JPH02362B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a soluble hydroxystyrene polymer substituted with a halomethyl group, which is a novel compound. This invention relates to a method for producing a soluble hydroxystyrene polymer substituted with a halomethyl group, which is characterized by introducing a halomethyl group by conducting a halomethylation reaction. The soluble hydroxystyrene polymer having a halomethyl group, which is a new compound obtained by the method of the present invention, can be used as a chelating agent, a polymer matrix agent, a polymer catalyst, a polymer metal complex, a highly sensitive photosensitive resin, and a gas barrier. It is a raw material for useful products such as films, water treatment membranes, organic liquid treatment membranes, etc. Furthermore, by subjecting this halomethylated hydroxystyrene polymer to a mensyutkin reaction with a tertiary amine compound, it can be made into a cationic type containing a quaternary ammonium group. A polymer electrolyte can be synthesized, which is used as a conductive treatment agent (Japanese Patent Publication No. 49-66579) and a flocculant (Japanese Patent Publication No. 49-66579).
55-16688), polyion complex membrane (Japanese Patent Publication No. 57-2362), etc. DIPackham performs a chloromethylation reaction on a cross-linked (insoluble) hydroxystyrene polymer, which is a copolymer of divinylbenzene and parahydroxystyrene, using chloromethyl methyl ether in the absence of a solvent and without a catalyst. have already obtained an insoluble chloromethylated hydroxystyrene polymer (Journal of
The Chemical Society (Journal of the
(Chemical Society), Vol. 1964, pp. 2620, 2623).
However, soluble chloromethylated hydroxystyrene polymers have not yet been obtained. If it is possible to produce a soluble chloromethylated hydroxystyrene polymer rather than a crosslinked (insoluble) one, it can be easily formed into a film or membrane. If it is made into a cationic polymer electrolyte containing a quaternary ammonium methyl group through the Menshyutkin reaction with an amine compound, it can be used as a water treatment agent or an organic liquid treatment agent.
Obtaining soluble chloromethylated or other halomethylated hydroxystyrene polymers is an important issue that has been strongly desired. Also, when considering its use as a raw material for photosensitive resins, soluble resins have a remarkable advantage over cross-linked and insolubilized resins in that the non-photosensitive areas can be dissolved and removed with an appropriate solvent, leaving an image of the photosensitive areas. have The present inventors conducted extensive research to produce a hydroxystyrene-based polymer having soluble halomethyl groups from the above point of view. The present invention was completed by discovering that the above object can be achieved by reacting methyl alkyl ether. In carrying out the method of the present invention, it is essential to carry out the reaction in the presence of an organic solvent; if the reaction is carried out in the absence of an organic solvent, crosslinking will occur and a soluble target product will not be obtained. Therefore, the gist of the present invention resides in a method for producing a soluble halomethylated hydroxystyrene polymer, which comprises subjecting the hydroxystyrene polymer to a halomethylation reaction with a halomethyl alkyl ether in the presence of an organic solvent. The structure of the soluble halomethylated hydroxystyrene polymer obtained by the method of the present invention is represented by the following formula. Here, 0<p<2, n is 3 or more, CM is a vinyl monomer, X is a halogen, and l is an arbitrary number including 0. The hydroxystyrenic polymer which is the starting material for the process of the invention can be a homopolymer of hydroxystyrene or a copolymer of soluble hydroxystyrene and other vinyl monomers, the polymerized units of hydroxystyrene being Although it may be any isomer, para or meta isomers are preferred. Examples of other vinyl monomers in the copolymer include styrene, α-methylstyrene, acrylonitrile, vinyl chloride, acrylic acid ester, methacrylic acid ester, maleic anhydride, and vinyl esters of various organic acids. can be given. Furthermore, the hydroxystyrene polymer used in the method of the present invention may be produced by any method, and its origin does not matter. For example, polyparahydroxystyrene, which is a parahydroxystyrene homopolymer, is easily prepared by cationic polymerization, radical polymerization, polymerization with an organic acid, or thermal polymerization of parahydroxystyrene. Polymerization using organic acids yields polymers with a weight average molecular weight of 1,000 to several hundreds of thousands, cationic polymerization yields polymers with a weight average molecular weight of tens to hundreds of thousands, and thermal polymerization yields polymers with a weight average molecular weight of 1,000 to 10,000. In addition, by radical polymerization and hydrolysis of para-acetoxystyrene, hundreds of thousands of
About 2 million polyparahydroxystyrene can be obtained. As the organic solvent used in the method of the present invention, cyclic ethers such as tetrahydrofuran and dioxane, and aprotic polar organic solvents such as acetonitrile are preferably used. Further, as the halomethyl alkyl ether used in the method of the present invention, those represented by the following formula are suitable. XCH ₂ O-R In this formula, X is halogen, preferably chlorine, bromine, or iodine, and R has 1 to 1 carbon atoms.
