JPH07500527A - Poly(phenylene sulfide) (PPS) microporous hollow fiber or film membrane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Poly(phenylene sulfide) (PPS) microporous hollow fiber or film membrane Public corporation 0 coins l x1 dust pan This application is a continuation-in-part of U.S. Application No. 329,666, filed March 28, 1989. The entire content of the application is hereby incorporated by reference.

Public corporation O branch The present invention relates to a technique for solubilizing solvent-resistant polymers to produce molded articles. . More specifically, the present invention involves the production of poly(phenylene sulfur) using a high-boiling organic solvent under heating. (PPS) and effective for separating liquids and/or gases. The present invention relates to a method for producing a permselective fiber or film.

Conventional technique distortion 1 Crystalline poly(phenylene sulfide) is an extremely useful high temperature polymer. Commercial P PS has the following properties: 1. It has a relatively high glass transition temperature of about 85-150°C.

2. It has an extremely high crystalline melting point of approximately 286°C.

3. Thermal stability 4. High solvent resistance Unfortunately, these properties make PPS difficult to use, e.g. as hollow fiber membranes or membranes. It is highly conical to form desired useful shapes such as film membranes.

The thermal stability and solvent resistance of PPS make it suitable for ultrafiltration membranes, hollow fibers, solid fibers, etc. It's ideal. The excellent heat resistance and solvent resistance of Shigashi PPS make this This poses a major problem when molding polymers into desired shapes.

Special solvents are required to produce PPS moldings.

Most of the conventional technologies involve dissolving the raw material reagents used to produce PPS from the monomers. discloses a simple, relatively low boiling point solvent used to Once PPS is formed When this happens, it usually separates from the polymerization solvent.

Poly(phenylene sulfide) is generally considered insoluble in most common solvents. ing. Many thermally polar organic compounds, per-alkylated cyclic ureas or N-alkyl lactams, such as N-methyl-2-pyrrolidone or N,N-diethylbenza mido, N,N-diethyltoluamide, N,N-dimethylethyleneurea, dimethyl Acetamide, hexamethylphosphoramide or N-methylcaprolactam is P It is known as a solvent during the synthesis of PS.

These organic compounds are certainly solvents (or separating agents and/or heat exchangers) for the reagents. agent), but PPS precipitates there.

In U.S. Patent No. 4,118,363, H.A. Hill states that PPS is difficult to solubilize. It is a polymer and diphenyl oxide can be used as a high boiling point solvent under heating. Discloses what was done. Hill also describes alkyl-substituted and halogen-substituted diphenyl It is also disclosed that nyl oxide was used to solubilize PPS.

Strongly acidic thermal substances such as concentrated sulfuric acid, chlorosulfonic acid, and trifluoromethylsulfonic acid is considered as a solvent for PPS. However, these substances have the aroma of polymers. This derivative reacts with the group moiety to form an acidic derivative with properties completely different from PPS. is soluble in the above hot solvent.

The peripheral edge, etc. is disclosed in Patent No. 59-120779 (1984, June 14) (Unexamined Japanese Patent Publication No. 1-432). ) has opened the use of poly(phenylene sulfide) as a composite film for gas separation. It shows.

H, W, H41l, Jr., C, Brady is Kirk-Othme Enaycropedia of Chemical Technology , 3rd Ed, , Vol, 18. P, 793-814 (1982) "Poly(phenylene sulfide)" details poly(phenylene sulfide) I have included it here for reference.

Other related known examples include the following: JP-A-63-2 ss 954 ( 1988, IO, 26, Azuma) disclosed a PPS membrane using lactam as a solvent. ing. There is no description of stretching or orientation steps for improving tensile or other properties.

The hydraulic permeability of this membrane is extremely low, perhaps zero, and is essentially unusable. JP 62-15323 (1987, 1, 23), 59-59, which is difficult to 917 (1984, 4, 5) and 58-67733 (Dainippon Ink) are porous or discloses a method for producing microporous hollow fibers. This method involves melt-spinning PPS and then It is made porous by stretching. This includes disclosure of solvents and gas or liquid permeability. There is no indication.

JP-A-61-432 (19g6.1.6, Dainippon Ink) is a porous film of PPS. lum is disclosed.

JP 60-248202 (1985, 12, 7, Dainippon Ink) melts PPS. Hollow fiber membranes are manufactured by extrusion and coagulation with a core liquid consisting of a mixture of solvent and non-solvent. Discloses that. There is no disclosure of the tensile process.

Full disclosure of all above-mentioned related patent applications, patent documents, standards etc. is included for reference. put.

In the present invention, poly(phenylene phosphate) is solubilized using a high boiling point solvent consisting of an organic compound and a non-solvent. Poly(phenylene sulfide) is molded into a molded product, organic compounds are removed, and poly(phenylene sulfide) is molded into a molded product. useful formations (fibers, films, etc.) of The known examples neither disclose nor suggest the present invention.

Public corporation 0! neck First, the present invention is made of a permselective microporous membrane made of poly(phenylene sulfide). It is related to the manufacturing method, and this method is (a) (i) Poly(phenylene sulfide) (ii) Poly(phenylene sulfide) forming a mixture of at least one solvent for (b) This mixture has a uniform viscosity sufficient to form a film. 7 (5) heating to a temperature under conditions that form a fluid; (c) extruding this homogeneous fluid in the form of a film; or cast, (d) passing the membrane through one or more areas under physical conditions that cause it to solidify; enching) or coagulation, and (e) simultaneously or sequentially at least one of the solvents for the poly(phenylene sulfide); immersing the membrane through the membrane into one or more areas under conditions where substantial potency is removed from the membrane; The selectively permeable membrane obtained in this way has a microporous structure. I have it.

In a preferred embodiment, the method according to the invention comprises steps before, during and/or after the leaching step (e). melting point of poly(phenylene sulfide) or mixtures above at ambient temperature or above Drawing (stretching) processing in uniaxial or biaxial mode at temperatures below the depressed melting point of (C'), which stretches the film and removes the poly(phenylene in the film). sulfides) and control micropore size.

Furthermore, the present invention (a) (i) Poly(phenylene sulfide) (ii) Ho’J (phenylene A small amount of solvent for (sulfide) (iii) From a small amount of non-solvent for (phenylene sulfide) forming a mixture of (b) Conditions that cause the mixture to form a homogeneous fluid of sufficient viscosity to form a film. and (c) extruding or casting this homogeneous fluid into a film. )death, (d) passing the membrane through cooling or solidify, and (e) simultaneously or sequentially at least one of the solvents for the poly(phenylene sulfide); immersing the membrane through the membrane into one or more areas under conditions where substantial potency is removed from the membrane; Selectively permeable micropores made of poly(phenylene sulfide) The semipermeable membrane thus obtained has a microporous structure. ing.

In a preferred embodiment, the method uses a solvent/non-solvent mixture and poly(phenylene) at ambient temperature or above before, during and/or after step (e). uniaxially or biaxially at a temperature lower than the melting point of It has a step (e') of drawing (stretching) in an axial mode, thereby stretching the membrane. stretching, inducing the orientation of poly(phenylene sulfide) in the film and control the

In a preferred embodiment, the method of the invention comprises at least 1 of the solvents described below and less than 1 of the solvents described below. At least 1 liter of non-solvent is used.

In yet another embodiment, the solvent is an organic compound as described below as a solvent or a mixture thereof. chosen independently from objects.

Furthermore, the present invention A, poly(phenylene sulfide) consisting essentially of carbon and hydrogen and optionally oxygen, Consists of nitrogen, sulfur, halogen or a mixture of these atoms, usually 160 to 450 It has a molecular weight between Daltons, has at least one 6-membered aromatic ring structure, and has a About 1 of the poly(phenylene sulfide) present at temperatures between 240 and 400°C a liquid that is stable for a sufficient period of time to dissolve more than 0% by weight and has oxygen at least one which is not diphenyl oxide or substituted diphenyl oxide contact with an organic compound; B. the poly(phenylene sulfide) of step (A) and the organic compound; Molding the solution of the compound into the desired molded form; CO at least one organic compound; remove; and remove the molded product made of poly(phenylene sulfide). Is it the polymer itself consisting of poly(phenylene sulfide) that consists of a recovery process? The present invention relates to a method for producing a permselective fiber or membrane.

Furthermore, the present invention relates to molded products of PPS obtained by the method described herein. . In particular, the moldings are porous, permeable, semi-permeable or selectively permeable.

Furthermore, the present invention A. poly(phenylene sulfide) containing (i) substantially carbon and hydrogen and optionally an acid. It usually consists of 160 to 4 atoms, nitrogen, sulfur, halogen, or a mixture of these atoms. having a molecular weight between 50 Daltons and at least one 6-membered aromatic ring structure; of poly(phenylene sulfide) present at temperatures between 240 and 400 °C under pressure. A liquid that is stable for a sufficient period of time to dissolve about 10% or more by weight and that contains oxygen. When it has at least one which is not diphenyl oxide or substituted diphenyl oxide one solvate organic compound; and optionally (ii) the same molecular weight range as the solvate; Contact with a non-solvent compound that has a temperature stability range and dissolves up to 5% by weight of PPS Let me; B. Add the solution of poly(phenylene sulfide) and organic compound from step (A) to the desired composition. forming into a shape; removing at least one organic compound and the non-solvent; and hand The process of recovering molded products made of poly(phenylene sulfide) A molded product made of a polymer itself made of poly(phenylene sulfide) Regarding manufacturing methods.

In a preferred embodiment, the present invention is solid at room temperature, but melts when heated above room temperature. , using at least one organic compound that produces a stable organic liquid or organic liquid mixture. There is. Organic compounds usually melt at temperatures of 80°C or higher. Solid organic compounds are independent may be heated and melted at 160 to 400°C by adding solid PPS. It may be melted at temperatures between.

The non-solvent compound is optionally selected in a manner similar to that described above.

In another preferred embodiment, a solid organic compound and a solid PPS are combined and then solid organic compounds are heated together as solids until they melt and form a stable liquid. Ru.

The liquid/solid mixture is then heated between about 160°C and 400°C to reduce about 50% by weight or solubilizes more PPS.

Gu Keigori Mono-emperor Theory■ FIG. 1(A) is a schematic diagram of the single-drum membrane casting method.

FIG. 1(B) is a schematic diagram of a twin drum film casting method using nip rolls.

FIG. 2(A) is a schematic diagram of a single-drum liquid (water) cooling film casting method.

FIG. 2(B) is a schematic diagram of a dual-drum liquid (water) cooling film cast.

Figure 3 shows 3o% PPS/CLTA (caprolacta) cast on an aluminum plate. FIG. 3 is a diagram of the effect of cooling conditions on nitrogen permeability of membranes in solution.

Figure 4 shows the liquid/solid phase separation and the resulting nodular bulk porosity structure. This is a scanning electron micrograph (5000x magnification) of the e-CLTA film.

Figure 5 shows 30/70 P showing liquid/liquid phase separation and the resulting vesicular bulk porous structure. This is an electron micrograph (5000x magnification) of a PS/diphenylsulfone (DPS) membrane.

FIG. 6 is a diagram illustrating a quantitative test for evaluating the stress resistance of a film.

Figure 7 shows nitrogen in PPS/DPS extruded film membranes as a function of cooling temperature. FIG. 3 is a diagram of gas permeability.

Figure 8 shows the nitrogen gas of the P　P　S/D　P　S film membrane as a function of cooling temperature. FIG. 3 is a diagram of transparency.

Figure 9 shows films made from PPS/DPS binary mixtures as a function of cooling temperature. FIG. 3 is a diagram of the water flux permeability of the membrane.

Figure 10 shows PPS/DPIP (diphenyl isophthalate) as a function of cooling temperature. ) Nitrogen permeability of PPS membranes made from binary mixtures.

Figure 11 shows the filament made from PPS/DPIP binary mixture as a function of cooling temperature. FIG.

FIG. 12 is a scanning electron micrograph of the PPS film produced in Example 14. Scale is 1cm: 0.89 micron.

The tongue spreads throughout the day) 3 Definition 2 is used as follows: Indicates a type article. Preferably the molded article is a hollow tube, hollow or solid fiber. these If the molded product is transparent, semi-permeable, selectively permeable, or selectively permeable, various materials can be used. Can be used for separation. The availability of the membrane-formed product depends on the membrane material and (pretreatment mode). (depending on its structure) and the manner in which it is operated. For example, the molded product may be exposed to oxygen or is the permeation of gases such as nitrogen, separation of suspended matter (solutes) from solutions, e.g. soluble waste from blood. Separation of substances (hemodialysis) or separation of suspended solids from dissolved molecules, colloids and small molecules It can be used for example in the production of rubber or cheese (ultrafiltration). The membrane, its transport and the mechanism of preparation, its structure, and examples are discussed in detail in numerous references. Ru. The following four editorials are incorporated herein with additional references: (a ) rMembrane Tec by D, R, Paul and G, Morel hnology J gu’Kirk-O1hmer Encyclo-pedi a of chemical Technology, “M, Grayson , and D, Eckroth, (eds) B John Wiley & 5ons, New York, 3rd ed. , Volume 15. pages 92-131 (1981)): (b) P, R, Klikowski's [υ1trafiltration] J (ibid, Vo123, page 439-461 (1983)) ; (c) R, E, Kestin's rSynthetic Poly- meric Membranes, A 5structural Perspe active J (John Wiley & 5ons.

