JPH0674297B2 - Method of adjusting concentration of aqueous solution - Google Patents

Description

The present invention relates to a method of insolubilizing a specific polymer of a (meth) acrylamide derivative of the present invention in water and then bringing the polymer into contact with an aqueous solution containing a useful substance to adjust the concentration of the aqueous solution.

Conventional technology and its problems: Conventionally, the concentration adjustment of an aqueous solution is performed by a combination of concentration by evaporation and dilution by addition of an aqueous solution, which consumes a lot of energy and a lot of labor in a laborious process. Has been spent. Further, in recent years, with the progress of biotechnology, the chances of handling bacterial cells, enzymes, proteins, amino acids and the like have increased, and most of them require the concentration adjustment of substances as an essential step. However, since these substances are usually weak to heat and easily foam under reduced pressure, various problems occur in the conventional concentration adjustment method, and new methods such as using a separation membrane have been tried. There is.

Means for Solving the Problems: As a result of intensive investigations made by the present inventors in view of the above points, the polymer of the specific (meth) acrylamide derivative previously found and disclosed by the present inventors (JP-A-60- No. 90010) has specific water separation and retention properties, and has been found to be useful for controlling the concentration of the above-mentioned substances, and has arrived at the present invention.

That is, the present invention provides a compound represented by the general formula (I) or the general formula (II). (In the above formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom,
A methyl group or an ethyl group, and R ₃ represents a methyl group, an ethyl group or a propyl group. ) General formula (In the above formula, R ₁ is a hydrogen atom or a methyl group, A is CH ₂ n
In n represents 4-6 or CH _{2 2} OCH _{2 2.} ) A method of copolymerizing a homopolymer or copolymer of N-alkyl or N-alkylene substituted (meth) acrylamide, or a copolymer with another copolymerizable monomer with a crosslinkable monomer, alkoxymethyl Copolymerization with (meth) acrylamide, copolymerization by increasing the proportion of lipophilic monomer, polymerization in bulk, heat treatment of polymer, integration with water-insoluble fibrous substance, From a method of reacting with a functional compound to crosslink, and a method of copolymerizing a substituent having an active hydrogen with a substituted monomer or a method of forming a complex with the polymer substituted with these substituents It is made insoluble in water by a method of making it insoluble in water, and then contacted with an aqueous solution containing a useful substance to absorb and retain water, and then the temperature of the aqueous solution is changed. And further adsorb or release water to adjust the concentration of the aqueous solution.

In the present invention, the specific N-alkyl- or N-alkylene-substituted (meth) acrylamide means the above-mentioned general formula (I).
And those represented by the general formula (II). Specifically, for example, Nn-propyl acrylamide (cloud point of polymer 32 ° C.), Nn-propyl methacrylamide, N
-Isopropylacrylamide (cloud point of polymer 29 ° C),
N-isopropylmethacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, N, N-dimethylmethacrylamide,
N-acryloylpyrrolidine (cloud point of polymer 51 ° C.), N
-Methacryloyl pyrrolidine, N-acryloyl piperidine, N-methacryloyl piperidine, N-acryloyl morpholine, etc. can be mentioned.