5, and this alkyl group contains chlorine,
It may be substituted with a halogen such as bromine or iodine, and the substitution position is preferably a carbon that is not bonded to oxygen. Examples of such halomethyl alkyl ethers include halomethyl methyl ether, halomethyl ethyl ether, halomethyl propyl ether, halomethyl butyl ether, halomethyl amyl ether, halomethyl halopropyl, where the halogen is chlorine, bromine or iodine. Examples include ether, halomethyl halobutyl ether, and among these, chloromethyl methyl ether, bromomethyl methyl ether, and chloromethyl chlorobutyl ether are preferably used. Furthermore, the halomethyl alkyl ether used in the method of the present invention does not necessarily have to be purified; for example, chloromethyl methyl ether is
It is generally obtained by reaction with formaldehyde, hydrogen chloride and methanol, but the product of the reaction to obtain chloromethyl methyl ether can also be used as it is. The halomethylation reaction of hydroxystyrene polymers in the method of the present invention uses the above-mentioned organic solvent, and the presence or absence of a Brønstedt acid such as hydrogen chloride, acetic acid, oxalic acid, thioglycolic acid, or maleic acid as a catalyst. If the reaction is carried out as described below, preferably using a small amount of acetic acid or oxalic acid as a catalyst, the rate of introduction of halomethyl groups into the hydroxystyrene polymer will be improved. It is not preferable to use a Lewis acid as a catalyst because it bonds with the phenolic hydroxyl group. The reaction temperature is 0°C to 150°C, preferably 40°C to 80°C, and the reaction time is 10 minutes to 100 hours, preferably 1 hour to 10 hours. The molar ratio of the halomethyl alkyl ether to be charged is within the range of 0.05 to 50 moles, preferably 0.5 to 10 moles per phenol nucleus of the raw material hydroxystyrene polymer, and the concentration of the hydroxystyrene polymer in the solvent is weight percent. within 50%, preferably within 30%, when using a catalyst.
The molar ratio of the catalyst used is 0.01 to 10 mol, preferably 2 mol or less, per phenol nucleus of the hydroxystyrene polymer as a raw material. It is done. After the reaction is completed, the halomethylated hydroxystyrene polymer can be isolated by reprecipitating the halomethylated reaction product using a non-solvent such as ether, petroleum ether, hexane, benzene, or the like. Further, after the reaction is completed, unreacted halomethyl alkyl ether can be removed using an evaporator, and the halomethylation reaction product in solution form can be used as it is for various uses. In the halomethylation reaction of the present invention, a part of the hydroxyl group of the hydroxystyrene unit reacts with the raw material halomethyl alkyl ether to form -OCH ₂ OR.
However, the rate of this side reaction is low, less than 20% of the introduction rate of halomethyl groups, and usually less than 10%. It goes without saying that the present invention also includes cases where such by-product impurities are included. The present invention will be further explained below with reference to Examples and Reference Examples, but these are merely illustrative. Reference example 1 12g of polyparahydroxystyrene with a weight average molecular weight of 5200 was added to a thermometer, dropping funnel, and reflux condenser.
