JPS60250014A - Concentrating resin - Google Patents

Abstract

PURPOSE:The title resin which has water absorptivity varying with temperature and can be fractionated based on MW, prepared by water-insolubilizing a specified N-alkyl- or N-alkylene-substituted (meth)acrylamide polymer. CONSTITUTION:A (co)polymer obtained by (co)polymerizing an N-alkyl- or N- alkylene-substituted (meth)acrylamide monomer of formula I or II [wherein R1 is H or methyl, R2 is H, methyl, or ethyl, R3 is methyl, ethyl, or propyl, A is -(CH2)n or -(CH2)2-O-(CH2)2-, and n is 4-6] with, optionally, other copolymerizable monomers (e.g., acrylamide) in the presence of a polymerization initiator (e.g., ammonium persulfate) is water-insolubilized by heating to 60-250 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a concentration resin made by making a polymer of a certain (meth)acrylamide derivative insoluble in water.

Conventional techniques and their problems: Conventionally, specific methods used to concentrate aqueous solutions include (1) separation using a membrane such as a reverse osmosis membrane or an ultra-E filtration membrane, and (2) multi-stage Furanosee evaporation method. There are methods of separation by phase change of water, such as freezing method, etc., which are in practical use.

However, with either method, problems such as membrane contamination occur in membrane separation, and energy efficiency is a problem in phase change separation, and these methods are not always satisfactory, and various improvements have been attempted. . In particular, this is a big problem when concentrating substances that are difficult to concentrate using evaporation methods, such as foods, amino acids, proteins, polysaccharides, enzymes, emulsions, and other substances that are easily altered by heat.

Means for solving the problem: In view of the above points, the present inventors were studying the water absorption and water release of water-retaining gels, and developed a polymer made of a specific (meth)acrylamide derivative that was made insoluble in water. It has a water absorption capacity that changes depending on the temperature, and even in the presence of a large excess of water, it has the property of contracting and releasing the absorbed water when heated, and by utilizing this property, it can be recycled and reused. We discovered that it is a condensing agent that can be fractionated by molecular weight.
We have arrived at the present invention.

That is, the present invention provides a general formula (I) or a general formula (Ill) (in the above formula, R1 is a hydrogen atom or a methyl group, R3 is a hydrogen atom, a methyl group or an ethyl group, and R3 is a methyl group, an ethyl group). or propyl group.) General formula (In the above formula, R is a hydrogen atom or a methyl group, A is +CH2
+rl and n is 4-6 or +CR2-);, 0÷CH
Represents 2-%. 1 liter fat for concentration made by insoluble in water a single or copolymer of N-alkyl or N-alkylene substituted (meth)acrylamide, or a copolymer with other copolymerizable monomers It is.

Examples of the N-alkyl- or N-alkylene-substituted (meth)acrylamide monomer used in the present invention include N-n-propylacrylamide, N-n-
Propylmethacrylamide, N-isopropylacrylamide, N-inpropylmethacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide , N-acryloylpyrrolidine, N-methacryloylpyro, lysine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylmorpholine, and the like.

In addition, monomers that can be copolymerized with the above monomers include:
Examples include hydrophilic monomers, ionic monomers, lipophilic monomers, etc., and one or more of these monomers can be applied. Specifically, examples of hydrophilic monomers include acrylamide, methacrylamide, N-methylacrylamide, diacetone acrylamide, hydroxyethyl methacrylate,
Hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxypolyethylene glycol methacrylates, various methoxypolyethylene glycol acrylates, N
-vinyl-2-pyrrolidone, etc., and
Furthermore, vinyl acetate, glycidyl methacrylate, etc. can be introduced by copolymerization and hydrolyzed to impart hydrophilicity. Examples of ionic monomers include acrylic acid, methacrylic acid, vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonate, 2-acrylamyl'-2-phenyl sulfonic acid, 2- Acrylamido-2-methyl-propanesulfonic acid, etc., and their salts, N.

