JPS58134119A - Preparation of aromatic polyester - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyester industrially and advantageously, by reacting an aromatic dibasic acid dihalide with a dihydric phenol and an alkali metalic salt of thiophenol in the presence of a crown ether and cryptand compound. CONSTITUTION:An aromatic dibasic acid dihalide, e.g. terephthaloyl dichloride, of the formula X-A-Ar-A'-X'[X and X' are halogen; A and A' are CO, SO, SO2, etc.; Ar is formulaI(Y is O, CO, etc.; m and n are 0 or 1), naphthalene or anthracene]is reacted with a dihydric phenol of the formula H-Z-Ar'-Z'-H[Z and Z' are O or S; Ar' is formula II (R2 and R3 are 1-20C alkyl, allyl, etc.; o and p are integers 0-4), etc.]and/or an alkali metallic salt of a dihydric thiophenol in the presence of a crown ether, e.g. dibenzo-18-crown-6, and/or a cryptand compound in an amount of 0.01-10mol% based on the number of bisphenol moles.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing aromatic polyester polymers.

Aromatic polyesters made of aromatic dicarboxylic acids and divalent phenolic compounds have been known for a long time.

The first manufacturing method is interfacial polymerization, that is, a method in which aromatic dicarboxylic acid dichloride dissolved in an organic solvent that is incompatible with water and bisphenols dissolved in an alkaline aqueous solution are mixed to a certain degree (especially Kosho 4O-1959)
, secondly, the liquor polymerization method, that is, a method in which aromatic dicarboxylic acid dichloride and bisphenols are reacted together in an organic solvent (Japanese Patent Publication No. 87-5599), and thirdly, a method in which phenyl ester of aromatic dicarboxylic acid and bisphenols are reacted together. Melt straightening method of heating to high temperature (Special Publication No. 38-15247, equity a)
il (48-28119) and the like are known. The aromatic polyester polymer thus obtained has heat resistance and
It has excellent mechanical and electrical properties, and can be used in a wide range of applications, including molded bodies, films, and fibers, either as a composition or as a single unit.

...-.

More specifically, the present invention relates to a novel method for producing such an aromatic polyester polymer, and relates to a novel method for producing such an aromatic polyester polymer, in which a novel process is performed in the reaction of an aromatic dibasic acid cybaride and a dihydric phenol K4-j thiophenol alkali metal salt. It is characterized by the presence of crackne ethers and/or cryptands as a catalyst.

As the aromatic dibasic acid dinolide used in the present invention, all conventionally known ones can be used.

Specifically, general formula (1) % formula % () 1 In the formula, X1x is a norogen atom, A and A are -CO-1
-8O-1502-1-PO-1-PO2-; Ar is the following general formula (1) % formula % -0-P -0-, -NH-1-N- (R1 is m1n is O or 1
] A compound represented by these is used. Specifically, terephthalic acid dichloride, isophthalic acid dichloride F, 2.2-
Bis(4-talololuponylphenyl)propane, 2.
2-bis(4-talolosulfonylphenyl)propane,
4.4-dichlorocarbonyl diphenyl ether, 4,
4-dichlorosulfonyldiphenyl ether, 4,4-
Dichlorocarbonyl diphenyl ketone, 4,4-dichlorosulfonyl diphenyl ketone, 4,4'-dichlorocarbonyl diphenyl sulfone, 4,4-dichlorosulfonyl diphenyl sulfone, 4,4-dichlorocarbonyl biphenyl, 4,4- Examples include cycloros/L/honylbiphenyl, naphthalene dicarboxylic acid dichloride, and acidoracene dicarboxylic acid dichloride. The aromatic ring of these compounds may have a substituent such as a halogen, an alkyl group, an alkoxy group, or a nitro group.

Further, these aromatic dibasic acid cybarides may be used as a mixture, or a part thereof may be replaced with an aromatic tribasic acid trinolide compound. The most common and inexpensive ones to use are tele-7curic acid dichloride and isophthalic acid dichloride. Among these, it is preferable to use a mixture of these two types of dichlorides (however, the molar ratio thereof is 9/1 to 9/9).

