JPS59161408A - Preparation of polymer containing functional group - Google Patents

Abstract

PURPOSE:To obtain a reactive polymer containing a formylphenyl group in high yield, by reacting a polymer containing a halogenomethylphenyl group with hexamethylenetetramine in the presence of a solvent, reacting the reaction product in the presence of water under heating with suppressing side reactions. CONSTITUTION:A polymer containing a halogenomethylphenyl group prepared by polymerizing a vinylbenzyl halide, etc. is dispersed into a medium such as ethanol, etc., and reacted with a solution obtained by dissolving hexamethylenetetramine in water, etc. Water is added to the reaction solution, and reacted in the presence of water under reflux. After the reaction is over, a solution of salt is added to it, to form precipitate sufficiently. The formed solid is separated by filtration, washed with water, and subjected to vacuum drying, to give the desired polymer containing a formylphenyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION An object of the present invention is to provide a new method for producing reactive polymers. More specifically, the method involves producing a polymer having a formylfer group by subjecting a polymer having a nologenomethylphenyl group to a specific polymer reaction.

Conventionally, as a method for obtaining aldehyde-containing polymers from polymers having halogenomethylphenyl groups, a method has been known in which a crosslinked polymer of vinylbenzyl chloride and divinylbenzene is subjected to a heating reaction in dimethyl sulfoxide in the presence of sodium bicarbonate. For example, R, L, Letsi
J. Amer.

Chem, Soe, 86. p5163 (1964).

However, this conventional method has been found to have some drawbacks due to the reactive properties of dimethyl sulfoxide (dimethyl sulfoxide), which acts as an oxidizing agent. Therefore, high temperature or long reaction times are required, which tends to involve side reactions. Therefore, there is a natural limit to the production rate of aldehyde, and a high production rate cannot be achieved. As a result of the ts reaction, the chemical changes into dimethyl sulfide, which has an unpleasant odor and is highly toxic, so it is extremely difficult to carry out the conventional method on an industrial scale in terms of safety.

The inventors conducted various studies to solve the problems in conventional manufacturing methods, and as a result, they arrived at the present invention. The feature of the present invention is that while taking advantage of the features of polymer reaction, especially the separation of products of polymer reaction against insoluble bridge i11 coalescence,
It is possible to convert an easily available halogenomethylphenyl group-containing polymer into a formyl phenyl group-containing monomer at a high production rate. That is, the present invention is a method for producing a formyl phenyl group-containing polymer by reacting a halogenomethylphenyl group-containing polymer with hexamethylenetetramine in the presence of a solvent, followed by a heating reaction in the presence of water. .

In the method for producing an aldehyde-containing polymer according to the present invention, it is thought that two stages of the reaction proceed from the top of the reaction mechanism. In the first step, the halogenomethyl group in the raw polymer reacts with hexamethylenetetramine to produce an amine salt as an intermediate. In the second step, the intermediate undergoes hydrolysis and the like by heating in the presence of water to produce the desired aldehyde-containing polymer.

Therefore, the production method of the present invention requires a raw material polymer containing vinylbenzyl halide as a constituent unit, hexamethylenetetramine, a solvent, and water.

The raw material polymer is not particularly limited as long as it is a polymer having a halogenomethylphenyl group in its side chain.

Specific examples include homopolymers or copolymers of vinylbenzyl halogenoids.

Vinylbenzyl halogenoids include vinylbenzyl chloride, vinylbenzyl bromide, and the like, and meta-, para-, or mixtures of these isomers are used. Furthermore, as the monomer constituting the copolymer with the vinylbenzyl halide, styrene and styrene derivatives are preferred.

Styrene derivatives include divinylbenzene, vinyltoluene, ethylstyrene, α-methylstyrene, chlorstyrene, halogenostyrene such as bromstyrene, vinylphenol, methoxystyrene, aminostyrene,
Examples include carboxystyrene. Particularly preferred monomers for copolymerization include divinylbenzene, styrene, vinyltoluene, and ethylstyrene.

These monomers for copolymerization can be used alone or in combination with vinylbenzyl halide to form a copolymer. A copolymer containing a divinyl monomer such as divinylbenzene as a constituent unit has a three-dimensional crosslinked structure and is insoluble, so in the post-treatment of the reaction for producing the aldehyde-containing polymer of the present invention,
It has the advantage that the produced polymer can be easily separated by a simple solid-liquid separation method. Further, as the raw material polymer, there is no problem in using a polymer in which a logenomethylphenyl group is formed by a polymer reaction. A typical example of such a raw material polymer is a chloromethylated copolymer of styrene and divinylbenzene.

