JPS6345663B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel amide compounds useful in the synthesis of polyesters having amide groups. More specifically, it relates to an amide compound represented by the following general formula. [R ₁ represents a 1,2-, 1,3- or 1,4-phenylene group. R ₂ is

【formula】

【formula】

【formula】

[expression] or

Represents [formula]. Moreover, X and Y represent hydrogen, a lower alkyl group, or a lower alkoxy group. ] Thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate obtained from terephthalic acid and aliphatic diols are useful for fibers, films, and other molded products due to their excellent mechanical properties, heat resistance, and chemical resistance. It is widely used as However, taking polyethylene terephthalate as an example, although it is possible to improve strength, elastic modulus, etc. in fibers and films by uniaxially or biaxially oriented, for example, in tire cords, magnetic tapes, etc., it is possible to improve strength and elastic modulus. Strong and high modulus materials have become desirable. Furthermore, when used in molded product applications, both polyethylene terephthalate and polybutylene terephthalate exhibit dimensional stability,
The glass transition temperature or glass transition temperature range, which is one index that determines the usable range, is generally low, and this causes the loss of rigidity of the molded product at a relatively low temperature. Improvement in temperature range is desired. In order to meet the above-mentioned requirements under these circumstances, aromatic amide copolyester polyesters have been proposed in JP-A-54-125271 and JP-A-55-67009. However, the polyesters disclosed in these publications have little effect on improving mechanical properties or glass transition temperature, and the resulting polyesters are severely colored and have poor practical use. The reason for this is that the amide compound must be added before or at the beginning of the esterification or transesterification reaction, and as a result, a large amount of free amino groups are produced as by-products, causing coloration and reducing the polymerization rate. This is to make it happen. If added at any other time, undesirable results such as the amide compound not being copolymerized or the degree of polymerization of the polyester not reaching a practically sufficient level cannot be adopted. As a result of various studies to solve these problems, the present inventors found that by introducing a specific group to the end of the amide compound, the amide compound can be added after the esterification reaction or the transesterification reaction, and the amide compound can coexist very smoothly. It was discovered that the polymerization reaction progresses, and a polymer with less coloration and improved glass transition temperature and mechanical properties can be obtained, and the present invention was achieved. The amide compound of the present invention has the following structure in which aromatic dicarboxylic acid residues are bonded to both sides of a diamine residue R ₂ and a phenyl group with or without a substituent is bonded to the terminal. R ₁ is a 1,2-, 1,3- or 1,4-phenylene group, and R ₂ is

【formula】

【formula】

【formula】

[expression] or

[Formula]. That is, the amide compound of the present invention comprises one or more dicarboxylic acids selected from orthophthalic acid, isophthalic acid and terephthalic acid, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, piperazine and dimethyl A specific group is bonded to both ends of an amide compound obtained from one or more diamines selected from piperazine. The amide compound of the present invention has

The most distinctive feature is that the allyl group of the formula [Formula] is bonded. Here, X and Y represent hydrogen, a lower alkyl group or a lower alkoxy group, and the lower alkyl group and lower alkoxy group refer to those having 6 or less carbon atoms. Since the above-mentioned groups are bonded to both ends, the amide compound of the present invention and polyester react smoothly, and a good polyester copolymer with little coloring can be obtained. If both ends are not such groups, such as carboxyl groups or lower alkyl esters, it is necessary to add an amide compound at the beginning of the reaction, and the reaction with the polyester will not proceed smoothly, resulting in a brown to black color. However, the degree of polymerization of the polyester may not be high enough. As a result, almost no improvement in mechanical properties or glass transition temperature is observed. The amide compound of the present invention is a monoallyl ester acid chloride of a dicarboxylic acid selected from orthophthalic acid, isophthalic acid or terephthalic acid.

It can be obtained by reacting [Formula] with a diamine. The monoallyl ester acid chloride of dicarboxylic acid can be produced, for example, by the method described below.
That is, dicarboxylic acid chloride and equimolar amount of phenol derivative

[Formula] is reacted in the presence of pyridine in an inert solvent such as benzene, and the reaction product is reacted with water to form an ester, and the remaining carboxylic acid chloride is converted to a carboxylic acid. Next, remove sodium from carboxylic acid using Na ₂ CO ₃ etc.
The sodium salt of the dicarboxylic acid soluble in water is separated from the monoallyl ester carboxylic acid Na, and the separated monoallyl ester carboxylic acid Na is treated with hydrochloric acid to return the carboxylic acid Na group to the carboxylic acid. The monoallyl ester carboxylic acid soluble in an organic solvent such as chloroform is extracted. A monoallyl ester acid chloride can be obtained by reacting the obtained monoallyl ester carboxylic acid with thionyl chloride or the like. In order to copolymerize the amide compound of the present invention into a polyester such as polyethylene terephthalate or polybutylene terephthalate, the amide compound is dissolved in a melt of bis-β hydroxyalkyl terephthalate, which is a precursor of polyester, or a low polycondensate thereof. , it is preferable to carry out a polycondensation reaction. That is, it is preferable to add the amide compound from the stage where the esterification reaction or ester conversion reaction between the dicarboxylic acid or its ester-forming derivative and the diol is completed to the initial stage of polycondensation. When the amide compound of the present invention is added to the reaction system, it is easily dissolved and reacts quickly with the polyester to form a copolymer. Phenol derivatives at the same time as reacting with polyester

