JPS6111961B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a novel polymer having a group containing a linear polyoxyalkylene chain in its side chain. More details in the molecule

[Formula] (Nuclear substitution is at para or meta position) By reacting a vinyl polymer compound containing a structural unit with a reactive acyclic polyoxyalkylene compound having 3 or more oxyalkylene units in the presence of a base. within the molecular chain

The present invention relates to a method for producing a novel polymer containing a unit of the formula: (nuclear substitution is at the para or meta position, Y is a group containing a linear polyoxyalkylene chain having 3 or more oxyalkylene units). Although this polymer is a novel polymer compound that was completely unknown until now, the group containing a polyoxyalkylene straight chain as a side chain has the ability to capture metal ions, so it can be applied in many fields as described below. It is a polymer capable of Further, the new polymer obtained by the method of the present invention can be transformed into granular, granular, or
The fact that it can be provided in any desired form, such as film or fiber form, has a major factor in expanding its application fields. Typical specific uses of the novel polymer obtained by the method of the present invention include, for example, catalysts for organic ion reactions, Lewis acid scavengers (separating agents) and Lewis acid catalyst modifiers, and metal salt scavengers (separating agents). ), heavy metal scavengers, metal cation permeable membranes, carriers for transition metal catalysts, etc., but are of course not limited to these, and can be expected to have a wider range of uses due to its basic properties as a polymer as described above. . The novel polymers obtained by the method of the present invention are polymers having sulfonic acid groups such as conventionally known ion exchange resins, ion exchange membranes, and ion exchange fibers, or polymers having amino groups such as anion exchange resins. Unlike the above-mentioned polymers, the molecules are neutral, so compared to the above-mentioned polymers, it has excellent chemical resistance and can be used under acidic and alkaline conditions, as well as in organic solvents, and is extremely thermally stable, so it can be used under a wide range of conditions. It has the advantages of being usable, and is expected to be used in a wide range of applications as described below, taking advantage of these advantages. Within the molecule used in the method of the invention

Examples of the vinyl polymer compound having a structural unit of the formula include a homopolymer of a styrene derivative unsubstituted at the meta or para position, or a combination of the above styrene derivative and styrene, acrylonitrile, vinylpyridine, methyl methacrylate, vinyl acetate, Copolymers with copolymerizable vinyl monomers such as butadiene, isoprene, and divinylbenzene are subjected to a chloromethylation reaction using chloromethyl ether in a conventional manner, and homopolymers or copolymers of chloromethylstyrene derivatives are produced. used. On the other hand, the reactive polyoxyalkylene compound, which is another characteristic raw material used in the method of the present invention, includes those represented by the following general formula. That is, In these general formulas () to (), P represents a straight chain or branched alkylene group having 2 to 4 carbon atoms, preferably

