JPH0160481B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a water-insoluble polymer, and more particularly to a method for producing a water-insoluble polymer having a desired shape.

Conventionally, manufacturing a water-insoluble polymer with a desired size and shape from a water-soluble radically polymerizable monomer and a crosslinkable monomer having two or more radically polymerizable vinyl groups has a wide range of moldability. There are problems with shape distribution, controllability of polymerization reaction, etc.
Industrial use was extremely difficult.

Suspension polymerization has been used as a method for producing particularly particulate water-insoluble polymers using the above-mentioned monomers. In this suspension polymerization method, an aqueous monomer solution and a surfactant are added to water and a medium that does not dissolve the monomer at all or hardly dissolves it, and is thoroughly stirred to turn the aqueous monomer solution into a fine suspension. By adding an easily soluble polymerization initiator, polymerization was carried out in suspended aqueous solution droplets to produce particulate water-insoluble polymers. The particle size of the granular water-insoluble polymer obtained by this conventional method varies depending on the medium used, the type of monomer and surfactant, the shape of the polymerization tank, the shape of the stirring blade, and the stirring speed, but it is usually small, 0.1 mm or less. Suitable for producing granular water-soluble polymers with a specific particle size, and the resulting particles have a wide particle size distribution, and when using a granular polymer with a specific particle size, the resulting particles must be sieved before use. However, the production method could not be called economical, as particulate polymers having a particle size other than the intended one were discarded.
Furthermore, it is extremely difficult to produce granular polymers with large particle diameters of several millimeters or more, and when attempting to produce granular polymers with large particle diameters, large lumpy polymers are generated and the walls of the polymerization tank are damaged. Fouling is likely to occur, making it difficult to continue polymerization. Another drawback is that water-insoluble polymers in shapes other than granules cannot be produced by this suspension polymerization method.

The present inventors have finally arrived at the present invention as a result of intensive research into a method for stably producing a water-insoluble polymer having a desired shape and a narrow shape distribution.

That is, in the present invention, a water-soluble radically polymerizable vinyl monomer and a crosslinkable vinyl monomer having at least two radically polymerizable vinyl groups are added to an aqueous solution of a water-soluble alginate, and the solution is dissolved in water to form an aqueous solution or suspension. By contacting the alginate with a solution having the ability to gel, a water-insoluble gel with a desired shape is formed, and then this gel is subjected to radical polymerization to form water with a desired shape. It is characterized by producing an insoluble polymer. The alginate contained in the water-insoluble polymer obtained in the present invention can be removed, if necessary, by bringing it into contact with a reagent that dissolves alginate gel. This produces a well-shaped water-insoluble polymer that does not contain alginate. According to the method of the present invention, not only can a polymer with a desired shape be produced, but also the polymerization heat accompanying polymerization can be easily removed, the polymerization reaction can be controlled, and the polymerization tank is hardly contaminated. There are also advantages such as not having

Typical examples of water-soluble radically polymerizable vinyl monomers used in the method of the present invention include salts of unsaturated carboxylic acids such as alkali metal salts such as sodium and potassium of acrylic acid or methacrylic acid, hydroxyethyl acrylate, and hydroxypropyl. Acrylate, aminoethyl acrylate, N-methylaminoethyl acrylate,
N,N-dimethylaminoethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, aminoethyl methacrylate, N-methylaminoethyl methacrylate,
Esters of acrylic acid and methacrylic acid such as N,N-dimethylaminoethyl methacrylate, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N- Acrylamide derivatives such as diethylacrylamide, alkali metal or magnesium salts of 2-acrylamidoethanesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid, methyl vinyl ketone, o, m and p-aminostyrene, vinylsulfonic acid or allyl Examples include alkali metal salts of sulfonic acid, alkali metal salts or magnesium salts of styrene sulfonic acid, and N-vinylpyrrolidone, and these monomers can be used alone or in combination of two or more.

