JPS6030685B2 - 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, and more specifically, a dissociation constant of 10-1 at room temperature.
This method is characterized in that parahydroxystyrene is polymerized using an organic carboxylic acid having a molecular weight of less than 4 as a polymerization catalyst.

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 characteristics during processing, and the molecular weight of the polymer are determined. There is a close relationship between becomes more difficult as the molecular weight of Therefore, it is desired to have an appropriate molecular weight and a small amount of created oligomer depending on each application, and those with a molecular weight of about 1,000 to 10,000 are particularly useful. Many studies have been conducted on polymerization methods for rose hydroxystyrene, but most of them are aimed at obtaining high polymers, with molecular weights ranging from 1,000 to 10,000 with good reproducibility. In addition, it was difficult to produce with a short polymerization time, a small number of created oligomers, and a narrow molecular weight distribution.

Traditionally, radical polymerization methods have had the disadvantages of requiring a large amount of catalyst and creating a large amount of oligomers in the product, while cationic polymerization methods that use strong acids such as hydrochloric acid and sulfuric acid have produced polymers resulting from runaway reactions. The molecular weight distribution of is widened, and the counter anion binds to the phenol nucleus and becomes difficult to separate.
There is a drawback that it remains as an impurity in the target polymer.

In addition, if the reaction is carried out at a low temperature to eliminate this, the polymerization time becomes longer, and furthermore, in the cationic polymerization method, there is a momme point at which the molecular weight distribution becomes broader. Therefore, in order to obtain a molecular weight of about 5 or less, Samurai Seki 51-9 Iso 82 recommended using a molecular weight regulator to suppress runaway polymerization. acid,
It has been described that the degree of polymerization can be increased by using an acid catalyst with a pKa of 0 to 40, such as glycolic acid, but in this case, it was thought that weak acids with a pKa>4 are ineffective as polymerization promoters. . However, as a result of further research, we found that magnetic acids with pK2>4 act effectively as polymerization catalysts in the absence of a molecular weight regulator or in the presence of a molecular weight regulator within a certain limit, leading to polymerization. speed up the process,
Moreover, they discovered that a polymer having an appropriate molecular weight could be selectively provided, and thus arrived at the present invention. In other words, the gist of the present invention is that rose hydroxystyrene has a dissociation constant (
The present invention relates to a method for producing a parahydroxystyrene polymer, which comprises polymerizing in the presence of an organic carboxylic acid having a K) of less than 10-4, ascorbic acid, carbonic acid, or carbonic acid gas.

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, cyclohexanosomes, and water.
Since these fers, cyclohexanone, and water act as molecular weight regulators, which will be described later, if their content is too large, the polymerization reaction will be inhibited. Therefore, if a large amount of impurities that act as molecular weight regulators are included,
It is purified to some extent so that its content is about 9% by weight or less, preferably about 8% by weight or less, based on the weight of the parahydroxystyrene, and then subjected to polymerization. As a method for producing and synthesizing parahydroxystyrene, a method starting from phenol and proceeding through the dehydration reaction of paraacetoxyphenylmethylcarpinol is known as a reliable method in the laboratory, and a method for producing parahydroxycinnamic acid is known as a reliable method in the laboratory. Examples include decarboxylation, decomposition of bisphenol ethane, dehydrogenation of 4-pinylcyclohexene of putadiene dimer, dehydrogenation of ethylphenol, and recovery from natural products.

Depending on the composition, the rose hydroxystyrene obtained by these various methods can be purified or not purified, that is, the crude rose hydroxystyrene can be used in the process of the present invention as it is. By the way, crude bulk hydroxystyrene obtained by the dehydration reaction of para-acetoxyphenylmethyl carbinol contains about 10% phenol and 5-20% ethylphenol as impurities, and the decarboxylation of para-hydroxycinnamic acid. Crude hydroxystyrene impurities obtained by
% fuel and 3 to 15% ethylphenol, and the one obtained by decomposing bisphenol ethane contains about 50% phenol, 5 to 20% ethylphenol, and about 10% cresol. The product obtained by dehydrogenation of 4-vinylcyclohexene of putadiene dibase contains 5 to 60% metahydroxystyrene, around 5 to 10% phenol, and 5 to 10% phenol.
% of cyclohexane, and the crude bulk hydroxystyrene obtained by dehydrogenating paraethylphenol also contains about 1 to 5% of phenol and cresol.
It contains 0 to 80% unreacted paraethylphenol, and even in the method of recovering it from natural products, a large amount of phenolic impurities may coexist. When carrying out the method of the present invention, crude parahydroxystyrene obtained by any method including these can be used as a raw material for polymerization as it is or after being purified.

