the broader framework of this invention.
Until quite recently, the only commercially available dibasic acid derived polyesters of the type under consideration here were the polyethylene terephthalate polyesters prepared by the condensation of dimethyl tere-phthalate and ethylene glycol. (Reference to dibasic acids and diols includes 20 polymerizable derivatives thereof.
Polymers of this type are sold in various forms under several trademarks including Mylar and Dacron.
I had postulated that if the alkyl chain were longer than that pro-- vided by polyethylene terephthalate, polyesters of the type under consideration would be excellent candidates for microporous membrane filter fabrication.
- I have now proved my postulate correct and discovered that polytetramethylene ~ :
terephthalate prepared from the condensation of dimethyl terephthalate and 1 ,4,tetramethylene glycol does indeed form microporous membrane filters having excellent chemical and physical characteristics.
A sufficiently high molecular weight polytetramethylene terephthalate is available from Eastman Chemical Company under the trademark Tenite Polyterepht~late, from General Electric Company under the trademark -Valox, and from Celanese Corporation under the trademark Celanex.
My familiarity with the process variables, the characteristics of the products obtained and the chemical and physical properties of the materials involved indicate with relative certainty that polyesters derived from aromatic dibasic acids (or polymerizable derivatives, e. g. esters, thereof) having 3 to 6 or 7 methylene groups in the alkyl moiety of the -polymer can be fabricated into good to excellent quality microporous mem-brane filters using the techniques and processes of this invention as described hereinafter .
In general, any polyester derived from an aromatic dibasic acid which is insoluble in water, possesses acceptable physical properties (is self-supporting at ambient temperature and is sufficiently dimensionally ~
stable), and is soluble within the range of 2% to 20% (by weight) in combina- - -tion with an assisting soluble polymer which also has solubility in the 2~o to 20% (by weight) range in a solvent which has a boiling point in the ambient to approximately 150C range must be regarded as an equivalent in the broadest sense, but not in the narrow sense of being interchangeable with polytetramethylene terephthalate with like results in the same casting solution system. Indeed, I regard only polytrimethylene terephthalate and poly-ZO pentamethylene terephthalate polyesters as substantially certain to be closely equivalent and functional in this latter sense.
The preferred polyester, polytetramethylene terephthalate, sold ~-under the trademark Tenite Polyterephthalate 6 PRO, has outstanding chemical properties illustrated by Table I which shows the effects of various chemicals on this grade of polytetramethylene terephthalate.
% Increase After One Year Chemical In Wei~htIn Thickness Acetic Acid (Glacial) 2. 65 1. 51 Acetic Acid (5%) * 0. 40 -0. 29 -30 Acetone 5. 56 2. 57 Ammonium Hydroxide (Conc. ) O. 80 -O. 16 Ammonium Hydroxide (10%) 0.49 _0.53 ' ~ 6 -. , ..
`
~047718 Aniline 6.69 4.17 Benzene 3.26 2.19 Carbon Tetrachloride 0.72 0. 42 Chromic Anhydride (40%) 0.10 -0.11 Citric Acid (10%) 0.37 0.16 Cottonseed Oil 0.09 -0.16 Alconox Detergent (0.25%) 0.37 -0.34 Diethyl Ether 0.95 . 45 Dimethyl Formamide 2.48 1.56 10 Deionized Water 0.39 - 0.53 Ethyl Acetate 3.30 1.93 Ethylene Dichloride 18.66 6.16 Heptane 0.13 - 0.26 Hydrochloric Acid (Conc . )0.56 0.03 Hydrochloric Acid (10%) 0.33 _0.05 Hydrogen Peroxide (28%) 0.41 0.00 Hydrogen Peroxide (3%)0.38 -0.05 Isooctane 0.08 -0.08 Kerosene 0.10 -0.16 20 Methanol 1.61 0.16 l_ Incr eas e After_One Year Chemical In Wei~ht In Thickness ~ -Mineral Oil 0.06 - 0.13 Nitric Acid (Conc . ) -disintegrated-Nitric Acid (40%) 0.68 0.05 Nitric Acid (10%) 0.36 -0.16 Oleic Acid (93 %) 0.26 - 0.18 Olive Oil 0.06 0.11 Phenol (5% in water )9.48 4.88 30 Sodium Chloride (10%)0.32 0.05 Sodium Carbonate (20%)0.31 0.05 Sodium Carbonate (2%)0.36 0.00 r` ~
~ ` 1047718 Sodium Hydroxide (10 %)-1. 20 -1. 16 Sodium Hydroxide ( 1 %)0. 37 0. 77 Sulfuric Acid (Conc . )-disintegrated-Sulfuric Acid (30%) 0.25-0.52 Sulfuric Acid (3~o) 0. 360. 00 Turpentine 0. 27-0. 03 -Toluene 2. 351. 40 - ~
Sodium Hypochlorite (3. 5%)0. 37 -0.11 ~ -Ethanol 0. 480. 21 10 Ethanol (50%) 0.470 03 ~ -Dibutyl Sebacate 0. 07- 0. 05 Di-2-Ethylhexyl Phthalate 0. 070. 08 Ivory Soap (1%) 0. 370. 08 Brake Fluid Transformer Oil 0. 06-0.18 ; - -* All percentages are concentrations in water. ~ - -These membranes are extremely tough, flexible, dimensionally stable over -a broad range of temperatures, maintain their strength at both high and low temperatures and possess other highl3r desirable physical characteristics.
The Polvester Membrane Product ., In terms of a manufacture or product, the present invention is directed to a polyester derived from a dibasic acid, as discussed herein- -~ -before, which is in the form of a microporous membrane. ;
The microporous membrane of this invention is composed of a polyester derived from a dibasic acid and may include a hydrophilic second polymer or a second polymer which is soluble in a fluid which is a non-solvent for the polyester.
Typically, the membrane of this invention, in finished form, is composed of a dibasic acid derived polyester, as discussed previously, and 30 a minor proportion of the second polymer, which is hydrophilic or soluble in a polyester non-solvent fluid, or includes, as a component, such a membrane composition.
_ 8 -,. . : . ~: , .
, ., . . , - : -- 10477~8 The membranes here disclosed may be used as membrane filters in microfiltration, ultrafiltration, in reverse osmosis, as reverse osmosis membranes or as porous support substrates for other reverse osmo~is membranes, the cellulose acetate membranes, for example, and in electro- ~ -phoresis, curtain electrophoresis, thin layer, gas and liquid chromatography and as substrates to which enzymes and other catalysts can be attached for solid-liquid reactions. The porous membrane filters in this invention may be produced in flat sheets, tubular forms on the inside or the outside of the tube, as hollow fibers, and in microporous bead configurations. These 10 microporous membrane filters are of special significance to the production of microporous tapes because of their strength and flexibility.
One particularly unique advantage of the subject membrane system ~ -results from the fact that the assisting polymer fills the incipient voids in the - ~
unleached membrane. The surface of the unleached membrane is, therefore, - -~ -still amenable to fabrication of multilayered membrane structures, with one membrane layer being used as the substrate for the next layer. This permits, inter alia, production of vexy thick membrane sections.
Other advantages possessed by the membranes of this invention are the absence of surfactants and of a tendency to build up static charges which, 20 in conventional microporous membranes, tracks dust and makes handling difficult and results sometimes uncertain.
- Other and more specific characteristics of the product will be apparent from the discussion of the process which follows and from the subsequent references to the product.
The Polvmer Assisted Phase Inversion Process These membranes are fabricated by forming a casting solution of a dibasic acid derived polyester, a second polymer which is soluble in a fluid which is a non-solvent for the polyester, and a liquid which is a solvent for both the polyester and the second polymer. This forms the casting solution 30 for forming the membrane~. The casting solution is then cast upon a sub-strate to form a film of desired dimensions. The solvent is permitted to evaporate from the film and at least a portion of the second polymer is _ 9 _ - :
104~718 leached from the film with the fluid which is a non-solvent for a polyester.
This leaves a microporous membrane which has excellent chemical and physical characteristics, the characteristics of which can be varied by controlling the nature and amount of the second polymer in the membrane, as well as by the selection of the polyester, and by control of process variables.
Polytetramethylene terephthalate is considered to be the first truly suitable aromatic dibasic acid based polyester for formation of microporous membrane filters because of its greater solubility (compared to polyethylene terephthalate) in suitably volatile solvents. This property makes it possible to prepare true, molecularly dispersed, solutions of polytetramethylene ~ -terephthalate in a few selected volatile solvents. Polytetramethylene tere-phthalate is more soluble (i.e. exhibits a higher degree of dispersion), than polyethylene terephthalate, probably because of the greater flexibility of the polymer chains, owing to the presence of four methylene groups in the former, rather than the two separating the terephthalate acid moieties in the latter.
