Method of making membranes

专利摘要:
1327990 Semi-permeable membranes RHONE-POULENC SA 8 Sept 1971 [9 Sept 1970] 41936/71 Heading B5B [Also in Division B1] A semi-permeable membrane used to separate two compartments in apparatus for the fractionation of liquids is prepared by treating a film containing at least one copolymer of acrylonitrile and an ionic or ionizable olefinically unsaturated monomer with water or an aqueous non-solvent mixture at a temperature of 60‹-250‹ C. Preferably the films consist of either (a) a copolymer of acrylonitrile and at least one ionic or ionizable monomer and, optionally, a non-ionic monomer or (b) a blend of at least two copolymers defined in (a) or of at least one copolymer defined in (a) and at least one copolymer of acrylonitrile and a non-ionic monomer, the ionic or ionizable monomer units representing from 1 to 80 mole per cent of the monomer units in one of said copolymers and 1 to 50% of the total monomer units in the membrane. Suitable ionic or ionizable monomers are the ethylenically unsaturated monomers of general formula where Y is an ionic or ionizable group, particularly a sulphonate, phosphonate or quaternary ammonium group; R 1 , R 2 and R 3 are hydrogen or alkyl groups and may be the same or different; and A is either (i) a divalent purely hydrocarbon radical; or (ii) a divalent chain in which purely hydrocarbon groups are bonded to each other by an oxygen or sulphur atom or a carbonyloxy or 1-oxo-2-aza-ethylene group; or (iii) a O-A- or S-A- group wherein A is as defined in (i) or (ii); or (iv) a group as defined above in which one or more carbon atoms carries an additional substituent. Preferred ionic or ionizable monomers are the vinyl-sulphonic or -phosphonic acids or their sodium, potassium or ammonium salts and the vinyl pyridinium salts. Suitable non-ionic or non-ionizable monomers are those conventionally used in acrylonitrile copolymers, preferred monomers being methyl methacrylate, butyl acrylate, vinyl benzoate, vinylidene chloride, acrylamide and styrene. The membranes may be prepared by casting a DMF solution of suitable composition on to a glass plate, drying the resultant film at 60‹ C. in an oven, removing the dried film from the plate and immersing it in hot water at a temperature of from 60‹ C. to 250‹ C. or by a process in which a copolymer solution in DMF is continuously cast on to an endless steel belt and passed into an oven heated to 150‹ C., the resultant film being cooled to 20‹ C., moisturized and stripped from the belt and then passed through a bath of hot water maintained at 90‹ C. The film may be stretched uni- or bi-axially between 20% and 1,000% and may be reinforced with a support e.g., a fabric or net. Examples relate to the production of membranes from copolymers of acrylonitrile and sodium methallylsulphonate, potassium vinyloxybenzene-sulphonate, sodium vinylsulphonate or N-methyl-4-vinylpyridinium sulphonate with or without one of the non-ionic monomers listed above and to the use of the membranes in the ultrafiltration of aqueous solutions of cattle albumen, pepsin, dextran, lysozyme and of human blood, whey, river water, milk and an ascitic liquid.
公开号:SU795493A3
申请号:SU772504503
申请日:1977-07-25
公开日:1981-01-07
发明作者:Марз Ксавье
申请人:Сосьете Дез Эндюстри-Пластик-Содип (Фирма)；
IPC主号:

专利说明:

