JPH0459806A - Production of macroporous-type spherical phenol-formaldehyde resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin having stable large pores by subjecting a prepolymer composition derived from the reaction of an aqueous solution containing phenols, aldehydes, a water-soluble organic solvent and an inorganic filler to suspension polymerization in a water-insoluble organic solvent. CONSTITUTION:At first, an aqueous solution containing phenols and aldehydes, and/or initial condensate of phenols and aldehydes, an organic solvent (preferably methyl cellosolve) miscible with water and a water-soluble inorganic filler (preferably NaCl) is allowed to react in the presence of a condensation catalyst (e.g. HaOH) preferably at 50-90 deg.C for 1-5hr to obtain a prepolymer composition. Next, said composition is added into an organic solvent not miscible with water (preferably carbon tetrachloride) and subjected to suspension polymerization to afford the objective resin.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to the adsorption, separation, and purification of organic substances, and the use of enzymes and
The present invention relates to a method for producing macroporous spherical phenol aldehyde resin used as a carrier for electrification of physiologically active substances such as microorganisms.

[Conventional technology]

BACKGROUND ART Conventionally, macroporous phenolic resins having large pore diameters have been manufactured by crushing and classifying blocks.

Furthermore, as a method for producing porous spherical phenolic resin, JP-A-53-113890 discloses a method of adding resin oligomer para-toluenesulfonic acid or inorganic salts. The publication proposes a method of adding sugars or organic salts.

Further, Japanese Patent Publication No. 62-36048 proposes a method for producing an aromatic amine-based macroporous resin, and describes a method using inorganic salts and a hydrophilic surfactant.

As a method for producing fine spherical resin, Japanese Patent Application No. 1-6337
No. 4 proposes a method using a dispersant.

[Problem to be solved by the invention]

In the conventional method described above, the crushed macroporous resin has poor handling properties compared to spherical resin, and when it is filled into a resin tower during use, it is difficult to fill the resin evenly, resulting in some voids and Due to the problem of short paths in the flow of liquid within the tower, the resin tends to break during use, fine powder is generated, and if the pipes become clogged, the pressure inside the tower increases, etc. , a spherical resin was desired.

Also, JP-A No. 53-113890 and JP-A No. 53-Sho.
The method of adding resin oligomers, inorganic salts, organic salts, and saccharides described in Publication No. 113891 only yields resin with small pores, and although it was possible to increase the adsorption rate as originally intended, it did not result in large pore diameters. It has been difficult to produce macroporous resins with a stable pore structure. It was insufficient to be used as a support for adsorption, separation, and purification of organic substances or as an immobilization carrier for enzymes, etc., which is the purpose of the water spraying invention.

Further, Japanese Patent Publication No. 62-36048 relates to an aromatic amine-based macroporous resin, and has the problem that amino groups are involved in crosslinking reactions and are not effectively utilized as functional groups. Therefore, a method for producing a macroporous resin having a free amine group as a functional group has been desired.

Furthermore, the method for producing a fine spherical resin described in Japanese Patent Application No. 1-63374 relates to a method for producing a gel-like resin, and cannot be applied to the method for producing a macroporous resin, which is the object of the present invention.

The object of the present invention is to provide a macroporous spherical phenolaldehyde resin having a stable and large pore structure, and a method for producing the same.

[Means to solve the problem]

As a result of intensive studies to solve these problems, the present inventors found that if a water-soluble organic solvent and an inorganic filler are added in advance in an appropriate ratio during polycondensation of resin, the process of polycondensation can be improved. In the above, it was discovered that a resin having large pores can be produced by the mutual effect of the dissolution effect of the reaction product by an organic solvent and the salting-out effect of the reaction product by an inorganic filler, and the present invention was achieved based on this discovery.

That is, the present invention provides an aqueous solution containing a phenol and an aldehyde (and/or an initial condensate of a phenol and an aldehyde), an organic solvent that is compatible with water, and a water-soluble inorganic filler as a catalyst. A macroporous spherical phenol aldehyde resin is prepared by reacting in the presence of water to prepare a prepolymer composition, and then adding the prepolymer composition to an organic solvent incompatible with water to carry out suspension polymerization. The gist is the manufacturing method.

