JPS60229921A - Aromatic polyester copolymer and production thereof - Google Patents

Abstract

PURPOSE:An inexpensive liquid crystal polyester terpolymer, consisting of an aromatic carboxylic acid, aromatic diol and aromatic hydroxy carboxylic acid, and having improved heat resistance and rigidity. CONSTITUTION:A copolymer, consisting of structural units expressed by formulas I -III (R<1>, R<2> and R<3> are bivalent aromatic group or R<4>-X<1>-R<5>; R<4> and R<5> are bivalent aromatic group; X<1> is O, S, sulfonyl, carbonyl, alkylene, alkylidene, etc.; H in the aromatic rings R<1>-R<5> may be substituted by halogen, hydrocarbon, etc.) at 45:55-55:45 molar ratio between the structural units expressed by formulas I and II and 5:95-95:5 molar ratio between the structural units expressed by formulas I and III, and having >=0.1dl/g inherent viscosity in p-chlorophenol in 0.5g/dl concentration at 50 deg.C. The above-mentioned copolymer is produced by ternary copolycondensation of the aromatic diol, aromatic dicarboxylic acid and aromatic hydroxy carboxylic acid using a phosphorus compound, e.g. diphenyl chlorophosphate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a tertiary copolymer polyester and its production method, in particular to a direct production method.

[Prior Art] In recent years, there has been an increasing demand for materials with excellent rigidity, heat resistance, and chemical resistance, regardless of whether they are fibers, films, or molded products. It is known that aromatic polyester is a heat-resistant polymer or a highly rigid polymer.

However, as a heat-resistant polyester, it has been well known for a long time that a polyaromatic polyester is produced by an interfacial polycondensation method by mixing an organic solvent solution of a mixture of terephthalic acid dichloride and isophthalic acid dichloride with an alkaline aqueous solution of bisphenol A. As one example, a thermoplastic liquid crystalline polymer produced using polyethylene terephthalate and acetoxybenzoic acid is well known, but from the point of view of heat resistance, it is preferable that the heat distortion temperature is 70 to 50°C. do not have.

[Object of the present invention]

In view of such drawbacks, the present inventor conducted intensive studies to find a polyester that is inexpensive and has good heat resistance, and a liquid crystalline polyester that is inexpensive and has heat resistance and high rigidity. The inventors have discovered that a ternary copolycondensate consisting of 3 and an aromatic oxycarboxylic acid has such properties and an advantageous manufacturing method for obtaining the terpolymer, and have thus arrived at the present invention.

[Means to solve the problem]

That is, the gist of the present invention is that the general formula (A), (11 and (0)-o-R"-0--□(Bn-0-R"-0--(0>) [wherein R1, Ra and R3 are divalent aromatic groups, R4
-xI-R5 group (however, R4 and RB are divalent aromatic groups, X' is an oxygen atom, a sulfur atom, a sulfonyl group,
Represents a carbonyl group, alkylene group, alkylidene group or ester group, and R1. R”.

The hydrogen atom of the aromatic ring of Ra, R4 and R8 may be substituted with a halogen, a hydrocarbon group, an alkoxy group or a phenoxy group), and the composition ratio is generally expressed as a molar ratio. Formula (A) D general formula (
B) is no good! :jj~SS:d3, general formula (A) and general formula (0) are z:qs~qs:z, and 0. ! An aromatic polyester copolymer whose logarithmic viscosity (ηinh) measured in l/dl at 50°C is not less than o, itu, yp, and its production method, that is, an aromatic carboxylic acid HOOOR represented by the general formula (D)
'co OH-(D) Aromatic diol HOR'OH represented by general formula (E)
(E) Aromatic oxycarboxylic acid HO represented by general formula (F)
R''(!OOH-(F) [In the formula, R@, R7 and Rs are divalent aromatic groups,
Rg-X"-R+7, where R9 and R" are covalent aromatic groups, X3 is an oxygen atom, a sulfur atom, a sulfonyl group,
Represents a carbonyl group, alkylene group, alkylidene group or ester group, and the hydrogen atom of the aromatic ring of Ra, , y, Ra, Ra and R″0 is substituted with... rogene, a hydrocarbon group, an alkoxy group or a phenoxy group. The ternary copolycondensation of the general formula (D) and the general formula (
K) has a molar ratio of lIs:5s-srSlIj, and the general formula (
D) The general formula (I') is used in a molar ratio of s:qr to 5:5, and the general formula (G') is used as a condensing agent.
) 1 yl, Y2 and zl represent an oxygen atom or a sulfur atom. Exists.

