JPH11302323A - Vinylphenol-based polymer containing water-soluble phosphate group and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a water-soluble vinylphenol-based containing phosphate group by a simple process. SOLUTION: This polymer is composed of structural units shown by formulae I to III (R<1> and R<2> are each H or phenylene bound to the polymer main chain), or structural units derived from the above structural units and a vinyl monomer other than vinylphenol, wherein the total of the structural units shown by formulae II and III account for 30 to 85 mol.% of the total structural units, structural units shown by formula III accounts for 0 to 20 mol.%, and the units derived from vinyl monomer 0 to 30 mol.%. The polymer is obtained by reacting a vinylphenol-based polymer with a phosphorus oxyhalide, and hydrolyzing the resultant halophosphorylated polymer in the presence of 0.001 to 0.020 pts.wt. of water per pt.wt. of the phosphorus oxyhalide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the introduction of phosphoric acid groups into homopolymers of vinylphenols, copolymers of vinylphenols or copolymers of these vinylphenols with vinyl monomers other than vinylphenols. And a method for producing the same.

[0002]

2. Description of the Related Art Vinylphenol-based polymers which are made water-soluble by introducing polar groups such as phosphoric acid groups, sulfonic acid groups and amino groups are useful as metal surface treatment agents, plating agents, flocculants and the like. For example, JP-A-7-90612 describes that a water-soluble vinylphenol polymer containing a phosphate group has excellent properties as a metal surface treating agent. However, this publication does not disclose any method for producing a phosphoric acid group-containing vinylphenol polymer used in Examples.

[0003] Conventionally, vinylphenol polymers have been
For polymers with phosphate groups and their production methods,
Several techniques have been proposed (JP-A-53-525).
94, JP-A-53-49094). However, these publications do not disclose specific disclosure of a water-soluble vinylphenol-based polymer containing a phosphate group.

This time, the present inventors have found that phosphoryl trihalide, O = PX ₃ , which is industrially easily available and relatively inexpensive
(Where X is a halogen atom) (in this specification, phosphoryl trihalide is referred to as "phosphorous oxyhalide", which is commonly used).
The method disclosed in Japanese Patent Publication No. 4 (4), that is, a method of introducing a halophosphate group into a vinylphenol-based polymer and then hydrolyzing the halophosphate group was further studied. As a result, if the rate of introduction of the phosphate group is low, it is not sufficient to make the compound water-soluble. On the other hand, if the rate of introduction of the phosphate group is increased, insolubilization is likely to occur due to a cross-linking reaction, and the water-soluble vinylphenol-based The polymer could not be obtained.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to find a method for producing a water-soluble vinylphenol polymer containing a phosphoric acid group by a simple process, and to further provide the polymer. It is in.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when a vinylphenol-based polymer is dissolved or dispersed in a solvent to react phosphorus oxyhalide, A specific amount of water is added to the system to perform a reaction to form a halophosphorylated polymer,
After separating and removing unreacted phosphorus oxyhalide, the present invention was found to be able to produce a completely water-soluble vinyl phenol-based phosphate-containing polymer without gelation by hydrolysis. Completed.

[0007] That is, the gist of the first invention is that the present invention comprises structural units represented by the general formulas (I), (II) and (III), or these structural units and vinyl monomers other than vinylphenols. The structural units of the general formulas (II) and (III) occupy 30 to 85 mol% of all the structural units, and the ratio of the structural units of the general formula (III) is 0 to 20 mol. % Of a water-soluble phosphoric acid group-containing vinyl phenol-based polymer in which the proportion of structural units derived from a vinyl monomer is 0 to 30 mol%