The phenols used in the present invention may be those commonly used in the preparation of phenolic resins, such as phenol itself, 0-cresol, l-cresol, p-cresol, 0-ethylphenol, l-ethylphenol, p-cresol, -Tylphenol, '213-xylenol,
2,5-xylenol, 3,4-xylenol, 3.5
- Alkyl-substituted phenols such as xylenol; polyhydric phenols such as resorcinol and catechol; α-naphthol,
Examples include compounds having a phenolic hydroxyl group such as β-naphthol. Among them, fer/-le, 0-cresol, ■
Cresol, p-cresol, 3.5-xylenol,
Resorcinol, catechol, etc. are preferred.

In the present invention, phenols into which aliphatic amines have been introduced can also be used as phenols.

By using such phenols, it becomes possible to produce a macroporous spherical phenolic aldehyde resin having 7 free amide groups as a functional group. Such phenols can be obtained, for example, by stirring and mixing the above-mentioned phenols, aliphatic amines, aldehydes, and acid catalysts according to known aminomethylation reactions.

Examples of aliphatic amines include dimethylamine, diethylamine, di-n-butylamine, di-1so-butylamine, di-n-propylamine, di-1sO-propylamine, N-methylhexylamine, di-ethylenetriamine, and triethylene. Tetramine, tetraethylenepentamine, etc. are mentioned, and diethylamine, diethylenetriamine, and triethylenetetramine are preferable.

Examples of the aldehydes include aldehyde derivatives such as formaldehyde and paraformaldehyde, aliphatic aldehydes such as acetaldehyde and propionaldehyde, and aromatic aldehydes such as henzaldehyde.

Among them, formaldehyde, paraformaldehyde and the like are preferred.

Examples of the acid catalyst include hydrochloric acid.

In the synthesis reaction, for example, 0% hydrochloric acid is added to 1 mole of the above amines.
．． Add 5 to 4.0 moles of the phenols and aldehydes, and add 0.5 to 4.0 moles of each of the phenols and aldehydes, and 10 to 10 moles of water.
Add 0 g and mix in a reaction vessel equipped with a stirring device.
It is obtained by heating to 50-80°C and reacting.

Specific examples of phenols into which the above aliphatic amines are introduced include p-diethylaminomethylphenol,
Examples include m-diethylaminomethylphenol and 0-diethylaminomethylphenol.

In preparing the phenolaldehyde resin of the present invention,
One or more of the above phenols can be used.

The aldehydes used as raw materials for the phenolic aldehyde resin of the present invention may be those commonly used.
Examples include those exemplified in the synthesis of phenols into which aliphatic amines are introduced, and one or more of these may be used.

In the present invention, an initial condensate of phenols and aldehydes may be used in combination with or instead of the phenol-aldehyde mixture. Examples of the phenols and aldehydes that serve as raw materials for the initial condensate include those listed above.

The above-mentioned initial condensate may be prepared according to the usual phenolaldehyde polycondensation method, for example, phenols,
It is prepared by condensing an aldehyde and a condensation catalyst under suspension in an aqueous medium such as water.

The condensation catalyst may be one commonly used for phenol-aldehyde polycondensation, such as sodium hydroxide,
Examples include basic catalysts such as potassium hydroxide, magnesium hydroxide, and ammonium hydroxide, and acidic catalysts such as hydrochloric acid, sulfuric acid, acetic acid, and formic acid.

The reaction composition is 1 mole of phenol, 0.2 to 0.8 mole of aldehyde, and 0.05 to 0.2 mole of condensation catalyst.
Moles are preferred.

Preferably, the condensation conditions are, for example, 50 to 90°C for 1 to 5 hours.

The precondensate prepared as described above generally has a degree of polymerization of 1 to 2.

Examples of organic solvents compatible with water used in the preparation of the prepolymer in the present invention include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl calpitol, ethyl calpitol, ethylene glycol, polyethylene glycol (molecular weight 2000 or less), methanol,
Examples include alcohols such as ethanol and propatool. These can be used alone or in combination of two or more.

Preferably ethyl cellosolve, methylcarpitol,
Polyethylene glycol, etc.

The water-soluble inorganic filler used in the present invention salts out the prepolymer and imparts macropores to the resin. Examples of such inorganic fillers include alkali or alkaline earth chlorides such as potassium chloride, sodium chloride, and magnesium chloride, potassium phosphate, dipotassium phosphate, sodium phosphate, and disodium phosphate. Examples include alkali phosphates, and one or more of these may be used. Preferred are potassium phosphate, sodium chloride, magnesium chloride, and the like.

