JPS6047284B2 - Method for producing new polymer compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a polymer compound having phase transfer catalytic ability.

More specifically, it relates to a method for efficiently producing a linear or three-dimensional polymer compound having a novel phase transfer catalytic ability, which has a polyether group whose end is blocked with an aromatic cyclic group in the side chain. It is. J In a heterogeneous reaction in which mutually immiscible reactants react, a substance that has the effect of solubilizing one reactant in the form of an ion pair in the other phase and promoting a bimolecular reaction is a so-called phase transfer catalyst. However, among these polyether-based polymerized compounds, polymer compounds having a crown ether type structure and polyethylene glycol have been known so far.

This crown ether type is thought to exhibit phase transfer catalytic action by incorporating metal ions into the pores formed by the cyclic polyether, but forming a crown type structure is This is extremely difficult and cannot be said to be practical. In addition, polyethylene glycol is thought to have a phase transfer catalytic effect by enveloping metal ions in its main chain and taking them in. do not have. The present inventors have conducted extensive research in order to overcome the difficulties of conventional polyether-based phase transfer catalysts and develop a polymer compound that can be easily produced and exhibits excellent catalytic activity. As a result, we discovered that polymer compounds such as polyethylene glycol, which do not have ether bonds in the main chain but have ether bonds in the side chains, have extremely excellent phase transfer catalytic ability.Based on this knowledge, we developed this book. He came up with an invention.

That is, the present invention provides at least one monomer selected from among the monomers represented by the general formula (in which R is an aromatic cyclic group and n is an integer of 1 to 6) and, if desired, At least one other copolymerizable ethylenic monomer is polymerized in the presence of a radical polymerization initiator or a cationic polymerization initiator,
The present invention provides a method for producing a polymer compound having phase transfer catalytic ability, which comprises at least a part of units represented by the general formula (R and n have the same meanings as described above).

The polymer or copolymer obtained by the method of the present invention is a new substance that has not been described in any literature.

R in the general formula (1) is a completely unsaturated carbocycle or heterocycle, a so-called aromatic ring, or a residue of a heterocycle treated as an aromatic ring, and is monocyclic or fused. Any one ring may be used, and the ring may be substituted or unsubstituted. Examples of such groups include phenyl, alkyl-substituted phenyl, alkoxy-substituted phenyl, nitrophenyl, naphthyl, pyridyl, quinolyl,
Isoquinolyl. '' group, an alkyl-substituted quinolyl group, an alkoxy-substituted pyridyl group, etc. On the other hand,
In general formula (1), n is an integer of 1 to 6, but in consideration of manufacturing problems and the like, n is usually in the range of 1 to 4.

In the method of the present invention, the general formula (
The monomers represented by 1) may be used alone or in combination of two or more. Furthermore, other monomers than the monomer represented by general formula (1) may be used in combination. General formula (1) used in the method of the present invention
Examples of monomers include 2-phenoxyethyl vinyl ether, 2-(2-methoxyphenoxy)7-methyl vinyl ether, 2-(4-methoxyphenoxy)ethyl vinyl ether, 2-(2-nitrophenoxy)ethyl vinyl ether, Vinyl ether derivatives such as 8-(2-vinyloxyethoxy)quinoline can be mentioned.

θ Examples of copolymerizable ethylenic monomers used in the present invention include styrene, vinylpyridine, vinylpyrrolidone, acrylamide, acrylic acid, methyl acrylate, ethyl acrylate, ethyl vinyl ether, butyl vinyl ether, and the like. Vinyl compound, α-
Isopropenyl compounds such as methyl styrene, methacrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, and 2-hydroxyethyl methacrylate; compounds with internal olefins such as maleic anhydride, maleimide, crotonic acid, fumaric acid, and crotonic acid methyl ester; , divinylbenzene, diisopropenylbenzene, phenylene diacrylamide, phenylene dimethacrylamide, phenylene diacrylate, phenylene dimethacrylate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and other divinyl and diisopropenyl compounds. can.

