JPH0714970B2 - Ethylene oxide adduct of p-vinylphenol polymer and process for producing the same - Google Patents

Description

The present invention relates to a novel p-vinylphenol polymer ethylene oxide adduct, that is, a compound represented by the general formula [I]. The present invention relates to an ethylene oxide adduct of p-vinylphenol polymer having a structural unit represented by the formula (n is an arbitrary integer of 1 to 100, M is hydrogen or an alkali metal), and a method for producing the same.

(Prior Art) Conventionally, for example, phosphorus oxyhalide or phosphorus thiohalide (JP-A-53-49094) and phosphorus trihalide (JP-A-53-50289) have been used for phenolic hydroxyl groups of p-vinylphenol polymers. No.), halogenated phosphoric acid diester or halogenated monothiophosphoric acid diester (JP
53-52594), halogenated lactones (JP-A-55-605)
No. 03) or acetohalogen sugar (JP-A-60-192704)
No.) etc. are added to the derivative of p-vinylphenol polymer. However, an ethylene oxide adduct of p-vinylphenol polymer according to the present invention in which ethylene oxide is added to the phenolic hydroxyl group of p-vinylphenol polymer has not been reported yet.

(Problems to be Solved) The p-vinylphenol polymer is a substance useful as a functional polymer by itself, but its properties are still insufficient depending on the use, and modification is often desired. .

The present inventors have conducted various studies on modification of p-vinylphenol polymer, and unintentionally replaced p-vinylphenol polymer with a phenolate by substituting part or all of hydrogens of the hydroxyl group with an alkali metal. None, by reacting ethylene oxide in an anhydrous state, an ethylene oxide adduct of p-vinylphenol polymer can be obtained almost quantitatively and efficiently with little side reaction such as by-product of ethylene oxide homopolymer. The present invention has been completed by discovering that the p-vinylphenol polymer can be modified appropriately such that the hydrophilicity is increased by using the adduct.

The adduct according to the present invention can be used, for example, as a nonionic polymer surfactant, and can also be used as a raw material for other various chemical products. For example, it can be used as a raw material for polyurethane resin, epoxy resin, etc., and is a polyurethane resin derived from the adduct,
Epoxy resins and the like can be used for laminated plates, cast products, molded products, films, paints, adhesives, sealants and the like.

(Means for Solving Problems) Therefore, the gist of the present invention is, firstly, the general formula [I]. The structural unit represented by the formula (n is an arbitrary integer of 1 to 100, M is hydrogen or an alkali metal) is 5 to 100 mol%, and the general formula [II] is used. The structural unit represented by the formula (wherein M is the same as above) has a substantial residual mol% as a main structural unit, and each structural unit has a structure in which a main chain is randomly bonded to a polymerization degree of 3 to 5000. Of ethylene oxide adduct of p-vinylphenol polymer, and secondly, p of 3 to 5000 degree of polymerization.
-A vinylphenol polymer is prepared by substituting hydrogen for a part or all of its hydroxyl groups with an alkali metal to obtain a phenolate, and then reacting with ethylene oxide in an anhydrous state. It depends on the manufacturing method.

As the p-vinylphenol polymer serving as the skeleton of the ethylene oxide adduct of p-vinylphenol (hereinafter, abbreviated as PVP-EO form) of the present invention, those prepared by various methods can be used regardless of its production origin. , For example p-
Prepared by hydrolyzing p-acetoxystyrene polymer obtained by polymerizing vinylphenol by various polymerization methods such as thermal polymerization, radical polymerization or cationic polymerization, or by polymerizing p-acetoxystyrene by various polymerization methods. What has been done can be used. Also, this p
-As a vinylphenol polymer, the degree of polymerization is 3 to 5000.
The number average molecular weight is in the range of 360 to 600,000, but the degree of polymerization is usually 10 to 333 (number average molecular weight of 1,200 from the viewpoint of versatility of the intended use of the ethylene oxide adduct).
Those of about 40,000) are preferable.

In synthesizing the PVP-EO form of the present invention, the p-vinylphenol polymer is first substituted with an alkali metal for some or all of the hydrogen atoms of its hydroxyl group to form a phenolate.