Examples of the catalyst used in the preparation of the prepolymer in the present invention include those exemplified in connection with the above-mentioned initial condensate.

The prepolymer composition in the present invention is prepared by dissolving (or dispersing) each of the above-mentioned ingredients in an aqueous medium such as water and mixing. The amounts of each of the above compounding agents used are 2 to 10 moles of aldehydes, 0.1 to 10 moles of water-compatible organic solvents, and 0.02 moles of water-soluble inorganic fillers to 1 mole of phenols. ~0.4 mol, catalyst is 0.0
5 to 0.2 mol is preferable, respectively. In addition, when using an initial condensate of phenols and aldehydes, the amount used is 2 to 1 of aldehydes per 1 mole of the initial condensate or a mixture of the initial condensate and phenols.
0 mol, 0.1 to 10 mol of an organic solvent compatible with water,
Water-soluble inorganic filler 0.02-0゜4mol, catalyst 0.05
~0.2 mol may be used.

If the amount of aldehydes used is too small than the above range, a strong resin cannot be obtained, and if it is too large than the above range, the loss of aldehydes will increase, which is not preferable. If the amount of the water-compatible organic solvent used is less than 0.1 mol, the condensation product cannot be sufficiently dissolved during polycondensation of the resin, making it difficult to form macropores, and if it exceeds 10 mol, , the precipitation of condensation products is delayed, and the formation of macropores is also less likely to occur. If the amount of the water-soluble inorganic filler added is less than 0.02 mol, the salting out effect on the condensation product will be reduced, making it difficult to form macropores, and if it exceeds 0.4 mol, the resin with low physical strength will be The result will be obtained.

In preparing the prepolymer composition of the present invention, the order of adding the above-mentioned ingredients is not particularly limited, but for example, after adding phenols and aldehydes, a water-compatible organic solvent and a water-soluble inorganic filler are added. It is preferable to add.

Next, these were put into a reaction vessel equipped with a stirring device,
It is prepared by adding a reaction catalyst, adding 1 to 300 g of water as needed, and stirring and mixing at 30° C. or lower for 30 to 60 minutes.

Next, the prepolymer composition obtained as described above is suspended in an organic solvent incompatible with water, preferably while maintaining fluidity, to undergo a polycondensation reaction. Examples of water-insoluble organic solvents used in the present invention include halogenated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, perchlorethylene, dichloroethylene, dichloroethane, and 1,2-dichloropropane; benzene; ,
Examples include aromatic hydrocarbons such as toluene, 0-xylene, m-xylene, and p-xylene; cyclic alcohols such as cyclohexanol and cyclopentanol; one or more of these may be used. Preferred are carbon tetrachloride and perchlorethylene.

In addition, as other additives, a dispersion stabilizer may be used as an aid to stabilize the suspension system, and if the viscosity of the organic solvent insoluble in water is low, a thickener etc. may be added. .

During suspension polymerization, the organic solvent that is not compatible with water is placed in a reaction vessel equipped with a stirring device, and while stirring,
Preferably, the prepolymer composition is added and suspended. At this time, the volume ratio between the prepolymer composition and the organic solvent that is incompatible with water is preferably 1.5 to 3. The suspended state is heated while being stirred, and polycondensation is carried out for 1 to 5 hours while water and other distillates are distilled out of the system, and the reaction is finally carried out at 100 to 120°C. complete it.

If you want to obtain a fine spherical resin with an average particle size of 1 to 30μ, use a high-speed stirrer as a stirring device, heat it while stirring at high speed in a suspended state, and when the resin precipitates, start stirring at high speed. The polycondensation may be completed by stopping the process and proceeding to the above-mentioned normal suspension polymerization method.

As the high-speed stirrer, for example, a homogenizer or an ultra-disperser (Yamato Scientific Co., Ltd.) is preferably used, and the stirring speed is 3000 rpm.
The above is preferable.