According to the method of the present invention, in order to produce a polymer compound having phase transfer catalytic ability by cationic polymerization, one or more of the above vinyl ether derivatives can be combined in any amount, and either directly or with methylene dichloride or ethylene dichloride. , carbon tetrachloride, toluene, nitromethane, etc., and stirred at -100°C to 30°C, preferably -80°C to 10°C, at a temperature of 0.01% per compound. ~10% by weight,
Preferably, the polymerization can be carried out by adding 0.5 to 5% by weight of a common cationic polymerization initiator such as boron trifluoride ether, tin chloride, aluminum chloride, or a complex salt of aluminum sulfate and sulfuric acid monohydrate. can.

After the polymerization is completed, a small amount of a base such as an amine is added to inactivate the initiator, and the reaction mixture is poured into a non-solvent for the resulting polymer such as n-hexane or petroleum ether to form a flocculent. releases high molecular weight compounds. Furthermore, 0.2 to 60 mol%, preferably 0.5 to 20 mol% of a cationically polymerizable compound among the vinyl compound, isopropenyl compound, or compound having an internal olefin is mixed in the vinyl ether derivative. , polymerization is carried out under the same conditions as above to obtain a linear polymer compound, or a cationically polymerizable compound is obtained from among the copolymerizable ethylenic compounds such as the divinyl compound or diisopropenyl compound. A three-dimensional polymer compound can also be obtained by selectively mixing 0.2 to 60 mol %, preferably 0.5 to 20 mol %, and polymerizing under the same conditions as described above. The three-dimensional polymer compound is used after being crushed and powdered. In order to produce a polymer compound having a phase transfer catalytic ability by radical polymerization according to the method of the present invention, one or more monomers of the general formula (1) and an appropriate copolymerization are used. 0.01 to 5% by weight, preferably 0.5 to 5% by weight of common monomers such as benzoyl peroxide, azobisisobutyronitrile, cumene hydroperoxide, etc. A radical polymerization initiator of 40 to 120' C1 is mixed, as it is or dissolved in a solvent commonly used for radical polymerization such as benzene, toluene, tetrahydrofuran, dioxane, etc., in a vacuum or in an inert gas atmosphere. This can be carried out by polymerizing at ~100'C. After polymerization,
The reaction mixture is poured into a non-solvent for the produced polymer, such as n-hexane or petroleum ether, to liberate the linear polymer. Furthermore, 0.2 to 60 mol%, preferably 0.5 to 50 mol% of the vinyl compound, isopropenyl compound, or compound having an internal olefin is mixed with the vinyl ether derivative, and the mixture is heated under the same conditions as above. Polymerization is combined to obtain a linear polymer compound, or 0.2 to 60 mol% of a copolymerizable ethylenic monomer such as the divinyl compound or diisopropenyl compound,
A three-dimensional polymer compound can be obtained by mixing preferably 0.5 to 50 mol % and polymerizing under the same conditions as above. The three-dimensional polymer is used after being crushed into powder. The linear and three-dimensional polymer compounds obtained in this way have the ability to incorporate metal ions, and selectively absorb one of the reactants that are separated into two phases, liquid-liquid or solid-liquid. They are solubilized in the form of ion pairs in other phases to perform bimolecular reactions (e.g., halogen substitution by the reaction between an alkyl halide and an alkali metal iodide, cyanation and halogenation by the reaction between an alkyl halide and an alkali metal cyanide). It can be suitably used as a phase transfer catalyst because it can promote esterification (e.g., esterification by reaction between an alkyl and an alkali salt of an organic acid) and can be easily recovered and reused.

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

Example 1 11.08y of 2-(2-methoxyphenoxy)ethyl vinyl ether was dissolved in 110q of dry methylene dichloride, cooled in a dry ice-acetone bath (-78°C),
While stirring in a nitrogen stream, 0.2 mt of boron trifluoride ether (BTE) was added and polymerization was carried out for 1 hour, and 0.1 ml of BTE was further added and polymerization was continued for 1 hour.