The substitution of hydrogen for the hydroxyl group with an alkali metal may be carried out by a known or arbitrary method. For example, the p-vinylphenol polymer is dissolved in a suitable solvent such as alcohol or ether, and methanol is added to the solution.
Aliphatic alcohols such as ethanol and propanol are mixed with alkali metal alcoholates such as lithium, potassium and sodium, and alcohol exchange reaction is carried out, or water of alkali metal such as lithium, potassium and sodium is added to the p-vinylphenol polymer solution. This can be easily carried out by allowing the aqueous solution of the oxide to act and then removing the water. The degree of substitution of hydrogen for the hydroxyl group with the alkali metal, that is, whether all of the hydroxyl groups of the p-vinylphenol polymer are replaced with the alkali metal or only a part thereof is replaced with the alkali metal is the target PVP. The degree of addition of the desired ethylene oxide to the EO form, the reaction conditions employed in the ethylene oxide addition reaction described below, and other conditions can be arbitrarily selected as necessary. Further, in the operation of substituting the hydrogen of the hydroxyl group with an alkali metal, when a skeleton prepared by hydrolysis of a p-acetoxystyrene polymer is used, a p-vinylphenol polymer is usually prepared by hydrolysis of the polymer. In doing so, the acetyl of the acetoxy group of the polymer is once replaced with an alkali metal, so if such an alkali metal substitute is used,
It goes without saying that it can be omitted.

Next, the above-mentioned p-vinylphenol polymer in which some or all of the hydrogen atoms of the hydroxyl groups are replaced with alkali metals is dissolved in ethers such as diethyl ether, tetrahydrofuran, dioxane, diglyme, or aromatic carbonization such as benzene and toluene. Either by suspending in hydrogen, or in the absence of a solvent, at 20 to 150 ° C., for 0.01 to 30 hours, it is mixed with ethylene oxide in an anhydrous state to react, and then the reaction mixture is treated with water, mineral acid or the like. If processed, the desired PVP-EO
The body is isolated. When this addition reaction is carried out in an anhydrous state, it proceeds almost quantitatively with little side reaction such as by-product of homopolymer of ethylene oxide. Therefore, by selecting the charging ratio of the p-vinylphenol polymer and ethylene oxide in this addition reaction, the degree of addition of ethylene oxide of the target PVP-EO compound can be arbitrarily designed.

As described above, in order to properly carry out the method of the present invention, it is necessary to react the raw material p-vinylphenol polymer with the alkali metal in advance, and the p-vinylphenol polymer which has not reacted with the alkali metal. However, the reaction does not occur, and even if the free p-vinylphenol polymer is reacted with ethylene oxide in the presence of an aqueous alkali metal hydroxide solution, the formation of the PVP-EO body does not proceed smoothly. However, when a raw material in which a part of the hydroxyl groups of the p-vinylphenol polymer has already reacted with the alkali metal is used, the addition of ethylene oxide smoothly occurs in the phenolic hydroxyl group of the entire polymer almost similarly. The reason for this has not been clarified yet, but the present inventors have found that the alkali metal bound to the phenolic hydroxyl group acts catalytically and binds to the alcoholic hydroxyl group generated at the end of the PVP-EO body. Since it is more likely to bond with the phenolic hydroxyl group, it is thought that it is because the free phenolic hydroxyl group is sought and bonded with this, and then activated. Therefore, it is usually sufficient to previously react about 5 to 10% of the hydroxyl groups in the raw material p-vinylphenol polymer with the alkali metal, and excessive reaction with the alkali metal has no particular remarkable advantage.
Rather, the effort to separate a large amount of by-produced alkali metal salt generated from it from the target PVP-EO body tends to increase.

Further, after the addition reaction, the PVP-EO compound obtained can be used as it is as a chemical raw material as it is, without any other purification treatment, except that the alkali metal removal treatment with a mineral acid is carried out if necessary. Further, in the above addition reaction, depolymerization of the p-vinylphenol polymer used does not substantially occur.

In the production of the PVP-EO body, PVP having the structural units represented by the general formulas [I] and [II] is used if the alkali metal removal treatment with a mineral acid is not performed or if the removal treatment is insufficient. In the —EO form, a structural unit in which M in the general formulas [I] and [II] is an alkali metal remains, and if the removal treatment is sufficiently carried out, it is represented by the general formulas [I] and [II]. The building blocks involved are considered where M is hydrogen.