Embedded image Wherein R ¹ and R ² represent a hydrogen atom or a phenylene group bonded to the polymer main chain, provided that R ¹ and R ² are not simultaneously a hydrogen atom. The gist of the invention is to provide a method for producing a phosphoric acid group-containing vinylphenol polymer by reacting a vinylphenol polymer with phosphorus oxyhalide and then hydrolyzing the resulting halophosphorylated polymer. The reaction is carried out in the presence of 0.001 to 0.020 parts by weight of water per 1 part by weight of phosphorus hydride. Lies in the manufacturing method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The vinylphenol-based polymer which is a raw material of the water-soluble polymer of the present invention includes homopolymers of vinylphenols of p-vinylphenol, m-vinylphenol and o-vinylphenol, or Copolymers of these vinyl phenols with each other or copolymers of these vinyl phenols with other vinyl monomers can be mentioned. Here, examples of the vinyl monomer include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, maleic acid, acrylamide, maleimide, methyl vinyl ether, vinyl acetate, and styrene. When the vinylphenol polymer is a copolymer,
In the case of monomers having high hydrophilicity such as acrylic acid, methacrylic acid, maleic acid, acrylamide, etc., the content of these vinyl monomer units can be maintained at 30 mol% or more, but other vinyl monomers having poor hydrophilicity can be maintained. In the case of, the water solubility cannot be maintained unless it is usually not more than 30 mol%.

Various methods have been known as methods for producing vinylphenol-based polymers. For example, a vinylphenol monomer obtained by a method such as dehydration of acetoxyphenylmethylcarbinol, decarboxylation of hydroxycinnamic acid, and dehydrogenation of ethylphenol is used as a monomer, and these are homopolymerized in the presence of a cation or a radical initiator. Or copolymerization of these isomers or copolymerization with another vinyl monomer.

Further, a compound in which the hydroxyl group of vinylphenol is protected by an acetyl group, a t-butyl group, a t-butoxycarbonyl group, a trimethylsilyl group, or the like is polymerized by radical polymerization, cationic polymerization or living anionic polymerization, and then the protecting group is obtained. May be removed and the polymer may be produced by returning to a hydroxyl group.

These vinylphenol-based polymers have an average degree of polymerization in the range of 4 to 1,000, and preferably have an average degree of polymerization in the range of 5 to 500 in view of the usefulness of the product.

In the method of the present invention, it is necessary to measure the water content of the vinylphenol polymer prior to use. Then, the amount is set within the range specified in the present invention in combination with other reaction raw materials, that is, phosphorus oxyhalide and water contained in the solvent. If the amount exceeds this range, the polymer may need to be dried.

As the other raw material of the method of the present invention, for example, phosphorus oxyhalide or phosphorus oxybromide is used. Since these phosphorus oxyhalides are hygroscopic and react quickly with water, their water content cannot be measured directly. Therefore, with respect to phosphorus oxyhalide, a new product specified in JIS K8211-94 must be specified as an anhydride having zero moisture, and moisture absorption after opening must be prevented as much as possible. However, if the operation is such that the commercial product is opened and weighed in a normal air atmosphere and charged into the reactor, the effect on the reaction is hardly recognized. Regarding the degree of moisture absorption of phosphorus oxyhalide, for example, in the case of phosphorus oxychloride that has absorbed water so that the reactivity changes, a δ value of 4. based on the phosphorus atom of phosphoric acid is determined by ³¹ P-NMR measurement. Dichlorophosphoric acid (P
OC1 ₂ OH) appears,
As a result, it can be determined whether or not it can be used.

In the method of the present invention, a solvent is generally used for the reaction between the vinylphenol polymer and the phosphorus oxyhalide. As the solvent, a solvent capable of dissolving or dispersing the vinylphenol-based polymer is suitable, for example, an aprotic polar solvent such as tetrahydrofuran, dioxane, acetone, dimethylformamide, and dimethylsulfoxide; and a halogenated hydrocarbon solvent such as dichloromethane and chloroform. Are used.

The amount of the solvent used is not particularly limited, but is usually 1 to 1 part by weight of the vinylphenol polymer.
It is used in the range of -50 parts by weight, preferably in the range of 3-30 parts by weight. The other phosphorus oxyhalide may be used as it is without diluting it, but may be used after diluting with the above-mentioned solvent. In this case, the amount of the solvent used is suitably in the range of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 1 part by weight of phosphorus oxyhalide.

The reaction of the first step of the present invention is carried out by mixing a vinylphenol polymer dissolved or dispersed in a solvent and a phosphorus oxyhalide and heating the mixture.
Here, the molar ratio of the phosphorus oxyhalide to the phenol nucleus of the vinylphenol polymer is an important factor.
When the molar ratio is small, the introduction ratio of the halophosphate group becomes low, and the water-soluble polymer as the target substance cannot be obtained even if the second stage hydrolysis reaction is carried out. On the other hand, if the molar ratio is too large,
The possibility of gel formation due to the crosslinking reaction increases. In addition, a large amount of unreacted phosphorus oxyhalide remains after the reaction in the first step, which increases the labor for the separation operation and wastes raw materials, which is not economical. Therefore, the molar ratio of the phosphorus oxyhalide to the phenol nucleus of the vinylphenol polymer is in the range of 0.2 to 5, preferably 0.5 to 3.

