JPS5989307A - Production of chloromethylated substance - Google Patents

Abstract

PURPOSE:In chloromethylating a high polymer compound containing an aromatic nucleus, to make the reaction proceed at low temperature in a short time, to reduce coloring of the reaction product, to dissipate fear of gelation caused by crosslinking, reacting it in the presence of a catalyst and an acid anhydride. CONSTITUTION:(A) A high polymer compound (e.g., polystyrene) containing an aromatic nucleus is reacted with (B) hydrogen chloride and (C) formaldehyde (polymer) in the presence of (D) a catalyst (preferably metal halide type Lewis acid and/or Brphinsted acid) and (E) an acid anhydride (preferably acetic anhydride and propionic anhydride) preferably at 40-90 deg.C for 2-30hr, to give a chloromethylated substance. 1 equivalent aromatic nucleus of the component A is used with preferably 0.7-2.0 equivalent component C and 0.3-1 (especially preferably 0.5-0.9 equivalent) equivalent component E, and the amount of the component C used is preferably 5-50wt% based on the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing chloromethylated products. More specifically, the present invention relates to a method for producing a chloromethylated polymer compound having an aromatic nucleus.

Conventionally, chloromethylation of polymeric compounds having aromatic nuclei, such as polystyrene, has been carried out using hydrogen chloride and formaldehyde or formaldehyde polymers. A method using sodium sulfate was used. ) With this method, there are unfavorable side effects.

In particular, there was a problem in that the reactants were colored, reducing the product value of the reactants.

The inventors of the present invention have conducted extensive studies with the aim of solving this problem, and as a result have arrived at the present invention. That is, the present invention provides a method for chloromethylating a polymer having an aromatic nucleus using hydrogen chloride and formaldehyde or a formaldehyde polymer in the presence of a catalyst and an acid anhydride. This is a method for producing chloromethylated molecular compounds.

The acid anhydrides used in the present invention include aliphatic monohydrides,
>auucm (pt=*2~6oniii-s7 Carboxylic acid anhydrides T-copies include acetic anhydride, propionic anhydride, caproic anhydride, etc.), alicyclic monocarboxylic anhydrides (cyclohexane monocarboxylic anhydride, etc.) ), aromatic monocarboxylic acid anhydrides (benzoic anhydride, etc.), aliphatic polycarboxylic acid anhydrides (anhydrides of aliphatic polycarboxylic acids having 3 to 6 carbon atoms, such as succinic anhydride, maleic anhydride, etc.), Alicyclic polycarboxylic anhydrides (cyclohexanedicarboxylic anhydride, etc.), aromatic polycarboxylic anhydrides (phthalic anhydride, trimellitic anhydride, etc.), anhydrides of aliphatic monocarboxylic acids and aromatic monocarboxylic acids (such as anhydrides of acetic acid and benzoic acid) and mixtures of two or more of these. Among these, preferred are aliphatic monocarboxylic acid anhydrides, and particularly preferred are acetic anhydride and propionic anhydride. Note that the acid anhydride may contain a portion of free carpocyrel groups in its molecule.

The catalyst used in the present invention is a metal/'1-ride type Lewis acid (AeC(13+ ZnCe2+ BFs +
FeCea, TlC641S nCe4, etc.), Brønsted acid (protonic acid) (H2SO4, H3PO4
, HF, CF3COOH, FSO3H.

Among them, metal halide type Lewis acids are preferred;
Particularly preferred is ZnCe2. AeCe3 and FeC (b). Also, a combination of a Brønsted acid and a metal halide Lewis acid is also preferred, and when used together, the weight ratio is usually 1:2 to 500, preferably 1:4 to 300.
It is.