Typical examples of crosslinkable vinyl monomers having two or more radically polymerizable vinyl groups used in the method of the present invention include N,N-methylenebisacrylamide, N,N-propylenebisacrylamide, and N-acrylamide. yl acrylamide, diacrylamide dimethyl ether, 1,2-diacrylamide ethylene glycol, ethylene urea bisacrylamide, polyethylene glycol, or an ester of acrylic acid or methacrylic acid of an ethylene oxide and propylene oxide copolymer having hydroxyl groups at both ends, and 1,
Examples include 3,5-triacrylhexahydro-s-triazine.

The ratio of the water-soluble radically polymerizable vinyl monomer and crosslinkable vinyl monomer used in the production of the water-insoluble polymer in the present invention is usually from 100:0.05 to 100:20, preferably 100:
It is preferable to use a ratio of 0.1 to 100:15. When the proportion of cross-linkable vinyl monomer is low, the resulting water-insoluble polymer easily swells with water, exhibits elasticity in the state of a so-called hydrous gel swollen with water, and has low tensile strength; When the water-insoluble polymer becomes higher, it becomes difficult to swell with water, and a water-containing gel swollen with water tends to have a strong tensile strength, but becomes brittle.

Before polymerization, these radically polymerizable monomers are dissolved in water together with a water-soluble alginate to form an alginate aqueous solution, and at this time, some of the monomers may be used in a state suspended in water. The concentration of the radically polymerizable monomer in the alginate aqueous solution is usually 0.1% to 50% by weight, preferably 1% to 20% by weight, expressed as the sum of the water-soluble radically polymerizable vinyl monomer and the crosslinkable vinyl monomer. can be,
or 20 to 45% by weight to obtain a harder polymer.
It can be done.

In the method of the present invention, a water-insoluble gel (hereinafter referred to as alginate gel) is prepared by incorporating a radically polymerizable monomer into the gel by gelling alginate;
This is subjected to a polymerization reaction, and it is usually preferable to use a radical initiator in this polymerization reaction. The radical initiators used include common water-soluble radical initiators such as hydrogen peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate.
These can usually be added to the alginate aqueous solution before preparing the alginate gel. Of course, a sparingly water-soluble or water-insoluble radical initiator can also be used after being dispersed in the alginate aqueous solution. That is, these radical initiators can be contained in the alginic acid gel in the same manner as the polymerizable monomers. Of course, before the subsequent radical polymerization reaction, it is preferable to suppress decomposition of the radical initiator by lowering the temperature or using a radical initiator that is difficult to decompose at low temperatures. As will be described later, when the polymerization reaction is carried out using radiation or the like, the alginic acid gel may not contain a radical initiator. The amount of radical initiator used is usually 0.01% based on the sum of radically polymerizable vinyl monomer and crosslinkable vinyl monomer.
to 10%, preferably from 0.1% to 5%. In addition to these radical initiators, there is no problem in adding anything that does not interfere with the alginate gel production reaction and polymerization reaction.

In the present invention, when producing a water-insoluble polymer with a desired shape, the above-mentioned radically polymerizable monomers (radically polymerizable vinyl monomer and crosslinkable vinyl monomer) and, if necessary, a radical initiator are added to water-soluble alginic acid in advance. The alginate is dissolved or partially suspended in water together with a salt, and this liquid is brought into contact with a liquid having the ability to gel the above-mentioned alginate to first gel it into a gel of the desired shape, and then polymerize the radically polymerizable monomer. The water-insoluble polymer is used, and the water-soluble alginates used to gel the radically polymerizable monomer solution include sodium alginate, potassium alginate, and ammonium alginate. Alginic acid is a copolymer of mannuronic acid and guluronic acid obtained from seaweed, and its composition varies depending on the place of production and the time of collection, but it can be gelled by a water-soluble alginate gelling agent regardless of its composition. Can be used. Moreover, the molecular weight of alginic acid used is in the range of 1,000 to 1,000,000. The concentration of alginate in the water-soluble alginate aqueous solution used to produce the alginate gel is usually from 0.1% by weight to 20% by weight, preferably from 0.5% by weight to 10% by weight.
When the alginate concentration is low, the strength of the alginate gel obtained is weak, making it difficult to form a gel in the desired shape, and the radically polymerizable monomer tends to flow out from the gel. Conversely, when the alginate concentration is high, the alginate gel obtained is weak. The strength of the gel increases, but
The viscosity of the alginate solution increases, making it difficult to handle, difficult to form into a gel of the desired shape, and uneconomical. It is preferable that dissolved oxygen be removed from the water-soluble alginate aqueous solution containing these radically polymerizable monomers in order to allow the subsequent polymerization reaction to proceed smoothly. It is advisable to introduce an inert gas such as nitrogen for this purpose.