In carrying out the reaction, if the total amount of the vinylphenol-based polymer and the total amount of the phosphorus oxyhalide are mixed at once, the reaction may run out of control and control may be difficult. It is preferable to gradually add the other raw material component to one of the raw material components heated in step (1).

In the reaction between the phosphorus oxyhalide and the vinylphenol-based polymer in the first step, the amount of water present in the reaction system is adjusted to obtain the desired water-soluble polymer by the hydrolysis reaction in the second step. Is a very important factor.

When phosphorus oxyhalide is reacted with a vinylphenol-based polymer in a substantially anhydrous state, the phosphorylation rate of the phosphorylated vinylphenol-based polymer formed after the hydrolysis reaction even when the reaction is carried out for a long time. Is low, so that a water-soluble target product cannot be obtained. On the other hand, if the amount of water is too large, the gelling reaction proceeds rapidly, and the product becomes a substance insoluble in water or an organic solvent. Therefore, an appropriate amount of water is required, and the amount is in the range of 0.001 to 0.020 parts by weight, preferably in the range of 0.002 to 0.010 parts by weight based on 1 part by weight of phosphorus oxyhalide. It is.

In the reaction, in order to adjust the amount of water present in the system to this range, phosphorus oxyhalide which does not substantially absorb moisture is used as described above, and the vinylphenol polymer and the solvent in the solvent are used. Measure the moisture of
It is necessary to determine the total amount of water contained in these raw materials, to remove excess water if it is excessive, and to add insufficient water to the reaction system if it is insufficient. Water may be added directly to the reaction system, but usually, a method of adding it to a solution of a vinylphenol polymer or phosphorus oxyhalide in advance is employed.

In the present invention, it is not clear why the presence of water renders the resulting polymer after hydrolysis, which is the second reaction, to have good water solubility, but it is not clear why acidic compounds formed by reaction of water with phosphorus oxyhalide are present. Is supposed to act as a catalyst for the reaction between the vinylphenol polymer and the phosphorus oxyhalide. From this viewpoint, it is considered that the addition of phosphoric acid, which is a reaction product of water and phosphorus oxyhalide, instead of water as an additive may be effective. However, when it was actually confirmed, the reaction promoting action was observed,
It was found that a gel-like substance was easily formed partially in the reaction in the step, and a water-insoluble substance was mixed in the final product, so that it did not show an excellent action comparable to that of water.

The first stage reaction is carried out under heating. That is, the reaction temperature is in the range of 50 to 150 ° C, preferably 90 ° C.
~ 130 ° C. In addition, the reaction time depends on other reaction conditions, but is in the range of 0.5 to 24 hours, preferably 2 to 10 hours. This reaction is generally performed in an atmosphere of an inert gas such as nitrogen or argon, and the pressure may be any of reduced pressure, normal pressure, or increased pressure, but usually normal pressure is sufficient.

In the present invention, in order to obtain the desired water-soluble polymer, the introduction rate of the phosphate group, that is, the sum of the structural units (II) and (III) in all the structural units of the polymer is required. Must be equal to or greater than a predetermined value. That is, the lower limit is at least 30 mol%, although it depends on whether the vinylphenol polymer is a homopolymer of vinylphenol or a copolymer with another vinyl monomer. On the other hand, if the reaction proceeds excessively, a part or all of the product gels and becomes insoluble in water or a solvent. This is because phosphorus oxyhalide first forms an ester bond with a phenolic hydroxyl group in a vinylphenol-based polymer by a dehydrohalogenation reaction, and then one or two halogen atoms are further added as the reaction proceeds. This is probably because a so-called crosslinked structure is formed by further ester bonding to the phenolic hydroxyl group of the same or another vinylphenol polymer molecule. Therefore, in order to obtain a water-soluble target substance, there is an upper limit to the introduction rate of a phosphate group, and it depends on whether the vinylphenol-based polymer is a homopolymer of vinylphenol or a copolymer with another vinyl monomer. Is the structural unit (II) occupying in all the structural units of the polymer and
The upper limit of the total ratio of (III) is about 85 mol%. The content of the structural unit (III) having a crosslinked structure in the polymer molecule is preferably as low as possible, and is preferably 0 to 20 mol%. In addition, the degree of progress of the target esterification reaction can be known by measuring the amount of generated hydrogen halide.