In the polymer compound having an aromatic nucleus used in the present invention, examples of the aromatic nucleus include a benzene nucleus and a naphthalene nucleus. Examples of the polymer compound having an aromatic nucleus include polymers or copolymers of vinyl aromatic hydrocarbons. Examples of vinyl aromatic hydrocarbons include styrene and substituted styrene (α-methylstyrene, etc.). Examples of vinyl aromatic hydrocarbon polymers or copolymers include polystyrene, styrene-substituted styrene copolymers (styrene-α-methylstyrene copolymers, etc.), polysubstituted styrenes (poly α-merate copolymers, etc.) Polymer (styrene-methyl acrylate copolymer, α
-methylstyrene-methyl methacrylate copolymer, etc.)
, (substituted) styrene-maleic anhydride copolymer, (substituted) styrene-butadiene copolymer, (substituted) styrene-
Vinylidene chloride copolymers, (substituted) styrene-divinylbenzene copolymers, vinyl polymers having condensed ring aromatic hydrocarbons (vinylnaphthalene polymers, vinylanthracene polymers, etc.), and mixtures of two or more of these. can be given. Among these, preferred are polystyrene, styrene-substituted styrene copolymer, polysubstituted methyl'.7-tyl/'-1-1 nylbenzene co-M polymer, vinylnaphthalene polymer, oyohibinylanthracene polymer, and theal.

The molecular weight of the polymer compound used varies depending on the purpose of use of the final product, and is not particularly limited, but the weight average molecular weight is usually 1,000 to 500,000, preferably 2,000 to 500,000.
It is 100,000.

Hydrogen chloride and formaldehyde or formaldehyde polymers are used as chloromethylating agents. Hydrogen chloride can be used in the form of hydrochloric acid in the presence of water, in addition to ordinary hydrogen chloride gas. As formaldehyde, formaldehyde water mH (5 to 60% by weight aqueous solution, usually 37% by weight)
formalin). Regarding formaldehyde polymers, there are no particular limitations on their molecular weight, and examples include paraformaldehyde and trioxane.

For the chloromethylation reaction, it is preferable to use a solvent, as most polymeric compounds with aromatic nuclei are solid or viscous liquid.
Perchloroethylene, 1,2-dichloroethane, 1,1
・1-Trichloroethane, chloroform, carbon tetrachloride, mixtures of two or more of these, etc.).

When carrying out chloromethylation, the amount of acid anhydride used is usually 0.8-1 equivalent, preferably 0.5 to 0.0 g equivalent, per equivalent of aromatic nucleus of the polymer compound. Even if more than 1 equivalent is used, the effect is only about the same as when 0.3 to 1 equivalent is used, which is not economical. Further, if the amount is less than 0.3 equivalents, there is not much effect.

The amount of the catalyst used is usually 2 to 70% by weight, preferably 5 to 50% by weight, based on the polymer compound.

The amount of formaldehyde or formaldehyde polymer used is usually 0.3 to 0.03 to 1 equivalent of the aromatic nucleus of the polymer compound.
25 equivalents, preferably 07 to 2.0 equivalents.

The amount of the solvent used is usually 1 to 20 times, preferably 2 to 10 times the weight of the polymer compound.

Examples of methods for carrying out the chloromethylation reaction include using a polymer compound having an aromatic nucleus, formaldehyde (polymerized product), etc.
, a catalyst, a solvent, etc. are prepared and the reaction is carried out. The acid anhydride may be added in its entirety at the start of the reaction, or may be added during the reaction.

The chloromethylation temperature is not particularly limited, but is usually 30 to 12
0°C, preferably 40-90°C. The reaction temperature is 30
If the temperature is lower than 120°C, the reaction rate decreases, and if it is higher than 120°C, coloring and crosslinking reactions tend to occur.

The pressure may be normal pressure, increased pressure, or reduced pressure, and is generally carried out under sealed conditions, although it is not particularly limited.

The chloromethylation reaction time is usually 2 hours to 30 hours, and the optimum time can be selected as appropriate depending on the degree of chloromethylation, reaction temperature, etc. Generally, the higher the reaction temperature, the faster the chloromethylation progresses, and the predetermined value is reached in a shorter time. The end point of the reaction can be checked by measuring the chloromethylation rate.

The method of the present invention has the advantage that the coloring of the reactants is much less than that of conventional methods. In addition to this effect, there is no need to worry about gelation due to crosslinking.) The reaction proceeds at a low temperature.
It also has the effect of shortening the reaction time.