Incidentally, such direct polycondensation of an aromatic dicarboxylic acid, an aromatic diol, and an aromatic oxycarboxylic acid in a tertiary system has not been known at all to date.

Next, to explain the present invention in detail, specific examples of the aromatic dicarboxylic acid represented by the general formula (D) used in the present invention include terephthalic acid, in7thalic acid, naphthalic acid, 6-dicarboxylic acid, Naphthalene/, terdicarboxylic acid, diphenyl ruta, q'-dicarboxylic acid, methyl terephthalic acid, methyl isophthalic acid, diphenyl ether, di'-dicarboxylic acid, diphenylthioether-p
4'-dicarboxylic acid, diphenylsulfonata, ri'-
Examples include dicarboxylic acid, diphenylkatonta, ri'-dicarboxylic acid, co-diphenylpropane-+, 1Lt'-dicarboxylic acid, diphenyl-+, 11'-dicarboxylic acid, etc.; Any aromatic dicarboxylic acid may be used, or a mixture of these may be used.

Further, specific examples of the aromatic diol represented by the general formula (K) include hydroquinone, resorcinol, methylhydroquinone, chlorohydroquinone, acetylhydroquinone, acetoxyhydroquinone, nitrohydroquinone, dimethylaminohydroquinone, /, 4(-dihydroxynaphthol) , l,!-dihydroxynaphthol, /, A-dihydroxynaphthol, 2,6-dihydroxynaphthol, λ,7-dihydroxynaphthol,
co, co'-bis(lI-hydroxyphenyl)furopane, -1λ'-bis(lI-hydroxy-31!-dimethylphenyl)furopane, co, λ'-bis(terhydroxy3.!; -dichlorophenyl)-furopane , ko, −
'-Bis(terhydroxy-3-methylphenyl)-propane, 2,2'-bis(lI-hydroxy-3-chlorophenyl)propane, bis(4I-hydroxyphenyl)-methane, bis(4!-hydroxy-3 ,3-dimethylphenyl)-methane, bis(4!-hydroxy-3
,5-dichlorophenyl)-methane, bis(terhydroxy-3,3=dibromophenyl)-methane, he/-his(lI-hydroxyphenyl)cyclohexane, 4t
14! '-dihydroxydiphenylbis(4t-hydroxyphenyl)-ketone, bis(4t-hydroxy-3
,5-dimethylphenyl)-ketone, bis(Q-H)
"Roxy a, s-dichlorophenyl)-ketone, bis(Hiro-hydroxyphenyl) sulfide, bis(terhydroxy-3-chlorophenyl) sulfide, bis(terhydroxyphenyl) sulfone, bis(terhydroxy-3,!r-dichlorophenyl) ) ether, a, ta
'-dihydroxydiphenyl etc., but are not necessarily limited thereto. Moreover, these may be used as a mixture.

Examples of the aromatic oxycarboxylic acid represented by the general formula (F) used in the present invention include p-hydroxybenzoic acid, m-hydroxybenzoic acid, syrin-n-acid, vanillic acid, and hydroxybenzoic acid. t'-carboxydiphenyl ether, glucoxyda'-carboxybiphenyl 1.2. A-cyclop-hydroxybenzoic acid, -
1-hydroxybenzoic acid, 2.A-difluoro-p-hydroxybenzoic acid, salicylic acid, co-hydroxy, 6-naphthoic acid, co-hydroxy 3-su7to[,/-human dioxy5 - Naphthoic acid etc., but
Any aromatic oxycarboxylic acid represented by the general formula (F) can be used, or they may be used as a mixture.

In the present invention, the general formula (D), (@, (F
) in a molar ratio of ys:ss to sr:IIs, and (D):
(F) has a molar ratio of S:9S~? ! ;:! Use at a ratio of ; The ternary polycondensation reaction of these compounds is carried out in a solvent, but in the present invention it is necessary to have a phosphorus compound represented by the above general formula (G) present as a condensing agent in the reaction system. By having a phosphorus compound present,
The polycondensation reaction of the three-stage compound can be accelerated, and an excellent polyester terpolymer can be directly obtained in one-stage reaction.

