JP3232785B2 - Fluorinated polyester and method for producing the same - 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 fluorine-containing polyester and a method for producing the same.

[0002]

2. Description of the Related Art Hitherto, polyester has been applied to fibers, coating materials and the like as an excellent material having high strength, high elastic modulus, heat resistance and flame retardancy. In addition, the fluoropolymer has a wide range of uses as a highly functional polymer, utilizing its unique properties such as excellent heat resistance, chemical resistance, water / oil repellency, and non-adhesion.

[0003]

However, in recent years,
Polyester is strongly required to have high functionality such as improved moisture absorption resistance. Polyesters that meet such requirements include those having a hexafluoroisopropylidene group in the molecular chain as shown in Chemical formula 9 and those having a fluorine atom directly bonded to an aromatic ring in the molecular chain (JMS-Rev.
Macromol. Chem. Phys. , C29,3
65-429 (1989)).

Embedded image However, according to the findings of the present inventors, it has been found that such a polyester cannot sufficiently satisfy the above requirements. Accordingly, the present invention provides a novel fluorine-containing polyester and a method for producing the same, which sufficiently satisfy the above requirements.

[0004]

The novel fluorine-containing polyester of the present invention is represented by the following general formula (I):

Embedded image [However, in reduction 10, Rf is -C _n F _2n-1 (where, n
Is an integer from 6 to 12), which indicates that the double bond is 1
And may be branched, and the hydrogen of the benzene ring may be appropriately substituted with a substituent, and X represents a divalent organic group. ]. Examples of the substituent that may be bonded to the benzene ring include a lower alkyl group, a lower alkoxy group, and a halogen.

In the general formula (I), X represents an alkylene group, an unsaturated alkylene group, a phenylene group, a naphthalene group, a general formula (a) of the formula (11), a general formula (b) of the formula (12),
There are groups represented by the general formula (c) in Chemical formula 13, and it is preferable that the hydrogen of the benzene ring in these groups is appropriately substituted with a substituent.

Embedded image [However, in Chemical formula 11, Y is a bond, -O-, -S-, -S
O ₂ —, —C (＝ O) —, —CH ₂ —, —C (CH ₃ ) ₂
—, —CF ₂ — or —C (CF ₃ ) ₂ —. ]

Embedded image [However, in Chemical formula 12, Y is the same as in the general formula (a);
Two Y's may be the same or different. ]

Embedded image [However, in Chemical formula 13, Y is the same as in the general formula (a);
The three Ys may be the same or different. Examples of the substituent that may be bonded to the benzene ring include a lower alkyl group, a lower alkoxy group, and a halogen.

The fluorine-containing polyester may further have, as a structural unit, a structural unit represented by the following general formula (II).

Embedded image [Wherein, in the chemical formula 14, Z is a divalent organic group containing an aromatic ring, and in the above general formula (I)

Embedded image And Z ′ represents a divalent organic group. ]

In the general formula (II), Z and X ′ represent an alkylene group, an unsaturated alkylene group, a phenylene group, a naphthalene group, the general formulas (a), (b) and (c) described above. Wherein hydrogen of the benzene ring in these groups may be appropriately substituted with a substituent, and those are preferred. Examples of the substituent that may be bonded to the benzene ring include a lower alkyl group, a lower alkoxy group, and halogen. Z and X 'may be the same or different. The structural unit represented by the general formula (I) includes a structural unit represented by the general formula (I) and a general formula (II)
Is preferably contained in an amount of 1 mol% or more based on the total of the structural units represented by If the amount of the structural unit represented by the general formula (I) is too small, the moisture absorption resistance of the fluorinated polyester tends to decrease. The constituent unit represented by the general formula (I) is more preferably contained in an amount of at least 10 mol%, particularly preferably at least 20 mol%.

[0008] The fluorine-containing polyester represented by the general formula (I) is obtained by converting the general formula (III)

Embedded image [However, in reduction 16, Rf is -C _n F _2n-1 (where, n
Is an integer from 6 to 12), which indicates that the double bond is 1
May be included and may be branched, and hydrogen of the benzene ring may be appropriately substituted with a substituent. And a fluorine-containing dihydroxy compound represented by the formula (IV):

Embedded image (However, Z in Chemical Formula 17 is the same as X in the general formula (I).) It can be produced by reacting a dicarboxylic acid component containing a dicarboxylic acid represented by the general formula (I) or an ester-forming derivative thereof. .

Fluorine-containing polyesters containing the structural units represented by the general formulas (I) and (II) can be obtained by the following method:

Embedded image [However, Formula 18 in, Rf is -C _n F _2n-1 (where, n
Is an integer from 6 to 12), which indicates that the double bond is 1
May be included and may be branched, and hydrogen of the benzene ring may be appropriately substituted with a substituent. And a fluorine-containing dihydroxy compound represented by the general formula (IV)

HO-Z-OH (IV) (wherein Z is the same as Z in the general formula (II)) and a fluorinated dihydroxy compound represented by the general formula (V) )

Embedded image (Wherein X in Chemical formula 20 is the same as X in the general formula (I)). The compound can be produced by reacting a dicarboxylic acid component containing a dicarboxylic acid represented by the general formula (I) or an ester-forming derivative thereof. .