Examples of solutions capable of gelling the aqueous solution of water-soluble alginate in the present invention include pH 7.
The following acidic aqueous solutions are aqueous solutions containing divalent or higher polyvalent metal ions other than magnesium and mercury. Examples of acidic aqueous solutions with a pH of 7 or less include hydrochloric acid, sulfuric acid,
Aqueous solutions of inorganic acids such as nitric acid, aqueous solutions of organic acids such as formic acid and acetic acid, and polyvalent metal ions.
Ca, Fe, Mn, Co, Ni, Zn, Cd, Sr, Cu, Pd,
This is a solution containing metal ions such as Ba metal.
As will be described later, when containing living microorganisms, it is preferable to use an acidic aqueous solution with a pH of 4 to 7.

In the present invention, the method for producing an alginate gel containing a radically polymerizable monomer and optionally a radical initiator is to mix an alginate aqueous solution or suspension containing a radically polymerizable monomer and optionally a radical initiator with an alginate gelling agent. This can be carried out by contacting with a solution.

The shape of the resulting alginate gel can be varied greatly depending on the contact method described above. For example, by dropping an alginate aqueous solution containing a radically polymerizable monomer into an alginate gelling agent solution, a spherical alginate gel with high sphericity and an extremely narrow particle size distribution can be formed. The particle size of the spherical gel depends on the viscosity of the alginate aqueous solution, the shape of the alginate aqueous solution dropping nozzle, etc. Furthermore, when an aqueous alginate solution containing a polymerizable monomer is injected into an alginate gelling agent solution, the shape of the alginate gel obtained can be changed depending on the shape of the injection port. Furthermore, by injecting an alginate aqueous solution into the mold in advance and immersing the mold in the gelling agent solution with a part of the mold open, the gelling agent solution enters the mold through the opening and comes into contact with the alginate aqueous solution, causing the surface It is also possible to form an alginate gel in a desired shape very easily by gelling the alginate solution and penetrating the inside of the mold, and finally gelling the entire alginate aqueous solution inside the mold. It is also possible to spread an alginate aqueous solution in a shallow dish and gently pour an alginate gelling agent solution from above to gel it into a thin plate, which can then be further stamped. Furthermore, a gel having a desired shape can be obtained by blending an alginate aqueous solution and an alginate gelling agent solution at high speed and immediately placing the mixture in a mold. During this gelling operation, alkali phosphate or alkali citrate may be added as a gelling retarder. Furthermore, once the gel has been shaped, operations such as cutting or cutting may be performed to give it a desired shape. The preparation of these alginate gels begins with the decomposition of the radical initiator;
It is necessary to operate below the temperature at which polymerization begins. It is usually preferable to carry out the process at a temperature range of 0°C to 100°C. Further, it is preferable to prepare the alginate gel under an inert gas (for example, nitrogen gas) atmosphere in order to smoothly proceed with the subsequent polymerization reaction.

