JPS6069137A - Production of aromatic polyester-amide copolymer - Google Patents

Abstract

PURPOSE:To form a high-polymerization degree polymer excellent in heat resistance, by setting the amount and concentration of an alkali used so that a specified condition may be satisfied in the production of an aromatic polyester- amide copolymer by an interfacial polymerization. CONSTITUTION:An aqueous alkaline solution of a mixture (molar ratio of 1:19- 19:1) of (A) 2,2-(4'-hydroxy-4''-amino-diphenyl)propane and 2,2-bis(4'-hydroxyphenyl)propane, and (B) a water-immiscible organic solvent solution of a mixture (molar ratio of 1:9-9:1) of isophthaloyl dichloride and terephthaloyl dichloride are mixed at 40 deg.C or below with stirring to effect the interfacial polymerization of the monomers. In this process, the alkali used in the aqueous alkaline solution is set at a value >= the number of equivalents of the hydrochloric acid formed during the reaction, and the alkali concentration of the reaction system at the time of completion of the reaction is set at a value <=0.02g equivalent/l.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to aromatic, j? The present invention relates to a method for producing an IJ ester amide copolymer, and more specifically to a method for producing a highly polymerized aromatic polyester-ad copolymer having excellent and useful properties such as heat resistance with good reproducibility.

[Technical background of the invention and its problems]

Aromatic esters and aromatic polyamides.

It has been awarded as a rounded and engineering plastics material with excellent heat resistance and mechanical strength.

Among these, aromatic polyester is particularly excellent in electrical properties 2 mechanical strength and moldability. However, there is a drawback that heat resistance is somewhat insufficient.

On the other hand, aromatic polyamides have excellent heat resistance and mechanical strength, but have the disadvantage of poor moldability.

For this reason, aromatic polyester amide, which can be said to be a combination of both, has been developed as a material that mutually compensates for the shortcomings of both, and has the excellent properties of both, such as heat resistance, electrical properties, mechanical strength, and moldability. °Copolymers are attracting attention as high-performance engineering plastics.

As a method for producing the aromatic polyesteramide copolymer, there is a method in which an aromatic dicarboxylic acid compound or its derivative, an aromatic hydroxyamino compound or an aromatic dihydroxy compound, and an aromatic diamino compound are reacted with each other. Common.

Such a manufacturing method is described, for example, in Japanese Patent Publication No. 39-2601
Publication No. 2, Japanese Patent Publication No. 46-37739.

Special Publication No. 47-13381, Special Publication No. 48-1923
7 Publication, Special Publication No. 54-20555, Journal of Polymer Science: Irimer Chemistry Editorial (Journal of Polymer Science)
mer81ence: Polymer Chemi
stry EdltIon) 20, 683 (19
82) and others.

Specifically, an aromatic carofic acid dino-1ride dissolved in an organic solvent that is incompatible with water is mixed with an aromatic hydroxyamino compound, an aromatic dihydroxy compound, or an aromatic diamino compound dissolved in an alkaline aqueous solution. An interfacial polymerization method in which an aromatic dicarboxylic acid dino-1ride is reacted with an aromatic hydroxyamino compound or an aromatic dihydroxy compound and an aromatic diamino compound together in an organic solvent; Aromatic dicarboxylic acid dino-1ride Methods such as a melt polymerization method are known in which the phenyl ester of the compound and an aromatic hydroxyamino compound, an aromatic dihydroxy compound, or an aromatic diamino compound are heated.

Among the above-mentioned various methods for producing aromatic polyesteramide copolymers, the interfacial polymerization method is characterized by the fact that the reaction is completed in a short time under conditions of normal temperature and normal pressure, and that the reaction is completed in a short time under normal temperature and normal pressure conditions. It has the advantage that the chemical equivalent ratio of components is not as strict as in solution polymerization.

