JPS5822098B2 - Basic monomer and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel basic monomer having a secondary amine group and a method for producing the same.

Polymers with basic nitrogen in their side chains utilize the basicity of nitrogen, the ability to coordinate with metals, and the cationic nature of quaternary nitrogen.
It is widely used as a functional polymer in polymer electrolytes, ion exchange resins, adsorbents, etc.

Among these, typical polymers containing aliphatic nitrogen include polyvinylamine, aminopolystyrene, aminemethylpolystyrene, and their derivatives.
In either case, it is difficult to synthesize the corresponding monomer or the polymerizability is low, so it cannot be produced by direct polymerization of the monomer, and a polymer reaction is performed on a polymer of other monomers. There is a need.

However, in this case, it is necessary to isolate and purify the intermediate, which makes the process complicated. In general, polymer reactions have a low reaction rate and require a long time to complete. In the case of originally cross-linked polymers, there are many problems such as the reaction is even slower and often does not go to completion.

As a result of repeated studies based on the above background, the present inventors have discovered a monomer represented by the following structural formula A (hereinafter referred to as "monomer Al").

(Herein, R represents an alkyl group having 2 to 8 carbon atoms.

) Since this monomer A has a nitrogen-containing substituent, it is possible to easily synthesize a polymer having an aliphatic nitrogen in the side chain by polymerizing it or copolymerizing it with other monomers. I can do it.

Furthermore, since monomer A and its polymer have secondary nitrogen, they can be converted into other derivatives by reactions specific to secondary amines, such as amidation.

A general method for producing monomer A is to convert an amine represented by the following structural formula B (hereinafter referred to as "amine B" or simply "amine") into a corresponding alkali metal amide C.
It should be reacted with divinylbenzene in the coexistence of .

R-NH2(B) R-NHM (C) (Here, R represents an alkyl group having 2 to 8 carbon atoms.

) In this case, lithium is preferred as the alkali metal due to its high reactivity and ease of reaction operation.

A preferred method for preparing lithium amide is to react an amine with alkyl lithium, phenyl lithium, aluminum lithium hydride, lithium hydride, etc. Among these, alkyl lithium is used due to its solubility in solvents, operability, etc. It is particularly preferable to do so.

The lithium amide corresponding to monomer A is hereinafter simply referred to as [lithium amide-I.

As divinylbenzene, p-divinylbenzene, m
-divinylbenzene, or mixtures thereof can be used.

Furthermore, generally commercially available divinylbenzene contains ethylvinylbenzene as an impurity, and such crude divinylbenzene can also be used.

However, when crude divinylbenzene is used as a starting material, a product derived from ethylvinylbenzene may be produced as a by-product.

It is preferable to use p-divinylbenzene for the following reasons.

First, in this reaction, the speed of p-divinylbenzene is faster than that of m-isomer, and the by-products described below are less likely to be produced.

Furthermore, in the polymer of monomer A, since the alkylaminoethyl group occupies a position farther from the polymer main chain, steric hindrance around nitrogen is small and performance as a functional polymer is high.

As the amine, an aliphatic primary amine having 2 to 8 carbon atoms can be used.

If the number of carbon atoms is too large, the molecular weight of the product will be too large, making isolation by distillation etc. difficult, and the nitrogen content per unit weight of monomer A will decrease, so monomer A is used as a polymer. This is not preferable because the function of the case is quantitatively reduced.

Preferred compounds as amines include cyclohexylamine, 5ec-butylamine, isopropylamine,
n-propylamine, ethylamine, etc.

Monomer A in which R is ethyl has a high nitrogen content per unit weight in itself or in a polymer derived therefrom, and the monomer or polymer is further reacted with nitrogen or nitrogen-hydrogen bonds. In this case, the steric hindrance of R is small, so the reaction is fast.

Furthermore, since the amine B in which R has 3 or more carbon atoms is liquid at room temperature, the reaction operation is easier.

In the reaction disclosed in the present invention, lithium amide C
performs a catalytic action.

This is one of the major features of this reaction.

That is, it is sufficient to use lithium amide C in an amount equal to or less than the molar amount of divinylbenzene, preferably in a molar ratio of o.ooi to 0.5 times, more preferably in an amount of 0.00 to 0.5 times.
01 to 0.2 times the amount.

At this time, it should be kept in mind that the concentration of lithium amide C controls the reaction rate.