In the general formula (III), examples of the substituent which may be bonded to the benzene ring include a lower alkyl group, a lower alkoxy group and a halogen. As the dihydroxy compound component, the dihydroxy compound represented by the general formula (III) is represented by the general formula (III) and the general formula (IV)
Is preferably used in an amount of 1 to 100 mol%, more preferably 10 to 100 mol%, and particularly preferably 20 to 100 mol%.

The dihydroxy compound represented by the general formula (III) includes 1,3-bis (hydroxymethyl)-
5- (perfluorononenyloxy) benzene, 1,3
-Bis (hydroxymethyl) -4-methyl-5- (perfluorononenyloxy) benzene, 1,3-bis (hydroxymethyl) -4-methoxy-5- (perfluorononenyloxy) benzene, 1,3 -Bis (hydroxymethyl) -2,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,3-bis (hydroxymethyl) -4-chloro-5- (perfluorononenyloxy) Benzene, 1,3-bis (hydroxymethyl) -4-bromo-5- (perfluorononenyloxy) benzene, 1,2-bis (hydroxymethyl) -4
-(Perfluorononenyloxy) benzene, 1,2-
Bis (hydroxymethyl) -4-methyl-5- (perfluorononenyloxy) benzene, 1,2-bis (hydroxymethyl) -4-methoxy-5- (perfluorononenyloxy) benzene, 1,2- Bis (hydroxymethyl) -3,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,2-bis (hydroxymethyl) -4-chloro-5- (perfluorononenyloxy) benzene , 1,2-bis (hydroxymethyl)
-4-bromo-5- (perfluorononenyloxy) benzene, 1,4-bis (hydroxymethyl) -3- (perfluorononenyloxy) benzene, 1,4-bis (hydroxymethyl) -2-methyl -5- (perfluorononenyloxy) benzene, 1,4-bis (hydroxymethyl) -2-methoxy-5- (perfluorononenyloxy) benzene, 1,4-bis (hydroxymethyl) -2,3 , 6-Trifluoro-5- (perfluorononenyloxy) benzene, 1,4-bis (hydroxymethyl) -2-chloro-5- (perfluorononenyloxy) benzene, 1,4-bis (hydroxymethyl )-
2-bromo-5- (perfluorononenyloxy) benzene, 1,3-bis (hydroxymethyl) -5- (perfluorohexenyloxy) benzene, 1,3-bis (hydroxymethyl) -4-methyl-5 -(Perfluorohexenyloxy) benzene, 1,3-bis (hydroxymethyl) -4-methoxy-5- (perfluorohexenyloxy) benzene, 1,3-bis (hydroxymethyl) -2,4,6-tri Fluoro-5- (perfluorohexenyloxy) benzene, 1,3-bis (hydroxymethyl) -4-chloro-5- (perfluorohexenyloxy) benzene, 1,3-bis (hydroxymethyl) -4-bromo- 5- (perfluorohexenyloxy) benzene, 1,2-bis (hydroxymethyl) -4
-(Perfluorohexenyloxy) benzene, 1,2
-Bis (hydroxymethyl) -4-methyl-5- (perfluorohexenyloxy) benzene, 1,2-bis (hydroxymethyl) -4-methoxy-5- (perfluorohexenyloxy) benzene, 1,2-bis (Hydroxymethyl) -3,4,6-trifluoro-5- (perfluorohexenyloxy) benzene, 1,2-bis (hydroxymethyl) -4-chloro-5- (perfluorohexenyloxy) benzene, 2-bis (hydroxymethyl) -4-bromo-5- (perfluorohexenyloxy) benzene, 1,4-bis (hydroxymethyl) -3- (perfluorohexenyloxy) benzene, 1,4-bis (hydroxymethyl ) -2-Methyl-
5- (perfluorohexenyloxy) benzene, 1,
4-bis (hydroxymethyl) -2-methoxy-5
(Perfluorohexenyloxy) benzene, 1,4-
Bis (hydroxymethyl) -2,3,6-trifluoro-5- (perfluorohexenyloxy) benzene,
1,4-bis (hydroxymethyl) -2-chloro-5-
(Perfluorohexenyloxy) benzene, 1,4-
Bis (hydroxymethyl) -2-bromo-5- (perfluorohexenyloxy) benzene and the like. In these compounds, the perfluoro root sulfonyl group, Rf in the general formula (I) are those of -C ₉ F _17, the general formula is a perfluoroalkyl hexenyl group Rf is at (I) -
C ₆ F ₁₁ , and so on. In the compounds exemplified above, instead of the perfluorononenyl group or the perfluorohexenyl group, a group -C ₁₀ F ₁₉ , a group-
Compounds having C ₁₂ F _{23 and the} like can be similarly exemplified.

Formula (III)

Embedded image [However, in reduction 21, Rf is -C _n F _2n-1 (where, n
Is an integer from 6 to 12), which indicates that the double bond is 1
May be appropriately branched, the hydrogen of the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and the two hydroxymethyl groups may be each substituted with an aromatic ring. Ortho to the ether bond,
Attached to the meta or para position. The fluorine-containing dihydroxy compound represented by the general formula (VI)

Embedded image [However, in reduction 22, Rf is -C _n F _2n-1 (where, n
Is an integer from 6 to 12), which indicates that the double bond is 1
May be appropriately branched, the hydrogen of the aromatic ring may be substituted with a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and two carboxyl groups may be
Each is bonded to the aromatic ring at the ortho, meta or para position relative to the ether bond. By subjecting the fluorinated aromatic dicarboxylic acid compound represented by the formula [1] to a reduction reaction.