Further, as the monomer copolymerizable with the above-mentioned monomer,
Examples thereof include hydrophilic monomers, ionic monomers, lipophilic monomers and the like, and one or more kinds of these monomers can be applied. Specifically, as hydrophilic monomers, for example, acrylamide, methacrylamide, N-methyl acrylamide, diacetone acrylamide, hydroxyethyl methacrylate,
Hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxy polyethylene glycol methacrylate, various methoxy polyethylene glycol acrylate, N
-Vinyl-2-pyrrolidone and the like can be mentioned,
It is also possible to introduce vinyl acetate, glycidyl methacrylate or the like by copolymerization and hydrolyze it to impart hydrophilicity. Examples of the ionic monomer include acrylic acid, methacrylic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid,
Acids such as 2-acrylamido-2-phenylpropanesulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid and salts thereof, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate,
N, N-dimethylaminopropyl methacrylamide, N, N-
Examples thereof include amines such as dimethylaminopropyl acrylamide and salts thereof. Also, by introducing various acrylates, methacrylates, acrylamides, methacrylamides, acrylonitriles, etc. by copolymerization,
It can also be hydrolyzed to impart ionicity.
Examples of the lipophilic monomer include Nn-butylacrylamide, Nn-butylmethacrylamide, N-ter.
t.-Butylacrylamide, N-tert.-butylmethacrylamide, Nn-hexylacrylamide, Nn
-Hexyl methacrylamide, Nn-octyl acrylamide, Nn-octyl methacrylamide, N-te
rt.-octyl acrylamide, Nn-dodecyl acrylamide, Nn-dodecyl methacrylamide, etc.
-Alkyl (meth) acrylamide derivative, N, N-diglycidyl acrylamide, N, N-diglycidyl methacrylamide, N- (4-glycidoxybutyl) acrylamide, N- (4-glycidoxybutyl) methacrylamide, N- (5-glycidoxypentyl) acrylamide, N- (6-glycidoxyhexyl) acrylamide and other N- (ω-glycidoxyalkyl) (meth) acrylamide derivatives, ethyl acrylate, methyl methacrylate, butyl methacrylate, Butyl acrylate,
(Meth) acrylate derivatives such as lauryl acrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, acrylonitrile, methacrylonitrile,
Olefin such as vinyl acetate, vinyl chloride, ethylene, propylene, butene, styrene, α-methylstyrene,
Examples thereof include butadiene and isoprene.

Next, as a method of insolubilizing the above-mentioned monomer polymer in water, there are a method of insolubilizing at the time of polymerization and a method of insolubilizing by a treatment after the polymerization, and as a specific insolubilizing method, at least two in the molecule. A method of copolymerizing a crosslinkable monomer having one or more double bonds with the (meth) acrylamide derivative described above, a method of copolymerizing an N-alkoxymethyl (meth) acrylamide derivative, and increasing the ratio of the lipophilic monomer described above. A method of copolymerizing with a (meth) acrylamide derivative, a method of polymerizing in bulk, a method of heat-treating the polymer,
A method of integrating a polymer with a water-insoluble fibrous substance such as cellulose, or when a hydroxyl group or an amino group is present in the polymer, they are reacted with a polyfunctional compound such as epichlorohydrin. Crosslinking and insolubilizing method, and further copolymerization with a substituted monomer having a substituent having an active hydrogen such as a carboxy group, a sulfonic acid group, and a hydroxyl value, or a polymer having the substituent substituted. It is possible to employ a method of forming a complex between the above and the insolubilization.