【formula】

【formula】

[Formula] etc., and particularly preferably -CH ₂ CH ₂ -. Moreover, A is a hydrogen atom or a sodium atom. All of the alkylene groups P in the same molecule do not have to be the same, and may be a mixture of different alkylene groups, such as a coadduct of ethylene oxide and propylene oxide. When A is a hydrogen atom, these polyoxyalkylene compounds can be easily synthesized by addition polymerization of olefin oxide to alcohols or phenols or partial etherification reaction of polyoxyalkylene glycol. When A is a sodium atom, the terminal hydroxyl group of the polyoxyalkylene compound and metallic sodium, sodium hydride, C-
Oxyalkylene can be synthesized by a reaction with an organometallic compound having a Na bond or by an alkoxy exchange reaction between a sodium alcoholate of a lower alcohol and a polyoxyalkylene glycol monoether (the lower alcohol produced is continuously distilled off). The number of units n is a number of 3 or more, and x and y are numbers larger than 0 such that the sum of both is 3 or more, but it is desirable that at least one of x and y is 3 or more. n or x+y is 1
In the case of 2 and 2, the metal ion trapping ability is extremely small and the obtained polymer has almost no practical use. Although there is no critical upper limit for n and (x+y), the use of polyoxyalkylene compounds with extremely large values is due to the mechanical properties of the resulting polymer and the metal ions per unit weight of the polymer. This is not necessarily practical in terms of capture ability, etc. That is, generally n and (x+y) are 3 to 25
A suitable range is from about 5 to about 5%.
The range is 15. The values of n and (x+y) are integers for one molecule, but in the general manufacturing method of polyoxyalkylene compounds, the values of n and (x+y) for each molecule are not uniform, but within a certain range. It is customary to have a molecular weight distribution. In the present invention, such polyoxyalkylene compound mixtures having a molecular weight distribution within a certain range may be used as they are without any problem. In the above general formulas () to (), R ¹ is hydrogen and a substituted or unsubstituted hydrocarbon group having 1 to about 20 carbon atoms, and R ² and R ³ are substituted or unsubstituted hydrocarbon groups having 1 to about 20 carbon atoms. Hydrocarbon groups such as methyl, ethyl, butyl, amyl, 2-ethylhexyl, octyl, decyl, stearyl, hexenyl, oleyl, methylphenyl, nonylphenyl, and benzyl. Among these hydrocarbon groups, the metal ion trapping ability of the final polymer is determined by the methyl group,
There is a tendency for the increase to occur particularly in the case of relatively lower alkyl groups such as ethyl, propyl, butyl, and amyl groups. Among the polyoxyalkylene compounds represented by the above general formulas () to (), considering chemical and thermal stability, price, metal ion trapping ability, etc., polyoxyalkylene glycols represented by the formula () and polyoxyalkylene Oxyalkylene glycol monoethers are particularly preferred. A simple method for converting a chloromethyl group into a polyoxyalkylenemethyl group that can be employed in the method of the present invention includes the following method. The first method is a more industrial method,
It is particularly preferably applied. This method requires that the polyoxyalkylene compound have a hydroxyl group at least at one end, and is a method newly developed by the present inventors. In this method, the reaction between the polyoxyalkylene compound and the chloromethyl group is carried out in the presence of a base. Particularly preferred bases in this case are sodium hydroxide and potassium hydroxide, and the reaction is carried out by pulverizing these bases and stirring vigorously under suspension in an organic solvent. Preferred organic solvents include benzene, toluene, xylene, chlorobenzene, cyclohexane, heptane, dibutyl ether, tetrahydrofuran, diglyme, triglyme, acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, pyridine,
Examples include triethylamine. After the reaction, the unreacted base and the metal chloride produced are filtered or centrifuged from the reaction mixture, washed with water and, if necessary, an organic solvent, and dried to remove the polyoxy A polymer having groups containing straight alkylene chains is obtained. In the case of this reaction, there are no particular restrictions on the reaction conditions, but generally the polyoxyalkylene compound is used in an amount equivalent to or more than the chloromethyl group, and at a temperature of 50 to 150°C in the presence of an excess amount of base. Allow to react while stirring vigorously. As a modification of this method, the substitution reaction can also be carried out using an aqueous solution containing the above-mentioned base. The polyoxyalkylene compound used in the present invention has an autocatalytic effect on this substitution reaction. In this reaction between different phases, benzene, toluene, xylene, chlorobenzene, etc. are preferably used as organic solvents. Although the above-mentioned water-soluble polar organic solvents can essentially be used, industrially, the use of these water-soluble organic solvents is not preferable because recovery of the solvent from the reaction mixture after the reaction becomes complicated. The concentration of the base in the aqueous solution containing the base is extremely important for the reaction to proceed smoothly, and generally a 40 to 75 weight percent aqueous solution is used. Since this is a reaction between different phases, vigorous stirring is required. The (co)polymer exists in suspension, but the Cl is replaced by a polyoxyalkylene group to give the desired product. In consideration of product separation and purification, process and economic efficiency, this reaction between different phases is considered to be the most preferred industrially. The second method is not necessarily a satisfactory method for industrial production, but is a process that applies the generally known Williams synthesis method. That is, This substitution reaction is carried out in an anhydrous organic solvent solution.
Preferred organic solvents include polar solvents such as tetrahydrofuran, diglyme, dimethylformamide, acetonitrile, dimethyl sulfoxide, and hexamethylphosphoramide, as in the general Williams ether synthesis method. Polyoxyalkylene sodium alcoholate can be synthesized by the method described above. In the molecule finally obtained by the method described above,

