JPS6232118A - Polyester resin and its production - Google Patents

Abstract

PURPOSE:To obtain the titled resin being soluble in an organic solvent and having a high glass transition point, by reacting a dicarboxylic acid dianhydride with a biphenol in an organic solvent. CONSTITUTION:At least one dicarboxylic acid dihalide (A) of formula I (wherein Ar is a bivalent tetrafluorobenzene or monochlorotrifluorobenzene nucleus, provided that when two or more kinds of Ar groups are used, other bivalent aromatic groups may be used also as Ar groups and X is a halogen), e.g., 2,4,5,6- tetrafluoroisophthaloyl chloride, is reacted with at least one biphenol of formula II (wherein R is a bivalent aromatic group), e.g., 2,2-bis(4-hydroxyphenyl)propane, at -20-200 deg.C for several min to several days in a two-phase system comprising a water-immisible organic solvent and an aqueous alkali solution to obtain a polyester resin of formula III (wherein n is 10-200).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyester resin, particularly a novel polyester resin that is soluble in various organic solvents and has a high glass transition point, and a method for producing the same.

(Prior Art) In the past, wholly aromatic polyester resins have excellent heat resistance and mechanical properties, and have been widely used as industrial materials. Among these polyester resins, those having a high glass transition point and excellent heat resistance exhibit low solubility in organic solvents and have problems in moldability. On the other hand, those exhibiting high solubility have a low glass transition point and have problems in heat resistance.

(Problems to be Solved by the Invention) As mentioned above, conventional wholly aromatic polyester resins have a high glass transition point, excellent heat resistance, and at the same time good solubility in organic solvents. The lack of a wholly aromatic polyester resin that has both heat resistance and processability has been a major problem in the commercial use of this resin.

Therefore, an object of the present invention is to provide a new polyester resin that is soluble in organic solvents and has a high glass transition point, and a method for producing the same.

(Means for Solving the Problems) The present inventors have made earnest efforts to produce a polyester resin that is soluble in an organic m-medium and has a high glass transition point, and have completed the present invention.

The first aspect of the present invention is a general formula (wherein R is one or more divalent organic groups, Ar is a divalent tetrafluorobenzene group when there is one type of Ar,
or a divalent monochlorotrifluorobenzene group, a divalent tetraphenylthiophene group, and when Ar is two or more types, one or two of them is a divalent tetrafluorobenzene group; monochlorotrifluorobenzene group, etc.) divalent aromatic group as species, n is 10-20
(representing an integer of 0) is a polyester resin represented by

The second invention of the present invention is based on the general formula (wherein, Ar is a divalent tetrafluorobenzene group or a divalent monochlorotrifluorobenzene group when there is one type of Ar; is one of them or
A dicarboxylic acid cybaride represented by a divalent tetrafluorobenzene group or a divalent monochlorotrifluorobenzene group as the two types, a divalent aromatic group as the other type, and X represents a halogen atom) A method for producing a polyester resin in which a species or two or more species are reacted with one or more biphenols represented by the general formula % (wherein R represents a divalent organic group) in an organic solvent. It is.

The polyester resin represented by the above general formula (1) is produced from the dicarboxylic acid civalide represented by the above general formula (n) and the biphenol represented by the above general formula (III), but the dicarboxylic acid dino-hydride is The dicarboxylic acid tubalides of the general formula (II) in which Ar is a divalent tetraph/L/o benzene group or a divalent monochlorotrifluorobenzene group can be used alone or in combination, Or 10-
99 mole of the above Ar is a divalent tetrafluorobenzene group, or a dicarboxylic acid civalide consisting of a divalent monochlorotrifluorobenzene group, alone or in combination, and 90-1 mole of the above Ar is one or two types. It is also possible to use a mixture of the above dicarboxylic acid cybarides comprising a divalent aromatic group. When a mixture of dicarboxylic acid cybarides is used, the feature of the present invention is that the dicarboxylic acid cybaride consisting of a single or mixed divalent tetrafluorobenzene group, or (and divalent monochloro) IJ fluorobenzene group is less than 10 mol. The glass transition point increases and the solubility in organic solvents becomes insufficient. As the dicarboxylic acid cybalide represented by the above general formula (II), a dicarboxylic acid cybalide in which Ar is a divalent tetrafluorobenzene group or a divalent monochlorotrifluorobenzene group is used alone or in combination, and the above-mentioned general It is also possible to use one kind or a mixture of two or more kinds of biphenols represented by the formula (I[I).