More specifically, in the first method, as the crosslinkable monomer,
For example, N, N'-methylenebisacrylamide, N, N-diallylacrylamide, triacrylformal, N, N
-Diacryloylimide, N, N-dimethacryloylimide, ethylene glycol acrylate, ethylene glycol dimethacrylate, various polyethylene glycol diacrylate, various polyethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol methacrylate, various polypropylene glycol diacrylate, various Polypropylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylol Propane trimethacrylate, trimethylolethane trimeta Relate, trimethylolethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane triacrylate, divinylbenzene, diallyl phthalate can be used. The N-alkoxymethyl (meth) acrylamide derivative in the second method also includes N-hydroxymethyl (meth) acrylamide, such as N- (methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxy. Methyl (meta)
Acrylamide, Nn-butoxymethyl (meth) acrylamide, N-tert.-butoxymethyl (meth) acrylamide, etc. can be used. The ratio of the lipophilic monomer to the (meth) acrylamide derivative having an amphiphilic property in the third method varies depending on the combination of the (meth) acrylamide derivative and the lipophilic monomer and cannot be generally determined, but generally Is 1% or more, preferably 3% or more. At this time, any of random copolymerization, block copolymerization, and graft copolymerization can be adopted as the copolymerization method. As the method of polymerizing in bulk according to the fourth method, a polymer block is obtained by polymerizing as it is without diluting with a solvent to obtain a polymer block, or by polymerizing in a monomer droplet while suspending in a solvent to obtain a particulate polymer. A method etc. can be adopted.
In the method of heat-treating the polymer which is the fifth method, the heating conditions vary depending on the polymer and are not uniform, but generally, at a temperature of 60 to 250 ° C., preferably 80 to 200 ° C., bulk polymerization, The polymer obtained by suspension polymerization, solution polymerization or the like is heat-treated. At that time, in the solution polymerization, drying or evaporation of the solvent and heat treatment may be combined. As a method of integrating with a fibrous substance or the like which is a sixth method, cellulose,
Fibers such as nylon, polyester, acrylic, or polypropylene, non-woven fabrics made of ethylene-propylene copolymer, etc., or water-insoluble fibrous substances such as silica, alumina, zeolite, etc. ) A method of impregnation polymerization or graft polymerization of an acrylamide derivative, a method of impregnating a polymer, or the like can be adopted. In the seventh method, in which a polyfunctional compound such as epichlorohydrin is reacted to crosslink and insolubilize, it is necessary to introduce a hydroxyl group or an amino group into the polymer in advance. Amino groups can be easily introduced by copolymerization, but in the case of hydroxyl groups, copolymerization with hydroxyethyl methacrylate, isopropenyl phenol, etc. or vinyl acetate, glycidyl methacrylate, etc. is introduced by a copolymerization method, and then a basic substance is used. There is also a method of introducing a hydroxyl group by saponification with. Then, the above-mentioned polymer is reacted with a polyfunctional compound such as epichlorohydrin in the presence of a basic substance to crosslink and insolubilize. At that time, if the aqueous solution is insolubilized as it is, it becomes agar-like, and it is put into practical use by crushing it. Further, when the aqueous solution is dispersed in oil to make it insoluble, it becomes a granular gel. The eighth method is to copolymerize with the above-mentioned monomer having active hydrogen, to combine these monomers with a copolymer, to replace the active hydrogen in the copolymer with ammonium ion, etc. After that, an acid is added to activate active hydrogen to form a complex and insolubilize it.

The above eight methods may be adopted individually or in combination. More effective results can be obtained when used in combination.

According to the above-described method, a more specific method of polymerization that can be adopted in producing the agent used for adjusting the concentration of the aqueous solution of the present invention, includes, for example, (1) polymerizing the monomer as it is without diluting it with a solvent. A method for producing a polymer block, (2) a method of polymerizing in a solvent to obtain a polymer by drying after polymerization or precipitating the polymer in a poor solvent, (3) obtaining a particulate polymer by suspension polymerization Method, (4) a method of obtaining a polymer latex by emulsion polymerization, (5) a method of integrating the polymer by a method such as impregnation of a polymer solution into a water-insoluble fibrous substance or a porous substance or graft polymerization, etc. Can be adopted. At that time, as a method for initiating the polymerization, heating alone can be used, but normally, a better result is obtained by using a polymerization initiator. The polymerization initiator is not limited as long as it has the ability to initiate radical polymerization, and includes, for example, inorganic peroxides, organic peroxides, combinations of those peroxides and ring formers, and azo compounds. . Specifically, there are ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl peroxide, benzoyl peroxide, cumene hydroxy peroxide, tert-butyl peroxy-2-ethylhexanoate, butyl perbenzoate and the like. , As reducing agents combined with them, sulfite, bisulfite, iron, copper, low ionic salts such as cobalt, organic amines such as aniline and aldose,
Reducing sugars such as ketose can be mentioned. As the azo compound, azobisisobutyronitrile, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4
-Cyanovaleic acid or the like can be used. It is also possible to use two or more of the above-mentioned polymerization initiators in combination. In this case, the addition amount of the polymerization initiator is sufficient in the normally employed quantitative range, for example, 0.01 to 0.01 per monomer.
It is in the range of 5% by weight, preferably 0.05 to 2% by weight.

Among the polymers obtained in this manner, a block-shaped one, or a polymer obtained by distilling off the solvent, is pulverized into a powder, or melted into a granule, a flake, a fiber or a film. Molded, the particulate polymer may be provided as it is, and the latex polymer may be impregnated into a fibrous or porous material such as cloth and paper or coated with a film or provided as a film for concentration adjustment. it can.

By the above-mentioned method, various forms can be produced, but the form is determined by how it is used. That is, for example, in the case of using by suspending / dispersing in a solution such as a fluidized bed, powdery products and granular products are often used.