N-dimethylaminoethyl methacrylate, N, N-
Examples include amines such as diethylaminoethyl methacrylate, N,N-dimethylamine ethyl acrylate, N,N-dimethylamine propylmethacrylamide, N,N-dimethylamine propyl acrylamide, and salts thereof. It is also possible to introduce various acrylates, methacrylates, acrylamide, methacrylamide, acrylonitrile, etc. by copolymerization and hydrolyze them to impart ionicity. Examples of lipophilic monomers include N-n-butylacrylamide, N-
-n-butylmethacrylamide, N-tert, -butylacrylamide, N-tert, -butylmethacrylamide, N-n-hexylacrylamide, N-n
-hexylmethacrylamide, N-n-octylacrylamide, N-n-octylmethacrylamide, N-
N-alkyl (meth)acrylamide derivatives such as tert, -octylacrylamide, N-n-dodecyl acrylamide, N-n-dodecylmethacrylamide, N
, N-diglycidyl acrylamide, N, N-diglycidyl methacrylamide, N~(4-glycidoxybutyl)acrylamide, N-(4-glycidoxybutyl)methacrylamide, N-(5-glycidoxypentyl) ) acrylamide, N-(6-gelisidoxyhexyl)
N-(w-glycidoxyalkyl)(meth)acrylamide derivatives such as acrylamide, (meth)acrylates such as ethyl acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, lauryl acrylate, 2-ethylhequinyl methacrylate, glycidyl methacrylate, etc. Examples include derivatives of acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, olefins such as ethylene, propylene, and butene, styrene, α-methylstyrene, butadiene, and isoprene.

Next, methods for making the above-mentioned monomer polymer insolubilized in water include a method of making it insolubilized during polymerization and a method of making it insolubilized by treatment after polymerization. A method of copolymerizing a crosslinkable monomer having 1 or more double bonds with the above-mentioned (meth)acrylamide derivative, a method of copolymerizing an N-alkoxymethyl (meth)acrylamide derivative, and a method of copolymerizing the above-mentioned lipophilic monomer by increasing the ratio of the above-mentioned lipophilic monomer. A method of copolymerizing with a (meth)acrylamide derivative, a method of polymerizing in bulk, a method of heat treating a polymer,
When a fibrous substance, etc. that is insoluble in water such as cellulose (combining method, or if there are hydroxyl groups or amino groups in the polymer, reacting them with a polyfunctional compound such as epichlorohydrin) Copolymerization with monomers substituted with substituents having active hydrogen such as carboxy groups, sulfonic acid groups, hydroxyl groups, etc., or polymers substituted with these substituents. A method such as forming a complex with and making it insolubilized can be adopted.

More specifically, in the first method, as a crosslinking monomer,
For example, N,N'-methylenebisacrylamide, N,
N-diallylacrylamide, triacryl formal, N,N-diacryloimide, N,N-dimethacryloimide, ethylene glycol acrylate,
Ethylene glycol dimethacrylate, various polyethylene glycol diacrylates, various polyethylene glycol dimethacrylates, propylene glycol diacrylate, propylene glycol dimethacrylate, various polypropylene glycol diacrylates, various polypropylene glycol dimethacrylates, 1,6-butylene glycol diacrylate, 1, 6-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, glycerol dimethacrylate, i.
Uses opentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolethane triacrylate, tetramethylolmethanetetramethacrylate, tetramethylolmethane triacrylate, divinylbenzene, diallyl phthalate, etc. can.

