JP2001048967A - Polyester polymer and the production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester polymer that can absorb a large amount of energy by including a specific structural unit, shows high solubility in organic solvents and is useful as an electronic material, a noise controlling material and a molding material. SOLUTION: This polyester polymer includes structural units represented by formula I (A is a divalent cycloalkane; B is a divalent bridge group in which at least one site that links to oxygen atom is an aromatic ring; R is an alkylene). The polyester is prepared by heating at least one of hydroxy compound, for example, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane or the like together with a dicarboxylic acid and/or its ester-formation derivative, for example, dimethyl hexane-1,4-dicarboxylate to effect the transesterification, followed by polycondensation reaction with additional heating under reduced pressure conditions. In a preferred embodiment, the content of the structural unit of formula I is >=30 mole % based on the whole weight of the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel energy-absorbing polyester polymer and a method for producing the same.

[0002]

2. Description of the Related Art Polyester has excellent mechanical properties,
It has been put to practical use in a wide range of fields because of its heat resistance and moldability. In the past, it was often used in low-cost, high-demand fields such as beverage bottles and general-purpose films.In recent years, along with the reduction in the weight of electrical and precision machinery products, specialty products such as optoelectronics In the field, expectations for polyester are increasing. In addition to polyester, development of polymer materials as energy absorbing materials, such as noise absorbing materials for highways and Shinkansen, has begun by utilizing the physical properties of polymers such as sub-dispersion. The energy absorbing material is required to absorb large energy without being destroyed. Polymers undergo a transition called sub-dispersion, which is a transition phenomenon that occurs at a temperature much lower than the glass transition.
These include rotation of side chains, deformation of main chains, and changes in intermolecular forces. This change, unlike the glass transition, can absorb externally applied energy without destruction or even deformation of the molded article. However, conventional polymers have rigidity in order to increase mechanical strength, and as a result, the motion of sub-dispersion is extremely small, the energy that can be absorbed by sub-dispersion is very small, and the noise of highways and Shinkansen However, there is a problem that such a large energy cannot be absorbed.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a polyester polymer having a large energy absorbing property and good electric properties when used as an electronic material, and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, the polyester polymer containing the structural unit represented by the general formula (I) has a large energy absorbing property. Have been found to have good electrical characteristics when used as an electronic material, and have completed the present invention.

The means for solving the above problems are as follows. That is, <1> a polyester polymer containing a structural unit represented by the following general formula (I).

[0006]

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(In the general formula (I), A represents a divalent cycloalkane group, B represents a divalent linking group in which at least one site bonding to an oxygen atom is an aromatic ring,
Represents an alkylene group. <2> The structural unit represented by the general formula (I) is a structural unit represented by the following general formula (II),
The polyester polymer according to <1>, which is at least one selected from the group consisting of a structural unit represented by I) and a structural unit represented by the following general formula (IV).

[0008]

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(In the general formula (II), R ₁ and R ₂ each independently represent a direct bond or an alkylene group having 1 to 7 carbon atoms, provided that R ₁ and R ₂ simultaneously represent a direct bond. R ₃ represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R ₄ and R ₅ each independently represent a hydrogen atom, a linear or branched alkylene group having 1 to 7 carbon atoms. Alkyl group, cycloalkane group having 3 to 10 carbon atoms, 6 to 1 carbon atoms
2 represents an aryl group, a halogen-substituted alkyl group, or a halogen atom, and R ₆ and R ₇ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, 10 cycloalkane groups, 6-1 carbon atoms
2 represents an aryl group, a halogen-substituted alkyl group, or a halogen atom. h and i each independently represent an integer of 1 to 4. )

[0010]

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(In the general formula (III), R ₁ , R ₂ , R ₃ ,
R ₆ , R ₇ , h and i have the same meanings as in the above formula (II). R ₈ represents a direct bond or a linear or branched alkylene group having 1 to 7 carbon atoms. )

[0012]

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(In the general formula (IV), R ₁ , R ₂ , R ₃ ,
R ₆ , R ₇ , h and i have the same meanings as in the above formula (II). <3> When the components constituting the polyester polymer are classified into a dicarboxylic acid component and a diol component, all of the dicarboxylic acid components are <1> or <2> represented by the following general formula (V). And the polyester polymer described in (1).

[0014]

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(In the general formula (V), R ₁ and R ₂ have the same meanings as those in the general formula (II). R ₉ is a hydrogen atom, a linear or branched type having 1 to 6 carbon atoms.) Represents an alkyl group or an aryl group having 6 to 12 carbon atoms.) <4> A molecule is obtained by adding an aromatic monocarboxylic acid represented by the following general formula (VI) and / or an ester-forming derivative thereof. <1> wherein the hydroxyl group at the chain end is blocked.
To <3>.

[0016]

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(In the general formula (VI), R ₁₀ is a hydrogen atom,
Represents an alkyl group having 1 to 6 carbon atoms or an aryl group;
₁₁ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an acetyl group, or a halogen atom.
j represents an integer of 1 to 5. <5> The method for producing a polyester polymer according to any one of <1> to <4>, wherein the method is represented by the following general formula (VI)
At least one dihydroxy compound selected from the group consisting of a compound represented by I), a compound represented by the following general formula (VIII), and a compound represented by the following general formula (IX); Heating the dicarboxylic acid represented by (V) and / or its ester-forming derivative under an inert atmosphere to cause esterification or transesterification;
A method for producing a polyester polymer, comprising performing polycondensation under reduced pressure.