The powdered product undergoes gel polymerization in an aqueous solution as described above,
Then, various methods such as dry pulverization may be used. On the other hand, although granular products are generally easily produced by the suspension polymerization method, the N-alkyl or N-alkylene-substituted (meth) acrylamide used in the present invention is generally highly water-soluble, so that the suspension weight is As a legal method, reverse phase suspension polymerization in which a monomer or an aqueous solution thereof is dispersed in oil, or salting-out suspension polymerization in which a large amount of an electrolyte or the like is dissolved in an aqueous solution to suppress the solubility of the monomer Further, a method such as precipitation suspension polymerization in which the polymer is precipitated by polymerizing it at a temperature higher than the cloud point of the polymer is adopted. Further, it is also possible to employ one in which the surface of a porous particle such as silica, alumina or zeolite is integrated with a polymer by a method such as impregnation with a polymer solution or graft polymerization. Further, at that time, it is possible to give a porous form by adding a third component which is compatible with the monomer but not compatible with the polymer.

The concentration adjusting agent produced as described above is in a solid state, absorbs and holds water by contact with an aqueous solution, and contracts by heating to release water even in the presence of a large excess of water. It has a unique property. More conveniently, the process of absorbing, retaining and releasing water can be repeated. The amount of water absorbed by the agent changes depending on the composition of the agent, the temperature, the composition of the aqueous solution, and the like. Speaking of the composition of the agent, in the copolymer with the lipophilic monomer among the above-mentioned copolymerizable monomers, the absorption amount decreases as the ratio increases, while the mechanical strength of the agent increases. . Further, in the copolymer with hydrophilic and ionic monomers, as the ratio increases, the water absorption itself increases,
The change in water absorption due to temperature decreases, and the mechanical strength also decreases. As described above, the amount of water absorption changes depending on the composition of the agent, but at room temperature (25 ° C), the water absorption is generally 2 to 100 times its own weight.
About twice as much water can be absorbed, and the absorption amount of water can be increased by lowering the temperature.

When a low molecular weight substance such as an inorganic salt, an organic salt, or a water-soluble organic substance is dissolved in the aqueous solution, it can be incorporated into the agent as an aqueous solution containing these substances. When the inorganic salt is dissolved, the water absorption amount of the conventional water-absorbing resin decreases sharply.For example, acrylamide-sodium acrylate copolymer crosslinked with methylenebisacrylamide (sodium acrylate content: 21% by weight) is distilled. Its water absorption decreases to 1/17 in water and 1N sodium chloride solution. On the other hand, in the agent for concentration adjustment of the present invention,
The reduction rate is around 10%, and it can be concluded that the effect of coexisting salts on water absorption is small. Also, depending on the type of coexisting salt,
For example, it has been obtained that calcium chloride increases the water absorption amount.

As described above, the agent for adjusting the concentration of the present invention has two cases depending on the molecular weight of the solute, that is, the case of incorporating into the gel at the time of water absorption and the case of eliminating it. That is, it has a molecular weight fractionation ability, and the molecular weight cutoff varies depending on the composition of the agent and the temperature. Generally, when the insolubilization ratio, for example, the degree of crosslinking, is low, or the water absorption is relatively large due to the copolymer with a hydrophilic or ionic monomer, the molecular weight cutoff becomes large. On the other hand, if the degree of cross-linking is high, or if it is a copolymer with a lipophilic monomer and the water absorption is relatively small,
The molecular weight cut-off becomes small. As a matter of course, in the concentration adjustment by the agent of the present invention, a solute having a molecular weight equal to or higher than the cutoff molecular weight of the agent is targeted.

The specific value of the molecular weight cut-off is not uniformly stated because it greatly changes depending on the composition of the agent, the temperature, the composition of the aqueous solution and the kind of the concentrated substance, but for example, poly N-acryloylpyrrolidine at around room temperature is not mentioned. In the concentration of polyethylene glycol with a methylenebisacrylamide cross-linked agent, the molecular weight cut-off is on the order of 1000. On the other hand, in dextran, protein, etc., the molecular weight cutoff exists in the order of 10,000, the molecular weight cutoff depends on the dissolved state of the molecule in an aqueous solution, that is, the spread of the molecule, and is naturally not uniquely determined. It has a distribution.