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 is selectively polymerized into vinyl, so it has the characteristics of a method for separating and purifying meta-hydroxystyrene and bulk-hydroxystyrene. As a result, it has.
Since separation of parahydroxystyrene and metahydroxystyrene is more difficult than separating orthohydroxystyrene, it is a great industrial advantage to be able to use a mixture of parahydroxystyrene and metahydroxystyrene as a raw material for polymerization. . The polymerization catalyst used in the present invention is ``as mentioned above, an organic carboxylic acid having a dissociation constant at room temperature of less than 10-4, preferably 10-9 to less than 10-4, ascorbic acid, carbonic acid, or carbon dioxide gas. , Specific examples of carboxylic acids include the following.
■Acetic acid, propionic acid, n-acid, iso-butyric acid (n-
Aliphatic saturated monocarboxylic acids such as cyanobic acid, iso cyanobic acid, methyl ethyl acetate, trimethyl acetic acid, caproic acid, heptonic acid, caprylic acid, belargonic acid, capric acid etc.■
Succinic acid, glutaric acid, adipic acid, pimelic acid, etc.Aliphatic polycarboxylic acids■ Acrylic acid, crotonic acid, methacrylic acid, etc.Aliphatic unsaturated monocarboxylic acids■ Levulinic acid■ Benzoic acid, m-hydroxybenzoic acid, p-hydroxy Benzoic acid, transcinnamic acid, m-toluic acid, p-
These include aromatic carboxylic acids such as toluic acid, methoxybenzoic acid, and p-brobenzoic acid.

The appropriate amount of the polymerization catalyst used is 0.01 to 10% by weight, preferably 0.1 to 50% by weight, based on parahydroxystyrene.

Polymerization of rose hydroxystyrene is carried out by adding the above polymerization catalyst to raw material rose hydroxystyrene and polymerizing it at a temperature of about 0 to 300 degrees. I can do that.

The polymerization reaction can also be carried out in the presence or absence of an inert solvent and in the presence or absence of a molecular weight modifier. In the present invention, even in the absence of a molecular weight regulator, a hydroxystyrene polymer with a controlled molecular weight of about 100,000 or less can be easily obtained, but in the presence of a group of molecular weight regulators as shown below, When the reaction is carried out, it becomes easier to control the molecular weight. However, if the amount of the molecular weight regulator used is too large, the polymerization reaction will be inhibited, so when using the molecular weight regulator, the amount used should be about 1 to 9% by weight, preferably about 10 to 8% by weight, based on the weight of the bulk hydroxystyrene. % by weight, more preferably about 15-6% by weight. As the molecular weight modifier, the following compounds having no carboxyl group can be used.

■Water 'B' Compound with alcoholic hydroxyl group 'C' Compound with phenolic hydroxyl group and no unsaturated side chain ■ Contains phenolic hydroxyl group, and unsaturated side chain forms a phenol nucleus Compounds that resonate 'E] Ketones [F - Compounds that have a sulfone group 'G' Compounds that have a sulfoxide group Compounds that have a nitro group '1' Compounds that have a cyclic ether group U' Compounds that have an amide group, or (K) A compound having a nitrile group or a mixture thereof is used.

Specific examples of these include the following. Masumizuhata Aliphatic, alicyclic or aralkyl alcohols such as methanol, ethanol, butanol, ethylene glycol, diethylene glycol, glycerin, cyclohexanol, benzyl alcohol ■ Phenol, cresol, xylenol, ethylphenol , phenols such as chirotechol, pyroganol, and hydroquinone■
Phenol derivatives having unsaturated side chains that do not resonate with the phenol nucleus, such as metahydroxystyrene, metaallylphenol, metaisoprobenylphenol, etc. Acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as holone, isophorone, cyclohexanone, and acetophenone Sulfone group-containing compounds such as dimethylsulfone, dibutylsulfone, and diphenylsulfone [q
Compounds containing sulfoxide groups such as dimethyl sulfoxide, dibutyl sulfoxide, and diphenyl sulfoxide Compounds containing nitro groups such as ditromethane, nitropropane, nitrobenzene, and nitrotoluene [11 Compounds containing cyclic ether groups such as tetrahydrofuran and dioxane ○} Formamide, acetamide, N , N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphortriamide, and other amide group-containing compounds (K
) Compounds containing nitrile groups such as acetonitrile and propionitrile.

During the polymerization of parahydroxystyrene, a mixture of parahydroxystyrene and the polymerization catalyst, which may or may not contain the molecular weight regulator, is heated as is, under a key frame or under flow at a temperature of 0 to 300°C; The desired polyhydroxystyrene polymer can be produced by polymerizing 1 part of sand for 4 hours, preferably 1 to 1q hours, preferably at 60 to 200 DEG C. under normal pressure or increased pressure.