Further, and of distinguishing importance, polytetramethylene -terephthalate represents a very close approach to, if not the actual accom-plishment of, the ideal balance between sufficient solubility to permit fabrica- -tion into membranes, and sufficient solvent resistance, to permit~utilization ~ - --of the re~ultant membrane in the filtration of solutions in common organic solvents. By comparison, polyethylene terephthalate is insufficiently soluble to permit fully satisfactory membrane fabrication. Cn the other hand, the - -inclusion of too many or too large substituents on the aromatic nucleus of the diacid or too long methylene chains or etheric links in the diol, or other substitution or modification which greatly increases the solubility of the poly-ester degrades the chemical and physical resistance of the resultant polyester and may require significant modification of the membrane fabrication process.
The first partially successful prototype membranes prepared -according to this invention were from polyethylene terephthalate solutions.
Such solutions are turbid, whereas polytetramethylene terephthalate solutions are clear indicating a finer dispersion in the latter solutions. Fine dispersion ~-, - 10 _ ,~ , - , : . -in the solution, and hence clear solutions, are highly desirable and are probably mandatory in any commercially feasible process, since only the latter clear casting solutions are sufficiently stable for utilization in the dry phase inversion process on a commercial scale.
The reader is referred to Kesting, SYNTHETIC POLYMERIC
MEMBRANES, referenced previously and my Canadian Patent 991,776 entitled INTEGRAL UNSKINNED HIGH VOID VOLUME POLYCARBONATE
MEMBRANES AND A DRY PROCESS FOR FORMING THE S~WE, for a detailed discussion of the phase inversion process for fabricating p~lymeric ~membra~es. The bEoad~principles of.phase inversion membrane formation are applicable to the present dry process;
however, the present process is believed to be the first satisfactory example of a phase inversion process for manufacturing microporous membranes in which the swelling agent consists of a solvated second polymer which assists in the phase inversion in~.à ~anner:similariT^to~-the~:manne~-in-whiah;-~typical~swelling~
agents of low molecular weight assist in the phase inversion in common phase inversion membrane formation. For this reason, the process is referred to as a Polymer Assisted~Phase .In~version Process, sometimes abbreviated "PAPI~ process.
The process consists in dissolving the polyester and one or more, usually only one, second polymer(s~ in a volatile solvent, (i.e., a solvent which has a boiling point below about 150C and preferably below about 100C~ or in a combination of solvents, swelling agents and non-solvents for both the polyester and second polymer, casting ~he solution as~a film ana ev.ap~orating theesolvents from the sol~ion. The process can be either wet Q~ dry;.t~at.~ t:ma~ lnv~.lve~either partia-l-or ~ompLete -~
e~a~oratl~on, the dry pOEocess being preferred whenever applicable.
1~47718 ' The overall process invo~lved herein is described as a polymer ass~sted phàse inversion process but it has elements of a leaching process as well. In those cases where a non-polyester polymer component is either desiæed or does not interfere with the end use of the filter, these non-polyester polymer components 3 may simply be left in the microporous membrane. In cases where the second polymer, i.e., the non-polyester polymer, would be objectionable, '. 10 -:
-, ~ '~.'"''.
.'' "'-,: ' - lla-.~ , . , . - : ~ . . .
. - 1047718 the second polymer may be leached out with a solvent for the second polymer which is a non-solvent for the polyester.
The process may be varied to form polymeric microporous mem-brane filters for specific end uses. For use in microfiltration, ultrafiltra-tion and electrophoresis, curtain electrophoresis, gas, liquid and thin layer chromatography, an unskinned (i.e., a more or less symmetrical membrane) is desired. In these cases the dried membrane may be either leached of its non-polyester component or components or may be used with the second polymer in place, depending upon the specific requirement~ of 10 the end use. It is also possible where two or more second non-polyester polymers have been included, to leach one or more of the polymers from the membrane, leaving behind one or more polymers together with a polyester.
Likewise, it is possible to employ in situ cross linking to permanent- -ly fix one or more otherwise leachable second polymeric components in the membrane .
Included second polymers may function to improve wettability of the polyester in one of several ways. They may be surfactants or they may sirnply possess an affinity for water, up to and including water solubility.
Where the included polymers are not actually surfactants an important new 20 dimension has been added to membrane filters, since the presence of sur-factants, present in commercially available membrane filters, is often deleterious to certain biological separations, and in handling foodstuffs, water for drinking purposes, etc. Therefore, one important feature of the invention is that wettability can be obtained by the inclusion of either leachable or, when necessary non-leachable hygroscopic, but not surface active, polymers.
Two types of asymmetric, i. e., skinned, reverse osmosis mem-branes and two separate processes for their preparation have been described.
These are the Loeb-Sourirajan wet process and the Kesting dry process.
Both of these processes use cellulose acetate polymers in their manufacture.
Cellulose acetate is, however, rather friable microporous membrane configurations. Stronger and less friable reverse osmosis membranes are, therefore, desirable.
.. , 1047'718 This difficult goal is accomplished, in the present invention, by casting a membrane either a thin dense or a thicker asymmetric membrane, of cellulose acetate or other polymer (such as the polyester itself), suitable for reverse osmosis upon the polyester membranes prior to leaching, so that the polyester membrane after leaching serves as a porous backing support for the cellulose acetate or other reverse osmosis polymeric membrane. Adhesion of the rever~e osmosis membrane to the microporous -support can be achieved by including, as a constituent of the casting solution for the reverse osmosis membrane, a solvent for the polyester. When - - -properly balanced (containing the correct amount of polyester solvent), this ~ -solvent system will sufficiently soften the surface of the polyester to permit good adhesion without destroying the porous characteristics of the polyester membrane support. Following the application of the second layer, the leachable assisting polymer of the substrate may be removed by washing with water, alcohol or other polyester non-solvent.
It is noteworthy also that dense polyester membranes themselves have the ability to function as reverse osmosis membranes, as do asymmetric ~
polyester membranes having a dense skin on a porous substructure. ; - -Solvents - 20 Solvent selection is extremely critical. Indeed, to date only two solvents, hexafluoroisopropanol and trifluoroacetic acid, are known to be acceptable for the dry process. The wet process is less desirable but the - ~ -same solvents can be used in such a process.
There are no known equivalent solvents for use with polytetra- -methylene terephthalate polyester of suitable molecular weight for membrane fabrication, and one has little basis for making reliable predictions as to potentially equivalent solvents. Probably only highly fluorinated substituted low molecular weight (1-4 carbon atom) alcohols, acids, ethers, esters and acids can now be considered as solvent candidates in the preparation of the subject membranes, and it is known that not all such compounds are satis-factory. Trifluoroethanol and the hexafluoroacetone-methanol hemiacetal, for example, are not satisfactory solvents for fabricating polytetramethylene - 13 _ ..
, ,1 . - . ~ ,, ` 1~47718 terephthalate membranes. Indeed, even trifluoroacetic acid is so vastly inferior to hexafluoisopropanol as to make the latter a component of a distinct discovery within the broad inventive concept here disclosed.
It may be suggested that where less solvating power is required, as with substituted aromatic dibasic acid or longer chain diol derived polyesters, other highly fluorinated compounds of the class discussed would be suitable, but ultimate solvent selection must, at present, be on an empirical basis.
Any desired solvating power, within the range of the solvents, may be obtained by mixing selected solvents. Hexa- -fluoroisopropanol and trifluoroacetic acid, for example, may be mixed or diluted with other solvents of the class under consideration.
It must be understood that solvent selection is not alone a function of the nature of the polyester. The nature of the assisting polymer and, more correctly, the nature of the combination of polyester and assisting polymer are also controlling, or at least very influential in solvent selection.
Assisting Polymers Suitable second or "assisting" polymers are very rare.
They include certain hygroscopic polymers, polyvinyl alcohol in particular. Polyvinyl pyrrolidone also functions, but is much less suitable than polyvinyl alcohol. These polymers can be softened and/or leached in water. Other polymers which are mutually soluble together with the polyester in a solvent, and which are soluble in polyester non-solvent are candidates as assisting polymers.
~ - 14 -1~)47718 rn a more general sense the assisting polymers must be soluble in a solvent which is a non-solvent for the polyesters and must also be soluble in a mutual solvent for themselves and the p~lyesters.
Mutual solubility of the type discussed here, in approximately equal weights of the polyester and the assisting polymer at the high total solids content, i.e., between approximately 5 and 20%, necessary for the practical production of membranes is extremely rare in most solvent systems and is made possible by the unusual solvent properties of the polar fluorinated compounds which are employed as mutual solvents. Becaaae of strong ~,...
' -~
- 14a -, ' ~
-10477~8 solvation, solvated chains of dissimilar polymers are apparently much less incompatible than they would be in the absence of solvation.
The void volume of the membrane produced by the polymer assisted phas0 inversion process can be controlled by varying the ratio of the second (leachable) polymer to the polyester. The higher the ratio, the higher the void volume. For the polytetramethylene terephthalate polymers of the molecular weights available today, e.g., from about 25,000 to 50,000, void volumes above about 60% are not achievable with the maintenance of the excellent physical properties found to date. It is to be predicted, however, as higher molecular weight polyesters become available higher void volumes will be achievable using the polymer assisted phase inversion process.