Further, when the temperature of the agent that has absorbed water is increased, the agent contracts and releases water. When the temperature is further raised, the contraction of the agent becomes extremely slow even if heated above a certain temperature, and a transition point may be observed. The transition temperature is determined by the composition of the agent and can be controlled within the range of about 10-100 ° C. The amount of shrinkage of the agent near the transition temperature varies depending on the composition of the agent, the composition of the aqueous solution, etc., but is generally about 20 times as much as 1 times its own weight. As described above, the heating and cooling of the agent are repeated to separate and retain water, and the water absorption temperature range of the resin at that time is generally 0 to 100 ° C. On the other hand, in order to heat and shrink the agent that has absorbed water, liquid water or gaseous water may be used, and its temperature varies depending on the purpose of use of this agent, but in general,
Generally from 10-200 ° C., as shown in Examples described later,
It is in the range of exceeding 0 ° C.

As a specific method for adjusting the concentration, the concentration can be adjusted by contacting the agent with an aqueous solution whose concentration is to be adjusted as it is or after swelling with an appropriate aqueous solution such as water and then contacting the agent to an arbitrary temperature. At that time, the aqueous solution is diluted by setting it at a high temperature, while the aqueous solution is concentrated by setting it at a low temperature. After that, the agent is settled, filtered,
An aqueous solution having a predetermined concentration can be obtained by separating by a method such as centrifugation or collecting the supernatant. By changing the temperature in the above process, it is possible to adjust the aqueous solution to various concentrations.
The adjustment range varies depending on the agent used, the addition ratio of the agent and the aqueous solution, the operating temperature range, etc., and cannot be said to be uniform, but an adjustment range of about 0.01 to 100 times that of the stock solution is possible.

At that time, when the low molecular weight substance coexists in the aqueous solution, the concentration of the low molecular weight substance does not change, but the concentration of only the high molecular weight substance changes.

Further, the agent thus used can be easily regenerated by washing the agent with water or by heating to shrink the agent to release the aqueous solution, and can be used any number of times. The fact that the agent can be easily regenerated is one of the advantageous features of the temperature control method for the aqueous solution of the present invention.

Actions: Specific applications of the method for adjusting the concentration of an aqueous solution of the present invention include, for example, foods, proteins, polysaccharides, enzymes, and antibiotics, which are difficult to adjust by adjusting the concentration of an aqueous solution containing various useful substances, especially by the evaporation method. , Concentration adjustment of an aqueous solution containing a substance that is easily deteriorated by heat such as bacterial cells and emulsion. They can be applied to any scale from industrial scale to laboratory stage.

As described above, the method for adjusting the concentration of an aqueous solution of the present invention can: (1) The concentration can be adjusted by simply changing the temperature of the aqueous solution without changing the phase, so that the loss due to the temperature of the solute or denaturation accompanying the phase change can be minimized. It can be limited. (2) Since there is a molecular weight cut-off by the agent, the concentration of low molecular weight compounds such as buffer agents can be left unchanged and only high molecular weight substances such as proteins and enzymes can be selectively adjusted. (3) As a property of the agent, water is released by heating even in an aqueous solution, and water diffuses rapidly in the agent, so that the agent can be easily washed and can be reused many times. Have an effect.

Hereinafter, the present invention will be further described with reference to examples.

Example 1 5 g of N-acryloylpyrrolidine was placed in a 5 ml sample tube, 0.02 g of t-butylperoxy (2-ethylhexanonate) was added, and solventless polymerization was carried out at 40 ° C. to obtain a block-shaped polymer. Got Grind the polymer to 20-10
A 0 mesh fraction was collected and used as a sample. When 0.5 g of the sample powder was added to 50 g of 43% concentration SBR latex (manufactured by Mitsui Toatsu Chemicals, Inc., Polylac 755) at room temperature and the concentration of the latex liquid was measured after sufficiently stirring 49
It had become%. Then, the latex liquid was cooled to 10 ° C., sufficiently stirred, and then the concentration was measured to be 58%. Further, the latex solution was heated to 40 ° C., and after sufficient stirring, the concentration was measured and found to be 45%. After the latex solution was thoroughly stirred again at room temperature, the concentration was measured.
It was 48%. When the sample powder before and after the measurement was observed with a microscope, no crushing of the sample powder due to temperature change or stirring occurred.