The obtained alginic acid gel containing the radically polymerizable monomer is subsequently subjected to a polymerization reaction. The polymerization reaction is preferably carried out by placing the alginic acid gel in a solvent that does not interfere with radical polymerization (eg, water, alcohol, hydrocarbon, etc.) and removing oxygen. Of course, the polymerization may be carried out without using a solvent under a stream of an inert gas from which oxygen has been removed. The polymerization temperature varies depending on the type of radical initiator used, but it may be carried out at a temperature equal to or higher than the decomposition temperature of the radical initiator. When it is preferable to conduct the polymerization at a low temperature, it is recommended to bring the gel into contact with a reagent that promotes the decomposition of the radical initiator or a liquid containing this reagent in order to lower the decomposition temperature of the radical initiator (for example, a solution containing this reagent may be brought into contact with the gel). (for tetramethylethylenediamine, ferrous ion for potassium persulfate, etc.). When the alginic acid gel containing the radically polymerizable monomer does not contain a radical initiator, the alginic acid gel can also be radically polymerized by irradiating the alginic acid gel with radiation. In the present invention, the operations of gelling an alginate aqueous solution or suspension and polymerizing the resulting gel may be performed separately, or may be performed continuously. In other words, if a gelling agent solution capable of gelling alginate is kept at a temperature higher than the decomposition temperature of the radical initiator, and an aqueous alginate solution containing a radically polymerizable monomer is brought into contact with this solution, an alginate gel will be formed. At the same time, polymerization starts, and a water-insoluble polymer with a desired shape can be synthesized. The water-insoluble polymer thus obtained contains a portion of the previously used and gelled alginate. If this alginate is unnecessary or has an interfering effect depending on the purpose of use, the alginate may be removed from the water-insoluble polymer gel. Things that can remove alginate include those that chelate polyvalent metal ions into water-soluble metal ions, such as sodium ethylenediaminetetraacetic acid, potassium acid, aqueous solutions of alkali metal phosphates, or aqueous solutions of alkali metal ions. Examples include aqueous solutions of oxides and carbonates, and the water-insoluble polymer after radical polymerization with these aqueous solutions is heated to 0°C.
It can be soaked or washed at temperatures between 100℃ and 100℃.

Although the water-insoluble polymer obtained by the method of the present invention does not dissolve in water, it has sufficient hydrophilicity, and the water-insoluble polymer obtained after polymerization is also in a swollen state. Depending on the purpose of use, the water-insoluble polymer may be used as it is after being swollen with water, or the water-insoluble polymer may be used after being thoroughly washed with water, or it may be dried to remove water. It may also be used.

The well-shaped water-insoluble polymer obtained by the present invention can take advantage of its well-shaped shape when used as a carrier for an enzyme active substance. In particular, if the desired microorganisms are added before preparing the alginate gel, it is possible to form a well-shaped water-insoluble polymer that encloses the microorganisms, making it effective for enzymatic reactions that utilize these microorganisms. It becomes possible to use it. In addition, the dried water-insoluble polymer obtained by the present invention has extremely high water absorption and can be used as a water-absorbing polymer, such as soil conditioners, paper diapers, etc.
Its characteristics as a well-shaped water-insoluble polymer can also be used as sanitary materials such as sanitary napkins.

Examples are given below to explain the present invention in more detail, but the present invention is not limited by these Examples.

Example 1 15g of acrylamide, 1g of N,N'-methylenebis(acrylamide), 2g of sodium alginate (Datsuku Algine NSPM manufactured by Kamogawa Kasei)
was dissolved in water to make a total of 100 g, and 1 ml of 1% by weight hydrogen peroxide solution was added to prepare an aqueous solution, and nitrogen gas was bubbled through the solution. The above aqueous solution was added dropwise to a solution prepared by dissolving 1 g of ferrous sulfate and 6 g of calcium chloride in 300 ml of water under a nitrogen stream while maintaining the liquid temperature at 20°C. The resulting solution containing the spherical particulate gel was maintained at 50°C under a nitrogen stream to carry out a polymerization reaction for 1 hour, resulting in the formation of spherical water-insoluble copolymer particles with a uniform particle size of 3 mm.

Example 2 20 g of water-insoluble polymer particles produced by the method of Example 1 were placed in container 1, 500 ml of 2N sodium hydroxide aqueous solution was added, and the mixture was stirred at 20°C for 5 hours to substantially remove the alginic acid portion. 4mm not included
Spherical water-insoluble polymer particles with uniform particle sizes were obtained.