The pore size and void volume of the membranes can be controlled by controlling the nature of the second, "assisting", polymer. The most suitable assisting polymer found to date, is polyvinyl alcohol.
Pore size is a function of the molecular weight and acetyl content of the assisting polymer. High (37-42% by weight) acetyl content (e. g.
Gelvatol*40-10) polyvinyl alcohols yields coarse structures. Low (0-4%
by weight) acetyl content resins (e. g. Gelvatol * 1-30 and 1 -60) yield fine structures. Intermediate size structures (void and pore size ~0.05,um to 1Ø2,um) are obtained with intermediate (19.5-22.7% by weight) acetyl content (e. g. Gelvatol * 20-30 and 20-60). Fineness also increases with increasing molecular weight although less dramatically than with decreasing acetyl content. In general the best physical properties are obtained by employing resins of intermediate (20 + 5% by weight) acetyl content and intermediate (10,000 to 14,000) molecular weight (e.g. Gelvatol* Z0-30) resins.
Polyvinyl pyrrolidone also functions as an assisting polymer, but gives such vastly inferior process and product result, as compared with polyvinyl alcohol, as to make the use of the latter material a distinct and very superior discovery within the broad concept of the invention.
* Trademark.
- : . ..................... . , :
. - . - , , , . - .
~04`7718 Examples Example I
A solution consis~ing of 5% by weight, Eastman Tenite * Polyterephthalate 6 PRO polytetramethylene terephthalate, 5% Monsanto Gelvatol * 20-30 DP Polyvinyl alcohol, and 90%
hexafluoroisopropanol was cast on a glass plate to a thickness of 0.020 inches and dried to completion. The result was a 0.003 inch thick microporous membrane which was rapidly wet by water which rapidly leached the polyvinyl alcohol from the membrane.
The membrane was homogeneous, opaque, strong and - flexible. It exhibited essentially the same solvent resistance as the bulk form of the material and is, therefore, applicable to filtrations in aqueous and in nonaqueous media. The-pore sized distribution was very narrow, with a median value of about 0.1~ m (a bubble point of about 90 psi~. The final membrane was a highly satisfactory unskinned microporous membrane filter ~-having physical and chemical characteristics vastly superior to cellulose acetate and other membranes which have been previously reported. These homogeneous unskinned membranes are useful in microfiltration, ultrafiltration and electrophoresis, curtain electrophoresis, and in gas, liquid and thin layer chromatography. For example, in electrophoresis a membrane produced the standard 5-line (albumin, ~ 2,;~and~ ~ spectrum for serum proteins. The application artifact was small and outside of the spec*rum when used with the Beckman *-Microzone cell (see, Microzone Electrophoresis System Brochures of the Beckman Instrument Company, Fullerton, California).
The bubble point of a membrane mentioned above is a means of determining pore size. See ASTM D-2499 which discusses the essential relationship between pressure, surface tension of ~ - 16-,, . . : , . .
-1~)47718 a wetting f~uid., and pore diameter. This relationship pr~dI~ts that a wetted membrane with applied differential air pressure will permit no flow of pressures beIow aacritical level referred to as the "bubble point". At the bubble point, wetting fluid is forced out of the smallest pores an~ flow thus begins. With pore size measured in micrometers (10- meters), pressure P, measured in pounds/~quare inch, and with kerosene as the wettlng fluid,. the relation between the pore size and pressure is ~4= 12.5.
P
* Trademark - 16~ -Example II 1~47718 A solution consisting of 5% Eastman Tenite * Polyterephthalate 6 PRO polytetramethylene terephthalate, 5% polyvinylpyrrolidone (molecular weight approximately 10,000) and 90% hexafluoroisopropanol was cast to a thickness of 0.020 inch on a glass plate and evaporated to dryness. The resultant membrane consisted essentially of a porous polyester substructure whose pores were filled with polyvinylpyrrolidone. A 1% solution of cellulose acetate in a solvent consisting of 49.5% hexafluoroisopropanol and 49.5% methylene chloride was cast on top of the unleached polyester mem-10 brane, forming a thin adherent cellulose acetate film. The compositemembrane consisting of a cellulose acetate skin and a porous polyester support was strong and flexible and was found suitable for reverse osmosis ~;
applications. The polyvinylpyrrolidone was leached from the polyester membrane as in Example I.
Exam~le III -.: , A solution consisting of 5% Eastman Tenite * Polyterephthalate 6 PRO polytetramethylene terephthalate, 5% polyvinyl alcohol Gelvatol* 20-60 (molecular weight approximately 86,000), acetyl content approximately Z0%, and 90% hexafluoroisopropanol was cast to a thickness of 0.020 inch on a 20 glass plate, and forcibly evaporated with a stream of hot dry air from a hair dryer. The resultant membrane was asymmetric as evidenced by the presence of a glossy skin which would not wet when a drop of water was placed there-upon and a matte finish, porous substructure which readily wet. This membrane was suitable for reverse osmosis and yielded a product flux of 2 gfd (gallons/ft2 day) and 28% salt rejection from a 5,000 ppm NaCl feed solution at 800 psi and 25C.
Example IV
A solution consisting of 5% Eastman Tenite * Polyterephthalate 6 PRO -polytetramethylene terephthalate, and 95% hexafluoroisopropanol was cast and 30 allowed to evaporate completely yielding a gray dense membrane .001 inch thick. This membrane was utilized in liquid permeation as follows A charge * Trademark . . . ' : . :
-: ' ' . ' ' --: , .
containing 95% methane and 5% n-pentane at a temperature of -150C and a differential pressure of psi was found to permeate the membrane at a rate of 144 grams/ft2hr yielding a permeate containing 98. 5% methane and 1. 5%
n-pentane. Such membranes are especially useful for this application when formed into the hollow fiber configuration.
Example V
A solution containing 0. 5 to 1. 0 percent Eastman Tenite * Poly-terephthalate 6 PRO polytetramethylene terephthalate and 0. 5 to 1. 0 percent polyvinyl alcohol Gelvatol* 20-30 and 98 to 99% hexafluoroisopropanol was 10 sprayed from an aspirator nozzle to yield fine droplets which quickly dried to a fine powder which when leached with water yielded microporous beads suitable for use in column chromatography for separation of, e.g., protein solutions. If denser powders or powders are desired, higher concentrations (similar to that described in Example I) may be employed.
Example VI
The solution described in Example I was cast 0. 020 inch thick onto a Mylar * backing yielding, after leaching, a microporous membrane intimately bonded to the Mylar *. This supported membrane yielded the typical 5 line spectrum for serum proteins when employed in the Beckman*
20 Microzone Electrophoresis System and was also suitable for thin layer chromatography.
Example VII
The solution described in Example I was cast 0. 020 inch thick on a glass plate and allowed to dry completely at which time another membrane was cast on top of it and allowed to dry completely. By repeating this procedure three times a 0. 009 inch thick membrane was produced. This process can be repeated as many times as necessary to produce a membrane with any desired thickness. Moreover, a membrane of e. g. coarse porosity can be coated onto one of fine porosity to produce a laminated prefilter- ---30 filter composite membrane in one piece. Laminates of dense membranes with porous membranes have been described in Example I1.
' ' * Trademark , , " : .
- ` ~' General Discussion Microporous membranes suitable for ultrafiltration, microfiltration and electrophoresis, reverse osmosis, liquid permeation, curtain electro-phoresis, gas, liquid and thin layer chromatography, are fabricated from polyesters produced by the condensation or aromatic dibasic acid and allcyl diols by a polymer assisted phase inversion process.
The limitations of the polyesters are that they must have at least as -great a flexibility and solubility as polyethylene terephthalate and preferably ~ -the degree of flexibility and solubility possessed by polytetramethylene terephthalate. The polyesters must be formed from the condensation of an -aromatic dibasic acid and a diol, polyesters formed by the condensation of an aromatic diol and an allcyl dibasic acid being unsatisfactory. Molecular weights in the range of 25 ,000 to 35, 000 are quite suitable but the molecular weight range is not so critical as in phase inversion processes employing low molecular weight swelling agents. The polyester must be soluble to the extent of at least about 0. 5% by weight and preferably greater than 1% or 2% by weight in a fluorinated compound such as hexafluoroisopropanol or trifluoro-acetic acid.
The second (phase inversion assisting) polymer must be mutually 20 soluble together with the polyester in one or more of the fluorinated solvents and must also be soluble in the polyester non-solvent. The assisting polymer must be mutually soluble in one of the fluorinated solvents to at least about 0. 5% by weight and preferably greater than 1% or 2% by weight in an amount ~-nearly equal to or greater than the weight of the polyester which is dissolved in the casting solution. The solubility of the assisting polymer in the polyester non-solvent may be less or more than its solubility in the polyester solvent, depending upon the end use characteristics. For some end uses, only gross swelling of the second polymer is sufficient "solubility" where the second polymer is to remain in the membrane. In other instances, where the second 30 polymer is to be removed essentially completely from the membrane, the second polymer must be highly soluble in the polyester non-solvent. There is no known reason other than the improbability of compatibility why 2, 3 or even .
