JP3437679B2 - Novel linear polyester with liquid crystallinity - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel linear polyester exhibiting liquid crystallinity.

[0002]

BACKGROUND OF THE INVENTION Since polyesters are produced by the condensation reaction of dicarboxylic acids and diols, many combinations of them have been proposed in the past. Among them, polyesters such as polyethylene terephthalate and polybutylene terephthalate, which are composed of aromatic dicarboxylic acid and aliphatic diol, have excellent mechanical properties, chemical resistance, electrical properties, etc. Are widely used for various purposes such as films, containers, fibers, molding materials, etc.

On the other hand, in applications where heat resistance is further required, wholly aromatic polyesters called so-called polyarylate and liquid crystal polyesters are used.
However, in these wholly aromatic polyesters, the higher the heat resistance is, the higher the molding temperature is required, and the moldability is lowered. Among them, the liquid crystal polyester forms a liquid crystal phase in a molten state, and therefore has excellent moldability such as fluidity and thinness. However, the wholly aromatic liquid crystal polyester usually has a melting point of 250 ° C. or higher. Since it is in such a high temperature range, a molding temperature of 30 to 50 ° C. higher than the melting point is required.

On the other hand, a polyester composed of an aromatic dicarboxylic acid and an aliphatic diol, such as polyethylene terephthalate and polybutylene terephthalate,
Those exhibiting liquid crystallinity have not yet been found. Further, as a polyester having an alkylene group in the molecule and showing liquid crystallinity, a polyester obtained by condensation of 4,4′-bis (2-hydroxyethoxy) biphenyl and terephthaloyl chloride is described in US Pat. No. 5,032,669. Disclosed are polyesters using 4,4'-bis (4-hydroxybutoxy) biphenyl, U. Roetz, et. Al., Mol.
Cryst. Liq. Cryst., 170, 185 (1989), and a polyester using 4,4′-bis (6-hydroxyhexyloxy) biphenyl is disclosed in B. Reck, et a.
l., Makromolk. Chem. rap. Commun., 6, 291 (1985); I
bid, 6, 691 (1985); Ibid, 7, 389 (1987). That is, it is known from these that some polyesters having 4,4′-bis (ω-hydroxyalkoxy) biphenyl as a diol component have liquid crystallinity. Since these liquid crystal polyesters have a highly flexible alkylene group in the molecular chain, they have a relatively low melting point and are therefore expected to have excellent moldability.

Further, if a fluorine atom is introduced into the molecular chain of such a liquid crystal polyester, it can be easily analogized from the properties of polytetrafluoroethylene which is currently usefully used as an industrial material and a consumer material. Flame resistance, heat resistance,
In addition to chemical resistance, it can be expected that electrical characteristics such as low dielectric properties and insulation properties will be further improved. However, conventionally, a liquid crystal polyester having a fluorine atom in the molecular chain and an alkylene group has not been known.

[0006]

DISCLOSURE OF THE INVENTION The present invention, in view of the prior art of polyester as described above, exhibits liquid crystallinity, is excellent in flame retardancy, heat resistance, chemical resistance, etc., and has low dielectric constant,
It is an object of the present invention to provide a linear polyester having excellent electrical properties such as insulating properties and further excellent moldability such as fluidity and thin-wall forming property.

[0007]

According to the present invention, the general formula (I)

[0008]

[Chemical 6]

(Where A is the general formula (II)

[0010]

[Chemical 7]

(Wherein X represents hydrogen or fluorine, of which at least two are fluorine), and a divalent aromatic group represented by the formula: R ¹ having 2 to 10 carbon atoms.
And an alkylene group having 2 to 10 carbon atoms is represented by R ² . ), And a substantially linear polyester having an intrinsic viscosity [η] in the range of 0.1 to 2 dl / g is provided.