Add 75.7 ml (80.51 ml) of chloromethyl methyl ether to a 300 ml four-necked flask and stir at room temperature.
g) was added from the dropping funnel over a period of 5 minutes. After the addition was completed, stirring was stopped and the supernatant liquid was allowed to stand still, and the supernatant liquid was colored pale yellowish orange, but most of the polyparahydroxystyrene remained solid, and the liquid was colored pale brown. Thereafter, when the mixture was stirred and reacted at room temperature for 1 hour and 55 minutes, most of the polyparahydroxystyrene remained solid and was colored brownish-purple. After a portion of this was removed, the polyparahydroxystyrene reaction product was insoluble in methanol or tetrahydrofuran (the starting material, polyparahydroxystyrene, is easily soluble in methanol or tetrahydrofuran). after that,
The temperature was further raised to 55° C. and the reaction was stirred for 5 hours. When the mixture was allowed to stand still, the supernatant liquid became a brown transparent solution, but most of the polyparahydroxystyrene remained as a light brown solid. This solid was separated, 150 ml of tetrahydrofuran was added, and after stirring at room temperature for 1 hour, a brown solid was obtained and was hardly dissolved in tetrahydrofuran. That is, a crosslinking reaction occurred, resulting in gelation and insolubility in the solvent. In addition, when both the reaction solution and the tetrahydrofuran extract of the reactant are added to a large amount of petroleum ether, only a very small amount of skin-white suspended precipitate is formed, and polyparahydroxystyrene or its chloromethylated reaction product is produced. was hardly included. Example 1 12 g of polyparahydroxystyrene (manufactured by Maruzen Sekiyu Co., Ltd., trade name: Resin M) with a weight average molecular weight of 5200 was placed in a 300 ml four-necked flask equipped with a thermometer, dropping funnel, and reflux condenser, and 100 ml of tetrahydrofuran was added. was stirred and dissolved uniformly at room temperature. The solution turned into a red, homogeneous and transparent solution. After adding 2.88 ml of acetic acid to this solution from the dropping funnel at room temperature with stirring, 37.87 ml of chloromethyl methyl ether was added little by little from the dropping funnel at room temperature while stirring, resulting in a slightly darker brown and uniform color. It became a clear solution. After the dropwise addition was completed in 10 minutes, the reaction was continued for 1 hour at room temperature with stirring, and then the temperature was raised to 66°C and boiling point reflux was carried out for 5 hours, resulting in a dark brown, homogeneous and transparent solution. This reaction solution was cooled to room temperature,
A tea udon polymer was obtained by pouring it into a mixed solvent of 750 ml of petroleum ether and 750 ml of ethyl ether. After this, the mixture was thoroughly washed with ethyl ether and petroleum ether and dried to obtain 14.0 g of a pale amber colored polymer. Elemental analysis revealed that this polymer had a Cl content of 12.3%.
It was confirmed that it was poly-3-chloromethyl-4-hydroxystyrene from the results of IR, ¹ H and ¹³ C-NMR analysis below. The introduction rate of chloromethyl groups was 0.50 per phenol nucleus of polyparahydroxystyrene, and it was easily soluble in methanol or tetrahydrofuran. IR result; KBr pellet method 1490cm ^-1 C〓C ring expansion and contraction (

[Formula]) 1268cm ^-1 ωCH ₂ pitch (-CH ₂ Cl) 1118cm ^-1 C-H in-plane deflection (

[Formula]) 890cm ^-1 Aromatic δCH out-of-plane of isolated H 750cm ^-1 νc-cl (-CH ₂ Cl) 680cm ^-1 C〓C ring out-of-plane bending angle (

[Formula]) has been newly recognized. ¹ H-NMR results; 27°C in 30% heavy THF (internal standard
TMS), the _main chain _-CH2 -CH-
Proton δ ₂ = 4.56ppm (4.3-4.8) with chloromethyl group -
Proton of CH ₂ Cl δ ₃ = 6.55 ppm (5.5 to 7.8), proton of phenolic nucleus δ ₄ = 7.3 ppm (7.1 to 7.8), 2 of phenolic OH
Proton (δ ₂ /2) / {(δ ₃ + δ ₄ + δ ₂ /2) / 5} = 0.50 (proton ratio) ¹³ C-NMR result; 27°C in 30% heavy THF (0 point is
TMS proton), ¹³ C of chloromethyl group -CH ₂ Cl was present at δ ₅ =42.0 ppm. Incidentally, a portion of ¹³ C of -O-CH ₂ -O- CH ₃ was present at δ ₆ =58.0 ppm, and ¹³ C of -O- CH ₂ -O-R was present at δ ₇ =92.0 ppm. The IR spectrum of the product is shown in Figure 1, ¹ H-
The NMR spectra are shown in Figure 2 and ^13C-
The NMR spectrum is shown in Figure 3. Example 2 12 g of polyparahydroxystyrene with a weight average molecular weight of 5200 was added to a thermometer, dropping funnel, and reflux condenser.