The unreacted phosphorus oxyhalide and the reaction solvent are then separated from the product obtained in the first stage reaction, that is, the halophosphorylation reaction. For separation, the reaction product is distilled off under reduced pressure to remove the solvent or the like, or phosphorus oxyhalide is dissolved, and the resulting product is poured into a solvent that hardly dissolves the polymer. It is carried out by a method of recovering the coalescence. As the solvent used at this time, for example, a hydrocarbon solvent such as hexane, heptane, and toluene is suitable. The halophosphorylated vinylphenol polymer obtained by these operations is usually subjected to a hydrolysis reaction, which is the second-stage reaction, without further purification.

The hydrolysis reaction in the second step can be performed in a water-containing organic solvent or an aqueous medium as a solvent. However, a method of simply adding water and heating without using an organic solvent is advantageous in that separation and recovery of the product after the reaction are easy and economical. If an organic solvent is used, an aprotic polar solvent such as tetrahydrofuran, dioxane, acetone, dimethylformamide, dimethylsulfoxide or the like; a solvent for dissolving or dispersing the halophosphorylated vinylphenol polymer; A hydrocarbon solvent or the like is used. Then, during the hydrolysis reaction, it can also be used as a scavenger for hydrogen halide that generates basic substances such as sodium hydroxide, ammonia and pyridine.

The amount of water used here is in the range of 5 to 500 parts by weight, preferably 10 to 100 parts by weight, per part by weight of the halophosphorylated polymer. The heating temperature is in the range of room temperature to 100 ° C, preferably in the range of 40 to 80 ° C. The reaction time ranges from 0.5 to 10 hours, preferably from 1 to 5 hours.

In the hydrolysis reaction, the halophosphorylated vinylphenol polymer is dissolved in water once with the progress of the reaction, and then becomes a solid again and precipitates.
The product can be easily separated from the aqueous layer by decantation or filtration. It is completely unexpected that the polymer dissolved in water once again becomes insoluble and precipitates in the aqueous layer of the hydrolysis reaction system. By utilizing this phenomenon, by-products such as phosphoric acid and hydrogen halide can be easily separated and removed together with water from the produced polymer by decantation or filtration.

The polymer thus obtained is a water-soluble polymer, and retains its water solubility even after drying treatment or after long-term storage. The reason that the polymer recovered as a solid from the aqueous layer upon hydrolysis is water-soluble is as follows:
Although not exactly confirmed, it is considered that the aqueous layer becomes acidic due to hydrogen halide generated by the hydrolysis as the hydrolysis reaction proceeds. In fact, when a strong acid such as hydrochloric acid is added to an aqueous solution of the polymer of the present invention, the polymer of the present invention precipitates and precipitates.

The resulting phosphorylated vinylphenol polymer can be dried at room temperature to 60 ° C. under normal pressure or reduced pressure to obtain a product.

The phosphorylated vinylphenol polymer thus obtained usually contains 0.01 to 0.2% by weight of halogen.

The phosphorylated vinylphenol polymer obtained by the above-described method has a molecular structure consisting of the structural units represented by the general formulas (I), (II) and (III) as described above. Or these structural units and structural units derived from vinyl monomers other than vinylphenols. The general formulas (II) and (II)
The total ratio of the structural units of I) is 30 to 85 mol%, the ratio of the structural units of the general formula (III) is 0 to 20 mol%, and the vinylphenol polymer is different from other vinylphenols. In the case of a copolymer with a vinyl monomer, the proportion of structural units derived from the vinyl monomer is 30.
Mol% or less. When the phosphorylated vinylphenol polymer of the present invention satisfies such structural units and composition ratios, it exhibits good water solubility.