However, when producing a polyesteramide copolymer using an interfacial polymerization method, the reproducibility of the reaction is generally low, making it difficult to produce a polymer with a high degree of polymerization with good reproducibility. This method has the disadvantage that it may not be possible to obtain a polymer having a sufficient degree of polymerization to exhibit sufficient properties such as moldability and mechanical strength.

[Purpose of the invention]

An object of the present invention is to provide a method capable of producing a high degree of polymerization aromatic polyesteramide ° copolymer having excellent and useful properties such as heat resistance with good reproducibility.

[Summary of the invention]

The method for producing the aromatic polyesteramide copolymer of the present invention includes 2,2-(4'-hydroxy-4''-aminodiphenyl)propane, !:2,2-bis(4'-hydroxyphenyl) tec+A molar ratio of 1:19 to 19:
The molar ratio of the aqueous alkali solution of the mixture of 1 and isophthalic acid dichloride and terephthalic acid dichloride is 1:9 to 9:1.
A method for producing an aromatic polyester amide copolymer by completely mixing the mixture with a non-reactive organic solvent solution and reacting the mixture, wherein the alkaline concentration of the alkali aqueous solution is 0.02 f equivalent/at the end of one reaction. It is characterized by the following.

The 2,2-(4'-hydroxy-4''-aminodiphenyl)propane used reacts with the carboxyl group of iso7-talic acid dichloride or terephthalic acid dichloride, and the hydroxyl group forms an ester bond.

By the amino group forming an amide bond.

It is an essential component for providing aromatic polyesteramide with excellent heat resistance.

t7'j, 2,2-bis(4'-hydroxyphenyl)
Propane is an essential component of rounding that improves moldability by reacting the cal of isophthalic dichloride or terephthalic dichloride with the xyl groups and the hydroxyl groups forming ester bonds.

The molar ratio of 2,2-(4'-hydroxy-4"-aminodiphenyl)propane and 2,2-bis(4'-hydroxyphenyl)propane is in the range of 1:19 to 19:1, preferably 1 The molar ratio of isophthalic acid dichloride and terephthalic acid dichloride is usually in the range of 1:9 to 9:1, preferably in the range of 2:8 to 8:2. 1. If the amount of these compounds used is out of this range, the heat resistance and moldability of the resulting polymer will decrease.

The total amount of isophthalic acid dichlorite and terephthalic acid dichloride used is 2,2-(4'-human).

Fuxi 4″-aminodiphenyl) propane and 2゜2-
The amount is preferably equivalent to the total stoichiometric amount of bis(4'-human oxyphenyl)propane, and usually 90
It is used in the range of 105 to 105 mol, preferably 95 to 101 mol.

As the non-reactive organic solvent used in the method of the present invention, it is preferable to use one that is incompatible with water, but in some cases it is also possible to use one that is compatible with water.

Examples of organic solvents include methylene chloride, chloroform, carbon tetrachloride, l,2-dichloroethyl, 1,1.2
-) Su/roloethane, chlorobenzene, α-dichlorobenzene, benzene, toluene.

Examples include xylene, cyclohexanone, methyl ethyl ketone, methyl-1so-butyl ketone, acetophenone, tetrahydro7rane, dioxane, diethyl ether, and the like. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, cyclohexanone, tetrahydrone, and dioxane are prized for their excellent solubility in the aromatic polyesteramide copolymer of the present invention. However, tetrahydrofuran or dioxane has excellent compatibility with water, and if used alone, the I-limer produced may precipitate, which is a disadvantage. Therefore, when using tetrahydrofuran or dioxane, other It is preferable to use it in combination with an organic solvent that is incompatible with water.

The alkalis used are usually alkali metal hydroxides or alkali metal carbonates, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate,
Examples include sodium carbonate and potassium carbonate.

