JPH07188405A - Preparation of polyarylate - Google Patents

Abstract

PURPOSE:To produce a polyarylate having a high degree of polymerization and a good color tone at a low cost with a good operation capacity by adding a particular amt. of a fatty acid anhydride and a particular compd. in the melt polymerization of particular amounts of isophthalic acid and terephthalic acid with bisphenol A. CONSTITUTION:An acid component composed of isophthalic acid and terephthalic acid in a molar ratio of (100:0) to (10:90) is reacted with bis(4- hydroxyphenyl)propane (bisphenol A) in an equimolar ratio to prepare a polyarylate. In this reaction, (a) a C2 to C8 fatty acid anhydride in a larger equivalent than the hydroxyl group of bisphenol A and (b) a compd. of the formula I (wherein B<1> and B<2> represent each a C6 to C18 alkyl group or an arylalkyl group, m is 0 or 1, X represents any one of groups of the formula II and R<1> and R<2> represent each H or a C4 or lower alkyl group) in an amount of 0.5 to 15wt.% of the polyarylate are added to regulate the intrinsic viscosity [eta]of the polyarylate to not less than 0.35.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyarylate having excellent heat resistance and color tone economically and with good operability by a melting method.

[0002]

2. Description of the Related Art Polyarylate composed of an aromatic dicarboxylic acid component and an aromatic diol component is well known as a thermoplastic having high heat resistance, excellent mechanical properties and chemical properties. It is widely used in the electric and electronic equipment fields, automobile fields, machine fields, etc. after being mixed with other resins or alloyed.

Many methods for producing polyarylate are described in the literature, and they are essentially classified into three methods. That is, (1) an aromatic diol in which an alkali metal salt is used and an aromatic dicarboxylic acid dihalide are respectively brought into solution and brought into liquid-liquid contact,
Interfacial polymerization method in which reaction occurs in solution or at the interface of both phases,
(2) A melt polymerization method in which an aromatic diol component is acetylated with acetic anhydride and then reacted with an aromatic dicarboxylic acid,
(3) A method of reacting an aromatic diol with a diaryl ester of an aromatic dicarboxylic acid is known. Among them, a melt polymerization method in which an aromatic diol component is acetylated with acetic anhydride and then reacted with an aromatic dicarboxylic acid Is known as a method for producing polyarylate at low cost (for example, JP-A-62-84116).

However, by the melt polymerization method, for example, bisphenol A (hereinafter sometimes referred to as BA).
When a polyarylate is produced from isophthalic acid (sometimes referred to as IPA) and terephthalic acid (sometimes referred to as TPA), depending on the compounding ratio of IPA and TPA, polyarylate of As the degree of polymerization increases, the melt viscosity increases, making it difficult to obtain polyarylate with a high degree of polymerization. Therefore, a method of reacting by adding a plasticizer such as a phosphoric acid ester or diphenyl ether (for example, JP-A-2-208319)
However, it is often necessary to use a large amount in order to sufficiently reduce the melt viscosity, which causes deterioration of the color tone of the polymer and deterioration of its physical properties, making practical application difficult. Therefore, in order to obtain a polymer having a good color tone, it is necessary to rely on the interfacial polymerization method, and in the case of the interfacial polymerization method, a large amount of raw material, separation and purification steps are required.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for producing a polyarylate having a good color tone and a high degree of polymerization by a melt polymerization method, which can be economically and efficiently operated. It is in.

[0006]

Means for Solving the Problems As a result of earnest studies for solving such a problem, the inventors of the present invention have found that if a specific compound is used for the reaction in the melt polymerization, a relatively small amount of the compound is reacted. The present inventors have found that the addition of the compound can produce a polyarylate having excellent physical properties and good color tone and a high degree of polymerization, and arrived at the present invention.

That is, the gist of the present invention is that the molar ratio of isophthalic acid to terephthalic acid as an acid component is 100/0 to 1
When the polyarylate is produced by reacting bis (4-hydroxyphenyl) propane (bisphenol A) with the acid component at a substantially equimolar ratio of 0/90,
(A) An anhydride of a fatty acid having 2 to 8 carbon atoms which is equal to or more than the equivalent of the hydroxyl group of bisphenol A, and (b) 0.5 to 15% by weight of the obtained polyarylate, represented by the following general formula (1).
The method for producing a polyarylate is characterized in that the intrinsic viscosity [η] is polymerized to 0.35 or more by adding the compound shown in.