On the other hand, as the dihydric phenol or uf offenol used in the present invention, all conventionally known compounds can be used. Specifically, the following general formula (1)% formula % () [wherein z and i are 10-1-5-; Ar is the following general formula (
IV) (Ylm, n is the same as above iR2, R3 is carbon number 1-
a monovalent group selected from 20 alkyl, allyl, aralkyl, alkoxyl and 'thenylalkoxy groups and their substituents, hadogen atoms (josp is an integer of θ to 4), and 2 selected from naphthalene groups and anthracene groups It is preferable to use a compound represented by the following formula. For example,
2.2-bis(4-hydroxyphenyl)propane, 1
, 1-bis(4-hydroxyphenyl)ethane, 1,2
-bis-(4-hydroxyphenyl)ethane, 2.4'
-(4-hydroxyphenyl)metapebis(4-hydroxyphenyl)methane, bis(hydroxyphenyl)-
Cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)furopane, l,1-bis(3-methyl-4-hydroxyphenyl)ethane, bis(8-/f-A-hydroxyphenyl)methane, 2.2-bis(8
, 5-dimethyl-4-hydroxyphenyl)pro, pan, 1.1-bis(8,5-dimethyl-4-hydroxyphenyl)ethane, bis(8,5-diif-4-hydroxyphenyl)methane, 2 .2-1(8-methyl-4-
Hydroxyphenyl-4'-hydroxyphenyl)propane, bis-(4-hydroxy2,6-cymethyl-3-
methoxyphenyl)methane, bis(4-hydroxy-2
, 6-diphenyl)methane, 2,2-bis(4-hydroxyphenyl-2,6-dichlorophenyl)furopane,
2,2-bis(4-hydroxyphenyl-2,6-sibromphenyl)propane, 2,2-bis(4-hydroxy-2,6-difluoro)furopane, bis(8-chloro-4-hydroxyphenyl) Propane, bis(8-I'
lolo-4-hydroxyphenyl)methane, 1,1-his(4-hydroxyphenyl)-2,2,2-)dichloroethane, 4,4'-dihydroxydiphenyloxydiphenyl ether, 8,8-dimef-4. 4-dihydroxy-diphenyl ether, 8-droxydiphenyl ether"s8',; fluoro 4,4-dihydroxydiphenyl ether, bis(8,5-dimethyl-4-hydroxyphenyl)ether, bis(8-isopropyl-4-hydroxy) phenyl) ether, bis(
8-Isophthalic acid 4-hydroxyphenyl) ether, his(8,5-siph'rom-4-hydroxyphenyl)ether %4*4'9 hydroxydiphenyl sulfide, 2. i-dimethyl-4,4'-dihydroxydiphenyl sulfide, 8,8'-dimethyl-4-4-dihydroxydiphenyl sulfide, bis(8,5-cyclo-4-hydroxyphenyl) sulfide, bis(3,5
-di-tert-butyl-4-hydroxyphenyl) sulfide, 4゜4-dihydroxydiphenylgtone, bis(8゜5-dichloro-4-hydroxyphenyl)ketone, bis(8,5-dibrom-4-hydroxyphenyl) ) Tetra,4,4'-dihydroxydiphenylsulfone1. Bis-(8,5-dichloro-4-hydroxyphenyl)sulfone, bis(8,5-dimethyl-4-hydroxyphenyl)sulfone, bis(2,5-dichloro-4-hydroxyphenyl)
human 80xyphenyl) sulfone, 4,4-dihydroxydiphenyl, 8,8',5,51'-tetramethyl-4,4'-dihydroxy7. e 7 diphenyl, 8,8,5.5-tetraphenyl-4,4
- Polynuclear aromatic bisphenols such as dihydroxydiphenyl, mononuclear aromatic bisphenols such as hydroquinone, resorcinol, and 2,4-dihydroxybenzaldehyde, condensed polycyclic bisphenols such as dihydroxynaphthalene and dihydroxyanthracene, and mono- or dithio of the above compounds. Analogs may be mentioned. Other special bisphenol compounds include alizarin, phenolphthalein, fluorescein, naphthophthalein, thymolphthalein, olin, phenolsulfophthalein,
Bisphenolic pigments such as cymlomophenolsulfo-7thalein, 2,2'-dihydroxy-1,1'-dinaphthylmethane, 4,4'-dihydroxydinaphthyl-1,1,2,2-dihydroxydinaphthyl- 1,1'
, 1,1-bis(4-hydroxynaphthyl)-2,2,
2-) Lichloroethane, 2,2'-dihydroxysinaphthalate, 1. : Dinaph and 'thyl compounds such as enylmethane can also be used as part of the bisphenols.

