JPH1045907A - Production of polyester amide copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester having excellent transparency. SOLUTION: This production process comprises reacting an aromatic dicarboxylic acid with a diol and an aminocarboxylic acid ester represented by the formula: H2 N-X-COOR (wherein X is an aromatic ring; and R is an alkyl) and polycondensing the formed reaction product. In this process, an amino compound as a DEG inhibitor is added to the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyesteramide copolymer and a polyesteramide copolymer.

[0002]

2. Description of the Related Art Polyester, especially polyethylene terephthalate (hereinafter abbreviated as PET), has a high initial modulus and excellent thermal stability among general-purpose polymers, and is used for industrial materials which require remarkable performance, especially for tires. Application to code is increasing rapidly. However, higher initial elastic modulus, better thermal dimensional stability and lower heat shrinkage are required for higher quality, higher performance and higher added value of products. Even with PET having the above properties, significant improvements are needed. For this reason, many proposals have been made with regard to the improvement of such properties, and among them, the use of a copolymerization reaction for the purpose of improving at the molecular level involves the addition of a segment for the purpose of improvement in the host molecular chain. Since it can be introduced, the type of additive and copolymerization are focused on the objective improvements such as thermal dimensional stability, heat shrinkage, initial elastic modulus, elongation, and toughness of the molded product of the copolymer. It is possible to select a percentage.

Accordingly, the present applicant has found that an aminocarboxylic acid can be used as the third component to provide a copolymerized polyesteramide having a high initial modulus, excellent thermal dimensional stability, and a low heat shrinkage.

The polyester is usually esterified directly with an aromatic dicarboxylic acid and a diol compound while heating and stirring under pressure or at normal pressure, or by transesterification between an alkyl ester of a dicarboxylic acid and a diol compound. Then, an esterification reaction is performed to obtain an ester compound and a low polymer thereof, and then a polycondensation reaction is performed while heating the polymer under high vacuum to produce a polymer. Also,
In the method for producing a polyesteramide copolymer, p
-A method of performing a polymerization reaction after acetylating the amino group of aminobenzoic acid [Jounal of Applied Polymer Science
Vol. 25, 1685-1694 (1980)], a method of conducting a polycondensation reaction by adding an aromatic diamine and an aromatic dicarboxylic acid or a substituted derivative thereof at the initial stage of melt polycondensation of a polyester [Japanese Patent Laid-Open No. No. 67009], and a method in which an aminocarboxylic acid compound having an aromatic ring is added at the initial stage of melt polycondensation of a polyester to carry out a polycondensation reaction [JP-A-55-137217], all of which have an amino group. Either a substituted derivative of the compound is used from the initial stage of the reaction, or a compound having an amino group is added at the initial stage of melt condensation of the polyester.

[0005] Accordingly, the applicant of the present invention has proposed that when aminocarboxylic acids are used as the third component, PET having a high initial elastic modulus, excellent thermal dimensional stability and low heat shrinkage can be obtained without largely changing the existing process. Can be provided (JP-A-7-126367). However, the copolymerized polyesteramide obtained by these methods contains a large amount of diethylene glycol, which is a by-product of the esterification reaction, and has a low melting point, resulting in poor thermal stability. Therefore, diethylene glycol (hereinafter referred to as DEG) as a by-product is usually used.
), A metal catalyst such as a lithium compound and a sodium compound is used.

[0006]

However, when polyester is produced by the above-mentioned method, the metal catalyst used as an inhibitor of DEG and the inhibitor of the polymerization reaction of the inhibitor itself increase the turbidity of the copolymer, This is harmful to later thread making and film processing.