[Chemical 3] (In the formula, B ¹ and B ² are alkyl groups or arylalkyl groups having 6 to 18 carbon atoms, m is 0 or 1, and X is

[Chemical 4] R ¹ and R ^{2 each} represent H or an alkyl group having 4 or less carbon atoms. )

The present invention will be described in detail below. The polyarylate obtained in the present invention is substantially composed of BA and IP.
A, or BA, IPA and TPA,
In the acid component, the molar ratio of IPA and TPA is 100.
/ 0 to 10/90, preferably 100/0 to 40/60
Is. When the molar ratio of IPA and TPA is less than 10/90, crystalline polyarylate is formed, and melt polymerization cannot be performed, which is not preferable.

The mixing ratio of BA and the acid component (IPA / TPA) is substantially equimolar, that is, usually 0.9.
5 to 1.05, preferably 0.99 to 1.01, and optimally 1.00. If this requirement is not satisfied, it is difficult to obtain a polyarylate having a high degree of polymerization.

Further, as the anhydride of fatty acid having 2 to 8 carbon atoms, anhydride of acetic acid compound is preferable, and acetic anhydride is more preferable. 2 to 2 carbon atoms other than acetic anhydride
As the fatty acid anhydride of 8, for example, chloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, bromoacetic anhydride, β-bromopropionic anhydride, propionic anhydride, butyric anhydride and the like can be used. The addition amount thereof is equal to or more than the equivalent of the hydroxyl group of BA used, preferably 1.01 to 1.25 times equivalent, and optimally 1.05 times equivalent. If it is less than this amount, the degree of polymerization does not increase,
On the other hand, if the amount is large, the color tone of the polymer deteriorates, which is not preferable.

Further, in the compound represented by the general formula (1), B ¹ and B ² having 6 to 18 carbon atoms are used, but they can be arbitrarily selected within the range of 6 to 18 carbon atoms. When the number of carbon atoms is less than 6, the molecular weight is too low and the polymer may boil at the melting temperature to generate bubbles. Further, if the carbon number exceeds 18, the compatibility with the polyarylate becomes poor, and the effect of addition is insufficient.
Specific examples of the groups of B ¹ and B ² include n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group,
Linear alkyl groups such as n-tetradecyl group, n-hexadecyl group and n-octadecyl group, branched alkyl groups such as 2-hexyldecyl group and methyl-branched octadecyl group, or arylalkyl such as benzyl group and 2-phenylethyl group. Groups. Specific examples of the compound represented by the general formula (1) used in the present invention include those shown below. Among them, compound 1 (trade name [KP manufactured by Kao Corporation
-L155]) is preferable.

[0012]

[Chemical 5]

The amount of the compound represented by the general formula (1) to be added is 0.5 to 15% by weight, preferably 1 to 5% by weight of the obtained polyarylate, and it is added at any stage before the completion of the polymerization. However, it is preferable to add them together with the raw materials at the start of the reaction. If the amount added is less than 0.5% by weight, the effect according to the present invention is not recognized, and if the amount added exceeds 15% by weight, no further effect can be expected and the degree of polymerization may be rather lowered. .

The intrinsic viscosity [η] of the polyarylate produced according to the present invention is 0.35 or more. Below this value, various physical and mechanical properties including heat resistance,
It has poor chemical properties.

In the present invention, a copolymerization component can be used within a range that does not impair the object of the present invention. Examples of the compound of the copolymerization component include 4,4′-dicarboxydiphenyl, bis (4-carboxyphenyl) propane,
Bis (4-carboxyphenyl) sulfone, bis (4-
Aromatic dicarboxylic acids such as carboxyphenyl) ether, 2,6-naphthalenedicarboxylic acid, hydroquinone,
Resorcin, 4,4'-dihydroxyphenyl, 4,4 '
-(Dihydroxyphenyl) sulfone, 9,10-dihydro-9-oxa-10- (2 ', 5'-dihydroxyphenyl) phosphenanthrene-10-oxide,
Aromatic diols such as 1,4-naphthalene diol, diphenyl (2,5-dihydroxyphenyl) phosphine oxide, 4-hydroxybenzoic acid, 2-hydroxy-6
-Aromatic hydroxycarboxylic acids such as naphthoic acid.

