JPS6017410B2 - Oxybenzoic acid ester aldehyde condensation product and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oxybenzoic acid ester aldehyde condensation product and a method for producing the same.

Phenols are polycondensed with aldehydes and are widely used as phenolic resins. General novolac-type phenol resins are condensed under acid catalysts and used as thermosetting resins, but the aldehyde condensation positions of phenol are at the ortho and para positions of the phenol group, so one of the positions is For example, aldehyde striped polymers that are already substituted with a group such as an alkyl group at the para position are
Since it is a substituted product, it forms a thermoplastic resin. Since paraoxybenzoic acid ester has an ester group at the para position, the two ortho positions are condensed and polymerized with aldehyde to form a thermoplastic resin. However, oxybenzoic acid ester has a high activation energy, and condensation polymerization is difficult to proceed when the activation energy is less than 10,000, unlike general phenol resins. As an example of polycondensation of oxybenzoic acid, Industrial Chemistry Magazine 74
Lid, No. 12, 2495-2499 (1971), in which polycondensation with formaldehyde is carried out in a fairly highly concentrated sulfuric acid solvent. The inventors
Formaldehyde condensation polymerization of oxybenzoic acid ester was similarly carried out using a sulfuric acid solvent to obtain a condensation polymer.

Among these oxybenzoic acid esters, paraoxybenzoic acid ester in particular has a wide range of industrial uses such as preservatives and plasticizers for polymers. This paraoxybenzoic acid ester formaldehyde vertical polymer is an ester having a phenol group, which increases its molecular weight by forming a condensation polymer,
Even though the volatility is extremely low, the phenol group remains as shown in the following formula even if a condensation polymer is formed, so the effect of the phenol group, ester group, etc. is reflected in the physical properties. It has characteristics. Therefore, oligomers with a small average degree of polymerization are useful. R: both alkylated groups <8 As a result of the inventors' intensive study of the influence of the degree of polymerization,
A striped polymer with a high average degree of polymerization becomes a brittle resin powder and is of little value.In condensation polymers with an average degree of polymerization of 10 or less, the effect of functional groups similar to those of the monomer appears greatly, especially when the average degree of polymerization is 10 or less. In Nos. 3 and 4, it was found that low volatility, functional group effects, etc. were optimal.

Among these paraoxybenzoic acid alkyl esters, those with short alkyl groups such as methyl, ethyl, and butyl groups are used as preservatives, but those with long alkyl groups (6 to 18 carbon atoms) are used as polymers. It has many uses as a plasticizer, particularly for polyamides.

This alkyl group has good compatibility with polymers, so it is compatible with polymers, and since this alkyl group has an ester bond, the plasticizing efficiency is also high. When used as a plasticizer, its volatility is an important factor, and the lower the volatility, the better, and the vertical polymer of the present invention is suitable for this use. When oxybenzoic acid esters and their striped polymers of the present invention are used as plasticizers for polyamides, in addition to the plasticizing effect, they have the great advantage of low moisture resistance, that is, low water absorption. Therefore, engineering plastics with low water absorption, such as nylon 11 and 12, work to further reduce the water absorption rate, which is a drawback of nylon, and are very useful industrially. When used as a polymer additive, such as in applications as a plasticizer, the number of carbon atoms in the alkyl group influences compatibility with the polymer matrix.

Good compatibility when the alkyl group has 6 to 18 carbon atoms,
Among them, 8 to 12 are optimal. The number of carbon atoms increases (1
2→18), the compatibility decreases, and conversely, as it becomes smaller (8→6), the plasticization efficiency decreases. Even if the alkyl group has the same number of carbon atoms, for example, the n-octyl group has a 2-
Various differences occur, such as the fact that ethylhexyl group has better compatibility. Next, the method for producing the alkyl oxybenzoate-formaldehyde striped polymer according to the present invention will be described. This subsequent polymer is obtained by condensation polymerization at a reaction temperature of 100 qo or more, but since oxybenzoic acid esters are immovable in water, the conventional method described above involves suspending or emulsifying it in a dilute sulfuric acid solvent. Polycondensation occurs through the reaction of

In this case, since the degree of reaction is extremely high and the reaction is non-uniform, it is extremely difficult to produce a product with a non-uniform molecular weight distribution and a constant average molecular weight. Therefore, the present invention provides a synthesis method using a homogeneous solution method.

That is, the reaction raw materials in the present invention are composed of a paraoxybenzoic acid alkyl ester, paraformaldehyde, and an acid catalyst, but the reaction does not proceed in an aprotic solvent, and a brotic solvent is suitable. Among these, a solvent that dissolves all of these, ie, alcohol, is preferable. On the other hand, although paraformaldehyde is insoluble in aromatic solvents, the reaction proceeds normally and the striped polymerization product dissolves. As the acid catalyst, acids that dissolve in these solvents are preferred, and benzenesulfonic acid catalysts such as baratoluenesulfonic acid and benzenesulfonic acid are suitable. Since paraoxybenzoic acid ester has a phenol group, intermolecular forces due to hydrogen bonding are strong, and an alcoholic solution of a vertical polymer may cause phenomena such as gelation. On the other hand, aromatic solvents are poor solvents, and although they do not have this tendency, they cause the condensation polymer to become heavily colored during the reaction and have a dissolving power of 4.
. Examples of the alcohol used in the present invention include butyl alcohol, amyl alcohol, hexyl alcohol, etc. with a boiling point of 1
An alcohol having a boiling point of 100 qo or more is suitable, and as an aromatic solvent, a solvent having a boiling point of 100° C. or more, such as toluene or xylene, is suitable.

