JP2003096174A - Process for producing aromatic polyester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing an aromatic polyester, which can realize solid-phase polymerization without causing powders to be fused to one another even when temperature is raised in a short time. SOLUTION: The process for producing an aromatic polyester is characterized in that monomers comprising a naphthalenedicarboxylic acid of formula (1), an acylated benzenediol of formula (2), and an acylated benzoic acid of formula (3), and if necessary, a benzendicarboxylic acid of formula (4) are copolymerized in the presence of an imidazole.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aromatic polyester.

[0002]

2. Description of the Related Art Aromatic polyesters are useful as thermoplastic resins having excellent heat resistance. As such an aromatic polyester, a repeating unit of formula (10) [In the formula, R ¹⁰ and R ¹¹ each independently represent a halogen atom, an alkyl group or an aryl group. a and b each independently represent an integer of 0 to 2, and a + b is 2 or less. When a is 2, R ¹⁰ may be the same or different from each other, and when b is 2, R ¹¹ may be the same or different from each other. ] The repeating unit represented by the formula (2
0) [In the formula, R ²⁰ represents a halogen atom, an alkyl group or an aryl group, and R ²¹ represents an alkyl group. c represents an integer of 0 to 2, and when c is 2, R ²⁰ may be the same or different from each other. ] The repeating unit and formula (30) [In the formula, R ³⁰ represents a halogen atom, an alkyl group or an aryl group, and R ³¹ represents an alkyl group. d represents an integer of 0 to 2, and when d is 2, R ³⁰ may be the same or different from each other. ] An aromatic polyester having a repeating unit represented by the following is also known (US Pat. No. 40678).
52, Special Table 2000-511220).

A method for producing such an aromatic polyester is represented by the formula (1) [In the formula, R ¹⁰ , R ¹¹ , a and b have the same meanings as described above. ] The naphthalene dicarboxylic acid shown by these, Formula (2) [In the formula, R ²¹ represents an alkyl group, and R ²⁰ and c have the same meanings as described above. ] And an acylated benzenediol represented by the formula (3) [In the formula, R ³¹ represents an alkyl group, and R ³⁰ and d have the same meanings as described above. ] The acylated oxybenzoic acid shown by these is used as a monomer, and the method of copolymerizing these monomers without a catalyst is mentioned. The degree of polymerization of the obtained aromatic polyester can be further increased by solid-phase polymerization in which it is powdered and heated to heat and polymerize in the solid-phase state.

[0004]

In such a conventional production method, when the aromatic polyester immediately after the copolymerization is made into a powder and the temperature is raised and heated in a short time, the powders tend to be fused to each other. Was particularly remarkable when the temperature was raised at 230 ° C. or higher for a short time. When the powders are fused to each other, it becomes difficult to handle the aromatic polyester after the solid phase polymerization. An object of the present invention is to provide a method for producing an aromatic polyester, which allows solid-phase polymerization without powders being fused to each other even when the temperature is raised in a short time.

[0005]

Under the circumstances, the inventors of the present invention have made diligent studies and found that the above-mentioned monomer was replaced by the formula (5). [Wherein R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, an alkyl group, a hydroxymethyl group, a cyanoalkyl group, a carboxyl group, an aminoalkyl group, a phenyl group, a benzyl group or a formyl group. . ] The aromatic polyester obtained by copolymerizing in the presence of imidazoles shown in the above, powdered this, found that even if the temperature is raised in a short time, solid-phase polymerization without fusion with each other The present invention has been reached.

That is, the present invention uses naphthalenedicarboxylic acids represented by formula (1), acylated benzenediols represented by formula (2) and acylated oxybenzoic acids represented by formula (3) as monomers. A method for producing an aromatic polyester, which comprises copolymerizing these monomers in the presence of an imidazole represented by the formula (5);
The benzenedicarboxylic acids represented by the formula (1), the formula (2), the formula (3) and the formula (4) are used as monomers, and these monomers are added in the presence of the imidazoles represented by the formula (5). The present invention provides a method for producing an aromatic polyester, which is characterized by copolymerization.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the naphthalene dicarboxylic acid represented by the formula (1), which is one of the monomers used in the production method of the present invention, the halogen atom in R ¹⁰ and R ¹¹ is a fluorine atom, Examples thereof include a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group include an alkyl group having about 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. Examples of the group include a phenyl group. a and b are each independently an integer of 0 to 2, and when a is 2, the two R ^10's may be the same or different from each other, and when b is 2, Two R ^11's may be the same or different. a + b is 2 or less, but when a = b = 1, R ¹⁰ and R ¹¹ may be the same as each other. It is preferable that a and b are a = b = 0.