Examples of the fluorine-substituted biphenylene group represented by the above general formula (II) include those represented by the formula (III)

[0013]

[Chemical 8]

4,4 '-(3,3'-difluoro) represented by
Hyphenylene group, formula (IV)

[0015]

[Chemical 9]

4,4 '-(3,3', 5,5'-tetrafluoro) biphenylene group represented by the formula (V)

[0017]

[Chemical 10]

4,4 '-(2,2', 3,3 ', 5,5', 6,
6'-octafluoro) biphenylene group and the like can be mentioned.

In the above general formula (I), R ¹ is an alkylene group having 2 to 10 carbon atoms.
Examples thereof include ethylene group, propylene group, butylene group, pentylene group, hexylene group and octylene group. The alkylene group having 3 or more carbon atoms may be linear or branched, but is preferably linear.

Further, in the above general formula (I), R ² is an alkylene group having 2 to 10 carbon atoms.
Examples thereof include ethylene group, propylene group, butylene group, pentylene group, hexylene group and octylene group. The alkylene group having 3 or more carbon atoms may be linear or branched, but is preferably linear.

Such polyesters according to the invention are
An α, ω-dihydroxy compound represented by the general formula (VI) HO-R ¹ -O-A-O-R ¹ -OH (VI) (wherein A and R ¹ are the same as above) and a general compound. It can be obtained by subjecting an aliphatic dicarboxylic acid represented by the formula (VII) HOOC-R ² —COOH (VII) (wherein R ² is the same as above) to a polycondensation reaction. Further, instead of the above aliphatic dicarboxylic acid, a corresponding dicarboxylic acid dihalide, for example, dicarboxylic acid dichloride can also be used.

First, the production of such an α, ω-dihydroxy compound will be described. The α, ω-dihydroxy compound is 1 mol of biphenyl-4,4′-diol represented by the general formula (VIII) HO—A—OH (VIII) (wherein A is the same as above). Ω-haloalcohol represented by the general formula (IX) HO-R ¹ -Y (IX) (wherein R ¹ is the same as defined above and Y represents a halogen atom). 1.5-
3 mol parts, preferably about 2 mol parts can be obtained by heating in the reaction solvent in the presence of a base to cause a condensation reaction by dehydrohalogenation. A catalyst is preferably used in this reaction. Examples of the catalyst include potassium iodide.

The above ω-halo alcohols are, for example, ω
-Chloro or ω-bromo alcohols are preferred, but ω-chloro alcohols are particularly preferred. Examples of the base include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and organic amines.
As the reaction solvent, alcohols or aqueous solutions thereof are usually used. The base is fluorine-substituted biphenyl-
It is usually used in the range of 2 to 3 parts by mole, but not limited thereto, with respect to 1 part by mole of 4,4′-diol. The reaction temperature is not particularly limited, but usually the reflux temperature is preferred.

For example, 6-chloro-1-hexanol is used as the ω-haloalcohol and 3,3′- is used as the fluorine-substituted biphenyl-4,4′-diol.
By using difluorobiphenyl-4,4'-diol, 3,3'-difluorobis (6-hydroxyhexyloxy) biphenyl can be obtained.

More specifically, a reaction solvent is charged with a predetermined amount of fluorine-substituted biphenyl-4,4'-diols, a base and a catalyst together with the reaction solvent in a reaction vessel and brought to a reflux temperature. Is gradually added (for example, added dropwise), and after the addition, the mixture is stirred for several hours to several tens of hours. Thus, after completion of the reaction, an acid such as, for example,
Hydrochloric acid is added to acidify the reaction mixture, and the obtained solid content is collected by filtration and washed with water to obtain the desired α, ω-dihydroxy compound. The α, ω-dihydroxy compound thus obtained may be purified by column chromatography or recrystallization, if necessary.

As a preferred specific example of such an α, ω-dihydroxy compound, a compound obtained by using 6-chloro-1-hexanol as the ω-chloroalcohol, for example, 3,3 ′ -Difluorobis (6-hydroxyhexyloxy) biphenyl, 3,3 ',
5,5'-tetrafluorobis (6-hydroxyhexyloxy) biphenyl, 2,2 ', 3,3', 5,5 ', 6,6'-octafluorobis (6-hydroxyhexyloxy) biphenyl, etc. Can be mentioned.