The macroporous spherical phenol aldehyde resin of the present invention produced as described above generally has an average particle size of l to
1000 μm, specific surface area 20-500 m'/g, pore volume 0.1-0.6 m (!/g, average pore diameter 20-2
00 people.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

In the present invention, the specific surface area, pore volume, and average pore diameter of the macroporous spherical phenolic resin are measured using a fluid phase type specific surface area measuring device (Cantasorb@, manufactured by Quantachrome Co., Ltd., USA).

Measured by gas adsorption method.

(Example 1) 0.5 mol of resorcin and 0.1 mol of magnesium chloride hexahydrate were placed in a 500-sized Mitsulo flask equipped with a regular stirring device.
150 g of water was added to dissolve resorcinol and magnesium chloride. There, methyl cellosolve 0
．． 33 mol, 1 mol of 37% formaldehyde aqueous solution,
Pour 10g of 24% hydroxide solution into 3Q
A reaction was carried out using a 'Ci trowel for 30 minutes to obtain a resin composition.

This Jugetsuji composition was added to 400 m of perchlorethylene (!
The mixture was placed in a 10100O ceno-slabble flask containing ζ and heated, water was distilled out of the system, and suspension polymerization was carried out at 100°C to obtain a spherical resin. Table 1 shows the results of measuring the specific surface area, pore volume, and average pore diameter of this spherical tree.

(Example 2) 0.25 mol of phenol and 0.2 mol of a 37% formaldehyde aqueous solution were placed in a 500 mQ tri-Solo flask equipped with a conventional stirring device, and 100 g of water and 6 g of a 24% sodium hydroxide aqueous solution were added thereto. Thereafter, the mixture was reacted at 70°C for 2 hours to obtain an initial condensate.

After this, 0.25 mol of resorcinol, 6 mol of magnesium chloride
Add 0.2 mole of aqueous salt and dissolve it, then add 0.2 mole of methyl cellosolve.
．． A resin composition was obtained by reacting with 53 mol, 37% formaldehyde. This resin composition was mixed with 200ml of toluene,
1000ml containing 200mC of carbon tetrachloride mixed solvent
After the mixture was placed in a separable flask and heated, water was distilled out of the system, the reaction was carried out by suspension polymerization at 100°C, and a spherical resin was obtained. The physical property values of this spherical resin were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3) In a 500 mC three-tube flask equipped with a normal stirring device,
0.2 mol of 0-cresol, 0.18 mol of 37% formaldehyde aqueous solution, 10 g of 20% potassium hydroxide aqueous solution
After adding 150 g of water, the reaction was carried out at 50°C for 5 hours to obtain an initial shrinkage product. Then, polyethylene glycol 0 with a molecular weight of 400.

0.5 mol of methyl cellosolve, 0.26 mol of methyl cellosolve, and 0.1 mol of barium chloride were added, and the reaction was carried out at 30°C for 30 minutes to obtain a resin composition. This resin composition was put into a separable flask containing 400mf2 of perchlorethylene, heated, water was distilled out of the system, and the reaction was carried out by suspension polymerization at 100°C. A spherical resin was obtained.The physical property values of this spherical resin were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Example 4) 500ml with a normal stirring device! Put 0.25 mol of phenol and 0.2 mol of 37% formaldehyde aqueous solution into a Mitsuro flask, add 15'Og of water, and 10g of 24% sodium hydroxide aqueous solution, and react at 70'C for 5 hours to obtain an initial condensate. I got it. Then resorcinol 0.2
After adding 5 mol of magnesium chloride hexahydrate, 0.1 mol of butyl cellosolve, and 0.8 mol of a 37% formaldehyde aqueous solution, the reaction was further carried out at 30°C for 1 hour to obtain a resin composition. This resin composition was poured into a 1000-separable flask containing 400 ml of perchlorethylene, heated, and the water was distilled out of the system.
Suspension polymerization was carried out at 00°C to obtain a spherical resin. The physical property values of this spherical resin were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1) The same procedure as in Example 1 was carried out except that the polycondensation reaction was carried out without adding magnesium chloride in the method of Example 1.
The physical properties of the obtained resin were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 2) The method of Example 1 was repeated except that the polycondensation reaction was carried out without adding methyl cellosolve, and the physical properties of the obtained resin were evaluated in the same manner as in Example 1. The results of the measurements are shown in Table 1.