The N-alkoxymethyl (meth)acrylamide derivatives in the second method also include N-hydroxymethyl (meth)acrylamide, such as N-methylol (meth)acrylamide.
Acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide,
N-n-butoxymethyl (meth)acrylamide, N
-tert, -butoxymethyl(meth)acrylamide, etc. can be used. The ratio of lipophilic monomer to (meth)acrylamide derivative having amphiphilic properties in the sixth method varies depending on the combination of (meth)acrylamide derivative and lipophilic monomer; The content is 1% or more, preferably 3% or more. The fourth method of bulk polymerization is a method of directly polymerizing without diluting with a solvent to obtain a polymer block, or a method of polymerizing in a monomer cylinder while suspending in a solvent to obtain a particulate polymer. etc. can be adopted. In the fifth method, which is a method of heat treating a polymer, the heating conditions vary depending on the polymer and are not uniform, but generally, bulk polymerization is carried out at a temperature of 60 to 250°C, preferably 8o to 200°C. A polymer obtained by suspension polymerization, solution polymerization, etc. is heat-treated. At this time, in the solution polymerization, drying or distillation of the solvent may be performed concurrently with heat treatment. The sixth method of integrating with fibrous materials, etc. is to use water-insoluble materials such as fibers such as cellulose, nylon, polyester, acrylic, or nonwoven fabrics made of polypropylene, ethylene-propylene copolymers, etc. A method of impregnating or graft polymerizing the above-mentioned (meth)acrylamide derivative onto a fibrous material or a water-insoluble porous inorganic material such as silica, alumina, or zeolite, a method of impregnating a polymer, etc. can be employed. 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 amine group into the polymer in advance. Amine groups can be easily introduced by copolymerization, but in the case of hydroxyl groups, they can be introduced by copolymerization with hydroxyethyl methacrylate, inopropenylphenol, etc., or by copolymerization with vinyl acetate, glycidyl methacrylate, etc., and then with a basic substance. Another method is to introduce hydroxyl groups by saponification.

Next, the above-mentioned polymer and a polyfunctional compound such as shrimp chlorhydride 7 are reacted in the presence of a basic substance to crosslink and insolubilize the polymer. At that time, when the aqueous solution is insolubilized as it is, it becomes agar-like, and it is put into practical use by crushing it. Further, when an aqueous solution is dispersed in oil to make it insolubilized, it becomes a granular gel.

The eighth method is copolymerization with the above-mentioned monomers having active hydrogen, complexing with copolymers of these monomers, replacing active hydrogen in the copolymer with ammonium ions, etc., and first mixing. This is a method in which a complex is formed by adding an acid to activate the active hydrogen and make it insolubilized.

Each of the eight methods described above may be used alone or in combination. In general, more effective results can be obtained when used together.

More specific polymerization methods that can be adopted in producing the resin for concentration of the present invention according to the above-mentioned method include:
For example, (1) a method in which the monomer is directly polymerized without diluting it with a solvent to produce a polymer block, (2) a method in which the monomer is polymerized in a solvent and post-polymerization': a method in which the polymer is precipitated in chestnut or a poor solvent and polymerized. (3) A method of obtaining a particulate polymer by turbid polymerization, (4) A method of obtaining a polymer latex by emulsion polymerization, (5) A fibrous substance or a porous inorganic substance insoluble in water. A method of integrating the polymer by impregnation with a polymer solution or graft polymerization can be adopted. At this time, the polymerization can be started by heating alone, but better results are usually obtained by using a polymerization initiator. The polymerization initiator is not limited as long as it has the ability to initiate radical polymerization, and examples include inorganic peroxides, organic peroxides, combinations of these peroxides and reducing agents, and azo compounds. be. Specifically, ammonium persulfate, potassium persulfate, hydrogen peroxide, te-10-butyl peroxide, benzoyl peroxide, cumene hydroxy peroxide, 1e(t-butylperoxy-2-ethylhexanoate, butyl perbenzoate) Reducing agents that can be combined with these include sulfites, hydrogen sulfites, salts with low ionic valences such as iron, copper, and cobalt, organic amines such as aniline, and reducing sugars such as aldoses and ketoses. Azo compounds (in ~, azobisinobutyronitrile, 2,2
'-Azobis-2-amidinopropane hydrochloride, 2,2'
-azobis-2,4-dimethylvaleronitrile, 4,4
'-Azobis-4-cyatubarein, silica, etc. can be used. It is also possible to use two or more of the above polymerization initiators in combination. In this case, the amount of the polymerization initiator added is within a commonly used quantitative range, for example, 0.01 to 5% by weight, preferably 0.05-5% by weight, based on the monomer.
It is in the range of 2% by weight.