New York, 2nd edition, 1985): Andori, R , Lloyd edited r　MaterialsScience　of　5ynthe tic MembranesJ (American Chemical 5o ciety.

Washington, D, C, AC3Symposium 5erie s No, 269. (1985)).

"Molding a molded product" means thermo-flexible poly(phenylene sulfide)/solvent (organic compound) mixture or heat flexible PPS/solvent/non-solvent (organic compound) mixture or heat Refers to the shaping of a flexible PPS/solvent/non-solvent mixture into the desired molded article form. Growth Mold extrusion, compression molding, solvent cast blow molding, or shaping flexible polymers This may be done by any conventional method used in the field.

"Halogen" refers to fluorine, chlorine, bromine, iodine or a mixture of these atoms, and Commonly found as organic compound bone replacements. Generally bromine and/or is preferably fluorine.

"Non-solvents" are the compounds listed in Table 1 at certain temperatures above 100'C. Refers to organic compounds that dissolve up to about 5% by weight of PPS polymer. Non-solvent for PPS Examples of organic compounds include 1,3.5-triphenylbenzene and tetraphenylsilica. diphenyl sulfoxide, diphenic acid, 4-acetylbiphenyl, bibe Diphenyl, diphenyl methyl phosphate, triphenyl phosphate, cyclo Xylphenyl ketone, mineral oil, butyl stearic acid, phenyl benzoate, l-phenyldecane, 1,3-diphenoxybenzene, 1,8-dichloroantho Laquinone, polyphosphoric acid, dioctyl phthalate, 5-chlorobenzoxazole on, bis-(4-chlorophenylsulfone), diphenylchlorophosphate , sulfolane, methyl myristate, methyl stearate, hexadecane, dimethyl tylphthalate, tetraethylene glycol dimethyl ether, diethylene glycol Cole dibutyl ether, tocosan, todoriacontane, tetraphenylene, Ntafluorophenol, paraffin oil, 1-methyl-2-pyrodinone, 4.4 ’-dihydroxybenzophenone, or mixtures thereof; Includes selected compounds.

"Optionally" refers to a step or existence in a process that may or may not be performed. Indicates ingredients that may or may not be added.

"Organic compounds" are generally composed of carbon and hydrogen and have a molecular weight of approximately 160 to 450 Daltons. It usually refers to an organic compound having at least one 6-membered aromatic ring structure. This includes trivia. Includes organic compounds such as phenylmethane, fluoranthene, pyrene, and others. Ma This further includes compounds containing oxygen, nitrogen, sulfur, halogens or mixtures of these atoms. including. Heteroaromatic compounds having a molecular weight of about 160 to 450 Daltons are included.

Organic compounds useful as solvents in the present invention can dissolve about 10% or more of the PPS polymer by weight. You'll understand. Incomplete solvents are the compounds listed in Table 1 and have a specific temperature of about 100°C or higher. It is an organic compound that dissolves 5 to 10% by weight of PPS polymer at temperature.

The present invention includes a more common method that dissolves the PPS solvent but does not dissolve the PPS. Contains a solvent for PPS that can be easily removed from the mixture by treatment with other organic solvents.

The present invention also provides for PPS that can be removed from the mixture with water or an aqueous alkaline solution. Although the solvent is disclosed, the water or aqueous alkaline soluble solvent is preferred for the treatment. Flame retardant, inexpensive, and filtration process with little potential for danger or toxicity It's for a reason.

“Phenyl” or “phenylene” refers to the following structure: R”, Rb, RC, R d, R'', and R1 to R8 are hydrogen, methyl, ethyl, propyl, butyl, respectively. independently selected from chlorine, fluorine, chlorine or bromine.

"Organic compound" refers to an organic compound with a high boiling point as a solvent for PPS (preferably It is solid at normal temperature and pressure, and usually contains about 50 lomobiphenyl, 1-phenylnaphthalene, Enothiazine, 2,5-diphenyl-1,3,4-oxadiazole, 2,5- diphenyloxazole, triphenylmethanol, N,N-diphenylform Amide, m-terphenyl, benzyl, anthracene, 4-benzoylbipheny dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, chlorophenol, benzophenone, 1-benzyl-2-pyrrolidione, 9 -Fluorenone, 2-benzoylnaphthalene, 1-promonaphthalene, diphenylene Rusulfide, 1,3-diphenoxybenzene, fluorene, tetraphenylmethane Tan, p-quarterphenyl, 1-phenyl-2-pyrrolidinone, 1-methoxy Sinapthalene, hydrogenated or partially hydrogenated terphenyl, l-ethoxynaphthalene , 1゜3-diphenylacetone, 1,4-dibenzoylbutane, phenanthrene , 4-benzoylbiphenyl, 0-terphenyl, 1. l-diphenylacetone , o, o'-biphenol, 2,6-diphenylphenol, ■.

2.3-triphenylbenzene, triphenylene, 4-bromobiphenyl, 2- Phenylphenol, thianthrene, 4,4'-diphenylbenzophenone, 3 -Phenoxybenzyl alcohol, 4-phenylphenol, 9.10-dichloro Loanthracene, p-terphenyl, 2-phenoxybiphenyl, triphenyl Methane, 4゜4'-dimethoxybenzophenone, 9.10-diphenylanthra Sen, fluoranthene, diphenyl sulfone, diphenyl phthalate, diphenyl carbonate, 2,6-cymethoxynaphthalene, 2,7-cymethoxynaphthalene 4-bromodiphenyl ether, pyrene, 9.9'-pyfluorene, 4. 4'-isopropylidenediphenol, 2,4.6-)dichlorophenol Epsilon-caprolactam, N-cyclohexyl-2-pyrrolidone, Diph Phenyl isophthalate, diphenyl-terphthalate, or mixtures of these compounds Contains things that are independently selected from a group of things.

These structures are part of the structures of PPS, PPS-like, and PPS-type polymers described herein. May be found as a minute.

Therefore, the poly(phenylene sulfide) type structure is structurally poly(2-chlorophene). nylene sulfide) or poly(2-methylphenylene sulfide) . Usually p-phenylene is preferred, provided that at least two groups R1 to R4 are hydrogen, and the other groups are methyl, ethyl, propyl, butyl, and fluorine, respectively , chlorine or bromine. Particularly preferred p-phenylene is R1 to R 4, three groups are hydrogen, and the remaining groups are methyl, ethyl, and propylene, respectively. independently selected from pyru, butyl, fluorine, chlorine or bromine.

Organic compounds (solvent/non-solvent mixture) using crystalline polymers as solvent (solubilizing reagent) medium The method of combination with the compound (including compounds) is not critical to the method of the invention. combination mixing, agitation, extrusion, gear pumps, rotary mixers, static mixers, or port This may be done suitably by reamers, membranes, and other means known in the art of mixing technology.

When practicing the present invention, the pressure of the atmosphere above or above the polymer (PPS) and the organic compound is Force and composition are not critical.

Normal pressure is generally used. Especially when a temperature higher than the boiling point of the organic compound is desired, In some cases this is possible above atmospheric pressure. Preferably prevents unnecessary side reactions of ingredients Therefore, the atmosphere above the polymer and organic compounds is essentially inert. Nitrogen is good A suitable inert atmosphere.

Dissolution of PPS in a given solvent is a function of polymer concentration and temperature. 13 typical Solvents for PPS, namely m-terphenyl, 4-phenylphenol, and diphenyl sulfone; anthracene, benzophenone, and 2-phenylph phenol; 1-cyclohexyl-2-pyrrolidonone, 0.0'-biphenol and epsilon-caprolactam (ε-caprolactam); benzyl and 9-fu Solubility curves for luorenone; and pyrene and fluoranthene were performed. That's it Any temperature-concentration combination above this curve represents a homogeneous single-phase composition; The combinations below represent multiphase mixtures in which the polymer is not completely dissolved. Therefore, U For example, 4-phenylphenol as described in SS No. 329,666 Temperatures above approximately 257°C are required for complete dissolution of the 50% PPS mixture in the bottle. required. Similarly, 40% PPS in anthracene requires approximately Temperatures in excess of 243°C are required.

PP using organic compounds and mixtures in combination with non-solvents or incomplete solvents as solvents. It is useful to make S films, fibers, tubes, and the like. Therefore, the solvent PPS was added if the and non-solvent were soluble in each other in combination at elevated temperature. Sometimes PPS will dissolve. Combining solvent/non-solvent makes PPS porous It is extremely useful in the production of permselective membranes. Typically, the solution for producing hollow fiber membranes is Approximately 50% by weight PPS and the remainder solvent, solvent/non-solvent, or solvent/incomplete solvent mixture It will consist of things. Ratio of solvent to non-solvent or solvent to incomplete solvent The ratio is typically about 1.5 mm depending on the relative solubility of the solvent and non-solvent or incomplete solvent. It will vary from 5/1 to about 20:1.

fillers, additives, antioxidants, pigments, dyes, inhibitors and other miscellaneous materials according to the invention It will be appreciated that the scales may be dissolved or dispersed in the PPS solubilized by the practice of child These materials may be used to improve processing or to improve specific physical and / or depend on it to impart chemical properties. Such materials are for example R,Gac Hter and H, Muller’s Plastics Additives H andbook” (2nd edl Munich HanserPubHsh ers, 1983), which is incorporated as a reference document.

Organic compounds or mixtures thereof are substantially inert to PPS at elevated temperatures It is. The obtained PPS molded product, such as a film or fiber, is substantially the same as the starting PPS. should have the same composition as

In another aspect, PPS moldings contain trace amounts of organic compounds used as solvents (and non-solvents). will contain compounds. These traces indicate that the solvent of the present invention is not used in the production of PPS molded products. This will be useful in determining whether it has been used or not.

Generally, the polymer/solvent mixture is formed into hollow fibers by methods known in the art. It will be done. Such a method is described by M. Grayson and Eckroth. rk-Othmer “Encyclopedia of Chemical T technology, “J (Volume 12. pages 492-5 17. John Wiley and 5oz.

l5rae in New York, 3rd edi mouth on, (1980)) l　Hollow　Fibre　MembranesJ by Cabasso It is described in.

The solvent/polymer mixture can also be solvent cast onto a flat surface and subjected to evaporation and/or vacuum. or by using a liquid that dissolves the solvent but not the polymer. may be removed. The membrane typically has a thickness between about 0.2 and 50.0 mils. is porous and suitable for ultrafiltration, microfiltration applications, and synthetic membranes for gas or liquid separation. It is useful for separation devices such as microporous carriers.

The rate of cooling is critical to obtaining the physical properties of the film. This is hollow fiber and The same applies to film production. Also, solvent flash-off (rapid The effect of vaporization) and the skin-forming properties obtained on the membrane are critical. film extrusion The following process may be used in the method. A series of experimental treatments were performed.

In addition to the cooling rate, the type of phase separation of the polymer/solvent mixture depends on the hollow fiber or film. It is important in determining the final bulk structure of the membrane. The type of phase separation is nodular (N) structure. liquid-solid (L-5), or liquid-liquid (which becomes a finer vesicular (C) bulk structure). LL) phase separation may be used (see FIGS. 4 and 5). phase separation that takes place The type depends on polymer concentration, solvent properties, and cooling rate. Nodular (N) or The vesicular (C) structure is not preferred in all cases and the choice depends on the end use of the membrane. Determined by the target. Showing the appearance of nodular (N) and vesicular (C) bulk structures. Scanning electron microscopy (SEM) photographs are shown in FIGS. 4 and 5.

In this field, a thermal polymer/solvent (11) is used as a mold ( 12) to a rotating drum (13) in the air that is usually heated to a predetermined temperature. is known to cast. The cooled membrane (14) is then obtained from the other end of the drum. It will be done. The method shown in this figure (A) is the same as casting on a flat surface in air and cooling it. This results in a similar polymer film.