Some of these solvents cause the reaction reflux temperature to gradually rise. In view of the above-mentioned drawbacks, a co-woven mixture of an alcoholic solvent and an aromatic solvent is suitable as the solvent used in the present invention. Specifically, coscale mixtures made by roughly combining the above-mentioned solvents can be considered, but among them, isoamyl alcohol-xylene, n-butanol-xylene, and n-butanol-toluene are inexpensive and have high industrial value. . Also, among these, the n-butanol-toluene co-condensed mixture is composed of 27% n-butanol and 73% toluene, and the reaction reflux temperature is higher than that of other azeotropic mixtures, which is about 140 to 16,000. is low and stable at 1270. This is a temperature that can be heated by steam heating in industrial equipment, making it an extremely desirable solvent for industrial production. Next, specific examples of the present invention will be described.

In the Shibokutai synthesis preparation composition in which 0.75 mol of paraformaldehyde is reacted with 1 mol of octyl paraoxybenzoate, isoamyl alcohol, isoamyl alcohol-xylene, n-butanol-xylene, n-butanol, n- FIG. 1 shows a comparison of reaction time and reaction temperature when monobutanol and toluene were used as solvents. The amount of solvent was 150', and 0.03 mol of baratoluensulfonic acid was used as the catalyst. From the figure, it can be seen that n-butanol is disadvantageous because the reaction temperature is not constant, but other solvents show a constant reaction reflux temperature, and among them, toluene-butanol system has a low temperature. FIG. 2 shows the time dependence of the amount of reaction dehydration that occurs as the reaction progresses under the same conditions as described above, when an isoamyl alcohol solvent is used.

In addition, under the same conditions, the amount of isoamyl alcohol solvent was changed,
FIG. 3 shows the relationship between the amount of solvent and the viscosity of the reaction product (paraoxybenzoic acid ester striped polymer) at 80 qo when the reaction time is 1 hour. In the figure, the amount of solvent is expressed as the amount per octyl paraoxybenzoate. This figure shows that the reaction rate is highly dependent on the amount of solvent. All of these reactions were carried out in a reaction flask with constant turbulence. After the reaction product was extracted with hot water to remove the catalyst, it was distilled under reduced pressure at 100 am and 1 day and evening, and a vertically polymerized product as a viscous liquid was taken out. The heating loss in Figure 3 shows that this condensation product is 10% of nylon 12.
This is the loss on heating after a sheet with a thickness of 1 fence in which 15 parts by weight was added to 15 parts by weight was left at 120 oo for 1 oG time. As with the condensation polymer used in the present invention, it has been reported that when phenol resins are heated in the presence of an acid catalyst, rearrangement of condensed methylene bonds occurs, making it difficult to remove or neutralize the acid catalyst. is important.

It is also clear that the use of a neutralizing agent can eliminate the water washing step, which is useful in industrial manufacturing processes. As mentioned above, the type and amount of solvent are important in the synthesis method of the present invention, but the most important factor determining the degree of polycondensation is the amount of formaldehyde, and the active ingredient ratio of solid paraformaldehyde and It goes without saying that weighing is important.

In the present invention, it is particularly useful for the aromatic-alcohol azeotrope system, alcohol system, etc. to dissolve paraformaldehyde well in order to minimize the amount of formaldehyde vaporized during the reaction. It can be said that toluene-butanol co-brood mixture is the most suitable solvent. As described above, the formaldehyde condensation product of paraoxybenzoic acid alkyl ester of the present invention is particularly useful as a polymer additive, and the method for producing the same is of great industrial value.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the relationship between reaction temperature and reaction time in various solvents in the condensation polymerization method of the present invention, and Figure 2 is a diagram showing the time dependence of the amount of condensation and dehydration when using an isoamyl alcohol solvent. , Figure 3 shows the relationship between the amount of isoamyl alcohol solvent, the viscosity of the condensation polymer, and the 120°C of the nylon composition to which it was added.
It is a figure which shows the relationship of heating loss with qo. Figure 1 Figure 3 Figure 2

Claims (1)

[Scope of Claims] 1. An oxybenzoic acid ester aldehyde condensation product represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an alkyl group, m≦8) 2. Oxybenzoate ester aldehyde condensation polymerization according to claim 1, where the alkyl has a carbon number of 6 to 18. thing. 3. A method for producing an oxybenzoic acid ester aldehyde condensation product, which comprises polycondensing paraoxybenzoic acid alkyl ester and paraformaldehyde under an acid catalyst using a reaction solvent consisting of at least one of an alcohol and an aromatic solvent. . 4. The method for producing an oxybenzoic acid ester aldehyde condensation product according to claim 3, wherein the acid catalyst is p-toluenesulfonic acid and the solvent is an azeotropic mixture of alcohol and an aromatic solvent. 5. The method for producing an oxybenzoic acid ester aldehyde condensation product according to claim 4, wherein the azeotrope is a triene-butanol azeotrope.