Hexamethylenetetramine can be used as a commercially available product. Although there is no particular limitation, it is desirable that the ash content is usually 1% or less. The amount used is from 0.8 mol to 10 mol, preferably from 1 mol to 3 mol, per mol of the methylphenyl group contained in the raw material polymer.

In the production method of the present invention, a solvent is used together with hexamethylenetetramine. The solvent used is a liquid that can dissolve either hexamethylenetetramine or a small amount of the raw material polymer.
It refers to having a solubility of 0.5% (wt, /Vol,) or more in either hexamethylenetetramine or the raw material polymer. Further, it is preferable that the solvent is inert to each 11i, family, and product under the reaction conditions. Among these, particularly preferred solvents are highly hydrophilic solvents. It is presumed that this is because the hydrophilic solvent has a high affinity for the amine salt of the reaction intermediate and thus promotes the reaction, but the details are not clear.

Specific examples of solvents include alcohols such as methanol, ethanol, impropatol, ethoxyethanol, and diethylene glycol; halogenated hydrocarbons such as chloroform, methylene chloride, tetrachloroethylene, and trichloroethane; carboxylic acids such as acetic acid and propionic acid; Ethers such as dimethoxyethane, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and toluene; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Nitriles such as acetonitrile and propionitrile; dimethylformamide, Amides such as dimethylacetamide and N-methylpyrrolidone; sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane; and water. These solvents can be used alone or in combination of two or more.

The amount of the solvent used is generally 1 to 50 times, preferably 2 to 20 times, the volume/weight ratio (v, 'w) of the raw material polymer.

In the production method of the present invention, the presence of water is essential in the two stages of the reaction. Water may be used as a solvent or a part thereof in the first stage of the reaction, or may be added after the first stage of the reaction is completed.

The total amount of water to be used is theoretically 6 mol based on the halogenomethylphenyl group of the raw material polymer, but usually 10 mol.
The amount is preferably 15 moles or more.

The manufacturing method of the present invention is embodied in the Examples described later, but the general outline is as follows.

A raw material polymer having a halogenomethylphenyl group is dispersed in a bath S or in an appropriate solvent. Add the required amount of hexamethylenetetramine to it while stirring. The reaction temperature is usually between room temperature and 60°C, which is sufficient to complete the first stage, but it may be heated from room temperature to a temperature of 60°C or higher for the second stage.

Water is required for the two-step reaction. If water has not yet been made to coexist in the reaction system at the first stage, or if the amount of water is insufficient, it is necessary to add a predetermined amount of water. The reaction temperature in the second stage is 60°C or higher, usually 60-180°C, preferably 80-150°C. The reaction is usually terminated after stirring for 1 to 24 hours.

In addition to the basic operations described above, this two-step reaction may involve some modified methods. For example, the objective can be achieved by heating to 60°C or higher and then blowing in steam for a predetermined period of time. When a high boiling point solvent such as , ethoxyethanol or dimethylacetamide is used, the reaction can be carried out under reflux at the highest liquid temperature that can be reached.In such cases, water may be added as necessary. good.

After the reaction, it can be treated and separated according to conventional methods. For example, the product can be separated by filtration or decantation, either as it is or, if necessary, by adding a poor solvent such as water to analyze the product. Alternatively, the solvent may be distilled off.

Finally, after washing with a solvent, washing with water, etc., the product is dried to obtain the desired product.

The polymer thus obtained usually exhibits a high aldehyde production rate of 50% or more. The resulting polymer can be used as a reactive polymer, for example, for immobilizing enzymes, or can be converted into an ion exchange resin.

The manufacturing method of the present invention will be specifically explained below using Examples, but the scope of the present invention is not limited thereto.

Example 1 Raw material polymer 50.8i obtained by solution polymerization of vinylbenzyl chloride (6:4 mixture of meta and halogen) was dispersed in 400 ml of ethanol, and hexamethylenetetramine 9? A solution of L59- dissolved in 200 d of water was added. After stirring at 40C for 3 hours, 200 d of water was added, and the mixture was stirred under heating under reflux for 6 hours to complete the reaction. After the reaction, add 200% of 20% brine to remove the sufficiently precipitated solid.
Separated. After washing three times with 2001 water, the product was vacuum dried at 60° C. overnight to obtain a polymer 44.5f. The analysis results were as follows.

elemental analysis C:81. ．． 40%, H; 6. ．． 14%.

0;11. ．． 45%, C4; 0.80% Infrared absorption spectrum (KBr tablet) 1700 cIrL-" (-HC,=O) strong, 1
262 cm-' (-CH2Cg) micronuclear magnetic resonance spectrum (using CDCl5S solution) δ: 9. ．． 50,
7-4-8. ．． 1 s, Z, 70, 1. ．． Signals for each of 53 protons were observed.