Next, preferred specific examples of the aliphatic dicarboxylic acid represented by the general formula (VIII) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. be able to.

More specifically, the polycondensation reaction between the α, ω-dihydroxy compound and the aliphatic dicarboxylic acid is as follows.
0.8 to 1.5 parts by mole, preferably about 1 part by mole, of an aliphatic dicarboxylic acid per 1 part by mole of the α, ω-dihydroxy compound is heated in the reaction solvent in the presence of an acid catalyst. It is done by reacting. The reaction solvent is preferably an aliphatic halogenated hydrocarbon such as 1,2-dichloroethane, and the acid catalyst is, for example, an inorganic acid such as sulfuric acid or an organic acid such as p-toluenesulfonic acid. Can be used, and among these, p-toluenesulfonic acid is particularly preferably used. The reaction temperature is
Although not particularly limited, the reflux temperature is usually preferable.

After the completion of the reaction, the reaction mixture obtained is poured into a large amount of alcohol, preferably methanol, to precipitate polyester, which is collected by filtration. If necessary, the obtained polyester is a hot alcohol,
For example, low molecular weight substances can be removed by repeated washing with hot ethanol. The polyester according to the present invention thus obtained has the general formula (I)
Which is a substantially linear polyester having a repeating unit represented by an intrinsic viscosity [η] of usually 0.1 to
2 dl / g, preferably 0.15 to 1.5 dl /
It is in the range of g.

All the polyesters according to the present invention are
As a result of DSC (Differential Scanning Calorimetry), two endothermic peaks and two exothermic peaks are observed at the time of temperature rise and at the time of cooling, so that the substance has properties as an enantiotropic liquid crystal. Furthermore,
The polyester according to the present invention is a result of observation under a polarizing microscope,
In both cases, the mosaic or focal conic texture that is characteristic of smectic liquid crystals is recognized,
It is a smectic liquid crystal. Further, these phase transition temperatures in observation with a polarization microscope coincide with the phase transition temperatures obtained from the DSC. Furthermore, the crystallinity of the polyesters according to the invention is usually between 5 and 40 as measured by wide-angle X-ray diffraction.
It is in the range of%.

[0031]

INDUSTRIAL APPLICABILITY The present invention provides a novel linear polyester having liquid crystallinity, which is obtained by condensation polymerization of fluorine-substituted bis (ω-hydroxyalkyleneoxy) piphenyl and an aliphatic dicarboxylic acid. Since this polyester exhibits liquid crystallinity, it excels in moldability such as fluidity and thin-film forming property, as well as flame resistance, heat resistance, chemical resistance, etc., as well as electrical characteristics such as low dielectric property and insulation property. Also excellent.

[0032]

The present invention will be described below with reference to examples and reference examples, but the present invention is not limited to these examples. In the examples, the differential scanning calorimeter
Using igaku TAS100 system DSC8230B, 10 mg of Al ₂ O ₃ was used as a standard sample, and measurement was performed on an aluminum pan. Sampling time 1.0 seconds, temperature rise,
Cooling rate 5 or 10K / min, DSC sensitivity 5 or 10mca
l, chart speed 5 mm / min, sample amount about 10 mg. Polarization microscope observation is for sample cell thickness 6μm or 12
It was carried out with an OLYMPUS BH-2 type polarizing microscope (magnification: 150 times) equipped with a hot stage with a temperature controller as a sandwich cell of μm. In addition, Rigaku RINT-2500 was used for X-ray diffraction measurement, and for small-angle X-ray diffraction measurement, the scanning range was 2θ = 1.00 to 10.0 °, the step width was 0.01 ° C, and the sampling time was 3.00 seconds. It was measured in FT mode.