[Formula] (Nuclear substitution is at the para or meta position, Y is a group containing a polyoxyalkylene linear chain) The new polymer has the unit because the side chain containing the polyoxyalkylene linear chain has the ability to capture metal ions. It can be used in various industrially important fields. As mentioned above, the novel polymer obtained by the method of the present invention can be produced by methods known per se, such as copolymerization, polymerization, polymer blending,
By appropriately combining molding methods, etc., the final shape can be made into granules, films, or fibers, so it has a wide range of applications. Hereinafter, typical application fields of the novel polymer obtained by the method of the present invention will be explained. First of all, the present inventors have filed an earlier application (patent application filed in 1973).
-73624, 51-82117, 51-82118), since polyoxyalkylene compounds have the ability to capture metal ions, the new polymers obtained by the method of the present invention can be used to capture various base-catalyzed organic ions. It can be used as a reaction catalyst. The new polymer can be made into granules, films, or fibers, so when used as a catalyst for organic ion reactions, it is easy to separate the catalyst from the reaction mixture, and the catalyst can be reused. In addition to this, it also provides the advantages recognized with conventional immobilized catalysts, such as not causing damage to the target product when it is separated, for example, by distillation, from the reaction mixture. Examples of industrially important base-catalyzed organic ion reactions in which the polymer is preferably applied as a catalyst include (1) substitution reaction, (2) base-catalyzed elimination reaction, and (3) activity of active hydrogen compounds. Examples include substitution reactions of hydrogen with organic groups, and (4) self- and interspecies condensation reactions of carbonyl compounds. The second preferred use of the polymer obtained by the method of the present invention is to use the ability to form a complex between a Lewis acid and ether-bonded oxygen as a scavenger (separator) for Lewis acid catalysts and to modify Lewis acid catalysts. It is used as a drug. Representative examples of Lewis acids include aluminum chloride, aluminum bromide, titanium tetrachloride,
Examples include tin tetrachloride, trifluoroboron, zinc chloride, etc., and the polymer obtained by the method of the present invention exhibits remarkable scavenging ability even for mixtures of these Lewis acids. As is well known, these Lewis acids are widely used industrially as catalysts for isomerization reactions, cyclization reactions, polymerization reactions, Friedel-Crafts reactions, telomerization reactions, carbonylation reactions, and the like. The reaction is carried out in an organic solvent solution, but when the reaction mixture is brought into contact with the polymer obtained by the method of the present invention after the reaction, the Lewis acid that is the catalyst is captured by the polymer, so the reaction mixture is It has industrial value, such as being able to selectively separate the products from the reaction mixture, not damaging the products when separating them from the reaction mixture, and being able to suppress corrosion in reaction equipment such as distillation columns. is extremely large. The Lewis acid in the reaction mixture can be brought into contact with the polymer obtained by the method of the invention under stirring or by a column method. Further, in the novel polymer obtained by the method of the present invention, the catalytic ability of the Lewis acid can be adjusted by the coordination of the Lewis acid with respect to ether oxygen. The resulting polymerized Lewis acid catalyst also exhibits a so-called polymeric effect and enables more selective reactions. In this case, it goes without saying that the reaction conditions employed in general organic reactions using Lewis acid catalysts can be applied. Further, the form of the polymer is generally preferably granular or film-like. A third preferred use of the polymer obtained by the method of the present invention is as a metal ion trapping agent (separating agent). Specifically, metal salts in organic solutions, such as sodium methylate in methanol, potassium t-butoxide in t-butanol, sodium acetate and potassium acetate in acetic acid, various metal salts in dimethylformamide, etc., are used in the method of the present invention. This is a method of separating the polymer obtained by contacting it with an organic solvent solution, and in this case, the stirring method and column method are also applied. On the other hand, if the metal salts (mainly heavy metal salts) in the aqueous solution are metal ions that form adducts with polyoxyalkylene groups, the polymer obtained by the method of the present invention can capture them. Can be used as a separating agent. Specific examples of such metals include Zn(), Mo
(), Co(), Fe(), Cu(), Hg()
etc. can be mentioned. Practically, aqueous solutions containing these heavy metals discharged from various processes are removed by passing them through a column packed with the polymer obtained by the method of the present invention. In the above method, the form of the polymer is particularly preferably granular; A metal ion permeable membrane is also a preferred practical example to which the polymer can be applied. A fourth preferred use of the polymer obtained by the method of the present invention is use as a support for various transition metal catalysts. The polymer can be molded into a desired shape such as granules, film, or fiber by a method known per se.
The expensive transition metal catalyst can be easily separated from the reaction mixture without loss, eg, through elution, attrition, etc. Further, the catalytic ability of the transition metal catalyst supported on the polymer obtained by the method of the present invention may differ from that of a catalyst supported on a normal inorganic carrier due to the so-called polymer effect.