The above reduction reaction can be carried out, for example, by the following method. There is a method in which borane is allowed to act on a solution obtained by dissolving the above-mentioned fluorinated aromatic zircarboxylic acid compound in an organic solvent such as tetrahydrofuran, benzene, toluene, xylene, monoglyme, diglyme, and the like to reduce the solution.
As a method of causing borane to act, a method of dissolving borane in an organic solvent such as tetrahydrofuran and adding the solution to the solution of the fluorine-containing aromatic dicarboxylic acid compound, reacting the boron trifluoride etherate with sodium borohydride Any method may be used, such as a method of adding the borane generated by the above to the solution of the fluorine-aromatic dicarboxylic acid compound. In the reaction of causing the borane to act on the fluoroaromatic dicarboxylic acid compound to reduce the borane, the borane is 0.1 to 30 equivalents based on the fluorinated aromatic dicarboxylic acid compound,
It is particularly preferable to use 0.5 to 5 equivalents, and the reaction temperature is preferably -80 to 80C, particularly preferably -20C to 50C.
Further, the reaction time is appropriately determined, but is usually preferably 2 minutes to 7 days, particularly preferably 5 minutes to 24 hours. The fluorine-containing dihydroxy compound represented by the general formula (I) thus obtained can be purified by recrystallization from alcohol or the like.

The dicarboxylic acids represented by the general formula (VI) include 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid,
2- (perfluorononenyloxy) terephthalic acid, 4
-Methyl-5- (perfluorononenyloxy) isophthalic acid, 2,4,6-trifluoro-5- (perfluorononenyloxy) isophthalic acid, 4-chloro-5-
(Perfluorononenyloxy) isophthalic acid, 4-bromo-5- (perfluorononenyloxy) isophthalic acid, 4-methyl-5- (perfluorononenyloxy)
Phthalic acid, 4-methoxy-5- (perfluorononenyloxy) phthalic acid, 3,4,6-trifluoro-5-
(Perfluorononenyloxy) phthalic acid, 4-chloro-5- (perfluorononenyloxy) phthalic acid, 4-
Bromo-5- (perfluorononenyloxy) phthalic acid, 2-methyl-5- (perfluorononenyloxy)
Terephthalic acid, 4-methoxy-5- (perfluorononenyloxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorononenyloxy) terephthalic acid,
2-chloro-5- (perfluorononenyloxy) terephthalic acid, 2-bromo-5- (perfluorononenyloxy) terephthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) ) Phthalic acid, 2- (perfluorohexenyloxy) terephthalic acid, 4-methyl-5- (perfluorohexenyloxy) isophthalic acid, 4-methoxy-5-
(Perfluorohexenyloxy) isophthalic acid, 2,
4,6-trifluoro-5- (perfluorohexenyloxy) isophthalic acid, 4-chloro-5- (perfluorohexenyloxy) isophthalic acid, 4-bromo-5-
(Perfluorohexenyloxy) isophthalic acid, 4-
Methyl-5- (perfluorohexenyloxy) phthalic acid, 4-methoxy-5- (perfluorohexenyloxy) phthalic acid, 3,4,6-trifluoro-5- (perfluorohexenyloxy) phthalic acid, 4- Chloro-5
-(Perfluorohexenyloxy) phthalic acid, 4-bromo-5- (perfluorohexenyloxy) phthalic acid, 2-methyl-5- (perfluorohexenyloxy) terephthalic acid, 4-methoxy-5- (perfluorohexenyl) Oxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorohexenyloxy) terephthalic acid, 2-chloro-5- (perfluorohexenyloxy) terephthalic acid, 2-bromo-5- (perfluorohexenyl) (Oxy) terephthalic acid.

The aromatic dicarboxylic acid represented by the general formula (VI) is described in, for example, JP-A-50-1212.
In accordance with the method described in JP-A-43-43, an oligomer of an ester such as diphenyl ester or dibenzyl ester of hydroxy-dicarboxybenzene and a fluoroalkene such as trimer of fluoropropene or pentamer of tetrafluoroethylene are used as a proton acceptor. In the presence, in an aprotic organic catalyst, after reacting in the presence of a base catalyst at or below room temperature, the reaction product is isolated, and the reaction product is treated with a basic compound such as sodium hydroxide or potassium hydroxide. In the presence of the compound,
It can be produced by hydrolyzing and further appropriately treating with an acid such as hydrochloric acid. The reaction product and the final product are appropriately purified by means such as washing and recrystallization.

In the above, examples of the perfluorononenyl group include, for example, those represented by the formula (a)

Embedded image The formula of formula 24

Embedded image Formula (25) of the formula

Embedded image Formula (d) of Chemical Formula 26

Embedded image The formula of formula 27 (e)

Embedded image And a perfluorohexenyl group represented by the formula (f)

Embedded image Formula (29)

Embedded image , The formula of formula 30

Embedded image And a perfluorodecenyl group represented by the following formula:
Equation (1) for 1

Embedded image And the like. In addition, general formula (I) or general formula (III)
In the formula, Rf may be linear or branched, but the branched one is likely to have a higher polyester glass transition temperature because the three-dimensional structure is more compact than the linear one.

