JPS6121246B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new polymer, a lactone group-containing vinylphenol polymer, and a method for producing the same. is 10 to 100 mol%, general formula (B) (wherein M is an alkali metal) is 0 to 90 mol%, general formula (C) (In the formula, D is a phenyl group or a cyano group) constitutes substantially the remaining mole% as the main structural unit, and each of the above structural units is randomly connected with the main chain, and has a polymerization degree of 10 to 500. This invention relates to lactone group-containing vinylphenol polymers and two methods for producing these polymers.

Examples of polymers having a lactone group in the side chain include a copolymer of beta-methylenepropiolactone and vinylidene cyanide (Japanese Patent Publication No. 3894-1989), a copolymer of diketene and propiolactone (Japanese Patent Publication No. 37-1989),
17696), 2-(3',4'-dihydro-2'H-pyran-
2′-yl)-β-propiolactone polymer or copolymer (Japanese Patent Publication No. 42-19327), γ-vinyl-
Copolymer of γ-butyrolactone and 4-vinylimidazole (Shimizu et al., Makromol.Chem., 175,
119 (1974)), a copolymer of β-vinyl-γ-butyrolactone and acrylonitrile (Shimizu et al.
Makromol.Chem., 178, 1923 (1977) is known. It has been described that these polymers can improve dyeing properties and can be used as hydrolysis catalysts for certain esters. However, lactone, which is a raw material monomer for these polymers, has the disadvantage that it is difficult to polymerize or synthesize it alone.

There has been no report on the lactone group-containing vinylphenol polymer according to the present invention, and it is a new compound. This lactone group-containing vinylphenol polymer has a lactone ring-containing group in its side chain, so it has the property of reversibly opening and closing rings depending on the pH of the system it comes in contact with, and can be used as an ion exchange resin or an ion exchange membrane. It can also be applied to the separation, concentration, and purification of various metal ions, solvents, fruit juices, milk, amino acids, pulp wastewater, painting wastewater, viruses, vitamins, rare gases, pickling wastewater, pickling wastewater, sewage, etc. In addition, the lactone group-containing vinylphenol derivative, which is a raw material monomer for the polymer of the present invention, can be copolymerized with styrene, acrylonitrile, etc., and can also be easily homopolymerized, increasing the lactone group content of the resulting polymer. Therefore, the above functions can be fully demonstrated.

The lactone group-containing vinylphenol polymer according to the present invention The group can be in the ortho, meta, or para position relative to the polymer backbone.

The first method for producing such a lactone group-containing vinylphenol polymer is based on the general formula It is obtained by polymerizing a lactone group-containing vinylphenol derivative having the formula alone or together with styrene or acrylonitrile.

Examples of the lactone group-containing vinylphenol derivatives which are the monomers mentioned above include α-(p-vinylphenoxy)-γ-butyrolactone, α-(m-vinylphenoxy)-γ-butyrolactone, and α-(o-vinylphenoxy)-γ-butyrolactone. It will be done. In addition, such a lactone group-containing vinylphenol derivative can be prepared, for example, by reacting vinylphenol with sodium hydride in tetrahydrofuran to produce vinylphenol sodium salt, and then reacting this in an aprotic solvent such as tetrahydrofuran at a reaction temperature of −50°C. General formula at ~+20℃ (In the formula, X is chlorine, bromine, or iodine.) It can be produced by dropping the compound and reacting it with a halogenated lactone. As vinylphenol, o-vinylphenol, m-
There are vinylphenol and p-vinylphenol. formula Compounds having the formula (wherein X is the same as above) are known and can be produced by halogenating γ-butyllactone according to the method of Bull. Soc. Chim. Fr., 294 (1971). , specifically α
-Bromo-γ-butyrolactone, α-chloro-γ
-butyrolactone, α-iodo-γ-butyrolactone.