(54) METHOD OF OBTAINING MEMBRANE
acid or phosphonic acid, instead of which a salt residue or a quaternary ammonium base residue may be present.
. As examples of ionic monomers that may be part of the same copolymer with acrylonitrile, the following compounds may be mentioned in particular:
a) a group of monomers that contain sulfonic acid residues includes monomers with residues of vinylsulfonic, metallic sulfonic, styrene sulfonic, methyldimethyl and ethylstyrene sulfonic acids of vinyl benzene sulfonic, allyloxy and metallic oxy benzene sulfonic acids; allyloxy- and metalloxybenzene sulfonic acids allyloxy- and metalloxyethylsulfonic acids, as well as salts of various ACIDS}
b) a group of monomers that contain residues of phosphinic acids, includes monomers with residues of vinylphosphonic acid, vinylbenzenephosphinic acid and their salts;
c) a group of monomers that contain quaternary ammonium residues includes monomers with residues of the following salts: 2-vinyl- and 4-vinyl-M-alkylpyridine with an alkyl radical that contains from 1 to 4 carbon atoms of N - alyl - and N - yutylpyridine } N-alkyl- and N-metal-trialkylamine, all alkyl radicals contain less than 13 carbon atoms of vinyl - N-alkyl picoline with alkyl 1 radical, which contains from 1 to 4 carbon atoms, vinyl-N-alkylkyludine with an alkyl radical, which contains from 1 to 4 carbon atoms, ortho and paravinyl phenyltrialkylammonium with alkyl radicals that contain less than 13 carbon atoms: vinyl-N-alkylmorpholine with an allyl radical, which contains from 1 to 4 carbon atoms acrylates and methacrylates 2-ethyltrialkylammonium, alkyl radicals that contain less than 13. carbon atoms of acrylamides and methacrylamides, homologues of the listed acrylates and methacrylates.
Copolymers of acrylonitrile and ionic monomers, which can be used to make membranes, proposed in accordance with the invention, may also include various units of other non-olefinic olefinic monomers / belonging to a group of monomers that are capable of copolymerizing with acrylonitrile, and as examples of examples monomers include ethylene hydrocarbon compounds, in particular, such as butadiene and styrene chlorides of vinyl and vinylidene; vinyl ethers saturation ketones,
particulars such as butenone, phenylvinyl ketone, methyl isopropyl ketone; carboxylic acid vinyl esters, in particular, such as formate, acetate, propionate, butyrate, e benzoate} alkyl esters, cycloalkyl or aryl esters of unsaturated mono- or polycarboxylic aliphatic acids, in particular, such as acrylates, methacrylate, copper, fumarates, cytoconates, mezaconates, itaconates and aconitates of methyl, ethyl, propyl, butyl, betaxyethyl acrylamide and methacrylamide and their N-substituted derivatives. In addition, in some cases, copolymers of acrylonitrile and ionic monomer can be crosslinked, in particular, with divinyl derivatives.
The polymers used by the proposed method, as well as the method of their preparation, are well known from the literature.
The temperature used in the treatment of water or water mixture at
5 implementation of the method, which is proposed in accordance with the invention, is in the range from 60 to, preferably from 80 to, In most cases,
 the upper temperature limit is held
 processing of films that are characterized by a low content of ionic monomer. On the contrary, at the lower temperature limit, films with a high content of ionogenic monomer are processed. For example, films whose molecules contain less
5 mol% of the units corresponding to the ionic monomer should, in accordance with the preferred modem of the invention, be treated with water at a temperature exceeding 105 ° C and vice versa.
Water or water mixtures that
5 is used in carrying out the method according to the invention, it can be used in the vapor phase, however preferably water or aqueous mixtures are used in the liquid phase. In some cases, treatment should necessarily be carried out at a temperature above that, since it is under this condition that it is possible to work under elevated pressure when it is desired to use water or liquid aqueous mixtures. However, beyond this effect on the physical nature of the processing environment, pressure is not a critical factor in obtaining
60 membranes, according to the invention.
In most cases, the water content in aqueous mixtures x that are used during the treatment process in accordance with the invention exceeds 50 wt.%, Respectfully this content should exceed 90 weight,% Water can be used in a mixture with organic solvents or mineral or by organic electrolytes, it is preferable to use chemically neutral non-basic / mixtures, which eliminates the possibility of chemical exposure to the acrylonitrile copolymer. In most cases, positive results are obtained with a pH from 6 to 8. Treatment of the film with water or an aqueous mixture is in most cases a wire by simply immersing this film in a treatment water bath. The process of such processing can be carried out. Periodically and continuously. The membranes obtained according to the invention are used for ultra filtration and dialysis, since they have little resistance, which they have to pass through them elements of low molecular weight, in particular, such as water, as well as the ability to trap elements that are characterized by higher rny weight. Examples 1-16. In the course of the experiments, a number of Mebran are prepared in accordance with the general embodiment of the proposed method described below, the specific conditions of the process are given in T abl. 1. The acrylonitrile copolymer, the ionic monomer and, in some cases, the third monomer is dissolved in dimethylformamide (DMF), taking into account the need to obtain a solution of the indicated concentration. After that, the solution prepared in this way is poured onto the surface of the glass plate, taking into account the need to produce a liquid film with a thickness of 0.5 mm, which is dried by blowing at a temperature for a specified period of time, after which the dried film is peeled off from the surface of the substrate and subjected to hot treatment water During this treatment, the dry film is immersed in a vessel in which water is contained, after which the entire system is heated to a specified maximum temperature, at which it is then kept for 10 minutes after (during the experiments, where the temperature of such treatment exceeds apply a closed vessel containing water and this film in which an elevated pressure is created) Then the heating of the vessel is stopped and the contents of the vessel are allowed to cool to room temperature, while the membrane remains at the same time loaded with the water in the