Example 2 507.5 g of N-acryloylpyrrolidine and 2.6 g of N, N'-methylenebisacrylamide were dissolved in 1,170 g of distilled water, and
N-containing 5 wt% N, N'-methylenebisacrylamide
An aqueous solution of acryloylpyrrolidine was prepared. After the aqueous solution was cooled to 10 ° C., it was transferred to a No. 2 stainless steel dewar and nitrogen gas was bubbled for 1 hour using a ball filter at a flow rate of 1 / min. Then, a solution prepared by dissolving 2.55 g of ammonium persulfate in 10 g of distilled water and a solution prepared by dissolving 1.16 g of sodium hydrogen sulfite in 10 g of distilled water were simultaneously added to the aqueous solution to polymerize the aqueous solution adiabatically. The obtained gel was shredded and dried, and then further pulverized to collect 20 to 100 Messille fractions, which were used as samples. 10 g of the gel obtained by swelling the sample powder in distilled water (water content: 9.5 g) was added to 10 g of a solution prepared by dissolving bovine serum albumin in 0.9% sodium chloride aqueous solution to a concentration of 1%, After stirring for a minute, the concentration of bovine serum albumin in the aqueous solution was calculated by measuring the absorbance of the supernatant at 254 nm, and it was 0.75%. On the other hand, the concentration of sodium chloride was 0.47% as determined by measuring the electric conductivity. When the solution was heated to 30 ° C., the concentration of bovine serum albumin became 0.71%. When it was cooled to 15 ℃, it was 0.
It became 78%, and when it was further cooled to 5 ° C, it became 0.83%.
Then, when the temperature was returned to room temperature again, the concentration of bovine serum albumin returned to 0.75%. The sodium chloride concentration was kept at 0.47% throughout the measurement.

Example 3 N containing 0.5 wt% N, N'-methylenebisacrylamide
Using a 30% aqueous solution of -n-propylacrylamide,
A sample powder was obtained in the same manner as in Example 2. The concentration of bovine serum albumin at each temperature was measured in the same manner as in Example 2 by using 10 g of the sample powder swollen in distilled water (content of water: 9.4 g), and the concentration was 0.65% at room temperature. , 0.63% when heated to 30 ℃, cooled to 15 ℃
0.70%, 0.84% at 5 ℃, 0 when returned to room temperature.
It was 69%. The sodium chloride concentration remained constant at 0.46% throughout the measurement.

Examples 4 to 8 0.5 g of the sample powder obtained in Example 2 was added to 20 g of a 0.5% aqueous solution of polyethylene glycol having the molecular weight shown in Table 1, and the mixture was stirred at a predetermined temperature for 30 minutes, and then the supernatant was refracted. The concentration of the supernatant was calculated by measuring the rate, and the results shown in Table 1 were obtained.

Examples 9 to 11 The concentration of the supernatant was measured in the same manner as in Example 4 using 0.6 g of the sample powder obtained in Example 3 and 20 g of a 0.5% aqueous solution of polyethylene glycol having the molecular weight shown in Table 2. Table-
The results shown in 2 were obtained.

Examples 12 to 16 An aqueous solution of N-acryloylpyrrolidine containing 4.7 wt% of sodium 2-acrylamido-2-phenylpropanesulfonate was subjected to salting-out suspension polymerization using Glauber's salt or the like. A sample was dried. 10 g of gel obtained by swelling the sample particles in distilled water (water content 9.75 g)
Then, the concentration of the supernatant was measured by the same method as in Example 4 using 10 g of a 1% aqueous solution of polyethylene glycol having the molecular weight shown in Table 3, and the results shown in Table 3 were obtained.

Examples 17 to 20 The sample powder obtained in Example 2 was swollen in distilled water (10 g) (water content: 9.5 g) and a 1% aqueous solution of dextran having a molecular weight shown in Table 4 was used. The concentration of the supernatant was measured by the same method as in 4, and the results shown in Table 4 were obtained.