Lithium amide C contains water, alcohol, and alcohol coexisting in the reaction system.
Because it is deactivated by reacting with substances containing active hydrogen such as acids,
It is preferable that the raw materials and solvents used be purified by dehydration or the like in advance, but if these active hydrogen-containing substances are unavoidably mixed, it is desirable to use more than the intended amount of lithium amide C.

As already mentioned, lithium amides can be easily prepared, for example, by reacting an alkyllithium with an amine.

As the alkyl lithium, methyl lithium, ethyl lithium, butyl lithium, etc. can be used, but among these, n-butyl lithium, which is also industrially produced, is particularly preferred from the viewpoint of manual labor.

Amine B causes a stoichiometric reaction with divinylbenzene, and the amount used is 0 in molar ratio to divinylbenzene.
．． The amount is preferably 3 to 2.5 times, more preferably 0.6 to 1.3 times.

If the amount of amine B is too small, the amount produced will naturally decrease.

Further, if an excessive amount is used, a product in which amine is added to both vinyl groups may be formed, which is not preferable.

There are, for example, the following two methods for reacting the mixed solution of lithium amide C and amine B with divinylbenzene.

The first method is to add the former mixture to divinylbenzene.

This method suppresses the formation of by-products. It has the following advantages.

The second method is to add divinylbenzene to a mixture of lithium amide and amine, but in this case, only one reaction vessel is required and there is no need to transfer the lithium amide solution. It has advantages such as:

In particular, when using ethylamine as the amine, since it is a gas in a room, it is
The second method of adding divinylbenzene under cooling is preferred.

The reaction in the present invention can also be carried out in the presence of an inert solvent.

As a solvent, pentane, hexane, cyclohexane,
Aliphatic hydrocarbons such as octane, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, dioxane and tetrahydrofuran, dimethyl sulfoxide N.

Liquids that do not react with lithium amide under the reaction conditions can be used, such as aprotic polar solvents such as N/-dimethylformamide and hexamethylphosphoric triamide.

Among these, hexane, cyclohexane, benzene, tetrahydrofuran and the like are more preferred.

In particular, when tetrahydrofuran is used, the reaction rate is high and the reaction time can be shortened.

Furthermore, aliphatic hydrocarbons such as hexane are commonly used as completely inert solvents.

The amount of the solvent used is preferably 0.1 to 50 times, more preferably 0.5 to 20 times, the volume of divinylbenzene.

The reaction generally slows down as the relative amount of solvent increases.

The temperature in which the reaction of the present invention is carried out is not particularly limited, but it is preferably -50°C to 100°C, more preferably -20°C to 50°C.

When carrying out the reaction above the boiling point of the amine or solvent, it is necessary to use a pressure vessel.

It is also preferred that the reaction mixture be stirred or shaken.

The reaction time is not limited, but preferably 1 minute to 24 hours, more preferably 5 minutes to 8 hours.

The reaction rate is largely controlled by temperature, type of amine, concentration of raw materials, type of solvent, etc., so the reaction time should be set depending on the conditions, but sampling should be performed at time points during the reaction, and gas chromatography It is recommended to determine the end time of the reaction by quantifying the raw materials and products using chromatography, liquid chromatography, etc.

To stop the reaction, methanol, ethanol,
It is necessary to deactivate the lithium compound with alcohol such as propatool, water, or the like.

Monomer A, which is a product, can be isolated by distillation, column chromatography, or by adding hydrochloric acid or hydrogen chloride gas to the reaction mixture to precipitate monomer A as a hydrochloride salt.

Isolation operations often become more efficient by adding water to the reaction mixture as a pretreatment and performing extraction and separation.

The novel monomer A obtained by the present invention is useful as a basic monomer.

For example, a polymer containing A as one of its constituent components can be used as a ligand for a polymer complex, a solvent extractant, a paint raw material, and the like.

Furthermore, a novel polymer flocculant is provided by subjecting the polymer to treatments such as amidation.

Furthermore, a three-dimensional crosslinked polymer of monomer A and a crosslinkable monomer can be used as an ion exchange resin, a basic adsorbent, a metal adsorbent, and the like.

Examples of the present invention will be shown below, but the present invention is not limited to the scope of these Examples.

” Example 1 In a stainless steel heat and pressure resistant reactor with an internal volume of 200 Tnl equipped with a stirring device, n was dried and distilled over sodium metal.
- After adding 80 TL of hexane, the apparatus was sufficiently cooled from the outside with a dry ice-methanol mixture.