[0018]

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(In the general formulas (VII) to (IX), R ₃ ,
R ₄ , R ₅ , R ₆ , R ₇ , h and i have the same meanings as those in formula (II). In formula (VIII), R ₈ has the same meaning as in formula (III). <6> The method for producing a polyester polymer according to <5>, further comprising adding an aromatic monocarboxylic acid represented by the general formula (VI) and / or an ester-forming derivative thereof.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polyester polymer of the present invention will be described in detail. [Polyester polymer] The polyester polymer of the present invention is characterized by containing a structural unit represented by the following general formula (I).

[0021]

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In the general formula (I), A represents a divalent cycloalkane group, B represents a divalent linking group in which at least one site bonding to an oxygen atom is an aromatic ring, and R is ,
Represents an alkylene group.

The polyester polymer of the present invention contains a cycloalkane structure in the structural unit as shown in the general formula (I). This cycloalkane structure is a very flexible structure in which σ bonds are connected. For example, cyclohexane can be freely deformed into a chair shape or a boat shape by sub-dispersion. The energy involved in this subdispersion is very large. Further, the polyester polymer of the present invention has a bisphenol derivative structure having a rigid phenylene ring directly bonded to cycloalkanedicarboxylic acid. This rigid structure promotes the deformation of the cycloalkane structure,
High mechanical strength can be realized when a polyester polymer is formed into a molded product.

Further, the polyester polymer of the present invention contains a carboxylic acid component which is not directly linked to an aromatic as shown by the general formula (I), so that it does not impair the conductivity when applied to electronics. There is an advantage.
Further, the polyester polymer of the present invention has a high solubility in an organic solvent, and can be applied to a molding method having good productivity such as coating, casting, and dipping.

In the polyester polymer of the present invention, the structural unit represented by the general formula (I) is represented by the following general formula (I)
It is preferably at least one selected from the group consisting of a structural unit represented by I), a structural unit represented by the following general formula (III), and a structural unit represented by the following general formula (IV).

[0026]

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In the general formula (II), R ₁ and R ₂ each independently represent a direct bond or an alkylene group having 1 to 7 carbon atoms. However, R ₁ and R ₂ do not simultaneously represent a direct bond. Examples of the alkylene group include a methylene group,
Examples include an ethylene group, a trimethylene group, and a tetramethylene group. In the general formula (II), R ₃ represents a linear or branched alkylene group having 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group.

In the general formula (II), R ₄ and R ₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms (for example, methyl, ethyl, n- Propyl group, iso-propyl group, n-butyl group, ter
a cycloalkane group having 3 to 10 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an aryl group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group) , A tolyl group, etc.), a halogen-substituted alkyl group, or a halogen atom.

In the general formula (II), R ₆ and R ₇ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms (for example, methyl, ethyl, n- Propyl group, iso-propyl group, n-butyl group, ter
a cycloalkane group having 3 to 10 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), an aryl group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group) , A tolyl group, etc.), a halogen-substituted alkyl group, or a halogen atom. h and i each independently represent an integer of 1 to 4.

[0030]

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In the general formula (III), R ₁ , R ₂ , R ₃ , R ₆ ,
R ₇ , h and i have the same meanings as those in the general formula (II). R ₈ represents a direct bond or a linear or branched alkylene group having 1 to 7 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and the like).

[0032]

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In the general formula (IV), R ₁ , R ₂ , R ₃ , R ₆ ,
R ₇ , h and i have the same meanings as those in the general formula (II).

Of the components represented by the general formulas (II) to (IV), those represented by the following structural formulas are particularly preferred.

[0035]

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Hereinafter, the components represented by formulas (II) to (IV) will be described in detail by dividing them into dicarboxylic acid components and diol components. When the components constituting the polyester polymer of the present invention are classified into a dicarboxylic acid component and a diol component, all of the dicarboxylic acid components are among the components represented by the general formulas (II) to (IV). It is very effective to use a dicarboxylic acid represented by the following general formula (V) or an ester-forming derivative thereof corresponding to the dicarboxylic acid component. That is, when a dicarboxylic acid and / or an ester-forming derivative thereof represented by the following general formula (V) is used, an extremely large energy can be absorbed by a flexible movement of a cyclohexane ring, and a strongly polar aromatic direct bond is formed. Since it does not contain a dicarboxylic acid, when the polyester polymer of the present invention is used in the electronic field such as an electrophotographic photoreceptor or an electromagnetic wave shielding film, it does not cause conductivity inhibition and can realize extremely excellent electric characteristics. it can.

[0037]

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In the general formula (V), R ₁ and R ₂ have the same meaning as in the general formula (II). R ₉ is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group). Or an aryl group having 6 to 12 carbon atoms (e.g., phenyl group,
Tolyl group).