Reference Example 1 (Synthesis of 3,3'-difluorobis (6-hydroxyhexyloxy) biphenyl (2FBHHBP)) 3,3'-in a 200 ml four-necked flask equipped with a dropping funnel and a calcium chloride tube. Difluorobiphenyl 8.00g (36.0mm
ol), potassium hydroxide 4.4 g (79.2 mmol), catalytic amount of potassium iodide, ethanol 100 ml and water 20 ml.
Was charged to the reflux temperature (100 ° C.), and 10.8 g (79.2 mmol) of 6-chloro-1-hexanol was added dropwise over 1 hour. After completion of dropping, while further heating and refluxing,
The reaction was carried out for 20 hours with stirring.

After the reaction was completed, the mixture was acidified with hydrochloric acid, filtered with suction,
Washed with water. The obtained crystals were purified by column chromatography (Wakogel C-200 packing material, chloroform solvent) and then recrystallized from ethanol to give the title compound 11.
6 g (yield 76.4%) was obtained.

Infrared absorption spectrum (KBr) ν (c
m ^-1 ): 3425, 3075, 2920, 1575, 1510, 1010, 810 Proton nuclear magnetic resonance spectrum (CDCl ₃ ) δ (pp
m): 1.22-1.91 (m, 18H,-(CH ₂ ) ₄ -OH) 3.67-3.74 (s, 4H, -CH _2- ) 4.06-4.13 (s, 4H, -O-CH _2- ) 6.95- 7.31 (m, 6H, aromatic hydrogen) Elemental analysis (as C ₂₄ H ₃₂ O ₄ F ₂ ): Calculated value C: 68.23%; H: 7.63% Found value C: 68.30%; H: 7.64%

DSC thermogram (differential scanning calorimetry curve): Shown in FIG. Two endothermic and exothermic peaks are observed at the time of temperature rise and at the time of cooling, which indicates that the liquid crystal is an enantiotropic liquid crystal. Small angle X-ray measurement: Shown in FIG. 2 and Table 1.

Reference Example 2 (Synthesis of 3,3 ', 5,5'-tetrafluorobis (6-hydroxyhexyloxy) biphenyl (4FBHHBP))
In a 200 ml four-necked flask equipped with a dropping funnel and a calcium chloride tube, 3,3 ', 5,5'-tetrafluorobiphenyl 7.0 g (27.1 mmol) and potassium hydroxide 3.4 g (59.
7 mmol), catalytic amount of potassium iodide, ethanol 100
After adding 20 ml of water and 20 ml of water to the reflux temperature (100 ° C), 8.2 g of 6-chloro-1-hexanol (59.7
mmol) was added dropwise over 1 hour. After completion of the dropping, the mixture was further reacted with stirring for 20 hours while heating under reflux.

After the reaction was completed, the mixture was acidified with hydrochloric acid, filtered with suction,
Washed with water. The obtained crystals were purified by column chromatography (filler Wakogel C-200, solvent chloroform) and then recrystallized from ethanol to give the title compound 10.
9 g (yield 87.6%) was obtained.

Infrared absorption spectrum (KBr) ν (c
m ^-1 ): 3400, 3100, 2960, 1580, 1530, 1020, 840 Proton nuclear magnetic resonance spectrum (CDCl ₃ ) δ (pp
m): 1.21-1.84 (m, 18H,-(CH ₂ ) ₄ -OH) 3.64-3.71 (s, 4H, -CH _2- ) 4.15-4.23 (s, 4H, -O-CH _2- ) 6.96- 7.27 (m, 6H, aromatic hydrogen) Elemental analysis (as C ₂₄ H ₃₀ O ₄ F ₄ ): Calculated value C: 62.87%; H: 6.59% Found value C: 63.09%; H: 6.35%

DSC thermogram: Shown in FIG. Two endothermic and exothermic peaks are observed at the time of temperature rise and at the time of cooling, which indicates that the liquid crystal is an enantiotropic liquid crystal. Small angle X-ray measurement: Shown in FIG. 2 and Table 1.

