JPS591257B2 - Production method of polyarylimine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves converting a compound represented by R' into the general formula R゜NH by mixing an aromatic amine and an aromatic hydroxy compound with a titanium compound described in the claims as a condensing agent in a solvent. By using in the presence, especially below the boiling point,
The present invention relates to a novel method for manufacturing by a one-step reaction operation.

Conventionally, so-called polyarylimines represented by the general formula have been synthesized from the corresponding phthalate esters (J, Hongl et al., J, Polymer.

Scl, (1968) O However, this method requires complicated reaction steps, and therefore the yield is not very good. Also, it is important to note that since phthalic acid ester is used as a starting material, the aromatic nucleus of phthalic acid naturally becomes the center of the linearly connected aromatic nucleus as shown in the general formula, so n is Either it is possible to obtain an even number, that is, an odd number of aromatic nuclei, or it is impossible to obtain an even number. In fact, according to the above-mentioned prior literature, the compound with n=3 is H゜NH convex NH2
It is obtained by deaminating the compound represented by R=R
'=H, a compound with n=5 has not been obtained.

According to the present invention, by appropriately selecting the aromatic amine as the starting material and the number of aromatic rings of the aromatic hydroxy compound,
It is possible to obtain any object, whether odd or even. Furthermore, since a solvent is used, there are fewer opportunities for the compound to come into contact with air, so it is not necessarily necessary to carry out the reaction in an inert gas. In addition, since the reaction proceeds extremely easily, the product can be obtained even below room temperature, and by selecting the type, amount, mixing ratio, etc. of the solvent, it is possible to obtain only the target product mainly as a precipitate. It is characterized by the fact that it is extremely easy to separate and purify reactants and condensing agents, and as a result, products of extremely high purity can be obtained. In addition, the compound represented by the general formula is usually easily oxidized and as a result is strongly colored, or according to the method of this invention,
Since the reaction takes place one step at a time, there is little chance of oxidation, and the result is a silvery-white crystal with photosensitivity. The features of this invention are 1) one-step reaction operation, and 2) by using the condensing agent shown in the claims in an appropriate solvent.
Since the dehydration condensation reaction is carried out at a relatively low temperature, such as room temperature or lower, it is energy saving, 3) the product is easy to separate, 4) the purity is high, 5) the yield is good, and 6) By appropriately selecting aromatic amines and aromatic hydroxy compounds, compounds in which n is an odd number or an even number can be easily produced.

The simplest example of the present invention is shown in the following reaction formula, but it is of course applicable to other applications. A preferred example of the present invention is the production of compounds with n = 3, 4, 5, etc., but it is of course possible to synthesize related compounds with n = 6 or more using other similar raw materials as starting materials. It is.

The amines of the present invention include those having one or more than two amino groups per aromatic nucleus, those having one or more than two amino groups in a plurality of aromatic nuclei,
Or, the hydroxy compound of the present invention is a compound that also shares a substituent other than an amino group in these aromatic nuclei)) Having one or two or more hydroxyl groups per aromatic nucleus. A compound having one or more than one hydroxyl group in a plurality of aromatic nuclei, or a compound that also shares a substituent other than a hydroxyl group in these aromatic nuclei Used as a condensing agent in the present invention TiX4 is a titanium compound in which X has an alkoxy group, an aryloxy group, a halogen atom, or a mixed substituent group of 4, and a mixture of these titanium compounds.

Next, examples will be shown.

Example 1 In a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen inlet, 1.849 p-aminodiphenylamine and p-
Hydroxydiphenylamine 1.859, benzene 50
7nf, tetraisopropoxy titanium (hereinafter referred to as T.P.
T. 2.139 was added and reacted at 6'C.

After the reaction was completed, compound n-3 was obtained by solution extraction. Yield 78% o Melting point 192-192.5°C o Example 2 In the same apparatus as above, aniline 1.869 and p,p'-dihydroxydiphenylamine 2.019 were mixed with T.I. in a benzene solvent. P. T. 4.259.

Unreacted aniline was distilled off together with benzene, and the residue was extracted with benzene or dioxane to obtain a compound with n=3. Yield 61% o Melting point 192-192.5°C. Example 3 Aniline 0.939,p-(
p-anilinoanilino) phenol 2.76f! ,T.
P. T. 2. 139 was reacted in a benzene solution, and after distilling off the benzene, a compound of n=3 was obtained by extraction. Yield 52,700 Melting point 192-192.5°C 0 Example 4 Using the same apparatus as above, p-aminodiphenylamine 1.849 and p-(p-anilinoanilino)phenol 2.76f1, T. P. T. 14.21 in a benzene solution, and after the reaction was completed, the precipitate was filtered and dried to obtain a compound with n=4.

In addition, the yield was 35,701 at a reaction temperature of 20°C and 4,570 at room temperature.
, 72% at 40°C and 63% at boiling point. Melting point 248
．． 5-249.5°C. Example 5 Using the same apparatus as above, p-aminodiphenylamine 1.849 and p-(p-anilinoanilino)phenol 2.769, T. P. T. A mixture of 7.19 and tetrabutoxytitanium (abbreviated as T.B.T.) 7.59 was reacted in a benzene solution, and after the reaction was completed, the precipitate was filtered and dried to obtain a compound with n=4. Ta.

Yield 52%. Melting point: 248.5-249.5°C. Example
6 Using the same apparatus as above, p-aminodiphenylamine 1.849 and p-(p-anilinoanilino)phenol 2.769, T. P. T. 14.29 was reacted in cyclohexane, and after the reaction was completed, it was filtered and dried to obtain a compound with n=4.

Yield 51,700 Melting point 248.5-249.5°C 0 Example 7 Using the same apparatus as above, 1.849 p-aminodiphenylamine and 2.76 f1 p-(p-anilinoanilino)phenol, T. P. T. 14.29 was reacted in a mixed solvent of benzene and citalohexane, and after the reaction was completed, it was filtered and dried to obtain a compound with n=4.

Yield 56%. Melting point 248.5-249.5℃0 Example
8 Using the same apparatus as above, p-aminodiphenylamine 3.68f9, p,p'-dihydroxydiphenylamine 2.019, T. P. T. 17.19 was reacted in a benzene solution, filtered and dried to obtain a compound with n=5.

Yield: 6570; melting point: 273.5-274°C. Example 9 Using the same apparatus as above, P,p7-diaminodiphenylamine 0.999, p-(p-anilinoanilino)phenol 2.769, T. P. T. 8.539 was reacted in a benzene solution, and after the reaction was completed, the precipitate was filtered and dried to obtain a compound with n=7.0 Yield: 26,700 Melting point: 321-3
22.5℃.

References

Claims (1)

[Claims] 1 Aromatic amines and aromatic hydroxy compounds are combined with Ti
Reaction in a solvent at a temperature at or below the boiling point of the solvent in the presence of a titanium compound represented by X_4 (X is an alkoxy group, an aryloxy group, a halogen atom, or a mixed substituent thereof) or a mixture thereof General formulas characterized by: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R, R' are substituents or hydrogen atoms, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ is an aryl group, and n is 3
7)).