Further, in the production of the PVP-EO, the general formula [I]
The constituent unit represented by the formula (1) is 5 mol% (substantially the remaining constituent units are constituent units represented by the general formula [II]) and the constituent unit represented by the general formula [I] is 100 mol%.
Up to the PVP-EO form (substantially consisting of the constitutional unit represented by the general formula [I]), and n in the general formula [I]
It is possible to obtain a PVP-EO compound having a molecular weight of 1 to 100, but the structural unit of the general formula [I] is usually 5 to 100 mol%, preferably 5 to 95 because of its ease of acquisition and versatility of use. Mol%
And the average value of n in the general formula [I] in the PVP-EO body is 1 ≦ n <1.5, preferably 1 ≦ n <1.3,
Alternatively, the constitutional unit represented by the general formula [I] is 95 to 100
It is preferable that the average value of n in the general formula [I] in PVP-EO form is 1.3 ≦ n <100 in mol%.

(Effect of the invention) Among the PVP-EO compounds of the present invention, the adduct to which a relatively small amount of ethylene oxide has been added has increased hydrophilicity as compared with the conventional p-vinylphenol polymer, so more applications are considered. In addition, the adduct with a relatively large amount of ethylene oxide added is a polymeric nonionic surfactant with a regular structure, which has a similar structure to conventional ones, such as an alkylphenol formaldehyde resin to which ethylene oxide is added. It has superior performance compared to.

On the other hand, polyurethanes, epoxy resins, etc. derived from PVP-EO are superior in heat resistance to conventional ones.

(Examples) The present invention will be specifically described below with reference to Examples, but the scope of the present invention is not limited thereto.

Example 1 A p-vinylphenol polymer (number average molecular weight (▲ ▼) 2,50 was placed in a glass polymerization tube having an inner volume of 100 ml and purged with nitrogen.
0, weight-average molecular weight (▲ ▼) 5,400) of phenolic hydroxyl group hydrogen having an average composition of 5% sodium substituted phenolate 5.6g, 1,4-dioxane 24ml and ethylene oxide 2g were charged (ethylene oxide / p-vinylphenol). (Unit ≈ 1 mol / mol) The tube was sealed, immersed in a hot water bath at 80 ° C, and shaken for 22 hours to continue the reaction.

After the reaction, an acetone-ethanol mixed solvent was added to the contents to uniformly mix them, and concentrated hydrochloric acid was added thereto to make it weakly acidic. Next, the solvent was evaporated until the system became considerably viscous, and 300 ml of benzene was added thereto to separate into a benzene-soluble portion and an insoluble portion. Yields were 0.17 g and 5.94 g, respectively.

When the benzene-soluble portion was treated with 100 ml of water and further separated into a water-soluble portion and a water-insoluble portion, the yields were 0.03 g and 0.14 g, respectively.

The former is a mixture of a homopolymer of ethylene oxide and an inorganic substance, and the latter is a PVP-EO compound having 1.25 molecules of ethylene oxide added as an average value per p-vinylphenol unit, which is substantially the unit of the above formula (I) ( (M is hydrogen)
It consisted of only one.

On the other hand, when the benzene-insoluble part was treated with 200 ml of water and further separated into a water-soluble part and a water-insoluble part, the yield was 0.
It was 18 g and 5.76 g. Of these, the former was an inorganic substance mainly containing sodium chloride produced in the neutralization process, and the latter was a PVP-EO compound to which about 1.3 molecules of ethylene oxide was added as an average value per unit of p-vinylphenol.
The IR and ¹ H-NMR spectra of this product are
Shown in Figures and FIG.

The main absorption assignments in the IR spectrum of FIG. 1 are as follows.

3400cm ^-1 aliphatic primary alcohol hydroxyl group O-H stretching vibration 1060cm ^-1 aliphatic primary alcohol hydroxyl group C-O stretching vibration 2900~3000cm ^-1 C-H stretching vibration 1620,1520,1460Cm ^-1 benzene nucleus -C = C-plane stretching vibration 1180cm ^-1 = C-O-C antisymmetric stretching vibration of CH out-of-plane bending vibration 1250 cm ^-1 aromatic ethers CH plane bending vibration 830 cm ^-1 benzene angle benzene nucleus = C-O-C symmetric stretching vibration of 1,050 to 1,080 cm ^-1 aromatic ether The assignment of each peak in the ¹ H-NMR spectrum of Fig. 2 is as follows.

Assignment of these peaks was carried out with reference to a model compound having a corresponding structure.

The average structure of the PVP-EO body, which was determined based on the above assignments by calculating the area ratio of each peak, was substantially composed of units of the following general formula [I].

This adduct was soluble in ether, ketone and alcohol, but almost insoluble in water, aliphatic and aromatic hydrocarbons.

A phenolate in which hydrogen of the phenolic hydroxyl group of p-vinylphenol polymer was replaced with 5% sodium as an average composition was synthesized as follows.