An ethylamine cylinder (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was connected to the apparatus, and the valve was opened to introduce ethylamine into the reaction apparatus.

From the change in the weight of the cylinder before and after introduction, ethylamine was 6.
It was confirmed that 3g was introduced.

15 of 8.45-n-butyllithium with stirring.
% n-hexane solution was introduced.

Then add 40 TIll of dry n-hexane to 18.2.9
A solution containing p-divinylbenzene was introduced.

The reactor was placed in a water bath at 25°C, and stirring was continued for 5 hours. 0.5g of methanol was added to the reaction mixture, and the mixture was heated to 20°C.
It was poured into 0ml of water.

Extraction was performed twice with n-hexane, the oil layer was dried over magnesium sulfate overnight, and then distilled.

14.7 g of distillate having a boiling point of 72°C to 73°C in 0.13 mmI (g) was obtained.

It was confirmed by gas chromatography that it was a single substance.

The refractive index of this reservoir is 1.53s at 22°C (NaD line)
Met.

The analysis results were as follows.

Infrared absorption spectrum; 3280.1620.1510.
1120.985.900.82051 CIn.

Nuclear magnetic resonance spectrum [100MHz1 tetramethylsilane (TMS) standard], δ value; o, 5o (singlet, I
H), 1.04 (triplet, J = 7.2 Hz.

3H), 2.55 (quadruple, J = 7.2 Hz, 2
H) (12,6-2.8 (multiplet, 4H), 5.08 (
Double line, J = 10.5 Hz s I H) 5.
60 (double line, J-17, 8Hz, IH), 6.5
6 (2 sets of double lines, J = 10.5.17.8Hz, IH
), 6.9-7.3 (multiplet, 4H).

Here, J represents a coupling constant, and nH represents hydrogen n7.

Elemental analysis: C: 81.9, H: 10. OlN: 8.1 These analytical results indicate that the product is vara-(β-ethylaminoethyl)styrene.

Example 2 The same operation as in Example 1 was carried out, except that tetrahydrofuran was added instead of n-hexane as the solvent for n-hexane and divinylbenzene that were initially added.

The reaction was carried out at 25°C for 1 hour. After the reaction was completed, methanol was added to the reaction mixture, the solvent was removed using an evaporator, water was added, and the mixture was extracted with n-hexane.

Distillation gave 171 g of product.

The infrared spectrum, nuclear magnetic resonance spectrum, and boiling point of this fraction were the same as in Example 1, indicating that the product was p-(β-ethylaminoethyl)styrene.

Example 3 Prepare a 200 TL eggplant flask with a three-way cock and purify it with nitrogen, and add 62.5 r of purified tetrahydrofuran with a syringe.
Add nl.

n-propylamine 20.6 with magnetic stirring
- was added, and 2 ml of a 2N cyclohexane solution of n-butyllithium was added, and the color of the solution changed from colorless and transparent to pale yellow.

Place this flask in a constant temperature bath at 30°C and continue stirring. p-Divinylbenzene 14.8 mA! added.

After 40 minutes, 0.1 rnl of methanol was added, and the same treatment as in Example 2 was carried out, followed by distillation.

9.6 g of distillate was obtained at 73-75° C. at 0.08 mmHg.

This product was confirmed to be p-(n-propylaminoethyl)styrene from the measurements shown below.

Proton nuclear magnetic resonance spectrum (90MHz s solvent;
Deuterium chloroform, reference material; TMS), δ value; 0.7
~1.0 ppm (multiplet, 4H) 1.42 (sextet, J-7Hz12H), 2.5 (triplet, J-7H2
12H), 2.6-2.9 (multiplet, 4H) 5.08 (
Double line, J = 10Hz, IH), 5.68 (Double line, J
= 17.5Hz, IH), 6.57 (2 sets of double lines, I
H), 6.95-7.35 (multiplet, 4H).

Infrared absorption spectrum (liquid film method); 3300.1635.
1510.1410.990.910, 1 830 (1771.

Elemental analysis; C: 82.2, H: 104, N: 7.
4 Example 4 The reaction was carried out using the same apparatus, method, and conditions as in Example 3.

