JPS6030687B2 - Method for producing parahydroxystyrene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a rose hydroxystyrene polymer, which is characterized in that the polymerization is carried out in the presence of a specific organic carboxylic acid catalyst and a molecular weight regulator as detailed below. It is something to do.

Parahydroxystyrene polymers are very useful substances as functional polymer materials.

When manufacturing a rose hydroxystyrene polymer by processing or chemically treating it to produce a product, the physical or mechanical properties of the product, various properties during processing, the molecular weight of the polymer, or by-product oligomers are important. In general, physical and mechanical properties improve as the molecular weight of a polymer increases, but processing of polymers or treatments that involve chemical reactions can lead to As it grows, it becomes more difficult. Therefore, a material with an appropriate molecular weight and a small amount of created oligomer is desired depending on each application, and a large number of studies have been conducted on the polymerization method of hydroxystyrene, in which molecular weights of about 1,000 to 10,000 are particularly useful. However, most of them are aimed at obtaining high polymers with molecular weights ranging from 1,000 to 10,000 with good reproducibility, shortening polymerization time, reducing by-product oligomers, and improving molecular weight distribution. were narrow and difficult to manufacture.

However, the radical polymerization method requires a large amount of catalyst and has the disadvantages of creating a large amount of oligomers in the product, while the cationic polymerization method, which uses strong acids such as hydrochloric acid and sulfuric acid, causes the reaction to run out of control and produces polymers. The molecular weight distribution of the coalescence becomes wider, and the counter anion binds to the Fer/Fe nucleus and becomes difficult to separate.
There is a problem that it remains as an impurity in the target polymer.

Furthermore, if the reaction is carried out at a low temperature in order to prevent this, the polymerization time becomes longer, and the cationic polymerization method has the disadvantage that the molecular weight distribution becomes broader. Therefore, in order to obtain a molecular weight of about 50,000 or less, Tokukan Sho 51-9 Skin Root 2 used a molecular weight regulator to suppress runaway polymerization. It is described that 0 to 4 acid catalysts are used in combination to increase the polymerization rate. As a result of our further research, we discovered that there are surprisingly many molecular weight regulators that have the effect of regulating the molecular weight of polymers during the polymerization of rose hydroxystyrene, including those shown in JP-A-51-98-2 published by Kamiko. Moreover, as the acid used as a polymerization accelerator, it is particularly preferable to use organic carboxylic acid among various organic acids and inorganic acids because of the excellent quality of the product polymer and the ease of purification. The heading is a completed version of the present invention, and the present invention is disclosed in the above-mentioned Japanese Patent Application Laid-Open No.
-96882, the polymerization catalyst is a selection and the molecular weight regulator is an extension of the invention.

That is, the gist of the present invention is to prepare rose hydroxystyrene by formic acid, cyanacetic acid, and dichloromethane.

Acetic acid, trichloroacetic acid, fluoroacetic acid, bromoacetic acid, iodoacetic acid, methoxyacetic acid, mercaptoacetic acid, maleic acid, fumaric acid, citric acid, tartaric acid, thioglycolic acid, lactic acid, ciscinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, Trimellitic acid, pyromellitic acid, chlorbenzoic acid (o-, m-, p-form), bromobenzoic acid, (o-,
m monolithic), iodinated benzoic acid, (o-, m-, p monolithic),
or feng shui in the presence of o-toluic acid and as a molecular weight regulator, 'B} A compound having an alcoholic hydroxyl group,'
C} Compounds that have a phenolic hydroxyl group and no unsaturated side chains, 'D} Compounds that have a phenolic hydroxyl group and whose unsaturated side chains do not resonate with the phenol nucleus, {E} Ketones, '
F}Compound having a sulfone group, (G) Compound having a sulfoxide group, (H) Compound having a nitro group, (1
) A method for producing a parahydroxystyrene polymer, which comprises polymerizing in the presence of a compound having a cyclic ether group, (J) a compound having an amide group, or (K) a compound having a nitrile group, or a mixture thereof. .
The rose hydroxystyrene used as a polymerization raw material in the present invention may be a pure product, but it may also be a crude rose hydroxystyrene that is normally obtained industrially. These crude hydroxystyrenes often contain impurities such as phenols, cyclohexanone, and water, and these phenols, cyclohexanone, and water function directly as molecular weight modifiers, which will be described later. As a method for producing and synthesizing rose hydroxystyrene, a method starting from phenol and proceeding through a dehydration reaction of rose acetoxyphenylmethycarbinol is known as a reliable laboratory method.
In addition, the decarboxylation method of parahydroxycinnamic acid, the decomposition method of bisphenolethane, the 4-
There are methods such as dehydrogenation of vinylcyclohexene, dehydrogenation of ethylphenol, and methods of recovery from natural products, and the rose hydroxystyrene obtained by these various methods is purified or not purified, that is, crude rose hydroxystyrene. The method of the present invention can be carried out as is.