In the present invention, an esterification reaction, a transesterification reaction, and a polycondensation reaction are involved, and it is usual to use a catalyst to promote each reaction. However, in the method of the present invention, the catalyst is not necessarily used. No need to use.

In the present invention, the melt polymerization method can be usually applied, but for example, it is preferable to carry out the following three steps (A), (B) and (C). Step (A): Substantially equimolar ratio of bisphenol A and acid component (molar ratio of isophthalic acid / terephthalic acid = 100/0 to 10/90), and (a) carbon equivalent to or more than the hydroxyl group of bisphenol A. An esterification tank was charged with an anhydride of a fatty acid having 2 to 8 atoms and (b) 0.5 to 15% by weight of the total amount of the above components, and the compound represented by the general formula (1). It is preferable to react at ˜140 ° C. for 1 to 5 hours. If the reaction is carried out at a temperature of less than 100 ° C. or lower, the degree of polymerization does not increase, and if the reaction is carried out at a temperature of higher than 140 ° C., the color tone of the polymer deteriorates, which is not preferable.

In step (B), the temperature is raised at 0.5 to 2 ° C./min in an inert gas atmosphere,
The reaction is preferably carried out for 1 to 4 hours when the temperature reaches 260 to 285 ° C. If the reaction is carried out at a temperature lower than 260 ° C., it tends to be crystallized and solidified, and if the reaction is carried out at a temperature higher than 285 ° C., the polymer color tone is deteriorated, which is not preferable. Further, with respect to the heating rate, a rate of 0.5 ° C./min or less is not preferable because the oligomer may crystallize and solidify during heating, and a rate of 2 ° C./min or more may cause a reaction. Is insufficient, which is not preferable.

Step (C) Further, the polyarylate prepolymer obtained in the esterification tank is transferred to the polymerization tank, the pressure reduction is started, and 0.5 to 1.
After holding for 0 hour, the temperature rise is started at 0.5 to 2 ° C./minute. If the rise is started in less than 0.5 hours, the amount of sublimate is large, and if it takes more than 1.0 hour, the oligomer may crystallize and solidify, which is not preferable. Then, finally, melt polymerization is performed at 300 to 315 ° C. to complete the reaction.

When the polyarylate is produced by the melt polymerization method as described above, a polyarylate having a good color tone and a high degree of polymerization can be obtained economically and with good operability. Moreover, since the obtained polyarylate has a high degree of polymerization and excellent heat resistance, plasma spray coating and high temperature molding are possible. In addition, aromatic acid anhydride bonds are formed in the polyarylate, which can be found in other polyesters, polyamides,
Since it has a suitable reactivity with a resin such as polyether, it is also useful as a resin for alloying.

[0021]

[Operation] The reason why a polyarylate having a good color tone and a high degree of polymerization can be obtained by the method for producing a polyarylate of the present invention is presumed as follows. That is, since the compound represented by the general formula (1) having a high boiling point and a low viscosity is present in the synthetic system, the increase of the melt viscosity due to the increase of the polymerization degree is suppressed, and the normal conditions for producing polyarylate are suppressed. It is speculated that the polymerization proceeds even if the reaction is carried out at.

[0022]

EXAMPLES Next, the present invention will be described more specifically by way of examples. In addition, in the examples, the intrinsic viscosity of polyarylate was determined from the melt viscosity measured at 20 ° C. using a mixed solvent of equal weight of phenol and ethane tetrachloride. The color tone of the polymer was measured using a color difference meter. The L value is the lightness (the larger the value is, the brighter it is), the larger the value is, and the a value is the red-green hue (the red side is reddish, the-side is greenish), and the closer to 0, the better the b value Is a yellow-blue hue (yellow on the + side, −
The side is bluish) and should be small unless it becomes extremely small. Further, the glass transition temperature and the melting point were measured at a temperature rising rate of 20 ° C./min using a differential scanning calorimeter (DSC-2 type manufactured by Perkin Elmer Co., Ltd.). The produced polyarylate was identified by infrared absorption spectrum, NMR spectrum and elemental analysis. In addition, the infrared absorption spectrum was measured by using a FT-IR-5M type manufactured by JASCO Corporation
It was measured by Br method, 4 cm ⁻¹ resolution, Gain 4, and 32 times averaging.