Formula (IV)

Embedded image As the dihydroxy compound represented by HO—Z—OH (IV) (wherein, Z is the same as Z in the general formula (II)), ethylene glycol, propylene glycol, diethylene glycol, Propylene glycol, neopentyl glycol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, hydrogenated bisphenol A, bisphenol A propylene oxide adduct,
Diglone neopentyl glycol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-
Dihydroxybenzene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,
1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,
7-dihydroxynaphthalene, 3,3′-dihydroxydiphenylether, 3,4′-dihydroxydiphenylether, 4,4′-dihydroxydiphenylether, 3,3′-dihydroxydiphenylmethane, 3,
4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenyldifluoromethane, 3,4'-dihydroxydiphenyldifluoromethane, 4,4'-dihydroxydiphenyldifluoromethane, 3,3'-dihydroxy Diphenylsulfone, 3,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfone, 3,3′-dihydroxydiphenylsulfide,
3,4'-dihydroxydiphenyl sulfide, 4,
4'-dihydroxydiphenyl sulfide, 3,3'-
Dihydroxydiphenylketone, 3,4′-dihydroxydiphenylketone, 4,4′-dihydroxydiphenylketone, 2,2-bis (3-hydroxyphenyl) propane, 2,2- (3-4′-dihydroxydiphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-hydroxyphenyl) hexafluoropropane, 2,2- (3-4′-dihydroxydiphenyl) hexafluoropropane, 2,
2-bis (4-hydroxyphenyl) hexafluoropropane, 1,3-bis (3-hydroxyphenoxy) benzene, 1,4-bis (3-hydroxyphenoxy) benzene, 1,4-bis (4-hydroxyphenoxy) Benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisphenol, 3,4 ′-(1,
4-phenylenebis (1-methylethylidene)) bisphenol, 4,4 ′-(1,4-phenylenebis (1-
Methylethylidene)) bisphenol, 2,2-bis (4- (3-hydroxyphenoxy) phenyl) propane, 2,2-bis (4- (4-hydroxyphenoxy)
Phenyl) propane, 2,2-bis (4- (3-hydroxyphenoxy) phenyl) hexafluoropropane,
2,2-bis (4- (4-hydroxyphenoxy) phenyl) hexafluoropropane, bis (4- (3-hydroxyphenoxy) phenyl) sulfide, bis (4-
(4-hydroxyphenoxy) phenyl) sulfide,
There are bis (4- (3-hydroxyphenoxy) phenyl) sulfone, bis (4- (4-hydroxyphenoxy) phenyl) sulfone and the like.

Formula (V)