Specific examples of the dicarboxylic acid represented by the general formula (V) or an ester-forming derivative thereof are shown below, but the present invention is not limited thereto. Cyclopropane-1,2-dicarboxylic acid, cyclobutane-1,
3-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclopentane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,
2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,1-dicarboxylic acid, cycloheptane-1,4-dicarboxylic acid, cyclooctane-
1,5-dicarboxylic acid, cyclononane-1,5-dicarboxylic acid, cyclodecane-1,6-dicarboxylic acid, cyclododecane-1,7-dicarboxylic acid, 2,5-dimethylcyclohexane-1,4-dicarboxylic acid, , 3,5,6
-Tetramethylcyclohexane-1,4-dicarboxylic acid, 2,2,3,3,5,5,6,6-octmethylcyclohexane-1,4-dicarboxylic acid, 1,4-dimethylcyclohexane-1,4- Dicarboxylic acid, dimethyl cyclopropane-1,2-dicarboxylate, cyclobutane-
Dimethyl 1,3-dicarboxylate, cyclobutane-1,2
Dimethyl dicarboxylate, dimethyl cyclopentane-1,3-dicarboxylate, dimethyl cyclohexane-1,4-dicarboxylate, dimethyl cyclohexane-1,2-dicarboxylate, dimethyl cyclohexane-1,3-dicarboxylate,

Dimethyl cyclohexane-1,1-dicarboxylate, dimethyl cycloheptane-1,4-dicarboxylate, dimethyl cyclooctane-1,5-dicarboxylate,
Dimethyl cyclononane-1,5-dicarboxylate, dimethyl cyclodecane-1,6-dicarboxylate, dimethyl cyclododecane-1,7-dicarboxylate, dimethyl 2,5-dimethylcyclohexane-1,4-dicarboxylate, 2,
Dimethyl 3,5,6-tetramethylcyclohexane-1,4-dicarboxylate, 2,2,3,3,5,5,6,6
Octomethylcyclohexane-1,4-dicarboxylate, 1,4-dimethylcyclohexane-1,4-
Dimethyl dicarboxylate, dimethyl 2,5-dimethylcyclohexane-1,4-dicarboxylate, 2,3,5,6-
Dimethyl tetramethylcyclohexane-1,4-dicarboxylate, dimethyl 2,2,3,3,5,5,6,6-octomethylcyclohexane-1,4-dicarboxylate,
Dimethyl 1,4-dimethylcyclohexane-1,4-dicarboxylate, diethyl cyclohexane-1,4-dicarboxylate, di-n-cyclohexane-1,4-dicarboxylate
-Propyl, di-iso-propyl cyclohexane-1,4-dicarboxylate, di-n-butyl cyclohexane-1,4-dicarboxylate, di-iso-butyl cyclohexane-1,4-dicarboxylate, cyclohexane-1,4
Di-tert-butyl dicarboxylate, di-n-pentyl cyclohexane-1,4-dicarboxylate, di-n-hexyl cyclohexane-1,4-dicarboxylate, diphenyl cyclohexane-1,4-dicarboxylate, cyclohexane-1 , 4-Dicarboxylic acid dinaphthyl, etc., of which cyclohexane-1,4-dicarboxylic acid dimethyl and cyclohexane-1,4-dicarboxylic acid represented by the following structural formulas have a large subdispersion energy. It is also chemically stable and particularly preferred.

[0041]

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When the components constituting the polyester polymer of the present invention are classified into a dicarboxylic acid component and a diol component, all of the diol components are represented by the general formulas (II) to (II).
Among the constituent components represented by (IV), at least one of the dihydroxy compounds represented by the following general formulas (VII) to (IX) corresponding to the diol component has a large energy in combination with the cycloalkane unit. It is preferable because it shows absorptivity.

[0043]

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In the general formula (VII), R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ , h and i have the same meanings as those in the general formula (II).

Specific examples of the dihydroxy compound represented by the general formula (VII) are shown below, but the present invention is not limited thereto. 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, bis (4-
(2-hydroxyethoxy) phenyl) methane, 2,2
-Bis (4- (2-hydroxyethoxy) -3-methyl-phenyl) propane, 1,1-bis (4- (2-hydroxyethoxy) phenyl) -1-phenylethane,
1,1-bis (4- (2-hydroxyethoxy) phenyl) diphenylmethane, 2,2-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) propane,
2,2-bis (4- (2-hydroxyethoxy) -3,
5-Diphenylphenyl) propane is particularly preferable because it has both rigidity and flexibility, and exhibits a large energy absorption in combination with a cycloalkane unit.

[0046]

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In the general formula (VIII), R ₃ , R ₆ , R ₇ , h and i have the same meanings as in the general formula (II). Also,
R ₈ has the same meaning as that in formula (III).

As specific examples of the dihydroxy compound represented by the general formula (VIII), in particular, 1,1-bis (4-
(2-Hydroxyethoxy) phenyl) cyclohexane is preferable because it has both rigidity and flexibility, and exhibits a large energy absorption in combination with a cycloalkane unit. The present invention is in no way limited to this compound.

[0049]

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In the general formula (IX), R ₃ , R ₆ , R ₇ , h and i have the same meanings as in the general formula (II).

Specific examples of the dihydroxy compound represented by the general formula (IX) are shown below, but the present invention is not limited thereto. Bis (4- (2-hydroxyethoxy) phenylene), bis (4- (2-hydroxyethoxy) -3-methylphenylene, bis (4- (2-
Hydroxyethoxy) -3-phenylphenylene and bis (4- (2-hydroxyethoxy) -3-fluorophenylene are particularly preferred because they have extremely high rigidity and exhibit large energy absorption in combination with a cycloalkane unit.