The polymerization reaction for obtaining the polymer of the present invention from this monomer can be easily carried out by radical polymerization, cationic polymerization or thermal polymerization in a conventional manner.
In the case of radical polymerization, benzoyl peroxide, cumene hydroperoxide,
T-butyl hydroperoxide, ditertiary-butyl peroxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, azobispropionitrile, diaminobenzene, etc. can be used, and for cationic polymerization, Lewis acid catalysts such as boron fluoride etherate or chloride tin (),
Titanium chloride etc. can be used. Although a solvent may not be used during the polymerization, it can be carried out in an organic solvent such as benzene, toluene, xylene, n-heptane, dimethylformamide, dimethyl sulfoxide, dichloroethane, or in water. You can use a solvent that dissolves both the raw material monomer and the polymer produced, such as dimethylformamide, or a solvent that is insoluble in only the produced polymer, such as benzene, or a solvent that is insoluble in both the monomer and the polymer, such as water, for the purpose of obtaining a spherical polymer. Suspension polymerization may be carried out in a solvent. The polymerization temperature can be selected from a suitable temperature above room temperature, and in the case of radical polymerization and cationic polymerization, it is preferably about 50 to 100°C, and in the case of thermal polymerization without adding a polymerization initiator, 90 to 150°C is suitable. If necessary, the produced polymer can be purified by washing with a solvent such as acetone or ether, and by reprecipitation.

A copolymer with styrene or acrylonitrile can also be reacted under the same polymerization conditions as above. Post-treatment of the resulting copolymer can be carried out in the same manner as for the homopolymer.

The polymer produced in the first production method above is a polymer that does not substantially contain the structural unit represented by the general formula (B), and a polymer that contains the structural unit represented by the general formula (B). In order to obtain it, it is preferable to use the second manufacturing method described below.

The second method for producing a lactone group-containing vinylphenol polymer according to the present invention is a homopolymer of vinylphenol having a degree of polymerization of 10 to 500 or a random copolymer with styrene or acrylonitrile (however, styrene or acrylonitrile in the copolymer is The unit is 80 mol% or less) of an alkali metal salt with the general formula (wherein X is the same as defined above). In the course of this reaction, cleavage of the polymer chain of the alkali metal salt of the raw material vinylphenol polymer does not substantially occur, so that the degree of polymerization of the raw material polymer remains substantially unchanged after the reaction.

The above-mentioned vinylphenol-based polymers and their alkali metal salts can be prepared by known methods, such as o-vinylphenol, m-vinylphenol or p-vinylphenol.
- It can be prepared by homopolymerizing or copolymerizing vinylphenol in the same manner as the polymerization method in the first production method, and treating the obtained polymer with an alkali metal compound in a conventional manner to obtain an alkali metal salt. can. Examples of alkali metal compounds include hydrides, hydroxides, and alkoxides of sodium, potassium, and lithium, such as sodium hydride, potassium hydride, sodium hydroxide,
Examples include sodium methoxide.

The above-mentioned halogenated lactones and their preparation methods are also known as described above. Specifically, the halogenated lactones used are α-bromo-γ-butyrolactone, α-chloro-γ-butyrolactone, and α-iodo-γ-butyrolactone.

The etherification reaction between the alkali metal salt of the vinylphenol polymer and the above-mentioned halogenated lactones can be carried out in an aprotic solvent. Examples of aprotic solvents include chain ethers, cyclic ethers, formamides, sulfoxides, hydrocarbons, ketones, etc. Specific examples include dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, diethyl sulfoxide, Acetone, methyl ethyl ketone, n-hexane, n-
Examples include pentane. Among these, solvents that dissolve the alkali metal salt of the vinylphenol polymer, such as tetrahydrofuran and dimethylformamide, are particularly preferred. The presence of water or alcohol is undesirable as it reduces the yield of the target product. The reaction temperature is not particularly restricted and may be, for example, -50 to +200°C, but particularly preferably -20 to +100°C. The reaction is carried out by mixing and stirring the alkali metal salt of the vinylphenol polymer and the halogenated lactones in a solvent, but it is preferable to add the vinyl into the solvent solution containing the halogenated lactones while stirring. This is a method in which an alkali metal salt of a phenolic polymer or its solvent solution is added little by little and reacted. The amount of the alkali metal salt of the vinylphenol polymer added to the halogenated lactone may be approximately equimolar.

In this etherification reaction, it is preferable to prepare an alkali metal salt of a vinylphenol polymer in advance as described above and react it with a halogenated lactone in a solvent. It is also possible to react the compound and the halogenated lactone directly in an aprotic solvent with stirring. Examples of alkali metal hydrides include sodium hydride, potassium hydride, and lithium hydride. The reaction conditions may be the same as those for the etherification reaction described above.

The lactone group-containing vinylphenol polymer, which is the object of the present invention, can be isolated and purified from the reaction mixture in the same manner as in the first production method.

In the second production method described above, although it is theoretically possible to lactonize all of the alkali metal salts of the phenolic hydroxyl groups in the polymer, in reality only 90% of the alkali metal salts can be lactonized. It is. Therefore, if a polymer in which all of the alkali metal salts of the phenolic hydroxyl groups in the polymer are lactonized is desired, the first production method described above is preferably used.