. . : ,: :
~ ' ~, -', - ~ -' ' ` 1~47718 more "second"polymers may be included, along with the polyester, in the casting solution, although such systems have not been explored. One or more of these may be leached out by appropriate selection of non-solvents for the polyester but which are solvents of selected strength for the second polymer which is to be leached, The nature of the second polymer, e.g.
polyvinyl alcohol, can be varied, e.g. as to molecular weight and acetyl content, to influence the pore and void size and physical properties.
The water soluble polymers, polyvinyl alcohol and polyvinyl pyrrolidone especially the former, are of greatest interest simply because 10 of the great utility of aqueous leaching media industrially, clinically, and in the laboratory, but the invention is not limited to the use of second polymers which are soluble in water or other hydroxyl containing solvents, and suitable second polymers may be selected on the basis of solubility as set forth hereinbefore .
Only hexafluoroisopropanol and trifluoroacetic acid are known to be entirely satisfactory casting solution solvents, i. e., have adequate solvent strength for polyesters and for the second polymers, proper boiling point and volatility, and result in strong coherent microporous membranes. However, the various hydrates of hexafluoroacetone may also be acceptable under 20 certain extreme conditions.
The casting solution for forming the microporous membranes of -this invention should contain at least about 2 and preferably from 5 to 20% by weight, of the resins, i.e., the total polyester and second polymer resin -content should be, preferably, greater than 5%by weight of the casting :
solution. Typically, no surfactant is required in the casting solution, thus obviating many of the difficult problems which have plagued manufacturers and users of microporous membranes in the past. ~ ~
Extreme care and highly controlled evaporation and casting condi- -tions are required to form even moderately satisfactory microporous 30 membranes using polyethylene terephthalate; however, casting solutions of polytetramethylene terephthalate are highly stable and the constitution of these casting solutions can vary over a wide range of concentration and the .~ . .
: ' : . ` ' .- - " .: ` ` - . :
/ - :
1~)47718 casting can be performed under a broad range of temperatures and atmos-pheric conditions. It is usually desirable for health and economic reasons to cast the microporous membranes in an enclosed hood system to prevent exposure to the solvents and to permit recovery of the solvents for reuse.
Other than these fairly simple precautions, no critical casting or process conditions have been observed.
Leaching of the second polymer can be done simply by immersing the membrane in the leaching solvent, e.g., water or an aqueous solution.
Leaching will, of course, be accelerated when the leashing solution is agitated to provide constant washing of the membrane. Time, temperature and process variables do not appear to be critical in either the casting or the leaching process.
Casting as used here includes the formation of any large surface area configuration, such as sheets, ribbons, particles, etc.
Summar y A fundamental polymer assisted phase inversion process has been discovered and disclosed which includes the following steps: a solvent resistant polymer, for example the polyesters discussed herein, and an assisting polymer are dissolved in a mutual solvent to a weight percent concentration of from about 2% to about 20% to form a membrane casting ~ - -solution. The casting solution is dried under conditions such that a large surface area is exposed, e. g. in the form of a thin film or small particles .
The mutual solvent can be extracted in other ways also, as in the well known wet process. This results in a membrane (using the term broadly to include small particles such as chromatographic micro-spheres) in which the inchoate ~-voids in the solvent resistant polymer phase are filled with the assisting polymer. The membrane is then exposed to a solvent (in the broad sense ~-discussed previously) for the assisting polymer which is a non-solvent for the solvent resistant polymer. This exposure may only solvate or swell the assisting polymer, but in most practical applications the assisting polymer will be leached partially or completely from the membrane to leave finished porous membrane. This leaching may be performed in preparation for use or as an incident to the desired end use.
:1 ' ' ' ' ' :
., ,~ . , 1~)47718 Another fundamental discovery here disclosed is a polyester mem-brane composed of a polyester having the following general formula ~ ~ - C - O- (CH2) a ~ O - C ~
wherein a is an integer from 2 to 7, preferably 3 to 5, and n is an integer from about 45 to greater than 225 (corresponding to a molecular weight of from about 10,000 to about 50,000) and preferably between about n=90 and n=225 (MW---20,000 to MW-50,000).
Lying within, and exemplifying, the fundamental process discovery i9 a process for forming polyester membranes which could not have been expected or predicted even if the more fundamental process had been known previously. According to this process, a polyester having the formula O O . ~. :
~ ~ - C - O- (CH2) a ~ - C ~n ~
wherein a is from 3 to 5 and n is preferably from 90 to 225 or greater and ~ ~ -an assisting polymer selected from the group consisting of polyvinyl alcohol and polyvinyl pyrrolidone or mixtures of these are dissolved to a total weight 20 percent of from 2% to 20% (preferably about 5%) in a solvent which consists essentially of (i.e. the solvating power for the polymers of interest is not -substantially reduced by diluents) hexafluoroisopropanol, trifluoroacetic acid or mixtures of these solvents. The polyester and assisting polymers are present in approximately equal volume percent (of the dry membrane) con-centrations in the casting solution i. e. the polyester and assisting polymer ` -are present in about 50 v/o + 10 v/o concentrations in the membrane as cast, before leaching. Generally, there will be a greater amount of assisting polymer in the casting solution on a volume percent basis. The process is carried out as in the fundamental process. It is recognized that the foregoing 30 may be the only possible examples of the fundamental process, but this has not been established.
Within the foregoing examplification of the fundamental process is a particular process which is so unexpectedly and strikingly superior that it ``` 1~47718 , constitutes a distinct major discovery which will have far reaching scientific and industrial consequences. It has been discovered that one, and only one, combination of constituents, when used in the polymer assisting phase inversion process under consideration, gives greatly superior results with greatly reduced process problems and significantly increased reliability.
These constituents are: R f, polyester: ~ -C-O-(CH2) a ~~C~n wherein a is 3 to 5 (preferably 4) and_ is 90 to 225.
assisting polymer:polyvinyl alcohol having a molecular weight of from about 5,000 to about 25,000 (10,000 to 14,000 - :- -preferred) and an acetyl content of from 0 to about 50% (15% to 25% preferred) .
- mutual solvent: hexafluoroisopropanol leaching solvent:water (or any solvent for polyvinyl alcohol which is - ~ -a non-solvent for the polyester). - -Of these constituent materials, only the leaching solvent is not critical to the achieving of the vastly superior results obtainable by this process.
The product of the foregoing superior process, i.e. the resulting ; ~ -polyester membrane, constitutes a distinctive and unique discovery not -expected and incapable of prediction, even in view of the more fundamental discoveries .
It is apparent, then, that this invention is both general and specific.
It is general in the sense of the more fundamental aspects of the process and resulting polyester membrane. It is specific with respect to the unique, unexpected and superior results (as compared with the more general results) which accrue from using the particular combination of the indicated polyester, polyvinyl alcohol and hexafluoroisopropanol in the process.
The following claims are drafted with these general, certain inter- - -mediate features and the specific features of the invention in mind.
~ :
, ~ ' . - , :
wherein a' is an integer of 7 or 8 or higher, are also not good candidates as equivalents to the extent that membranes formed from such materials would be less stable, less resistant and generally inferior and would require a different solvent system. The dry process disclosed herein could be used, however, if a suitable solvent could be found.
Obviously, not all criteria for equivalence are set forth, and not all 10 parameters are known. I do not, however, wish to be limited to those materials specifically set forth in the examples, nor do I wish to ignore the ~
fact that one particular combination of materials (polytetramethylene tere- ;
phthalate polyester, polyvinyl alcohol assisting polymer, and hexafluoro- -isopropanol) possesses such unexpected advantages as to be a distinct discovery within the broader framework of this invention.
Until quite recently, the only commercially available dibasic acid derived polyesters of the type under consideration here were the polyethylene terephthalate polyesters prepared by the condensation of dimethyl tere-phthalate and ethylene glycol. (Reference to dibasic acids and diols includes 20 polymerizable derivatives thereof.
Polymers of this type are sold in various forms under several trademarks including Mylar and Dacron.
I had postulated that if the alkyl chain were longer than that pro-- vided by polyethylene terephthalate, polyesters of the type under consideration would be excellent candidates for microporous membrane filter fabrication.
- I have now proved my postulate correct and discovered that polytetramethylene ~ :
terephthalate prepared from the condensation of dimethyl terephthalate and 1 ,4,tetramethylene glycol does indeed form microporous membrane filters having excellent chemical and physical characteristics.
A sufficiently high molecular weight polytetramethylene terephthalate is available from Eastman Chemical Company under the trademark Tenite Polyterepht~late, from General Electric Company under the trademark -Valox, and from Celanese Corporation under the trademark Celanex.