12 g of p-vinylphenol polymer was dissolved in 50 ml of dry methanol, and 10 ml of a methanol solution of sodium methylate synthesized by the reaction of methanol and metallic sodium (0.5 mol /) was added thereto.

The system immediately changed to dark greenish brown, but then at 60 ° C.
The stirring was continued for 3 hours. After distilling out most of the methanol, 200 ml of dried dioxane was added and dissolved,
Dioxane was distilled off.

The residue was suspended in 200 ml of dried benzene to distill off benzene.

The residue was dried under vacuum and then used in the experiment.

Example 2 p-Vinylphenol polymer (▲ ▼ 2,500, ▲ ▼ 5,400) was placed in a glass polymerization tube having an internal volume of 25 ml which was replaced with nitrogen.
1.4g of phenolate in which hydrogen of phenolic hydroxyl group of 10% is replaced by 10% sodium and ethylene oxide 0.25g are charged (ethylene oxide / p-vinylphenol unit ≈0.5mol / mol), sealed and put in a bath at 80 ℃. And continued shaking for 8 hours.

After the reaction, an acetone-ethanol mixed solvent was added to the contents to uniformly mix them, and concentrated hydrochloric acid was added thereto to make it weakly acidic.

Then evaporate the solvent until the system is fairly viscous and add 10
The polymer was suspended by adding 0 ml of water, filtered, washed with water and dried to recover the polymer, and the yield was 1.4 g.

The IR and ¹ H-NMR spectra of this PVP-EO form are shown in FIGS. 3 and 4, respectively.

In the IR spectrum of Fig. 3, no new absorption is observed as compared with Fig. ¹ , but the aromatic ether at 1250 cm ^-1 = CO
The absorption of the -C antisymmetric stretching vibration overlaps with the = CO stretching vibration (1230 cm ^-1 ) of the residual phenolic hydroxyl group, resulting in a wide width.

In addition, the C—O of the aliphatic primary alcohol hydroxyl group of 1060 cm ⁻¹
Stretching vibration and aromatic ether of 1050 to 1080 cm ^-1 = C-
The strength of the OC symmetrical stretching vibration is weaker than that in FIG.

In the ¹ H-NMR spectrum of FIG. 4, in addition to the peaks of FIG. 2, a new signal appearing at δ = 8.3 ppm, which can be assigned to the phenolic hydroxyl group proton, appeared.

The average structure of the PVP-EO body obtained from the area ratio of each peak is 76 mol% in the unit of the following general formula [I],
The unit of [I] consisted of 24 mol%.

This adduct was soluble in ether, ketone and alcohol, but almost insoluble in water, aliphatic and aromatic hydrocarbons. The phenolate was synthesized in the same manner as in Example 1.

Example 3 Phenolate 2.8 g, in which hydrogen of the phenolic hydroxyl group of p-vinylphenol polymer (▲ ▼ 1,600, ▲ ▼ 2,600) was replaced with 10% sodium as an average composition in a glass-made tube having an internal volume of 25 ml which was replaced with nitrogen, 1 , 4-dioxane 3 ml
Then, 0.1 g of ethylene oxide was charged (ethylene oxide / p-vinylphenol unit≈0.1 mol / mol), the tube was sealed, and the tube was immersed in an 80 ° C. water bath and shaken continuously for 24 hours.

After the reaction, the same post-treatment as in Example 2 was applied, and the yield of the recovered polymer was 2.32 g.

The IR and ¹ H-NMR spectra of this PVP-EO form are shown in FIG. 5 and FIG. 6, respectively.

In the IR spectrum of Fig. 5, it is 1250cm ^-1 compared to Fig. 1.
The absorption of the aromatic ether = C—O—C antisymmetric stretching vibration was weakened, and the absorption of the residual C—O stretching vibration of the phenolic hydroxyl group appeared at 1230 cm ⁻¹ as a shoulder.

In addition, the C—O of the aliphatic primary alcohol hydroxyl group of 1060 cm ⁻¹
Stretching vibration and aromatic ether of 1050 to 1080 cm ^-1 = C-
The absorption intensity based on the OC symmetrical stretching vibration is further weaker than that in FIG.

In the ¹ H-NMR spectrum of Fig. 6, δ = 3.8 ppm. No signal based on.

The average structure of the PVP-EO form determined by calculating the area ratio of each peak and determining based on the above assignment has a unit of the following general formula [I] of 20 mol% and a unit of the general formula [II]. Was 80 mol%.