Example 1 BA, IPA and acetic anhydride (Ac ₂
O) and 100) / 210/210 in molar ratio, and compound 1 (trade name [KP-L155] manufactured by Kao Corporation) was added in an amount of 5% by weight of polyarylate, and N _{2 was} added. The mixture was reacted under atmospheric pressure at 140 ° C. for 2 hours while mixing. Then, the temperature was raised at 2 ° C./min under N ₂ flow, and when the temperature reached 280 ° C., the reaction was carried out for 2 hours. The obtained polyarylate prepolymer was transferred to a polymerization tank at 280 ° C., depressurization was started, the temperature was raised 30 minutes later, and finally melt-polymerized at 310 ° C. under reduced pressure of 1 torr for 2 hours. The results of the obtained polyarylate are shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 3 Reactions were carried out in the same manner as in Example 1 except that BA, IPA, TPA and compound 1 were charged in the proportions shown in Table 1.
The results of the obtained polyarylate are shown in Table 1.

Example 6 The reaction was performed in the same manner as in Example 1 except that the compound 1 was replaced with the compound 2. The results of the obtained polyarylate are shown in Table 1.

Comparative Example 4 The reaction was carried out in the same manner as in Example 1 except that the molar ratio of IPA and TPA was 5/95, but the polyarylate prepolymer crystallized and solidified at 260 ° C. during the reaction temperature rise. .
The melting point of the crystals of this polyarylate prepolymer was measured and found to be 295 ° C.

Comparative Example 5 BA, IPA and Ac ₂ O in a molar ratio of 100/100 /
The reaction was carried out in the same manner as in Example 1 except that the amount was adjusted to 190, but the degree of polymerization did not increase, and finally 310 ° C.
Melt polymerization was conducted under a reduced pressure of 1 torr for 10 hours, and the obtained polyarylate had an [η] of 0.22. The results of the above Examples and Comparative Examples are shown in Table 1.

[0028]

[Table 1]

Reference Example (Example of alloying) A PCM45 type twin-screw compounder (manufactured by Ikegai Tekko Co., Ltd.) was used, and 40 kg of polyarylate obtained in Example 1 and nylon 6 having a relative viscosity of 2.30 (including an impact resistance improver). .) 60k
Alloying with g (kneading condition of cylinder temperature of 270 ° C. and screw rotation speed of 180 rpm) was performed. AST of 1/2 "x 1/8" x 5 "using the obtained compound
The M test piece was molded by a J-100S type molding machine (manufactured by Japan Steel Works, Ltd.), and the notched Izod impact strength (IZ) and heavy load heat distortion temperature (HDT) specified in ASTM D-256 and D-648, respectively. Was measured. As a result, IZ =
Good results of 25 kgf · cm / cm and HDT = 155 ° C. were obtained.

[0030]

EFFECTS OF THE INVENTION According to the present invention, a polyarylate having a high degree of polymerization can be produced by melt polymerization with extremely high operability and economically. The resulting polyarylate is
It has excellent heat resistance and color tone, and is useful as a film, fiber, and molding material used in applications requiring heat resistance. Further, an aromatic acid anhydride bond is formed in the polyarylate, which has a suitable reactivity with other polyesters, polyamides, polyethers, and other resins, so it can also be used as an alloying resin. It is useful.

Claims (1)

[Claims] 1. A molar ratio of isophthalic acid and terephthalic acid as an acid component is 100/0 to 10/90, and bis (4-
When a polyarylate is produced by reacting hydroxyphenyl) propane (bisphenol A) with the above acid component in a substantially equimolar ratio, (a) the number of carbon atoms is 2 to 8 which is equal to or more than the equivalent of the hydroxyl group of bisphenol A. 0.5 to 15 of anhydrous fatty acid and (b) polyarylate obtained
A method for producing a polyarylate, comprising adding the compound represented by the following general formula (1) in an amount of% by weight to polymerize it to an intrinsic viscosity [η] of 0.35 or more. [Chemical 1] (In the formula, B ¹ and B ² are alkyl groups or arylalkyl groups having 6 to 18 carbon atoms, m is 0 or 1, and X is R ¹ and R ^{2 each} represent H or an alkyl group having 4 or less carbon atoms. )