(Reference Example 1 Preparation of Phenol Introduced Nidiethylamine) 2.4 mol of diethylamine was placed in a 500-mituro flask equipped with a stirring device, and 250 g of a 35% hydrochloric acid aqueous solution was slowly added dropwise at 30° C. or below, and then , 2.4 moles of phenol, 48 g of water, and 2.4 moles of 92% paraformaldehyde were added and reacted at 70°C for 2 hours.
An aqueous solution of phenol introduced with diethylamine was obtained.

(Example 5) The phenol aqueous solution obtained in Reference Example 1 was added to a 1000 m 12 Mitsuro flask equipped with a normal stirring device.

6 mol, 0.6 mol of resorcin, 0.09 mol of potassium phosphate, 80 g of water, 1.56 mol of methyl cellosolve, and after adding 1.8 mol of 37% formaldehyde aqueous solution, heated at 50°C for 15 mol. The reaction was carried out for a minute to obtain a resin composition. This resin composition was mixed with 900ml of perchlorethylene.
The mixture was poured into a 2000 m12 separable flask containing f2, heated, water was distilled out of the system, and then reacted by suspension polymerization at 120'C to obtain a spherical resin. The physical property values of this spherical resin were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Example 6) In a 500 m12 Mitsuro flask equipped with a normal stirring device, 0.3 mol of the phenol aqueous solution obtained in Reference Example 1, 0.3 mol of resorcin, 0.05 mol of potassium phosphate, and 40 mol of water were added.
After adding 0.5 mol of g1 methylcarpitol and adding 0.9 mol of 37% formaldehyde aqueous solution, the mixture was reacted at 50°C for 15 minutes to obtain a resin composition. This resin composition was added to 10100ml containing 450ml of perchlorethylene.
O! The mixture was placed in a separable flask and heated, water was distilled out of the system, and the mixture was reacted by suspension polymerization at 120'C to obtain a spherical resin. The physical property values of this spherical resin were measured in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 3) The polycondensation reaction was carried out in the same manner as in Example 5 except that potassium phosphate was not added, and the physical properties of the resulting resin were measured in the same manner as in Example 1. It is shown in Table 1.

(Comparative Example 4) The polycondensation reaction was carried out in the same manner as in Example 5 except that methyl cellosolve was not added, and the physical properties of the resulting resin were measured in the same manner as in Example 1. The results are shown in Table 1. Shown below.

(Example 7) Into a 500 m (!3) flask equipped with a normal stirring device, 0.2 mole of resorcinol, 60 g of water, 0.04 mole of magnesium chloride hexahydrate, and 0.1 mole of methyl cellosolve were added.
After adding 3 mol, 24% sodium hydroxide aqueous solution 0
．． 0.024 mol and 0.4 mol of a 37% aqueous formaldehyde solution were added, and the mixture was reacted at 306C for 300 minutes to obtain a resin composition. This resin composition was mixed with 200ml of perchlorethylene.
(!) was placed in a beaker containing ! and heated while stirring at 400 rpm using an Ultra Tea Purser (Yamato Co., Ltd.) to distill water out of the system, and then precipitate the resin. When this was confirmed, suspension polymerization using a normal stirrer was carried out, and when the temperature reached 100°C, the polymerization was terminated to obtain a microspherical resin.The physical properties of this spherical resin were as shown in Example 1. Table 1 shows the results of measurements made in the same manner and the results of measurements of particle size distribution.

(Example 8) A resin composition was obtained in the same manner as in Example 7, and then Example 7
Suspension polymerization was carried out in the same manner as in Example 1 using an ordinary stirrer instead of the high-speed stirrer, to obtain a spherical resin. The physical property values of the obtained spherical resin were measured in the same manner as in Example 7, and the results are shown in Table 1.

〔Effect of the invention〕

According to the present invention, a spherical macroporous resin having a large pore diameter, a stable pore structure, and good handling properties, and capable of having a functional group (for example, an amine group) is used. It can be obtained simply and easily.

Claims (1)

[Claims] (1) An aqueous solution containing phenols and aldehydes (and/or an initial condensate of phenols and aldehydes), an organic solvent compatible with water, and a water-soluble inorganic filler in the presence of a catalyst. A method for producing a macroporous spherical phenol aldehyde resin, which comprises reacting to prepare a prepolymer composition, and then adding the prepolymer composition to an organic solvent that is incompatible with water to perform suspension polymerization.