The amount of alkali used is equivalent to or more than the amount of HCt produced, more specifically, the amount is equivalent to or more than the sum of the stoichiometric amounts of isophthalic acid dichloride and terephthalic acid dichloride used at the end of one reaction. The alkali concentration in the aqueous solution is 0.02 F equivalent/or less, preferably 0.01 V equivalent/or less. The amount of alkali at the end of the reaction is more influenced by the concentration than the absolute amount of alkali. Therefore, adjustment of the amount of solvent is also an important factor. The reason why the amount of alkali used was limited within the above range was to obtain a polymer with a high degree of polymerization with good reproducibility.)
If the amount of alkali used exceeds the above range, the degree of polymerization of the resulting polymer will be poorly reproducible, and in many cases, only a polymer with a degree of polymerization low enough to exhibit sufficient mechanical properties may be obtained. Furthermore, as the alkali concentration in the aqueous solution at the end of the reaction increases beyond the above range, the degree of polymerization of the obtained polymer tends to decrease and/or the reproducibility of the degree of polymerization tends to decrease. .

In the present invention, 2,2-(4'-human °4x-4#
+ 7 minodiphenyl) deronochen,! :2,2-
Bis(4'-)nitroxyphenyl)zo1:I/? The concentration of the mixture in an alkaline aqueous solution is usually 2 to 25% by weight.
, preferably 5 to 15% by weight is used, and the concentration of the mixture of isophthalic acid dichloritro and terephthalic acid dichloride in a non-reactive organic solvent solution is also usually 2 to 25% by weight, preferably 5 to 15% by weight. .

The interfacial polymerization method in the present invention involves the use of 2,2-(4'-human0roxy4''-aminodiphenyl)pronobutyl and 2.
A non-reactive organic solvent solution of isophthalic acid dichloride and terephthalic acid dichloride is added to an alkaline aqueous solution of a mixture of 2-bis(4'-human-90xyphenyl)amino 4, and stirred vigorously, or conversely, isophthalic acid dichloride and terephthalic acid dichloride and terephthalic acid dichloride in a non-reactive organic solvent solution.
This is carried out by adding an alkaline aqueous solution of 0xyphenyl) Delonon. The polymerization reaction is usually carried out at 40°C or lower, preferably at 5°C.
Perform at ~25°C. The reaction time is usually 10 minutes to 3 hours.
Preferably it is about 1 hour. In order to allow the polymerization reaction to proceed smoothly, it is preferable to perform strong mechanical stirring to obtain a uniform dispersion system. In addition, dispersants include anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, cetyltrimethylammonium chloride, and cetylpyridinium chloride. Cationic surfactants such as benzyltrimethylammonium chloride, nonionic surfactants such as polyethylene oxide° can also be used. The amount of surfactant is usually preferably 10% by weight or less based on the weight of the organic solvent. However, when using a solvent that is compatible or has good affinity with water, such as cyclohexanone, methyl ethyl ketone, methyl-1so-butyl ketone, tetrahydrofuran, and dioxane, or a mixed solvent containing one or more of these, a dispersant is used. In many cases, it is not particularly necessary.

After completion of the above polymerization operation, the produced aromatic polyesteramide copolymer is isolated and purified according to a conventional method. That is, method 1: mixing the reaction mixture with a non-solvent 5 for the aromatic polyester amide copolymer, such as methanol, ethanol, isopronol, acetone, etc., to precipitate the polymer; After separation into an organic phase containing an alkali halide salt and an aqueous phase containing an alkali halide salt, the organic phase is mixed into a non-solvent for the polymer to precipitate the polymer, and the solvent is distilled off from the organic phase to isolate the polymer. be. In the aromatic polyesteramide copolymer obtained in this way, residual alkali salts generated during the polymerization reaction, alkalis used in the reaction, or surfactants used as dispersants remain. There are cases. These impurities remaining in the polymer may accelerate the complete decomposition of the polymer or cause discoloration during thermoforming or heating, so these impurities should be thoroughly washed with water or reprecipitated. In order to obtain good properties of the aromatic polyesteramide copolymer, it is desirable to remove the aromatic polyesteramide copolymer by performing operations such as the following.