Embedded image (In the formula, X is the same as X in the general formula (I).) Examples of the dicarboxylic acid represented by 1,2-dicarboxylethane, 1,3-dicarboxylpropane, 1,4 -Dicarboxylic butane, 1,5-dicarboxylpentane, 1,6-dicarboxylhexane,
1,7-dicarboxylic heptane, 1,8-dicarboxylic octane, 1,9-dicarboxylic nonane, 1,1
0-dicarboxylic decane, fumaric acid, itaconic acid, 5
-(Perfluorononenyloxy) isophthalic acid, 4-
(Perfluorononenyloxy) phthalic acid, 2- (perfluorononenyloxy) terephthalic acid, 4-methyl-
5- (perfluorononenyloxy) isophthalic acid, 4
-Methoxy-5- (perfluorononenyloxy) isophthalic acid, 2,4,6-trifluoro-5- (perfluorononenyloxy) isophthalic acid, 4-chloro-5-
(Perfluorononenyloxy) isophthalic acid, 4-bromo-5- (perfluorononenyloxy) isophthalic acid, 4-methyl-5- (perfluorononenyloxy)
Phthalic acid, 4-methoxy-5- (perfluorononenyloxy) phthalic acid, 3,4,6-trifluoro-5-
(Perfluorononenyloxy) phthalic acid, 4-chloro-5- (perfluorononenyloxy) phthalic acid, 4-
Bromo-5- (perfluorononenyloxy) phthalic acid, 2-methyl-5- (perfluorononenyloxy)
Terephthalic acid, 4-methoxy-5- (perfluorononenyloxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorononenyloxy) terephthalic acid,
2-chloro-5- (perfluorononenyloxy) terephthalic acid, 2-bromo-5- (perfluorononenyloxy) terephthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) ) Phthalic acid, 2- (perfluorohexenyloxy) terephthalic acid, 4-methyl-5- (perfluorohexenyloxy) isophthalic acid, 4-methoxy-5-
(Perfluorohexenyloxy) isophthalic acid, 2,
4,6-trifluoro-5- (perfluorohexenyloxy) isophthalic acid, 4-chloro-5- (perfluorohexenyloxy) isophthalic acid, 4-bromo-5-
(Perfluorohexenyloxy) isophthalic acid, 4-
Methyl-5- (perfluorohexenyloxy) phthalic acid, 4-methoxy-5- (perfluorohexenyloxy) phthalic acid, 3,4,6-trifluoro-5- (perfluorohexenyloxy) iftalic acid, 4- Chloro-
5- (perfluorohexenyloxy) phthalic acid, 4-
Bromo-5- (perfluorohexenyloxy) phthalic acid, 2-methyl-5- (perfluorohexenyloxy) terephthalic acid, 4-methoxy-5- (perfluorohexenyloxy) terephthalic acid, 2,3,6-tri Fluoro-5- (perfluorohexenyloxy) terephthalic acid, 2-chloro-5- (perfluorohexenyloxy) terephthalic acid, 2-bromo-5- (perfluorohexenyloxy) terephthalic acid, phthalic acid, isophthalic acid, terephthalic acid Acid 3,3′-dicarboxyl diphenyl ether, 3,4′-dicarboxyl diphenyl ether, 4,4′-dicarboxyl diphenyl ether,
3,3′-dicarboxydiphenylmethane, 3,4 ′
-Dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylmethane, 3,3'-dicarboxydiphenylolomethane, 3,4'-dicarboxydiphenylolomethane, 4,4'-dicarboxydiphenylolomethane, 3,3 '-Dicarboxyl diphenyl sulfone, 3,4'-dicarboxyl diphenyl sulfone, 4,4'-dicarboxyl diphenyl sulfone,
3,3′-dicarboxydiphenyl sulfide, 3,
4'-dicarboxyl diphenyl sulfide, 4,4 '
Dicarboxylic diphenyl sulfide, 3,3′-dicarboxylic diphenyl ketone, 3,4′-dicarboxylic diphenyl ketone, 4,4′-dicarboxylic diphenyl ketone, 2,2-bis (3-carboxylphenyl) propane, , 2- (3-4'-dicarboxyldiphenyl) propane, 2,2-bis (4-carboxylphenyl) propane, 2,2-bis (3-carboxylphenyl) hexafluoropropane, 2,2- (3-
4'-dicarboxydiphenyl) hexafluoropropane, 2,2-bis (4-carboxylphenyl) hexafluoropropane, 1,3-bis (3-carboxylphenoxy) benzene, 1,4-bis (3-carboxylphenoxy) Benzene, 1,4-bis (4-carboxylphenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid,
3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid,
2,2-bis (4- (3-carboxylphenoxy) phenyl) propane, 2,2-bis (4- (4-carboxylphenoxy) phenyl) propane, 2,2-bis (4- (3-carboxylphenoxy)) Phenyl) hexafluoropropane, 2,2-bis (4- (4-carboxylphenoxy) phenyl) hexafluoropropane, bis (4- (3-carboxylphenoxy) phenyl) sulfide, bis (4- (4-carboxylphenoxy)) Phenyl) sulfide, bis (4- (3-carboxylphenoxy) phenyl) sulfone, bis (4-
(4-carboxylphenoxy) phenyl) sulfone and the like.

The aromatic dicarboxylic acid represented by the general formula (III) and the amide-forming derivative of the aromatic dicarboxylic acid represented by the general formula (IV) are reacted with the diamine represented by the general formula (V). And an acid halide such as dichloride and dibromide of the aromatic dicarboxylic acid, dialkyl esters such as dimethyl ester and diethyl ester of the acid, and acid anhydride of the acid.

The above-mentioned dichloride can be obtained in high yield, for example, by reacting the above-mentioned perfluoroalkenyloxyisophthalic acid or the above-mentioned aromatic dicarboxylic acid with thionyl chloride.

The above dialkyl esters such as dimethyl ester and diethyl ester can be obtained by reacting an alcohol such as methanol and ethanol with the above perfluoroalkenyloxyisophthalic acid or the above aromatic dicarboxylic acid in the presence of an acid catalyst. it can. The condensation reaction between the dicarboxylic acid component and the dihydroxy compound component can be performed in an aprotic organic solvent in the presence or absence of a hydrochloric acid trap material, an activator, and the like. In this case, the dicarboxylic acid component and the dihydroxy compound component are preferably used in an equimolar or almost equimolar manner, and the order of addition of each component is arbitrary.

Specific examples of the aprotic organic solvent include amide solvents such as dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, benzene, toluene, anisole, nitrobenzene. , Dichlorobenzene, aromatic solvents such as benzonitrile, dibutyl ether, tetrahydrofuran (THF), dioxane, di (methoxyethyl)
Examples thereof include ether solvents such as ether, and halogenated hydrocarbon solvents such as chloroform. The hydrochloric acid trapping agent is used to neutralize hydrochloric acid generated in the condensation reaction, and it is preferable to use a base such as pyridine, triethylamine and dimethylaniline.The hydrochloric acid trapping agent is used for a dicarboxylic acid component or a dihydroxy compound. It is preferable to use 0.8 to 3 equivalents,
It is preferable to use 1.5 times equivalent. It is preferable to use dicyclohexylcarbodiimide, polyphosphoric acid, imidazole, or the like as a substance used for activating the above-mentioned activator and dicarboxylic acid component. The activator is preferably used in an amount of 0.8 to 3 equivalents, more preferably 1 to 1.5 equivalents, based on the dicarboxylic acid component or the dihydroxy compound component.