Below is v;1. F! The aldehyde production rate determined by method A was 95%.

The aldehyde production rate in the produced polymer was approximately determined as follows.

As an approximate formula, It was used.

Here, W and the number of moles of halogenomethyl groups in the family polymer lt are calculated, for example, from the charged weight and molecular weight of each monomer during synthesis of the raw material polymer.

Also, the number of moles of aldehyde groups in the product polymer lt is
The absorbance at 1700 cm'' absorption in the infrared absorption spectrum was calculated by converting it into the number of moles using a calibration curve.

The aldehyde production rate was determined in the manner described above, and this method was also followed in the following examples.

Example 2 50.8f of raw material polymer (same as Example 1) was dissolved in 40011L of chloroform, a solution of 93.51L of hexamethylenetetramine dissolved in 500d of chloroform was added thereto, and the mixture was stirred at 40°C for 3 hours. did.

Steam was blown into it, and chloroform was distilled off by steam distillation. The residual mixture of polymer and hot water was heated to reflux for 2 hours to complete the reaction. After filtration, it was washed three times with 200 d of water, and then vacuum dried at 60°C overnight to obtain a polymer of 44.
．． I got 8f.

elemental analysis C: 79.80%, H: 6.14%.

0: 9.57%, C4: 4.19% Aldehyde production rate: 81% Example 3 Three-dimensional crosslinking obtained by suspension polymerization of vinylbenzylchloride 85.09- and divinylbenzene 15.0i Polymer 100? Add 400 m/t of ethoxyethanol to disperse, and add hexamethylenetetramine 117? A solution of 200 d of water was added.

After stirring at 55°C for 3 hours, the mixture was heated under reflux at 125°C for 12 hours. After filtration, wash with water and vacuum dry to obtain polymer 8.
9.0) was obtained.

elemental analysis C; 8L 15%, H; 6. ．． 72%.

0;8. ．． 50%, z, zs% for C, aldehyde production rate 2 85% Example 4 An experiment was carried out in exactly the same manner as in Example 3, except that 196t of hexamethylenetetramine was used, and the resulting polymer was 8.
I got 8.7 de.

“Aldehyde production rate = 92% Example 5 Example 3 except that the stirring operation at 55°C for 3 hours was omitted.
and total (produced polymer 89.8i was obtained in the same manner.

Aldehyde production rate = 80% Example 6 Vinylbenzyl bromite 96. O? Toshihini 1 Rubenzene 4. Three-dimensional crosslinked polymer 100? obtained by suspension polymerization of Oi and To this, 300 d of glacial acetic acid was added to disperse, and 190 t of hexamethylenetetramine was added thereto. After stirring for 2 hours' at room temperature, 150 d of water was added. The mixture was stirred for 6 hours while heating under reflux. Filtration, water washing, and vacuum drying were performed to obtain 67.8 i of a produced polymer.

elemental analysis C: 81.86%, H: 6.24%.

0; 10.77%, Br; 0.78% Aldehyde production rate = 95% Example 7 Vinylbenzyl chloride 60.0i, styrene 35.0i.
0i and divinylbenzene5. Dimethylacetamide 4 was added to the three-dimensional crosslinked polymer 100i obtained by suspending Oi.
00d was added and dispersed.

Hexamethylenetetramine 66 in this? and 60℃
The mixture was stirred for 2 hours. After adding water xzoxl, 140
The mixture was stirred at ℃ for 6 hours. Filtration, washing with water, and vacuum drying were performed to obtain a polymer 9λOt.

elemental analysis C; 86.32%, H; &91%.

0:6.32%, c4; o, oo% Aldehyde production rate = 92% Example 8 Vinylbenzyl chloride 7 LOf and methoxystyrene 25.0? Raw material polymer 100 obtained by solution polymerization
t was dissolved in 500 g of toluene, 117 t of hexamethylenetetramine was added thereto, and the mixture was stirred at 50° C. for 8 hours. Steam was blown into it to steam distill the toluene. The residue was filtered through F1, washed with water, and dried under vacuum to obtain 90.6f of the resulting polymer.

elemental analysis C: 80.95%, H: 7.00%.

0; 8.85%, C; 0.76% Aldehyde generation: 64% \ Additional applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] A method for producing a polymer having a formylphenyl group, which comprises reacting a polymer having a halogenomethylphenyl group with xamethylenetetramine in the presence of a solvent, and then heating the reaction in the presence of water.