My familiarity with the process variables, the characteristics of the products obtained and the chemical and physical properties of the materials involved indicate with relative certainty that polyesters derived from aromatic dibasic acids (or polymerizable derivatives, e. g. esters, thereof) having 3 to 6 or 7 methylene groups in the alkyl moiety of the -polymer can be fabricated into good to excellent quality microporous mem-brane filters using the techniques and processes of this invention as described hereinafter .
In general, any polyester derived from an aromatic dibasic acid which is insoluble in water, possesses acceptable physical properties (is self-supporting at ambient temperature and is sufficiently dimensionally ~
stable), and is soluble within the range of 2% to 20% (by weight) in combina- - -tion with an assisting soluble polymer which also has solubility in the 2~o to 20% (by weight) range in a solvent which has a boiling point in the ambient to approximately 150C range must be regarded as an equivalent in the broadest sense, but not in the narrow sense of being interchangeable with polytetramethylene terephthalate with like results in the same casting solution system. Indeed, I regard only polytrimethylene terephthalate and poly-ZO pentamethylene terephthalate polyesters as substantially certain to be closely equivalent and functional in this latter sense.
The preferred polyester, polytetramethylene terephthalate, sold ~-under the trademark Tenite Polyterephthalate 6 PRO, has outstanding chemical properties illustrated by Table I which shows the effects of various chemicals on this grade of polytetramethylene terephthalate.
% Increase After One Year Chemical In Wei~htIn Thickness Acetic Acid (Glacial) 2. 65 1. 51 Acetic Acid (5%) * 0. 40 -0. 29 -30 Acetone 5. 56 2. 57 Ammonium Hydroxide (Conc. ) O. 80 -O. 16 Ammonium Hydroxide (10%) 0.49 _0.53 ' ~ 6 -. , ..
`
~047718 Aniline 6.69 4.17 Benzene 3.26 2.19 Carbon Tetrachloride 0.72 0. 42 Chromic Anhydride (40%) 0.10 -0.11 Citric Acid (10%) 0.37 0.16 Cottonseed Oil 0.09 -0.16 Alconox Detergent (0.25%) 0.37 -0.34 Diethyl Ether 0.95 . 45 Dimethyl Formamide 2.48 1.56 10 Deionized Water 0.39 - 0.53 Ethyl Acetate 3.30 1.93 Ethylene Dichloride 18.66 6.16 Heptane 0.13 - 0.26 Hydrochloric Acid (Conc . )0.56 0.03 Hydrochloric Acid (10%) 0.33 _0.05 Hydrogen Peroxide (28%) 0.41 0.00 Hydrogen Peroxide (3%)0.38 -0.05 Isooctane 0.08 -0.08 Kerosene 0.10 -0.16 20 Methanol 1.61 0.16 l_ Incr eas e After_One Year Chemical In Wei~ht In Thickness ~ -Mineral Oil 0.06 - 0.13 Nitric Acid (Conc . ) -disintegrated-Nitric Acid (40%) 0.68 0.05 Nitric Acid (10%) 0.36 -0.16 Oleic Acid (93 %) 0.26 - 0.18 Olive Oil 0.06 0.11 Phenol (5% in water )9.48 4.88 30 Sodium Chloride (10%)0.32 0.05 Sodium Carbonate (20%)0.31 0.05 Sodium Carbonate (2%)0.36 0.00 r` ~
~ ` 1047718 Sodium Hydroxide (10 %)-1. 20 -1. 16 Sodium Hydroxide ( 1 %)0. 37 0. 77 Sulfuric Acid (Conc . )-disintegrated-Sulfuric Acid (30%) 0.25-0.52 Sulfuric Acid (3~o) 0. 360. 00 Turpentine 0. 27-0. 03 -Toluene 2. 351. 40 - ~
Sodium Hypochlorite (3. 5%)0. 37 -0.11 ~ -Ethanol 0. 480. 21 10 Ethanol (50%) 0.470 03 ~ -Dibutyl Sebacate 0. 07- 0. 05 Di-2-Ethylhexyl Phthalate 0. 070. 08 Ivory Soap (1%) 0. 370. 08 Brake Fluid Transformer Oil 0. 06-0.18 ; - -* All percentages are concentrations in water. ~ - -These membranes are extremely tough, flexible, dimensionally stable over -a broad range of temperatures, maintain their strength at both high and low temperatures and possess other highl3r desirable physical characteristics.
The Polvester Membrane Product ., In terms of a manufacture or product, the present invention is directed to a polyester derived from a dibasic acid, as discussed herein- -~ -before, which is in the form of a microporous membrane. ;
The microporous membrane of this invention is composed of a polyester derived from a dibasic acid and may include a hydrophilic second polymer or a second polymer which is soluble in a fluid which is a non-solvent for the polyester.
Typically, the membrane of this invention, in finished form, is composed of a dibasic acid derived polyester, as discussed previously, and 30 a minor proportion of the second polymer, which is hydrophilic or soluble in a polyester non-solvent fluid, or includes, as a component, such a membrane composition.
_ 8 -,. . : . ~: , .
, ., . . , - : -- 10477~8 The membranes here disclosed may be used as membrane filters in microfiltration, ultrafiltration, in reverse osmosis, as reverse osmosis membranes or as porous support substrates for other reverse osmo~is membranes, the cellulose acetate membranes, for example, and in electro- ~ -phoresis, curtain electrophoresis, thin layer, gas and liquid chromatography and as substrates to which enzymes and other catalysts can be attached for solid-liquid reactions. The porous membrane filters in this invention may be produced in flat sheets, tubular forms on the inside or the outside of the tube, as hollow fibers, and in microporous bead configurations. These 10 microporous membrane filters are of special significance to the production of microporous tapes because of their strength and flexibility.
One particularly unique advantage of the subject membrane system ~ -results from the fact that the assisting polymer fills the incipient voids in the - ~
unleached membrane. The surface of the unleached membrane is, therefore, - -~ -still amenable to fabrication of multilayered membrane structures, with one membrane layer being used as the substrate for the next layer. This permits, inter alia, production of vexy thick membrane sections.
Other advantages possessed by the membranes of this invention are the absence of surfactants and of a tendency to build up static charges which, 20 in conventional microporous membranes, tracks dust and makes handling difficult and results sometimes uncertain.
- Other and more specific characteristics of the product will be apparent from the discussion of the process which follows and from the subsequent references to the product.
The Polvmer Assisted Phase Inversion Process These membranes are fabricated by forming a casting solution of a dibasic acid derived polyester, a second polymer which is soluble in a fluid which is a non-solvent for the polyester, and a liquid which is a solvent for both the polyester and the second polymer. This forms the casting solution 30 for forming the membrane~. The casting solution is then cast upon a sub-strate to form a film of desired dimensions. The solvent is permitted to evaporate from the film and at least a portion of the second polymer is _ 9 _ - :
104~718 leached from the film with the fluid which is a non-solvent for a polyester.
This leaves a microporous membrane which has excellent chemical and physical characteristics, the characteristics of which can be varied by controlling the nature and amount of the second polymer in the membrane, as well as by the selection of the polyester, and by control of process variables.
Polytetramethylene terephthalate is considered to be the first truly suitable aromatic dibasic acid based polyester for formation of microporous membrane filters because of its greater solubility (compared to polyethylene terephthalate) in suitably volatile solvents. This property makes it possible to prepare true, molecularly dispersed, solutions of polytetramethylene ~ -terephthalate in a few selected volatile solvents. Polytetramethylene tere-phthalate is more soluble (i.e. exhibits a higher degree of dispersion), than polyethylene terephthalate, probably because of the greater flexibility of the polymer chains, owing to the presence of four methylene groups in the former, rather than the two separating the terephthalate acid moieties in the latter.
Further, and of distinguishing importance, polytetramethylene -terephthalate represents a very close approach to, if not the actual accom-plishment of, the ideal balance between sufficient solubility to permit fabrica- -tion into membranes, and sufficient solvent resistance, to permit~utilization ~ - --of the re~ultant membrane in the filtration of solutions in common organic solvents. By comparison, polyethylene terephthalate is insufficiently soluble to permit fully satisfactory membrane fabrication. Cn the other hand, the - -inclusion of too many or too large substituents on the aromatic nucleus of the diacid or too long methylene chains or etheric links in the diol, or other substitution or modification which greatly increases the solubility of the poly-ester degrades the chemical and physical resistance of the resultant polyester and may require significant modification of the membrane fabrication process.
The first partially successful prototype membranes prepared -according to this invention were from polyethylene terephthalate solutions.
Such solutions are turbid, whereas polytetramethylene terephthalate solutions are clear indicating a finer dispersion in the latter solutions. Fine dispersion ~-, - 10 _ ,~ , - , : . -in the solution, and hence clear solutions, are highly desirable and are probably mandatory in any commercially feasible process, since only the latter clear casting solutions are sufficiently stable for utilization in the dry phase inversion process on a commercial scale.