The reagents shown below were added in the following order. (1) 74.4 ml of tetrahydrofuran, (2) 8.6 rILl of inglobilamine, (3) 2 rul of 2N cyclohexane bath solution of n-butyllithium, (4) 14.8 ml of p-divinylbenzene.The reaction mixture was orange. It was the color.

The reaction was carried out at 30°C for 3 hours.

11.8.9 volumes of product were obtained with a boiling point around 67°C at 0.07 mmHg.

It was confirmed from the following data that this product was p-(isopropylaminoethyl styrene).

Proton nuclear magnetic resonance spectrum (100MHz.

Solvent: deuterated chloroform, reference material TMS), δ value: 0.
8 (IH), 0.96 (double line, J = 7 Hz, I
H), 2.6-2.9 (multiplet, 5H), 5.1 (doublet, J-11Hz, IH) 5.6 (doublet, J=18H
z, IH), 6.5 (2 sets of double lines, IH), 7.0~
7.35 (multiplet, 4H).

Infrared absorption spectrum (liquid film); 3300.1630.
1510.1470.1380, = 1 1080.990.910.835 cm.

Elemental analysis; C: 82.1, H: 10.3, N near, 6 Example 5 3e of 10.1 rrLl instead of inglobilamine
The reaction and isolation procedure was carried out in exactly the same manner as in Example 4, except that c-butylamine was used.

The product was p(sec-butylaminoethyl)styrene, with a boiling point of 78°C at 0,08 mmHg.

The isolated yield was 10.6.9.

Proton nuclear magnetic resonance spectrum, δ value; 090 (triplet, J-7H213H), 0□95 (double, J-7H2
13H), 1.1 to 1.6 (multiplet, J-7Hz, 2H
), 2.4-2.7 (multiplet, IH), 2.7-3.0
(Multiplet, 4H), 5.15 (Doublet, J=11Hz,
IH), 5.65 (double line, J=18Hz, IH), 6
．． 66 (two sets of doublets, IH) 7.0-7.4 (multiplet, 4H).

Infrared absorption spectrum (liquid film); 3300.1630, 1
510,990.905,8301 confirmed.

Elemental analysis: C: 82.2, H: 108, N near, 0 Example 6 The reaction was carried out in exactly the same manner as in Example 4, except that 11.51 rLl of cyclohexylamine was used instead of inglobilamine. .

After reacting at 30°C for 3 hours, a small amount of water was added.

At that time, the white precipitate that was generated was collected from house to house.

Most of the tetrahydrofuran was removed using an evaporator.

Ethanol was added to this solution, and some concentrated hydrochloric acid was added to make the solution acidic.

When this solution was cooled to 0°C, white powder was precipitated.

The product was p-(cyclohexylaminoethyl)styrene, and the yield was 7 g.

Infrared absorption spectrum (KBr tablet); 2490.24
40.1630.1515.99(), 905, 1 830cm.

Elemental analysis: C: 84.0, H: 10.3, N: 5.7 Example 7 85 m of benzene was placed in a glass wall thick bottle of 300 rn melt, and then 4 (7) of n-propylamine was added. Add.

Furthermore, 25TfLl of a 15% n-hexane solution of n-butyllithium was added and thoroughly mixed, and finally 85ml of p-
After adding divinylbenzene, the reactor was sealed and shaken for 2 hours at room temperature.

When distilled, 39 g of p-(n-propylaminoethyl→styrene) was obtained.

The boiling point and spectroscopic data of the product were similar to Example 3.

Example 8 A reaction was carried out under the same conditions and operations as in Example 4, except that 2 ml of a 2N engineered methyl ether solution of methyllithium was used instead of n-butyllithium, and 12.2 g of product was obtained. .

The boiling point and spectroscopic data of the product were the same as in Example 4, and it was confirmed to be p-(isopropylaminoethyl)styrene.

Example 9 A reaction was carried out at 20°C for 3 hours using the same raw materials and solvent as in Example 1, except that 6.4 rul of ethylamine was used and m-divinylbenzene was used instead of p-divinylbenzene. 9.81 of the product was obtained.

It was confirmed from the following analysis cheater that this product was meta-(β-ethylaminoethyl)styrene.

Infrared absorption spectrum; 3280.1600, 1 990.900.790.700cm.

Elemental analysis: C: 81.8, H: 10, ■, N: 8.1 Example 1 42 TfLl of tetrahydrofuran was placed in a 100 ml eggplant-shaped flask equipped with a three-way cock, and 11.9.9 cyclohexylamine was added. .