Reference Example 3 (2,2 ', 3,3', 5,5 ', 6,6'-octafluorobis (6-hydroxyhexyloxy) biphenyl (8FBHHB
Synthesis of P) 2 with dropping funnel and calcium chloride tube
2,2 ', 3,3', 5,5 ', 6,6' in a 00 ml four-necked flask
Octafluorobiphenyl 9.0 g (27.3 mmol), potassium hydroxide 3.1 g (60.1 mmol), catalytic amount of potassium iodide, 100 ml of ethanol and 20 ml of water were charged,
After reaching the reflux temperature (100 ° C.), 7.5 g (60.1 mmol) of 6-chloro-1-hexanol was added dropwise over 1 hour. After completion of the dropping, the mixture was further reacted with stirring for 20 hours while heating under reflux.

After the reaction was completed, the mixture was acidified with hydrochloric acid and filtered with suction.
Washed with water. The obtained crystals were purified by column chromatography (Wakogel C-200 packing material, chloroform solvent) and then recrystallized from ethanol to give the title compound 5.0.
g (yield 34.8%) was obtained.

Infrared absorption spectrum (KBr) ν (c
m ^-1 ): 3360, 2936, 2860, 1560, 1543, 1100, 810 ¹³ C The magnetic resonance spectrum (CDCl ₃ ) δ (pp
m): 25.4-32.6 (m, - (CH 2) 4 -) 63.0 (s, -CH 2 -OH) 75.3 (s, OH, -CH 2 -) 99.8,139.1-146.0 (m, aromatic) Elemental analysis (as _{C 24 H 26 O 4 F 8} ): calculated C: 54.43%; H: 4.94 % Found C: 54.75%; H: 4.45 %

DSC thermogram: Shown in FIG. Two endothermic and exothermic peaks are observed at the time of temperature rise and at the time of cooling, which indicates that the liquid crystal is an enantiotropic liquid crystal. Small angle X-ray measurement: Shown in FIG. 2 and Table 1.

[0045]

[Table 1]

Reference Example 4 (Synthesis of 4,4'-bis (6-hydroxyhexyloxy) biphenyl (FBHHBP)) Hyphen 35.0 g (188) was placed in a 200 ml four-necked flask equipped with a dropping funnel and a calcium chloride tube. 0.1 mmol), potassium hydroxide 18.8
g (413.8 mmol), catalytic amount of potassium iodide, 100 ml of ethanol and 20 ml of water were charged, and the reflux temperature (1
00 ° C) and then 6-chloro-1-hexanol 56.
5 g (413.8 mmol) was added dropwise over 1 hour. After completion of the dropping, the mixture was further reacted with stirring for 20 hours while heating under reflux.

After the reaction was completed, the mixture was acidified with hydrochloric acid and filtered with suction.
Washed with water. The obtained crystals were purified by column chromatography (filler Wakogel C-200, solvent chloroform) and then recrystallized from ethanol to give the title compound 57.
8 g (yield 79.5%) was obtained.

Infrared absorption spectrum (KBr) ν (c
m ^-1 ): 3300, 2940, 2850, 1610, 1500, 1480, 1280, 1250, 10
80, 1040, 820, 800 Proton nuclear magnetic resonance spectrum (CDCl ₃ ) δ (pp
m, built-in standard tetramethylsilane, same below) 1.22-1.91 (m, 18H,-(CH ₂ ) ₄ -OH) 3.67-3.74 (s, 4H, -CH _2- ) 4.06-4.13 (s, 4H, -O-CH _2- ) 6.95-7.31 (m, 6H, aromatic hydrogen) Elemental analysis (as C ₂₄ H ₃₄ O ₄ ): Calculated value C: 76.58%; H: 6.43% Found value C: 76.97%; H : 5.98%

DSC thermogram: Shown in FIG. Two endothermic and exothermic peaks are observed at the time of temperature rise and at the time of cooling, which indicates that the liquid crystal is an enantiotropic liquid crystal. Small angle X-ray measurement: shown in FIG. 4 and Table 2.