When supporting various transition metal components on the polymer obtained by the method of the present invention, it is desirable to fully utilize the affinity of these transition metal salts for polyoxyalkylene groups. The various transition metal salts captured by the polyoxyalkylene linear chain-containing group of the polymer are reduced by a method known per se to finally obtain a supported catalyst. As the reduction method, a reagent reduction method using an organoaluminum compound, sodium borohydride, lithium aluminum hydride, hydrazine, carbon monoxide, hydrogen, etc. is generally preferably applied. The catalyst thus supported on the polymer may also contain other co-catalyst components, if desired. The catalyst thus obtained is capable of reacting in an organic solvent solution with hydrogenation reactions, isomerization reactions, various oligomerization reactions, carbonylation reactions, etc., which are generally contacted with a catalyst supported on an inorganic carrier. Needless to say, all of them are applicable. As described above, the polymer obtained by the method of the present invention has the metal ion (salt) trapping ability of the group containing a polyoxyalkylene linear chain, the ease of polymer form conversion, and the polymer effect on catalytic ability. It has such characteristic properties that it can be applied to a wide range of fields. Considering the ease of synthesis (including molding), it can be said to be an extremely valuable polymer industrially. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 Contents 200 with stirrer, thermometer and cooler
A granular styrene-divinylbenzene copolymer (divinylbenzene content: Divinylbenzene was used at a commercially available concentration of 40% by weight.) was chloromethylated with chloromethyl ether using a conventional method (Experimental Methods of Polymer Synthesis, Kagaku Dojin (1972), p. 373). As a result of elemental analysis, the chlorine content in the resin was 17% by weight.)10
g, dimethylformamide 50ml, polyethylene glycol monomethyl ether (average molecular weight;
370) 10g and 12g of micronized potassium hydroxide
was added and stirred vigorously at 70°C for 24 hours. After the reaction, 50 ml of water was added to dissolve potassium hydroxide and potassium chloride, and then the resin was filtered off using a glass filter. The resin collected by filtration was thoroughly washed with a dilute aqueous hydrochloric acid solution, distilled water, and then acetone, and then vacuum-dried at 50° C. overnight. The weight of the resin after vacuum drying is
It had increased to 11.8g. The results of elemental analysis of this resin revealed that the resin contained no chlorine at all. In addition, when the infrared absorption spectrum of this resin was measured using the KBr tablet method, 670 cm ^-1 was observed in the raw resin immediately after chloromethylation.
The absorption at 1100 cm -1 (C--Cl bond) completely disappeared, and a new absorption was observed at 1100 cm ^-1 (C--O--C bond). Next, add 1 g of the final resin to 10 ml of concentrated hydrochloric acid.
Pour into a 50 ml flask and incubate at 100℃ for 24 hours with stirring.
Allowed time to react. After the reaction, the resin was filtered off and thoroughly washed with water. When a part of the filtrate was analyzed by gas chromatography, the presence of a peak of raw material polyethylene glycol monomethyl ether was confirmed. Furthermore, when the infrared absorption spectrum of the resin treated with concentrated hydrochloric acid was measured by the KBr tablet method, absorption at 670 cm ^-1 was again observed. As a result of elemental analysis of the resin treated with concentrated hydrochloric acid, the chlorine content in the resin was 2.3%.
It was hot. On the other hand, the amount of polyethylene glycol monomethyl ether in the filtrate was measured by the barium phosphotungstate method and was found to be 0.2 g.
From the above, it can be seen that by this reaction, the chlorine of the chloromethyl group in the side chain of the styrene-divinylbenzene copolymer was partially replaced by polyethylene glycol monomethyl ether. (Polyethylene glycol monomethyl ether is calculated to be 0.65 mmol bonded per 1 g of resin.) 100 g of the resin synthesized according to the above method was packed in a column, thoroughly washed with 6M hydrochloric acid, and then Fe ³⁺ was added 1x to 6M hydrochloric acid. 100ml of an aqueous solution containing 10 ^-2 M per minute
When I flushed the water at a rate that was like a drop, some water was found in the runoff.
Fe ³⁺ was not detected. When 100 ml of water was similarly poured through the resin that had captured Fe ³⁺ , 0.91×10 ^-2 M of Fe ³⁺ was found in the dilute hydrochloric acid that flowed out. Similarly, 100g of resin is packed in a column and HgCl ₂ is added to it.
When 500 ml of an aqueous solution containing 5.3×10 ^-3 M was poured out, no HgCl ₂ was detected in the flowing water. Example 2 The same lot of chloromethylated styrene-divinylbenzene copolymer (granular) as used in Example 1
10g, monochlorobenzene 50ml, polyethylene glycol monobutyl ether (average molecular weight 370)
and 30 ml of a 65% by weight aqueous potassium hydroxide solution were added to the same reactor as in Example 1, and reacted with vigorous stirring at 100° C. for 7 days. After the reaction, 50 ml of water was added and the resin was separated by filtration through a glass filter, and this resin was treated and dried in the same manner as in Example 1, yielding 11.8 g. Elemental analysis and infrared absorption spectrum measurement of the resin after vacuum drying confirmed that the resin contained no chlorine at all and that ether groups were newly present. The resin obtained by the reaction with polyethylene glycol monobutyl ether was subjected to the same treatment as in Example 1, and the amount of polyethylene glycol monobutyl ether was analyzed. As a result, the amount of polyethylene glycol monobutyl ether was 0.57 per gram of resin.
It was found that millimoles of polyethylene glycol monobutyl ether were bound. Examples 3 to 8 Various granular styrene-divinylbenzene copolymers were synthesized in the same manner as in Example 1 by pearl polymerization while changing the composition ratio of styrene and divinylbenzene. The various copolymers thus synthesized were chloromethylated in the same manner as in Example 1. 10g of resin after chloromethylation
Substitution reactions with various polyoxyalkylene compounds were carried out in accordance with Example 1. The analytical method and reaction operation were in accordance with Example 1. The results obtained are shown in Table 1. All reactions were carried out at a reaction temperature of 70°C and a reaction time of 24 hours.