FIG. 1(B) shows a method for producing a film that is air melt cast and cooled. Similarly, The remer/solvent (11) is melt cast through the mold 12 into the drum 15.16. Ru. The rotating drums can each be at the same predetermined temperature, or more often at different temperatures. Ru. A shaped polymer membrane (17) is obtained from the circular surface of the drum (15). Figure 1 (B) Method was cast between two heated metal plates in air for the characteristics yields a polymer film similar to that of

Figure 2(A) is similar to Figure 1(A), but the polymer is cooled in the liquid and optionally dissolved. The difference is that the medium is leached into the liquid. Alternatively the leachate may be in a separate container . The molten polymer/solvent/optional non-solvent 21 is extruded through a mold 22 to form a hot polymer. mer/solvent 23. The drum 24 is rotating, and the formed film is rotating. Cooled (and optionally simultaneously pulled) between drum 24 and drum 25,26 ).

Figure 2(B) is similar to Figure 1(B), but the polymer is cooled in the liquid (and Optionally leached at the same time). Molten polymer/solvent and/or non-solvent 2 1 is extruded through a mold 22 and shaped into a membrane film. Thermal film is rotated Passing between rams 27, 28 further shapes the membrane to the desired dimensions. Then the membrane is liquid 2 9 (e.g. water), optionally using rotating drums 30 and 31. At the same time, it can be pulled (stretched).

The following description is specifically incorporated by reference to U.S. Pat. No. 4,904,429. Follow the method described for poly(etheretherketone) (PEEK) . PEEK is replaced by approximately equal weight of PPS.

The selection of components for the extrusion mixture can be non-interconnected or interconnected pore structures or selectively permeable. It depends on which sex you want. For use in fiber or film reinforced composites The fiber or film may have either a non-interconnected or an interconnected porous structure. . In non-interconnected pore structures, the pores within the membrane are not completely interconnected; There is no direct contact between the surface and the other surface of the membrane, but the flow of liquid through the dense polymer region of the membrane Fluid still flows through the membrane due to solution diffusive transport.

In an interconnected porous structure, the pores are completely interconnected, and the pores extend from one side of the membrane to the other. In direct communication, fluid flows through the membrane primarily by transport through the pores of the membrane.

Factors that determine the formation of interconnects and non-interconnects include the polymer concentration in the extrusion mixture. , the volatility of the solvent, the cooling rate of the generated fiber or film, and the Includes non-solvent composition. Polymer is preferably used to form fibers with non-interconnecting pores. An extrusion mixture containing polymer and solvent is used. Formation of fibers with interconnecting pores Preferably, an extrusion mixture containing polymer, solvent and non-solvent is used.

The component concentrations in the extrusion mixture may be varied, depending on the desired type of fiber pore structure ( interconnecting and non-interconnecting pores), depending on porosity and pore size. in extrusion mixture The concentration of poly(phenylsulfide) is so that the mixture can be extruded at the extrusion temperature to have a suitable viscosity. The viscosity of the mixture is such that the fluid is too viscous to extrude or so high that it cannot be cast, and the fluid must not be so high that it cannot be cast. The viscosity should not be so low that it cannot emerge and retain the desired shape. PPS polymer pressing Brew mixtures generally have non-Newtonian viscosity behavior and therefore the mixtures have a viscosity of Shows shear rate dependence. The mixture preferably has a shear rate of about 10 to 1 at the extrusion temperature. 0,000/sec, a viscosity between about 100 poise and 10,000 poise, more preferably has a shear rate of about 50 to 1000/sec and a viscosity of about 300 to 1000 poise. have In non-interconnected porous structures, the concentration of PPS polymer is preferably about 10 about 90% by weight, more preferably about 20 to 80% by weight. Mutual communication porous structure In manufacturing, the concentration of poly(phenylene sulfide) type polymer is preferably from about 20 to About 70% by weight, more preferably about 30 to about 65% by weight. The concentration of solvent is Preferably from about 1 to about 90% by weight, more preferably from about 2 to about 80% by weight.

The concentration of any non-solvent is preferably from about O to about 90% by weight, more preferably from about O to about 90% by weight. About 80% by weight. If a non-solvent is used, the solvent/non-solvent ratio is approximately 0.05 to 24, more preferably about 0.1 to 12.

The fiber or film is made from the poly(phenylene sulfide) polymer composition described above. Extruded or cast. The components of the extrusion mixture can be prepared using, for example, a Hobart mixer, etc. They may be compounded prior to extrusion by any suitable means of mixing in conventional mixing equipment. extrusion The mixture may also be blended and mixed under heat in a resin kettle. alternatively extrusion The mixture is then extruded through a twin-screw extruder, the extrudate is cooled, and milled or pelleted to a particle size that can be easily fed into a single- or twin-screw extruder. It may be homogenized by homogenization. Alternatively, the components of the extruded composition can be melted in a melt pot or twin screws. It may be directly compounded in a Liu extruder and extruded into fibers in one step. static mixer The use of helps homogenize the mixture.

The mixture is heated to a temperature such that a homogeneous fluid has a viscosity suitable for extrusion. P The temperature is not high enough to cause significant decomposition of the PS polymer, solvent and any non-solvent. The exposure time is also not long. The temperature is such that the fluid becomes so viscous that it cannot be extruded. Should not be at low temperatures. The extrusion temperature is preferably between about 170 and 400°C; More preferably between about 275 and 350°C.

The mixture of polymer, solvent, and optional nonsolvent can be used in solid or hollow fiber molds. It is extruded through spinnerets). Solid fibers refer to fibers that are not hollow. Said solid fiber The fiber mold or hollow fiber spinneret is typically multi-hole, with multiple fibers. Manufacture tau. The hollow fiber spinneret includes means for supplying fluid to the extrudate core. nothing. The core fluid is used to prevent hollow fibers from collapsing when they emerge from the spinneret. It will be done. The core fluid may be a gas such as nitrogen, air, carbon dioxide or other inert gas. well, or dioctyl phthalate, methyl stearate, polyglycols, minerals oil, paraffin oil, e.g. Mobiltherm 600.603.605 heat exchange oil (Mobiltherm 600.603.605 heat exchange oil) - Petroleum such as Bill Oil Corporation (registered trademark), e.g. DC-704, DC -71O silicone oil (registered by Dow Corning Chemical, Midland, Michigan) It may be a liquid such as silicone oil (Trademark) etc. Using liquid non-solvent as core fluid In particular, the core fluid mixture may be used to control the morphology of the inner skin.

Extrudate exiting the mold enters one or more cooling zones. The environment in the cooling area is gas Or it may be a liquid. In the cooling zone, the extrudate is cooled to cause solidification of the fibers. , optionally the solvent and any non-solvent moieties are removed simultaneously. In a preferred embodiment, the fiber The fibers are first cooled in a gaseous environment such as air, nitrogen, or an inert gas. gas cooling area The temperature in the zone is preferably in the range of about 0 to about 100°C, more preferably in the range of about 10 to about It is in the range of 40°C. The residence time in the gas cooling zone is preferably about 120 seconds or less; More preferably, it is about 30 seconds or less. Gas flow, temperature in the gas cooling area using a cover temperature characteristics may be controlled.

In another aspect, the least amount of one organic compound is evaporation, heating, sublimation, depressurization, organic the use of solvents that dissolve organic compounds (and/or non-solvents) but not PPS; is removed by a combination of these means. Molded organic compound PPS molded product is cooled somewhat, preferably between about room temperature and 100°C, and one or more Remove organic compounds (and/or non-solvents present) by contacting with the above removal solvent. However, the form of PPS molded products such as fibers, tubes, or films is maintained. For removal solvent For example, acetone, methylene chloride, dimethyl sulfoxide, methanol, ethanol or a mixture thereof, and further water, and an aqueous salt. groups (5-10% NaOH or KOH). Aqueous base is phenol organic It is particularly useful for dissolving and removing compounds. In another embodiment, organic compound/PP The S molded product is cooled to approximately 150°C and placed under reduced pressure (approximately 1 mm and 0.001 micron). to remove organic compounds.

Following or instead of gas cooling, the fiber or film is optionally cooled in a liquid environment. It's okay to be. This is essentially water or a non-containing material for PPS polymers such as ethylene glycol. The solvent may optionally include an effective amount of a swelling reagent. The optimum temperature for a given liquid is The temperature is such that the fibers are not adversely affected.

The temperature is preferably between about 0°C and about 200'C, more preferably between about 0°C and about 200'C. It is between 100°C. The residence time in the liquid cooling zone is preferably about 120 seconds or less; More preferably, it is 30 seconds or less.

Following cooling, the fibers are passed through one or more leaching baths to remove the solvent and/or any insoluble material. At least a portion of the medium may be removed. The leaching bath removes all solvent and/or There is no need to remove non-solvent. Preferably the leaching bath contains a solvent and/or a non-solvent. The water content in the produced fibers is removed to about 2% by weight or less. The leaching bath is for PPS polymer. The solution consists of a solution that is a non-solvent and an extrusion solvent and/or a solvent with respect to the non-solvent. good Preferred leachants are toluene, xylene, acetone; methylene chloride, carbon tetrachloride, and Lichlorethylene and 1. Containing chlorinated hydrocarbons such as l, 1-1 dichlorothane nothing. The optimum temperature is the temperature at which solvent and/or non-solvent removal from the fiber occurs at a reasonable rate. It is. The temperature of the leaching bath is preferably between about 0°C and about 200°C, more preferably about It is between 0°C and about 80°C. The residence time in the infusion bath is preferably about 14 hours or less; More preferably, it is about 1 hour or less.

The fibers may be drawn to the appropriate dimensions using conventional godet equipment. tension is leaching It can be before, during, or after. Linear velocity is not critical and may vary widely.

Typical linear velocities range from about 30 feet/minute to about 300 feet/minute.

When hollow fibers are used in membrane applications, the fibers preferably have an outer diameter of about 50 to about 300 mm. microns, more preferably from about 80 to about 2000 microns, with a wall thickness of about 10 microns. from about 400 microns, more preferably from about 20 to about 400 microns. fiber When the fibers are used in fiber-reinforced composites, the fibers preferably have an outer diameter of about 5 to about 100 mm. microns, more preferably from about 5 to about 50 microns, and optionally the fibers have a wall thickness of Preferably from about 2 to about 45 microns, more preferably from about 2 to about 20 microns. May be hollow.

Following leaching, the fibers are dried. drying to reduce the possibility of cave-ins during drying. Optionally, in advance, the leachate remaining in the fibers is treated with a solvent that has a low surface tension. may be replaced with a volatile, non-polar dry reagent that is a non-solvent for the polymer. stomach. A preferred dry reagent is Freon 113 chlorofluorocarbon (EID). (Registered Trademark). Exchange should be performed at a temperature that does not adversely affect the membrane. The temperature may be about 0°C to 45°C, preferably about 0°C to 45°C. Fibers are inert such as air or nitrogen May be dried in gas. The drying may also be carried out under reduced pressure. It is reasonable to dry fibers Drying may occur at a reasonable rate and at a temperature that does not adversely affect the membrane.

The drying temperature is preferably from 0°C to about 140°C, more preferably from about 10°C to about 80°C. It is ℃. Drying time is preferably about 24 hours or less, more preferably about 6 hours or less It is.

The microporous fibers or films of the invention are characterized by their porosity and pore size. It's fine. Porosity refers to the volumetric hollow volume of the fibers. The porosity is 1oOX[1(d r/dI, o, )] <where d is the density of the maximum leached fiber or film, and a pps is the density of the PPS polymer). have non-mutual communication holes The fibers or films of the invention preferably have a porosity between about 10 and 90%, more preferably Preferably between about 20 and about 80%. Fibers of the invention having interconnecting pores are preferred. or the porosity is between about 20 and about 70%, more preferably between about 30 and about 65%. be.

Pore size was measured by scanning electron microscopy and/or bubble point measurement, solvent flow rate (flux) It is measured by a method including molecular weight cutoff, etc. The above method uses microporous membranes. Techniques for characterizing pore size are known in the art, e.g. t Kesting's synthetic polymeric Membr anesJ (2ndedition, John Wiley & 5ons , New York, 1985. pp, 46-56): Channin g R. Robertson (Stanford University) r Molecular and Macromolecular Sievin g by Asymmetric Ultrafiltration Memb ranesJ (OWRT Repon, NTl5 No, PB85-157 7661EAR, September 1984); and ASTM Test Method F 3l6-84, which are incorporated herein by reference. Hole size is preferably between about I x 10-3 microns and about 3.0 microns, more preferably More preferably, it is between about 3 x lO remicrons and about 1.0 microns.

In a preferred embodiment of the invention, the method comprises microporous hollow fibers having interconnecting pores or Manufacture film membranes.

The membrane is suitable for membrane separation processes such as microfiltration, ultrafiltration, reverse osmosis, perevaporation, and membrane distillation. It is useful for liquid treatment.