Among the polymers obtained in this way, those in block form or the polymers obtained by distilling off the solvent can be crushed into powder K, or melted into granules, flakes, fibers, or films. Molded, particulate polymers can be provided in their raw form, and latex and sliver polymers can be impregnated and coated on fibrous materials such as cloth and paper, or formed into films to provide concentrated resins. .

By the above-mentioned method, it is possible to produce various forms of concentrating 4-4 fat, but the form depends on how the la@ resin is used, so it cannot be uniformly defined.

However, these resins are generally used in powder or granule form in many cases.

The powdered product undergoes gel polymerization in an aqueous solution as described above.
Thereafter, a number of methods can be used, such as drying and grinding. On the other hand, granular products are generally easily produced by suspension polymerization, but since the N-alkyl- or tri-alkylene-substituted (meth)acrylamide used in the present invention is generally highly water-soluble, Suspension polymerization methods include reverse-phase suspension polymerization in which a monomer or its aqueous solution is dispersed in oil, and a method in which a large amount of electrolyte, etc., is dissolved in an aqueous solution to suppress the solubility of the monomer. Methods such as salting-out suspension polymerization and further precipitation suspension polymerization in which polymerization is performed at a high temperature higher than the clouding point of the polymer to precipitate the polymer are employed. Furthermore, porous inorganic particles such as silica, alumina, and zeolite, whose surfaces are impregnated with a polymer solution or integrated with a polymer by a method such as graft polymerization, may also be used. Furthermore, it is also possible to produce porous [TF fat] by adding a third component that is compatible with the monomer but not compatible with the polymer. .

The concentration resin produced as described above is in a solid state,
It has a very unique ability to absorb and retain water when it comes into contact with an aqueous solution, and even in the presence of a large excess of water, it shrinks and releases water when heated.

Furthermore, advantageously, the water absorption, retention and release processes described above can be repeated. Further, the amount of water absorbed by the nucleating agent changes depending on the composition of the resin, temperature, composition of the aqueous solution, etc. Regarding the resin composition, in a copolymer of lipophilic monomers among the copolymerizable monomers mentioned above, as the ratio increases, the amount of water absorbed decreases, and the mechanical strength of the growing. In addition, in copolymers with hydrophilic or ionic monomers, as the ratio increases, the water absorption itself increases, but the change in water absorption due to temperature is small (and the mechanical strength also decreases. As shown above, the water-absorbing bone changes depending on the resin composition, but generally at room temperature (25°C)
can absorb about 2 to 100 times its own weight of water, and lowering the temperature can increase the amount of water absorbed.

When low-molecular substances such as inorganic salts, organic salts, and water-soluble organic substances are dissolved in the aqueous solution, the aqueous solution containing these substances can be incorporated into the resin as is. No 1
When geometric salts are dissolved, the amount of water absorbed by conventional water-absorbing resins decreases rapidly. Therefore, it can be concluded that the effect of coexisting salts on the amount of water absorbed in distilled water and 1N aqueous sodium chloride solution is small.

Furthermore, depending on the type of coexisting salt, for example, calcium chloride has been found to increase water-absorbing bone.

As mentioned above, the concentration resin of the present invention can be incorporated into the gel during water absorption or excluded depending on the molecular weight of the solute.
There are two cases in which the concentration resin has a molecular weight fractionation ability, and the molecular weight fraction changes depending on the composition and temperature of the resin. Generally, if the water absorption is relatively large due to a low insolubilization rate, such as a low degree of crosslinking, or a copolymer with a hydrophilic or ionic monomer, the molecular weight cut-off will be large. Become. On the other hand, if the degree of crosslinking is high (such as when the polymer is a copolymer with a lipophilic monomer and the amount of water absorbed is relatively small), the molecular weight cutoff will be small.