In the polyester polymer of the present invention, the ratio of the constitutional unit represented by the general formula (I) to the whole polymer is preferably at least 30 mol%, more preferably at least 50 mol%. . If this ratio is less than 30 mol%, the structural unit represented by the general formula (I) may not exhibit sufficient energy absorption.

The polyester polymer of the present invention can be prepared by adding an aromatic monocarboxylic acid represented by the following general formula (VI) and / or an ester-forming derivative thereof as a terminal blocking agent to obtain an electronic material such as an electromagnetic wave shielding film. When used in the field, the electrical properties are improved.

[0054]

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[0055] In the general formula (VI), R ₁₀ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, R ₁₁
Represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an acetyl group, or a halogen atom. j
Represents an integer of 1 to 5. That is, by blocking the hydroxyl group present at the terminal of the molecular chain, trapping of carriers by the hydroxyl group can be prevented, and the conductivity can be improved.

Specific examples of the aromatic monocarboxylic acid represented by the general formula (VI) or an ester-forming derivative thereof are shown below, but the present invention is not limited thereto. Methyl-3,5-dimethoxybenzoate, methyl-4-acetylbenzoate, methylbenzoate, methyl-4-methylbenzoate, methyl-3-methylbenzoate, methyl-4-ethylbenzoate, methyl-3-ethylbenzoate, methyl-4 -Propylbenzoate, methyl-3-propylbenzoate, methyl-4-isopropylbenzoate, methyl-3-is
o-propylbenzoate, methyl-4-butylbenzoate, methyl-3-butylbenzoate, methyl-4-
isobutyl benzoate, methyl-3-isobutyl benzoate, methyl-4-tertbutyl benzoate, methyl-3-tertbutyl benzoate, methyl-4-pentyl benzoate, methyl-3-pentyl benzoate, methyl-4-iso pentyl benzoate, Methyl-3-isopentylbenzoate, methyl-4-hexylbenzoate, methyl-3-hexylbenzoate, methyl-4-heptylbenzoate, methyl-3-heptylbenzoate, methyl-3,5-dimethylbenzoate, methyl-3,5 -Diethylbenzoate, methyl-3,5-dipropylbenzoate, methyl-3,5-diisopropylpropylbenzoate, methyl-
3,5-dibutylbenzoate, methyl-3,5-dii
sobutyl benzoate,

Methyl-3,5-ditertbutylbenzoate, methyl-3,5-dipentylbenzoate, methyl-3,5-dipentylbenzoate, methyl-3,5-dihexylbenzoate, methyl-3,5-
Diheptyl benzoate, methyl-4-methoxybenzoate, methyl-3-methoxybenzoate, methyl-
4-ethoxybenzoate, methyl-3-ethoxybenzoate, methyl-4-propoxybenzoate, methyl-3-propoxybenzoate, methyl-4-iso
Propoxybenzoate, methyl-3-isopropoxybenzoate, methyl-4-butoxybenzoate,
Methyl-3-butoxybenzoate, methyl-4-is
obutoxybenzoate, methyl-3-isobutoxybenzoate, methyl-4-tertbutoxybenzoate, methyl-3-tertbutoxybenzoate, methyl-4-pentoxybenzoate, methyl-3-pentoxybenzoate, methyl-4-isopen Toxibenzoate, methyl-3-isopentoxybenzoate, methyl-3,5-diethoxybenzoate, methyl-3,5-dipropoxybenzoate, methyl-3,5
-Diisopropoxybenzoate, methyl-3,5-
Dibutoxybenzoate, methyl-3,5-diisobutoxybenzoate, methyl-3,5-ditertbutoxybenzoate, methyl-3,5-dipentoxybenzoate, methyl-3,5-diisopentoxybenzoate,

Methyl-4-phenylbenzoate, methyl-3-phenylbenzoate, methyl-4-naphthylbenzoate, methyl-3-naphthylbenzoate, methyl-3,5-diphenylbenzoate, methyl-3,
5-dinaphthylbenzoate, methyl-4-benzylbenzoate, methyl-3-benzylbenzoate, methyl-4- (2-phenylethyl) benzoate, methyl-3- (2-phenylethyl) benzoate, methyl-
4- (3-phenylpropyl) benzoate, methyl-
3- (3-phenylpropyl) benzoate, methyl-
4- (2-phenyl-isopropyl) benzoate,
Methyl-3- (2-phenyl-isopropyl) benzoate, methyl-4- (4-phenylbutyl) benzoate, methyl- (3-phenylbutyl) benzoate,
Methyl-4- (5-phenylpentyl) benzoate,
Methyl-3- (5-phenyl) pentylbenzoate,
Methyl-4- (6-phenylhexyl) benzoate,
Methyl-3- (6-phenylhexyl) benzoate,
Methyl-4- (7-phenylheptyl) benzoate,
Methyl-3- (7-phenylheptyl) benzoate,
Methyl-3,5-dibenzylbenzoate, methyl-
3,5-diethylphenylbenzoate, methyl-3,
5-di (3-phenylpropyl) benzoate, methyl-3,5-di (4-phenylbutyl) benzoate,

Methyl-3,5-di (5-phenylpentyl) benzoate, methyl-3,5-di (6-phenylhexyl) benzoate, methyl-3,5-di (7-phenylheptyl) benzoate, methyl- 4-fluorobenzoate, methyl-3-fluorobenzoate, methyl-3,5-difluorobenzoate, methyl-4-bromobenzoate, methyl-3-bromobenzoate, methyl-3,5-dibromobenzoate, methyl-4-chloro Benzoate, methyl-3-chlorobenzoate, methyl-3,5-dichlorobenzoate, 3,5-dimethoxybenzoate, ethyl-3,5-dimethoxybenzoate, propyl-3,5-dimethoxybenzoate,
n-butyl-3,5-dimethoxybenzoate, isobutyl-3,5-dimethoxybenzoate, tertbutyl-3,5-dimethoxybenzoate, n-heptyl-
3,5-dimethoxybenzoate, n-hexyl-3,5
-Dimethoxybenzoate, phenyl-3,5-dimethoxybenzoate and the like.