Example 3 After dissolving 10 g of 2-acrylamide-2-methylpropanesulfonic acid and 1 g of N,N'-methylenebis(acrylamide) in water, the pH of the solution was adjusted to 7 with sodium hydroxide, and further dissolved with water. Dilute the total solution to 98 g, and add 2 g of sodium alginate (Datsuk Algin NSPM manufactured by Kamogawa Kasei).
An aqueous solution was prepared by dissolving 1 ml of a 5% by weight ammonium persulfate aqueous solution. Nitrogen gas was poured into this aqueous solution to drive out dissolved oxygen.
1g of tetramethylethylenediamine and 6g
The above aqueous solution was added dropwise to a solution prepared by dissolving 300 g of calcium chloride in water under a nitrogen stream while keeping the temperature of the aqueous solution at room temperature. The solution containing the generated spherical gel was maintained at 80° C. under a nitrogen stream to carry out a polymerization reaction for 1 hour to produce spherical water-insoluble copolymer particles. Pack 20g of the above particles into a column with an internal volume of 60ml, and add 20ml/1N sodium hydroxide aqueous solution to the column.
By flowing the mixture at a rate of H for 10 hours, spherical water-insoluble copolymer particles substantially free of alginic acid moieties and having a uniform particle size of 5 mm were obtained.

After filling 20 g of the obtained gel into a 40 ml tubular reactor, it was sterilized in a steamer at 120° C. for 15 minutes. 10% glycose, 0.15 yeast extract
%, ammonium chloride 0.25%, sodium chloride
0.1%, dipotassium phosphate 0.55%, magnesium sulfate 0.01%, calcium chloride 0.001%, and citric acid 0.3g. 24 to the reactor while keeping the reactor temperature at 30 °C at a rate of hr.
Time supplied. Thereafter, the circulating solution was switched to the growth medium described in Example 7, and the reactor was kept at 30° C. and circulated for 3 days, and the ethanol concentration in the effluent from the reactor outlet was 4% by weight.

Example 4 After dissolving 9 g of 2-acrylamido-2-methylpropanesulfonic acid, 1 g of 2-hydroxyethyl methacrylate, and 1 g of N,N'-methylenebis(acrylamide) in water, a solution was added with sodium hydroxide. Adjust the pH of the solution to 7, dilute it with water to make a total solution of 98 g, add 2 g of sodium alginate (Kamogawa Kasei Datsuku Alginate)
After dissolving NSPM), 1 ml of 1% by weight hydrogen peroxide solution was added to prepare an aqueous solution. Nitrogen gas was poured into this aqueous solution to drive out dissolved oxygen. 1g
After dissolving ferrous sulfate in 300 ml of water, the pH of the solution was adjusted to 1 using concentrated sulfuric acid, nitrogen gas was poured into the solution to drive out dissolved oxygen, and the above aqueous solution was heated to a temperature of 20°C. It was added dropwise under a nitrogen stream while maintaining the temperature.
The resulting solution containing the spherical gel with uniform particle size was maintained at 50° C. under a nitrogen stream to carry out a polymerization reaction for 3 hours to produce water-insoluble copolymer particles.
By treating 20g of these particles by the method of Example 2, particles with a particle size of 3.
mm spherical water-insoluble copolymer particles were obtained.

Example 5 An aqueous solution containing a vinyl monomer prepared by the method of Invention 3 was mixed with sulfuric acid dibasic acid prepared by the method of Example 4.
A spherical gel was produced by injecting the iron into an aqueous solution containing iron using a syringe under a nitrogen stream while keeping the temperature at 20°C. When the aqueous solution containing ferrous sulfate containing this spherical gel was subjected to a polymerization reaction for 3 hours by keeping it at 50°C under a nitrogen stream, spherical water-insoluble copolymer particles with a uniform particle size of 8 mm were produced. . By treating 20 g of the obtained water-insoluble copolymer particles by the method of Example 2, spherical water-insoluble copolymer particles substantially free of alginic acid moieties and having a uniform particle size of 10 mm were obtained. .