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

Reference example 1 28.5g (0.238 mol) of p-vinylphenol
13.7 g of sodium hydride-oil mixture (NaH content 50
%, 0.238 x 12 mol) and reacted at 0°C for 2 hours to obtain the sodium salt. The p-vinylphenol sodium salt solution from which excess NaH was removed was mixed with 39.2 g of α-promo-γ-butyrolactone.
(0.238 mol. Prepared by bromination of γ-butyrolactone according to the method of Bull. Soc. Chim. Fr., 294 (1971)) and 50 ml of tetrahydrofuran. . After the dropwise addition was completed, the reaction was continued at 0°C for an additional 48 hours. Filter the reaction solution to remove NaBr, evaporate the solvent,
The remaining crystals were recrystallized three times in ethanol to obtain 23.3 g of white needle-like crystals. This crystal had a melting point of 88°C, and was confirmed to be α-(p-vinylphenoxy)-γ-butyrolactone from elemental analysis, IR and NMR spectra.

Example 1 25 ml of dimethylformamide in a sealed tube, Reference Example 1
α-(p-vinylphenoxy)-γ-butyrolactone 5.10 g (1 mol/) and azobisisobutyronitrile 0.0411 g (0.01 mol/) prepared in
The mixture was sealed and reacted at 60°C for 20 hours. After the reaction, the solvent was evaporated to obtain a polymer. The yield was 68.3%. ηsp/C of this polymer (C is
0.5g/d) in DMF at 30°C is 0.30d/g (weight average molecular weight approximately 15000), soluble in dimethylformamide, dimethyl sulfoxide, benzene,
It was insoluble in chloroform and tetrahydrofuran. The IR spectrum (KBr method) was as shown in Figure 1, and it was confirmed that the product was a polymer poly(α-(p-vinylphenoxy)-γ-butyrolactone) having the following repeating unit.

Example 2 0.799 g of α-(p-vinylphenoxy)-γ-butyrolactone prepared in Reference Example 1 was reacted in a sealed tube at 120° C. for 1 hour without a catalyst or solvent. The yield of the obtained polymer was 46.2%, and ηsp/C was 0.91d.
/g (weight average molecular weight approx. 66000, degree of polymerization approx. 330)
The IR spectrum (KBr method) was as shown in Figure 2. The resulting polymer was poly(α-(p-vinylphenoxy)-γ) as in Example 1.
- butyrolactone).

Example 3 0.331 g of α-(p-vinylphenoxy)-γ-butyrolactone and boron fluoride etherate in a sealed tube
A mixture of 0.05 ml and 4 ml of dichloroethane was sealed and reacted at 0°C for 1 hour. The yield of the obtained polymer was 0.311g (yield 94%) ηsp/C was 0.2d
/g (weight average molecular weight approximately 8700), and the IR spectrum (KBr method) is as shown in Figure 3, and the produced polymer is poly(α-(p-vinylphenoxy)-γ-butyrolactone) as in Example 1. It was confirmed that

Example 4 In a sealed tube, 2.93 g of α-(p-vinylphenoxy)-γ-butyrolactone and 1.78 g of acrylonitrile (α
-(p-vinylphenoxy)-γ-butyrolactone and acrylonitrile in a molar ratio of 3:7 and a mixed molar concentration of 2 mol/molar. ), azobisisobutyronitrile
A solution consisting of 3.94×10 ^-3 g (0.01 mol/) and 24 ml of dimethylformamide was melt-sealed and heated at 60°C for 10
Allowed time to react. The yield of the obtained polymer was 4.70g.
(yield 100%), ηsp/C was 0.6 d/g (weight average molecular weight approximately 38,000, degree of polymerization approximately 400), and the IR spectrum (thin film) was as shown in FIG. As a result, it was confirmed that the resulting polymer was a copolymer having the following two types of repeating units in a ratio of 3:7.

Example 5 A reaction was carried out in the same manner as in Example 4, except that 4.87 g of styrene (proportion of styrene in the raw material was 77 mol %) was used instead of acrylonitrile, and the reaction time was changed to 20 hours. The yield of the obtained polymer was 4.64g
(yield 60%), ηsp/C was 0.2 dl/g (weight average molecular weight approximately 8700), and the IR spectrum (KBr method) was as shown in FIG. It was confirmed that the resulting polymer was a copolymer having the following two types of repeating units.