A specific example of the phosphorus compound represented by the general formula (G) used in the present invention is diphenylchlorophosphate.
dinonylphenylchlor 7-osphenate, dibenzyl chlorphosphate, diothylchlor 7-osphate, dicyclohexylchlor 7-osphate, cyhexylchlor 7-osphate, dioctylchlor 7-osphate, didodecyl chlorphosphate, dienylpromophosphate , diphenylfluorophos-7ate phenylbutylchlor-7-phosphate, benzyloctylchlor-7-osphate, diphenylchlorothio-7
Examples include male 7ate, dinonylphenylchlorothiophosphate, and seabenzylchlorothiophosphate, but any of those represented by general formula (G) can be used, or a mixture of one or more may be used. .

As the solvent used in the present invention, it is preferable to use a base or a combination of a base and another solvent. Such bases include, for example, pyridine, α-picoline, β-picoline, γ-picoline, 3J-lutidine, 3. daltidine,
2. lI-lutidine, ko, 6-lutidine, ko, 3-lutidine, yu,! -lutidine, 2. Examples include I,b-collidine, quinoline, inquinoline, dimethylaniline, etc., but any tertiary amine can be used.

Other solvents include chlorobenzene, 0-dichlorobenzene, carbon tetrachloride, dichloromethane, chlorinated solvents such as tetrachloroethane, dimethylformamide, dimethylacetamide, N-methylpyrrolid, γ-butyrolact/, dimethylsulfoxide, Examples include polar solvents such as sulfolane and hexamethylphosphoramide, and aromatic hydrocarbons such as he/yne, toluene and xylene.

As mentioned above, by allowing the phosphorus compound to exist in the reaction system, the compounds represented by general formulas (4), (B), and (0) can be copolycondensed. It is more preferable to further include an amide compound, a norogenated product of an alkali or alkaline earth metal, or a mixture thereof in the reaction system, since a high polymer can be easily obtained.

When an amide compound is present in the present invention, the general formula (
(wherein R'', R'' and R'' represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group) or/and an amide compound represented by the general formula (1) (wherein R'' represents an optionally branched alkylene group having 3 or more carbon atoms, and R17 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group.)
It is preferable to use an amide compound represented by the following, specific examples of which include N,N-dimethylformamide,
N,N-diethylformamide, N,'N-dibutylformamide, N-methylfolumamide, formamide, N,N-dimethylacetamide, N,N-diethylacedoide, N-methylacetamide, acetanilide, N,N - Diphenylformamide, benzoylamide, N,N-dimeterpenzoylamide, N-methylbenzoylamide, NN-diethylacetamide, etc., where R'', R'' and R'' are hydrogen atoms, alkyl groups, etc. and those having an aryl group are particularly preferred. Among those represented by the general formula (1), N-methylcopyrrolidone is preferred from the viewpoint of cost.

Further, specific examples of alkali and alkaline earth halides used in the reaction include lithium chloride, lithium buquamite, lithium iodide, calcium chloride, magnesium chloride, rubidium chloride, and strontium chloride. Any halide can be used.

Among them especially lithium tetramite and lithium,
It is preferable to use iodide because a polymer with a high degree of polymerization can be obtained.

1 When polymerizing using an alkali or alkaline earth metal halide, a base alone or a base and another solvent may be used as a phosphorus compound represented by the general formula (G) and an alkali or alkaline earth metal. When placed in contact with a halide and dropped into a solution consisting of an aromatic dicarboxylic acid, an aromatic diol, an aromatic oxycarboxylic acid and a base, or a solution consisting of a base and another solvent, a very high degree of polymerization occurs. A polymer is obtained. In addition, when an amide compound is present, a mixture of an aromatic dicarboxylic acid, an aromatic diol, and an aromatic oxycarboxylic acid is added to a solution containing an amide compound, a phosphorus compound, a base, or a solvent in addition to the base. It is preferable that the compound be dissolved in at least one solvent selected from the compound and other solvents, and then added all at once. In the former case, the reaction proceeds by forming a complex between an alkali or alkaline earth metal halide, a phosphorus compound, and a base, and in the latter case, a Vilsmeier complex is formed from an amide compound and a phosphorus compound. It is presumed that the reaction is progressing.

The polycondensation temperature varies depending on the solvent, but is usually between θ and -〇θ℃.
The temperature is preferably about 100 to 100°C.

The system during polymerization varies depending on the combination of monomers used, such as homogeneous system, precipitation system, gel-like system, solvent, additives, etc., but the isolation of the polymer can be performed using a system such as a lower flucol or a lower ketone. This can be carried out by reprecipitation in an organic solvent, reprecipitation with water alone, washing, etc.