When the phosphorylated vinylphenol-based polymer contains a structural unit of the general formula (III) and forms an intermolecular crosslink, the average molecular weight, in other words, the average degree of polymerization may increase. However, since the conditions of the halophosphorylation reaction and the hydrolysis reaction of the present invention are mild conditions that do not cause cleavage of the polymer chain, the average degree of polymerization of the polymer of the present invention is:
It does not fall below the average degree of polymerization of the starting polymer used.

The phosphorylated vinylphenol polymer obtained according to the present invention can be used as it is or by further processing to obtain a metal surface treatment agent, a plating agent, a flocculant,
It can be used for a wide range of applications, such as flame retardants, ion exchange resins, metal scavengers, antistatic agents, and surfactants.

[0034]

The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited by these examples. The percentages in the following Examples and Comparative Examples are based on weight unless otherwise specified.

Example 1 Phosphorus oxychloride 100 according to JIS K8211-94
g was diluted with 100 g of dioxane (water content 0.005%), placed in a 1 L flask equipped with a dropping funnel, a thermometer and a reflux condenser, and stirred at 90 ° C. with a magnetic stirrer.
Heated. On the other hand, 30 g of poly-p-vinylphenol (weight average molecular weight 2,400, number average molecular weight 1,400, average degree of polymerization 11.6), which was previously heated at 80 ° C. under reduced pressure and dried to a water content of 0.2%, was obtained. Dioxane (moisture 0.005
%), Dissolved in 200 g, and 0.40 g of water was added. This solution was added dropwise to the above-mentioned phosphorus oxychloride little by little over 2 hours. During this time, the heating temperature was further increased, and the temperature of the reaction solution at the time of dropping was kept in the range of 100 to 105 ° C.
After completion of the dropwise addition, heating was further continued at 115 ° C. for 6 hours. After allowing this product to cool, it was poured into 2 L of hexane,
Stirred for minutes. The precipitate deposited at this time was separated from the hexane layer by decantation, and subsequently dried at room temperature under reduced pressure.

Next, 1.2 L of water was added to the obtained dried resin, followed by stirring at 65 ° C. for 3 hours to carry out a hydrolysis reaction.
The resin was once dissolved in water and then precipitated again as a solid. After separating this solid from the aqueous layer, the solid
After drying under reduced pressure for 3 hours, 33.9 g of a light brown solid was obtained.

This solid product was water-soluble and dissolved in organic solvents such as methanol, tetrahydrofuran, dioxane and dimethylformamide. ¹³ C-NM of product
The R spectrum was measured (solvent: deuterated methanol), and the results are shown in FIG. The δ value of the peak in the spectrum was identified as follows.

[0038]

Embedded image

(In the formula, R ′ represents a hydrogen atom or a phenylene group bonded to the polymer main chain, that is, a phenylene group derived from a vinylphenol unit of the raw polymer main chain.)

A ': 137.3 ppm a: 143.0 ppm b': 129.5 ppm b: 129.5 ppm c ': 115.9 ppm c: 120.8 ppm d': 155.8 ppm d: 150.3 ppm From the area of c 'and peak c, the introduction rate of the phosphate group was calculated to be 49.1 mol%.

Further, the ³¹ P-NMR spectrum of the solid product was measured (solvent: deuterated methanol) and is shown in FIG. Each peak in the figure is based on the phosphorus atom of phosphoric acid (δ
Value: 0.00 ppm). Here, R represents a phenylene group bonded to the polymer main chain.

[0042]

Embedded image

Δ value of A: -5.92 ppm δ value of B: -11.90 ppm, -13.87 ppm δ value of C: -18.98 ppm

Each peak in FIG. 2 indicates the presence of a phosphate group having a different structure, and the composition (mol%) of the phosphate group of each structure is represented by A (mono-substituted product, ie, the general formula (II) ) Is 78.0, and B (a disubstituted product, that is, when ^one of R ¹ and R ² among the structural units of the general formula (III) is a hydrogen atom and the other is a phenylene group) is 1
9.3, C (tri-substituted, ie, when both R ¹ and R ² are phenylene groups in the structural unit of the general formula (III)) is 2.0, and D (bonded to the polymer) (Free phosphoric acid without) was calculated to be 0.7. Also, this ³¹
Based on the measurement results of the P-NMR spectrum and the ¹³ C-NMR spectrum, the product of this example was found to contain 31.2 mol% of the structural unit of the general formula (II) and 17% of the structural unit of the general formula (III). It was found to contain 0.9% by mole.