This adduct was soluble in ether, ketone, alcohol, etc., but almost insoluble in water, aliphatic and aromatic hydrocarbons.

The phenolate is the same as that used in Example 2.

Example 4 A p-vinylphenol polymer (▲ ▼ 9,000, ▲ ▼ 25,00) was placed in a glass polymerization tube having an internal volume of 25 ml which had been purged with nitrogen.
0) hydrogen of phenolic hydroxyl group of 10% as an average composition
Sodium-substituted phenolate (1.4 g), 1,4-dioxane (5 ml) and ethylene oxide (1 g) were charged (ethylene oxide / p-vinylphenol unit ≈ 2 mol / mol).
The tube was sealed, immersed in a hot water bath at 80 ° C., and shaken continuously for 23 hours.

After the reaction, ethanol was added to the contents and mixed uniformly, and concentrated hydrochloric acid was added to the contents to make them weakly acidic. Then, the solvent was evaporated and the polymer was recovered, and the yield was 2.2 g.

The IR and ¹ H-NMR spectra of this PVP-EO form are shown in FIGS. 7 and 8, respectively.

In the IR spectrum of FIG. 7, it is 1060 cm ^-1 as compared with that of FIG.
The absorption intensity based on the C—O stretching vibration of the hydroxyl group of the aliphatic primary alcohol was increased, and the absorption based on the C—O—C antisymmetric stretching vibration of the aliphatic ether newly appeared at 1110 cm ⁻¹ .

In the ¹ H-NMR spectrum of FIG. 8, a sharp peak due to the ethylene oxide chain appeared at δ = 3.7 ppm.

The average structure of the PVP-EO form determined by calculating the area ratio of each peak and based on the above assignment was substantially composed of the units of the following general formula [I].

This adduct is soluble in ethers, ketones, and alcohols, insoluble in aliphatic hydrocarbons, and slightly soluble in water and aromatic hydrocarbons.

A phenolate in which hydrogen of the phenolic hydroxyl group of p-vinylphenol polymer was replaced with 10% sodium as an average composition was synthesized as follows.

A solution of 6 g of p-vinylphenol polymer in 100 ml of dioxane and 1 m of an aqueous solution containing 0.2 g of sodium hydroxide.
l was added.

The system immediately turned green-brown, but the stirring was continued for 2 hours at 80 ° C. After distilling most of the dioxane, 20
The procedure of adding 0 ml of dried benzene to suspend it and distilling benzene off was repeated twice to completely remove water in the system, and the residue was vacuum dried.

Example 5 A p-vinylphenol polymer (▲ ▼ 1,600, ▲ ▼ 2,600) was placed in a glass polymerization tube having an internal volume of 25 ml which had been replaced with nitrogen.
0.7 g of phenolate in which hydrogen of phenolic hydroxyl group of 10% is substituted with 10% potassium as an average composition, 3 ml of 1,4-dioxane
And 5 g of ethylene oxide (ethylene oxide / p-vinylphenol unit ≈ 20 mol / mol) and sealed,
Soak in 80 ° C water bath and continue shaking for 2.5 hours.

After the reaction, ethanol was added to the contents and mixed uniformly, and concentrated hydrochloric acid was added to the contents to make them weakly acidic. Then, the solvent was evaporated and the polymer was recovered, and the yield was 5.4 g.

The IR and ¹ H-NMR spectra of this PVP-EO form are shown in FIGS. 9 and 10, respectively.

In Fig. 9, the absorption at 1110 cm ^-1 based on the C-O-C antisymmetric stretching vibration of the aliphatic ether is large, and in Fig. 10, there is a large sharp peak at δ = 3.7 ppm based on the ethylene oxide chain. It is characteristic. The average structure of the PVP-EO body calculated from the area ratio of each peak in FIG. 10 was substantially composed of the units of the following general formula [I].

This adduct is water, alcohols such as methanol, ethanol, propanol, butanol, acetone, MEK, MIBK.
Ketones, benzene, toluene and other aromatic hydrocarbons, TH
It is soluble in F, methylene chloride, etc., but cyclohexane,
It was insoluble in saturated hydrocarbon such as hexane, diethyl ether and dibutyl ether.

The phenolate was synthesized in the same manner as in Example 1 except that the calculated amount of potassium methylate was used instead of sodium methylate in the phenolate synthesis example shown in Example 1.