The specific value of the molecular weight fraction cannot be stated uniformly because it varies greatly depending on the composition of the resin, the temperature, the composition of the aqueous solution, and the type of concentrated substance. When concentrating polyethylene glycol with a relatively expanded molecular chain in an aqueous solution using a resin in which acryloylpyrrolidine is crosslinked with methylenebisacrylamide, the molecular weight cutoff is on the order of 1.000. On the other hand, there are compounds that have a compact structure in aqueous solutions such as text run, tanning, and zeolization, and their molecular weight fractions exist on the order of io and ooo. In addition, the fractionated molecular bone is of course not uniquely determined;
It becomes something with a distribution.

In addition, when the temperature of the resin that has absorbed water is increased, the resin contracts and releases water.As the temperature is further increased, the contraction of the resin becomes extremely slow even when heated above a certain temperature. A transition point may be observed.The transition temperature is determined by the composition of the resin and can be controlled within the range of approximately 1o-ioooC.The amount of shrinkage of the resin near the transition temperature depends on the composition of the resin, the composition of the aqueous solution, etc. Although it varies, it is generally between 1 and 20 times its own weight.As mentioned above, the resin is repeatedly heated and cooled to separate and retain water, but the temperature range at which the resin absorbs water at that time is generally 0~100°C
It is. On the other hand, it absorbed water. To heat and shrink fI fat, liquid water or gaseous water may be used, and the temperature varies depending on the purpose of use of the resin, but is generally 10-
The temperature is 200°C.

A specific method for concentrating is to bring the resin into contact with an aqueous solution to be concentrated to absorb water, separate the absorbed resin from the aqueous solution, and place the separated resin in a higher temperature atmosphere to release water. By repeating this series of operations, a large amount of aqueous solution can be concentrated. At this time, if a low molecular weight substance coexists in the aqueous solution, only the high molecular weight substance is concentrated without the low molecular weight substance being laterally tightened.

In a basic embodiment, a concentrating resin in the form of powder, flakes, beads, fibers, or film is first brought into contact with the aqueous solution to be concentrated to absorb water, and then the vaginal resin is dissolved in the aqueous solution. Specific methods for water absorption and subsequent separation include: ``Directly adding water to the aqueous solution to absorb water, and then separating by sedimentation, filtration, centrifugal separation, etc.; A method in which the nucleating agent is placed in something that can isolate it from the aqueous solution, such as a bag, and brought into contact with the aqueous solution to absorb water and separate the resin; Methods such as immersing in an aqueous solution to absorb water and then pulling it up can be adopted.Also, the above operation may be performed in multiple stages. convenient.

Methods for releasing water from the resin that has absorbed water in a high-temperature atmosphere include immersing it in high-temperature water, blowing heated gas such as steam, and leaving it in high-temperature air such as in a dryer. methods etc. can be adopted.Also,
When using repeatedly, it is effective to drain the water well in order to increase the subsequent water separation efficiency.

Function: Examples of specific applications of the concentrating resin of the present invention include condensation of various water bath liquids, foods, amino acids, dandelions, polysaccharides, enzymes, antibiotics, and emulsion bacteria, which are difficult to use with evaporation methods. Concentration of aqueous solutions containing substances that are easily altered by body heat, etc. and crystallization as a result can be mentioned.

The paving fat of the present invention can be easily regenerated by utilizing the characteristics of swelling and absorption ≦4 due to temperature changes, and even in the coexistence of inorganic salts, the water absorption bone decreases little and it absorbs water. It has excellent properties such as good shape retention after drying, and has the following effects. In other words, first of all, since water separation does not utilize phase changes such as evaporation or freezing, water separation is possible at low energy and energy costs, and does not necessarily require large-scale equipment. It is possible to install it anywhere. Second, at low temperatures, the amount of water is 14#
Since the capacity is large, it is extremely effective for condensation or crystallization of aqueous solutions containing substances that are easily altered by heating. Third, in an aqueous solution in which buffering agents such as enzymes, polysaccharide-1 proteins, and antibiotics 6 coexist, the electrolyte serving as the buffering agent is not concentrated, but remains at its original concentration, and only polymeric substances such as proteins are present. It has the effect of being able to concentrate.