By the way, crude bulk hydroxystyrene obtained by the dehydration reaction of para-acetoxyphenylmethylcarpinol contains about 10% phenol and about 5-20% ethylphenol as impurities, and it is obtained by decarboxylation of para-hydroxycinnamic acid. The crude bulk hydroxystyrene produced contains about 5 to 20% of phenol and 3 to 15% of impurities.
% of ethylphenol, and the product obtained by decomposition of bisphenolethane contains about 50% of phenol, about 5 to 20% of ethylphenol, and about 10% of cresol as impurities, and contains about 4% of butadiene dimer. - those obtained by dehydrogenation of vinylcyclohexene contain 5-60% metahydroxystyrene, around 5-10% phenol, around 5-10% cyclohexanone, and those obtained by dehydrogenation of paraethylphenol. Crude hydroxystyrene also contains about 1 to 5% of phenol and cresol and 40 to 80% of unreacted paraethylphenol, and a large amount of phenolic impurities can coexist even in the method of recovering it from natural products. When carrying out the method of the present invention, it is possible to use crude bulk hydroxystyrene obtained by any method including these as it is as a raw material for polymerization. The parahydroxystyrene used in the method of the invention may also contain metahydroxystyrene.

In the method of the present invention, meta-hydroxystyrene is not substantially polymerized, and only para-hydroxystyrene can be selectively vinyl-polymerized, so that the method can be used to separate and purify the meta- and para-hydroxystyrene. It has a certain value. Since separation of parahydroxystyrene and metahydroxystyrene is more difficult than separating orthohydroxystyrene, it is industrially advantageous to use a mixture of parahydroxystyrene and metahydroxystyrene as raw materials for polymerization. . The polymerization catalyst used in the present invention is the following organic carboxylic acid. ■ Formic acid, cyanacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, bromoacetic acid, iodoacetic acid, methoxyacetic acid, mercaptoacetic acid ■ Maleic acid, fumaric acid, citric acid, tartaric acid,
■ Thioglycolic acid, lactic acid ■ Cicinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, chlorbenzoic acid, (o-, m-, p-form), brombenzoic acid, (o (mono-, m-mono), iodinated benzoic acid, (o-, m-, p-mono), o-toluic acid.

The amount of the organic carboxylic acid polymerization catalyst used is 0.01 to 100% by weight, preferably 0.
．． A range of 1 to 5% by weight is suitable.

Typical examples of molecular weight regulators used in the present invention include aliphatic and fatty acids such as Feng Shui alcohol, ethanol, ethanol, butanol, ethylene glycol, diethylene glycol, glycerin, cyclohexanoyl, and zincyl alcohol. Cyclic or aromatic alcohols 'C' phenol, cresol, xylenol, ethylphenol, chirotechol,
Phenols such as pyroganol and hydroquinone Phenol derivatives with unsaturated side chains that do not resonate with the phenol nucleus such as hydroxystyrene, metaallylphenol, and metaisoprobenylphenol Acetone,
Carponyl group-containing compounds such as methyl ethyl ketone, methyl isoptyl ketone, holon, isophorone, cyclohexane, acetophenone, etc. Sulfone group-containing compounds such as dimethyl sulfone, dibutyl sulfone, diphenyl sulfone (G) Dimethyl sulfoxide, dibutyl sulfoxide, diphenyl sulfoxide, etc. Sulfoxide group-containing compound (H) Nitro group-containing compound (1) such as nitromethane, nitropropane, nitrobenzene, nitrotoluene, etc.
Compounds containing cyclic ether groups such as tetrahydrofuran and dioxane (J) Formamide, acetamide, N,N-
Examples include amide group-containing compounds such as dimethylformamide, N,N-dimethylacetamide and hexamethylphosphortriamide (K) nitrile group-containing compounds such as acetonitrile and propionitrile, either singly or in mixtures thereof.

