JPS594604A - Manufacture of isopropenyl phenol polymer - Google Patents

Abstract

PURPOSE:To obtain titled polymer in high yield with high molecular weight, useful as feedstocks for adhesives, photosensitive materials, by the esterification of isopropenyl phenol, carrying out a cationic polymerization at a specific temperature followed by hydrolysis to suppress oligomer production. CONSTITUTION:Isopropenyl phenol is esterified using acetic anhydride etc., in the presence of an acid and/or a base to prepare its ester, followed by distillation under reduced pressure to recover the ester in a purified form; which is then subjected to cationic polymerization at -50 deg.C-+30 deg.C using an initiator such as tin tetrachloride, etc. The polymer thus obtained is hydrolyzed by heating under reflux in the presence of both a lower alcohol and a dilute hydrochloric acid. The resulting polymer is dissolved in a lower alcohol followed by mixing with water to deposit the polymer as a powdered form and separating it through filtration, thus obtaining the objective polymer.

Description

Detailed Description of the Invention The present invention provides an isopropenylphenol polymer which is very useful as a raw material for stabilizers, adhesives, chelate resins, photosensitive materials, flame retardants, ionic and water-soluble polymer materials, etc. This invention relates to an industrially advantageous manufacturing method.

Isopropenylphenol polymers are required to have mechanical or thermal performance when the polymer itself is used as a substrate material, or when a derivative from the polymer is mixed with a low-quality material. Generally molecular weight is 500-800
00 is required.

On the other hand, it is difficult to polymerize isopropenylphenol by ordinary methods such as radical polymerization because of the methyl group at the a-position of the side chain. In addition, a polymerization method for forming a so-called charge transfer complex, and JP-A-2007-255105
A cationic polymerization method such as that seen in No. 48 has been proposed. However, in the synthesis of isopropenylphenol polymers by such a method, a large proportion of oligo(1) dimer and octamer oligomers are produced, making it difficult to obtain a polymer with a large molecular weight.

(It) When attempting to obtain a polymer with a large molecular weight, the polymerization rate decreases and unreacted monomers remain.

From an industrial perspective.

It was difficult to say that it was necessarily a useful method.

In view of the current situation, the present inventors have conducted intensive studies on the production of isopropenylphenol polymers, and have found a main method for producing a polymer with a large molecular weight that is industrially very advantageous and consists of the steps described below. discussed.

That is, the present invention comprises: (A) a step of esterifying isopropenylphenol to synthesize an isopropenylphenol ester; (B) a step of purifying and recovering the isopropenylphenol ester obtained in step (A); ) A step of cationically polymerizing the isopropenylphenol ester obtained in step (B) at a temperature of -50 to 80°C.

(1)) A step of hydrolyzing the polymer of isopropenylphenol ester obtained in step (0) to produce a polymer of isopropenylphenol, (E) Isopropenylphenol obtained in step (D) isopropenylphenol polymer consisting of bonds in each step of the process of recovering the polymer.
The present invention relates to a method for manufacturing a combination.

The method for producing isopropylphenol of the present invention is not particularly limited, but generally includes the alkaline decomposition method of bisphenol A shown in Japanese Patent Publication No. 88-1868, the dehydrogenation method of isopropylphenol, and the method of producing diisopropylbenzene. (2-hydroxy-2-propyl)-cumene hydroperoxide (hereinafter referred to as 3HPO) obtained by partial reduction of diisopropylbenzene dihydroperoxide obtained by phase air oxidation, or during the production of diisopropylbenzene dihydroperoxide. It can be obtained by acid decomposition of the by-produced 0HPO using an acid catalyst.

The esterification reaction of isopropenylphenol in step (A) of the present invention is usually carried out in the presence of a base or
A common method is to react with an acid chloride or an acid anhydride under an acid catalyst.

There are no particular limitations on the acid chloride or acid anhydride, but when considering treatment during the reaction or after the reaction, it is preferable to use acetic anhydride, which simplifies the process and is relatively inexpensive and easily available. preferable.

The reaction is carried out in the presence of the industrially advantageous isopropenylphenol group under the action of acetic anhydride at temperatures ranging from 20 DEG C. to 90 DEG C. The amount of acetic anhydride used is 1 part of isopropenylphenol.
It is preferable that the mole W1 is 1.02 to 1.80 moles, which is a slightly excessive amount.

The amount of the small amount of acid and/or base serving as a catalyst is sufficient to be 1) 0.01 to 1% by weight per part by weight of isopropenylphenol. The reaction temperature is 20°C to 90°C, preferably 25°C to
It is preferable to carry out the reaction at 80°C. If the temperature exceeds 90°C, dimerization of isopropylphenol and 8'ftk formation will increase, and the yield of the desired reactant will drop significantly, which is not preferable.