Example 6 In a sealed tube, 30 ml of benzene, 3.06 g of α-(p-vinylphenoxy)-γ-butyrolactone (0.5 mol/
), azobisisobutyronitrile 0.0492g (0.01
mol/) was melt-sealed and reacted at 60°C for 6 hours. The polymerization system was non-uniform as the polymer precipitated from the initial stage of polymerization, and the resulting polymer was also insoluble in dimethylformamide. The yield of the obtained polymer was 0.706 g (yield 23.1%), and the IR spectrum was almost exactly the same as that of the polymer obtained in Example 2. )-γ-butyrolactone).

Example 7 12 g of poly(p-vinylphenol) (Range M manufactured by Maruzen Oil Co., Ltd., number average molecular weight 2300, phenolic hydroxyl group 0.1 mol) was dissolved in 100 ml of tetrahydrofuran, and 12 g of sodium hydride-oil mixture was dissolved at 0°C.
(NaH content: 25%) and reacted at 0° C. for 2 hours to obtain a sodium salt. The sodium salt solution of poly(p-vinylphenol) from which excess NaH was removed was mixed with 20 g of α-bromo-γ-butyrolactone.
(0.12 mol) and tetrahydrofuran (50 ml) under heating under reflux. After the dropwise addition was completed, the reaction was continued for another 48 hours. Pass the reaction solution
The NaBr was removed, the solvent was evaporated, and the residue was washed with acetone and diethyl ether to prepare the polymer.
Got 10g. IR spectrum of this polymer (KBr
method) is shown in Figure 6, and approximately 30% of the polymer units
One had the structure of poly(α-(p-vinylphenoxy)-γ-butyrolactone), and the rest had the structure of the sodium salt of poly(p-vinylphenol).

Reference Example 2 When the poly(α-(p-vinylphenoxy)-γ-butyrolactone) obtained in Example 1 was suspended in a 5 wt% aqueous sodium hydroxide solution, the
It dissolved in about an hour. When a 0.1N aqueous hydrochloric acid solution was added dropwise to this aqueous solution, the pH reached 3 and precipitation of polymer was observed. Figure 7 shows the IR spectrum of the polymer at PH12 and PH7PH2 (1780cm ^-1 )
is the lactone ring, and 1600 cm ^-1 is the absorption peak of COO. ). These results indicate that this polymer becomes water-soluble in alkaline conditions due to the opening of the lactone ring.
It was confirmed that in acidic conditions, it becomes water-insoluble due to ring closure. This indicates that this polymer can be used in applications such as ion exchange resins, ion exchange membranes, selective transport of metal ions, and active transport.

[Brief explanation of the drawing]

Figures 1 to 7 are IR spectra of the produced polymers of Examples 1 to 5 and 7 and Reference Example 2, respectively.

Claims (1)

[Claims] 1 General formula (A) is 10 to 100 mol%, general formula (B) (wherein M is an alkali metal) is 0 to 90 mol%, general formula (C) (In the formula, D is a phenyl group or a cyano group) has a polymerization degree of 10 to 500, and has a structure in which substantially the remaining mole% is the main structural unit, and each of the above structural units is randomly connected through the main chain. Lactone group-containing vinylphenol polymer. 2 General formula It is characterized in that a lactone group-containing vinylphenol derivative having the following formula is polymerized alone or together with styrene or acrylonitrile. General formula (A) is 10 to 100 mol%, general formula (C) (In the formula, D is a phenyl group or a cyano group) constitutes substantially the remaining mole% as the main structural unit, and each of the above structural units is randomly connected with the main chain, and has a polymerization degree of 10 to 500. A method for producing a lactone group-containing vinylphenol polymer. 3. An alkali metal salt of a homopolymer of vinylphenol with a degree of polymerization of 10 to 500 or a random copolymer of it and styrene or acrylonitrile (however, the styrene or acrylonitrile unit in the copolymer is 80 mol% or less), with the general formula (wherein X is chlorine, bromine or iodine)
General formula (A) characterized by reacting with a halogenated lactone having is 10 to 90 mol%, general formula (B) (wherein M is an alkali metal) is 10 to 90 mol%, general formula (C) (In the formula, D is a phenyl group or a cyano group) constitutes substantially the remaining mole% as the main structural unit, and each of the above structural units is randomly connected with the main chain, and has a polymerization degree of 10 to 500. A method for producing a lactone group-containing vinylphenol polymer.