The catalysts that the present inventors use for these aromatic dibasic acid cybarides and dihydric phenols or thiophenols are kurakune ethers and cryptands. It has been revealed that these crackane ethers and cryptands form complexes with alkali metal ions. As a result, inorganic salts and alkali metals can be dissolved even in nonpolar solvents, and the paired anion can be present in the solution as an unsolvated, highly active, so-called naked anion. When bisphenols are used as this anion source,
The present inventors have discovered that a highly active phenoxy anion can be generated in the system by the action of this compound, and the reaction with aromatic dicarboxylic acid dichloride can easily proceed to produce an aromatic polyester polymer. I found it.

Examples of the kurakune ethers that can be used in the present invention include dibenzo-18-kurakune-6, dicy.::talohexyl-1"'Is-kurakune-6, dibenzo-
24-kurakun-8,12-kurakun-4,15-kurakun-5,18-kurakun-6, cyclohexyl-12
-Crown-4, tribenzo-18-kracune-6, tetrabenzo-18-kracune-6, dibenzo-26-kracune-6, or azakracune ether containing an iota or nitrogen atom in place of the oxygen atom in these kurakun compounds , and thiachracune ethers. For example 18
-Diacyclocurine-6, 1, 10-dithia-18-curacune-6, etc. Typical examples of cryptand compounds include those represented by the following formula.

These compounds are shown, for example, in ``Crown Compounds'' (written by Michio Hiraoka, Kodansha 1978), and all of them can be suitably used.

As mentioned above, these kurakun compounds or cryptand compounds have the effect of forming a complex with an alkali metal ion and activating the counter anion. In forming a complex, the size of the pore formed by the heteroatom in these compounds and the ionic radius of the alkali metal ion are related, and appropriate alkali metal ions are present for each of these compounds.

For example, for dibenzo-18-cracune-6, + is most appropriate, followed by Na+. Accordingly, an appropriate compound may be selected from the above-mentioned crackane compound or cryptand compound, depending on the alkali metal ion that forms a pair with bisferrate.

The amount of these catalysts used is 0.01 to 10 mol%, more preferably 0.1 to 5 mol%, based on the number of moles of bisphenol.

Various methods can be applied to supply the bis7erate used in the present invention. For example, there is a method in which an alkali metal salt of bisphenol is separately produced and used in this reaction, or in combination with an acid acceptor. Examples of this acid acceptor include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium hydrogen carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. Examples include weakly basic alkali metal inorganic compounds.

Furthermore, it is of course possible to use such bis-7E/retochloride in the form of an aqueous solution in the polymerization reaction of the present invention.

In the present invention, it is preferred to use organic solvents. As the applicable solvent, it is preferable to use one that dissolves or swells the aromatic polyester polymer to be produced. Examples thereof include methylene chloride, chloroform, 1,1,2-trichloroethane, 1,2-dichloroethane, 1,1 .2-
) Aromatic halogenated hydrocarbons such as 1'-chloroethylene, tetrachloroethane, and tetrachloroethylene bot-class halogenated hydrocarbons, such as chlorobenzene and dichlorobenzene. Furthermore, it is also possible to use solvents that are inert to this reaction, such as aromatic hydrocarbons such as toluene and xylene, and nitrobenzene. Further, abrotic solvents such as tetrahydrofuran, acetone, cyclohexquinone, 2,4-dimethyltetramethylene sulfone, etc. can also be used.

In the present invention, the polymerization reaction is usually carried out at 0 to 200°C. If water is present, hydrolysis of the aromatic dicarboxylic acid civalide may occur, which may lead to unfavorable results. Therefore, the reaction is preferably carried out at 0 to 20°C, more preferably 0 to 20°C.

By producing an aromatic polyester polymer according to the present invention, a polymer in which [η] is greater than or equal to i' can be obtained.

Such polymers can be applied to industrial applications as molded bodies and film sheets, either alone or in compositions with other polymers such as inorganic fillers, anti-aging agents, ABS1 polycarbonate, PPO, polystyrene, polyethersulfone, etc. .

Examples of the present invention will be shown below, but the present invention is not limited only by these examples.