[Effects of the present invention]

According to the method of the present invention, the general formulas (A), (B)
It consists of structural units represented by (0) and (0), and has the general formula (
The molar ratio of A):(B) is Das:5s-ss:
: DaS is the general formula (A) i (0) is S in molar ratio
:95 to 95:S, and 0,! in p-chlorophenol! It is possible to easily obtain an excellent aromatic polyester terpolymer having heat resistance or heat resistance and high rigidity, which has an logarithmic viscosity (ηinh) of 0, /dt/11 or more when measured at 50° C. with f 117 dl. Furthermore, the method of the present invention can directly obtain an excellent polyester terpolymer, so it can be produced at low cost and is an industrially advantageous method.

Hereinafter, the present invention will be explained in detail using examples.

Example/Add DMF (5 mL) to a solution of diphenylchlorophosphate (/, 2 mmol) in pyridine/(10 mL),
Stirred at room temperature for 30 minutes. Add inphthalic acid (
, z, tmmol) *Bisphenol A (2,6 mm
ol) and p-hydroxybenzoic acid (!; mmo
Add a solution of pyridine (0 mL) in which i
The reaction was carried out in an oil bath at 0.degree. C. for 3 hours.

The reaction solution was poured into methanol, and η1nh (0.5% in p-chlorophenol, measured at 50°C) was 0. A
Example 0 where a polymer of Odt/11 was obtained in quantitative yield:
1~! The following results were obtained in the same manner as in Example except that the dicarboxylic acid, diol and oxycarboxylic acid were changed as shown below.

Example 6 Pyridine (/θmmol) dissolved in lithium bromide (/θmmol)
, 2θmL) solution to diphenylchlorophosphate) (
/,? mmol) and stirred at room temperature for 30 minutes.

Isophthalic acid (2,!r mmol), bisphenol A (,
2,tmmol) and p-oxybenzoic acid (!r
mmol) of 1 in pyridine (10 mL) over 30 minutes, and the mixture was further reacted in an oil bath at 7.20°C for 3 hours.

Similarly to Example 1, ηinh is θ, AIIdt/g
of polymer was obtained in quantitative yield.

Example? , /I+ The following results were obtained in the same manner as in Example 6, except that the dicarboxylic acid, diol, and oxycarboxylic acid were changed as shown below.

Claims (2)

[Claims] (1) General formulas (A), (B) and (C)-o-
R"-0--(B) -o-R"-c --(0) [In the formula, R1, R2 and R3 are covalent aromatic groups, uA
xI R5 group (however, R'o! and R6 are divalent aromatic groups, xl is an oxygen atom, a sulfur atom, a sulfonyl group,
Representing a carbonyl group, alkylene group, alkylidene group or ester group or a direct bond, and R', R2, R3
, R4 and Rs] the hydrogen atom of the aromatic ring is
(which may be substituted with a hydrocarbon group, an alkoxy group or a phenoxy group))
The proportion of the composition is determined by the molar ratio of the general formula (the general formula (B) is das'', ss~ss'', pr, the general formula (A) is the general formula (
C) is a molar ratio of j-:91 to qA':j, and katsup
- Logarithmic viscosity (ηtnh) measured at go°C with O, U, and U in chlorophenol is 0. /dt/g or more. (2) Aromatic carboxylic acid Ho represented by general formula (D)
oaR"cooH-(D) Aromatic diol HOR'OH represented by general formula (E)
-(E) Aromatic oxycarboxylic acid H represented by general formula (F)
OR'000H-(F) [In the formula, R6, R? and R8 is a covalent aromatic group, R'-
X! RIG group (where 2 and R" are covalent aromatic groups, "" represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an alkylidene group, or an ester group, and RM. R7, The hydrogen atoms of the aromatic rings of I, , * and RM represent [optionally substituted with rogene, hydrocarbon group, alkoxy group, or phenoxy group]] in general formula (D). General formula (E) is molar ratio lI's:ss
~55: Da5, general formula (D) D general formula (F) has a molar ratio of 4-:9j--9! :! ; As a condensing agent, R1' and R12 represent an aromatic group, an aliphatic group (including alicyclic group), or an aralkyl group, and G represents a halogen atom. A method for producing an aromatic polyester copolymer, characterized in that the method is carried out using a phosphorus compound represented by the following formula: Yl, YM and 2' represent an oxygen atom or a sulfur atom.