The polymerization reaction may be carried out in an immutable 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 was prepared by a conventional method.
For example, the target hydroxystyrene polymer is purified by at least one operation such as filtration, distillation, evaporation, precipitation, and drying.
912). When complete polymerization (polymerization rate of 100%) is carried out without using a solvent or a molecular weight regulator, the desired polymer can be obtained without purification. Although relatively high molecular weight rose hydroxystyrene polymers can be produced by the process of the invention, the process of the invention has a molecular weight of about 1
It is particularly suitable for producing a rose hydroxystyrene polymer having a relatively low molecular weight of about 0 or less. The molecular weight of a polymer is generally influenced by the polymerization conditions used; for example, higher polymerization temperatures tend to result in lower molecular weights. Moreover, when a molecular weight regulator is added and the reaction is carried out, the molecular weight becomes even smaller. The polymer obtained by the method of the present invention has a controlled molecular weight, fewer oligomers, and a narrower molecular weight distribution than the polymer obtained by conventional radical polymerization or cationic polymerization. There is no difference in micron structure, infrared absorption spectrum, IH-NMR
, 13C-NMR spectra confirmed that it was a parahydroxystyrene polymer produced by pinyl polymerization.

The polymerization reaction of parahydroxystyrene according to the method of the present invention has the following advantages compared to conventional polymerization reactions.

'11 Only rose hydroxystyrene can be selectively polymerized. '21 The polymerization rate of parahydroxystyrene can be made about 10 to 100 times faster than conventional thermal polymerization methods.

The polymerization rate of '3' rose hydroxystyrene can be approximately 100% (complete polymerization). '41 Control the molecular weight of polyparahydroxystyrene produced from low molecular weight to high molecular weight.

'5} The molecular weight distribution of the polyvarahydroxystyrene produced is narrow and can be close to monodisperse.

(2) Polyparahydroxystyrene produced contains a very small amount of oligomers (those having a 4-base structure or less). '7' Crude bulk hydroxystyrene produced by the dehydrogenation reaction of ethylfer/fer is produced as a polyparahydroxystyrene polymer continuously without separation or purification, and by shortening the polymerization reaction time. can be manufactured.

■ Because there are fewer by-product oligomers in the produced poly-para-hydroxystyrene, the unit consumption in the polymerization reaction of poly-para-hydroxystyrene is improved, and the de-oligomerization process (
(purification) is not required. '91 Since there are few oligomers in the polyparahydroxystyrene produced, the tackiness is reduced, the process of forming powder by crushing is shorter than before, and the process of dissolving it in a solvent can be shortened. As described above, the polymerization reaction of parahydroxystyrene in the presence of an organic carboxylic acid, etc. is more effective than known polymerization methods in terms of time, unit consumption, joining method, and product quality. It turned out to be a great and much improved method. Organic carboxylic acids, etc. can be easily removed during the polymer purification process by appropriately selecting the type and amount added, and even if organic carboxylic acids, etc. remain in ethyl phenol that is collected 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, and can be used as a heat-resistant resin, photosensitive resin, antistatic agent, conductive treatment agent, polymer flocculant, polyisocomplex material, etc. outer furnace filtration membrane,
It is a functional polymer material that has a wide range of uses as a raw material for ion exchange membranes, elutriation agents, paint resins, liquid chromatography fillers, chelate resins, etc.

EXAMPLES The present invention will be further illustrated by examples below, but these are merely for illustrative purposes and are not intended to limit the scope of the present invention. Examples Medium length is an abbreviation for gas chromatography, and GPC is an abbreviation for gel permulation chromatography. Also, PEP is paraethylphenol, P
HS stands for parahydroxystyrene and MHS stands for metahydroxystyrene. Example 1 A predetermined amount of recrystallized purified rose hydroxystyrene (purity of rose hydroxystyrene by GC analysis: 7%) and a predetermined amount of recrystallized purified paraethylphenol (GC analysis) were placed in a 50° polymerization test tube that had been purged with nitrogen in advance. Purity: 99.
0%) and 14 wt% of pure water were quickly dissolved almost uniformly.