Example 6 A p-vinylphenol polymer (▲ ▼ 9,000, ▲ ▼ 25,00) was placed in a glass-made polymerization tube having an internal volume of 25 ml and purged with nitrogen.
0) hydrogen of phenolic hydroxyl group of 10% as an average composition
Sodium-substituted phenolate (1.4 g), tetrahydrofuran (5 ml) and ethylene oxide (2.5 g) were charged (ethylene oxide / p-vinylphenol unit≅5 mol / mol), the tube was sealed, placed in a 100 ° C. water bath and shaken for 2 hours.

After the reaction, ethanol was added to the contents and mixed uniformly, and concentrated hydrochloric acid was added to the contents to make them weakly acidic. After that, the solvent was evaporated to recover the polymer, and the yield was 3.6 g.

The IR and ¹ H-NMR spectra of this PVP-EO form are shown in FIG. 11 and FIG. 12, respectively.

In FIG. 11, absorption at 1110 cm ⁻¹ based on the C—O—C antisymmetric stretching vibration of the aliphatic ether was stronger than that in FIG. 7.
In Figure 12, δ = 3.7p based on the ethylene oxide chain.
The sharp peak at pm was larger than in Fig. 8.

The average structure of the PVP-EO body calculated from the area ratio of each peak in FIG. 12 was substantially composed of only the unit of the following general formula [I].

This adduct is a highly viscous liquid at room temperature and is soluble in water, alcohols, ketones, and aromatic hydrocarbons, but not in aliphatic hydrocarbons.

The phenolate, which is one component of the raw material, is the same as that used in Example 2.

Example 7 A p-vinylphenol polymer (▲ ▼ 9,000, ▲ ▼ 25,00) was placed in a glass-made polymerization tube having an internal volume of 25 ml which was replaced with nitrogen.
50% of the average composition of hydrogen of phenolic hydroxyl group of 0)
Sodium-substituted phenolate (1.4 g), 1,4-dioxane (3 ml) and ethylene oxide (1.5 g) were charged (ethylene oxide / p-vinylphenol unit ≈3 mol / mol), sealed, and placed in a 80 ° C water bath and shaken for 0.5 hours. Continued.

After the reaction, ethanol was added to the contents and mixed uniformly, and concentrated hydrochloric acid was added to the contents to make them weakly acidic.

Next, the solvent was evaporated and the polymer was recovered.
It was 2.8 g.

The IR and ¹ H-NMR spectra of this PVP-EO form are shown in FIGS. 13 and 14, respectively.

In FIG. 13, the absorption at 1110 cm ⁻¹ based on the C—O—C antisymmetric stretching vibration of the aliphatic ether showed an intermediate intensity between FIGS. 7 and 11. In FIG. 14, the sharp peak at δ = 3.7 ppm based on the ethylene oxide chain showed an intensity intermediate between those in FIGS. 8 and 12.

The average structure of the PVP-EO body calculated from the peak area ratios in FIG. 14 consisted essentially of the following units.

This adduct is a highly viscous liquid at room temperature and dissolves in water, alcohol, ketone, and the like.

As the phenolate, the calculated sodium methylate was used and was synthesized according to the synthesis example of Example 1.

Example 8 A p-vinylphenol polymer (▲ ▼ 2,500, ▲ ▼ 5,400) was placed in a glass polymerization tube having an internal volume of 25 ml which was replaced with nitrogen.
Of phenolate having an average composition of hydrogen in the phenolic hydroxyl group of 50% sodium, 0.2 g, 1,4-dioxane
After charging 1.5 ml and 5.5 g of ethylene oxide (ethylene oxide / p-vinylphenol unit ≈ 75 mol / mol), the tube was sealed, placed in a water bath at 80 ° C., and shaken continuously for 24 hours.

After the reaction, ethanol was added to the contents and mixed uniformly, and concentrated hydrochloric acid was added to the contents to make them weakly acidic. When the solvent was evaporated and the polymer was recovered, the yield was 5.7 g.

The IR and ¹ H-NMR spectra of this PVP-EO form are shown in FIGS. 15 and 16, respectively.

From these spectra, it can be seen that the ethylene oxide chain is longer than that of the PVP-EO form obtained in Example 5.

It was concluded from the spectrum of FIG. 16 that the average structure of the PVP-EO body obtained here was substantially composed of units of the following general formula [I].

This adduct is a solid at room temperature and dissolves in water, alcohol, ketone and the like.

The phenolate is the same as that used in Example 7.