Among the dicarboxylic acid cybalides represented by the above general formula (n), the dicarboxylic acid cybalide in which Ar is a divalent tetrafluorobenzene group refers to 2,4゜5.6-tetrafluoroisophthalic acid cybalide; The dicarboxylic acid cybaride consisting of a monochlorotrifluorobenzene group refers to 5-chloro-2,4,6-)lifluoroisophthalic acid cybaride. Chlorine, bromine or fluorine can be used as the halodane atom in these dicarboxylic acid cybalides. These dicarboxylic acid cybalides are obtained by hydrolyzing the known 2.4.5.6-tetrafluoroisophthalonitrile or 5-chloro-2,4,6-)IJ fluoroisophthalonitrile, and producing 2.4.5. 6
-tetrafluoroinphthalic acid or 5-chloro-2,4
, 6-) is obtained by converting it into trifluoroisophthalic acid and dino-logonizing it with various conventionally known no-logonizing agents for caldefic acid.

Among the dicarboxylic acid cybalides represented by the above general formula (n), examples of the dicarboxylic acid cybalides comprising a divalent aromatic group include dichloride, difluoride, and dibromide of the following dicarboxylic acids. That is, terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid,
2.6-naphthalene dicarboxylic acid, 4.4'-diphenyl ether dicarboxylic acid, 3.3'-diphenyl ether dicarboxylic acid, 4.4'-diphenylmethane dicarboxylic acid, 3.3'-diphenyl methane dicarboxylic acid, 4.
Examples include chloride, difluoride, and dibromide such as 4'-diphenylsulfonedicarboxylic acid and 3,3'-diphenylsulfonedicarboxylic acid.

As the biphenol represented by the above general formula (II[), resorcinol, hydroquinone, 4,4'-dihydroxybiphenyl, 9-bis(4-hydroxyphenyl)
Fluorene, 2.2-bis(4-hydroxyfer)zolopane, 1.1.1.3.3.3-hexafluoro-2
, 2-bis(4-hydroxyfer)propane, 4.4
'-dihydroxydiphenyl ether, 4.4'-dihydroxydiphenylmethane, 4.4'-dihydroxydiphenyl sulfone, 3-(4-hydroxyphenyl)
-1,1,3-)dimethyl-5-indanol, 1,4
- Biphenols such as naphthalene diol, 1.5-naphthalene diol and 2.6-naphthalene diol can be exemplified. The polyester resin represented by the above general formula (1) is produced using an organic solvent that is immiscible with water - an alkali It is carried out by reacting the dicarboxylic acid cybalide represented by the above general formula (Il) and the biphenol represented by the above general formula (I [I) in a two-phase system of an aqueous solution at -20-200°C for several minutes to several days. It is something. In this method, the molecular weight of the polyester resin represented by the general formula (1) is limited by the charged amounts of the dicarboxylic acid tubalide represented by the above general formula (n) and the biphenol compound represented by the above general formula (I[[), and these When the reaction components are used in equimolar amounts, a high molecular weight polyester resin represented by the above general formula (1) can be produced. The above general formula (1
), n is 10-2
The reason for limiting n to an integer of 00 is that if n is smaller than 10, the mechanical properties and heat resistance of the molded product formed into a film etc. will not be sufficient, and if n exceeds 200, the solubility in organic solvents etc. will be poor. Because it will get worse.

Organic solvents that can be used in this method include carbonized wood-based solvents such as hexane, pentane, octane, and cyclohexane, benzene, anisole, and diphene.
Examples include aromatic solvents such as chlorine, nitrobenzene, and benzonitrile, and halogenated solvents such as chloroform, dichloromethane, 1,2-dichloroethane, and 1.1.2.2-tetrachloroethane. . It is effective to coexist all quaternary ammonium salts and quaternary phosphonium salts together with such organic n-solvents. Such salts include tetrabutylammonium chloride, tetrahexylammonium chloride, pennortriethylammonium chloride, cetyltrimethylammonium chloride, tetrabutylammonium bromide,
Tetrahexylammonium bromide, benzyltriethylammonium bromide, cetyltrimethylammonium bromide, tetrabutylphosphonium chloride, tetrahexylphosphonium chloride, pennortriethylphosphonium chloride, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, tetrahexylphosphonium bromide , and salts such as benzyltriethylphosphonium bromide. Other methods for producing the polyester resin represented by the above general formula (1) include hexane, pentane, octane,
Hydrocarbon solvents such as cyclohexane, benzene, anisole, diphenyl ether, nitrobenzene, benzonide.