Further, 0.10 g of the solid product was used as an aqueous solution and titrated with a 0.095N aqueous potassium hydroxide solution. The result was as shown in FIG. In addition, monophenyl phosphate 0.10 g (0.57 g) was used as a model substance.
mmol) and add this to water-ethanol (weight ratio 30).
/ 70) was titrated in the same manner as above (FIG. 4). 3 and 4, from the comparison of the PH value at the inflection point of the titration curve, the product of this example is a dibasic acid having an acid strength similar to that of monophenyl phosphate, and the acid amount is 5. It was found to be 2 meq / g. The acid amount was in good agreement with 5.2 meq / g calculated from the phosphoric acid group introduction ratio and composition determined by ¹³ C-NMR and ³¹ P-NMR.

From the above analysis results, it is concluded that the solid product of this example is a phosphorylated poly-p-vinylphenol having three types of phosphate groups and a partially crosslinked structure.

The chlorine ion content in the product was measured by silver nitrate titration, and the total chlorine content of the sample was treated by oxyhydrogen flame combustion, followed by silver nitrate titration. 0.08%, the total chlorine content was 0.10%.

Comparative Example 1 A dichlorophosphorylation reaction with phosphorus oxychloride followed by hydrolysis was carried out in the same manner as in Example 1 except that water was not added to the dioxane solution of poly-p-vinylphenol. The material was worked up. Product yield 27.4 g
The introduction rate of the phosphate group by ¹³ C-NMR was 28.0 mol%, and the composition (mol%) of the phosphate group of each structure by ³¹ P-NMR was 81.2 A (monosubstituted) and B ( Disubstituted) 1
5.3, C (trisubstituted) 2.7, D (phosphate) 0.8
Met. Therefore, the phosphorylation rate of this comparative example was as shown in Example 1.
It turns out that it is lower than the case of. Further, the product obtained here was soluble in methanol but insoluble in water. Incidentally, the total chlorine content was 0.06%.

Comparative Example 2 A dichlorophosphorylation reaction with phosphorus oxychloride was carried out in the same manner as in Example 1 except that 2.0 g of water more than the specified amount in the present invention was added to a dioxane solution of poly-p-vinylphenol. . During the dropwise addition of poly-p-vinylphenol to phosphorus oxychloride, turbidity was observed in the reaction.
After an hour, the whole became agar-like. Most of this agar-like product was insoluble in water and methanol.

Example 2 After diluting 100 g of phosphorus oxychloride with 100 g of dioxane in Example 1, 0.5 g of water was added, and poly-p was added.
-Except that no water was added to the vinylphenol solution
A dichlorophosphorylation reaction was carried out in the same manner as in Example 1, and then the product was put into hexane to precipitate and be recovered. Subsequently, the recovered solid was subjected to hydrolysis reaction in the same manner as in Example 1, and the product was post-treated. As a result, the yield of the obtained solid product was 33.0 g. This product is ¹³ C-NM
The rate of introduction of a phosphate group by R was 56.4 mol%, and ³¹ P-
The composition (mol%) of the phosphate group by NMR is 78.1 for A (mono-substituted), 18.8 for B (di-substituted), 2.6 for C (tri-substituted), and 0.5 for D (phosphoric). Met. This product was soluble in water and methanol.

Example 3 Poly-m-vinylphenol containing 1.2% by weight of water (weight average molecular weight 5,100, number average molecular weight 3,40
0, average degree of polymerization 28.3) 30.0 g of dioxane 20
The solution was dissolved in 0 g, placed in a reactor, and heated to 90 ° C. while stirring as in Example 1. After diluting 57.0 g of phosphorus oxychloride with 100 g of dioxane, a solution obtained by adding 0.15 g of water was added to the above poly-m-vinylphenol solution by 1.5 times.
It dripped over time. A dichlorophosphorylation reaction was carried out in the same manner as in Example 1, followed by a hydrolysis reaction.