[0050]

[Table 2]

Example 1 (Synthesis of poly (hexyloxy fluorinated biphenyloxyhexyl succinate) (PH2FBS)) 3,3 'in a 100 ml round bottom flask equipped with a Dean Stark trap and a condenser with a calcium chloride tube. -Difluorobis (6-hydroxyhexyloxy) biphenyl (2F
BHHBP) 3.00 g (7.11 mmol), succinic acid 0.84 g
(7.11 mmol) and p-toluenesulfonic acid 0.072 g
(0.42 mmol) was charged with dried 1,2-dichloroethane and stirred at a reflux temperature (13
(0 ° C.), the mixture was heated under reflux for 56 hours for reaction.

After completion of the reaction, the obtained contents were put into a large amount of methanol to precipitate a polymer, and in order to remove low molecular weight substances, hot ethanol treatment was repeated for purification.
After filtering with a glass filter, the intrinsic viscosity [η] is 0.43.
2.93 g (yield 81.8%) of the title polymer of dl / g was obtained.

Infrared absorption spectrum: shown in FIG. DSC thermogram: shown in FIG. Two endothermic and exothermic peaks are observed at the time of temperature rise and at the time of cooling, which indicates that the liquid crystal is an enantiotropic liquid crystal.

X-ray diffraction: FIG. 7 shows the measurement results of small-angle X-ray diffraction.
Shown in. Further, the crystallinity was obtained from the measurement of wide-angle X-ray diffraction. The results are shown in Table 3. Elemental analysis (as _{C 28 H 34 O 6 F 2} ): Calculated C: 66.65%; H: 6.80 % Found C: 66.14%; H: 6.45 %

Example 2 (Synthesis of poly (hexyloxyfluorinated biphenyloxyhexyl succinate) (PH4FBS)) 3,3 'in a 100 ml round bottom flask equipped with a Dean Stark trap and a condenser with a calcium chloride tube. 3,5,5'-Tetrafluorobis (6-hydroxyhexyloxy) biphenyl (4FBHHBP) 3.00 g (6.54 mmol), succinic acid 0.52 g (6.54 mmol) and p-toluenesulfonic acid
0.066 g (0.39 mmol) was charged with dried 1,2-dichloroethane, and the mixture was stirred with a magnetic stirrer and brought to a reflux temperature (130 ° C.), and then heated under reflux for 56 hours,
It was made to react.

After completion of the reaction, the obtained contents were put into a large amount of methanol to precipitate a polymer, and in order to remove low molecular weight substances, hot ethanol treatment was repeated for purification.
The intrinsic viscosity [η] is 0.24 after filtering with a glass filter.
3.06 g (yield 86.6%) of the title polymer with dl / g was obtained.

Infrared absorption spectrum: shown in FIG. DSC thermogram: shown in FIG. Two endothermic and exothermic peaks are observed at the time of temperature rise and at the time of cooling, which indicates that the liquid crystal is an enantiotropic liquid crystal.

X-ray diffraction: FIG. 7 shows the measurement results of small-angle X-ray diffraction.
Shown in. Further, the crystallinity was obtained from the measurement of wide-angle X-ray diffraction. The results are shown in Table 3. Elemental analysis (as _{C 28 H 32 O 6 F 4} ): Calculated C: 62.22%; H: 5.97 % Found C: 61.58%; H: 6.02 %

Example 3 (Synthesis of poly (hexyloxyfluorinated biphenyloxyhexylsuccinate) (PH8FBS)) 2,2 'in a 100 ml round bottom flask equipped with a Dean Stark trap and a condenser with a calcium chloride tube. , 3,3 ', 5,5', 6,
6'-octafluorobis (6-hydroxyhexyloxy) biphenyl (8FBHHBP) 2.00 g (3.77)
mmol), succinic acid 0.45 g (3.77 mmol) and p-toluenesulfonic acid 0.038 g (0.22 mmol) were dried 1,
After charging with 2-dichloroethane, the mixture was stirred with a magnetic stirrer, brought to a reflux temperature (130 ° C.), and heated under reflux for 56 hours to cause a reaction.

After completion of the reaction, the obtained contents were put into a large amount of methanol to precipitate a polymer, and in order to remove low molecular weight substances, the treatment with hot ethanol was repeated for purification.
After filtering with a glass filter, the intrinsic viscosity [η] is 0.19.
1.09 g (yield 47.1%) of the title polymer having a dl / g was obtained.