A predetermined amount of various commercially available special grade organic carboxylic acids was quickly added to this solution 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 thermostatic polymerization tank at a predetermined temperature. After the polymerization reaction, a part of the polymerization solution was diluted with 2 specific amounts of tetrahydrofuran, and then GC and GPC analyzes were performed to measure the polymerization rate, oligomer production rate, molecular weight, and molecular weight distribution. The results are shown in Table 1. Shown below. After the reaction was completed, the remaining polymer solution was poured into a large excess of water to precipitate* the resulting polymer, which was then separated by filtration and dried under vacuum until it reached a constant weight of 6-0. The microstructures of the produced polymers were measured by IR analysis and NMR analysis, and the vinyl polymerization content was 99% or more in all products. Table 1 Total amount of polymerization solution 109 Example 2 A predetermined amount of recrystallized purified bulk hydroxystyrene (purity of bulk hydroxystyrene by GC analysis: 98.7%) and predetermined amounts of various molecular weight adjustments were placed in a 50' polymerization test tube that had been previously purged with nitrogen. and quickly dissolve it almost uniformly.

A predetermined amount of various commercially available special grade organic carboxylic acids was quickly added to this solution at room temperature, and after the solution was turned upside down two to three times, a polymerization reaction was quickly carried out for a predetermined time in a thermostatic polymerization tank at a predetermined temperature. After the polymerization reaction, add a portion of the polymerization solution to 2 volumes of tetrahydride. After diluting with furan, GC analysis section GPC analysis was performed to measure the polymerization rate, oligomer production rate, molecular weight, and molecular weight distribution. Table 2 shows the results. After the reaction was completed, 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 6000 ml until it reached a constant weight. The micron structure of this polymer is I
As a result of measurement by R analysis and NM old analysis, the vinyl polymerization content of all products was 99% or more. Table 2
Total amount of polymerization solution 109 Example 3 Into a 50' polymerization test tube that had been purged with nitrogen in advance, a predetermined amount of recrystallized purified rose hydroxystyrene (rose hydroxystyrene purity 37% by GC analysis) and a predetermined amount of various commercially available organic carpons were added. An acid was charged, and this solution was quickly subjected to a polymerization reaction for a predetermined time in a temperature polymerization tank at a predetermined temperature.

After the polymerization reaction, a part of the polymerization solution was diluted with 2 volumes of tetrahydrofuran, and then GC analysis and GPC analysis were performed.
Table 3 shows the results of measuring the polymerization rate, oligomer production rate, molecular weight, and molecular weight distribution. After the reaction was completed, 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 until it reached a constant temperature of 60°C. The micron structure of the resulting polymer was determined by IR
As a result of measurement by analysis and NMR analysis, the vinyl polymerization content of all products was 99% or more. Table 3 Example 4 Rose hydroxystyrene was polymerized in the same manner as in Example 2.

The results are shown in Mugi 4 Example 22. Example 5 A Yotsuro flask similar to LOO, which had been purged with nitrogen in advance, was equipped with a Nada gas vessel, a thermometer, a carbon dioxide gas inlet tube, and a Dimroth reflux condenser. .7%).

A predetermined amount of carbon dioxide* gas was introduced from a cylinder through a carbon dioxide gas inlet pipe, and Toazusa polymerization was carried out for a predetermined period of time in a constant temperature polymerization tank at a predetermined temperature. After the polymerization reaction, GC analysis, GPC analysis, m analysis and NMR analysis were performed. GC analysis and G
By PC analysis, the polymerization rate, oligomer production rate, molecular weight,
The results of measuring the molecular weight distribution are shown in Table 4, Experimental Example 23.
Further, as a result of melon analysis and NMR analysis, the microstructure of the produced polymer showed that the vinyl polymerization content was 99% or more. Table 4 Example 6 Rose hydroxystyrene was polymerized in the same manner as in Example 5.

After the polymerization reaction, GC analysis, GPC analysis, IR analysis, and NMR analysis were conducted in exactly the same manner as in Example 5.
Table 5 shows the results of measuring the polymerization rate, oligomer production rate, molecular weight, and molecular weight distribution by GC analysis and GPC analysis. Further, as a result of IR analysis and NMR analysis of the micron structure of the produced polymers, the vinyl polymerization content of all products was 99% or more. Table 5 Total amount of polymerization solution 509 Comparative Example In the same manner as Experiment No. 7 of Example 1, benzoic acid 1. Book t
% instead of concentrated sulfuric acid 1. When the polymerization reaction of parahydroxys tyrene was carried out under exactly the same conditions except that skin t% was used, the solution was colored red when concentrated sulfuric acid was added.

Claims (1)

[Claims] 1 Parahydroxystyrene has a dissociation constant of 1 at room temperature.
1. A method for producing a parahydroxystyrene polymer, which comprises polymerizing in the presence of an organic carboxylic acid of less than 0^-^4, ascorbic acid, carbonic acid, or carbonic acid gas.