Examples of such naphthalenedicarboxylic acids (1) are 2,6-naphthalenedicarboxylic acid, 4-chloro-2,6-naphthalenedicarboxylic acid, 4-methyl-2,
6-naphthalenedicarboxylic acid, 5-methyl-2,6-naphthalenedicarboxylic acid, 4-phenyl-2,6-naphthalenedicarboxylic acid, 4-chloro-8-methyl-2,6-
Examples thereof include 2,6-naphthalenedicarboxylic acids in which a carboxyl group such as naphthalenedicarboxylic acid is introduced at the 2nd and 6th positions. Such naphthalenedicarboxylic acids (1) are used alone or in combination of two or more.

Acylated benzenedioe represented by the formula (2)
R²⁰Halogen atom, alkyl in
Naphthalenedicarboxylic acid as the group and the aryl group
R in class (1)^TenAnd R¹¹Same as illustrated in
Like halogen atom, alkyl group and aryl group
I can name each one. R^{twenty one}The alkyl group represented by
For example, methyl group, ethyl group, propyl group, butyl group,
Examples include alkyl groups having about 1 to 5 carbon atoms such as ethyl groups.
These alkyl groups are, for example, fluorine atoms, salts
Substituted with halogen atoms such as elementary and bromine atoms
Good. Two R ^{twenty one}May be the same or different
It may be. c is an integer of 0 to 2, but c is 2
Two R if²⁰May be the same as each other
And may be different. c is preferably 0
Yes.

Such acylated benzenediols (2)
For example, 1,4-diacetoxybenzene, 1,
4-diacetoxy-2-methylbenzene, 1,4-diacetoxy-2-phenylbenzene, 1,4-diacetoxy-2-chlorobenzene, 1,4-diacetoxy-2-
Methyl-3-phenylbenzene, 1,4-diacetoxy-3-methyl-2-phenylbenzene, 1,4-diacetoxy-2-chloro-3-methylbenzene, 1,4-diacetoxy-3-chloro-2-methyl Benzene, 1,4
-Diacetoxy-2-chloro-3-phenylbenzene,
Acylated hydroquinones such as 1,4-diacetoxy-3-chloro-2-phenylbenzene,

1,3-diacetoxybenzene, 1,3-
Diacetoxy-2-methylbenzene, 1,3-diacetoxy-2-phenylbenzene, 1,3-diacetoxy-
2-chlorobenzene, 1,3-diacetoxy-2-methyl-4-phenylbenzene, 1,3-diacetoxy-
2,4-dimethylbenzene, 1,3-diacetoxy-2
-Chloro-4-methylbenzene, 1,3-diacetoxy-4-chloro-2-methylbenzene, 1,3-diacetoxy-2-chloro-4-phenylbenzene, 1,3-diacetoxy-4-chloro-2- Examples include acylated resorcinols such as phenylbenzene.

Such acylated benzenediols (2)
Can be used alone or in combination of two or more kinds. When two or more kinds are used in combination, an acylated hydroquinone and an acylated resorcinol may be used in combination, 2 of the modified hydroquinones
One or more kinds may be used in combination, or two or more kinds of acylated resorcinols may be used in combination.

In the acylated oxybenzoic acid represented by the formula (3), the halogen atom, alkyl group and aryl group represented by R ³⁰ are the same as those exemplified for R ¹⁰ and R ¹¹ in the naphthalenedicarboxylic acid (1). And a halogen atom, an alkyl group and an aryl group. Examples of the alkyl group represented by R ³¹ include
The same alkyl groups as those exemplified as R ²¹ in the acylated benzenediols can be mentioned. d is an integer of 0 to 2, and when d is 2, two R ^30's may be the same or different. d is preferably 0.