Among them, methyl-3,5-dimethoxybenzoate and 3,5-dimethoxybenzoate represented by the following structural formulas have good reactivity, high productivity of polyester polymer, high terminal blocking rate, This is preferable because it hardly causes a carrier trap. Of these, methyl-3,5-dimethoxybenzoate is particularly preferred because of its high heat resistance and no coloration of the polyester polymer.

[0061]

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The blocking ratio of molecular chain terminals by these terminal blocking agents is preferably 70% or more, more preferably 80% or more. When the blocking ratio is less than 70%, carrier traps due to terminal hydroxyl groups cannot be ignored, and the conductivity decreases when used for applications in which carrier hopping is performed to impart conductivity.

In the polyester polymer of the present invention, as the dicarboxylic acid component, other than the dicarboxylic acid represented by the general formula (V) or the ester-forming derivative thereof, the dicarboxylic acid or the ester-forming derivative thereof includes: Known materials used as a raw material of the polyester polymer are exemplified. For example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-
Naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid Acid, 2,3-naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as 2,7-naphthalenedicarboxylic acid and 4,4′-biphenyldicarboxylic acid or ester-forming derivatives thereof, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and dicyclodecanedicarboxylic acid and ester-forming properties thereof Derivatives, succinic acid, maleic acid, aliphatic dicarboxylic acids such as sebacic acid or ester-forming derivatives thereof, and the like.Of these, the reactivity is good, the productivity of the polyester polymer is high, and the heat resistance is also high. Of these, terephthalic acid and 2,6-naphthalene acid are most preferred.

In the polyester polymer of the present invention, as the dihydroxy compound that can be used in addition to the above-mentioned dihydroxy compound, there may be mentioned known ones used as a raw material of the polyester polymer. For example, ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3- (2-methyl) propanediol, 1,5-pentyl glycol, 1,4- (2-methyl) butanediol, 1,3- Aliphatic diols such as (2-ethyl) propanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol;

1,4-cyclohexanediol, 1,4
-Cyclohexane dimethylol, 1,2-cyclohexanediol, 1,2-cyclohexane dimethylol,
1,3-cyclohexanediol, 1,3-cyclohexane dimethylol, 1,3-cyclopentanediol,
1,3-cyclopentane dimethylol, 1,2-cyclopentanediol, 1,2-cyclopentanedimethylol, 1,5-cyclooctanediol, 1,5-cyclooctanedimethylol, 1,4-cyclooctanediol 1,4-cyclooctane dimethylol, 1,3-cyclooctanediol, 1,3-cyclooctane dimethylol, 1,2-cyclooctanediol, 1,2-cyclooctane dimethylol, tricyclodecane dimethylol, etc. An alicyclic diol,

1,4-benzene dimethylol, 1,3-
Benzene dimethylol, 1,2-benzene dimethylol, 2,6-naphthalenedimethylol, 1,2-naphthalenedimethylol, 1,3-naphthalenedimethylol,
1,4-naphthalenedimethylol, 1,5-naphthalenedimethylol, 1,6-naphthalenedimethylol, 1,
7-naphthalenedimethylol, 1,8-naphthalenedimethylol, 2,3-naphthalenedimethylol, 2,4-
Examples include aromatic diols such as naphthalenedimethylol, 2,5-naphthalenedimethylol, and 2,7-naphthalenedimethylol. Of these, ethylene glycol and 1,4-butylene glycol having extremely high productivity are preferable. .

The polyester polymer of the present invention is characterized by being dissolved in an organic solvent containing any one of tetrahydrofuran, methyl ethyl ketone and toluene as a main component in an amount of 10% by weight or more. Conventionally, polyethylene terephthalate, which is a generally used polyester, has high crystallinity and therefore has extremely low solubility in organic solvents. However, since the polyester polymer of the present invention contains the structural unit represented by the general formula (I), it is amorphous, has high solubility in an organic solvent, and can be formed by coating, casting, dipping, or the like. It is possible, and is particularly suitable for fields requiring lightness and shortness such as the electronics field.

Examples of the solvent for dissolving the polyester polymer of the present invention include the following, in addition to the above three kinds of organic solvents. Aromatic hydrocarbons such as xylene and styrene, chlorinated aromatic hydrocarbons such as monochlorobenzene, chloroaliphatic hydrocarbons such as dichloromethane and chloroform, methanol, ethanol, isopropyl alcohol, 1-butanol and 2-butanol Alcohols, esters such as methyl acetate, ethyl acetate, propyl acetate, and isopropyl acetate; ethers such as 1,4-dioxane and ethyl ether; ketones such as acetone and methyl isobutyl ketone; ethylene glycol monomethyl ether; ethylene glycol mono Ethyl ether,
Examples thereof include glycol ethers such as ethylene glycol monobutyl ether, alicyclic hydrocarbons such as cyclohexanone and cyclohexanol, and aliphatic hydrocarbons such as n-hexane. These may be used alone or in combination of two or more.