After adding 10 mt of ethanol containing a small amount of diethylamine to inactivate BTE, the solution was poured into a large amount of n-hexane to precipitate the polymer compound. This precipitate was again dissolved in methylene dichloride, poured into n-hexane, and reprecipitated, which was repeated twice for purification. The yield of the polymer compound was 11.10y (100%), and the intrinsic viscosity of the polymer compound measured at 30° C. using tetrahydrofuran (THF) as a solvent was 0.10. Example 2 Using the method of Example 1, 5.00 q of 2-(4-methoxyphenoxy)ethylvinyl"ether was mixed with the same solvent,
After carrying out cationic polymerization according to the blending ratio of BTE, the produced polymer compound was purified in the same manner.

The yield of the polymer compound was 5.10y (100%), and the intrinsic viscosity measured by the method of Example 1 was 0.12%.
Example 3 2-(2-nitrophenoxy)ethyl vinyl ether 5
．． 30y using the method of Example 1 and the same solvent, BTE.
After cationic polymerization was carried out at a blending ratio of , the resulting polymer compound was purified in the same manner.

The yield of the polymer compound was 5.32y (100%), and the intrinsic viscosity measured by the method of Example 1 was 0.16. Example 4 3.00 y of 2-(2-methoxyphenoxy)ethyl vinyl ether and 3.00 y of 2-(2-nitrophenoxy)ethyl vinyl ether were mixed, dissolved in 60 y of dry ethylene dichloride, and mixed in a dry ice-acetone bath (-
The mixture was cooled to 78° C., and while stirring in a nitrogen stream, 0.5 ml of a 10% solution of tin chloride in ethylene dichloride was added, and polymerization was carried out for 2 hours.

The polymer compound produced after polymerization was purified in the same manner as in Example 1. The yield of the polymer compound was 5.95y (100%
), and the intrinsic viscosity measured by the method of Example 1 was 0.14. Example 5 5.16v of 8-(2-vinyloxyethoxy)quinoline and 2.33V of maleimide were dissolved in 5y of THF, 0.04y of benzoyl peroxide was added, and the mixture was heated under vacuum at 70°C for 24 hours.
Subsequently, polymerization was carried out at 100° C. for 24 hours to obtain an insoluble polymer compound.

This was crushed and purified. The yield of polymer compound is 4.88
y (65%). Reference Example 1 Using the linear polymer obtained in the above example, the effect of promoting the following reaction was investigated.

0.01 mol of polymer compound converted to monomer unit,
Potassium acetate 0.01 mol and benzyl bromide 0.0
1 mol was placed in a container, a mixture of 9 ml (7) THF and 1 ml cumene was added to dissolve it, and a reflux condenser was attached to measure the rate of decrease of benzyl bromide at 60°C, and the initial rate of reaction was calculated. .

The results are shown in Table 1. Reference Example 2 Three-dimensional polymer powder obtained in the above example (100 to 20
0 mesh) was used to investigate the effect of promoting the following reaction.

n-C4H9Br (organic liquid phase) + NaI (aqueous phase) → n-C4l (91 (organic liquid phase) + NaBr (aqueous phase) 7.88
m01/' sodium iodide aqueous solution 25mt and 2.5
6m01/e (7) Take 5 mt of a benzene solution of n-butyl bromide in a container, and add 11 mt to n-butyl bromide.
After adding the polymer compound powder converted to the number of moles of monomer units of 10 and stirring at 80°C for 6 hours with a reflux condenser, the reaction rate was determined by measuring the amount of decrease in residual n-butyl bromide in the benzene solution. I asked for

Claims (1)

[Claims] 1 General formula CH_2=CH-O-(CH_2CH_2O)_n-R
(wherein R is an aromatic cyclic group and n is an integer of 1 to 6) is polymerized in the presence of a cationic polymerization initiator. A polymer with phase transfer catalytic ability, consisting of a repeating unit represented by the general formula ▲ mathematical formula, chemical formula, table, etc. Production method. 2 General formula CH_2=CH-O-(CH_2CH_2O)_n-R
(In the formula, R is an aromatic cyclic group, n is an integer of 1 to 6) and at least one copolymerizable ethylenic monomer General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R and n in the formula have the same meanings as above). A method for producing a copolymer having phase transfer catalytic ability, in which a unit represented by