Examples of such acylated oxybenzoic acids (3) include 4-acetoxybenzoic acid, 4-acetoxy-2-methylbenzoic acid, 4-acetoxy-3-methylbenzoic acid and 4-acetoxy-2-phenylbenzoic acid. Acid, 4
-Acetoxy-3-phenylbenzoic acid, 4-acetoxy-2-chlorobenzoic acid, 4-acetoxy-3-chlorobenzoic acid, 4-acetoxy-2-methyl-3-phenylbenzoic acid, 4-acetoxy-3-methyl 2-Phenylbenzoic acid, 4-acetoxy-3-chloro-2-methylbenzoic acid, 4-acetoxy-2-chloro-3-methylbenzoic acid, 4-acetoxy-3-chloro-2-phenylbenzoic acid, 4 -Acetoxy-2-chloro-3-phenylbenzoic acid and the like can be mentioned.

By repeating the copolymerization of naphthalenedicarboxylic acids (1), acylated benzenediols (2) and acylated oxybenzoic acids (3), a repeating unit represented by the formula (10), represented by the formula (20). An aromatic polyester having a repeating unit represented by the formula and a repeating unit represented by the formula (30) can be obtained.

In the production method of the present invention, naphthalenedicarboxylic acids (1), acylated benzenediols (2) and acylated oxybenzoic acids (3) are used as monomers.
Together with formula (4) [In the formula, R ⁴⁰ represents a halogen atom or an alkyl group.
e represents an integer of 0 to 2, and when e is 2, R ^{40 s} may be the same or different. ] Benzene dicarboxylic acids represented by the following may be used. By using naphthalenedicarboxylic acids (1), acylated benzenediols (2), acylated oxybenzoic acids (3) and benzenedicarboxylic acids (4) as monomers, and copolymerizing these monomers, Repeating unit represented by formula (10), repeating unit represented by formula (20), repeating unit represented by formula (30) and formula (40) [In the formula, R ⁴⁰ and e have the same meanings as described above. ] It is possible to obtain an aromatic polyester having a repeating unit represented by the following.

In the benzenedicarboxylic acid represented by the formula (4), the halogen atom represented by R ⁴⁰ , the alkyl group and the aryl group are the same halogens as those exemplified for R ¹⁰ and R ¹¹ in the naphthalene dicarboxylic acid (1). Atoms, alkyl groups and aryl groups are included respectively. e is an integer of 0 to 2, but when e is 2, R ^40's may be the same as or different from each other. It is preferable that e is 0.

Examples of such benzenedicarboxylic acids (4) include terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 2-phenylterephthalic acid, 2-chloroterephthalic acid, 2-methyl-3-phenylterephthalic acid, 2- Methyl-3-phenyl terephthalic acid, 2-chloro-3-methyl terephthalic acid, 3-chloro-2-methyl terephthalic acid, 2-chloro-3-phenyl terephthalic acid, 3-chloro-2-phenyl terephthalic acid and the like can be mentioned. To be

In the production method of the present invention, the naphthalenedicarboxylic acids (1), the acylated benzenediols (2), the acylated oxybenzoic acids (3) and the benzenedicarboxylic acids (4) are used in the following ratios. 1) and benzenedicarboxylic acids (4)
The total amount used and the amount used of the acylated benzenediols (2) are usually substantially 1: 1 in terms of substance amount ratio (molar ratio), and are appropriately selected depending on the target aromatic polyester. For example, the obtained aromatic polyester is obtained by copolymerizing four kinds of naphthalenedicarboxylic acids (1), acylated benzenediols (2), acylated oxybenzoic acids (3) and benzenedicarboxylic acids (4). When it is an aromatic polyester, it is used (1) to
About 5 to 32.5 mol of the naphthalenedicarboxylic acids (1) and about 15 to 37.5 mol of the acylated benzenediols (2) based on 100 mol of the total monomers of (4),
The amount of the acylated oxybenzoic acid (3) is about 25 to 70 mol and the amount of the benzenedicarboxylic acid (4) is about 5 to 32.5 mol. An aromatic polyester obtained by using a monomer in the above range is preferable because the melting point tends to decrease and the moldability tends to improve.

The aromatic polyester obtained is obtained by copolymerizing only three kinds of naphthalene dicarboxylic acids (1), acylated benzenediols (2) and acylated oxybenzoic acids (3). When, the total amount of the monomers (1) to (3) used is 10
The naphthalene dicarboxylic acid (1) is 1 mol to 0 mol.
It is about 0 to 32.5 mol, the acylated benzenediols (2) is about 10 to 32.5 mol, and the acylated oxybenzoic acid (3) is about 35 to 80 mol. An aromatic polyester obtained by using a monomer in the above range is preferable because the melting point tends to decrease and the moldability tends to improve.