Aromatic solvents such as chlorine and organic solvents such as halogenated solvents such as chloroform, dichloromethane, 1,2-dichloroethane, and 1.1.2.2-tetrachloroethane are used alone, and pyridine, triethylamine, etc. This is done in the presence of an acid acceptor.

The thus produced polyester resin represented by the above general formula (I) is combined with the dicarboxylic acid cybaride represented by the above general formula (II) used and the above general formula (■) used.
Although its solubility changes depending on the type of biphenol represented by Partly soluble. The above general formula (
Even when the polyester resin represented by 1) is heated to around 350'C, no significant weight change is observed.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 0.57 to 5.1 mL of IM-NaOH water it
1 g (2.5 mmol) of 2,2-bis(4-hydroxyphenyl) 7'opy and 15η of benzyltriethylammonium chloride were dissolved, and 5. Om
0,68711 (2,
5 mmol) of 2.4°5.6-tetrafluoroisophthalic acid chloride was added at once, and the mixture was stirred at 10°C for 40 minutes. The reaction bath liquid was poured into 300 mL of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield: 94% Intrinsic viscosity: 0.85 dL/II (measured in o-chlorophenol at 30°C, concentration of 0.5!i/di) Infrared absorption spectrum (KBr) ・cs-': 1750 (C
-0) Elemental analysis value C) 1 Calculated value (chi) 53.90 4.22 Actual value <To>
53.21 4.34 10% weight loss by thermogravimetric method Temperature: 440°C in fresh air 382°C in nitrogen The solubility in organic media is shown in Table 1.

Example 2 8 rnL glue 0.57111 (2,
5 mmol) of 2,2-bis(4-hydroxyphenyl)furonoyan and 0.610.9 of triethylamine were dissolved, and to this was added 0.7291 (2.5 mmol) of 5-chloro-2,4, Rotrifluoroisophthalic acid chloride was added, and the mixture was stirred at 5°C for 30 minutes. reaction m solution,
The mixture was poured into 300 mL of methanol to obtain a white flaky polymer.

Intrinsic viscosity 0.45 dL/11 (measured in o-chlorophenol at 30° C. (at a concentration of 151 i'/dl)) Solubility in organic solvents is shown in Table 1.

Example 3 0.67 to 5.1 mL of IM-NaOH water bath solution
0.9 (2.5 mmol) of 3-(4-hydroxyphenyl)-1,1,3-trimethyl-5-indanol and 15 m9 of benzyltriethylammonium chloride were dissolved, and to this was added 5.0 mL of I in dichloromethane
PN 0, 687F (2,5 Cabinet o1) 2.4.5
．． 6-Tetrafluoroisophthalic acid chloride was added all at once, and the mixture was stirred at 10°C for 40 minutes. The reaction mixture was poured into 300 mL of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield 98% Intrinsic viscosity 0.49 dL/, f (measured in o-chlorophenol at 30°C at a concentration of 0.5 J9/di) 10*ii! by thermogravimetry! Decreasing temperature in air 45
Table 1 shows the decomposition properties for organic solvents at 447°C in nitrogen at 0°C.

Example 4 To 5.1 mL of IM-NaOH water bath solution, o.87
5II (z, 5 mmol) of 9.9-bis(4-hydroxyphenyl)fluorene and 151n9 of pencil triethylammonium chloride were added to 5. O
0,6879 (2,
5 mmol) of 2°4,5.6-tetrafluoroisophthalic acid chloride was added all at once, and the mixture was stirred at 10°C for 40 minutes. Reaction solution M was poured into 300 mL of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield 96% Intrinsic viscosity 0.31 dL/I (measured in o-chlorophenol at 30°C at a concentration of 0.5.9/dl) Weight loss temperature of 10 cm by thermal 1iu measurement temperature in air 44
Solubility in organic solvents at 3°C is shown in Table 1.

Example 5 5.0.81 in 1 mL of IM-NaOH water bath solution
1.1.1.3.3.3- of 011 (2.5 mmol)
Hexafluoro-2,2-bis(4-hydroxyphenyl)propane and 15 μm of pencil triethylammonium chloride were dissolved, and 5. 0,68717 (2,5 mmol) dissolved in OmL dichloromethane
2.4.5.6-Tetrafluoroisophthalic acid chloride was added all at once and the reaction solution was stirred at 10°C for 40 minutes. Added a small amount of hydrochloric acid and poured into 300 mL of boiling water. A flaky polymer was obtained.