Compounds that also contain carboxyl groups are excluded from the definition of molecular weight modifiers, even if they meet the above concept.

Generally speaking, the amount of these molecular weight regulators used can be about 1 to 500% by weight, preferably about 10 to 100% by weight, based on the weight of parahydroxystyrene.

During the polymerization of rose hydroxystyrene, a mixture of rose hydroxystyrene, the polymerization catalyst, and the molecular weight regulator is used as it is, or under rope or flow, to a concentration of 0 to 0.
300 qC, preferably at a temperature of 60 to 200 pm, under normal pressure or pressure for 48 hours, preferably 10
A desired rose hydroxystyrene polymer can be produced by polymerizing for minutes to 1 field time.

The polymerization reaction may be carried out in the presence of an inert solvent. The polymerization reaction can be carried out not only in a batch manner but also in a continuous manner since the polymerization rate is high. The obtained reaction mixture is purified by a conventional method, for example, by at least one operation such as filtration, distillation, evaporation, precipitation, drying, etc., to obtain the target bulk hydroxystyrene polymer.
(see 19912). Although it is possible to produce a rose hydroxystyrene polymer with a relatively high molecular weight using the method of the present invention, the method of the present invention is suitable for producing a rose hydroxystyrene polymer with a relatively low molecular weight of about 100,000 or less. Particularly suitable.

The molecular weight of a polymer tends to decrease as the polymerization temperature increases or as the amount of molecular weight regulator increases. The polymer obtained by the method of the present invention has, compared to the polymer obtained by conventional radical polymerization or cationic polymerization,
It is a polymer with a controlled molecular weight, few by-product oligomers, and a narrow molecular weight distribution.There is no difference in microstructure.It is a rose hydroxystyrene polymer obtained by pinyl polymerization according to infrared absorption spectra, IH-NMR, and 13C-NMR spectra. Something has been confirmed.

The polymerization reaction of rose hydroxystyrene according to the method of the present invention has the following advantages compared to conventionally known polymerization reactions.

Only '1' hydroxystyrene can be selectively polymerized. '2) It is possible to increase the polymerization rate of parahydroxystyrene by about 10 to 10 steps compared to conventional thermal polymerization methods.

'3' Polymerization rate of rose hydroxystyrene is approximately 100%
(complete polymerization). ■ The molecular weight of the polyparahydroxystyrene produced can be controlled from low to high molecular weight.

'51 The molecular weight distribution of the polyparahydroxystyrene produced is narrow and nearly monodisperse.

[6} The polyparahydroxystyrene produced contains very little oligomer (tetramer or less). '7} Separation of crude bulk hydroxystyrene produced by dehydrogenation of ethylphenol,
A polyvarahydroxystyrene polymer can be produced continuously without purification, as it is, and in a shortened polymerization reaction time.

'8) Since there are few oligomers produced as by-products in the polyparahydroxystyrene produced, the unit consumption in the polymerization reaction of parahydroxystyrene is improved, and a de-oligomerization step (purification) is not required. ■ Because there are fewer oligomers in the polyparahydroxystyrene produced, the stickiness is reduced, and the powdering process by crushing is shorter than before.
Furthermore, the step of dissolving it in a solvent can be shortened.

As described above, the polymerization reaction of parahydroxystyrene in the presence of a molecular weight regulator and a specific organic carboxylic acid has a higher time, basic unit, It turned out to be an innovative method that greatly improved the operating method and product quality. Organic carboxylic acids can be easily removed during the polymer purification process by appropriately controlling the type and amount added, and even if organic carboxylic acids remain in ethylphenol that is recovered and reused, they can be easily removed. It was also found that it is possible to select conditions that have no effect on the dehydrogenation reaction. The polymer obtained by the method of the present invention has excellent physical and chemical properties, such as heat-resistant resin, photosensitive resin,
As a raw material for antistatic agents, conductive treatment agents, polymer flocculants, polyion complex materials, extraocular filter membranes, ion exchange membranes, flame retardants, paint resins, liquid chromatography fillers, chelate resins, etc. It is a functional polymer material with a wide range of uses.