Examples 21 to 24 The sample powder obtained in Example 3 was swollen in distilled water to give 10 g of gel (content of water 9.4 g) and Table-5. The concentration of the supernatant was measured by the same method as in Example 4 using 10 g of a 1% aqueous solution of dextran having the molecular weight shown in Table 5, and the results shown in Table 5 were obtained.

Examples 25 to 28 The concentration of the supernatant was measured by the same method as in Example 4 using 0.25 g of the sample particles obtained in Example 12 and 20 g of a 0.5% aqueous solution of dextran having the molecular weight shown in Table-6. The results shown in Table 6 were obtained.

Examples 29 to 33 The concentration of the supernatant was measured in the same manner as in Example 2 by using 0.05 g of the sample powder obtained in Example 2 and 2 g of a 0.5% aqueous solution of a protein having the molecular weight shown in Table-7. The results shown in -7 were obtained.

Examples 34 to 38 Using 0.06 g of the sample powder obtained in Example 3 and a 0.5% aqueous solution of the protein having the molecular weight shown in Table-8, the concentration of the supernatant was measured by the same method as in Example-2. The results shown in 8 were obtained.

Examples 39-41 N containing 0.5 wt% N, N'-methylenebisacrylamide
-Using a 30% aqueous solution of isopropylacrylamide,
A sample powder was obtained in the same manner as in Example 2. The concentration of the supernatant was measured by the same method as in Example 4 using 0.5 g of the sample powder and 20 g of a 0.5% aqueous solution of polyethylene glycol having the molecular weight shown in Table-9, and the results shown in Table-9 were obtained.

Examples 42-44 N, containing 0.5 wt% N, N'-methylenebisacrylamide
A 30% N, N-dimethylformamide solution of N-diethylacrylamide was transferred to a Dewar bottle, the solution was replaced with nitrogen, and 1.5% of azobisisobutyronitrile was added at 30 ° C to polymerize adiabatically. did. The resulting gel is shredded to 120
After drying at ℃, it was further pulverized and 20 to 100 mesh fraction was collected and used as a sample. 1.0 g of the sample powder and 20 g of a 0.5% aqueous solution of polyethylene glycol having the molecular weight shown in Table-10
Was used to measure the concentration of the supernatant in the same manner as in Example 4, and the results shown in Table 10 were obtained.

Examples 45-47 N containing 0.5 wt% N, N'-methylenebisacrylamide
Sample powder was obtained in the same manner as in Example 2 using a 30% aqueous solution of acryloylmorpholine. The concentration of the supernatant was measured by the same method as in Example 4 using 0.5 g of the sample powder and 20 g of a 0.5% aqueous solution of polyethylene glycol having the molecular weight shown in Table-11, and the results shown in Table-11 were obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09K 3/00 Z 9155-4H (72) Inventor Hideo Kamio 728-5 Sogabesho, Odawara-shi, Kanagawa 56) References JP 54-99188 (JP, A) JP 54-83085 (JP, A)

Claims (1)

[Claims] 1. Represented by the general formula (I) or (II) (In the above formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom,
A methyl group or an ethyl group, and R ₃ represents an ethyl group or a propyl group. ) (In the above formula, R ₁ is a hydrogen atom or a methyl group, and A is (CH ₂ ) n
And n represents 4 to 6 or (CH ₂ ) ₂ O (CH ₂ ) ₂ . ) A method of copolymerizing a homopolymer or copolymer of N-alkyl or N-alkylene substituted (meth) acrylamide, or a copolymer with another copolymerizable monomer with a crosslinkable monomer, alkoxymethyl Copolymerization with (meth) acrylamide, copolymerization by increasing the proportion of lipophilic monomer, polymerization in bulk, heat treatment of polymer, integration with water-insoluble fibrous substance, From a method of reacting with a functional compound to crosslink, and a method of copolymerizing a substituent having an active hydrogen with a substituted monomer or a method of forming a complex with the polymer substituted with these substituents It is made insoluble in water by a method of making it insoluble in water, and then contacted with an aqueous solution containing a useful substance to absorb and retain water, and then the temperature of the aqueous solution is changed. A method for adjusting the concentration of an aqueous solution, which comprises adsorbing or releasing water to adjust the concentration of the aqueous solution.