The mixture was placed in a 300 ml four-necked flask, and 100 ml of tetrahydrofuran was added thereto, and the mixture was stirred and dissolved uniformly at room temperature. When 3.8 g of oxalic acid was added to this solution and stirred and dissolved, the solution became a brown-red and uniform transparent solution. Add 7.57ml (8.05g) to this solution from the dropping funnel.
of chloromethyl methyl ether was added little by little at room temperature while stirring, and the dropwise addition was completed in about 10 minutes. After the reaction was further stirred at room temperature for 50 minutes, the temperature was raised to 66°C and boiling point reflux was carried out for 5 hours, resulting in a dark red and transparent solution. This reaction solution was cooled to room temperature and poured into a mixed solvent of 750 ml of ethyl ether and 750 ml of petroleum ether to obtain a brown polymer. After this, 13.1 g of light brown polymer was obtained by thoroughly washing with ethyl ether and petroleum ether and drying. As a result of elemental analysis, this polymer has a Cl content of 6.2%,
It was confirmed from the results of IR and NMR analysis that it was poly-3-chloromethyl-4-hydroxystyrene. The introduction rate of chloromethyl groups was 0.23 per phenol nucleus, and it was easily soluble in methanol or tetrahydrofuran. Example 3 In Example 2, 1.73ml of acetic acid was used instead of oxalic acid.
(1.8 g) was used, and the reaction was carried out in the same manner as in Example 2, except that the reaction was carried out at a reaction temperature of 50° C. for 8 hours.
After purification and drying, 12.5 g of a pale amber polymer was obtained. Elemental analysis revealed that this polymer had a Cl content of 3.4%.
According to the results of IR and NMR analysis, poly-3-
It was confirmed to be chloromethyl-4-hydroxystyrene. The introduction rate of chloromethyl groups was 0.12 per phenol nucleus, and it was easily soluble in methanol or tetrahydrofuran. Example 4 The reaction was carried out in the same manner as in Example 1 except that acetic acid was not added. After purification and drying, 12.8 g of a pale amber polymer was obtained. As a result of elemental analysis, this polymer has a Cl content of 6.0%,
It was confirmed from the results of IR and NMR analysis that it was poly-3-chloromethyl-4-hydroxystyrene. The introduction rate of chloromethyl groups was 0.22 per phenol nucleus, and it was easily soluble in methanol or tetrahydrofuran. Example 5 In Example 1, acetic acid was not added, and the amount of chloromethyl methyl ether was 75.7 ml (80.51 g).
The reaction was carried out in the same manner as in Example 1, except for the following. After purification and drying, 13.6 g of skin-colored polymer was obtained. As a result of elemental analysis, this polymer has a Cl content of 9.0%.
According to the results of IR and NMR analysis, poly-3-
It was confirmed to be chloromethyl-4-hydroxystyrene. The introduction rate of chloromethyl groups was 0.35 per phenol nucleus, and it was easily soluble in methanol or tetrahydrofuran. Example 6 The reaction was carried out in the same manner as in Example 1 except that acetic acid was not added and 22.8 ml (24.2 g) of chloromethyl methyl ether was used. After purification and drying, 12.7 g of an auburn polymer was obtained. This polymer has a Cl content of 4.1 as determined by elemental analysis.