Of these, chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons are extremely high in solubility, but are not preferred because they contain chlorine harmful to the human body and the environment. Since the polyester polymer of the present invention dissolves in an organic solvent mainly containing any of tetrahydrofuran, methyl ethyl ketone and toluene having low solubility as compared with these, human body, without adversely affecting the environment, dipping,
It is particularly excellent in that it can be formed by dissolving a polyester polymer in a solvent once, such as coating and casting.

[Production Method of Polyester Polymer] The production method of the polyester polymer of the present invention is represented by the general formula (V):
And a dicarboxylic acid and / or an ester-forming derivative thereof, an arbitrary dicarboxylic acid and / or an ester-forming derivative thereof, and at least one selected from the group of compounds represented by formulas (VII) to (IX). One kind of dihydroxy compound and any dihydroxy compound, and if necessary, an aromatic monocarboxylic acid represented by the general formula (VI) and / or an ester-forming derivative thereof together with a known catalyst under an inert atmosphere. Heating and stirring, discharging the condensed distillate, and further creating a vacuum atmosphere promote the discharge of the distillate and produce the polyester polymer in one step. In this method, a polyester polymer can be produced at very low cost.

The method for producing the polyester polymer of the present invention will be described in detail. As a raw material, the general formula (V)
A dicarboxylic acid and / or an ester-forming derivative thereof, and an optional dicarboxylic acid, and the compound represented by the general formula (VII)
To (IX), at least one dihydroxy compound selected from the group of compounds represented by formulas (IX), an arbitrary dihydroxy compound, and, if necessary, an aromatic monocarboxylic acid represented by the formula (VI) and / or Or an ester-forming derivative thereof, and the necessary amount thereof and an esterification or ester exchange catalyst such as a metal acetate are heated and stirred at 120 to 140 ° C. under a nitrogen atmosphere to perform esterification or ester exchange. Confirm the distillation of water or alcohol resulting from. If distillation is confirmed, raise the temperature to 5-30.
The temperature is raised at a rate of ° C / hr to reach 180 to 210 ° C. Thereafter, at a rate of 5-15 ° C./hr, 220-23
Raise the temperature to 0 ° C. This temperature is maintained for 1 to 3 hours, and the amount of water or alcohol distilled out is distilled at 95% or more of the theoretical amount that can be calculated from the preparation.

Next, a polymerization catalyst and an antioxidant are added, and the system is evacuated. First, the pressure is gradually reduced from normal pressure to 1 Torr or less and the temperature is gradually increased to 250 to 280 ° C. over 1 to 2 hours. Maintain a state of 250 to 280 ° C. at 1 Torr or less, and wait until the stirring torque reaches a desired value. When the stirring torque reaches a desired value, the stirring is stopped, nitrogen pressure is applied to extrude the produced polyester polymer, cooled through water, and cut with a rotary cutter to form pellets. Thus, a polyester polymer can be obtained in one step. In addition, since no solvent is used, the environment is not adversely affected and the cost can be reduced.

As the esterification or transesterification catalyst used in the method for producing a polyester polymer of the present invention, known catalysts used for ordinary polyester polymerization can be used. For example, zinc acetate, calcium acetate, acetic acid Acetates such as manganese, lead acetate and cobalt acetate, iron oxides,
Oxides such as zinc oxide and lead oxide; titanates such as tetrabutoxytitanium; Among these,
Zinc acetate is particularly preferred because it has relatively high catalytic activity, can be added in a small amount, and does not easily become contaminated in the polyester after polymerization.

As the polymerization catalyst used in the method for producing a polyester polymer of the present invention, known catalysts used for ordinary polyester polymerization can be used. For example, germanium oxide, antimony trioxide, tetrabutoxytitanium and the like can be used. Is mentioned. Among these, germanium oxide is particularly preferred in view of the transparency of the polyester.

As the antioxidant used in the process for producing the polyester polymer of the present invention, known antioxidants used in ordinary polyester polymerization can be used. Phosphate esters such as trimethylphosphoric acid and triethylphosphoric acid can be used. Kind
It is particularly preferable without inhibiting the polymerization reaction.

[0076]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following description, “parts” means “parts by weight”. Example 1 0.4 mol of dimethyl cyclohexane-1,4-dicarboxylate was used as a starting dicarboxylic acid ester,
As the dihydroxy compound, 2,2-bis (4- (2-
0.28 mol of hydroxyethoxy) phenyl) propane, 0.8 mol of ethylene glycol, and 4 × 10 ⁻⁴ mol of zinc acetate as a transesterification catalyst were charged into a 300 ml flask, the atmosphere in the flask was changed to a nitrogen atmosphere, and the temperature in the flask was lowered. The temperature was raised to 150 ° C. The top temperature of the rectification column provided in the flask rose from room temperature to 62 ° C., and methanol as a transesterification distillate started to distill.
The heating was continued at a rate of 0 ° C./hr. The temperature inside the flask is 21
At 0 ° C., 65% of the theoretical amount of methanol calculated from the raw material charge was distilled off. The temperature in the flask was further increased to 230 ° C. at a rate of 10 ° C./hr. When the temperature in the flask reached 220 ° C., the overhead temperature increased to 140 ° C., and methanol and ethylene glycol excessively charged were distilled off azeotropically, and soon the overhead temperature reached 189 ° C. The only product was ethylene glycol. The amount of methanol distilled before azeotropic distillation was 90% of the theoretical amount, and the total amount of methanol and ethylene glycol distilled after heating to 230 ° C. was 98% of the theoretical amount.