The reader is referred to Kesting, SYNTHETIC POLYMERIC
MEMBRANES, referenced previously and my Canadian Patent 991,776 entitled INTEGRAL UNSKINNED HIGH VOID VOLUME POLYCARBONATE
MEMBRANES AND A DRY PROCESS FOR FORMING THE S~WE, for a detailed discussion of the phase inversion process for fabricating p~lymeric ~membra~es. The bEoad~principles of.phase inversion membrane formation are applicable to the present dry process;
however, the present process is believed to be the first satisfactory example of a phase inversion process for manufacturing microporous membranes in which the swelling agent consists of a solvated second polymer which assists in the phase inversion in~.à ~anner:similariT^to~-the~:manne~-in-whiah;-~typical~swelling~
agents of low molecular weight assist in the phase inversion in common phase inversion membrane formation. For this reason, the process is referred to as a Polymer Assisted~Phase .In~version Process, sometimes abbreviated "PAPI~ process.
The process consists in dissolving the polyester and one or more, usually only one, second polymer(s~ in a volatile solvent, (i.e., a solvent which has a boiling point below about 150C and preferably below about 100C~ or in a combination of solvents, swelling agents and non-solvents for both the polyester and second polymer, casting ~he solution as~a film ana ev.ap~orating theesolvents from the sol~ion. The process can be either wet Q~ dry;.t~at.~ t:ma~ lnv~.lve~either partia-l-or ~ompLete -~
e~a~oratl~on, the dry pOEocess being preferred whenever applicable.
1~47718 ' The overall process invo~lved herein is described as a polymer ass~sted phàse inversion process but it has elements of a leaching process as well. In those cases where a non-polyester polymer component is either desiæed or does not interfere with the end use of the filter, these non-polyester polymer components 3 may simply be left in the microporous membrane. In cases where the second polymer, i.e., the non-polyester polymer, would be objectionable, '. 10 -:
-, ~ '~.'"''.
.'' "'-,: ' - lla-.~ , . , . - : ~ . . .
. - 1047718 the second polymer may be leached out with a solvent for the second polymer which is a non-solvent for the polyester.
The process may be varied to form polymeric microporous mem-brane filters for specific end uses. For use in microfiltration, ultrafiltra-tion and electrophoresis, curtain electrophoresis, gas, liquid and thin layer chromatography, an unskinned (i.e., a more or less symmetrical membrane) is desired. In these cases the dried membrane may be either leached of its non-polyester component or components or may be used with the second polymer in place, depending upon the specific requirement~ of 10 the end use. It is also possible where two or more second non-polyester polymers have been included, to leach one or more of the polymers from the membrane, leaving behind one or more polymers together with a polyester.
Likewise, it is possible to employ in situ cross linking to permanent- -ly fix one or more otherwise leachable second polymeric components in the membrane .
Included second polymers may function to improve wettability of the polyester in one of several ways. They may be surfactants or they may sirnply possess an affinity for water, up to and including water solubility.
Where the included polymers are not actually surfactants an important new 20 dimension has been added to membrane filters, since the presence of sur-factants, present in commercially available membrane filters, is often deleterious to certain biological separations, and in handling foodstuffs, water for drinking purposes, etc. Therefore, one important feature of the invention is that wettability can be obtained by the inclusion of either leachable or, when necessary non-leachable hygroscopic, but not surface active, polymers.
Two types of asymmetric, i. e., skinned, reverse osmosis mem-branes and two separate processes for their preparation have been described.
These are the Loeb-Sourirajan wet process and the Kesting dry process.
Both of these processes use cellulose acetate polymers in their manufacture.
Cellulose acetate is, however, rather friable microporous membrane configurations. Stronger and less friable reverse osmosis membranes are, therefore, desirable.
.. , 1047'718 This difficult goal is accomplished, in the present invention, by casting a membrane either a thin dense or a thicker asymmetric membrane, of cellulose acetate or other polymer (such as the polyester itself), suitable for reverse osmosis upon the polyester membranes prior to leaching, so that the polyester membrane after leaching serves as a porous backing support for the cellulose acetate or other reverse osmosis polymeric membrane. Adhesion of the rever~e osmosis membrane to the microporous -support can be achieved by including, as a constituent of the casting solution for the reverse osmosis membrane, a solvent for the polyester. When - - -properly balanced (containing the correct amount of polyester solvent), this ~ -solvent system will sufficiently soften the surface of the polyester to permit good adhesion without destroying the porous characteristics of the polyester membrane support. Following the application of the second layer, the leachable assisting polymer of the substrate may be removed by washing with water, alcohol or other polyester non-solvent.
It is noteworthy also that dense polyester membranes themselves have the ability to function as reverse osmosis membranes, as do asymmetric ~
polyester membranes having a dense skin on a porous substructure. ; - -Solvents - 20 Solvent selection is extremely critical. Indeed, to date only two solvents, hexafluoroisopropanol and trifluoroacetic acid, are known to be acceptable for the dry process. The wet process is less desirable but the - ~ -same solvents can be used in such a process.
There are no known equivalent solvents for use with polytetra- -methylene terephthalate polyester of suitable molecular weight for membrane fabrication, and one has little basis for making reliable predictions as to potentially equivalent solvents. Probably only highly fluorinated substituted low molecular weight (1-4 carbon atom) alcohols, acids, ethers, esters and acids can now be considered as solvent candidates in the preparation of the subject membranes, and it is known that not all such compounds are satis-factory. Trifluoroethanol and the hexafluoroacetone-methanol hemiacetal, for example, are not satisfactory solvents for fabricating polytetramethylene - 13 _ ..
, ,1 . - . ~ ,, ` 1~47718 terephthalate membranes. Indeed, even trifluoroacetic acid is so vastly inferior to hexafluoisopropanol as to make the latter a component of a distinct discovery within the broad inventive concept here disclosed.
It may be suggested that where less solvating power is required, as with substituted aromatic dibasic acid or longer chain diol derived polyesters, other highly fluorinated compounds of the class discussed would be suitable, but ultimate solvent selection must, at present, be on an empirical basis.
Any desired solvating power, within the range of the solvents, may be obtained by mixing selected solvents. Hexa- -fluoroisopropanol and trifluoroacetic acid, for example, may be mixed or diluted with other solvents of the class under consideration.
It must be understood that solvent selection is not alone a function of the nature of the polyester. The nature of the assisting polymer and, more correctly, the nature of the combination of polyester and assisting polymer are also controlling, or at least very influential in solvent selection.
Assisting Polymers Suitable second or "assisting" polymers are very rare.
They include certain hygroscopic polymers, polyvinyl alcohol in particular. Polyvinyl pyrrolidone also functions, but is much less suitable than polyvinyl alcohol. These polymers can be softened and/or leached in water. Other polymers which are mutually soluble together with the polyester in a solvent, and which are soluble in polyester non-solvent are candidates as assisting polymers.
~ - 14 -1~)47718 rn a more general sense the assisting polymers must be soluble in a solvent which is a non-solvent for the polyesters and must also be soluble in a mutual solvent for themselves and the p~lyesters.
Mutual solubility of the type discussed here, in approximately equal weights of the polyester and the assisting polymer at the high total solids content, i.e., between approximately 5 and 20%, necessary for the practical production of membranes is extremely rare in most solvent systems and is made possible by the unusual solvent properties of the polar fluorinated compounds which are employed as mutual solvents. Becaaae of strong ~,...
' -~
- 14a -, ' ~
-10477~8 solvation, solvated chains of dissimilar polymers are apparently much less incompatible than they would be in the absence of solvation.
The void volume of the membrane produced by the polymer assisted phas0 inversion process can be controlled by varying the ratio of the second (leachable) polymer to the polyester. The higher the ratio, the higher the void volume. For the polytetramethylene terephthalate polymers of the molecular weights available today, e.g., from about 25,000 to 50,000, void volumes above about 60% are not achievable with the maintenance of the excellent physical properties found to date. It is to be predicted, however, as higher molecular weight polyesters become available higher void volumes will be achievable using the polymer assisted phase inversion process.
The pore size and void volume of the membranes can be controlled by controlling the nature of the second, "assisting", polymer. The most suitable assisting polymer found to date, is polyvinyl alcohol.
Pore size is a function of the molecular weight and acetyl content of the assisting polymer. High (37-42% by weight) acetyl content (e. g.
Gelvatol*40-10) polyvinyl alcohols yields coarse structures. Low (0-4%
by weight) acetyl content resins (e. g. Gelvatol * 1-30 and 1 -60) yield fine structures. Intermediate size structures (void and pore size ~0.05,um to 1Ø2,um) are obtained with intermediate (19.5-22.7% by weight) acetyl content (e. g. Gelvatol * 20-30 and 20-60). Fineness also increases with increasing molecular weight although less dramatically than with decreasing acetyl content. In general the best physical properties are obtained by employing resins of intermediate (20 + 5% by weight) acetyl content and intermediate (10,000 to 14,000) molecular weight (e.g. Gelvatol* Z0-30) resins.