Furthermore, isopropenylphenol can be reacted by gradually dropping it into acetic anhydride containing an acid and/or a base; this method can minimize dimerization and octamerization. be. Usually, by carrying out the esterification reaction for 1 to 10 hours under the above conditions, a conversion rate of isopropenylphenol of 100% and a selectivity to isopropenyl phenylacetate of 98% or more are ensured.

Isopropenylphenol esterified product is 1, (C)
In order to undergo cationic polymerization in the process, the acid by-produced in the esterification reaction is removed by washing with water, dehydrated under reduced pressure, and then
It is purified by distillation under reduced pressure and recovered. (Step (B)) Distillation purification is carried out in order to prevent the isopropylphenol ester from becoming heavy, and from an industrial standpoint, 5subf1
% to 100 mFIP and at a temperature of 125 to 200°C.

The cationic polymerization of the isopropenylphenol ester compound in step (C) of the present invention is carried out by adding a polymerization catalyst and maintaining the isopropenylphenol ester compound at a predetermined temperature for a predetermined time while cooling the isopropenylphenol ester compound in a solvent solution. In this case, the polymerization solvent is benzene, toluene,
Aromatic solvents such as nitrobenzene, dichloroethane,
The monopolymerization catalyst is preferably a halogenated hydrocarbon such as dichloromethane, nitromethane, or a nitrated aliphatic hydrocarbon such as nitroethane, and is preferably aluminum chloride, tin tetrachloride, boron trifluoride, or an etherate thereof. The amount of the catalyst to be used is 0.05 to 10 mol%, preferably 0.05 to 10 mol%, based on 1 mol of the isopropenylphenol ester monomer.
1 to 5 mol% is sufficient. Polymerization temperature is -50℃~80℃
Preferably, the reaction is carried out at a relatively low temperature of .degree. Usually, when cationic polymerization of isopropenylphenol ester compound is carried out under the above conditions for 1 to 24 hours, the molecular weight is 500 to 8000 o.
can be obtained with a polymerization rate of 100%.

The hydrolysis in step (D) of the present invention is performed on the polymer 1 of the isopropenylphenol ester compound obtained in step (C).
t) per part by weight, 0.2 to 5 times the amount, preferably 0.5 to 8
1 to 20 times, preferably 2 to 20 times, per 1 part by weight of the lower alcohol solution of the polymer.
The mixture is mixed with 10 times the amount of hydrochloric acid water and reacted under heating under reflux. As hydrolysis progresses, isopropenylphenol polymer precipitation is observed. □Generally, ester hydrolysis is carried out using an aqueous alkaline solution of the method of the present invention,
Alternatively, there is a method of carrying out the reaction using an alcoholic aqueous solution, but there is a problem that the isopropenylphenol polymer produced is colored when the hydrolysis is carried out using an alkaline aqueous solution, and the reaction time is longer when the hydrolysis is carried out using an alcoholic aqueous solution. I don't like it because of such problems.

If the amount of lower alcohol used to dissolve the polymer of isopropenylphenol ester compound is less than 0.2 times per 1 part by weight of the polymer, the viscosity will become high and difficult to handle, and if it is more than 5 times the amount, the salt will not be used. Although it depends on the amount of lower alcohol used, the amount is 0.0% per part by weight of lower alcohol in the polymer.
If the amount is less than 5 times, precipitation of the polymer will not be easy, and separation and recovery of the polymer will be difficult. Also, it is not preferable to use more than 20 times the amount because it would be wasteful. As the lower alcohol, methanol and ethanol are preferred from the viewpoint of polymer solubility, low cost, and easy availability. Although the concentration of hydrochloric acid water varies depending on the amount used, a concentration of 0.1 normality to 6 normality is usually used. Generally, when hydrolysis is carried out for 1 to 24 hours under the above conditions, 100% of the isopropenylphenol ester polymer is converted to an isopropenylphenol polymer.

In this way, the isopropenylphenol polymer precipitated in step (D) is separated from the aqueous layer, and then in step (E), 1 part by weight of the polymer is added in an amount of 0.2 to 5 times, preferably 0.5 to 5 times. 8
When dissolved in twice the amount of lower alcohol and poured into water cooled to below 50° C. in an amount equal to or more than twice the amount per 1 part by weight of the lower alcohol solution of the polymer while stirring, the polymer precipitates out as a white powder. The amount of lower alcohol that dissolves the polymer is preferably less than 0.2 times the amount per 1 part by weight of the polymer, as it will result in high viscosity and become difficult to handle, and if it exceeds 5 times the amount, the amount of water will increase, so it is preferable. do not have. If the amount of water is less than twice the amount, the polymer will not become powdery, which is not preferable. Further, if the temperature exceeds 50°C, the precipitated powder will re-agglomerate and cannot be obtained as a powder, which is not preferable. As the lower alcohol, methanol and ethanol are preferred from the viewpoint of polymer solubility, price, and availability.