Example 6 Sodium alginate (Kerugin MV manufactured by Sansho)
100 g of a 5% aqueous solution of was sterilized by heating at 120°C for 10 minutes, then 1 g of polyethylene glycol dimethacrylate with a molecular weight of 1000, 5 g of sodium 2-acrylamide-2-methyl-propanesulfonate, and 0.05 g of ammonium persulfate were added. Sterilized nitrogen gas was blown into this solution, and 50 platinum loops of Kyokai No. 6 yeast were added. Next, 5 of calcium chloride
% aqueous solution was placed in a 500 ml separable flask and heated at 120°C for 10 minutes, 1 g of tetramethylethylenediamine was added, and sterilized nitrogen gas was blown into the flask. This calcium chloride solution was heated at 20°C.
When the sodium alginate solution was dripped dropwise through a sterilized microtube pump while gently stirring, a gel with a particle size of about 3 mm was produced (this operation was performed using a sterilized nitrogen gas stream). (I went below). This gel suspension was then postpolymerized for 4 hours at 40°C. The obtained gel was aseptically packed into a jacketed glass column with a diameter of 2 cm and a height of 10 cm, and from the bottom, 10% glycose, 0.15% fermentation extract, 0.25% ammonium chloride, 0.1% sodium chloride, and dipotassium phosphate were added. 8 ml of yeast nutrient medium containing 0.55% magnesium sulfate, 0.01% magnesium sulfate, 0.001% calcium chloride and 0.3% citric acid/
The internal temperature was maintained at 30°C. One week after the nutrient medium started flowing, the gel was removed from the column, cut, and the cross section was observed under a microscope, and it was found that many yeast colonies were present near the gel surface. Furthermore, when this gel was placed in a 2% aqueous solution of tetrasodium ethylenediaminetetraacetate, the gel remained intact even after one day, making it clear that this gel was not an alginate gel.

Example 7 After dissolving 2g of sodium alginate (Datsukalgin NSPM manufactured by Kamogawa Kasei) in 87g of water,
An aqueous solution obtained by sterilizing by heating at 120℃ for 10 minutes and 9
g of sodium 2-acrylamide-2-methylpropanesulfonate, 1 g of N,N'-methylenebis(acrylamide) and 1 ml of 5% by weight ammonium persulfate aqueous solution were dissolved, and 10 platinum loops of Kyokai No. 6 yeast were added. The yeast cells were suspended. Next, 1 g of tetramethylethylenediamine was added to a 2% by weight aqueous calcium chloride solution that had been previously sterilized by keeping it at 120° C. for 10 minutes, and then sterilized nitrogen gas was blown into the solution. A spherical alginate gel was formed by dropping the suspension into this solution using a syringe. The average particle size of the alginate gel was 3 mm. Next, a polymerization reaction was carried out by heating the alginate gel-containing solution to 40°C while gently stirring it under a stream of sterilized nitrogen gas, and the resulting water-insoluble polymer containing alginate gel had a particle size of 3 mm. They were spherical particles. 20 g of these particles were packed into a glass column with a jacket of 40 ml volume, and kept at 30°C in a growth medium containing 10% glucose (composition: 0.15 yeast extract).
wt%, ammonium chloride 0.25 wt%, sodium chloride 0.1 wt%, dipotassium phosphate 0.55 wt%,
Magnesium sulfate heptahydrate 0.025% by weight, calcium chloride 0.001% by weight and citric acid 0.3% by weight
When the pH adjusted to 5 was fed from the bottom of the reactor, the ethanol concentration in the reactor outlet liquid was 5% by weight 4 days after the start of distribution.

Claims (1)

[Claims] 1 A water-soluble alginate, a water-soluble radically polymerizable vinyl monomer, and a crosslinkable vinyl monomer having two or more radically polymerizable vinyl groups are dissolved or partially suspended in water, and this aqueous solution or suspension is A well-shaped water-insoluble polymer is produced by contacting a water-insoluble alginate with an aqueous solution to form a well-shaped water-insoluble gel, and then radically polymerizing this gel to produce a water-insoluble polymer. Method of manufacturing coalescence.