Since the mixture was sufficiently stirred, 1.
3.6 yd of 5% n-hexane solution was added.

Next, 13.9 g of p-divinylbenzene was added, the mixture was replaced with nitrogen, the mixture was sealed, and stirring was continued at 30° C. for 3 hours.

Then, the same treatment as in Example 2 was carried out, followed by distillation.

4.6 sho of 116-118℃ at 0.1 mmHg!
I got 9.

The fact that this distillate was p-(cyclohexylaminoethyl) styrene 7 was supported by the following data.

Proton nuclear magnetic resonance spectrum (solvent: deuterochloroform, reference material: tetramethylsilane), δ value: 0.8-2
．． 0 (multiplet, 11H), 2.3-2.6 (multiplet, I
H), 2.65-3.05 (multiplet, 4H), 5.1
0 (double line, J = 11 Hz SI H) 5.7
0 (duplex, J=17Hz, IH), 6.68 (two sets of doublets, IH), 7.1-7.4 (multiplet, 4H).

Carbon-13 nuclear magnetic resonance spectrum (solvent: deuterated chloroform, reference material: tetramethylsilane), chemical shift value: 2
5.0.36.2.33.6.36.5.48.1.5
6.6.112.9.126.2.128. ! (135
,5,136,6,139,9cps.

Infrared absorption spectrum (liquid film); 1820.1640.1
520.1410.995.91o.

1 835Crn.

Elemental analysis: C: 83.9, H: 104, N: 5.7 Example 11 Partially saponified polyvinyl alcohol (saponification degree 88 100 g of pure water in which 2 g of sodium chloride was dissolved were added, and while stirring, 16.4 g of p-(β-ethylaminoethyl)styrene synthesized in Example 1 and divinylbenzene (purity) were added. 56 chimeta body: separate body = 7 = 3.44 (contains ethylvinylbenzene) 3.6. y, 2. A mixture of 0.2 g of 2'-azobisisobutyronitrile was added, and the mixture was heated at 60°C for 1 hour.
Stirring was continued at 70°C for 2 hours and then at 80°C for 4 hours.

The copolymer produced was spherical particles with a particle size of 50 to 200 microns.

This copolymer was packed several times into a glass column equipped with a glass filter having an inner diameter of 1.2 cIn, and 200 rILl of IN hydrochloric acid was passed through the column, followed by 100 mA' of acetone, and then 1001 rILl of IN potassium nitrate solution was passed through the column.

Chlorine ions in the potassium nitrate solution that passed through the column were quantitatively determined using the faance method.

After further flowing 100ml of IN hydrochloric acid into the column, the copolymer was taken out and vacuum dried at 80°C for 18 hours.
I calculated the weight.

As a result, the exchange capacity per dry weight is 3.98 meg
/, 9.

Claims (1)

[Scope of Claims] 1. A novel basic monomer represented by the following structural formula A. (Here, R represents an alkyl group having 2 to 8 carbon atoms.) 2. Claims No. 1 in which R is any one of ethyl group, n-propyl group, isopropyl group, 5ec-butyl group, and cyclohexyl group. Monomer according to item 1. 3. The monomer according to claim 1 or 2, wherein the alkylaminoethyl group and the vinyl group are in the cup position. 4. A novel method represented by the following structural formula A, which is characterized in that an amine represented by the following structural formula B is reacted with divinylbenzene in the presence of an alkali metal amide represented by the corresponding structural formula 〇. Monomer production method. (Here, R represents an alkyl group having 2 to 8 carbon atoms, and M represents an alkali metal.) 5. The method for producing a monomer according to claim 4, in which lithium amide is used as the alkali metal amide C. 6. A method for producing a monomer according to claim 5, using a lithium amide prepared from an amine represented by structural formula B and an alkyl lithium. 7. The method for producing a monomer according to claim 6, using n-butyllithium as the alkyllithium. 8. A method for producing a monomer according to any one of claims 4 to 7, wherein the reaction is carried out in the presence of an inert organic liquid. 9 Tetrahydrofuran, n- as inert organic liquid
Claim 8 uses either hexane, cyclohexane, or a mixture of two or more of these liquids.
Method for producing the monomer described in Section 1. Claim 4: Adding divinylbenzene to the mixture of amine and alkyl lithium represented by structure 2B
A method for producing the monomer according to any one of Items 9 to 9.