[0007]

That is, a first aspect of the present invention is to react an aromatic dicarboxylic acid and a diol with an aminocarboxylic acid ester compound represented by the following general formula (Chemical Formula 1), and to form a reaction product thereof. In the method for producing a polyesteramide copolymer by a polycondensation reaction,
A method for producing a polyesteramide-based copolymer, which comprises adding a compound having an amino group as an EG inhibitor. <Chemical Formula 1> H ₂ NX-COOR (where X is a group having any aromatic ring selected from benzene, naphthalene, pyrene, biphenyl, anthracene, and phenanthrene, and R is an alkylene group or an aromatic ring. Group, or any hydrocarbon selected from saturated cyclic hydrocarbon machines.) Further, the preferred requirement is that the compound having an amino group is
Morpholine, N-methylmorpholine, N-ethylmorpholine, piperidine, N-methylpiperidine, N-ethylpiperidine, cyclohexylamine, benzylamine,
At least one kind of N-methylpyrrolidine, more preferably at least one kind of amine among N-ethylpiperidine, morpholine and cyclohexylamine, wherein the diol is ethylene glycol and the aromatic dicarboxylic acid is terephthalic acid Is most effective when Furthermore, it is preferable to react the compound (1) having an amino group with an aromatic dicarboxylic acid in an amount of 0.015 to 10 mol%. A second aspect of the present invention is a polyesteramide-based copolymer produced by any of the above-mentioned methods, the melting point of which is 220 ° C or more, or the glass point transition of which is 75 ° C or more. Is preferred.

In the present invention, a compound having an amino group must be used. As the compound having an amino group, any compound having an amino group and capable of suppressing the generation of DEG may be used.Specifically, as the primary amine, cyclohexylamine, benzylamine, and secondary amine As the piperidine, morpholine and tertiary amine, N-ethylmorpholine, N-methylpyrrolidine and the like are preferable. Particularly preferred are N-methylpiperidine, morpholine, and cyclohexylamine, which have a high DEG inhibitory effect. These compounds may be used alone or in combination of two or more. Although the amount of the DEG inhibitor is not particularly limited, it is preferable to use 0.015 to 10 mol% with respect to the aromatic dicarboxylic acid from the viewpoint of the addition property to the molecular terminal of the copolymer and the coloring property of the copolymer. Good. Furthermore, since the step in which the generation rate of DEG is high is a step in which the concentration of released DEG is high, that is, during the direct esterification reaction or transesterification reaction, it is effective to allow the DEG inhibitor to be present in the reaction system from the beginning of the reaction. In the case of a direct esterification reaction or a polycondensation reaction which is a reduced pressure step after the transesterification reaction, it is preferable to distill the compound out of the system.

The aromatic dicarboxylic acid used in the present invention is not particularly limited, and specific examples thereof include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and diphenyldicarboxylic acid. It is preferable from the viewpoint of the objective. These may be used alone or in combination of two or more.

The diol used in the present invention is not particularly limited. Specifically, diols such as catechol, resorcin, hydroquinone, aromatic diols such as 2,6-dihydroxylnaphthalene, ethylene glycol, trimethylene glycol, tetramethylene glycol, Aliphatic diols such as hexamethylene glycol and cyclohexane-1,4-dimethylol are exemplified, with aliphatic diols being preferred.

In the present invention, an aromatic aminocarboxylic acid ester is used as the third component of the copolymer. The type of the compound is not particularly limited, but is preferably a compound having an aromatic ring such as a benzene ring, a naphthalene ring, a pyrene ring, and a biphenyl ring. Specifically, terephthalic acid, dimethyl terephthalate, -Naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylate. The amount of the aromatic aminocarboxylic acid ester is not particularly limited, but from the viewpoint of the glass transition temperature and the melting point of the copolymer, 0.5 to 3 based on the aromatic dicarboxylic acid.
It is preferable to add 0 mol%.

The catalyst used in the present invention may be any antimony compound having a polycondensation catalytic activity.
Oxides such as antimony trioxide, antimony tetroxide and antimony pentoxide, halides such as antimony trichloride and antimony tribromide, and alcoholates such as antimony glycolate are preferable, and oxides are preferable. These compounds may be used alone, or two or more of them may be used in combination. One of these compounds may be used in combination with another catalyst.

The amount of the catalyst to be added is not particularly limited, but is 2.5 × 10 ^{−4 to} 5.0 × 10 ⁴ based on the aromatic dicarboxylic acid.
^-4 mol% is preferred.