same vessel. The degree of salt retention of all membranes so manufactured is zero. In addition, in the course of the experiments, the permeability of the finished membranes to water is determined in accordance with the following procedure. A piece of membrane with a surface area of 12 cm is placed on a porous sintered metal plate, after which the outer or open side of the membrane is brought into contact with water, which is pressurized with 2 bar. The amount of water that passes through the membrane is determined. This amount or flow rate of water, which is expressed in liters per day and square meter, corresponds to the degree of permeability of the membrane with water. Examples 17-37. During the experiments, the membranes obtained in examples 1-16 / are used for ultrafiltration (A) and for diapysis {B) A. A membrane with a surface area of 12 cm is placed on the surface of a sintered sintered metal plate, followed by a free, or external, the membrane side is contacted with an aqueous solution of the macromolecular product. In tab. 2 and 3 indicate the nature of the initial solution, which is ultrafiltered as well as the flow rate of the ultravs of the filtrate and: l the degree of retention of the macromolecules. B. The dialysis bath is divided into two chambers, which are separated from each other by means of a membrane whose surface area is 10 cm. The first chamber is washed by a closed stream of an aqueous solution which contains 9 g / l sodium chloride, 1 g / l thiourea and 10 g / l bovine albumin (molecular weight approximately 70,000) This solution, which is called the artificial croque, in an amount of 100 cm is circulated in the chamber in the form of a continuous flow, the flow rate of which is 1 l / h. The second chamber is bathed in a stream of an aqueous solution, the amount of which is 100 cm, containing 10 g / l of sodium chloride. This solution is called diaiznoy bath. This solution circulates in the second chamber as a continuous flow, the flow rate of which is 0.9 l / h. The speed of the dialysis process is determined by measuring the time interval in minutes, after which the concentration of thiourea in the dialysis bath becomes 0.1 g / l. This value
listed in Table. 2 for some membranes.
Example 38. 330 g of acrylonitrile copolymer with sodium metal sulfonate in a weight ratio of 91: 1 are loaded into a glass reaction apparatus, the specific viscosity of this copolymer, determined at a temperature using a solution of copolymer in DMF with a concentration of 2 g / l, is 1 and 1600 see dimethylformamide.
The mixture is stirred for 1 h, at a temperature of 20 ° C, followed by stirring for 4 h at a temperature of 90 ° C. Next. In the reaction apparatus create a reduced pressure of 100 mm. Hg and maintain it for 30 minutes, at which time the gaseous products dissolved in the mixture are removed, the viscosity of the solution at a temperature of approximately 220 P.
This solution was applied by continuous irrigation onto a continuous tape 17 cm wide, made of stainless steel, the rate of translational motion of which was 50 cm / min. Thus a liquid film is applied with a thickness of 0.2 Å. After that, the tape is sent to a 1.2 m long ventilated oven, the temperature of which is maintained, then it is cooled to a temperature. Next, the acrylonitrile copolymer film is moistened by passing it over the surface of a cloth moistened with water, and removed from the surface of the steel tape on which it is located, after which the film is passed through
a 10 cm long water bath heated to a temperature of 90 ° C and removed to a temperature of 90 ° C and removed from this bath at a speed of 140 cm / min, which corresponds to a degree of stretching of 180%. The stretched film is passed through a water bath at a temperature of 2 m without affecting any mechanical stresses. The rate of withdrawal of the ribbon from the bath is 100 cm / min. The film is then passed through a glycerin bath (a mixture of water and glycerin in a weight ratio of 20:80, respectively), which is 2 m long, and pressed by passing between two rollers to remove excess glycerin from it. In this way, a membrane with a thickness of 30 µm is made, whose permeability to
The water litpH relative pressure of 2 bar is 860 l / day m, and this membrane is characterized by the ability of xopcttuo to be kept in a dry environment.
The membrane retention rate of bovine albumin, the molecular weight of which is 70,000, and of egg albumin, the lulecular weight of which is 45,000 is 100%, but with respect to dextran, the molecular weight of which is 40,000, the retention rate is only 53%.
Examples 39-41. In the course of the experiments, the process described in Example 38 is repeated, changing the degree of film stretching. So get the results shown in table. four.
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About with fM and Nature of macromolecules. Nature of the filtered solution. Average molecular weight of macromolecules 70000 Macro molecule concentration, g / l 10 Ultrafiltrate consumption, l / day m 480
Retention rate 99 90
The degree of relative stretching of the film,%
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albumin whose molecular weight is
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pepsin whose molecular weight is 36,000
Liouaine whose molecular weight is
dextran whose molecular weight is 40,000
invention formula
A method of producing membranes by molding a polymer film and a. the next treatment with water, about tT and l and c a 3
90 96 93 90 100
100
135
165
216
505
360
100
100
100
100
Over 90 Over 90 100
Sviai 90 Sveche 90 100
85
78
74
in order to apply a membrane for blood purification, the film is formed from an acrylonitrile copolymer and an ionic ionogenic monomer 65 or Cow albumin. 70000 70000 70000 70000 70000 70000 10 10 10 10 10 720 1000 1000 1000 1330 360
 . .- “jV: - -
19 79549320
cationic type, a film processing sources of information,
it is carried out by immersing it in water or taken into account in the examination of a mixture of water and an organic solvent. 1. French patent 1521021,
bodies at a temperature of 60-250 ®С in leak-cl. At 01/13/00, published 1968
from 5 s to 2 h. I (prototype).
 . , . - ..
, -: - l. .-.,. l.

权利要求:
Claims (1)
[1]
Claim
A method of producing membranes by forming polymer pleikia according to the following treatment with water, characterized in that, in order to use the membrane for blood purification, the film is formed from an acrylonitrile copolymer and
65 ionogen, anionic monomer or
Λ

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR7032762A|FR2105502A5|1970-09-09|1970-09-09|

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