【table】

[Table] Example 9 Commercially available pelleted polystyrene (Styron,
(manufactured by Asahi Dow) was dissolved in 30 ml of chloromethyl ether in a 200 ml four-necked flask. A solution of 1.5 g of tin tetrachloride dissolved in 30 ml of chloromethyl ether was slowly added dropwise to this polystyrene solution under stirring at a rate such that the internal temperature reached 5°C.
(Total 2 hours). After the dropwise addition was completed, the temperature was raised to room temperature, and stirring was continued at room temperature for 2 hours. 300ml of reaction mixture
The resulting polymer was precipitated by pouring it into methanol. The obtained polymer was separated by filtration, thoroughly washed with methanol, and then vacuum-dried at 50°C overnight.
The dried resin obtained in this way (chlorine content
18.2%) 5 g toluene in a 100 ml four-necked flask equipped with a stirrer, condenser, and thermometer.
Dissolved in 20ml. In this toluene solution

[Formula] 20g and 20g of a 60% by weight aqueous sodium hydroxide solution were added, stirred vigorously, and reacted at 100°C for 10 hours. After the reaction is complete, pour the reaction mixture into 50ml of water and add 200ml of chloroform.
Extracted 3 times with ml. chloroform layer in saline solution 150
After washing with 100 ml of distilled water three times and finally twice with 100 ml of distilled water, 20 g of anhydrous calcium chloride was added and stirred at room temperature for 4 hours. After that, the precipitate (excess calcium chloride and unreacted

