DD272340A1 - EBENFLAECHIGE GROBPORIGE MEMBRANEN FROM ACRYLNITRILPOLYMERISATEN AND METHOD FOR THE PRODUCTION - Google Patents

Abstract

Flat-faced coarse-pore membranes made of acrylonitrile polymers with a uniform pore size in the surface layer and an open-pore structure with pore openings of 10 to 100 mm in the opposite boundary layer. The membranes are characterized by a sharp cut-off and high flow rates and are suitable for the microfiltration of substances or particles from liquids or gases as well as carriers for composite membranes. The process for making these membranes involves the coagulation of a bilayer film formed from the solution of an acrylonitrile polymer and the solution of another incompatible polymer. The surface layer of the polyacrylonitrile membrane is subjected to a certain energy density before or after its separation from the two-layer molding of a treatment with a low-temperature plasma.

Description

For this 2 pages drawings Application of the Irftnduno

The invention relates to membranes made of acrylamide polymer ethers and to processes for the production of rubber. Separating gents and high permeation water solubles for the separation of dissolved and / or ^1- g species from liquids or particles or Qaien.

Cherekteristk de · known covenant ·· the Teehnlk Membranes with a Possible Pore Size · In the Act and not Only from a Theoretical Point of View Upper part of the substance separation behavior on sokh 'n membranes, of interest, but also for practical use

Significantly, they have a narrower cut-off and thus a better fractional effect. Special at the

Microfilters intended to separate only solutes or particles above a particular molecular or particle size

a membrane with very uniform and elongated pores of the effective size arrangement desirable because of the separation capacity and the eritelbsren flow rates.

Ee are already technically very complicated processes known to produce membranes with unitary pores. So that was the The preparation of such membranes is described in the context of self-explanatory Bskterlenprotelnsn, with customary MikroflHer after

a specific method with aqueous suspensions of cell fragments of bacteria are coated (DO-AS 237 793,

M. Sm. U.B. S etyr: J.Membr. Be. »311887) 27-49). Membranes of extracellular synthetic polymers with a relatively uniform pore size have come in the form of

so-called Kemspurfilter iuglnglkh become. In doing so, dl · Foil becomes energized with the focused beam

Radiation radiates punctually and the pores are developed by the same kind of damage at the so-called imperfections. The Asymmetrlegred of these membranes and the number of pores per unit area and, consequently, the fii Nuclear trackers are limited Ee was described to you for the preparation of Dietysemembrenen, directly through in metal parts up to 10000 A holes Readers ·, electron beams or ion beams produce and these holes are subsequently staged to the desired uniform one Narrowing diameter tu, preferably by electrolytic coating and subsequent vapor deposition with Precious metals takes place (DE-OS 2869332, DE-OS 2888408). Although the treatment of membranes of new acrylonitrile polymers has also been described with plasma

However, the formation of a very dense, selective permeable film with increased crosslinking occurred

Surface of the membrane. These processes promote the induction of reverse osmosis selenium by the Compaction of the membrane surface (JP-OS 6488382, DE-OS 2838086, DE-OS 2942783, JP-A 68-206606). These Plasmabetrieblung kenn also be combined with other Behendlungeschritten (DE-OS 2960238, DE-OS 2868138,

DE-OS 2910413).

Coarse-pored membranes new Acrylnltrilpolymoren, in particular suitable for microfiltration membranes with ennlhernd

uniform pore size in the Aktivschkht or processes for the preparation of such membranes have not been described.

Object of the invention

The aim of the invention are ebenfllchlge coarse-pored membranes of Acrylnitrilpotymei Isaten, eufweisen a special morphological structure and thus favorable separation properties at the same time high Permeetflußl. Acting condition as well as a method for economical, technically simple production of such membranes from solutions of Acrylnitrilporymerlsaten.

-2- 272140

Presentation of Weeeni 4m lrflndung Influence of dissolution in the liquid state · In the presence of coarsened coarse-pored "" membrane type in the Aery1nltrllporym "rliitefl mil

• In their morphological membrane structure, adding to the separation line

Predominantly uniform · large · and · ·η · opposite Begrschschht mil «Irw extremely open pores

This means that it is possible to stir up the membrane of the membrane with high speed.

It is therefore technically possible for the preparation of the membrane to be carried out in the case of the preparation of a membrane

and to develop processes on the bail of acrylonitrile solutions.

According to the invention, the task is governed by the fact that the membranes are of new morphological type.