The yield of the obtained solid product was 30.1 g, and the rate of introduction of phosphate groups by ¹³ C-NMR was 43.7.
The composition (mol%) of the phosphoric acid group of each structure according to mol% and ³¹ P-NMR is 74.9 for A (mono-substituted), 21.0 for B (di-substituted), and 4 for C (tri-substituted). 0, D (phosphoric acid)
0.1. This product was soluble in water and methanol.

Example 4 A copolymer of p-vinylphenol and methyl methacrylate instead of poly-p-vinylphenol (molar ratio of p-vinylphenol / methyl methacrylate 81/1)
9, weight average molecular weight 4,500, number average molecular weight 2,65
0, average degree of polymerization 22.8) The reaction with phosphorus oxychloride was carried out in the same manner as in Example 1 except that 33.0 g was used, followed by a hydrolysis reaction.

The yield of the recovered solid product was 34.5 g.
The rate of introduction of phosphate groups by ¹³ C-NMR was 57.2 mol%, and the composition (mol%) of phosphate groups of each structure by ³¹ P-NMR was 79.0 A (monosubstituted), B (Disubstituted)
16.5, C (tri-substituted) 3.5, D (phosphate)
It was 0. This product was soluble in water and methanol.

[0055]

According to the method of the present invention, a vinylphenol polymer is reacted with a phosphorus oxyhalide in the presence of water in an amount within a specific range based on the phosphorus oxyhalide used, and then the hydrolysis is carried out. By a simple method to be carried out, a water-soluble phosphoric acid group-containing vinylphenol-based polymer, which has conventionally been difficult to synthesize, can be obtained.

Phosphoric acid group-containing vinylphenol-based polymers include metal surface treatment agents, plating agents, flocculants, flame retardants,
It can be used for a wide range of applications, such as ion exchange resins, metal scavengers, antistatic agents and surfactants.

[Brief description of the drawings]

FIG. 1 is a ¹³ C-NMR spectrum of a product obtained in Example 1.

FIG. 2 is a ³¹ P-NMR spectrum of the product obtained in Example 1.

FIG. 3 is a titration curve of an aqueous solution of the product obtained in Example 1 with an aqueous potassium hydroxide solution.

FIG. 4 is a titration curve of a water-ethanol solution of monophenyl phosphate with an aqueous potassium hydroxide solution.

Claims (6)

[Claims] Claims: 1. A structural unit represented by the general formulas (I), (II) and (III) or a structural unit derived from a vinyl monomer other than vinylphenols, The general formulas (II) and (II)
The ratio of the total of the structural units of I) is 30 to 85 mol%, the ratio of the structural units of the general formula (III) is 0 to 20 mol%, and the ratio of the structural units derived from the vinyl monomer is 0 to 30 mol%.
A water-soluble vinyl phenol-based polymer having a phosphoric acid group (In the formula, R ¹ and R ² represent a hydrogen atom or a phenylene group bonded to the polymer main chain, except that R ¹ and R ² are simultaneously a hydrogen atom.) 2. A method for producing a phosphoric acid group-containing vinylphenol polymer by reacting a phosphorus oxyhalide with a vinylphenol polymer and then hydrolyzing the resulting halophosphorylated polymer. The reaction is carried out in the presence of 0.001 to 0.020 parts by weight of water per 1 part by weight of phosphorus.
A process for producing the water-soluble phosphate group-containing vinylphenol-based polymer according to the above. 3. A halophosphorylated polymer obtained by reacting a vinylphenol polymer with phosphorus oxyhalide is hydrolyzed in an aqueous medium, and then a solid hydrolysis product is separated from an aqueous layer. 3. The method according to claim 2, wherein
A process for producing the water-soluble phosphate group-containing vinylphenol-based polymer according to the above. 4. The vinylphenol-based polymer is a homopolymer of vinylphenols, a copolymer of vinylphenols or a copolymer of these vinylphenols with a vinyl monomer other than vinylphenols. Item 4. The method for producing a water-soluble phosphate group-containing vinylphenol polymer according to item 2 or 3. 5. The method according to claim 1, wherein the vinylphenol-based polymer is poly-p.
The method for producing a water-soluble phosphate group-containing vinylphenol-based polymer according to claim 2 or 3, which is -vinylphenol, poly-m-vinylphenol or p-vinylphenol-methyl methacrylate copolymer. 6. The method according to claim 2, wherein the phosphorus oxyhalide is phosphorus oxychloride.