The present invention will be further explained below with reference to Examples.

Example 1 N-acryloylpyrrolidine 50' 7.59 and N,
N'-methylenebisacrylamide 267 and water 1.1
An aqueous solution of N-acryloylpyrrolidine containing 0.5 wt% N,N-methylenebisacrylamide dissolved in 70f was prepared. After cooling the aqueous solution to 10°C, 2t
The solution was transferred to a stainless steel Ziwer bottle, and nitrogen gas was bubbled through it for 1 hour using a ball filter at a flow rate of 1 t/=. Next, a solution prepared by dissolving ammonium persulfate 2552 in water 1olP and sodium bisulfite 116 were added to the aqueous solution.
2 was dissolved in 10 g of water, and 1 solution was added at the same time, and the aqueous solution was polymerized adiabatically.

The obtained gel was shredded, dried, and further crushed to give 20
A fraction of ~100 meth was collected and used as a sample. 0.
The sample powder of No. 52 was added to 0.5% bovine serum albumin aqueous solution M20, stirred for 1 hour at a specified temperature, left to stand for 5 minutes, and the absorbance of the supernatant liquid was measured at 254 nm. The immersion degree of the clear liquid was calculated. The concentration of the supernatant at each temperature is 0.71% at 30°C and 0.78% at 15°C.
, 086% at 5°C. Furthermore, when the sample powder was observed under a microscope before and after the measurement, it was found that the sample powder was not crushed due to temperature changes or stirring.

Example 2 A sample powder was obtained in the same manner as in Example 1 using a 60% aqueous solution of Nn-propylacrylamide containing 0.5 wt% of N, N-methylenebisacrylamide. The sample powder 062 and 0.5% bovine serum albumin aqueous solution 20rn1. Using the same method as in Example 1, the concentration of bovine serum albumin crystal liquid was measured at each temperature.
%, and 0.84% at 5°C.

Example 6 After salting out and suspension polymerizing an aqueous N-acryloylpyrrolidine solution containing 4 and 7 wt% of sodium 2-acrylamido-2-phenylpropanesulfonate using Glauber's salt etc.
The obtained gel particles were dried and used as a sample. The sample particles 052 were added to a commercially available milk filter 02 at 15°C, stirred, and then distributed from house to house. 182 pieces of liquid F were obtained, and 127 pieces of water could be dehydrated.

Example 4 0.5ii' of the sample particles obtained in Example 6 were added to 50f of SBR latex (manufactured by Mitsui Toatsu Kagaku, Polylac 755) with a concentration of 43% at room temperature and stirred. After thorough stirring, the concentration of tear fluid was measured at each house and found to be 52%.

Examples 5 to 12 Sample powder 052 obtained in Example 1 was added to 20 ml of a 05% aqueous solution of polyethylene glycol having the molecular weight shown in Table 1.
After stirring at the specified temperature for 1 hour, let stand for 5 minutes,
The concentration of the supernatant was calculated by measuring the refractive index of the supernatant, and the results shown in Table 1 were obtained.

Examples 13 to 17 The concentration of the supernatant liquid was measured in the same manner as in Example 5 using the sample powder 062 obtained in Example 2 and 05% aqueous solution 20 of polyethylene glycol having the molecular weight shown in Table 2. The results shown in Table 2 were obtained.

Examples 18 to 22 A supernatant liquid was prepared in the same manner as in Example 5 using 0.25 f of sample particles obtained in the example filter and 20 mm of a 0.5% aqueous solution of polyethylene glycol having the molecular weight shown in Table 6. The concentration was measured and the results shown in Table 3 were obtained.