EXAMPLES The present invention will be illustrated in more detail by way of Examples below, but these are merely given for the purpose of illustration and are not intended to limit the scope of the present invention. In the examples, GC is an abbreviation for gas chromatography, and GPC is an abbreviation for gel permulation chromatography. Also, PEP is paraethylphenol, M
HS stands for metahydroxystyrene and PHS stands for parahydroxystyrene. Example 1 A predetermined amount of recrystallized purified rose hydroxystyrene (variety hydroxystyrene purity unevenness: 7% by GC analysis) and a predetermined amount of recrystallized purified paraethylphenol (GC analysis Purity: 99.
0%) and 14 wt% of pure water were prepared and quickly and almost uniformly dissolved.

To this solution, a predetermined amount of a commercially available special grade organic carboxylic acid was quickly added at room temperature, and after the solution was inverted up and down 2 to 3 times, a polymerization reaction was quickly carried out for a predetermined time in a temperature polymerization tank at a predetermined temperature. After the polymerization reaction, a portion of the polymerization solution was diluted with tetrahydrofuran at a volume of 2, and then GC analysis and GPC analysis were performed to measure the polymerization rate, oligomer production rate, molecular weight, and molecular weight distribution. The results are shown in Table 1. After the polymerization reaction, the remaining polymer solution was poured into a large excess of water to precipitate the resulting polymer, which was then separated by filtration and vacuum-dried at 60° C. until it reached a constant weight. The microstructures of the produced polymers were measured by m-analysis and NMR analysis, and the vinyl polymerization content was 99% or more in all products. Table 1 Here, oligomer is a general term for dimers to tetramers of PHS.

Example 2 A predetermined amount of recrystallized purified bulk hydroxystyrene (GC
Analysis of rose hydroxy. Styrene purity. 7%) and predetermined amounts of various molecular weight regulators were added and quickly and almost uniformly dissolved.

A predetermined amount of a commercially available special grade organic carboxylic acid was quickly added to this solution at room temperature, and after the solution was inverted up and down two to three times, a polymerization reaction was quickly carried out in a thermostatic polymerization tank at a predetermined temperature for a predetermined period of time.
After the polymerization reaction, GC analysis and GPC analysis, as well as IR analysis and NM old analysis, were carried out in exactly the same manner as in Example 1. G
Table 2 shows the results of measuring the polymerization rate, oligomer production rate, molecular weight, and molecular weight distribution by C analysis and GPC analysis.
Furthermore, as a result of IR analysis and NMR analysis, the microstructure of the produced polymers revealed that the pinyl polymerization content of all products was 9.
It was over 9%. Table 2 Comparative Examples In the same manner as Experiment No. 7 of Example 1, lactic acid 1. Concentrated sulfuric acid 1. instead of skin t%. When a polymerization reaction of rose hydroxystyrene was carried out under exactly the same conditions except that skin t% was used, the solution turned red and colored when concentrated sulfuric acid was added.

Claims (1)

[Claims] 1 Parahydroxystyrene in formic acid, cyanacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, bromoacetic acid, iodoacetic acid, methoxyacetic acid, mercaptoacetic acid, maleic acid, fumaric acid, citric acid, tartaric acid, thioglycolic acid, lactic acid, silica Acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, chlorbenzoic acid (o-, m-, p-form), brobenzoic acid, (
o-, m-form), iodobenzoic acid, (o-, m-, p-
(A) water, (B) a compound having an alcoholic hydroxyl group, (C) a compound having a phenolic hydroxyl group and no unsaturated side chain in the presence of o-toluic acid or o-toluic acid as a molecular weight regulator. , (D) a compound having a phenolic hydroxyl group and whose unsaturated side chain does not resonate with the phenol nucleus, (E) ketones, (F) a compound having a sulfone group, (G) a compound having a sulfoxide group, (H ) A compound having a nitro group, (I) a compound having a cyclic ether group, (J) a compound having an amide group, or (K) a compound having a nitrile group, or a mixture thereof. Method for producing parahydroxystyrene polymer.