Example 1 2.2-bis(4-hydroxyphenyl)propane 15
Millimoles are dissolved in 20+/- of a 1.25N caustic potassium aqueous solution under a nitrogen atmosphere and cooled to 5°C.

On the other hand, 7.5 mmol of terephthalic acid chloride, 7.5 mmol of isophthalic acid chloride, and 6.0,8 mmol of dibenzo-18-cracune as a catalyst were dissolved in 0-dichlorobenzene 20°C and cooled to 5°C. The mixture was quickly added to the above bisphenol aqueous solution and reacted with strong stirring. The polymerization reaction proceeded with initial heat generation. 1
．． After 5 hours, the organic phase containing the polymer was separated, and the organic phase containing the polymer was
It was neutralized and washed with 0.05 g/diluted hydrochloric acid. Furthermore, after washing the organic phase twice with water, the viscous organic phase was precipitated with a large amount of acetone. The intrinsic viscosity of the polymer was 0.62 (at 82° C. in chloroform).

Example 2 Dicyclohexyl-18-curacune as catalyst 60.8
The same procedure as in Example 1 was carried out except that mmol was used. The intrinsic viscosity of the obtained polymer was 0.70 (in chloroform at 82° C.).

Example 3 Under a nitrogen atmosphere, 5 mmol of 2,2-bis(4-hydroxyphenyl)propane and 5 mmol of resorcin were added to 1
．． Dissolve in 20s/25N caustic potash and cool to 5°C. On the other hand, 5 mmol each of terephthalic acid dichloride and isophthalic acid dichloride were dissolved in 20+/1.1,2.2-tetrachloroethane, and dipenzo-dichloride was added as a catalyst.
After dissolving 18-Kracun-60.25 mmol, 5
Cool to °C. Add this 1,1 to the above alkaline aqueous solution.
, 2. quickly add the 2-tetrachloroethane solution,
The reaction was allowed to proceed for 2 hours with vigorous stirring. Upon standing, the system separated into a viscous organic and aqueous layer. The aqueous layer was neutralized, decanted and washed twice with 50 g of water. After standing to separate, the organic layer was mixed with methanol weekly to precipitate the polymer. The yield was 100%. Phenol/1,1,2.
The intrinsic viscosity of the polymer in 2-tetrachloroethane=1/1 (82°C) was [η)=0.54.

Example 4 The same procedure as in Example 1 was conducted except that a cryptand compound having the following structural formula was used as a catalyst. The intrinsic viscosity of the obtained polymer was 0.82 (in chloroform at 82° C.). , Patent applicant Kanebuchi Chemical Industry Co., Ltd. Agent Patent attorney Makoto Asano

Claims (5)

[Claims] (1) Aromatic construction When producing an aromatic polyester polymer by reacting the basic acid sybaride and the alkali metal salt of divalent phenol and/or divalent thiophenol, crown ethers and/or cryptand compounds are used as a catalyst. A method for producing an aromatic polyester, characterized in that the amount of dihydric phenol is present in an amount of 0.01 to 10 mol %. (2) Aromatic dibasic acid cybaride has the following general formula (1) % formula % (1) l: where x and x are halogen atoms; 'A is -co''
The divalent group HAr selected from -1-8O-1-8O□-1-PO-1-PO2- has the following general formula (11) (% formula % divalent hydrocarbon group) and carbon & 1 to 10 a divalent group selected from a divalent substituted or unsubstituted hydrocarbon group) and a divalent group selected from a crene group and an acitracene group; m and n are 0 or 1] described in claim 1. manufacturing method. (3) The alkali metal salt of divalent phenol and/or divalent thiophenol has the following general formula (ill) H-Z-A r
-Z H(1) [In the formula, 2,2 is -0-1-5-; Ar is the general formula (1v) (Y, m, n are as above, iR2, R3 is the carbon number 1-2
0 alkyl, allyl, aralkyl, alkoxyl and hyphenylalkoxy groups and their substituents; The manufacturing method according to claim 1, which is represented by: (4) The manufacturing method according to claim 2, wherein the aromatic dibasic acid cybaride is terephthalic acid dichloride or isophthalic acid dichloride. (5) The manufacturing method according to claim 2, wherein the aromatic dibasic acid cybaride is a mixture of terephthalic acid dichloride and isophthalic acid dichloride (wherein the molar ratio is from 1 to 9/).