Separate the complex compound of [formula] and anhydrous calcium chloride, and collect 100ml of the filtrate.
After washing once with water and drying over anhydrous sodium sulfate, chloroform and toluene were distilled off under reduced pressure. 16 g of rubbery polymer was thus obtained. Elemental analysis of this rubbery polymer revealed that it contained no chlorine at all. Measurement of the infrared absorption spectrum revealed strong absorption of ether groups at 1100 cm ^-1 . 1 g of this rubbery polymer, 500 ml of ethanol,
Add palladium sponge, 0.2 g, to an autoclave with contents 1, and heat at 50°C with hydrogen pressure of 10 atm.
Hydrogenated for an hour. The catalyst was separated by filtration and the ethanol was distilled off under reduced pressure, and the residual liquid was liberated by the barium phosphotungstate method.

Analysis of [Formula] revealed that 1.4 mmol per gram of resin.

It turns out that [formula] is connected. Example 10 14 g of commercially available chloromethylstyrene (meta, para mixture, Tokyo Kasei product), 10 g of styrene, 6.5 g of commercially available divinylbenzene (40% concentration by weight), 14 g of dibutyl phthalate, and 8 mg of lauroyl peroxide were stirred in a flask under nitrogen. A portion of the mixture was placed in an injection polymerization apparatus consisting of two glass plates (10 cm x 10 cm, distance: 1 mm), and injection polymerization was performed at 80° C. for 48 hours. This copolymer thin film was treated in ethyl alcohol for 24 hours under refluxing alcohol to extract dibutyl phthalate. Thereafter, it was vacuum dried at room temperature. The film-like copolymer thus obtained was cut into small pieces of 1 cm x 1 cm. Place 1 g of the film-like pieces in a 100 ml four-necked flask, and add 10 g of a 60% by weight aqueous sodium hydroxide solution.
ml, _{orthodichlorobenzene} 20ml and _C2H5O
(C ₂ H ₄ O) ₁₀ The mixture was reacted with 5 g of H at 100° C. for 4 days with stirring. After the reaction, the copolymer was taken out by filtration, thoroughly washed with a dilute aqueous hydrochloric acid solution, distilled water, and acetone in that order, and then vacuum-dried at 50°C overnight. The weight after drying is 1g, and as a result of elemental analysis, chlorine is
It changed from 10.68% to 1%. In addition, we measured the infrared absorption spectrum using the KBr tablet method.
There is almost no absorption of 670cm ^-1 , and a new 1100cm
Absorption was observed at ^-1 . The amount of polyethylene glycol monomethyl ether in 1 g of resin was 0.25 mmol. Example 11 According to the styrene-divinylbenzene pearl polymerization method of Example 1, chloromethylstyrene (meth,
Para mixture, Tokyo Kasei products) 30 mol%, styrene
Pearl polymerization of 60 mol% and 10 mol% of acrylonitrile was carried out. The obtained powdery copolymer was collected by filtration, thoroughly washed with methanol, and then air-dried.
Elemental analysis revealed that this polymer contained 9.4% by weight of chlorine. 60ml of toluene solution of 5g of this granular copolymer
30 ml of sodium hydroxide aqueous solution and
The mixture was charged into a 200 ml three-neck flask together with 6 g of C ₄ H ₉ O (C ₂ H ₄ O) ₇ H, and the mixture was stirred vigorously at 90° C. for 5 hours to react. After the reaction, the toluene layer was separated and thoroughly washed with diluted hydrochloric acid aqueous solution, brine, and distilled water in that order, and the toluene was partially removed under reduced pressure. The obtained concentrated liquid was poured into 500 ml of methanol. . The resulting white precipitate was collected by filtration, thoroughly washed with methanol, and then dried in vacuum. The weight of the polymer after drying is 9g.
It was hot. From elemental analysis, Cl in this powder polymer
No content was observed. In addition, the infrared absorption spectrum measured using the KBr tablet method was 1100 cm ^-1
A strong absorption of ether groups was observed.

Claims (1)

[Scope of Claims] 1. A vinyl polymer compound containing a structural unit of the formula (nuclear substitution is at para or meta position) in the molecule as a reactive acyclic polyoxyalkylene compound having 3 or more oxyalkylene units. By reacting in the presence of a base, the molecular chain contains units of the formula A method of producing novel polymers.