[Formula] is produced, but this is quickly distilled out of the reaction system and is hardly contained in the polyester. The polyester copolymerized with the amide compound of the present invention has high strength, high modulus of elasticity, and high glass transition temperature, and is therefore suitable for applications such as tire cords, magnetic tapes, containers, and electrical insulation materials. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited only to these Examples. Reference Example Synthesis of p-carbo(o-tertbutylphenoxy)benzoyl chloride Pour 200 ml of distilled benzene into a 4-necked flask equipped with 100 ml, dropping funnel, nitrogen gas introduction tube, calcium chloride tube, and stirrer, and add 200 ml of distilled benzene to 0.25 mol of yl chloride was added and dissolved by heating under reflux. Then, 0.50 mol of pyridine was added, and while heating under reflux, the o-
0.25 mol of tert-butylphenol was added over 60 minutes.
It was added dropwise to react. Furthermore, after proceeding with the reaction for 60 minutes, cool to room temperature, add 80 ml of pyridine and 50 ml of water.
was added and stirring was continued for 30 minutes to hydrolyze the remaining acid chloride. The reaction solution containing the precipitate was transferred to a rotary evaporator, and benzene was completely distilled off. Add 500ml of water to the residue and add 150ml of concentrated hydrochloric acid.
ml and continued shaking for 30 minutes to convert the remaining pyridine into hydrochloride, filtered through a glass filter, washed the precipitate with water, transferred to an aqueous solution containing 0.5 mol of sodium carbonate, and stirred for 1 hour. continued. The insoluble diester was separated, concentrated hydrochloric acid was added to the solution to make it weakly acidic, and the resulting precipitate consisting of terephthalic acid and monoester was separated using a glass filter, washed with water, and then vacuum-dried at room temperature for 24 hours. Add this to 100ml of methanol and 500ml of chloroform.
The mixture was stirred for 1 hour to dissolve the monoester, and the insoluble terephthalic acid was removed. The liquid was transferred to an evaporator and the solvent was distilled off. The obtained crude monoester was purified by a recrystallization method using benzene as a solvent. Yield: 19.78g
It was hot. Elemental analysis results C72.37%, H6.05%
The value calculated as monoester, C72.16%,
In good agreement with H6.06%, terephthalic acid mono-o-
It was found to be tert-butylphenol ester. The obtained monoester was placed in a 300 ml eggplant flask, 39.6 ml of distilled thionyl chloride and a few drops of pyridine were added, a reflux ring with a drying tube was attached to the top of the column, and the reaction was carried out at 30°C for 24 hours. After reacting for 1 hour under reflux, thionyl chloride was removed by distillation, and the residue was recrystallized using petroleum ether to obtain colorless dice-shaped crystals. The yield was 17.28g, 78.1%. Example 1 Synthesis of N,N'di[p-carbo(o-tertbutylphenoxy)benzoyl]p-phenylenediamine In a flask equipped with a stirrer, a nitrogen gas inlet tube, and a calcium chloride tube, N- Add 100ml of methylpyrrolidone and cool with ice. Add and dissolve 0.02 mol of finely powdered p-phenylenediamine. Next, 0.04 mol of p-carbo(o-tertbutylphenoxy)benzoyl chloride synthesized in Reference Example 1 was added, and the reaction was carried out while the mixture was kept in an ice bath for 2 hours. The reaction solution was transferred to water 1, and the formed precipitate was separated with a glass filter, washed several times with water, and vacuum-dried overnight. The product was a white fine powder with a yield of 91.5%. Elemental analysis results: C75.08%, H6.07%
Compound with N4.10% It was in good agreement with the calculated values of C75.45%, H5.99%, and N4.19%. Moreover, the NMR spectrum is shown in FIG. Chemical shifts: phenyl proton of terephthaloyl at δ = 8.0 ppm, phenyl proton of p-phenylenediamine at δ = 7.6 ppm, o-tert at δ = 7.1 ppm
Phenyl proton of butylphenol and δ=
1.3 ppm of tert-butyl group protons are separated and provide absorption. The ratio of their integrated intensities is approximately 8:
The ratio of 4:8:18 matches the value expected from the chemical structural formula. Furthermore, the melting point of this substance was measured with a differential scanning calorimeter (UNIX manufactured by Rigaku Denki Co., Ltd.) at a heating rate of 10°C/min, and was found to be 329°C. Examples 2 to 5 In the same manner as in Reference Example, using the dicarboxylic acid chloride shown in Table 1 instead of terephthaloyl chloride, and using the phenol derivative shown in Table 1 instead of o-tert butylphenol. Monoesters of dicarboxylic acids were synthesized. Next, an amide compound was synthesized in the same manner as in Example 1 except that p-phenylenediamine in Example 1 was replaced with the diamine shown in Table 1. Table 1 shows the elemental analysis values of the obtained amide compound.

【table】

[Table] Experimental example: 100 g of dimethyl terephthalate, 66 ml of ethylene glycol, and 0.10 g of calcium acetate at 200°C.
Bis-β hydroxyethyl terephthalate was obtained by transesterification for a period of time. To this, 0.04 g of triphenyl phosphate and 0.04 g of Sb ₂ O ₃ were added, and further 3.25 g of the amide compound obtained in Example 1 was added.
The temperature was raised to 250°C, and then the pressure inside the system was gradually reduced to 2 mmHg, the temperature was raised to 280°C, and the pressure was further reduced to 0.2 mmHg to proceed with polycondensation for 2 hours. The resulting polymer is pale yellow and has an intrinsic viscosity of 0.709.
dl/g, resulting in a high molecular weight polymer with little coloring.

[Brief explanation of drawings]

Figure 1 shows the amide compound obtained in Example 1.
This is an NMR spectrum.

Claims (1)

[Claims] 1. An amide compound represented by the following general formula. [R ₁ represents a 1,2-, 1,3- or 1,4-phenylene group. R ₂ represents [Formula] [Formula] [Formula] [Formula] or [Formula]. Moreover, X and Y represent hydrogen, a lower alkyl group, or a lower alkoxy group. ]