Example 9 p-vinylphenol polymer [number average molecular weight (▲
▲) 2,520, weight average molecular weight ▲ ▼) 5,390, ▲ ▼
/ ▲ ▲ = 2.14] was repeated solvent separation with diethyl ether and a mixed solvent of diethyl ether and 1,4-dioxane to obtain a p-vinylphenol polymer [number average molecular weight (▲▲) 5,000, weight average as close to monodisperse as possible. Molecular weight (▲ ▼) 5,840, ▲ ▼ / ▲▲ ＝
1.17], a phenolate was prepared in which the hydrogen of the phenolic hydroxyl group had an average composition and was replaced with 10% sodium.

A glass polymerization tube having an internal volume of 25 ml, which had been purged with nitrogen, was charged with 1.4 g of the above-mentioned phenolate, 3 ml of 1,4-dioxane and 1.5 g of ethylene oxide (ethylene oxide / p-vinylphenol unit ≈3 mol / mol), and the tube was sealed at 80 ° Soak in the bath 24
I continued shaking for hours.

After the reaction, ethanol was added to the contents and mixed uniformly, and concentrated hydrochloric acid was added to the contents to make them weakly acidic. When the solvent was evaporated and the polymer was recovered, the yield was 2.9 g. By the analysis of the ¹ H-NMR spectrum, the PVP-
It was found that the average structure of the EO form is substantially composed of the structure of the general formula [I].

As a result of GPC analysis of this adduct, a number average molecular weight of 7,440,
The weight average molecular weight was 8,720, and the value of ▲ ▼ / ▲▲ which is a scale showing the molecular weight distribution of the polymer was 1.17.

Since the value of ▲ ▼ / ▲▲ is in good agreement with that of the p-vinylphenol polymer which is a raw material for the addition reaction, it can be seen that the addition of ethylene oxide uniformly occurs for each phenolic hydroxyl group.

Example 10 A glass polymerization tube having an internal volume of 25 ml replaced with nitrogen was charged with 0.76 g of the phenolate used in Example 9, 3 ml of 1,4-dioxane and 2.2 g of ethylene oxide (ethylene oxide / p-
(Vinylphenol unit ≈ 8 mol / mol) The tube was sealed, immersed in a water bath at 80 ° C., and shaken for 24 hours.

After the reaction, the same post-treatment as in Example 9 was applied, and the polymer yield was 3.0 g. ^From the analysis of ¹ H-NMR spectrum, it was found that the average structure of the obtained PVP-OE body was substantially composed of the structure of the general formula [I].

As a result of GPC analysis of this adduct, number average molecular weight 9,530,
Weight average molecular weight 11,450, therefore ▲ ▼ / ▲▲ = 1.
It was 20.

The value of ▲ ▼ / ▲▲ is p, which is the raw material for the addition reaction.
-It agrees well with that of the vinylphenol polymer that the addition of ethylene oxide occurs uniformly for each phenolic hydroxyl group.

Comparative Example 1 p-Vinylphenol polymer (▲▲ 2,500, ▲ ▼ 5,400) was placed in a glass polymerization tube with an internal volume of 25 ml which was replaced with nitrogen.
Charge 0.7 g, 1,4-dioxane 3 ml and ethylene oxide 5 g (ethylene oxide / p-vinylphenol unit ≈
The tube was sealed (20 mol / mol), immersed in a hot water bath at 80 ° C., and shaken continuously for 24 hours.

After the reaction, the contents were dissolved with ethanol and the solvent was evaporated. As a result, the charged p-vinylphenol polymer was only recovered unreacted, and no ethylene oxide adduct was obtained.

Comparative Example 2 p-Vinylphenol polymer (▲ 2,500, ▲ ▼ 5,400) was placed in a glass polymerization tube with an internal volume of 25 ml which was replaced with nitrogen.
1.36 g, 1,4-dioxane 3 ml and 30% by weight sodium hydroxide aqueous solution 0.15 ml were added and mixed, and 5 g of ethylene oxide was charged therein (ethylene oxide / p-vinylphenol unit ≈10 mol / mol) and sealed, Soaked in a hot water bath at 80 ℃ and continued shaking for 23 hours.

After the reaction, ethanol was added to the contents and mixed uniformly, and concentrated hydrochloric acid was added to the contents to make them weakly acidic. Then, the solvent was evaporated and the polymer was recovered, and the yield was 1.5 g.

The IR and ¹ H-NMR spectra of this PVP-EO form are shown in FIGS. 17 and 18.