Table 1 Table 2 Examples 23 to 27 Supernatant was prepared in the same manner as in Example 5 using the sample powder 052 obtained in Example 1 and 20 m of a 0.5% aqueous solution of dextran having the molecular weight shown in Table 4. Measure the concentration of the liquid and Table 4
The results shown are obtained.

Examples 28 to 32 The concentration of the upper 1 q solution was measured in the same manner as in Example 5 using 0.61 of the sample powder obtained in Example 2 and 20 rnl of a 05% aqueous solution of dextran with the molecular weight shown in Table 5. The results shown in Table 5 were obtained.

Examples 36-36 Sample particles 0252 obtained in Example 6 and 0.5% aqueous solution of dextran with the molecular weight shown in Table 6 20#+7
! The surface area of the supernatant liquid was measured using the same method as in Example 5, and the results shown in Table 6 were obtained.

Table-6 Table-4 Table-5 Table-6 Examples 37 to 41 Example 1 was prepared using sample powder 0052 obtained in Example 1 and 2rnl of a 05% aqueous solution of a protein having the molecular weight shown in Table 7. The concentration of the supernatant was measured using the same method and Table 7
The results shown are obtained.

Examples 42 to 46 The concentration of the supernatant liquid was measured in the same manner as in Example 1 using the sample powder 0062 obtained in Example 2 and 2 m7 of a 05% aqueous solution of a protein with the molecular weight shown in Table 8. The results shown in Table 8 were obtained.

Table-7 Table-8 Procedures Amendment Written by Manabu Shiga, Commissioner of the Patent Office, dated 30th month, 1985. 1. Display of the case. 1984 Patent Application No. 106464. 2. Name of the invention. Concentrating resin. 6. Case of person making an amendment. Relationship with Patent Applicant Address: 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo 4゜Number of Inventions Increased by Amendment Column 6 of “Detailed Description of the Invention” of the Specification, No. 31 of the Specification of Contents of the Amendment Add the following example after page 1 [-8J.

Example 47 A sample powder was obtained in the same manner as in Example 1 using a 60% aqueous solution of N-isopropylacrylamide containing 0.5 wt% of N,N'-methylenebisacrylamide. Commercially available milk at 15°C6
After adding to 02 and stirring, it was separated into F.

242 ml of p liquid was obtained, and 6 f of water could be dehydrated.

Example 48 0.5 wt% N, N with N'-methylenebisacrylamide, 30% N in N-diethylacrylamide
.

The N-dimethylformamide solution was transferred to a dewar bottle, and after the liquid was purged with nitrogen, 1.5% azobisin butyronitrile was added at 30°C, and polymerization was carried out adiabatically.

The resulting gel was cut into pieces, dried at 120°C, and further ground to collect 20 to 100 mesh fractions, which were used as samples. The sample powder 052 was mixed with SBR latex (manufactured by Mitsui Toatsu Chemicals, trade name, Polylac 755) with a concentration of 43%.
0f at room temperature and stirred. After thorough stirring, the concentration of the filtrate was measured by F separation and found to be 45%.

Example 49 Using a 30% aqueous solution of N-acryloylmorpholine containing 05% N, N-methylenebisacrylamide,
A sample powder was obtained in the same manner as in Example 1. 0.5f of the sample powder was mixed with 5BI (latex (manufactured by Mitsui Toatsu Chemicals, trade name, Polylac 755) at a concentration of 43%)
f and stirred at room temperature. After thorough stirring, the concentration of Solution F was measured at each door and found to be 50%. ” Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) General formula (1) or general formula (Ill) (in the above formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, a methyl group, or an ethyl group, and R8 is a methyl group, an ethyl group, or a propyl group) represents a group.) General formula (In the above formula, R1 is a hydrogen atom or a methyl group, A is +CI-
I,, -4 and n is 4 to 6 or +CH2+20 + C
Represents H2+1. ) N-alkyl- or N-alkylene-substituted (meth)acrylamide homo or copolymers;
Or a concentration resin made by making a copolymer with other copolymerizable monomers insoluble in water.