The hollow fibers may also be useful as porous carriers for composite gas or liquid separation membranes. . In particularly preferred embodiments, the method provides microporous filters useful for ultrafiltration or microfiltration. Manufacture hollow fiber membranes. Ultrafiltration and microfiltration separate particles or solutes from solvent. This is a pressure-driven filtration method using microporous membranes that separate the membranes. Separation is based on particle size or minute This is done based on the difference in molecular weight. Membranes of the invention useful for ultrafiltration and microfiltration include Preferably a molecular weight cutoff of about 10 to 500 Angstroms is used for ultrafiltration applications. molecular weight cutoff of approximately 0.05 to 7.0 microns for microfiltration and microfiltration applications. has. Ultrafiltration and microfiltration must be carried out at temperatures that do not adversely affect the membrane. stomach. The operating temperature is preferably about 0 to about 130°C. The operating pressure depends on the membrane pore size and and the particles or solutes separated from the solution. The preferred operating pressure is from about 5 to about It is in the range of 150psi.

Haba Uniaxial or biaxial mode of tension, stretching or elongation of membranes Application U, S, S, No. 380,058 is filed against PEEK. However, this will be included as a reference. PEEK is replaced by PPS.

You can also use the following:

Before, during and/or after leaching, the membrane is stretched or stretched to the appropriate dimensions and thickness. May be lengthened. Stretching or stretching is performed by increasing the length of the membrane at the end of the stretching or stretching process. Stretched to become longer and thinner. tension is membrane The mechanical strength of the film is increased by introducing orientation into the film. The tensile temperature is the point of tension. depends on whether the membrane contains a solvent and any non-solvent. Virtually any solvent For non-solvent dependent membranes, the membrane is between the glass transition temperature of PPS and the melting point of PPS. heated to temperature. Preferred lower temperatures are at least about 90°C, more preferably preferably at least about 100°C, with a preferred upper temperature of no more than about 280°C, more preferably The temperature is approximately 270°C or less. For membranes containing solvent and optional non-solvent, the membrane temperature to the melting point of PPS or the depressed melting point of the PPS/solvent/optional non-solvent mixture. heated to a temperature of The preferred lower temperature is at least about below the depressed melting point. It is lO°C. The membrane is stretched by stretching the membrane under tension. flat sheet The membrane may be uniaxially or biaxially stretched.

Uniaxial tension or orientation generally means that later godets move at a faster rate than earlier godets. This is done by running a membrane over a pair of godets. Tensile elongation ratio is the start of the membrane length and the final length of the membrane. The lower limit of the tensile or elongation ratio is preferably 1.05 , more preferably 1.1. The upper limit of the tensile or elongation ratio is preferably lO. Ru. Membranes can optionally use different temperatures, pull ratios, and pull speeds in each step. may be stretched in one or more steps. Linear velocity is generally not critical; You can change it a lot.

The lowest practical preferred linear velocity is at least about 10 feet/minute, preferably less than At least about 30 feet/minute. Practical maximum preferred linear velocity is approximately 200 0 ft/min or less, preferably about 1000 ft/min or less.

Biaxial orientation or tension can be achieved by tenter frame method, double bubble method or blow fill method. This may be done by methods known in the art, such as the encyclopedia method. a of Polymer 5science and EngineeringJ John Wiley & 5ons, New York, Vol, 7 ．． (See Pages 98-102 (1987)).

Depending on the method used, the biaxial orientation of tension may be carried out sequentially or simultaneously. . For example, tensioning by a tentering operation can be carried out sequentially (e.g. by performing a transverse orientation and then transverse or elongated orientation, or vice versa), or both transverse or elongated orientation at once. (i.e. simultaneously).

Orientation by the blown film method may involve simultaneous transverse and longitudinal operations.

For example 5 below and elsewhere, the fabrication of asymmetric membranes involves different phase changes on the two sides of the membrane. This is usually done by having a speed of Phase changes include solidification, phase inversion, and liquid-liquid phase. separation, or liquid-solid phase separation. Methods of controlling the rate of phase change, and results One way to control morphology, pore size and asymmetry is to use hollow fibers and flat contacting one of the membranes with a second liquid. This second liquid is initially a polymer. It may or may not be a solvent in which it is dissolved. Asymmetric planar membranes can be inspected by surface inspection. can be easily identified visually. Side with smaller pores and less porosity The surface appears shiny compared to a more porous, larger pore size surface.

The latter film appears dull compared to the shiny surface. Therefore "teka teka" (smooth) Membranes with sides and "blunt" sides are defined as asymmetric.

For Examples 12 and 13 below, this experimental portion describes the details of these permselective membranes. It has the following description. In Examples 12 and 13, PPS/solvent/optional nonsolvent was 0. The reaction mixture turns dark (but clear solution) for 5 to 2 hours, preferably about 1 hour. Heat until warmed. Even after further heating for 0.2 to 1 hour, the reaction mixture becomes even darker. It won't be.

The membrane exhibits good permselectivity and tensile properties.

The microporous fiber or membrane described in another aspect has a hydraulic permeability of at least 500 m1/hour·M”-cmHg or more.

The microporous fibers or membranes described in another aspect have a low gas flow rate through the membrane. Both l　X　I　0-5cm3/cm''・sec・cmHg or more.

The microporous PPS fibers or membranes described in another aspect have a hydraulic permeability of at least 2000 m1/hour・M2・cmHg.

The microporous PPS fibers or membranes described in another aspect have a gas flow rate of at least I 　X　10-'cm3/cm2・sec・cmHg.

In another aspect, PPS membranes fabricated for microfiltration applications using a tensile process are flat. The average pore size is 0.05 microns or greater.

PP manufactured for ultrafiltration applications by a method with a tensile process in another aspect S has an effective pore size of 0.05 microns or less.

The following examples shall be construed as illustrative only and shall not be construed as imposing any limitations. Shouldn't.

Senshiga people P′ in ゛8 [Poly(phenylene sulfide)] or rPPSJ is poly(phenylene sulfide). Refers to a polymer material made of Usually this polymer is p-dichlorobenzene and PhillipsPet, Oklahoma. roleum or Aldrich Chemica1 (or as above) Obtain from.

Aldrich Chemica1 PPS lot number #1726CJ was used for solubility determination as received. Many of the organic compounds tested as high temperature solvents was obtained from Aldrich Chemica 1 and used as received. other organic The compound is from Directories Publ, Boca Ratan, Florida. rChemical published annually by isshin, Co., Inc. Obtained from suppliers listed in Sources U, S, and AJ.

Accurately add PPS and solvent to 0.001 g in glass vials ranging in size from l to 4 g. A mixture of PPS and solvent with a total weight of 2 g or less was prepared by measuring the weight. each vial The resulting space depends considerably on large differences in the bulk densities of the compounds, which can be Purge with nitrogen. Seal the vial with a screw cap with an aluminum foil liner.

Solubility is usually determined at about 10% polymer by weight, followed by about 25% and 5% by weight, if necessary. Additional determinations were made at 0% by weight.

Table 1 below lists the organic compounds tested for their solvent effect on PPS. . The approximate solubility of each polymer at the indicated temperatures is shown. Organized for easy reference The compounds were numbered (starting with 200). Also, if the physical properties are known Approximate molecular weight, melting point, and boiling point are shown for Batter 1.

In the table, the solubility column rgJ means "greater than", rsJ means "less than", and "engine" means "less than". It means "equal to".

Table 1 2oO triphenylmethanol 260 161 360 g55%? 3492 01 Triphenylmethane 244 93 359 g50.0% 349202 Triphenylene 2211 196 4311 g 49.9% 350203 1.2,3-) Riphenylbenzene 306 158 - 149.9% 34 9204 1.3.5-) Riphenylbenzene 306I F3 460 slo , 4% 349205 Tetraphenylmethane 320 2111 431 s 25.2% 349205 Tetraphenylmethane 320 2g + 43 Summer = s50.3ν 349206 Tetraphenylsilane 337 231 4 22 g 9.9% 349207 Diphenylsulfoxide 202 70 350 slo, 4% a349208 diphenyl sulfone 218 124 379 g 50.0% 34 g209 2.5-diphenyloxazole 2 21 72 360 g 50.1% 349210 Dipheninochic acid 242 228 - slo, 1% 1I34921 + 1.1-diphenylacetone 210 60 - 149.9% 302212 1.3-diphenylacetone 210 33 330 g 49.8% 3022I34-acetylbipheny Lu +96 117 - = s11.6% 3022I42-biphenylcarbo phosphoric acid 198 109 349 g 50.2% 3492154-biphenyl Carboxylic acid 198 225 - = s25.7%? 349216 m-Turf phenyl 230 83 379 g 50.2% 3022174-benzoyl Biphenyl 258 100 419 g 50.2% 3492I74-ben Zoylbiphenyl 29 100 419 s 49.2% 3022111 4.4°, Di7: 1.1 ・Benzo 7z/n 334 - - g50.0 % 3022I9 Topenzoyl-4-piperidone 203 5 399 gIO, 2%? 34g (continued) Table 1 (continued) 2202-benzoylnaphthalene 232 il + 3113 g 50.5% 349221 Diphenyl carbonate 214 79 301 g 24. 9% 302221 diphenyl carbonate 214 79 301 g50 ．． 0%? a 302222 Bipenzil 1112 51 284 s 10. 1% 2F 4223 diphenylmethyl phosphate 264-3119 sIO, 2% 3492241-bromonaphthalene 207-1 2110 g 50.6% 274225 N,N-diphenylformamide 197 7 1 337 g 50.2% 302226 3-7z Noxyhenzyl Alcohol Le 200-329 g50.0% 302227 Fluoranthene 202 10!1 384 g 50.0% 3492282-phenoxybiphenyl 246 49 342 g 50.0% 302229 Triphenylphosphene 326 51 2111 s 10.3% 274230 cyclohexy Luphenyl ketone 188 56 - = slO, 0% 302231 2.5 -Diphenyl-1,3,4-oxanoazole 222 139 382 g 50.1% 349232 1.4-dibenzoylbutane 266 107 - g49.8% 3022339-fluorenone 180 113 342 g 50.4% 302234 1.2-dibenzoylbenzene 286 146 - s50.2%a349235 dibenzoylmethane 224 78 36 0 g 50.2% 349236 2.4.6-) dichlorophenol 19 7 65 246 g 25.0% 242236 2.4.6-) Dichlorof Enol 197 65 246 s 50.1% 24723fu Benzyl 210 94 347 150.2% 302238p-terphenyl 230 212 3119 g 50.0% 302239 Anthracene 178 216 340 g 50.2% 302 (continued) Table 1 (continued) 240 Mineral oil --3608 Tsuta o, o% 349241 Butyl stearate 341 - 343 s Month % 302242 9-7 E=F9 Ren 25 4 151 417 gio, o%? a 349243 1-7, Z Nirna Phthalene 204 - 324 g50.1% 302244 4-7z Nil 7z /-le 170 166 321 g50.0% 3022452-Phenylphene Nord 170 59 282 g 50.0% 274246 1-engine) Kishi Naphthalene 172-280 g49.8% 274247 Phenylbe ) 1911 69 298 s9.8% 2742481-phenyl Decane 218-293 slo, 4% 274'249+-methoxynaf Talen +511-269 g411.9% 2472502-Methoxina Phthalene 158 74 274 g 24.11% 2422502-Methoki Sinapthalene 158 74 274 s 50.0% 247251 Concentrated sulfuric acid 9g 11 340 0.0% 252524-bromobiphenyl 233 86 310 g 50.0% 2582524-Promobifueni J 233 116 3 Summer Ogll, 3% 2342524-bromobiphenyl 233 86 310 g 26.9% 2402534-bromodiphenyl ether 249 18 305 g 24.7% 2432534-bromodiphenyl ether 249 1) 1 305 g55% 274254 1.3-dipheno Xybenzene 262 60-sll, 3% 255254 1.3-diph Phenoxybenzene 262 60 - = s50.0% 274255 1.8 -Dichloroanthraquinone 277 20 - sll, 5% 254255 1.11-dichloroanthraquinone 277 20 - = s9.7% 274 Topsoil (continued) 256 9, violet 0-dichloroanthracene 247 214 - gll, 4% 252256 9.10-dichloroanthracene 247 214 - g5 0.0% 302257 4.4°, dibromobiphenyl 312 170 3 55 g 11.4% 234257 4.4"-dibromobiphenyl 312 170 355 g 50.1% 302257 4.4'-Dibromobife Nil 3+2 170 355 s 24.11% 242258 Benzophe Non 182 50 305 g 50.4% 274259 Bolijofelino Citric acid---s4.4%a302260 Tokuro naphthalene 162-20 258 s 10.0% 203260 1-chloronaphthalene +62 -2 0 2511 g 24.3% 2362601-chloronaphthalene +62 -20 258 s 49.8% 237261 diphenyl ether +70 27 259 = s9fu% 247262 1-/Chlohexyl-2-pylori Zinone +67 - 302 s 9.5% 203262 1-cyclohexyne Ru 2-pyrrolidinone +67-302 +24.6% 2362621- Cyclohexyl-2-pyrrolidinone +67 - 302 s50θ% 237 262 l-cyclohexyl-2-pyrrolidinone +67 - 302 g50 ．． 2% 302263 Tobenzyl-2-pyrrolidinone 175 - - slo , 2% 2332631-benzyl-2-pyrrolidinone 175 - - g5 0.4% 302264 o, o'-biphenol 11116 109 31 5 g 49.9% 302265) IB-40 (hydrogenated terphenyl + 2 44-325 g49.4% 302 (Monsanto) 266 Dioctyl phthalate 391-50 384 s 10.0% 3 49267 5-chloro-2-benzoxazolone +70 191 - ilo, 2%a 349268 Dibenzothiophene 184 98 332 g 50.3% Table 302” 2 (continued) 269 bis(4-chlorophenylsulfone) 2117 +46 412 s 9.9%a349270 diphenyl phthalate 318 75-524. 8% 349270 diphenyl phthalate 3111 75 - 150. o %? 349271 2.6-diphenylphenol 246 101 - g4 9.9% 349272 diphenyl sulfide 186 -40 296 = s49.4% 2.74273 Schiff, vinyl chlorophosphate 269 - 360 slO, 0% a349274 Fluorene 166 113 291i -550,1% 2fu 4275 7z Nanthrene 178100 340 g4 9.9% 302276 Sulfolane 120 27 285 slo, 0% 27 4277 Methyl myristate 242 Ill 323 g7.4% 302 2F8 Methyl stearate 299 38 3511 s, IO, 1% 34 9279 7e/thiazine 199 11112 371 g50.1% 349 280 Hexadecane 226 19 288 s 10.0% 274281 Dimethyl phthalate 194 2 282 s9.6% 274282 Tetra Ethylene glycol dimethyl ether 222-30 275 s 9.8% 242283 Diethylene glycol knob 1,000 ether 218-60 2 56 s 9.8% 242284 Tokosan 31j 44 369 s 5 ．． 2% 349286 Todoria Contan 451 70 476 sIO, 1% 349287 2.7-Simethoxynaphthalene 18g +38 - 15 0.1% 274288 2.6-Simethoxynaphthalene 188 153 - g55% 274289c-terphenyl 230 58 337 g 4 9.9% 302290 4.4-dimethoxy, benzophenone 242 14 2 - g50.0% 349 (continued) Table 1 (continued) 291　9,jO-diphenyl anthracene 33Q　246　-　g　50 ．． 0% 349292 1.1-diphenylethylene 180 6 270 - 525.1% 243292 1.1-diphenylethylene 1110 6 2 70 148.8% 247293c-caprolactam 113 71 271 g 25.1% 242293c-caprolactam 113 71 271 s 50.1% 247294 Tetraphenylethylene 332 223 4 20s 9.8% 302295 Pentafluorophenol 184 35 143 g4.6% 141296 Thianthrene 216 158 365 g50.0% 3022971-methyl-2-pyrrolidinone 99-24 202 s 10.0% 203298 Pentachlorophenol 266 1 89 3+Og 50.3%a? 302299 Pyrene 202 150 4 04 g 50.0% 273300 Benzanthrone 230 169 - s50. o%ab 323301 9.9-Bifluorene 330 247 - g50.1% 275302 Santowax R-145364g50.0 % 273 (Monsaruo company) 303 Therminol 66240-340 g50.0% 273 (Mon sarno) 3051-phenyl-2-pyrrolidinone 161 611 345 g 50. 0% 273306 4.4'-Isopropylenediphenol 228 1 56 402 s 50.0%a 323306 4.4°, Isoprobili, De Diphenol 228 156 402 g 24.9% 275307 4 ．． 4-dihydroxyben! Fenon 214 214 - slo, 3% 31 9a - black or very dark b = reaction Table 2 below describes those compounds that dissolve at least 50% by weight of PPS.