The acylated benzenediols (2) are represented by, for example, the formula (21) [In the formula, R ²⁰ and c each have the same meaning as described above. ] The benzenediols represented by the formula (62) [In the formula, R ²¹ has the same meaning as described above. ] It can manufacture by the method of making it react with the acid anhydride shown by these.

The acylated oxybenzoic acids are (3)
Is, for example, formula (31) [In the formula, R ³⁰ and d each have the same meaning as described above. ] The oxybenzoic acid represented by the formula (63) [In the formula, R ³¹ has the same meaning as described above. ] It can manufacture by the method of making it react with the acid anhydride shown by these.

Examples of the acid anhydrides represented by the formula (62) and the acid anhydrides represented by the formula (63) include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride and pivalic anhydride. Acid, 2-ethylhexanoic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, monochloroacetic anhydride, dichloroacetic anhydride,
Examples thereof include trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, and propionic anhydride. These acid anhydrides can be used alone or in admixture of two or more.

The amount of the acid anhydrides (62, 63) used is benzenediols (21) and oxybenzoic acids (3).
1 mol or more per 1 mol of the total amount of hydroxyl groups of 1),
It is preferably 1.1 mol or more, usually 1.5 mol or less, and preferably 1.2 mol or less.

The reaction is usually carried out without solvent and without catalyst, and the reaction temperature is usually 100 ° C. or higher, preferably 130 ° C. or higher, usually 200 ° C. or lower, preferably 160 ° C.
It is the following.

The reaction is carried out, for example, with benzenediols (2
The reaction between 1) and acetic anhydride (62) is carried out by mixing them, and the reaction between the oxybenzoic acid (31) and acetic anhydride (63) is also carried out by mixing them.

When R ²¹ and R ³¹ are the same, the benzenediols (21) and the oxybenzoic acids (31) can simultaneously react with the acid anhydrides (62, 63), for example benzenediols. An acylated benzenediol (2) and an acylated oxybenzoic acid (3) are obtained by a method of mixing (21) and an oxybenzoic acid (31) with an acid anhydride represented by the formula (62) or the formula (63). Can be manufactured simultaneously.

During the reaction, naphthalenedicarboxylic acids (1) and / or benzenedicarboxylic acids (4) may be present in the reaction system. Since the naphthalenedicarboxylic acids (1) and the benzenedicarboxylic acids (4) do not substantially react with the acid anhydrides (62, 63), the naphthalenedicarboxylic acids (1) and / or benzene used in the reaction mixture after the reaction are used. The dicarboxylic acids (4) will be included.

Such a reaction usually proceeds quantitatively, and is carried out by benzenediols (21) and oxybenzoic acids (3
When 1) is simultaneously reacted with acid anhydrides (62, 63), the reaction mixture after the reaction contains acylated benzenediols (2) and acylated oxybenzoic acids (3), Furthermore, when the reaction is carried out in the presence of naphthalenedicarboxylic acids (1) and / or benzenedicarboxylic acids (4), the reaction mixture contains naphthalenedicarboxylic acids (1) and / or benzenedicarboxylic acids (4).
It is included.

The production method of the present invention is a method of copolymerizing the naphthalenedicarboxylic acids (1), the acylated benzenediols (2) and the acylated oxybenzoic acid (3) in the presence of the imidazoles (5). Yes, naphthalene dicarboxylic acids (1), acylated benzenediols (2), acylated oxybenzoic acids (3) and benzenedicarboxylic acids (4) are copolymerized as monomers in the presence of imidazoles (5). May be.

In the imidazoles represented by the formula (5), the alkyl group in R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group or the like. Examples of the cyanoalkyl group include an alkyl group having about 1 to 5 and substituents having a cyano group introduced into an alkyl group having about 1 to 4 carbon atoms such as a cyanoethyl group, and examples of the aminoalkyl group include:
Examples thereof include a substituent in which an amino group is introduced into an alkyl group having about 1 to 4 carbon atoms such as an aminoethyl group.