As a more specific method for producing the polyester according to the present invention, for example, a usual solution polycondensation method, interfacial polycondensation method, direct polycondensation method, melt polycondensation method and the like can be used. Among these, the solution polycondensation method is
First, after dissolving the dihydroxy compound component and, if necessary, the hydrochloric acid trapping agent in an aprotic organic solvent, the temperature is usually about −50 to + 150 ° C., preferably −20 to +80.
While stirring the solution at ℃, in the form of a solution in which an acid halide such as diacid chloride or diacid bromide as a dicarboxylic acid component is dissolved in a powder form or an aprotic organic catalyst,
The reaction is allowed to take place all at once or slowly. The reaction occurs immediately and the viscosity of the reaction system increases. Usually 1 to 72
Continue stirring for hours. The reaction product after the reaction can be directly used as a stock solution for molding. Further, the polymer can be isolated by treating with methanol, water, or the like.

The interfacial polycondensation method is carried out by dissolving an acid halide such as diacid chloride or diacid bromide as a dicarboxylic acid component and a dihydroxy compound component in a solvent which is not mixed with each other. For example, dissolving diacid chloride in carbon tetrachloride, chloroformbenzene, etc., while dissolving the dihydroxy compound component in an alkaline solution, and adding this over an acid halide solution, condensation occurs immediately at the interface layer and a polymer precipitates. . When this is continuously withdrawn, a polymer is obtained. In some cases,
A phase transfer catalyst such as tetrabutylammonium bromide may be used in the reaction system.

In the direct polycondensation method, a dicarboxylic acid component and a dihydroxy compound component are dissolved in an organic solvent, and dicyclohexylcarbodiimide, polyphosphoric acid,
The reaction is performed by adding imidazole or the like.

In the melt polycondensation method, an acid halide such as diacid chloride, or a dicarboxylic acid or a dicarboxylic acid ester is used as a dicarboxylic acid component, and a dihydroxy compound component is added thereto. The mixture is heated and melted at 50 to 300 ° C. in a polymerization tube provided with a side tube, and the reaction is performed for 0.5 to 24 hours. At this time, compounds such as calcium, magnesium, titanium, and zinc may be added as a catalyst. In the reaction, the temperature is gradually increased, the degree of vacuum is gradually increased, and hydrogen halide generated in the polycondensation reaction is used.
Water and alcohol are distilled off to obtain the desired polyester.

The fluorinated aromatic polyester in the present invention is dimethylacetamide (DMAc) 0.1 g / d
1 and a reduced viscosity of 0.03 measured at 30 ° C.
It is preferably at least 1 dl / g, particularly preferably at least 0.04 dl / g, and particularly 0.1 dl / g when producing a film.
It is preferable that this is the case. The fluorine-containing polyester of the present invention exhibits excellent water repellency. For this purpose, the fluorine content based on Rf in the general formula (I) is 10%.
It is preferably at least 15% by weight, especially at least 15% by weight.
The fluorine-containing polyester according to the present invention is useful as a coating agent, and can be formed into a film by a conventionally known solution casting method or the like.

[0028]

【Example】

Synthesis Example 5- (Perfluorononenyloxy) isophthalic acid 1
5.3 g (0.025 mol) was charged into a 200 ml four-necked flask, and dissolved by adding 30 ml of THF. To this, 100 ml of a 0.1 mol borane solution in THF was added dropwise. The reaction was carried out at -5 ° C for 2 hours and at room temperature for 14 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with ether and recrystallized from a mixed solvent of metamenol / water to obtain the desired 1,3-bis (dihydroxymethyl) -5- (perfluorononenyloxy) benzene. (1) Yield: 11.6 g (79% yield) (2) Melting point: 143 to 147 ° C. (3) ¹ H-NMR spectrum (FIG. 1) (solvent: DMSO-d ₆ , standard TMS) 7.14 ppm (1H, aromatic) S) 6.85 ppm (2H, aromatic, s) 5.37 ppm (2H, OH, t) 4.50 ppm (4H, CH ₂ , d) (4) ¹⁹ F-NMR spectrum (FIG. 2) (solvent DMSO- d _6, standard _{benzotrifluoride) 6.01 (3F, CF 3,} d) -9.13 (6F, CF 3, s) -10.30 (6F, CF 3, d) -105.57 (1F, (CF, quart.) -107.80 (1F, CF, quint.) (5) IR absorption spectrum (FIG. 3) 3200 cm ^-1 (OH), 1240 cm ^-1 (CF) (6) Elemental analysis value (%)

[0029]

[Table 1] CHF0──────────────────────────── Theoretical value 34.9 1.5 55.3 8.3 Observed value 35.3 1.3 55.0 8.4 From the above, it was confirmed that the compound was the target compound. The structural formula of this compound is as follows.

Embedded image

Example 1 A polymerization reaction tube equipped with a nitrogen introduction capillary was charged with 1,3
-Bis (hydroxymethyl) -5- (perfluorononenyloxy) benzene 1.00 g (1.76 mmol)
And 0.357 g of terephthalic acid dichloride (1.76 m
mmol) and reacted at 250 ° C. for 11 hours.
The reaction product was dissolved in THF, precipitated in methanol, filtered and dried under reduced pressure to obtain Polymer 1. Table 2 shows the yield and molecular weight of the obtained polymer 1.