Yield 98% Intrinsic viscosity 0.33 dL/# (measured in o-chlorophenol at 30°C, concentration of 0.5.9/di) 10% reduced temperature produced gas by thermogravimetry 390
Table 1 shows the solubility in organic solvents.

Example 6 0.81011 (2.5t
nmol) of 1.1.1.3.3.3-hexafluoro-2,2-bis(4-hydroxyphenyl)flonoyay
4M of 0.610IO tritechnylamine, and 0.729N (2.5 mmol) of 5-chloro-2
, 4, add rotifluoroisophthalic acid chloride,
The mixture was stirred at 5°C for 30 minutes. The reaction bath liquid was poured into 300 mL of methanol to obtain a white flaky polymer.

Yield 98% Intrinsic viscosity 0.31 dL/! i' (measured in o-chlorophenol at 30°C at a concentration of 0.5.9/di) Example 7 0.57 in 5.1 mL of I M -NaOH water bath solution
Dissolve 1F (2.5 mmol) of 2.2-bis(4-hydroxyphenyl) glomerol and 1 km of 15 m9 of benzyltriethylammonium chloride, and add 5. Om
0,069# (0,2
5 mmol) of 2°4,5,6-tetrafluoroisophthalic acid chloride and 0.457 fI (2,25 mmol
) Add the mixture of isophthalic acid Loli P at once and add 1
The mixture was stirred at 0°C for 40 minutes. The reaction mixture was poured into 300 mL of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield: 98% Intrinsic viscosity: 0.68 dL/l (measured in o-chlorophenol at 30°C, concentration of 0.51/m) 10s weight loss temperature by thermogravimetry: 468% in air
℃ The solubility in organic solvents is shown in Table 1.

Example 8 0.4 to 5.1 mL of IM-NaOH aqueous solution
1.1.1.3.3.3 of 2ON (1.25 mmol)
-hexafluoro-2,2-bis(4-hydroxyphenyl)fluoroamine, 0.28611 (1,25mmo
2-bis(4-hydroxyphenyl)pronogne, 15vI9 of benzyltriethylammonium chloride t-resolved, and 5. 0,687 Ji' (2,5 mmol
2.4.5.6-tetrafluoroisophthalic acid chloride (2.4.5.) was added all at once and stirred at 10°C for 40 minutes. The reaction solution was poured into 300 mL of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield 97% Intrinsic viscosity 0.62 dL/Ii (measured in o-chlorophenol at 30°C at a concentration of 0.5!j/di) Thermogravimetric weight loss of 10 cm in air 432
℃ The solubility in organic solvents is shown in Table 1.

(Effects of the Invention) The present invention provides a polyester resin represented by the above general formula (1) and an advantageous method for producing this polyester resin. While many conventional polyester resins have excellent heat resistance but have low solubility in organic solvents, making them difficult to mold, the polyester resin of the present invention is soluble in organic solvents and can be molded. It is easy to use, and has excellent heat resistance, electrical properties, and mechanical properties, so it has great value as an industrial material.

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is one or two types of divalent aromatic group, Ar is A
When r is one type, a divalent tetrafluorobenzene group or a divalent monochlorotrifluorobenzene group, Ar is 2
In the case of more than one species, one or two of them is a divalent tetrafluorobenzene group, or a divalent monochlorotrifluorobenzene group, the other species is a divalent aromatic group, n is 10- (representing an integer of 200) A polyester resin represented by: 2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is one or more divalent organic groups, Ar is a divalent tetrafluorobenzene group if there is only one type of Ar,
or a divalent monochlorotrifluorobenzene group, in the case of two or more types of Ar, one or two of them is a divalent tetrafluorobenzene group, or a divalent monochlorotrifluorobenzene group, and other In manufacturing polyester resins represented by a divalent aromatic group as a species, n is an integer from 10 to 200, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (Ar is one type of Ar is a divalent tetrafluorobenzene group, or a divalent monochlorotrifluorobenzene group, and when Ar is two or more types, one or two of them is a divalent tetrafluorobenzene group, or, and monochlorotrifluorobenzene group, other species are divalent aromatic groups, and X represents a halogen atom); A method for producing a polyester resin, which comprises reacting one or more biphenols represented by (wherein R represents a divalent aromatic group) in an organic solvent.