Imidazoles in which R ⁵¹ is an alkyl group are preferable in that the flow initiation temperature of the aromatic polyester obtained can be increased, and more preferably R ⁵¹ is an alkyl group, and R ⁵² , R ⁵³ and R ⁵⁴ is a hydrogen atom.

Examples of such imidazoles (5) include imidazole, 1-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2,4-dimethylimidazole, 2-
Phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenylimidazole,
Examples include 4,5-imidazole dicarboxylic acid, 1-aminoethyl-2-methylimidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, 4-formylimidazole and the like.

The amount of the imidazoles (5) used is the total amount of the monomers used in the present invention, that is, as the monomers, naphthalene dicarboxylic acids (1), acylated benzenediols (2) and acylated oxys. When benzoic acids (3) are used, their total amount used, and when benzenedicarboxylic acids (4) are further used as a monomer, naphthalene dicarboxylic acids (1) and acylated benzenediols (2) are used. , 0.001 part by mass or more, preferably 0.003 parts by mass or more and usually 1 part by mass or less, per 100 parts by mass of the total amount of the acylated oxybenzoic acids (3) and benzenedicarboxylic acids (4) used, preferably 0.5 parts by mass or less, but especially preferably not more than 0.1 part by weight, R ⁵¹ is an alkyl group as imidazoles (5) Imidazole compounds, and further R
^When imidazoles in which ⁵¹ is an alkyl group and R ⁵² , R ⁵³ and R ⁵⁴ are hydrogen atoms are used, 0.004 parts by mass or more produces an aromatic polyester having a higher flow starting temperature. It is preferable because it is possible.

For copolymerization, for example, naphthalenedicarboxylic acids (1), acylated benzenediols (2), acylated oxybenzoic acids (3) and imidazoles (5) may be mixed, and benzenedicarboxylic acids ( When copolymerizing 4), benzenedicarboxylic acids (4) may be further mixed. Further, an acylated benzenediol (2) and an acylated oxybenzoic acid are reacted with an acid anhydride (62, 63) in the presence of naphthalene dicarboxylic acid (1) and further in the presence of benzenedicarboxylic acid (4). When it is allowed to react, the reaction mixture after the reaction may be mixed with the imidazoles (5).

The copolymerization temperature is usually 200 ° C. or higher, preferably 250 ° C. or higher, usually 400 ° C. or lower, preferably 320 ° C. or lower.

By copolymerization, aliphatic carboxylic acids corresponding to the used acid anhydrides (62, 63), specifically the formula (62-1) Or an aliphatic carboxylic acid represented by the formula (63-1) Although an aliphatic carboxylic acid represented by the formula (3) is produced, it is preferable to copolymerize while removing the aliphatic carboxylic acids out of the system. The copolymerization is performed until, for example, the aliphatic carboxylic acid (62-1, 63-1) is not produced.

Thus, naphthalenedicarboxylic acids (1), acylated benzenediols (2) and acylated oxybenzoic acids (3), and further benzenedicarboxylic acids (4) are copolymerized to form an aromatic polyester. After the copolymerization, the obtained aromatic polyester may be solid-phase polymerized. In order to carry out solid phase polymerization, the obtained aromatic polyester may be made into powder and heated.

The obtained aromatic polyester may be powdered, for example, by cooling and solidifying the aromatic polyester and then pulverizing it. The particle size of the powder is, for example, about 0.05 mm or more and about 3 mm or less. Solid phase polymerization is carried out by heating such a powder in a solid phase state, and usually 15
It may be heated to a temperature of 0 ° C. or higher, preferably 250 ° C. or higher, usually 400 ° C. or lower, preferably 330 ° C. or lower.
The heating is usually performed while raising the temperature, and the heating rate is usually 7 ° C /
More than time. By heating, the polymerization of the aromatic polyester proceeds in the solid state, and the degree of polymerization increases.

The aromatic polyesters obtained by the production method of the present invention do not fuse with each other even when the temperature of the powders is raised in a short time during solid phase polymerization. ℃ / hour or more, further 15 ℃
Even if the powder is heated at a high heating rate of not less than / hour, the powders do not fuse with each other to form an agglomerate, and the powdery material can be solid-phase polymerized to increase the degree of polymerization. The heating rate depends on the heating capacity of the heating device, but is usually 100
C./hour or less.