Polyvinyl pyrrolidone also functions as an assisting polymer, but gives such vastly inferior process and product result, as compared with polyvinyl alcohol, as to make the use of the latter material a distinct and very superior discovery within the broad concept of the invention.
* Trademark.
- : . ..................... . , :
. - . - , , , . - .
~04`7718 Examples Example I
A solution consis~ing of 5% by weight, Eastman Tenite * Polyterephthalate 6 PRO polytetramethylene terephthalate, 5% Monsanto Gelvatol * 20-30 DP Polyvinyl alcohol, and 90%
hexafluoroisopropanol was cast on a glass plate to a thickness of 0.020 inches and dried to completion. The result was a 0.003 inch thick microporous membrane which was rapidly wet by water which rapidly leached the polyvinyl alcohol from the membrane.
The membrane was homogeneous, opaque, strong and - flexible. It exhibited essentially the same solvent resistance as the bulk form of the material and is, therefore, applicable to filtrations in aqueous and in nonaqueous media. The-pore sized distribution was very narrow, with a median value of about 0.1~ m (a bubble point of about 90 psi~. The final membrane was a highly satisfactory unskinned microporous membrane filter ~-having physical and chemical characteristics vastly superior to cellulose acetate and other membranes which have been previously reported. These homogeneous unskinned membranes are useful in microfiltration, ultrafiltration and electrophoresis, curtain electrophoresis, and in gas, liquid and thin layer chromatography. For example, in electrophoresis a membrane produced the standard 5-line (albumin, ~ 2,;~and~ ~ spectrum for serum proteins. The application artifact was small and outside of the spec*rum when used with the Beckman *-Microzone cell (see, Microzone Electrophoresis System Brochures of the Beckman Instrument Company, Fullerton, California).
The bubble point of a membrane mentioned above is a means of determining pore size. See ASTM D-2499 which discusses the essential relationship between pressure, surface tension of ~ - 16-,, . . : , . .
-1~)47718 a wetting f~uid., and pore diameter. This relationship pr~dI~ts that a wetted membrane with applied differential air pressure will permit no flow of pressures beIow aacritical level referred to as the "bubble point". At the bubble point, wetting fluid is forced out of the smallest pores an~ flow thus begins. With pore size measured in micrometers (10- meters), pressure P, measured in pounds/~quare inch, and with kerosene as the wettlng fluid,. the relation between the pore size and pressure is ~4= 12.5.
P
* Trademark - 16~ -Example II 1~47718 A solution consisting of 5% Eastman Tenite * Polyterephthalate 6 PRO polytetramethylene terephthalate, 5% polyvinylpyrrolidone (molecular weight approximately 10,000) and 90% hexafluoroisopropanol was cast to a thickness of 0.020 inch on a glass plate and evaporated to dryness. The resultant membrane consisted essentially of a porous polyester substructure whose pores were filled with polyvinylpyrrolidone. A 1% solution of cellulose acetate in a solvent consisting of 49.5% hexafluoroisopropanol and 49.5% methylene chloride was cast on top of the unleached polyester mem-10 brane, forming a thin adherent cellulose acetate film. The compositemembrane consisting of a cellulose acetate skin and a porous polyester support was strong and flexible and was found suitable for reverse osmosis ~;
applications. The polyvinylpyrrolidone was leached from the polyester membrane as in Example I.
Exam~le III -.: , A solution consisting of 5% Eastman Tenite * Polyterephthalate 6 PRO polytetramethylene terephthalate, 5% polyvinyl alcohol Gelvatol* 20-60 (molecular weight approximately 86,000), acetyl content approximately Z0%, and 90% hexafluoroisopropanol was cast to a thickness of 0.020 inch on a 20 glass plate, and forcibly evaporated with a stream of hot dry air from a hair dryer. The resultant membrane was asymmetric as evidenced by the presence of a glossy skin which would not wet when a drop of water was placed there-upon and a matte finish, porous substructure which readily wet. This membrane was suitable for reverse osmosis and yielded a product flux of 2 gfd (gallons/ft2 day) and 28% salt rejection from a 5,000 ppm NaCl feed solution at 800 psi and 25C.
Example IV
A solution consisting of 5% Eastman Tenite * Polyterephthalate 6 PRO -polytetramethylene terephthalate, and 95% hexafluoroisopropanol was cast and 30 allowed to evaporate completely yielding a gray dense membrane .001 inch thick. This membrane was utilized in liquid permeation as follows A charge * Trademark . . . ' : . :
-: ' ' . ' ' --: , .
containing 95% methane and 5% n-pentane at a temperature of -150C and a differential pressure of psi was found to permeate the membrane at a rate of 144 grams/ft2hr yielding a permeate containing 98. 5% methane and 1. 5%
n-pentane. Such membranes are especially useful for this application when formed into the hollow fiber configuration.
Example V
A solution containing 0. 5 to 1. 0 percent Eastman Tenite * Poly-terephthalate 6 PRO polytetramethylene terephthalate and 0. 5 to 1. 0 percent polyvinyl alcohol Gelvatol* 20-30 and 98 to 99% hexafluoroisopropanol was 10 sprayed from an aspirator nozzle to yield fine droplets which quickly dried to a fine powder which when leached with water yielded microporous beads suitable for use in column chromatography for separation of, e.g., protein solutions. If denser powders or powders are desired, higher concentrations (similar to that described in Example I) may be employed.
Example VI
The solution described in Example I was cast 0. 020 inch thick onto a Mylar * backing yielding, after leaching, a microporous membrane intimately bonded to the Mylar *. This supported membrane yielded the typical 5 line spectrum for serum proteins when employed in the Beckman*
20 Microzone Electrophoresis System and was also suitable for thin layer chromatography.
Example VII
The solution described in Example I was cast 0. 020 inch thick on a glass plate and allowed to dry completely at which time another membrane was cast on top of it and allowed to dry completely. By repeating this procedure three times a 0. 009 inch thick membrane was produced. This process can be repeated as many times as necessary to produce a membrane with any desired thickness. Moreover, a membrane of e. g. coarse porosity can be coated onto one of fine porosity to produce a laminated prefilter- ---30 filter composite membrane in one piece. Laminates of dense membranes with porous membranes have been described in Example I1.
' ' * Trademark , , " : .
- ` ~' General Discussion Microporous membranes suitable for ultrafiltration, microfiltration and electrophoresis, reverse osmosis, liquid permeation, curtain electro-phoresis, gas, liquid and thin layer chromatography, are fabricated from polyesters produced by the condensation or aromatic dibasic acid and allcyl diols by a polymer assisted phase inversion process.
The limitations of the polyesters are that they must have at least as -great a flexibility and solubility as polyethylene terephthalate and preferably ~ -the degree of flexibility and solubility possessed by polytetramethylene terephthalate. The polyesters must be formed from the condensation of an -aromatic dibasic acid and a diol, polyesters formed by the condensation of an aromatic diol and an allcyl dibasic acid being unsatisfactory. Molecular weights in the range of 25 ,000 to 35, 000 are quite suitable but the molecular weight range is not so critical as in phase inversion processes employing low molecular weight swelling agents. The polyester must be soluble to the extent of at least about 0. 5% by weight and preferably greater than 1% or 2% by weight in a fluorinated compound such as hexafluoroisopropanol or trifluoro-acetic acid.
The second (phase inversion assisting) polymer must be mutually 20 soluble together with the polyester in one or more of the fluorinated solvents and must also be soluble in the polyester non-solvent. The assisting polymer must be mutually soluble in one of the fluorinated solvents to at least about 0. 5% by weight and preferably greater than 1% or 2% by weight in an amount ~-nearly equal to or greater than the weight of the polyester which is dissolved in the casting solution. The solubility of the assisting polymer in the polyester non-solvent may be less or more than its solubility in the polyester solvent, depending upon the end use characteristics. For some end uses, only gross swelling of the second polymer is sufficient "solubility" where the second polymer is to remain in the membrane. In other instances, where the second 30 polymer is to be removed essentially completely from the membrane, the second polymer must be highly soluble in the polyester non-solvent. There is no known reason other than the improbability of compatibility why 2, 3 or even .
. . : ,: :
~ ' ~, -', - ~ -' ' ` 1~47718 more "second"polymers may be included, along with the polyester, in the casting solution, although such systems have not been explored. One or more of these may be leached out by appropriate selection of non-solvents for the polyester but which are solvents of selected strength for the second polymer which is to be leached, The nature of the second polymer, e.g.
polyvinyl alcohol, can be varied, e.g. as to molecular weight and acetyl content, to influence the pore and void size and physical properties.
The water soluble polymers, polyvinyl alcohol and polyvinyl pyrrolidone especially the former, are of greatest interest simply because 10 of the great utility of aqueous leaching media industrially, clinically, and in the laboratory, but the invention is not limited to the use of second polymers which are soluble in water or other hydroxyl containing solvents, and suitable second polymers may be selected on the basis of solubility as set forth hereinbefore .