%, and from the results of IR and NMR analysis, poly-3
-Chloromethyl-4-hydroxystyrene was confirmed. The introduction rate of chloromethyl groups was 0.15 per phenol nucleus, and it was easily soluble in methanol or tetrahydrofuran. Example 7 In Example 1, acetic acid was not added and the solvent was p-dioxane 100 instead of tetrahydrofuran.
The reaction was carried out in the same manner as in Example 1, using 6.08 ml of chloromethyl methyl ether at a reaction temperature of 89°C. After purification and drying, 12.3 g of pale white, auburn polymer was obtained. Elemental analysis of this polymer revealed that the Cl content was 3.1%, and IR and NMR analysis confirmed that it was poly-3-chloromethyl-4-hydroxystyrene. The introduction rate of chloromethyl groups was 0.11 per phenol nucleus, and it was easily soluble in methanol or tetrahydrofuran. Example 8 Maleic acid was used instead of oxalic acid in Example 2.
The reaction was carried out in the same manner as in Example 2 except that 3.48 g was used. After purification and drying, 12.8 g of a light thiocholate colored polymer was obtained. As a result of elemental analysis, this polymer had a Cl content of 4.6%, and it was confirmed from the results of IR and NMR analysis that it was poly-3-chloromethyl-4-hydroxystyrene. The introduction rate of chloromethyl groups was 0.17 per phenol nucleus, and it was easily soluble in methanol or tetrahydrofuran. Example 9 The reaction was carried out in the same manner as in Example 2 except that 2.09 ml (2.76 g) of thioglycolic acid was used instead of oxalic acid. After purification and drying, 12.5 g of light thiocholate colored polymer was obtained. Elemental analysis of this polymer revealed that the Cl content was 3.1%, and the IR,
From the results of NMR analysis, it was confirmed that it was poly-3-chloromethyl-4-hydroxystyrene. The introduction rate of chloromethyl groups was 0.11 per phenol nucleus, and it was easily soluble in methanol or tetrahydrofuran. Example 10 12 g of polymethahydroxystyrene with a weight average molecular weight of 5000 was added to a thermometer, dropping funnel, and reflux condenser.
The mixture was placed in a 300 ml four-necked flask, and 100 ml of tetrahydrofuran was added thereto, and the mixture was stirred and dissolved uniformly at room temperature. 3.8 g of oxalic acid was added to this solution and stirred and dissolved at room temperature. Add 7.57ml to this solution from the dropping funnel.
(8.05 g) of chloromethyl methyl ether was added little by little at room temperature while stirring, and the dropwise addition was completed in about 10 minutes. After further reacting at room temperature for 50 minutes with stirring,
The temperature was raised to 66°C and boiling reflux was carried out for 10 hours. This reaction solution was cooled to room temperature and poured into a mixed solvent of petroleum ether (1) and 500 ml of ethyl ether to obtain a light brown polymer. After this, washing thoroughly with petroleum ether and drying produces a auburn colored polymer.
13.2g was obtained. As a result of elemental analysis, this polymer
The Cl content was 6.9%, and it was confirmed from the results of IR and ¹ H-NMR analysis that it was poly-3-hydroxy-4-chloromethylstyrene. The introduction rate of chloromethyl groups was 0.26 per phenol nucleus, and this polymer was easily soluble in methanol or tetrahydrofuran. Example 11 12 g of polyparahydroxystyrene with a weight average molecular weight of 6500 was added to a thermometer, dropping funnel, and reflux condenser.
The mixture was placed in a 300 ml four-necked flask, and 100 ml of tetrahydrofuran was added thereto, and the mixture was uniformly dissolved at room temperature.
2.88 ml of acetic acid was added to this solution, and the mixture was stirred and dissolved at room temperature. Add 1-chloro- to this solution from the dropping funnel.
4-bromomethoxybutane ( _BrCH2O − _CH2−
CH2 _{- CH2} - _CH2Cl , bp94℃/5mmHg) 100.8g
was added little by little at room temperature while stirring, and the dropwise addition was completed in about 30 minutes. After further reacting at room temperature for 30 minutes with stirring, the temperature was raised to 60°C and the reaction was continued for 10 hours. After the reaction was completed, the reaction solution was cooled to room temperature and poured into a mixed solvent of ethyl ether (1) and petroleum ether (500 ml) to obtain a brown polymer. After this, by thoroughly washing with ethyl ether and drying, a light brown polymer is obtained.