The reason for using an antimony compound as a catalyst is as follows. As a criterion for selecting a catalyst, a reaction promoting action and a polymerization inhibiting action can be mainly mentioned. Titanium compounds, tin compounds, and the like have a higher polymerization rate than antimony compounds, but have a higher rate of occurrence of irreversible decomposition reactions, and therefore, the quality of the final product is not always preferable. On the other hand, the antimony compound is not the best in promoting the polymerization, but hardly causes a decomposition reaction of the produced polymer, and a stable product can be obtained.

The reason for this will be described below with reference to ethylene glycol and terephthalic acid. The polyester polymerization reaction includes a dehydration reaction in which a hydroxyl group of ethylene glycol reacts with a carboxyl group of terephthalic acid, and a deethylene glycol reaction between a terminal hydroxyl group and a terminal hydroxyl group. Therefore, when the abundance ratio of both is extremely deviated, it is impossible to produce a high molecular weight polyester. In addition, an ester having a glycol at the terminal reacts to a larger ester by transesterification when the polymerization reaction starts, but in a state with a dicarboxylic acid at the terminal, the esterification reaction is performed unless a hydroxyl group is present. Don't wake up. Therefore, when the number of terminal carboxyl groups increases in the system, the polymerization does not proceed.

In the present invention, besides the above, a stabilizer, an antioxidant, a heat-resistant agent, an antioxidant, etc., which are usually used in the textile industry, may be optionally added according to the purpose. Can be blended.

The reaction temperature and the reaction time of the esterification reaction are not particularly limited as long as they are generally performed, but are preferably 235 ° C. to 260 ° C. and 2 hours to 5 hours, respectively.

The polycondensation reaction includes melt polymerization, solution polymerization, etc.
Although not particularly limited, melt polymerization is preferred in terms of productivity.

Since the polyester produced by the production method of the present invention has good moldability, it can be used as films, bottles for molding, various fiber materials, and various injection molding materials.

[0020]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto without departing from the gist of the present invention. Parts and% in Examples are based on weight unless otherwise specified. Various measurements were made according to the following methods.

A: Molecular weight of polymer A sample obtained by quenching the copolymer at the end of the polycondensation reaction in ice water was used as a sample, and 5.0 mg of the copolymer was added to 100 μl of 1,
After dissolving in 1,3,3,3-hexafluoro-2-propanol, 12.5 ml of chloroform was added and measurement was performed by high-speed GPC (HLC8020 manufactured by Tosoh Corporation). The weight average molecular weight (in terms of polystyrene) at this time is shown in Table 1 as Mw.

B: DEG content in the copolymer A sample obtained by decomposing the copolymer at the end of the polycondensation reaction with methanol was used as a sample, and subjected to gas chromatography (HEWL).
It was measured using ETT PACKARD (HP5890A). Regarding the amount of DEG, the ratio of ethylene glycol (EG) to DEG, EG / DEG, was determined and quantified from a calibration curve.

Turbidity of copolymer 2.0 g of the copolymer at the end of the polycondensation reaction is dissolved in 1: 1 (volume ratio) of p-chlorophenol: 1,1,2,2-tetrachloroethane. Using a haze meter (HGM-2k manufactured by Suga Test Instruments) as a sample
It measured based on STM-D-1003-52.

D: Melting point of copolymer, glass transition temperature Using a suggestive scanning calorimeter (Model 9900, manufactured by Du Pont), a sample weight of 5 mg was raised to 290 ° C. under a nitrogen atmosphere at a temperature rising rate of 40 ° C./min. After warming and maintaining at this temperature for 5 minutes, the material rapidly cooled in ice water was heated at a rate of 10 ° C./min, and its melting point and glass transition temperature were measured. The melting point is the peak temperature of the melting peak, and the glass transition temperature is shown in FIG.
, The temperature at the intersection B of the base line a and the tangent at the inflection point C of the curve ABCD was taken.