The thus precipitated polymer powder is recovered by a normal t-separation operation, washed with water, and then dried to obtain a white powder.

The present invention will be explained in more detail with reference to examples below, but the scope of the present invention is not limited by these examples.

Example 1 (A) Synthesis of isopropenyl phenylacetate In an 8-bottle flask equipped with a stirrer, 0.189- of p-)luenesulfonic acid and 122.5 F (1.2 mol) of glacial acetic acid-free were charged at 60°C. It was set to There, m-isopropenylphenol 184.2f! (1.0 mol) was slowly added dropwise over 2 hours, and the reaction was then continued for 8 hours. After the reaction was completed, 800ml of pure water was added and washed at 50°C to remove by-produced acetic acid.

The thus obtained oil layer was dehydrated under reduced pressure and heating to obtain a yellow transparent liquid. As a result of infrared absorption spectrum analysis, m-isopropenylphenol was found to be based on the 10H group (no absorption was observed at all, but a new absorption based on the 10000H3 group was observed, indicating that 100g6 of esterification had been carried out). Further, as a result of gas chromatography analysis, the selectivity to nt-isopropenyl phenylacetate was 98.7%.

(B) Recovery of isopropenyl phenyl acetate by YNT The In-isopropenyl acetate obtained in the above (A) was distilled under reduced pressure for 10 may, and after removing the initial fraction, the fraction with a distillation temperature of 127 to 180°C was extracted. 156.5y- was recovered.

(C) Cationic polymerization process of isopropenyl acetate.
-isopropenylphenyl acetate 50y- and dichloroethane 400y. After the reaction was completed, a cold NHa-methanol solution was added to terminate the polymerization, and the solvent was subsequently removed under reduced pressure and heating.

(D) Hydrolysis Step Methanol 50- was added to the polymer of m-isopropenylphenyl acetate obtained by cationic polymerization and dissolved at 50°C. 2N hydrochloric acid (800 g) was added dropwise thereto, and a hydrolysis reaction was carried out under reflux for 12 hours. As the hydrolysis progressed, precipitation of m-isopropenylphenol polymer was observed.

(E) Recovery of isopropenylphenol polymer After separating the m-isopropenylphenol polymer precipitated by hydrolysis from the aqueous layer, 100 methanol was added and dissolved. When this methanol solution was stirred and poured into a beaker containing 1,500 ml of water previously cooled to 10 DEG C., a white powdery polymer of m-isopropenylphenol was precipitated. This was filtered under reduced pressure, washed with water, and then vacuum dried at 50° C. for a day and night. As a result, 87.9 P of a polymer of m-isopropenylphenol was obtained, and the polymerization rate was substantially 100%. Results of infrared absorption spectrum analysis - ococna
i to! Absorption based on 1 completely disappeared, and absorption based on the -0H group was observed, confirming that 100% hydrolysis was performed. Further, as a result of molecular weight measurement, the number average molecular weight was 1,650.

Example 2 m-isopropenylphenyl acetate obtained in Example 1 50? , and 400- of dichloroethane were prepared, -
The temperature was set at 20°C. 0.15 P of tin tetrachloride as a catalyst was added and cationic polymerization was carried out for 10 hours. After reaction, cold N■3
- Polymerization was stopped by adding methanol solution, and the solvent was removed by heating under reduced pressure. Thereafter, the same operation as in Example 1 was carried out, and the polymer of m-isopropenylphenol in the form of white powder was 87.7%
F was obtained. The polymerization rate was substantially 100%, infrared absorption spectrum analysis showed that 10,051 hydrolyses had been carried out, and molecular weight measurement showed that the number average molecular weight was 5,270.

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Claims (1)

[Scope of Claims] (1) A step of (~ esterifying isopropenylphenol to synthesize an isopropenylphenol esterified product, (to)) a step of purifying and recovering the isopropenylphenol esterified product obtained in the step, 0 (b) The isopropenylphenol ester obtained in step 160~
A step of cationic polymerization at a temperature of 80° C. (a step of hydrolyzing the polymer of isopropenylphenol ester obtained in the homogeneous step to obtain a polymer of isopropenylphenol), (a step of hydrolyzing the polymer of the isopropenylphenol ester obtained in the step M A method for producing an isopropenylphenol polymer consisting of combining each step of the step of recovering a polymer of isopropenylphenol. (2) In the esterification reaction of step (A), in the presence of an acid and/or a base, anhydrous Patent g%IN-method described in section 1 of the patent for esterification with acetic acid. (3) The hydrolysis in step (4)
(A patent for dissolving a polymer of isopropenylphenol in a lower alcohol in the El process, pouring it into water while stirring, precipitating the polymer of isopropenylphenol as a powder, and recovering the polymer of isopropenylphenol by oral separation. The method according to claim 1. (5) The method according to claims 8 and 4, wherein the lower alcohol is methanol and/or ethanol.