15.3g was obtained. As a result of elemental analysis, the Br content of this polymer was 19.5%, and poly-3-3-3 had 0.38 bromomethyl groups introduced per phenol nucleus.
It was confirmed from the results of IR and ¹ H-NMR analysis that it was bromomethyl-4-hydroxystyrene. This polymer was easily soluble in tetrahydrofuran and methanol. Example 12 17.9 g of a radical copolymer of parahydroxystyrene and styrene (parahydroxystyrene content 67 mol%) was placed in a 300ml four-necked flask equipped with a thermometer, dropping funnel, and reflux condenser, and 150ml of tetrahydrofuran was added. was stirred and dissolved uniformly at room temperature. 3.8 g of oxalic acid was added to this solution and stirred and dissolved at room temperature. 7.57 from the dropping funnel into this solution.
ml (8.05 g) of chloromethyl methyl ether was added little by little at room temperature with stirring, and the dropwise addition was completed in about 10 minutes. After further reacting at room temperature for 50 minutes with stirring,
The temperature was raised to 66°C and boiling reflux was carried out for 5 hours. This reaction solution was cooled to room temperature and poured into a mixed solvent of ethyl ether (1) and petroleum ether (500 ml) to obtain a light brown polymer. After this, wash thoroughly with ethyl ether and dry to obtain a mauve-colored polymer.
18.9g was obtained. As a result of elemental analysis, this polymer
The Cl content was 4.3%, and 0.22 chloromethyl groups were introduced per hydroxystyrene, and no chloromethyl groups were introduced into the styrene moiety. This chloromethylated parahydroxystyrene and styrene copolymer was easily soluble in tetrahydrofuran and soluble in isopropanol. Reference Example 2 Poly-3-chloromethyl- obtained in Example 1
4-Hydroxystyrene (introduction rate of chloromethyl group is 0.50 per hydroxystyrene unit)
6.5g into a 200mm tube equipped with a thermometer, dropping funnel, and reflux condenser.
40 ml of tetrahydrofuran was placed in a 4-neck flask, and the mixture was stirred and dissolved at room temperature. At room temperature, 15.7 g of triethylamine was added drop by drop from the dropping funnel over a period of 10 minutes. temperature
After raising the temperature to 40°C and reacting with stirring for 1 hour, the reaction solution was cooled to room temperature and poured into a mixed solvent of 200 ml of petroleum ether and 200 ml of ethyl ether to obtain 8.7 g of a pale white polymer. . As a result of elemental analysis, this polymer has a N content of 3.59
%, and the Cl content was 9.10%, and it was confirmed from IR and NMR analysis that it was poly-4-hydroxystyrene-3-trisethylammonium methyl chloride. That is, unreacted chloromethyl groups were not detected and were all converted to trisethylammonium methyl chloride groups. Furthermore, this poly
4-Hydroxystyrene-3-trisethylammonium methyl chloride was easily soluble in methanol or tetrahydrofuran.

[Brief explanation of drawings]

FIG. 1 shows the IR spectrum of the product obtained in Example 1, FIG. 2 shows its ¹ H-NMR spectrum, and FIG. 3 shows its ¹³ C-NMR spectrum.

Claims (1)

[Scope of Claims] 1. A method for producing a soluble halomethylated hydroxystyrene polymer, which comprises subjecting the hydroxystyrene polymer to a halomethylation reaction with a halomethyl alkyl ether in the presence of an organic solvent. 2 The starting material hydroxystyrene polymer is , and halomethyl alkyl ether is
XCH ₂ OR, and the product halomethylated hydroxystyrenic polymer has the formula () The manufacturing method according to claim 1 represented by (where X is Cl, Br or I, 0<p<
2. CM is a vinyl monomer, l is any number including 0, n is 3 or more, and R is an alkyl group having 1 to 5 carbon atoms). 3. The manufacturing method according to claim 1 or 2, wherein the organic solvent is an aprotic organic solvent.