In Table 2, rgJ in the solubility column means "greater than", "S" means "less than", and " =” means “equal to”.

Table 1 2491-methoxynaphthalene g489% 247265 HB-40 (hydrogen 3022461-ethoxynaphthalene 14 9.11% 274212 1.3-diphenylacetone g 49. )1% 302232 1,4-dibenzoylbutane g498% 302275 Fe Nanthrene 8499% 3022534-bromodiphenyl ether 849 9% 3022 Kan74-benzoylbiphenyl 289o-terphenyl 8499% 302211 1,1-diphenylacetate Tons 8499% 302264 0,0-biphenol 8499% 302 271 2,6-diphenylphenol 8499% 349203 1, 2. 3-) Liphenylbenzene 8499% 349202 Triphenylene 849 9% 3502524-bromobiphenyl 8500% 2582452-phenylene Nylphenol g 50.0% 274296 Thianthrene 8500% 302218 4, 4°, diphenylbenzophenone 8500% 3021 ( continuation) 2263η Enoquine Benzyl Alcohol 8500% 3022444-Pheny Lephenol 8500% 302256 9,10-dichloroanthracene 8500% 302238p-terphenyl 8500% 3022282-terphenyl Phenoxybiphenyl 8500% 302z01 Triphenylmethane 8500 % 349290 4,4-dimethoxybenzophenone 8500% 3492 91 9,10-diphenylanthracene 8500% 34922 Fluo Roanthracene g 50.0% 349208 Diphenylsulfone 850 0% 349270 Diphenylphthalate 8500% 349221 Diph Phenyl carbonate 8500% a302288 2,6-cymethoxy naphtha Rate 8500% 274287 2,7-Simethoxynaphthalene 8500 % 2742534-bromodiphenyl ether g 50.1% 27425 7 4,4'-dibromobiphenyl 1 50.1% 3022431-pheny Lunaphthalene g 50.1% 302279 Phenothiazine 8501% 349231 2,5-sophenyl-1.3.4-oxadiazole g 50 ．． 1% 349209 2,5-diphenyloxazole 8501% 349 200 triphenylmethanol g 50.1% to 3492621-cyclo Kinru 2-Viridinone g 50.2% 302225 N,N-diphenyl Formamide 8502% 302216 m-terphenyl g 50.2% 302 Table 1 (continued) 257 4,4'-dibromobiphenyl g 50.2% 3492174-be dibenzoyl biphenyl 1 50.2% 349235 dibenzoylmethane g 50.2% 3492142-biphenylcarboxylic acid g 50.2% 34 9268 Dibenzothiophene g 50.3% 302298 Pentafluoro Phenol g 50.3%? 3o2258 Benzophenone 1 50.4% 274263 +-Hensil-2. Pyrrolidinone g 50.4% 30223 39-fluorenone g 50.4% 3022022-benzoylnaphthalene g 50.5% 3492241-bromonaphthalene g 50.6% 27 4272 diphenyl sulfide = s 49.4% 274254 1, 3- Diphenoxybenzene = s 50.0% 274274 Fluorene = s 5 0. 1% 274205 Tetraphenylmethane = s 50.3% t349 299 Pyrene g 50.0% 273301 9,9'-Bifluorore>g 50.1% 2753051-phenyl-2-pyrrolidinone g 50.0% 　273 fruit 1m day ″′・゛　mu　P.PS’Pa (a) A PPS solution was prepared in the same manner as in Example 1 above, but the solvent was mixed with solvent/non-solvent. The difference is that it has been replaced with a compound.

For example (a) PPS (50%), anthracene solvent (32%) and 1,3.5= ) Riphenylbenzene non-solvent (18%), or (b) PPS (40%), 4-phenylbenzene Solution consisting of phenylphenol solvent (35%) and sulfolane non-solvent (15%) may be cast on a flat surface at elevated temperatures. Solvent/non-solvent mixture to toluene, chloride Remove with a solvent such as methylene or in the case of (b) with aqueous potassium hydroxide to a thickness of approximately 20 mm. Mill porous membranes may be produced.

The polyphenylene sulfide used in later examples was obtained from Quantum, New Chassis. HOECHST Fortron Grade 30 obtained from Celanese It was 0. The viscosity of this polymer is approximately 7000 poise at 300°C. Po The melting point of the remer was 281° C. as determined by differential scanning calorimetry (DSC).

How many times will it be carried out? ε-Caprolactam゛゛　PPS Pa Cram school sex and video acquisition (A) PPS and water-soluble ε-caprolactam were weighed and placed in a mechanical stirrer and Placed in a 2L resin kettle equipped with a heating mantle. PPS weight % in mixture was 50%. The mixture was heated to 260 °C under N2 atmosphere to ensure complete dissolution. Ta. The homogeneous mixture was then cooled. A portion of the mixture is equipped with a spindle number 4C. Transferred to a heated Brookfield Viscometer Model RVT. Viscosity at some temperatures The degrees were recorded at a spindle speed of 20 RPM. As follows.

1st degree uni student, 1st grade private school, 1st grade, 1st grade (B) Solution of PPS and diphenylsulfone (DPS) All methods of Example 1 (A) and It was prepared in the same manner and heated to 290°C. DSC the cooled polymer solvent mixture. Testing was performed to determine the depressed melting point (TM) of PPS. As follows.

%PPS　DPS%　Workyyu℃1 By DSC, a sample of 40% PPS in diphenylsulfone started to reach a temperature of 207°C. It was recrystallized. This is a temperature below the depressed melting point of PPS, where a film of PPS and solvent forms. We have shown that it can be manufactured.

Example 1 (A) A mixture of PPS and aqueous alkali soluble 4-phenylprenol It was prepared in the same manner as in the above method and heated to 270°C. The concentration of PPS in the mixture is 50% Met. The mixture exhibited a depressed melting point of approximately 264°C.

Tips and tricks 1 PPS and diphenyl sulfone DPS is 30% PPS and diphenyl sulfone Prepare the mixture in a 2oz (= about 57g) bottle and dry the bottle at 290°C. Placed in the oven for approximately 40 minutes.

The 290° C. solution was then cast onto a preheated metal plate. Cast the second one immediately. covered with a metal plate. The composite was cooled on a heated aluminum block and allowed to warm up. still Remove the upper metal plate while it is still warm and remove the disc from the PPS/DPS film. I cut out the screen. The membrane was leached in acetone for 1 hour and then dried. Membrane selection The porosity and pore size were determined. The final thickness of the membrane was approximately 10 mils.

N2 flow rate=FN2=42　X　I　0-2cc/cm"sec・cmHg, water flow rate= FH20=’l l　X　10’ml/hour・M2・cmHg, average pore size=O, 154 microns, Maximum pore size = 0.298 micron.

As can be seen from Figure 7, as the temperature of the aluminum plate used for casting PPS increases, Therefore, the nitrogen selective permselectivity of the final cooling film also increases. This effect is due to the rapid release of solvent during processing. It is most effective under experimental conditions where the solvent is removed by vaporization.

This kind of method of rapidly vaporizing the solvent can be of great importance in the production of asymmetric membranes.

The same applies to the alternative methods of Examples 1(A) and 1(B), for example.

FIG. 4 is a type of nodular bulk structure with liquid/solid phase separation.

Figure 5 shows a type of vesicular bulk structure due to liquid/liquid phase separation, and the nodular bulk structure shown in Figure 4. Alternatively, the fabrication of the vesicular bulk structure of FIG. 5 depends on the desired use of the final membrane. This method It is possible to suitably condition these membranes using

Disaster treatment doctor Yu ε-caprolactam in the same manner as in Example 2 for PPS and 7 ε-caprolactam. Membranes were prepared by casting a 30% PPS solution in lactam onto a metal plate.

Epsilon-caprolactam was extracted from the membrane by washing in water at 40°C for 2 hours. membrane final The thickness was approximately 10 mils.

N2 flow rate = FN2 = 7XIO-2cc/cm” seconds cmHg, water flow rate = FHzO =1.5XI O’ml/hour・M2・cmHg, average pore size=0.159 micro hmm, Maximum pore size = 0.272 micron.

implementation crab PPS and Alka IG'・4-phenyl trinounihihe O membrane A 30% PPS solution in 4-phenylphenol was prepared on a metal plate as in Example 2. Cast into a membrane. The cast membrane was allowed to air cool to room temperature. 40℃ Phenylphenol was removed by washing in 3% NaOH solution for 1-172 to 2 hours. Extracted. The dried membranes were then evaluated for permselectivity and pore size. The final thickness of the membrane is It was approximately 6 mils.

N2 flow rate = FN2 = 22X10-2cc/cm” seconds cmHg, water flow rate = FH2 0 = 5XIO’cc/hour・M”・cmHg, average pore size=0.349 micron , Maximum pore size = 0.925 micron.

Souse Dango D P 8 60% PPS Text 7. Prepare a 60% PPS solution in DPS. Ta. The membrane was produced by casting the solution onto a glass plate and then dipping the plate into the liquid. . After soaking, the membrane was leached and dried as described in Example 2. Cooling (quench) The dramatic effects of solution properties and temperature are illustrated by the following two experiments.