Next, 3.2 × 10 ^-4 mol of germanium oxide as a polymerization catalyst and 4.4 × 10 ^-4 mol of trimethyl phosphate as an antioxidant were gradually added to the flask in an aqueous solution state. After stirring for about 30 minutes, the catalyst and the antioxidant were uniformly dispersed. Next, the pressure inside the flask was gradually reduced while increasing the temperature. In 2 hours, the degree of vacuum was increased to 0.7 Torr, and the temperature in the flask was increased to 280 ° C. The amount of ethylene glycol as a condensed distillate was 95% of the theoretical amount calculated from the charged amount. Set the degree of vacuum to 0.
At 8 Torr or less, while keeping the temperature in the flask at 280 ° C., the polymerization was allowed to proceed, and it was confirmed that the stirring torque was sufficiently increased. The polymerization was terminated, and the nitrogen pressure was increased to 4 kgf / cm.
Over a period of ² hours, the polyester polymer was extruded into a quench pool to obtain pellets. The yield of the polyester polymer was 97 g. Gel Permeation Chromatography (GPC) for the obtained polyester polymer
The weight average molecular weight in terms of polystyrene as measured with HLC8020 (manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent was 85,000. When the glass transition temperature was measured by DSC3110 (manufactured by Material Analysis and Characterization Co., Ltd.), it was found to be 65 ° C.
Met.

The temperature and energy at which the sub-dispersion of the polyester polymer occurs are determined by the rheograph solid S-1.
(Manufactured by Toyo Seiki Co., Ltd.), and the subdispersion energy of polyethylene terephthalate synthesized in Comparative Example 1 described later was 1
As a result of the evaluation using the relative value of the above, a very large value of 150 was shown. Furthermore, the solubility of this polyester polymer was evaluated as to whether it was soluble or insoluble under the condition of 10% by weight of the polymer for three types of tetrahydrofuran, methyl ethyl ketone / toluene mixed solvent (weight ratio: 8/2), and toluene. . As a result, this polyester polymer was soluble in all solvents. Further, the structure of the obtained polyester polymer was confirmed by IR. The spectrum is shown in FIG.

Example 2 In Example 1, 0.28 mol of 1,1-bis (4- (2-hydroxyethoxy) phenyl) cyclohexane and 0.8 mol of ethylene glycol were used as the starting dihydroxy compound. except,
A polyester polymer was synthesized in the same manner as in Example 1, and the same evaluation was performed.

Example 3 Example 1 was repeated except that 0.28 mol of bis (4- (2-hydroxyethoxy) phenylene) and 0.8 mol of ethylene glycol were used as the starting dihydroxy compound. A polyester polymer was synthesized in the same manner as in Example 1, and the same evaluation was performed.

Example 4 In Example 1, 0.4 mol of 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane and 0.8 mol of ethylene glycol were used as the starting dihydroxy compound. Except for Example 1,
A polyester polymer was synthesized in the same manner as described above, and the same evaluation was performed.

Example 5 In Example 1, 0.12 mol of 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane and 0.8 mol of ethylene glycol were used as starting dihydroxy compounds. Except for the above, a polyester polymer was synthesized in the same manner as in Example 1, and the same evaluation was performed.

Example 6 Example 1 was repeated except that 0.12 mol of dimethyl cyclohexane-1,4-dicarboxylate and 0.28 mol of dimethyl 2,6-naphthalenedicarboxylate were used as the starting dicarboxylic acid ester. Is
A polyester polymer was synthesized in the same manner as in Example 1, and the same evaluation was performed.

Example 7 In Example 1, 0.008 mol of methyl-3,5-dimethoxybenzoate was added as a terminal blocking agent, and 2,2-bis (4- (2-hydroxy) was used as a starting dihydroxy compound. A polyester polymer was synthesized and evaluated in the same manner as in Example 1 except that 0.272 mol of ethoxy) phenyl) propane and 0.8 mol of ethylene glycol were used.

Comparative Example 1 In Example 1, dimethyl terephthalate 0.4 was used as the starting dicarboxylic acid ester.
A polyester polymer (polyethylene terephthalate) was synthesized in the same manner as in Example 1, except that 0.8 mol of ethylene glycol was used as the raw material dihydroxy compound.

Comparative Example 2 In Example 1, dimethyl terephthalate 0.4 was used as the starting dicarboxylic acid ester.
A polyester polymer was synthesized in the same manner as in Example 1 except that mol was used, and the same evaluation was performed.

Comparative Example 3 A polyester polymer was synthesized in the same manner as in Example 1 except that 0.8 mol of ethylene glycol was used as the raw material dihydroxy compound, and the same evaluation was performed. .

Comparative Example 4 A commercially available bisphenol A-type polycarbonate (Panlite manufactured by Teijin Limited) was evaluated in the same manner as in Example 1.