The chloromethylated polymer compound having an aromatic nucleus obtained by the present invention can be made water-soluble by, for example, washing and neutralizing it in accordance with a conventional method, and then reacting it with a tertiary amine to quaternize it if it has a relatively low molecular weight. It can be a polymer. The tertiary amine used and the quaternization method may be the same as those conventionally used, and for example, the description in Japanese Patent Publication No. 52-22992 can be applied. This water-soluble polymer is useful as a dispersant, a binder, a conductive agent, an antistatic agent, and the like. Further, a high molecular weight water-insoluble polymer quaternized product can be used as an ion exchange resin. The method of the present invention is particularly effective in obtaining water-soluble polymers.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Polystyrene (weight average molecule 15000) 50F
, paraformaldehyde (88% active ingredient) 801
, Mb5y chloride, 300 g of 1,2-dichloroethane, and 859 g of acetic anhydride were charged into a 1000 mg autoclave equipped with a stirrer, a thermometer, and a gas inlet tube, and 4
The temperature was maintained at 0°C±8°C and hydrogen chloride gas was blown into the reactor. After blowing, the reaction was carried out at a reaction temperature of 60±2° C. for 5 hours. After adding 500 g of reaction condensate and stirring thoroughly, the aqueous layer was separated, and then 5%
The washed aqueous layer was separated using 200 g of an aqueous sodium carbonate solution.

The organic layer was then added to methanol 5β to precipitate white powdery chloromethylated polystyrene.

This was passed through the mouth, washed several times with methanol, and then dried.

In this way, chloromethylated polystyrene 6FM with a chloromethylation rate of 70% was obtained. There was no coloration of the reaction product. This material became a water-soluble polymer by reacting with triethylamine.

Example 2 In the same manner as in Example 1, using 5 og of polyα-methylstyrene (weight average molecular weight 8000) instead of polystyrene, the chloromethylation rate was increased at a reaction temperature of 60°C ± 2°C and a reaction time of 5 hours. A 65% chloromethylated poly-alpha-methylstyrene 60j' was obtained. There was no coloration of the reaction product. This material became a water-soluble polymer by reacting with trimethylamine.

Example 3 Propionic anhydride 2 was used instead of acetic anhydride in Example 1.
Using 8 g, the reaction temperature was 60°C in the same manner as in Example 1.
62 g of chloromethylated polystyrene with a chloromethylation rate of 65% was obtained in a reaction time of 5 hours at ±2°C. The coloring of the reaction product was slow.

Example 4 In Example 1, 5 g of ordinary salt chloride was used instead of 5 g of zinc chloride.
A chloromethylated polystyrene 65f having a chloromethylation rate of 72% was obtained in the same manner as in Example 1 using 0.5 g of sulfuric acid and a reaction time of 60±2° C. and a reaction time of 5 hours. There was no coloration of the reaction product.

Reference Example 1 In Example 1, 51 g of chloromethylated polystyrene with a chloromethylation rate of 20% was obtained in the same manner as in Example 1 in the absence of acetic anhydride at a reaction depth of 80° C. and a reaction time of 20 hours. The reaction product was strongly colored.

Reference Example 2 As a result of performing chloromethylation using phosphoric anhydride in the same manner as in Example 1 instead of acid anhydride, the reaction temperature was 80
℃ and reaction time for 20 hours, the chloromethylation rate was 25%, and the reaction product was strongly colored.

Claims (1)

[Claims] 1. In chloromethylating a polymer compound having an aromatic nucleus using hydrogen chloride and formaldehyde or a formaldehyde polymer. 1. A method for producing a chloromethylated polymer compound having an aromatic nucleus, the method being carried out in the presence of a catalyst and an acid anhydride. 2. The production method according to claim 1, wherein the amount of acid anhydride used is 0.3 to 1 equivalent per equivalent of aromatic nucleus of the polymer compound having an aromatic nucleus. 8. The production method according to claim 1 or 2, wherein the catalyst is a metal halide Lewis acid and/or Brønsted acid.