[0041]

EFFECTS OF THE INVENTION According to the production method of the present invention, an aromatic polyester can be produced by solid-phase polymerization without fusion of the powders even if the temperature is raised in a short time. It is possible to shorten the time required for solid phase polymerization by increasing the rate of temperature rise.

[0042]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 [Copolymerization] 2,6-naphthalenedicarboxylic acid 4 at room temperature
43.62 g ((1), 2.052 mol), hydroquinone 377.9 g ((2), 3.432 mol), 4-hydroxybenzoic acid 711.04 g ((3), 5.148 mol), terephthalic acid 227.27 g ((4), 1.36
8 mol) and acetic anhydride 1348.94 g (13.2 mol) were charged into a polymerization tank, and after stirring at the same temperature for 15 minutes,
The temperature was raised with stirring. When the temperature reached 145 ° C, the same temperature was maintained for 3 hours with stirring, and 44.62 g of 2,6-naphthalenedicarboxylic acid, 664.43 g of 1,4-diacetoxybenzene, 927.4 of 4-acetoxybenzoic acid.
A mixture containing 6 g and 227.27 g terephthalic acid was obtained.

After adding 0.046 g of 1-methylimidazole to the obtained mixture at the same temperature, the temperature rising rate was 0.57 ° C.
The temperature was raised to 310 ° C./min. Acetic acid was produced during the temperature rise, but the temperature was raised while removing the acetic acid outside the system.
Then, the temperature was kept at the same temperature for 3.5 hours to obtain an aromatic polyester. The obtained aromatic polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic polyester powder (particle size: about 0.1 mm to about 1 mm). The amount of 1-methylimidazole used was 2,6 contained in the mixture.
It corresponds to 0.002 parts by mass per 100 parts by mass of the total amount of naphthalenedicarboxylic acid, 1,4-diacetoxybenzene, 4-acetoxybenzoic acid and terephthalic acid.

[Solid Phase Polymerization 1 at Slow Temperature Rising Rate (Solid Phase Polymerization Time 8 Hours)] The powder obtained above was heated from 25 ° C. to 235 ° C. over 1 hour, and then from the same temperature to 305 ° C. The temperature is raised over 8 hours (the temperature rising rate is about 8.7 ° C./hour),
Then, the temperature was kept at the same temperature for 5 hours for solid phase polymerization. Then, the powder after solid-phase polymerization is cooled, and the powder after cooling is subjected to a flow tester [manufactured by Shimadzu Corporation, "CFT-500".
Mold ”] and extruding from a nozzle having an inner diameter of 1 mm and a length of 10 mm at a pressure of 9.81 mPa while heating at a temperature rising rate of 4 ° C./min, and the melt viscosity at the time of extruding is 4800 poise seconds (P).
It was 320 ° C. when the temperature indicating aS) was measured as the flow start temperature.

Example 2 [Solid Phase Polymerization 2 at Rapid Temperature Rise (Solid Phase Polymerization Time 3 hours)] The aromatic polyester powder obtained in Example 1 was heated from 25 ° C. to 235 ° C. over 1 hour. After heating, the temperature was raised from the same temperature to 305 ° C. over 3 hours (the temperature rising rate was about 23.3 ° C./hour), and then the temperature was kept at the same temperature for 5 hours for solid phase polymerization. The powder after solid state polymerization was cooled, and the flow starting temperature of the powder after cooling was measured in the same manner as above, and it was 319 ° C.

Examples 3 to 8 The amount of 1-methylimidazole used was 0.308, respectively.
g (Examples 3 and 4), 0.772 g (Examples 5 and 6), and 1.543 g (Examples 7 and 8) were operated in the same manner as in Example 1 to obtain a powder. Subsequently, regarding Examples 3, 5 and 7, as in Example 1, 23
The temperature was raised from 5 ° C. to 305 ° C. over 8 hours and solid phase polymerization was performed to obtain an aromatic polyester powder. For Examples 4, 6 and 8, 235 ° C. to 305 were used in the same manner as in Example 2.
The temperature was raised to 3 ° C. over 3 hours to carry out solid phase polymerization to obtain an aromatic polyester powder.

Comparative Example 1 The same procedure as in Example 1 was carried out except that 1-methylimidazole was not used, and the temperature was raised from 235 ° C. to 305 ° C. over 3 hours for solid phase polymerization. The fusion of the powder after the solid-state polymerization was strong, and the powder could not be loosened. Therefore, the flow initiation temperature after the solid-state polymerization was not measured.