Although the spectrum of FIG. 17 resembles that of FIG. 3 as a whole, the absorption at 1110 cm ⁻¹ based on the C—O—C antisymmetric stretching vibration of the aliphatic ether is slightly stronger than that of FIG.

The ¹ H-NMR spectrum of FIG. 18 is similar to that of FIG. 4, but there is a peak attributable to the phenolic hydroxyl group proton at δ = 8.3 ppm, but a sharp peak due to the ethylene oxide chain is also δ = Appeared at 3.7 ppm. Therefore, the product is calculated from the respective peak area ratios, and the average unit of the following general formula [I] is 68 mol%,
It is considered that the unit of [I] consists of 32 mol%.

By the way, the calculation method of z in the above formula [I] is the same as the calculation method of n in the above-mentioned embodiment, but it is difficult to think from the result that it means the same content as n in the embodiment. The symbol z is used for the purpose of distinction.
That is, since a sharp peak (δ = 3.7 ppm) based on the ethylene oxide chain appears as described above, it is considered that the distribution is quite wide. Therefore, in this product, an ethylene oxide homopolymer by-product, unreacted p-vinyl Phenol polymer may remain.

Further, under such conditions, the ethylene oxide content in the product is far from the charging ratio, indicating that ethylene oxide does not react quantitatively and molecular design is difficult.

Reference Example 1 0.5 g of the PVP-EO product obtained in Example 5 was dissolved in 100 ml of water and agitated vigorously to produce bubbles. However, the foam disappeared within 10 minutes.

The solution was then mixed with 0.1 ml of xylene and stirred vigorously to form a stable emulsion.

[Brief description of drawings]

FIG. 1 and FIG. 2 show IR and ¹ H-NMR spectra of the PVP-EO product recovered as a water-insoluble part of the reaction product obtained in Example 1 by treating the benzene-insoluble part with water. Each spectrum is shown in FIGS. 3 and 4 for the PVP-EO obtained in Example 2.
Each spectrum of the IR and ¹ H-NMR of the body, IR of FIG. 5 and FIG. 6 is PVP-EO body obtained in Example 3 and ¹ H-N
FIGS. 7 and 8 show MR spectra and IR and ¹ H-NMR spectra of the PVP-EO form obtained in Example 4, and FIGS. 9 and 10 show Example 5 in Example 5. PVP-EO
Each spectrum of the IR and ¹ H-NMR of the body, FIG. 11 and FIG. 12 is the IR PVP-EO body obtained in Example 6 and ¹ H-N
Each spectrum of MR, FIGS. 13 and 14 are IR and ¹ H-NMR spectra obtained in Example 7, and FIGS. 15 and 16 are PVP-EO obtained in Example 8. Body IR and ¹
17 and 18 show IR and ¹ H-NMR spectra of the reaction product polymer obtained in Comparative Example 2, respectively.

Claims (4)

[Claims] 1. A general formula [I] The structural unit represented by the formula (n is an arbitrary integer of 1 to 100, M is hydrogen or an alkali metal) is 5 to 100 mol%, and the general formula [II] is used. The structural unit represented by the formula (wherein M is the same as above) has a substantial residual mol% as a main structural unit, and each structural unit has a structure in which a main chain is randomly bonded to a polymerization degree of 3 to 5000. Ethylene oxide adduct of p-vinylphenol polymer. 2. A structural unit represented by the general formula [I], n.
The ethylene oxide adduct of p-vinylphenol polymer according to claim 1, wherein the average value of the adduct is 1 ≦ n <1.5. 3. A structural unit represented by the general formula [I], n.
, The average value of the adduct is 1.3 ≦ n <100, and the structural unit represented by the general formula [I] is 95 to 100
The ethylene oxide adduct of the p-vinylphenol polymer according to claim 1, which is in mol%. 4. A p-vinylphenol polymer having a degree of polymerization of 3 to 5,000 is converted into a phenolate in which some or all of the hydrogen atoms of the hydroxyl groups are replaced with alkali metals, and then reacted with ethylene oxide in an anhydrous state. Formula [I] The structural unit represented by the formula (n is an arbitrary integer of 1 to 100, M is hydrogen or an alkali metal) is 5 to 100 mol%, and the general formula [II] is used. The structural unit represented by the formula (wherein M is the same as above) has a substantial residual mol% as a main structural unit, and each structural unit has a structure in which a main chain is randomly bonded to a polymerization degree of 3 to 5000. A method for producing an ethylene oxide adduct of p-vinylphenol polymer.