Infrared absorption spectrum: shown in FIG. DSC thermogram: shown in FIG. Two endothermic and exothermic peaks are observed at the time of temperature rise and at the time of cooling, which indicates that the liquid crystal is an enantiotropic liquid crystal.

X-ray diffraction: FIG. 7 shows the measurement results of small-angle X-ray diffraction.
Shown in. Further, the crystallinity was obtained from the measurement of wide-angle X-ray diffraction. The results are shown in Table 3. Elemental analysis (as _{C 28 H 28 O 6 F 8} ): Calculated C: 54.91%; H: 4.61 % Found C: 55.50%; H: 4.45 %

[0063]

[Table 3]

Reference Example 5 (Synthesis of poly (hexyloxybiphenyloxyhexylsuccinate (PHFBS)) 100 m equipped with a Dean Stark trap and a cooling tube with a calcium chloride tube
1.00 g of 4,4'-bis (6-hydroxyhexyloxy) biphenyl (0FBHHBP) was added to a 1-volume round bottom flask.
(5.17 mmol), succinic acid 0.84 g (5.17 mmol) and p
-Toluenesulfonic acid (0.053 g, 0.31 mmol) was added together with dried 1,2-dichloroethane, and the mixture was stirred with a magnetic stirrer and brought to reflux temperature (130 ° C).
The mixture was heated to reflux for a time to react.

After completion of the reaction, the obtained content was put into a large amount of methanol to precipitate a polymer, and in order to remove low molecular weight substances, the treatment with hot ethanol was repeated for purification.
Filtered with a glass filter, the intrinsic viscosity [η] is 0.54
2.31 g (yield 92.4%) of the title polymer of dl / g was obtained.

Elemental analysis (as C ₂₈ H ₃₆ O ₆ ): Calculated value C: 72.09%; H: 7.35% Found value C: 72.35%; H: 7.28% DSC thermogram: Shown in FIG. X-ray diffraction: The measurement results of small-angle X-ray diffraction are shown in FIG. Further, the crystallinity was obtained from the measurement of wide-angle X-ray diffraction. The results are shown in Table 4.

[0067]

[Table 4]

[Brief description of drawings]

FIG. 1 is a DSC thermogram of an α, ω-dihydroxy compound.

FIG. 2 is a measurement view of small-angle X-ray diffraction of an α, ω-dihydroxy compound.

FIG. 3 is a DSC thermogram of α, ω-dihydroxy compound.

FIG. 4 is a measurement view of small-angle X-ray diffraction of α, ω-dihydroxy compound.

FIG. 5 is an infrared absorption spectrum of the polyester according to the present invention.

FIG. 6 is a DSC thermogram of polyester according to the present invention.

FIG. 7 is a measurement view of small angle X-ray diffraction of the polyester according to the present invention.

FIG. 8 shows D of poly (hexyloxybiphenyloxyhexyl succinate (PHFBS) as a reference example.
It is an SC thermogram.

FIG. 9 is a measurement view of small-angle X-ray diffraction of poly (hexyloxybiphenyloxyhexyl succinate (PHFBS) as a reference example.

Front page continued (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 63/00-63/91 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A compound represented by the general formula (I): (In the formula, A is a general formula (II) (In the formula, X represents hydrogen or fluorine.
At least two are fluorine. ) Represents a divalent aromatic group, R ¹ represents an alkylene group having 2 to 10 carbon atoms, and R ² represents an alkylene group having 2 to 10 carbon atoms. ), A substantially linear polyester having an intrinsic viscosity [η] in the range of 0.1 to 2 dl / g. 2. A is of the formula (III): The polyester according to claim 1, which is a group represented by: 3. A is of formula (IV): The polyester according to claim 1, which is a group represented by: 4. A is of the formula (V): The polyester according to claim 1, which is a group represented by: 5. The polyester according to claim 1 , wherein R ¹ is a hexylene group. 6. The polyester according to claim 1 , wherein R ² is an ethylene group.