On the other hand, there is a uniform diameter of pore size b in a range of 0.06 Ma 60pm, from 0.9 to 6μ in the area of the surface and a largely open - pored structure the opposite boundary show with

Porous opening diameters of 10 bit 100mm. Upon completion of the invention, the new type of membrane will be achieved by an inert medium. Plaque treatment of membranes of acrylic nitrate polymer with an energy transferred to the membrane

(Energledkhte) of 330 bla 3300 W · cm cm ¹ , whereby the membranes are confessed to akh

Borrowed Zwelsehkhiformkörpsr, the by anlelnlichen Anelnanderechkhten a dae memb / snblldende Acrylic polymer containing alkylation and a solution incompatible therewith in "other" membrane Polymers and subsequent coagulation is formed and wherein dl. Acrylnrtrltpotymermombran before or after the Plaimabehandlung aua the ZwelschkhtformkOrper is separated. In the method according to the invention, it is known that in the present case, it is known that they form a torque generator Acrylic nitrile polymer containing a slip solution and thus an incompatible solution of one another Polymers successively or almultionally flattened. The Zwelichkhtfllm is with or without Interconnection of an Andunit · or AbkOhktreck · koeguliert, freed from Löiungimlttel, possibly further Subjected to Nechbehandlungsstufen and dried. According to the invention, the membrane is then removed AcrylnitralpolymerlMt before or after the separation of Zwchschkhtkörper a Nertertemperaturplaimebehandlung with

an energy transferred to dl · Membrane of 330 »> li 3300 W · β · cm * ¹ subjected.

As the acrylonitrile polymer, it is possible to classify film-forming polymers and copolymers of acrylonitrile. Special

vceignet are the homopolymer and copolymers of the acrylonitrile with up to 16 Me. *% elnea or more comonomers,

v. (Meth) Acrylilureeetsr, Vlnylecetei, vinylidene chloride, styrene sulfonate, allyl or Vlnykulfonet.

As a result of incompatible, far-flung polymer, they can all dissolve in the solubilizer used,

These polymers are classified as suitable by a precipitating agent and suitable for film formation, as far as they are

Have property when mixing their solutions with the solution of Acryllltrilpolymerisste a multi-phase Potymmermlschungilöiung iu form, i. be incompatible with each other. Special events «; and cellulose acetate oi? r Potysulfon. To the casting solvents and to the soldering capability of the polymers, special requirements are imposed on the polymers such that <β1

known per se · solvents or mixtures thereof can be used. Of course you may

Gleq solvent used to solve the -wide polymer, no case agent for the acrylonitrile polymer

represent and vice versa. Vonugswelse and both OeBlötungtmittel Identiich. The voriugtwelse turned around

Solvent Is Ν, Ν-Olmethylforinemld. The dissolution solution of the twelft membrane-forming polymer will be useful for the preparation of even-sized membranes

confessed catfish · by means of Elnus drawing box, FilmglcQer, Rekels o.i. on a QieQ underlay, such as t. As metal or Qletplatte, metal strip or drum and then applied to the same catfish with a film of

Acrylonitrile Porymerlsat'Qleßlötung flächchengg overgrown. Advantageously, the two Q "under With the help of a Doppelilehkottent simulten turn Zwelechkhtfilm be deformed. In consideration of the In DD- PS 282646 described Koagulationsregimes the two casting solutions you tlmulten aua Bicomponent wide slit will be deformed. Due to the incompatibility of the two polymers Imsen skh the fllchlg joined components of the Secondary body after coagulation separate from each other. Before or after the separation of the two-body molded body, the surface layer, i. H. the uraprünglkh the Koeguletlonsmedlum directly autgesettte fliehe the membrane aue the Acrylnitritporymerlut, nech the drying of Influenced a plesmaa from an inert gene in a high-frequency field. Old suitable here t. For example the In Ada Polymeric · 30 (1979) 8,720 bla 723 bethrlebene apparatus for low-tempereturplaimabehandlung erwleten. She works with you

a high frequency of 27,12 MHt with a superimposed level of 0 Bla 2 kV, 0.1 mA controllable, at room temperature and a pressure of about 1 Pa. Ala inert carrier is used by argon. On the contrary, in the state of

Technique ready described formation of a dense, dense surface layer when a Plssmes on a Pol / acrylntrilmembren was found to be found in the presence of a membrane through the membrane

transferred energy of 330 bla tu 3300W · a · cm * 'In the inert medium In the surface layer of the membrane a remarkably uniform pore system is produced. The mean pore opening diameters are in the range of 0.08 to 60 μm, and in general 0.6 to 6 μm. Ce diameter of the respective pore openings which only slightly from the middle

Pore diameter off. Ea a maximum Streuberekh of 1 30% of the mean value was found. The performance of the plasmageneretor and the effects of the plasma must be regulated in such a way that the Acrylonitrile Porymermembran an energy of at least 330W · s · cm * 'is transmitted. Amounts of energy from more ice

3JOOW-S-Cm " ¹ on the other hand lead to partial destruction of the membrane.