Example 5 (A): Cooled in 0°C water, FN2=5X10-7cc /cm” seconds・cmHg.

Example 5(B): Cooled in a glycerol solution at 150°C, FN2=5XI O-'cc/cm2・sec・cmHg.

Thus, the effect of thermoglycemic cooling increases the permeability to N2 by a factor of 1000. I added it. The N2=5X10-4 membrane was distinctly asymmetric in character. Grise The side (surface) in contact with the roll is "shiny", while the surface facing the glass is It was completely dull in contrast.

Tsimchuan PS Pomer's A schematic diagram shows the membrane tensioning steps at various steps of the method.

This step may be used to modify the pore size, pore size distribution, permeability, or tension properties of the membrane. stomach. The membrane may be stretched before, during or after the leaching step.

6(A) Tensile polymer before leaching A 60% PPS solution in DPS was prepared. Cast on a glass plate Membranes were produced at various thicknesses using Since DPS is not soluble in water, the membrane remains unleached when removed from water. film A small piece of was cut into rectangular shapes for tensile experiments. Approximately 20 seconds in glycerol at tensile temperature The piece was dipped and then pulled until it broke. The maximum tension before tearing is listed.

1 degree ℃ side fear % Ku The membranes subjected to the stretching process had significantly improved tensile properties relative to the unstretched samples.

The stretched sample is flexible and easier to handle without tearing compared to the unstretched sample. It was possible to bend it.

6(B) Post-leaching tension at elevated temperature Membranes were prepared from a 60% PPS solution in DPS as described in Example 6(A).

The membranes for this experiment were cast at a thickness of 5 mils and immediately cooled in water at 40°C. film was leached in acetone and then dried. Temperature glycerin to pull the leached membrane It was immersed in a bath and then pulled to maximum tension until it broke. The membrane pieces are initially 4. Oc m length, and was pulled at a speed of 15 cm/min. The maximum tension obtained is; The membranes subjected to the process had significantly improved tensile properties relative to the unstretched samples. Pulled The stretched specimens are flexible and can be handled and bent without tearing compared to unstretched specimens. It was possible.

6(C) Tensile leached film at room temperature Membrane prepared as in Example 6(B) produced and leached. The Tg of PPS is 88°C, but if the proper liquid is selected The leached microporous membrane can be stretched even at room temperature. Obtained in chloroform at room temperature Maximum tension as a function of residence time in chloroform before tension is attempted Decided.

in chloroform 60 seconds 28 Acupuncturist J Examples 6A and 6B above illustrate the improvement in tensile properties of membranes subjected to a stretching (stretching) process. It's clear. Furthermore, the permselectivity of the membrane was tested with and without the pre-leaching tensile process. I tried it. Membranes were prepared from 60% PPS solution in diphenyl sulfone (DPS). Ta.

The membrane was cast at 5 mil thickness and then cooled in 40°C water. The membrane is described in Example 6. Leached and dried as shown.

7A-(No tension process) FN2= 6.0×l0-7cc/cm2・sec-cmHg, 6, 4×10’cc/ cm2°sec - cmHg.

Thus, the tensile process that improves the tensile properties of the membrane did not adversely affect the permeability. .

The pre-leaching tensile step is important and its beneficial effects are due to the membrane (hollow fiber or film) ) is preferably continuously handled prior to the leaching step. two membrane samples were prepared, both by cooling PPS/DPS in water at 40°C. . One side of the membrane was placed in a glycerin bath at 110°C for approximately 60 seconds without tension. Ta. The second membrane was placed face-up in a glycerin bath for the same amount of time and was stretched 10% during immersion. Untensioned They improve the tensile properties of the membrane (tensile and unleached) for the sample. This is shown by comparing the extent to which the surface can be deformed without shattering, cracking, or damage. sample was cut to a length of about 4.5 inches x 0.25 inches (= about 11 x 6 cm).

Each sample was bent into a ring until it broke. The degree to which the sample can be bent without breaking Defined by the annular radius (R-C) of the film. Please refer to FIG.

Figure 6 is a quantitative test of raw or leached membranes.

The distance d is a key parameter. The results were as follows: Cooling - (glycerol bath treatment, no tension) - Unleached - RC-d/　2　=　1 ．． 5mm.

Cooling - (10% tension in glycerol bath) - Unleached - RC - 〇, 75° Films stretched in this way are easier to handle and process than unstretched samples. I was able to understand.

Aiming at the foot of the mountain”A engineer PPS　ε-CLTA　Rolactam　Neem 12g of PPS powder (for Tron 0300-BO) and 28 g of tCLTA (Tm = 70°C, b, p, = 280° C.) was placed in a glass bottle and sealed with a small piece of aluminum foil and wire.

Samples in glass bottles were placed in a forced drying oven at 275°C. PPS is about 30 It dissolved in 45 minutes. The solution was thoroughly mixed by rotating the bottle. a pair of aluminum The aluminum substrate was kept at room temperature, 100°C, 200°C, or 275°C. 30 at 275℃ %PPS solution was poured onto one side of the substrate. Pour and immediately cover the mixed solution with another substrate. Pressure was applied to produce sheets with a thickness of 0.5 to 1 mm. After cooling to room temperature, these two The original mixture sheet was immersed in a water bath for 12 hours to leach out the ε-CLTA, then for 6 hours. Vacuum dried. This casting method is a two-roll film extrusion method (implemented). (see the method of Example IB).

The sample produced by this pour-and-press method has two different regions on its air side surface. area and area■), which are suitable for the rapid vaporization of the solvent removed by the pour-and-press method. It depended on it. The molten mixture takes on a hemispherical shape after being poured onto the bottom substrate, and The solvent continued to evaporate rapidly from the surface until the upper substrate was pressed down. upper board When pressed, the molten mixture flows outward and the previously unexposed portion of the molten mixture forms a base. It came into contact with the board. When covered, the PPS binary is removed without further loss of solvent. Solidification of the mixture occurred. This solidification results in two different regions of the poured and pressed sample. caused to arise. Region ■ is located in the center of the sample, where air is absorbed prior to assimilation. Rapid evaporation of the solvent from the side surfaces occurred. The membrane produced from this area is on the air side. It had dense 5kin on the surface. In region ■ surrounding region I, melting occurs. Solidification of the newly exposed (squeezed) molten mixture occurred without loss of medium.

The membranes prepared from the region had no skin on the air side surface.

225 ■ Five hill value The PPS membrane thus obtained was tested for nitrogen permeability and water permeability. Hole size Distribution was determined by bubble point measurement method (ASTM F316-86). Conclusion The results are summarized in Tables 3 and 4 below.

Table 1 ′・Bipa・　1″′ 30 Room temperature Area I 6.22E-4 30 room temperature area II 1.72E-2 30100 area I 1.35E-3 30100 Area I [1,95B-21,56E+330 200 Area I 5. 09E-330200 Area II 4.26B-25,92E+330 275 Area I 1.93E-2 Not measured 30 275 Area n 3.56E-2 Not measured 3 0 (200℃ solution) 200 Area I 2.06E-2 Not measured 30 (200℃ Solution) 200 Area II 3.13B-2 Not measured 40 (d) 200 Area I t 1.54E-2 Not measured 35 (d) 200 Area n 1.69E-230 (d) 200 Area II 4.26E-25,92E+325 (d) 20 0 Region II 7.04E-22,70E+3a) Region 1: Rapid vaporization of solvent Therefore, the membrane had a surface skin (one side).

Area ■: The film does not have a surface skin because the rapid evaporation of the solvent is suppressed.

b) cc/sec・0m2・cmHg c) cc/hour゛m2°cmHg d) Values are for formulated compositions.

topsoil Kong J Ging J Bing self value 275℃ solution, 200℃ substrate 0.320.1430/70PPS/e-CLT A 275℃ solution, 100℃ substrate 0.1425n5 PPS/e-CLTA 275℃ solution, 200℃ substrate 0.33 0.07 value is after water flow rate test, i.e. Obtained after exposure to high pressure.

Based on these results, microporous PPS can be obtained from binary PPS mixtures with low molecular weight solvents. Controlling the type and extent of thermally induced phase separation is critical to producing membranes. is important. By controlling the cooling rate, the solidification behavior of PPS is controlled. PPS films with favorable properties can be produced. Solvent flush during production ・Off (rapid evaporation) effects must be minimized to prevent dense surface skin formation. stomach. However, this phenomenon can be exploited to produce asymmetric membranes with a thin skin on one side. I can do it.

Oudo Jyu 1e Polyphenylene sulfide and ε-caprolactam CLTA combination: with polymer A homogeneous polymer is produced by heating the solvent mixture to a temperature sufficient to melt and mix both components. - A solvent mixture was prepared. This is a heated 2L nitrogen applied resin kettle.

and the mixture was made using a motor-driven vane. The minimum temperature for the production of mixtures is polymer is the depressed melting point of the solvent mixture.

To ensure rapid mixing, the temperature should be raised to 1 degree above the melting point of the pure polymer. can be done.

-5n order 5: In this example, two Pyrex casting plates were used. There is. Pour the molten PP5-molten mixture into the heated first plate. P the first plate Maintain above the solidification temperature of the P5-solvent mixture, then the solution (casting - Cast along the first plate (using a bar) to the second cooling plate. this The procedure mimics the film extrusion of the process of Figure 1(A).

The experimental details of the casting procedure are as follows: Gai Cast Film pm= (1) Turn the oven to the melting and first plate temperature and the drying oven to the second plate temperature. Preheat to yeast temperature.

(2) Place a l/8 thick aluminum sheet on the inside of the two hot plates. (See Figure 1).

(3) Set the hot plate to casting temperature (setting is not absolute).

(4) Attach a Pyrex glass plate (6-172″ x 8″XI/8″) Clean with a button.

(5) Casting with appropriate gap (3 mil to 20 mil) for desired film thickness Choose a bar. Clean the bar thoroughly (casting bar radius = 6 inches) .

(6) Weigh approximately 40 g of mixed granules into a 202 (= approximately 57 g) glass bottle, The mouth of the bottle is then sealed with an aluminum fan and a plastic cap.

(7) Glass bottle containing mixed granules and a clean first glass plate (with caps on the surface) (with Sting Bar on top) in the preheated oven and place the second glass plate on a drying oven. Place it in the oven. The mixture melts in 3 to 5 minutes and is placed on a glass plate and caster. The casting bar reaches casting temperature.

(8) After about 15 minutes, remove the first glass plate from the furnace and place it on the second glass plate. Remove the sheets from the drying oven and place them on an aluminum hot plate. Place it on the sheet. Allow the glass plate to equilibrate with the top of the hot plate. .

(9) Take out the casting bar from the furnace and place it on the first glass plate.

(lO) Remove the bottle containing the molten mixture from the furnace and immediately Remove the cap and all boxes from the bin.

(11) Spread the molten mixture onto the surface of the first glass plate before the casting bar. Pour into.

(12) Move the casting bar into the mass of the mixture in a smooth and quick motion. 1 glass plate to a second cooling plate.

(13) Allow the mixture to cool for 60 seconds on a glass plate to solidify the film. let Separate the glass plates using a razor blade and then remove the newly formed Peel the film off the second glass plate.

Christ film Kawa B' Step B' is similar to step A' but with an electric heating plate and supporting aluminum plate. The difference is that it does not use a root.

The glass plates are heated in a furnace or oven to different temperatures. (different temperatures) Remove the first and second plates and place them on unheated ceramic tiles. P When the temperature of the plate reaches the desired temperature, cast the film as in step A'. (See Table 5 below).

Real W PPS DPS knee 6 12g PPS powder (Fortron 0300-BO) and 28g Diphenylus Ruhon (DPS, Tm = 128℃, i), p, = 379℃) in a glass bottle. Placed and sealed with a small piece of aluminum foil and wire. 310 samples in a glass bottle Placed in a forced drying oven at °C. The PPS dissolved in about 30 to 45 minutes. B The solution was thoroughly mixed by rotating the tube. A pair of substrates (aluminum, Teflon, or (glass) was kept at room temperature, 100°C, and 200°C. 30% PPS solution at 310°C was poured onto one side of the substrate at the indicated temperature. Immediately pour the mixed solution into another at the same temperature. A sheet with a thickness of 0.5 to 1 mm was produced by covering with a substrate and applying pressure. cool to room temperature After cooling, this binary mixture sheet was immersed in an A7 bath for 2 hours to leach out the DPS, and then It was vacuum dried for 2 hours.

And daytime 1Ω still and slight The PPS membrane thus obtained was tested for nitrogen permeability. Pore size distribution is bubble Determined by point counting method (ASTMF316-86). The results are shown in Table 6 below. summarized in. Figure 7 shows the top and bottom bases for cooling the molten PPS/solvent mixture. It shows the effect of plate temperature. The nitrogen permeability of the final leaching membrane is changing. General The higher the cooling temperature, the higher the nitrogen permeability (and Fig. 1 (A), (B) or 2 ( B).

deep red P S DPS at cold '5 (℃) (cc/sec"cm"cmHg) t micron) (micron) 25 1.34*10-3 200 6.03 out of 10' 25 1.50 umbrella 10゛4 Extrusion 25 6.81 Umbrella 10' <0.13 - Disaster 1 S and diphenyl sulfone DPS A permselective membrane was produced by adapting the procedure described in Example 8(B). Proportions and physical properties The properties are shown in Table 7 below. Figure 8 shows the final leached PPS membrane by varying the effective cooling temperature. shows the effect of on nitrogen permeability. These PPS/DPS films were Example 8(A) Or produced by adapting the process of 8(B). In general, the higher the cooling temperature, the lower the , l (B), 2 (A) and 2 (B) also have high nitrogen permeability using the treatments shown in .

FIG. 9 is a graph showing the water permeability of a 30/70 PPS/DPS mixture. Figure 9 is The temperature effect of liquid solution cooling on the final water permeability of the leached membrane is shown in Figure 2(A) or 2(B). ). When the cooling temperature is high, the final leaching membrane water High transparency.

Actual difference jLL needlework An DPTP, DPIP and commercially available PPS and diphenyl phthalate DPP DPTP/DP I　P mixture (75%/25%) mixed with PPS (50150 W/W) to 315°C for 20 minutes, allow to mix passively, then mix Stirring was achieved by gentle mixing motions of the filled glass jar. All samples are the same It had a translucent amber color. Translucency is a good visual confirmation of miscibility. coagulation The mixtures all then had the same dark/light brown color. DP I P/DPTP mixture Differential scanning calorimetry (DSC) thermograph shows that PPS is DPIP/DPTP mixed The melting point for complete dissolution in the substance decreased from 24°C. Observed melting point depression and reconsolidation The crystal temperature is similar to that of diphenyl sulfone, a substance known as a good solvent for PPS. It's pretty much the same. See Figure 8.

Special Table Sen7-500527 (21) Figure 10 shows the nitrification of PPS films of PPS/DPIP binary mixture as a function of cooling temperature. This is a graph of elementary permeability. Figure 10 shows the results obtained by processing in Figure 1 (A) or 1 (B). The effect of cooling plate temperature on the nitrogen permeability of the final leached membrane as prepared ing. Generally, the higher the cooling temperature, the higher the nitrogen permeability.

Figure 11 shows the water content of PPS membranes of PPS/DPIP binary mixtures as a function of cooling temperature. This is a graph of transparency. Figure 11 shows the final Figure 3 shows the effect of cooling plate temperature on the water permeability of the leached membrane. Generally cooling temperature The higher the degree, the higher the water permeability.

Execution torso side 1 top PPS and diphenyl isophthalate according to the procedure described in DPIP Example 8(B) (see conditions in Table 5). Table 8 shows the PPS/DPIP mixture.

Traditional land of the Yi tribe Ri and S and V Dan■5 Micronized by extrusion of the PPS/diphenylsulfone primary mixture followed by acetone leaching. A porous PPS membrane was produced. The results are summarized below.

30 or 40% by weight PPS powder and 70 or 40% by weight diphenyl sulfone Mixed freely in a plastic bag.

This powder mixture was mixed in a KOCH static mixer with 4-172 mixing units and 2 and l/4 width. It was extruded with a twin screw with a slit mold. Temperature characteristics and other operating conditions It is shown in Table 9 below.

The extruded mixture was cooled on the surface of an aluminum roller. This elution is close to 1 was operated at a speed that produced a tensile ratio of . 30/70 PPS/DPS mixture is Extrusion is difficult due to the low viscosity of I had to constantly adjust it.

For this reason, the shear rate at the mold tip could not be determined. Approximately 1 to 0.5 mm Films with widths between 0.5 and 1 mm and thicknesses between 0.5 and 1 mm were obtained. extruded film was further processed in the same manner as in the above section. The extrusion process and settings are conventional.

Back road po LLz Ee JJI usage price The PPS membrane prepared in Example 11 was tested for nitrogen permeability. their pore size Distribution was determined by bubble point measurement (ASTMF316-86). result are summarized below (see further Figure 7).

Composition Cooling temperature N2 flow rate Maximum pore size Average pore size ('C) (cc/sec Umbrella cm2 Umbrella cmHg) (micron) (micron) 3000 25 6.81” IO' <0.13 -40/60 25 1.67 Umbrella 10-' <0.13 - Water flow rate measurements and bubble point measurements were not performed.

The maximum pore size is determined by the maximum pressure that can be set (70 psi) without any bubbles. did.

See table above.

Implementation history 1 PPS NCHP'-'- 0.6 g of PPS powder was added to 4 g of N-cyclohexyl-2-pyrin according to the following procedure. Mix with a solvent consisting of lolidone and 2 g of α-chloronaphthalene.

Ph1lips registered trademark Rydon P-6 in powder form from Petroleum , secure the PPS and mix with the specified solvent. 5ybron solvent and PPS Maximum setting on Nuova-II hot plate (surface temperature becomes approximately 290℃) to dissolve the PPS. Continue heating until the solution turns clear and dark brown.

A glass plate was preheated on a hot plate. Glass plate heated with PPS solution It was cast in the form of a flat sheet membrane onto a plate and then cooled to room temperature.

After casting and water washing, the membrane was washed in excess acetone for 30 minutes and then dried. Ta. The dried film appeared white and opaque. Figure 12 shows the air contact of the membrane formed in this way. This is a scanning electron micrograph of the surface.

1 cm of SEM scale is 0.89 microns. Interconnecting pore structure revealed from electron micrographs it is obvious. The pore size visible in electron micrographs ranges from 0.2 to 0.8 microns. be. Membranes are useful for microfiltration.

Ijongshu Jodo PPS NCHP'Paka 1 0.6g of PPS released (destination - high molecular weight) was mixed with 6 cc of NCHP in a glass bottle. The mixture was prepared in the same manner as in Example 12. The film was cast according to the following steps. The membrane is white and transparent, and the water contact surface is shiny. Looked. Several films were made with varying times between casting and soaking. Am The flow rate and filterability were tested using a 1con 50cc stirring cell. Retention % is purple Evaluation was based on external light (UV) absorption. The result is: Molecular weight - 360,000 Fruit 1 ke Lmdan DanfJ11 closing system Experiments using various concentrations of PPS and solvent are listed in Tables 10 and 11 below. Table 10 In the experiment, the mixing temperature was 260'C. However, PPS/DPS is an exception at 280℃. be.

Mixing time was approximately 1 hour.

As a footnote to Tables 10 and 11, (a) The flexibility of the leached polymer here is ``bendable'' for easier handling. means "ability".

(b) Tensile strength of the leached membrane.

(c) Regarding leached membranes.

(d) The immature strength is the flexibility of the unleached membrane immediately after the casting process (the polymer is warm, and cool). If the immature strength is high, it will be difficult to handle later or during processing. It's easier.

In Table 11, the first six experiments were conducted at 280°C for 1 hour. The last 6 experiments are 26 The test was carried out at 0°C for 1 hour. The footnotes in Table 11 are the same as in Table 1O. The results are specific to the evident under the reaction conditions. The acceptability of the results may be improved by conducting additional experiments. .

Although only a few aspects of the invention have been presented and described herein, those skilled in the art Moldings, preferred permselective fibers or dissolve poly(phenylene sulfide) to form a film membrane or product It will be apparent that various modifications and changes may be made to the compounds and methods.

All such modifications and changes within the scope of the appended claims are included within the scope of the appended claims. It will be done.

Figure 1A Figure IB Figure 2A Figure 3 0 1.00 200 300 Temperature (’C) Figure 4 Liquid-solid phase separation and the resulting nodular bulk porous structure 30/70 PPS/ε-CLTA Cast on a glass plate at room temperature (5000x) Figure 5 Liquid-liquid phase separation and its The resulting vesicular bulk porous structure 30/70 PPS/DPS Cast on a glass plate at room temperature (5000x) ■ Figure 7 Effect of cooling conditions on nitrogen permeability 0 100 2o.

(Phase 1, slope 1, -/kuku) m 1!2*Figure 10 Nitrogen permeability of pps membranes made from PPS/DPIP binary mixtures Temperature ('C) Manufactured from PPS/DPIP binary mixture Water permeability of pps membrane Temperature (’C) Arts and crafts 1 Figure 1 2 (Scale 1cm = 0.89 microns) International investigation report Continuation of front page (51) Int, C1, 6 identification code Office reference number DOIF 6100B 7199-3B6/76D 7199-3B (72) Inventor Wang, Hawk Varnish 94509 Antioch Field Frest for California, USA Way 4627 (72) Inventor Chow, Chae-Chun Minnesota, USA 48640 Midland Boulevard Street 4205 (72) Inventor Finney , Timothy M. Freeland Hot, Michigan, USA 48623 Chikis Street 1810I (72) Inventor: Wessling, Ritchie, California, USA 94707 Bakery Shirtless Avenue (72) Inventor Kawamo Tojiro 94596 Walnut Creek Benha for California, USA Mu coat 2345 (72) Inventor: Sonnenschen, Mark F. California, USA For 94598 Anti-Oc Bliza Drive 3512

Claims (1)