Comparative Example 2 The same procedure as in Example 1 was carried out except that 1-methylimidazole was not used, and the temperature was raised from 235 ° C. to 305 ° C. over 8 hours for solid phase polymerization. The powder after the solid phase polymerization was fused. After loosening it by hand. The flow starting temperature was measured and found to be 317 ° C.

Amounts of monomers used in Examples 1 to 8 and Comparative Examples 1 and 2 and amounts of 1-methylimidazole ((1), (2), (3) and Te (4) monomers) The total amount is expressed in parts by mass per 100 parts by mass), the solid phase polymerization time, the flow initiation temperature of the aromatic polyester obtained by solid phase polymerization, and the fusion between the particles of the aromatic polyester. The results of “with and without” are summarized in Table 1.

[0051]

[Table 1]

Example 9 [Copolymerization] 2,6-naphthalenedicarboxylic acid 6 at room temperature
48.57 g ((1), 3.00 mol), hydroquinone 330.33 g ((2), 3.00 mol), 4-hydroxybenzoic acid 828.72 g ((3), 6.00 mol), and anhydrous After charging 1408.84 g (13.8 mol) of acetic acid in a polymerization tank and stirring at the same temperature for 15 minutes,
The temperature was raised with stirring. When the temperature reached 145 ° C., the same temperature was maintained for 3 hours with stirring, and 648.57 g of 2,6-naphthalenedicarboxylic acid, 582.54 g of 1,4-diacetoxybenzene and 108-acetoxybenzoic acid 108 were added.
A mixture containing 0.96 g was obtained. The resulting mixture was heated to 310 ° C at a heating rate of 0.57 ° C / min. Acetic acid was produced during the temperature rise, but the temperature was raised while removing the acetic acid outside the system. Then, 1-methylimidazole 1.8
After further adding 08 g, the temperature was kept at the same temperature for 1 hour to obtain an aromatic polyester. The obtained aromatic polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic polyester powder (particle size: about 0.1 mm to about 1 mm).
The amount of 1-methylimidazole used is 0.078 parts by mass per 100 parts by mass of the total amount of 2,6-naphthalenedicarboxylic acid, 1,4-diacetoxybenzene, and 4-acetoxybenzoic acid. The temperature of the powder obtained above was raised from 25 ° C. to 235 ° C. over 1 hour, then raised from the same temperature to 310 ° C. over 5 hours (heating rate was about 15.0 ° C./hour), and then the same. Solid phase polymerization was carried out by keeping the temperature for 3 hours. The powder after solid-phase polymerization was cooled, and the flow starting temperature of the powder after cooling was measured in the same manner as in Example 1, and it was 334 ° C. The resulting aromatic polyester did not show fusion between particles.

(Examples 10 to 14 and Comparative Examples 3 to 5) Examples 10 to 14 are 2,6-naphthalenedicarboxylic acid (1), hydroquinone (2) and 4-hydroxybenzoic acid in the weights shown in Table 2. Each monomer of acid (3), acetic anhydride and 1-
Methylimidazole was added, an acylation reaction and a transesterification reaction were carried out according to Example 1, and solid phase polymerization was carried out until the solid phase polymerization temperature shown in Table 2 was reached. Comparative Example 3
For # 5, the same operations as in Examples 10 to 14 were performed, except that 1-methylimidazole was not added.

The amounts of the monomers used in Examples 10 to 14 and Comparative Examples 3 to 5 and the amount of 1-methylimidazole ((1), (2) and (3) per 100 parts by weight of the total amount of the monomers). The solid phase polymerization time, the solid phase polymerization temperature, and the fusion between the particles of the aromatic polyester are collectively shown in Table 2. still,
In Comparative Examples 3 to 5, the fusion of the powder after the solid phase polymerization was strong and the powder could not be loosened, so that the flow starting temperature after the solid phase polymerization was not measured.

[0055]

[Table 2]

Regarding the above-mentioned Examples 2, 4, 6 and 8 and Comparative Example 2, the flow starting temperature of the powder obtained by the solid-state polymerization and the temperature of 235 ° C. to 305 ° C. for 8 hours and 1- Figure 1 shows the relationship with the amount of methylimidazole added.
Shown in.