Example 2 A 50 ml three-necked flask equipped with a stirrer was charged with 1,3
-Bis (hydroxymethyl) -5- (perfluorononenyloxy) benzene 1.00 g (1.76 mmol)
3.6 ml of a 1M aqueous solution of NaOH was added and stirred at 50 ° C., and 0.357 g of terephthalic acid dichloride was added thereto.
(1.76 mmol) and a solution of 15 mg of tetrabutylammonium bromide in 6.2 ml of benzene were added, and the mixture was stirred at room temperature. The reactant was dissolved in THF, precipitated in distilled water, filtered, dissolved again in THF, precipitated in methanol, filtered and dried under reduced pressure to obtain polymer 2. Table 2 shows the yield and molecular weight of the obtained polymer 2.

Example 3 In Example 1, 0.357 g of isophthalic acid dichloride was used instead of using terephthalic acid dichloride.
(1.76 mmol) was obtained in the same manner except that polymer 3 was used. Table 2 shows the yield and molecular weight of the obtained polymer 3.

Example 4 A polymer 3 was obtained in the same manner as in Example 1 except that 0.445 g (1.76 mmol) of 2,6-naphthalenedicarboxylic acid dichloride was used instead of terephthalic acid dichloride. Table 2 shows the yield and molecular weight of the obtained polymer 3.

Example 5 A polymerization tube equipped with a vacuum stirrer, a nitrogen gas inlet tube and a distillation side tube was charged with 1,3-bis (hydroxymethyl) -5-
1.00 g of (perfluorononenyloxy) benzene
(1.76 mmol) and 0.292 g of terephthalic acid
(1.76 mmol). Separately, aqueous ammonia is added to a 5% aqueous solution of titanium tetrachloride to adjust pH 8 to
The resulting white precipitate was filtered to obtain a titanium catalyst. 4.8 mg of this titanium catalyst was added to the polymerization tube, and the mixture was further added at 220 ° C. for 1.5 hours and at 280 ° C. for 1 hour.
The pressure was reduced to 3 mmHg and the reaction was carried out at 280 ° C. for 2 hours, and water generated during the polymerization reaction was distilled off. The reaction was dissolved in THF, precipitated in methanol, filtered, dried in vacuo,
Polymer 5 was obtained. Table 2 shows the yield and molecular weight of the obtained polymer 5.

Example 6 A polymerization tube equipped with a vacuum stirrer, a nitrogen gas inlet tube and a distillation side tube was charged with 1,3-bis (hydroxymethyl) -5-
1.00 g of (perfluorononenyloxy) benzene
(1.76 mmol) and 0.341 g (1.76 mmol) of dimethyl terephthalate were charged. Here, 4.8 mg of a titanium catalyst obtained in the same manner as in Example 5
Was added, and 150 ° C. for 3 hours and 200 ° C. for 8 hours, followed by 0.1 hour.
The pressure was reduced to 3 mmHg and the reaction was carried out at 280 ° C. for 6 hours, and methanol generated during the polymerization reaction was distilled off. Reactant T
Dissolved in HF, precipitated in methanol, filtered and dried under reduced pressure to obtain polymer 6. Table 2 shows the yield and molecular weight of the obtained polymer 6.

Example 7 A polymerization tube equipped with a vacuum stirrer, a nitrogen gas inlet tube and a distillation side tube was charged with 1,3-bis (hydroxymethyl) -5-
1.00 g of (perfluorononenyloxy) benzene
(1.76 mmol) and 0.292 g of isophthalic acid
(1.76 mmol). Here, 4.8 mg of a titanium catalyst obtained in the same manner as in Example 5 was added, and 20
The pressure was reduced to 0 ° C. for 2 hours and 250 ° C. for 7 hours, and further reduced to 0.3 mmHg, and the reaction was carried out at 250 ° C. for 7 hours, and water generated during the polymerization reaction was distilled off. The reaction product was dissolved in THF, precipitated in methanol, filtered and dried under reduced pressure to obtain Polymer 7. Table 2 shows the yield and molecular weight of the obtained polymer 7.

Example 8 A polymerization tube equipped with a vacuum stirrer, a nitrogen gas inlet tube and a distillation side tube was charged with 1,3-bis (hydroxymethyl) -5-
1.00 g of (perfluorononenyloxy) benzene
(1.76 mmol) and 1.08 g (1.76 mmol) of 5- (perfluorononenyloxy) isophthalic acid
And was charged. Here, 4.8 mg of a titanium catalyst obtained in the same manner as in Example 5 was added, and 200 ° C. for 1 hour and 250 ° C.
6 hours, further reduce the pressure to 0.3 mmHg,
The reaction was allowed to proceed for a period of time, and water generated during the polymerization reaction was distilled off.
The reaction product was dissolved in THF, precipitated in methanol, filtered and dried under reduced pressure to obtain Polymer 8. Table 2 shows the yield and molecular weight of the obtained polymer 8.