[Claims] 1. (a) forming a mixture comprising at least one solvent for (i) poly(phenylene sulfide) (ii) poly(phenylene sulfide); and (b) rendering the mixture homogeneous with a viscosity sufficient to form a film. (c) extruding or casting the homogeneous fluid into a film; and (d) applying the film to one or more regions under physical conditions that solidify the film. Cool or condense the membrane through and (e) simultaneously or sequentially subjecting the membrane to one or more regions under conditions in which at least a substantial amount of the solvent for the poly(phenylene sulfide) is removed from the membrane. A method for producing a permselective microporous membrane containing poly(phenylene sulfide), characterized in that the permselective membrane thus obtained has a microporous structure. 2. The solvent is 4,4'-dipromopyphenyl, 1-phenylnaphthalene, phenol Thiazine, 2,5-diphenyl-1,3,4-oxadiazole, 2,5-diph phenyloxazole, triphenylmethanol, N,N-diphenylformamide de-, m-terphenyl, benzyl, anthracene, 4-benzoylbiphenyl, dibenzoylmethane, 2-piphenylcarboxylic acid, dibenzothiophene, pentachlorophenol, benzophenone, 1-benzyl-2-pyrrolidione, 9-phenyl Luorenone, 2-benzoylnaphthalene, 1-promonaphthalene, diphenyl Ruphide, 1,3-diphenoxybenzene, fluorene, tetraphenylmethane, p-quarterphenyl, 1-phenyl-2-pyrrolidinone, 1-methoxyna Phthalene, hydrogenated or partially hydrogenated terphenyl, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4-dibenzoylbutane, phenanthrene, 4-benzoylpiphenyl, 0-terphenyl, 1,1-diphenyl Acetone, 0,0'-pyphenol, 2,6-diphenylphenol, 1,2,3-triphenylene Nylbenzene, triphenylene, 4-promopiphenyl, 2-phenylphenol ole, thianthrene, 4,4'-diphenylbenzophenone, 3-phenoxybene dill alcohol, 4-phenylphenol, 9,10-dichloroanthracene, p-terphenyl, 2-phenoxypiphenyl, triphenylmethane, 4,4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluora Nthene, diphenyl sulfone, diphenyl phthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-promo diphenyl ether, pyrene, 9,9'-peafluorene, 4,4'-isopropylene Pyrlidene diphenol, 2,4,6-trichlorophenol, epsilon-caprolactam, N-cyclohexyl-2-pyrrolidone, diphenyl isophthalene 2. The method of claim 1, wherein the organic compound is independently selected from the group consisting of salt, diphenyl terphthalate, and mixtures of these compounds. 3. 3. The method of claim 2, wherein the solvent is independently selected from diphenylsulfone, N-caprolactam, or N-cyclohexyl-2-pyrrolidone. 4. The solvent is N-cyclohexyl-2-pyrrolidone, and in step (b) 2. The method of claim 1, wherein the homogeneous fluid is heated for a time and at an elevated temperature sufficient to change the color of the homogeneous fluid from light to dark (tan). 5. further (a) before, during and/or after the leaching step (e), stretching the membrane at ambient temperature or above and below the melting point of the poly(phenylene sulfide) or the depressed melting point of said mixture; and Induces orientation of polyphenylene sulfide 2. The method of claim 1, further comprising the step of stretching the membrane so as to 6. The solvent is 4,4'-dipromopyphenyl, 1-phenylnaphthalene, phenol Thiazine, 2,5-diphenyl-1,3,4-oxadiazole, 2,5-diph phenyloxazole, triphenylmethanol, N,N-diphenylformamide Do, m-terphenyl, benzyl, anthracene, 4-benzoylbiphenyl, dibenzoylmethane, 2-piphenylcarboxylic acid, dibenzothiophene, pentachlorophenol, benzophenone, 1-benzyl-2-pyrrolidione, 9-phenyl Luorenone, 2-benzoylnaphthalene, 1-promonaphthalene, diphenyl Ruphide, 1,3-diphenoxybenzene, fluorene, tetraphenylmethane, p-quarterphenyl, 1-phenyl-2-pyrrolidinone, 1-methoxyna Phthalene, hydrogenated or partially hydrogenated terphenyl, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4-dibenzoylbutane, phenanthrene, 4-benzoylpiphenyl, 0-terphenyl, 1,1-diphenyl Acetone, 0,0'-pyphenol, 2,6-diphenylphenol, 1,2,3-triphenylene Nylbenzene, triphenylene, 4-promopiphenyl, 2-phenylphenol , thianthrene, 4,4'-diphenylbenzophenone, 3-phenoxyben dial alcohol, 4-phenylphenol, 9,10-dichloroanthracene, p-terphenyl, 2-phenoxypiphenyl, triphenylmethane, 4,4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluoran Thene, diphenyl sulfone, diphenyl phthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-promodi Phenyl ether, pyrene, 9,9'-pyfluorene, 4,4'-isopropylene Luridane diphenol, 2,4,6-trichlorophenol, epsilonka Prolactam, N-cyclohexyl-2-pyrrolidone, diphenyl isophthalate and diphenyl terphthalate, and mixtures of these compounds. 6. The method according to claim 5, wherein the method is selected based on 7. 7. The method of claim 6, wherein the solvent is independently selected from diphenylsulfone, N-caprolactam, or N-cyclohexyl-2-pyrrolidone. 8. (a) a mixture consisting of (i) poly(phenylene sulfide) (ii) at least one solvent for the poly(phenylene sulfide); and (iii) at least one non-solvent for the poly(phenylene sulfide). (b) heating the mixture to a temperature under conditions to form a homogeneous fluid of sufficient viscosity to form a film; and (c) extruding or extruding the homogeneous fluid into a film. (d) cooling or solidifying the film through one or more regions under physical conditions that solidify the film; and (e) simultaneously or sequentially applying poly(phenylene sulfate). under conditions such that at least a substantial amount of the solvent and non-solvent for the The method includes the step of leaching the membrane through one or more areas containing the membrane. The semipermeable membrane obtained by A method for producing a selectively permeable microporous membrane containing sulfide. 9. The solvent is 4,4'-dipromopyphenyl, 1-phenylnaphthalene, phenol Thiazine, 2,5-diphenyl-1,3,4-oxadiazole, 2,5-diph phenyloxazole, triphenylmethanol, N,N-diphenylformamide Do, m-terphenyl, benzyl, anthracene, 4-benzoylpiphenyl, dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, pentachlorophenol, benzophenone, 1-benzyl-2-pyrrolidione, 9-phenyl Luorenone, 2-benzoylnaphthalene, 1-promonaphthalene, diphenyl Ruphide, 1,3-diphenoxybenzene, fluorene, tetraphenylmethane, p-quarterphenyl, 1-phenyl-2-pyrrolidinone, 1-methoxyna Phthalene, hydrogenated or partially hydrogenated terphenyl, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4-dibenzoylbutane, phenanthrene, 4-benzoylpiphenyl, 0-terphenyl, 1,1-diphenyl Acetone, 0,0'-pyphenol, 2,6-diphenylphenol, 1,2,3-triphenylene Nylbenzene, triphenylene, 4-promopiphenyl, 2-phenylphenol , thianthrene, 4,4'-diphenylbenzophenone, 3-phenoxyben dial alcohol, 4-phenylphenol, 9,10-dichloroanthracene, p-terphenyl, 2-phenoxypiphenyl, triphenylmethane, 4,4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluoran Thene, diphenyl sulfone, diphenyl phthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-promodi Phenyl ether, pyrene, 9,9'-pyfluorene, 4,4'-isopropylene Luridane diphenol, 2,4,6-trichlorophenol, epsilonka Prolactam, N-cyclohexyl-2-pyrrolidone, diphenyl isophthalate and diphenyl terphthalate, and mixtures of these compounds. 9. The method according to claim 8, wherein the organic compound is a randomly selected organic compound. 10. The non-solvent is 1,3,5-triphenylbenzene, tetraphenylsilane, diphenyl sulfoxide, diphenic acid, 4-acetylpiphenyl, pipendi. diphenyl methyl phosphate, triphenyl phosphate, cyclohexyl Ruphenyl ketone, mineral oil, butyl stearic acid, phenyl benzoate, 1-phenyldecane, 1,3-diphenoxybenzene, 1,8-dichloroanthrachloride Non, polyphosphoric acid, dioctyl phthalate, 5-chlorobenzoxazolone, pisu(4-chlorophenylsulfone), diphenylchlorophosphate, sulphate Ruforan, methyl myristate, methyl stearate, hexadecane, dimethyl phthalate, tetraethylene glycol dimethyl ether, diethylene glycol Claim 9, wherein the compound is independently selected from the group consisting of dibutyl ether, docosan, dotriacontane, tetraphenylene, pentafluorophenol, paraffin oil, 1-methyl-2-pyrodinone, and 4,4'-dihydroxybenzophenone. Method. 11. The non-solvent is 1,3,5-triphenylbenzene, tetraphenylsilane, diphenyl sulfoxide, diphenic acid, 4-acetylpiphenyl, pibenzi diphenyl methyl phosphate, triphenyl phosphate, cyclohexyl Ruphenyl ketone, mineral oil, butyl stearic acid, phenyl benzoate, 1-phenyldecane, 1,3-diphenoxybenzene, 1,8-dichloroanthrachloride Non, polyphosphoric acid, dioctyl phthalate, 5-chlorobenzoxazolone, pisu(4-chlorophenylsulfone), diphenylchlorophosphate, sulphate Ruforan, methyl myristate, methyl stearate, hexadecane, dimethyl phthalate, tetraethylene glycol dimethyl ether, diethylene glycol independently selected from the group consisting of dibutyl ether, docosan, dotriacontane, tetraphenylene, pentafluorophenol, paraffin oil, 1-methyl-2-pyrodinone, 4,4'-dihydroxybenzophenone, and mixtures thereof. The method described in Section 8. 12. and (a) before, during and/or after the leaching step (e) at ambient temperature or above the melting point of poly(phenylene sulfide) or the depressed melting point of the above mixture. 9. The method of claim 8, further comprising the step of stretching the film at a lower temperature than that of the polyphenylene sulfide and stretching the film to induce orientation of the polyphenylene sulfide in the film. 13. The solvent is 4,4'-dipromopyphenyl, 1-phenylnaphthalene, Notiazine, 2,5-diphenyl-1,3,4-oxadiazole, 2,5-di Phenyloxazole, triphenylmethanol, N,N-diphenylformua mido, m-terphenyl, benzyl, anthracene, 4-benzoylpiphenyl, dibenzoylmethane, 2-piphenylcarboxylic acid, dibenzothiophene, pen Tachlorophenol, benzophenone, 1-benzyl-2-pyrrolidione, 9-fluorenone, 2-benzoylnaphthalene, 1-promonaphthalene, diphenyl sulfide, 1,3-diphenoxybenzene, fluorene, tetraphenylmeth p-quarterphenyl, 1-phenyl-2-pyrrolidinone, 1-methoxy naphthalene, hydrogenated or partially hydrogenated terphenyl, 1-ethoxynaphthalene, 1,3-diphenylacetone, 1,4-dibenzoylbutane, Phenanthrene, 4-benzoylpiphenyl, 0-terphenyl, 1,1-diphenylacetone, 0,0'-pyphenol, 2,6-diphenylphenol, 1,2,3-trifhenyl phenylbenzene, triphenylene, 4-promopyphenyl, 2-phenylphenol ole, thianthrene, 4,4'-diphenylbenzophenone, 3-phenoxybene dill alcohol, 4-phenylphenol, 9,10-dichloroanthracene, p-terphenyl, 2-phenoxypiphenyl, triphenylmethane, 4,4'-dimethoxybenzophenone, 9,10-diphenylanthracene, fluora Nthene, diphenyl sulfone, diphenyl phthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-promo diphenyl ether, pyrene, 9,9'-peafluorene, 4,4'-isopropylene Pyrlidene diphenol, 2,4,6-trichlorophenol, epsilon-caprolactam, N-cyclohexyl-2-pyrrolidone, diphenyl isophthalene 13. The method of claim 12, wherein the organic compound is independently selected from the group consisting of salt, diphenyl terphthalate, and mixtures of these compounds. 14. The non-solvent is 1,3,5-triphenylbenzene, tetraphenylsilane, diphenyl sulfoxide, diphenic acid, 4-acetylbiphenyl, pibenzi diphenyl methyl phosphate, triphenyl phosphate, cyclohexyl Ruphenyl ketone, mineral oil, butyl stearic acid, phenyl benzoate, 1-phenyldecane, 1,3-diphenoxybenzene, 1,8-dichloroanthrachloride Non, polyphosphoric acid, dioctyl phthalate, 5-chlorobenzoxazolone, pisu(4-chlorophenylsulfone), diphenylchlorophosphate, sulphate Ruforan, methyl myristate, methyl stearate, hexadecane, dimethyl phthalate, tetraethylene glycol dimethyl ether, diethylene glycol independently selected from the group consisting of dibutyl ether, docosan, dotriacontane, tetraphenylene, pentafluorophenol, paraffin oil, 1-methyl-2-pyrodinone, 4,4'-dihydroxybenzophenone, and mixtures thereof. The method described in item 13. 15. The non-solvent is 1,3,5-triphenylbenzene, tetraphenylsilane, diphenyl sulfoxide, diphenic acid, 4-acetylpiphenyl, pibenzi diphenyl methyl phosphate, triphenyl phosphate, cyclohexyl Ruphenyl ketone, mineral oil, butyl stearic acid, phenyl benzoate, 1-phenyldecane, 1,3-diphenoxybenzene, 1,8-dichloroanthrachloride Non, polyphosphoric acid, dioctyl phthalate, 5-chlorobenzoxazolone, pisu(4-chlorophenylsulfone), diphenylchlorophosphate, sulphate Ruforan, methyl myristate, methyl stearate, hexadecane, dimethyl phthalate, tetraethylene glycol dimethyl ether, diethylene glycol independently selected from the group consisting of dibutyl ether, docosan, dotriacontane, tetraphenylene, pentafluorophenol, paraffin oil, 1-methyl-2-pyrodinone, 4,4'-dihydroxybenzophenone, and mixtures thereof. The method according to item 12. 16. A permselective polymer membrane produced by the method according to claim 1. 17. A permselective polymer membrane produced by the method according to claim 5. 18. A permselective polymer membrane produced by the method according to claim 8. 19. A permselective polymer membrane produced by the method according to claim 12. 20. Poly(phenylene sulfide) microporous permselective membrane with interconnecting pores. 21. Claims in which the membrane is stretched during at least one processing step of its manufacture. Poly(phenylene sulfide) microporous membrane according to item 20. 22. 22. The poly(phenylene sulfide) microporous membrane of claim 21, wherein the membrane is in the form of a hollow fiber or a thin sheet membrane. 23. 23. The microporous membrane of claim 22, having a hydraulic permeability of at least 500 ml/hr.M2.cmHg or more. 24. 23. The microporous membrane of claim 22, wherein the gas flux through the membrane is at least 1.times.10@-5 cm@3 /cm@2.sec.cmHg or greater. 25. 4. The method of claim 3, wherein the solvent in step (a) is independently selected from diphenyl phthalate, diphenyl isophthalate, diphenyl terphthalate or mixtures thereof. 26. Applications for microfiltration with an average effective pore size of 0.05 microns or more A PPS membrane produced by the method described in item 5. 27. The person according to claim 5 whose average effective pore size is smaller than 0.05 micron. PPS membrane for ultrafiltration manufactured by the method. 28. 6. The method of claim 5, wherein the membrane is stretched to a stretch ratio between about 1.05 and about 10. Law. 29. 13. The method of claim 12, wherein the membrane is stretched to a stretch ratio between about 1.05 and about 10. 30. 6. The microporous membrane of claim 5, having a hydraulic permeability of at least 2000 ml/hr.M2.cmHg or more. 31. 6. The microporous membrane of claim 5, wherein the gas flux through the membrane is at least 1 x 10-4 cm3/cm2.sec.cmHg or more. 32. 13. The microporous membrane of claim 12, having a hydraulic permeability of at least 2000 ml/hr.M2.cmHg or more. 31. 13. The microporous membrane of claim 12, wherein the gas flux through the membrane is at least 1.times.10@-4 cm@3 /cm@2.sec.cmHg or greater.