Example 1 2 moles of terephthalic acid, 3 moles of ethylene glycol and, as a catalyst, antimony trioxide (2.0 × 10 ^-4 mole% based on terephthalic acid) ethyl P-aminobenzoate were converted to terephthalic acid. 0.1 mol%, and N-ethylpiperidine was added to terephthalic acid at 1.82 × 10
^-4 mol% was charged into a reaction vessel equipped with a stirrer, and after sufficiently replacing with nitrogen gas, the inside of the reactor was filled with nitrogen gas at 1.8 kg / c.
The reaction was carried out at 240 ° C. by applying pressure to m ² . After a predetermined amount of water was distilled off, 1 m at 40 mmHg and 255 ° C. for 60 minutes
The polycondensation reaction was carried out at a temperature of 275 ° C. or lower at a pressure of not more than mHg, and immediately after completion of the reaction, the mixture was cooled in ice water. Table 1 shows the physical property values of the polycondensed copolymer.

Comparative Example 1 The procedure of Example 1 was repeated, except that lithium acetate and polyphosphoric acid were used instead of N-ethylpiperidine. Table 1 shows the physical property values of the obtained copolymer.

Comparative Example 2 Table 1 shows the physical properties of the copolymer obtained in the same manner as in Example 1 except that the DEG inhibitor was not used.

Examples 2 to 5 A polycondensation reaction was carried out in the same manner as in Example 1 except that the amount of N-ethylpiperidine was changed. Table 1 shows the physical property values of the obtained copolymer.

Examples 6 and 7 A polycondensation reaction was carried out in the same manner as in Example 1 except that morpholine or cyclohexylamine was used instead of N-ethylpiperidine. Table 1 shows the physical property values of the obtained copolymer.

[0030]

[Table 1]

[0031]

According to the production method of the present invention, heat stability and mechanical properties are excellent, and furthermore, since the turbidity is low, the spinning properties are improved.
Polyester-based congestion having excellent film processability can be used as it is in a conventional apparatus configuration.

[Brief description of the drawings]

FIG. 1 shows copolymers of Examples and Comparative Examples of the present invention.
It is a figure explaining the measuring method of the glass transition point by a differential scanning calorimeter.

Claims (8)

[Claims] 1. A polyesteramide copolymer is produced by reacting an aromatic dicarboxylic acid and a diol with an aminocarboxylic acid ester compound represented by the following general formula (1), and subjecting the reaction product to a polycondensation reaction. A method for producing a polyesteramide copolymer, which comprises adding a compound having an amino group as a DEG inhibitor. <Chemical Formula 1> H ₂ N—X—COOR where X is a group having any aromatic ring selected from benzene, naphthalene, pyrene, biphenyl, anthracene, and phenanthrene; R is an alkylene group;
Any hydrocarbon selected from an aromatic ring group and a saturated cyclic hydrocarbon machine. 2. The compound having an amino group is at least one of morpholine, N-methylmorpholine, N-ethylmorpholine, piperidine, N-methylpiperidine, N-ethylpiperidine, cyclohexylamine, benzylamine and N-methylpyrrolidine. The method for producing a polyester-based copolymer according to claim 1, wherein the amine comprises: 3. The polyester copolymer according to claim 1, wherein the compound having an amino group contains at least one kind of amine such as N-ethylpiperidine, morpholine, and cyclohexylamine. Manufacturing method. 4. The diol is ethylene glycol,
The method for producing a polyester-based copolymer according to claim 1, wherein the aromatic dicarboxylic acid is terephthalic acid. 5. The polyester resin according to claim 1, wherein a compound having an amino group is reacted with an aromatic dicarboxylic acid in an amount of 0.015 to 10 mol%. A method for producing a polymer. 6. A polyesteramide-based copolymer produced by the method according to any one of claims 1 to 8. 7. The polyester amide copolymer according to claim 6, having a melting point of 220 ° C. or higher. 8. The polyester copolymer according to claim 6, wherein the glass point transition is 75 ° C. or higher.