COMPARATIVE EXAMPLE 0.59 g (1.76 mmol) of 2,2-bis (4-hydroxyphenyl) hexafluoropropane was charged into a polymerization tube equipped with a vacuum stirrer, a nitrogen gas inlet tube and a distillation side tube.
And 0.292 g (1.76 mmol) of isophthalic acid were charged. Here, 4.8 mg of a titanium catalyst obtained in the same manner as in Example 5 was added, and the mixture was added at 200 ° C. for 2 hours and at 250 ° C.
℃, 7 hours, further reduced to 0.3 mmHg 250
The reaction was carried out at 7 ° C. for 7 hours, and water generated during the polymerization reaction was distilled off. The reaction product was dissolved in THF, precipitated in methanol, filtered and dried under reduced pressure to obtain Polymer 9. Table 2 shows the yield and molecular weight of the obtained polymer 9. Table 2 shows the yield and molecular weight of the obtained polymer, and Table 3 shows physical properties. Also, ¹ of polymer 1 obtained in Example 1 in FIG. 4
1 shows an H-NMR spectrum.

[0039]

Table 2 Example Polymer Alcohol component Carboxylic acid component Yield Mn ¹ ) (%) (X10 ³ ) １ 11 1 3-bis (hydroxyterephthalic acid 758.1 methyl) -5- (perful dichloride orononenyloxy) benzene 22 {terephthalic acid 355.4 dichloride 33} isophthalic acid 806.7 dichloride 44} 6-naphthalene 93 10.1 dicarboxylic acid dichloride 55 〃 terephthalic acid 40 11.066 〃 terephthalic acid 73 12.3 dimethyl ester 77 〃 isophthalic acid 65 7.6 88 8 〃 5- (perfluoro 88 4. 9 Nonenyloxy) isophthalic acid Comparative Examples 9 2,2-bis (4-hydroxy isophthalic acid 95 15.2
(Ciphenyl) hexafluoropropane １ 1) The molecular weight is calculated by the GPC method in terms of polystyrene. by.

[0040]

Table 3 ──────────────────────────────────── 5% weight of polymer IR spectrum ¹ ) Contact Angle ² ) Main absorption value (cm ^-1 ) Decreasing temperature (° C) (Deg.) ──────────────────────────── １ 1 CF (1244), C = O (1750) 368 105 2 CF (1244), C = O (1750) 358 105 3 CF (1240), C = O (1746) 390 102 4 CF (1242), C = O (1744) 395 102 5 CF (1244), C = O (1750) 362 1056 CF (1244), C = O ( 1750) 360 1047 CF (1240), C = O (1746) 392 1028 CF (1240), C = O ( 748) 355 107 9 CF (1246), C = O (1744) 398 88 ────────────────────────────── ────── 1) 5% weight loss temperature is by thermogravimetric analysis (TGA). Heating rate 10 ° C / min. 2) Contact angle is the contact angle of water to the polymer surface at 20 ° C.

[0041]

The fluorine-containing polyester obtained according to the present invention is a novel compound and is useful as a high-performance polyester having a low moisture absorption, a low dielectric constant and a high transparency.

[Brief description of the drawings]

FIG. 1 shows the relationship between 1,3-bis (hydroxymethyl) -5- (perfluorononeloxy) benzene obtained in a synthesis example.
¹ H-NMR spectrum.

FIG. 2 shows the relationship between 1,3-bis (hydroxymethyl) -5- (perfluorononeloxy) benzene obtained in a synthesis example.
¹⁹ F-NMR spectrum.

FIG. 3 is an IR spectrum of 1,3-bis (hydroxymethyl) -5- (perfluorononeloxy) benzene obtained in Synthesis Example.

FIG. 4 shows ¹ H-NMR of polymer 1 obtained in Example 1.
Spectrum.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masami Yusa, 48, Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd. (56) References JP-A-1-256522 (JP, A) JP-A-62-206019 (JP, A) JP-A-62-197419 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 63/00-63/91

Claims (4)

(57) [Claims] ## STR1 ## 1. The general formula (I) of the chemical formula 1. [However, in reduction 1, Rf is -C _n F _2n-1 (where, n represents a is 6-12 integer) indicates, which includes one double bond, it may be branched And hydrogen of the benzene ring may be appropriately substituted with a substituent, and X represents a divalent organic group. ] The fluorine-containing polyester which has a structural unit represented by these. 2. The structural unit represented by the general formula (I) according to claim 1 and the general formula (II) of the general formula (2) Wherein Z is a divalent organic group containing an aromatic ring, and in the general formula (I) according to claim 1, X ′ represents a divalent organic group. ] The fluorine-containing polyester which has a structural unit represented by these. 3. A compound represented by the general formula (III): [However, in reduction 4, Rf is -C _n F _2n-1 (where, n represents a is 6-12 integer) indicates, which includes one double bond, it may be branched The hydrogen of the benzene ring may be appropriately substituted with a substituent. And a fluorinated dihydroxy compound represented by the general formula (V): (Wherein, X represents a divalent organic group in Chemical Formula 5). A process for producing a fluorine-containing polyester, comprising reacting an acid component containing a dicarboxylic acid or an ester-forming derivative thereof represented by the formula: 4. A compound represented by the general formula (III): [However, in reduction 6, Rf is -C _n F _2n-1 (where, n represents a is 6-12 integer) indicates, which includes one double bond, it may be branched The hydrogen of the benzene ring may be appropriately substituted with a substituent. HO-Z-OH (IV) (wherein Z is the same as Z in the general formula (II)). )) And the general formula (V) of the formula (8) (Wherein X 'represents a divalent organic group in Chemical formula 8). A process for producing a fluorine-containing polyester, comprising reacting an acid component containing a dicarboxylic acid or an ester-forming derivative thereof represented by the formula: