JP2820574B2 - New polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyester, and more particularly, to a novel polyester having excellent heat resistance and solubility using 2,3-bis (4-carboxyphenyl) quinoxaline as an acid component.

[0002]

2. Description of the Related Art Polyester can obtain polymers having various properties such as crystallinity, non-crystallinity or liquid crystallinity depending on the type and combination of dicarboxylic acids, dihydroxy compounds or hydroxycarboxylic acids used as constituents. , Film, plastics, etc.

[0003] Among these, amorphous polyester is a material excellent in moldability, mechanical properties, dimensional stability and transparency, but the heat resistance of an amorphous polymer is determined by its glass transition temperature (Tg). For this reason, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and diphenols such as bisphenol A are generally used as constituent components of the amorphous polyester. By using these components, for example, an amorphous polyester having a Tg of about 180 ° C. can be obtained. However, in order to produce the above-mentioned aromatic polyester (polyarylate), polyethylene terephthalate, polybutylene terephthalate is used. Unlike polyesters using an aliphatic diol as a dihydroxy compound as described above, an interfacial polymerization or solution polymerization method (method A) using an acid chloride of a dicarboxylic acid and a diphenol, or a melt polymerization method using a diaryl dicarboxylate and a diphenol. It must be carried out by a melt method (Method C) using a dicarboxylic acid and an acetyl compound of diphenols (Method C). Here, the method A uses expensive acid chloride, and further purifies, isolates,
And a step of recovering the solvent and the like. In the method B, a polymer can be produced by melt polymerization, but it is necessary to use an expensive diaryl dicarboxylate as a raw material. In the method C, a relatively inexpensive raw material is used and a polymer can be produced by a melt polymerization method. However, since acetic acid is generated by the polymerization reaction, it is necessary to use a corrosion-resistant reaction vessel. As described above, the methods for producing amorphous polyarylate each have problems.

[0004] Makromol. Chem. Rapid. Commun. 8 , 113
Describes polyarylate using 2,3-bis (4-carboxyphenyl) quinoxaline as an acid component and various bisphenols as a diol component, and these use acid chloride as a raw material as described above.

On the other hand, polyesters using aliphatic diols, for example, polyesters with general-purpose aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, generally have a lower Tg than polyarylate and have a low crystallinity or poor crystallinity. However, there are problems such as poor solubility in organic solvents.

[0006]

Accordingly, an object of the present invention is to use an aliphatic diol as a diol component, and to provide an excellent heat resistance and an organic solvent by a melt polymerization method similar to that used for polyethylene terephthalate. An object of the present invention is to provide a novel polyester having excellent solubility.

[0007]

That is, the present invention provides a phenol / tetrachloroethane (1,1,2,2-tetrachloroethane) having at least 60 mol% of a structure represented by the following formula (I). In a mixed solvent (weight ratio 60/40), the reduced viscosity measured at a concentration of 1.2 g / dl and a temperature of 35 ° C. is as follows:
It is a new polyester of 0.3 or more.

[0008]

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[In the formula (I), X represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and 6 to 6 carbon atoms.
Represents 12 aryl groups or halogens. n represents 0, 1 or 2. In the formula (I), X is an alkyl group having 1 to 6 carbon atoms, 5
A cycloalkyl group having 10 to 10, an aryl group having 6 to 12 carbon atoms, or halogen. More specifically, a methyl group, an ethyl group, a propyl group or the like as an alkyl group, a cyclopentyl group or a cyclohexyl group as a cycloalkyl group, a phenyl group, a tolyl group, a naphthyl group as an aryl group, and chlorine as a halogen can be exemplified. n is 0, 1 or 2.

The polyester of the present invention has a structure represented by the above formula (I) in an amount of 60 mol% or more, but may partially contain another kind of structure as a subcomponent. Examples of the other structure include a repeating unit represented by the following formula (II) and / or (III).

[0011]

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[In the formulas (II) and (III), X and n
Is the same as in the above formula (I), and Y represents a divalent aliphatic, alicyclic or aromatic residue. R ₁ represents an alkylene group having 2 to 12 carbon atoms or a cycloalkylene group. Specific examples of Y include a p-phenylene group, an m-phenylene group, a 4,4′-diphenylene group, a 2,6-naphthylene group,

[0013]

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[M represents an alkali metal, and examples thereof include Na and K. ] Etc. can be exemplified.

Further, as R ₁ , an ethylene group,
Trimethylene group, tetramethylene group, propylene group,

[0016]

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And the like.

The polyester of the present invention may further contain a structure represented by the following (IV) or (V) as a subordinate component.

[0019]

Embedded image —OC—Z—CO—OR ₂ —O— (IV) —O—Z—CO— (V) [In the formulas (IV) and (V), Z is a divalent fat. Represents an aromatic, alicyclic or aromatic residue. R ₂ represents an alkylene group having 2 to 12 carbon atoms and a cycloalkylene group. Specific examples of Z include p-phenylene group, m-phenylene group, 4,4'-diphenylene group, 2,6-naphthylene group,

[0020]

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[M represents an alkali metal, and examples thereof include Na and K. ] Can be exemplified.

R ₂ represents an alkylene group or a cycloalkylene group having 2 to 12 carbon atoms, specifically, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group,

[0023]

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And the like.

These formulas (II), (III), (IV),
The other kinds of structures represented by (V) may be used alone or in combination of two or more, and the content thereof is preferably from 0 to 40 mol% of all repeating units in the polyester of the present invention,
More preferably 0 to 30 mol%, particularly preferably 0 to 2 mol%.
It is about 0 mol%.

The polyester of the present invention has the following formula (VI)

[0027]

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[In the formula (VI), X and n are the same as defined in the formula (I). Can be produced from an ester-forming derivative of 2,3-bis (4-carboxyphenyl) quinoxaline represented by the formula (I) and a dihydroxy compound corresponding to the polyester represented by the above formula (I), that is, neopentylene glycol.

Here, the ester-forming derivatives of the dicarboxylic acid represented by the formula (VI) include alkyl esters,
Aryl esters and the like can be mentioned.

The method for producing the polyester is not particularly limited, and a conventionally known method can be used.
For example, a direct polymerization method in which a dicarboxylic acid and a glycol are directly esterified and then polymerized, and a transesterification method in which a dicarboxylic acid dimethyl ester and a glycol are transesterified and then polymerized, can be preferably exemplified.

The polyester of the present invention was prepared in a phenol / tetrachloroethane (1,1,2,2-tetrachloroethane) mixed solvent (weight ratio: 60/40) at a concentration of 1.2 g /
dl, the reduced viscosity measured at a temperature of 35 ° C. is 0.3 or more. If the reduced viscosity is less than 0.3, the heat resistance and mechanical properties of the molded product obtained therefrom will be insufficient. The reduced viscosity is preferably 0.4 or more, particularly preferably 0.5 or more, and its upper limit is about 2.0.

The Tg of the polyester of the present invention is preferably 150 ° C. or higher, more preferably 160 ° C. or higher.

[0033]

The polyester of the present invention is mainly composed of 2,2
It has 3-bis (4-carboxyphenyl) quinoxaline as an acid component and neopentylene glycol as a diol component, and has excellent heat resistance, toughness, and excellent solubility in organic solvents. The polyester of the present invention has a high Tg of 160 ° C. or higher, which is high in polyarylate.
However, it can be industrially advantageously produced by basically the same melt polymerization process as general-purpose polyesters such as polyethylene terephthalate and polybutylene terephthalate. That is, the present invention provides an acid component of 2,
By using 3-bis (4-carboxyphenyl) quinoxaline and using a specific aliphatic diol, ie, neopentylene glycol, as the diol component, the above-mentioned excellent effects have been achieved.

The polyester of the present invention can be utilized as various molded articles, films and sheets, or as a solution or aqueous dispersion for coating films and the like, by utilizing the above-mentioned properties.

[0035]

EXAMPLES The present invention will be described below with reference to examples, where "parts" means parts by weight. Tg was measured by DSC at a rate of temperature rise of 10 ° C./min.