[Brief description of drawings]

1 is a graph of Examples 1 to 5 and Comparative Example 1;
It is a figure which shows the relationship between the flow start temperature of the powder obtained by carrying out solid-phase polymerization, and the usage-amount of 1-methyl imidazole which made the temperature rising time from 5 degreeC to 305 degreeC 8 hours, and the horizontal axis is 2,6-. The amount of 1-methylimidazole used per 100 parts by mass of the total amount of naphthalenedicarboxylic acid, 1,4-diacetoxybenzene, 4-acetoxybenzoic acid and terephthalic acid (parts by mass), the vertical axis represents the flow start temperature (° C). Are shown respectively.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Satoshi Okamoto             6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd.             Inside the company F-term (reference) 4J029 AA01 AA06 AB01 AB04 AC02                       AD10 BB04A BB04B BB05A                       BB05B BG05X CB05A CB06A                       CB06B CC06A CC06B CG06                       CG14X EB05A EB05B EE05                       HA03A HB01 JC273 KE12                       KF07

Claims (8)

[Claims] 1. A formula (1) [In the formula, R ¹⁰ and R ¹¹ each independently represent a halogen atom, an alkyl group or an aryl group. a and b each independently represent an integer of 0 to 2, and a + b is 2 or less. When a is 2, R ¹⁰ may be the same or different from each other, and when b is 2, R ¹¹ may be the same or different from each other. ] The naphthalene dicarboxylic acid shown by these, Formula (2) [In the formula, R ²⁰ represents a halogen atom, an alkyl group or an aryl group, and R ²¹ represents an alkyl group. c represents an integer of 0 to 2, and when c is 2, R ²⁰ may be the same or different from each other. ] And an acylated benzenediol represented by the formula (3) [In the formula, R ³⁰ represents a halogen atom, an alkyl group or an aryl group, and R ³¹ represents an alkyl group. d represents an integer of 0 to 2, and when d is 2, R ³⁰ may be the same or different from each other. ] An acylated oxybenzoic acid compound represented by the following is used as a monomer, and these monomers are represented by the formula (5): [In the formula, R ^{51 to} R ⁵⁴ each independently represent a hydrogen atom, an alkyl group, a hydroxymethyl group, a cyanoalkyl group, a carboxyl group, an aminoalkyl group, a phenyl group, a benzyl group or a formyl group. ] The method for producing an aromatic polyester, which comprises copolymerizing in the presence of imidazoles. 2. A naphthalenedicarboxylic acid represented by the formula (1), an acylated benzenediol represented by the formula (2), an acylated oxybenzoic acid represented by the formula (3) and a formula (4). [In the formula, R ⁴⁰ represents a halogen atom or an alkyl group.
e represents an integer of 0 to 2, and when e is 2, R ^{40 s} may be the same or different. ] The manufacturing method of Claim 1 which uses benzene dicarboxylic acid shown by these as a monomer. 3. The acylated benzenediols (2) represented by the formula (2) have the formula (21): [In the formula, R ²⁰ and c each have the same meaning as described above. ] The benzenediols represented by the formula (62) [In the formula, R ²¹ has the same meaning as described above. ] An acylated oxybenzoic acid represented by the formula (3) is obtained by reacting with an acid anhydride represented by the formula (31) [In the formula, R ³⁰ and d each have the same meaning as described above. ] The oxybenzoic acid represented by the formula (63) [In the formula, R ³¹ has the same meaning as described above. ] The manufacturing method of Claim 1 or Claim 2 obtained by making it react with the acid anhydride shown by these. 4. The production method according to claim 1, wherein R ⁵¹ in the formula (5) is an alkyl group. 5. The production method according to claim 4, wherein R ⁵² , R ⁵³ and R ⁵⁴ in the formula (5) are hydrogen atoms. 6. The amount of the imidazoles represented by the formula (5) is 0.00 per 100 parts by mass of the total amount of the monomers used.
It is 1 mass part or more and 1 mass part or less, The manufacturing method in any one of Claims 1-5. 7. The method according to any one of claims 1 to 6, wherein after the copolymerization, the obtained aromatic polyester is made into a powder and heated to be solid-phase polymerized. 8. The manufacturing method according to claim 7, wherein heating is performed at a temperature rising rate of 7 ° C./hour or more at 230 ° C. or more.