JP2535452B2 - Polyarylates with spiro orthocarbonate structure - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyarylate. More specifically, it relates to a polyarylate having an aromatic spiro orthocarbonate structure in its main chain. This is a polyarylate having excellent transparency, heat resistance and mechanical properties.

[0002]

2. Description of the Related Art Conventionally, a wide variety of polyarylates have been synthesized and put into practical use as polyesters of dihydric phenols and aromatic dicarboxylic acids. They have mechanical properties,
It has excellent chemical properties and heat resistance, so it can be used for fiber, film,
Widely used as plastics.

Among these polyarylates, polyarylate obtained from bisphenol A and mixed phthalic acid is currently industrialized as an engineering plastic because it has excellent properties. However, even in those cases, the second-order transition temperature (Tg) is 180 to 200 ° C., and a material having a higher second-order transition temperature (Tg) is expected.

[0004]

OBJECT OF THE INVENTION It is an object of the present invention to provide a polyarylate having higher heat resistance, higher mechanical properties and higher transparency than conventional polyarylate.

[0005]

The structure of the present invention is represented by the following formula (I):

[0006]

Embedded image [Here, Ar is a divalent aromatic group. ] A polyarylate having an intrinsic viscosity of 0.3 or more, which is mainly composed of repeating units represented by

In the formula (I), Ar is a divalent aromatic group. Preferably it has 6 to 20 carbon atoms, more preferably 6 to
15 aromatic groups. Specifically, Ar includes a divalent aromatic group represented by the following general formula. These may be used alone or in combination of two or more.

[0008]

Embedded image [Where Y is a direct bond, -O-, -S-, -CO
-, - SO ₂ -, alkylidene, cycloalkylidene,
Or

[0009]

Embedded image Is. ] As a specific example,

[0010]

Embedded image And the like.

As Ar

[0012]

[Chemical 6] Is preferred.

[0013] repeating unit of the above formula constituting the polyarylene les over preparative (I) is 50% or more of the total repeating units, preferably 70% or more, more preferably accounts for 90% or more.

The polyarylate obtained by the present invention has an intrinsic viscosity of 0.3 or more measured at 35 ° C. in a mixed solvent of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane, It is preferably 0.4 or more. When the intrinsic viscosity is less than 0.3, the mechanical properties of the polymer are insufficient, which is not preferable.

The method for producing the polyarylate of the present invention is not particularly limited as long as a polymer can be produced, but the method described below is particularly preferable.

The following formula (II)

[0017]

[Chemical 7] [Where X is a halogen atom. ], 2,
2'-spirobis (1,3-benzodioxol-5-
Carbonyl halide) as the main acid halide component and substantially the same molar amount of the following formula (III) OH—Ar—OH (III) [where Ar is the formula (I ) Is the same as the definition of Ar. ] The manufacturing method which makes it react with the dihydric phenol compound shown by these in a solvent in presence of a basic substance.

In the above method, the reaction is not particularly limited as long as a polymer is produced, but more specifically, it can be further classified into two methods.

(I) A method in which a dicarboxylic acid halide and at least one of a diphenol compound are reacted in a solvent in the presence of a basic substance.

(Ii) A dicarboxylic acid halide and a diphenol compound and a basic substance are dissolved in one of two types of solvents which are incompatible with each other, and the two solutions are mixed to react with each other. And a method for producing polyarylate.

In the above methods (i) and (ii), the optimum method differs depending on the reaction conditions such as the type of diphenol compound to be reacted and the solvent used, but in many cases, the method (ii) is preferably used. The method (ii) will be described in detail below.

Examples of the diphenol compound used in the method (ii) include those represented by the above general formula (III). These may be used alone or in combination of two or more kinds. Good. Specific examples include hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 2,2-
Bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxydiphenyl ether, 3,4 ′ -Dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide,
1,4-bis (4-hydroxybenzoyl) benzene,
1,3-bis (4-hydroxybenzoyl) benzene,
Etc. can be mentioned. Of these, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are particularly preferable.

The reaction solvent is not particularly limited, but water is used as the solvent for the diphenol compound and the basic substance, and dichloromethane, dichloroethane, as the other solvent.
Halogenated hydrocarbons such as chlorobenzene and aromatic hydrocarbons such as benzene and toluene are preferably used.

As the basic substance used in the reaction, hydroxides such as sodium hydroxide and potassium hydroxide can be preferably used, but there is no particular limitation as long as it can form a water-soluble salt with the diphenol compound. Absent.

Further, β-naphthol as a viscosity stabilizer,
Phenols such as phenol and phenylphenol can be used.

The reaction temperature may be any number as long as it is a temperature at which the reaction occurs, but it is preferably 0 ° C to 100 ° C.
More preferably, the reaction is carried out in the range of 20 ° C to 40 ° C.

The pressure is not particularly limited, but usually the reaction can be preferably carried out under normal pressure.

Although the reaction depends on the temperature, a polymer having a preferable degree of polymerization is usually obtained in 30 minutes to several hours.

In the reaction, it is also preferable to use a monohydric phenol compound as a catalyst for promoting the reaction of a quaternary ammonium salt or the like and a viscosity modifier.

[0030]

Example 1 2,2-bis (4-vidroxyphenyl)
4.20 g of propane, 0.08 g of β-naphthol, 1.68 g of sodium hydroxide and 0.03 g of benzyltriethylammonium chloride were dissolved in 50 ml of water,
Hold at 20 ° C. 2,2'-spirobis (1,
3-benzodiocryl-5-carbonyl chloride)
6.83 g was dissolved in 50 ml of methylene chloride and added dropwise. The time required for dropping was about 5 minutes. After that, the liquid temperature was maintained at 20 ° C. and the reaction was performed for 90 minutes. Polymer flakes were obtained by reprecipitating the reaction solution with methanol. The polymer was washed 3 times with water. The polymer thus obtained had an intrinsic viscosity of 1.80 measured at 35 ° C. in a mixed solvent of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane. The second-order transition temperature (Tg) of this polymer was 249 ° C. as measured by DSC. ¹ H nuclear magnetic resonance spectrum ( ¹ H
-NMR) is shown in the figure. This is measured at a temperature of 20 ° C. using deuterated chloroform as a solvent.
In addition, a colorless transparent tough film was obtained by the casting method using a 1,2-dichloroethane solution.

[0031]

Example 2 In Example 1, 2,2'-spirobis (1,3-benzodioxol-
Instead of using 5-carbonyl chloride, 2,
A mixture of 5.46 g of 2'-bis (1,3-benzodioxol-5-carbonyl chloride) and 0.79 g of terephthalic acid chloride was used as a diphenol compound.
Instead of using 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl)
When an experiment was performed in the same manner as in Example 1 except that 4.94 g of cyclohexane was used, a polymer having an intrinsic viscosity of 1.64 and a second-order transition temperature (Tg) of 254 ° C. was obtained. Similarly, a colorless and transparent tough film was obtained by the casting method.

[0032]

INDUSTRIAL APPLICABILITY The polyarylate of the present invention has a very high second-order transition temperature, excellent heat resistance, and mechanical properties,
It is also highly transparent and excellent.

[Brief description of drawings]

FIG. 1 ¹ H nuclear magnetic resonance spectrum of the polymer obtained in Example 1.

Claims (1)

(57) [Claims] 1. The following formula (I): [Here, Ar is a divalent aromatic group. ] The polyarylate which consists mainly of the repeating unit shown by these, and has intrinsic viscosity of 0.3 or more.