[0036]

Example 1 40 parts of 2,3-bis (4-carbomethoxyphenyl) quinoxaline, neopentylene glycol 2
0 parts and 0.014 parts of tetrabutyl titanate were placed in a reaction vessel equipped with a stirrer and a rectification column, and heated to 230 ° C. to distill off methanol produced by the transesterification reaction. After 6 parts of methanol have been distilled off, the reaction mixture is placed in a reaction vessel equipped with a stirrer and a vacuum distillation system, and at 290 ° C. for 30 minutes in a nitrogen stream at normal pressure, then about 20 mmHg
Under reduced pressure for 15 minutes, and further under reduced pressure of 0.5 mmHg for 90 minutes.
Allowed to react for minutes.

The obtained polymer was pale yellow and transparent, had a reduced viscosity of 0.86, and had a Tg of 177 ° C. This polymer was soluble in dimethylformamide, N-methyl-2-pyrrolidone, dioxane, tetrahydrofuran and chloroform.

[0038]

Example 2 40 parts of 2,3-bis (4-carbomethoxyphenyl) quinoxaline, neopentylene glycol 1
4 parts, 5 parts of ethylene glycol and 0.014 part of tetrabutyl titanate were placed in the same reaction vessel as in Example 1,
The methanol produced by heating to 180 ° C. was distilled off.
The reaction temperature was raised to 220 ° C. so that ethylene glycol was not distilled off, and a transesterification reaction was performed.

The amount of methanol distilled was 5.9 parts.
Next, the reaction mixture was placed in a reactor equipped with a stirrer and a vacuum distillation system, and was placed in a nitrogen stream at normal pressure for 30 minutes at 280 ° C., 15 minutes under a reduced pressure of about 20 mmHg, and 70 minutes under a reduced pressure of 0.5 mmHg. Allowed to react for minutes. The obtained polymer was pale yellow and transparent, had a reduced viscosity of 0.94, and had a Tg of 163 ° C.

The polymer comprises dimethylformamide,
It was dissolved in N-methyl-2-pyrrolidone, tetrahydrofuran, dioxane, and chloroform. Also NMR
The proportion of the neopentylene glycol component in the polymer determined by analysis was 83 equivalent% with respect to the acid component.

[0041]

Example 3 32 parts of 2,3-bis (4-carbomethoxyphenyl) quinoxaline, dimethyl terephthalate 4
Parts, 20 parts of neopentylene glycol and 0.014 part of tetrabutyl titanate in the same reaction vessel as in Example 1,
Transesterification and polymerization were carried out by a reaction method to obtain a pale yellow transparent polymer. The polymer has a reduced viscosity of 0.93, T
g was 164 ° C., and the compound was soluble in tetrahydrofuran, dioxane, chloroform, and dimethylformamide.

[0042]

Comparative Example 1 40 parts of 2,3-bis (4-carbomethoxyphenyl) quinoxaline, 16 parts of ethylene glycol,
Then, 0.014 part of tetrabutyl titanate was placed in the same reaction vessel as in Example 1, and heated to 190 ° C., whereby methanol was gradually distilled out by a transesterification reaction. Keep the reaction temperature 2 without removing ethylene glycol.
The temperature was raised to 20 ° C., and finally 5.8 parts of methanol was distilled off.

The reaction mixture was placed in the same reaction vessel for polymerization as in Example 1, and the mixture was heated at 280.degree.
Minutes, then under reduced pressure of about 20 mmHg for 15 minutes,
The reaction was performed under reduced pressure of mmHg for 110 minutes.

The obtained polymer was pale yellow and transparent, had a reduced viscosity of 1.04, and had a Tg of 189 ° C. However, when this polymer was immersed in tetrahydrofuran, the surface was whitened and completely insoluble.

Claims (1)

(57) [Claims] 1. A phenol / tetrachloroethane mixed solvent (weight ratio 60/40) having a concentration of 1.2 g / dl and a temperature of 35 ° C. A novel polyester having a measured reduced viscosity of 0.3 or more. Embedded image [Wherein X is an alkyl group having 1 to 6 carbon atoms, 5 to 1 carbon atoms.
A cycloalkyl group of 0, an aryl group having 6 to 12 carbon atoms, or halogen. n represents 0, 1 or 2. ]