The evaluation results of Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 1 below.

[0090]

[Table 1]

From the results shown in Table 1, all of the polyester polymers of the present invention obtained in Examples 1 to 7 have a large subdispersion energy, and absorb external energy without destruction of the polymer structure. It turns out that the ability to do is high. Further, it has high solubility in an organic solvent and has extremely good moldability. On the other hand, the polyester polymer and the polycarbonate obtained in Comparative Examples 1 to 4 each have a small subdispersion energy, and when a large amount of energy is applied from the outside, they cannot absorb it, and the structure of the polymer is destroyed. Would. Furthermore, in Comparative Examples 1 and 4, the solubility in the organic solvent is low, and the molding method or the solvent used is limited. Further, in Comparative Example 2, the dihydroxy compound represented by the general formula (VII) was contained, and in Comparative Example 3, the subdispersion was carried out despite the fact that the dicarboxylic acid represented by the general formula (V) was contained. Low energy and low energy absorption. That is, as in the present invention, by having a structural unit in which the dihydroxy compound represented by the general formula (VII) and the dicarboxylic acid represented by the general formula (V) are directly bonded, the low-temperature molecular chains of each other can be obtained for the first time. It can be seen that exercise can be increased, and large subdispersion energy and high energy absorption can be realized.

[0092]

Since the polyester polymer of the present invention contains the structural unit represented by the above general formula (I), it shows a large subdispersion energy, shows a high energy absorption, and can be used for, for example, electronics and highways. And as a noise-preventing material for Shinkansen. Further, since the polyester polymer of the present invention contains a carboxylic acid component that is not directly linked to aromatics, there is an advantage that the conductivity is not impaired when applied to electronic applications. Further, the polyester polymer of the present invention has a high solubility in an organic solvent, and can be applied to a molding method having good productivity such as coating, casting, and dipping.

[Brief description of the drawings]

FIG. 1 shows the I of the polyester polymer obtained in Example 1.
It is a figure showing an R spectrum.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Ichiro Takekawa 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture F-Terms in Fuji Xerox Co., Ltd. JF571 KE02

Claims (6)

[Claims] 1. A polyester polymer comprising a structural unit represented by the following general formula (I). Embedded image (In the general formula (I), A represents a divalent cycloalkane group, B represents a divalent linking group in which at least one site bonding to an oxygen atom is an aromatic ring, and R represents an alkylene group. Represents a group.) 2. The structural unit represented by the general formula (I) includes a structural unit represented by the following general formula (II), a structural unit represented by the following general formula (III), and a structural unit represented by the following general formula (I)
The polyester polymer according to claim 1, which is at least one member selected from the group consisting of structural units represented by V). Embedded image (In the general formula (II), R ₁ and R ₂ each independently represent a direct bond or an alkylene group having 1 to 7 carbon atoms.
R ₁ and R ₂ do not simultaneously represent a direct bond. R
₃ represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R ₄ and R ₅ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms. Represents a cycloalkane group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group, or a halogen atom, and R ₆ and R ₇ are each independently a hydrogen atom, a carbon atom having 1 to 7 carbon atoms. Represents a linear or branched alkyl group, a cycloalkane group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group, or a halogen atom. h and i each independently represent an integer of 1 to 4. ) (In the general formula _{(III), R 1, R} 2, R 3, R 6, R 7, h and i are, .R ₈ have the same meaning as the general formula (II)
It represents a direct bond or a linear or branched alkylene group having 1 to 7 carbon atoms. ) (In the general formula (IV), R ₁ , R ₂ , R ₃ , R ₆ , R ₇ , h and i have the same meanings as those in the general formula (II).) 3. When the components constituting the polyester polymer are classified into a dicarboxylic acid component and a diol component,
3. The polyester polymer according to claim 1, wherein all of the dicarboxylic acid components are represented by the following general formula (V). Embedded image (In the general formula (V), R ₁ and R ₂ have the same meanings as in the general formula (II). R ₉ is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms.) Or carbon number 6-1
2 represents an aryl group. ) 4. The method according to claim 1, wherein the hydroxyl group at the terminal of the molecular chain is blocked by adding an aromatic monocarboxylic acid represented by the following general formula (VI) and / or an ester-forming derivative thereof. The polyester polymer according to the above. Embedded image (In the general formula (VI), R ₁₀ is a hydrogen atom, having 1 to 6 carbon atoms.
R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an acetyl group, Or a halogen atom. j is 1 to
Represents an integer of 5. ) 5. The method for producing a polyester polymer according to claim 1, wherein the compound has the following general formula (VI)
At least one dihydroxy compound selected from the group consisting of a compound represented by I), a compound represented by the following general formula (VIII), and a compound represented by the following general formula (IX); Heating the dicarboxylic acid represented by (V) and / or its ester-forming derivative under an inert atmosphere to cause esterification or transesterification;
A method for producing a polyester polymer, comprising conducting polycondensation under reduced pressure. Embedded image (In the general formulas (VII) to (IX), R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ , h and i have the same meanings as those in the general formula (II). In formula (VIII), R ₈ has the same meaning as in formula (III). ) 6. The method for producing a polyester polymer according to claim 5, further comprising adding an aromatic monocarboxylic acid represented by the general formula (VI) and / or an ester-forming derivative thereof.