At the same time, the treatment increases the mechanical resistance of the membrane, which in turn results in a decrease in the mechanical resistance of the membrane. a. through a Insolubilization of the surface layer of the treated membrane in N, N * indicates dimethylformamide. The porosity of the active layer of the membrane, which is characterized by the permeability of the membrane, can be determined by a Increasing the amount of energy applied to the door can be increased within the scope of the present invention. About that

In addition, the porosity of nanotubes can also be determined by the parameters of the formation of the double-shelled body, in particular

by the concentration of the acrylic polymer solution used and the applied coagulation medium. The parameters can be brought into contact with the membrane membrane by a relatively small amount even in the course of a membrane morphology which has been measured by means of an auxiliary wave. The membranes produced in this way are characterized by the fact that, in the separation-active layer on the membrane above existing pores, almost uniform QrAB * is formed. DI · PIg. Fig. 1 shows the increase in volume of a membrane produced under conditions which are more suitable for use in the embodiment 4, and shows a very narrow pore size distribution in the upper part of the invention in the membranes of the invention. DI · membranes betluen continues "In open-pored · · Membranunteraelte with an average Porenöffnungsdurchmeeser of> 10mm, The WaaMrdurchllaalgkeHen are above 10 * 1 m * ¹ h" \ InabMondere large 10 ¹ I m * ¹ * ¹ h at a PrO'riruck 0 2MPa. 81 are particularly suitable for the microfiltration of dissolved or dissolved substances or particles of liquids or acids. · Membranes and carriers of dl · Preparation of compo- nents with particular favorable effluent behavior Elaetibar. · Deactivated in the present invention The process of preparing top-filled membranes from acrylonitrile polymers is also prudently available on other polymers and thus opens up an opportunity for the development of membranes of uniform pore size in the release-active layer and an open-pore membrane-bottomed membrane and the resulting high permeate flux

 The following examples are intended to illustrate the invention in more detail.

AusfOhrungsbetsplele

Medium · a · double-duo ·, whose 8peltbrelten on 0,2 biw. 0.4 mm, a solution containing 17% by weight Celluloee 2 1/2 acetate (CA) is dissolved in an olmethylformamide (DMF) sublayer and a 20% by weight of an acrylamide copolymer (11H acrylic methyl ester in copolymer; * ": 61000g mol" ¹ ) Dissolving solution In DMF ice-layer, dilute a plate of Zwelschkhtfllms on an Oles plate.The Zwelschichtfllm is coagulated by immersion in water at Reumtemperetur, the Entstendene Zwelschlchiformkörper of the Qlssplstte dissolved and up to the removal of the remaining DMF certain The Membren from the acrylonitrile polymer load is separated from the CA membrane by light stripping, dried at re-tempering temperature, and subjected to a high-frequency enthalpy reaction of different amounts and duration using the apparatus described in Acts Polymerice 10 (1970), 8,720 ble 723 Elgenscheften the membrane obtained are summarized in Tebelle 1 The topsheets of the conditioned membranes have pores of almost uniform pore diameter and regular distribution of pores above the membrane surfaces. The Flg. The narrow pore size distribution of a membrane produced according to Example 4, FIG. 2 the rest electron microsphere pick up their top.

Tebelle 1

No. Dee example Parameters of the plasma treatment Pressure Pa 7 1 Tent • Pia ims performance ·· density " ¹ Energy * Frequency density Wi cm ' ¹ MHi Membrane characteristics Water-permeability l-h-m "» average pore opening diameter topside bottom pm 26 2b Oat untreated Ar 7 120 1.1 132 27.12 Prödruek MPa 37.6 no river <0.01 <0.01 26 26 26 1 (comparative) 2belsplele) Ar Ar Ar 300 600 1200 1.1 2.3 2.3 330 27,12 1360 27,12 2760 27,12 0.2 216 0.40 0.66 0.66 3 4 6 0.2

Diaphragms produce a high flow rate even without pressurization, the value of which is above the value of the hyrostatic pressure

Claims (2)

-ι- 272140 PatentanaprQehe: 1. Coarse-pored kinking membrane. Membranes of aoryl-chloride polymtrles, characterized by the presence of morbanthoquale kohlrantaa pore ayetem allied to Qbar, with a uniform pear-like color, wanlgar ala ± 3OH, from the middle pore-opening strainer and in the barrel of O ₁ OB bla 60pm Oberfllohenaohloht and a weltgehend openporlgon structure in the opposite Begraungaaohloht pore openingdurchmeeaea of 10 bla ΙΟΟμηι, bulge. 2. A method for the production of ebenfllchlgon, coarse-pored membranes auyl Aerylnltrllpolymerlaaten, which were deformed by successive or glelchieltlgei flächchenförmlgea Anelnanderachlchten a daa Acryllltrllpolymeriaat containing Gleßlöiung and an incompatible Lotung a «second polymers and subsequent coagulation to a Zwelichlcht'ormkörper, characterized in that before or after separation of the Zwelachlchtformkörpera the surface layer of the Acryllltrllpolymeriaat formed membrane of a Nätertemperaturplaamaabehandlung In the inert medium with an energy transferred to the membrane of 330 bla3300W · a · cm ' ^{1 is} subjected.