Only hexafluoroisopropanol and trifluoroacetic acid are known to be entirely satisfactory casting solution solvents, i. e., have adequate solvent strength for polyesters and for the second polymers, proper boiling point and volatility, and result in strong coherent microporous membranes. However, the various hydrates of hexafluoroacetone may also be acceptable under 20 certain extreme conditions.
The casting solution for forming the microporous membranes of -this invention should contain at least about 2 and preferably from 5 to 20% by weight, of the resins, i.e., the total polyester and second polymer resin -content should be, preferably, greater than 5%by weight of the casting :
solution. Typically, no surfactant is required in the casting solution, thus obviating many of the difficult problems which have plagued manufacturers and users of microporous membranes in the past. ~ ~
Extreme care and highly controlled evaporation and casting condi- -tions are required to form even moderately satisfactory microporous 30 membranes using polyethylene terephthalate; however, casting solutions of polytetramethylene terephthalate are highly stable and the constitution of these casting solutions can vary over a wide range of concentration and the .~ . .
: ' : . ` ' .- - " .: ` ` - . :
/ - :
1~)47718 casting can be performed under a broad range of temperatures and atmos-pheric conditions. It is usually desirable for health and economic reasons to cast the microporous membranes in an enclosed hood system to prevent exposure to the solvents and to permit recovery of the solvents for reuse.
Other than these fairly simple precautions, no critical casting or process conditions have been observed.
Leaching of the second polymer can be done simply by immersing the membrane in the leaching solvent, e.g., water or an aqueous solution.
Leaching will, of course, be accelerated when the leashing solution is agitated to provide constant washing of the membrane. Time, temperature and process variables do not appear to be critical in either the casting or the leaching process.
Casting as used here includes the formation of any large surface area configuration, such as sheets, ribbons, particles, etc.
Summar y A fundamental polymer assisted phase inversion process has been discovered and disclosed which includes the following steps: a solvent resistant polymer, for example the polyesters discussed herein, and an assisting polymer are dissolved in a mutual solvent to a weight percent concentration of from about 2% to about 20% to form a membrane casting ~ - -solution. The casting solution is dried under conditions such that a large surface area is exposed, e. g. in the form of a thin film or small particles .
The mutual solvent can be extracted in other ways also, as in the well known wet process. This results in a membrane (using the term broadly to include small particles such as chromatographic micro-spheres) in which the inchoate ~-voids in the solvent resistant polymer phase are filled with the assisting polymer. The membrane is then exposed to a solvent (in the broad sense ~-discussed previously) for the assisting polymer which is a non-solvent for the solvent resistant polymer. This exposure may only solvate or swell the assisting polymer, but in most practical applications the assisting polymer will be leached partially or completely from the membrane to leave finished porous membrane. This leaching may be performed in preparation for use or as an incident to the desired end use.
:1 ' ' ' ' ' :
., ,~ . , 1~)47718 Another fundamental discovery here disclosed is a polyester mem-brane composed of a polyester having the following general formula ~ ~ - C - O- (CH2) a ~ O - C ~
wherein a is an integer from 2 to 7, preferably 3 to 5, and n is an integer from about 45 to greater than 225 (corresponding to a molecular weight of from about 10,000 to about 50,000) and preferably between about n=90 and n=225 (MW---20,000 to MW-50,000).
Lying within, and exemplifying, the fundamental process discovery i9 a process for forming polyester membranes which could not have been expected or predicted even if the more fundamental process had been known previously. According to this process, a polyester having the formula O O . ~. :
~ ~ - C - O- (CH2) a ~ - C ~n ~
wherein a is from 3 to 5 and n is preferably from 90 to 225 or greater and ~ ~ -an assisting polymer selected from the group consisting of polyvinyl alcohol and polyvinyl pyrrolidone or mixtures of these are dissolved to a total weight 20 percent of from 2% to 20% (preferably about 5%) in a solvent which consists essentially of (i.e. the solvating power for the polymers of interest is not -substantially reduced by diluents) hexafluoroisopropanol, trifluoroacetic acid or mixtures of these solvents. The polyester and assisting polymers are present in approximately equal volume percent (of the dry membrane) con-centrations in the casting solution i. e. the polyester and assisting polymer ` -are present in about 50 v/o + 10 v/o concentrations in the membrane as cast, before leaching. Generally, there will be a greater amount of assisting polymer in the casting solution on a volume percent basis. The process is carried out as in the fundamental process. It is recognized that the foregoing 30 may be the only possible examples of the fundamental process, but this has not been established.
Within the foregoing examplification of the fundamental process is a particular process which is so unexpectedly and strikingly superior that it ``` 1~47718 , constitutes a distinct major discovery which will have far reaching scientific and industrial consequences. It has been discovered that one, and only one, combination of constituents, when used in the polymer assisting phase inversion process under consideration, gives greatly superior results with greatly reduced process problems and significantly increased reliability.
These constituents are: R f, polyester: ~ -C-O-(CH2) a ~~C~n wherein a is 3 to 5 (preferably 4) and_ is 90 to 225.
assisting polymer:polyvinyl alcohol having a molecular weight of from about 5,000 to about 25,000 (10,000 to 14,000 - :- -preferred) and an acetyl content of from 0 to about 50% (15% to 25% preferred) .
- mutual solvent: hexafluoroisopropanol leaching solvent:water (or any solvent for polyvinyl alcohol which is - ~ -a non-solvent for the polyester). - -Of these constituent materials, only the leaching solvent is not critical to the achieving of the vastly superior results obtainable by this process.
The product of the foregoing superior process, i.e. the resulting ; ~ -polyester membrane, constitutes a distinctive and unique discovery not -expected and incapable of prediction, even in view of the more fundamental discoveries .
It is apparent, then, that this invention is both general and specific.
It is general in the sense of the more fundamental aspects of the process and resulting polyester membrane. It is specific with respect to the unique, unexpected and superior results (as compared with the more general results) which accrue from using the particular combination of the indicated polyester, polyvinyl alcohol and hexafluoroisopropanol in the process.
The following claims are drafted with these general, certain inter- - -mediate features and the specific features of the invention in mind.
~ :
, ~ ' . - , :
Claims (3)
1. A polymer assisted phase inversion process for forming microporous polyester membranes comprising the steps of:
casting a solution containing a polyester derived from an aromatic dibasic acid and an alkyl diol of the general formula:
wherein a is an integer of at least 3 and not greater than 7, and n is an integer greater than about 45, and an assisting polymer, in concentrations of between about 2% and about 20% by weight total polymer, in a mutual solvent for the polymers into a large surface area configuration; and extracting the mutual solvent for the polymers from the configuration to thereby form a membrane, said membrane having inchoate pores filled with the assisting polymer.
casting a solution containing a polyester derived from an aromatic dibasic acid and an alkyl diol of the general formula:
wherein a is an integer of at least 3 and not greater than 7, and n is an integer greater than about 45, and an assisting polymer, in concentrations of between about 2% and about 20% by weight total polymer, in a mutual solvent for the polymers into a large surface area configuration; and extracting the mutual solvent for the polymers from the configuration to thereby form a membrane, said membrane having inchoate pores filled with the assisting polymer.
2. The process set forth in claim 1 further including the step of leaching at least some of the assisting polymer from the pores by exposing the membrane to a solvent for the assisting polymer which is a non-solvent for the polyester.
3. The process set forth in claim 1 further including the step of casting, from a solution containing a solvent for the polyester, at least one additional membrane layer on the surface of the membrane having inchoate pores filled with assisting polymer
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20892871A | 1971-12-16 | 1971-12-16 | |
| CA159,248A CA1025590A (en) | 1971-12-16 | 1972-12-18 | Microporous polyester membranes and polymer assisted phase inversion process for making same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1047718A true CA1047718A (en) | 1979-02-06 |
Family
ID=25667174
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA290,214A Expired CA1047719A (en) | 1971-12-16 | 1977-11-04 | Microporous polyester membranes and polymer assisted phase inversion process for making same |
| CA290,213A Expired CA1047718A (en) | 1971-12-16 | 1977-11-04 | Microporous polyester membranes and polymer assisted phase inversion process for making same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA290,214A Expired CA1047719A (en) | 1971-12-16 | 1977-11-04 | Microporous polyester membranes and polymer assisted phase inversion process for making same |
Country Status (1)
| Country | Link |
|---|---|
| CA (2) | CA1047719A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9561473B2 (en) | 2014-02-28 | 2017-02-07 | Pall Corporation | Charged hollow fiber membrane having hexagonal voids |
| US9737860B2 (en) | 2014-02-28 | 2017-08-22 | Pall Corporation | Hollow fiber membrane having hexagonal voids |
| US9302228B2 (en) | 2014-02-28 | 2016-04-05 | Pall Corporation | Charged porous polymeric membrane with high void volume |
-
1977
- 1977-11-04 CA CA290,214A patent/CA1047719A/en not_active Expired
- 1977-11-04 CA CA290,213A patent/CA1047718A/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CA1047719A (en) | 1979-02-06 |
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