The aromatic polyesteramide copolymer produced by the above-mentioned operation has the following formula (% formula %): (Formula [I)] The nyl groups are in the meta and para positions of each other. ) For more details, use the following formula (■), (v), (vx:
] and [■]:] ] wa (in the formula, the car-nyl groups are in the meta or para position to each other), and each structural unit is connected by an amide bond and/or an ester bond. It consists of a structure.

In the present invention, an aromatic polyester atom copolymer having the above-described structure and having a desired high degree of polymerization can be obtained. Generally, the degree of polymerization of a polymer has a close relationship with its molecular weight and is expressed by the logarithmic viscosity, which is a measure of the molecular weight of the polymer. 0.4 dt/or more. If the logarithmic viscosity is less than 0.3 dt/f, the mechanical strength will decrease, making it impossible to obtain a good molded product. The above-mentioned logarithmic viscosity refers to the viscosity of a dilute solution of polysaccharide having a concentration of 0.5 t/dt measured at 30° C. using cyclohexanone' as a solvent using an Ubbelohde viscometer.

The logarithmic viscosity ηinh is calculated using the following formula: [In the formula, t is? The flow time of the remer solution, to is the flow time of only the solvent, and C is the concentration of the polymer (unit: y/dL).
represents. ] It is indicated by.

The aromatic polyesteramide ° copolymer obtained by the method of the present invention has excellent heat resistance and electrical insulation properties.

It has mechanical strength, excellent compatibility with other resins and various fillers, and is easy to mold. Therefore, the copolymer can be formed into a film by festering, casting from solution,
Extrusion, injection molding, compression molding, fiberization and papermaking as solution or melt.

It can be processed into sheets and used for electrical insulating materials, electronic component molding materials, mechanical component molding materials, heat-resistant adhesives, paints, etc.

〔Effect of the invention〕

According to the present invention, an aromatic polyester amide having sufficient reproducibility, a desired high degree of polymerization, and excellent properties such as heat resistance, moldability, thermal properties, and mechanical properties.
Copolymers can be produced in a short time.

[Embodiments of the invention]

The following examples were carried out under a nitrogen atmosphere unless otherwise specified. Moreover, all parts indicate parts by weight.

Example 1 734.214 parts of 2,2-(4'-hydoxy-4#-aminodiphenyl)pronotal and 2,2-bix
(4'-Hydroxyphenyl)propane 34.686 parts and concentration i, o o o specified aqueous sodium hydroxide solution 6
14.5 parts and 400 parts of water were added. Add this solution to 10
While maintaining the temperature at 10°C and stirring vigorously, a solution containing 30.630 parts of isophthalic acid dichloride and 30.774 parts of terephthalic acid dichloride dissolved in 600 parts of total cyclohexanone was quickly injected.Then, while continuing to maintain the temperature at 10°C, The reaction was carried out for 1 hour. After the reaction was completed, the reaction mixture was allowed to stand and the aqueous layer and organic layer were separated. The aqueous layer was 500 ml.
After collecting a portion and putting it in a centrifuge to separate the organic layer partially suspended in the aqueous layer, the alkali concentration of the aqueous layer was adjusted to o, i.
o Measured by titration using standard hydrochloric acid. As a result, the alkali concentration in the aqueous solution after the completion of 1 polymerization reaction was 0.00
5 was 91/L.

The amount of alkali used in this example was 0.0 at the end of one polymerization.
009 f quotient/l.

On the other hand, the organic layer was poured into 6000 parts of methanol to precipitate a polymer. The polymer was thoroughly washed with water and methanol and dried under reduced pressure. The yield of the resulting aromatic polyesteramide was 104 parts (yield: 96 parts). This polymer is m-cresol.

It was soluble in cyclohexanone, tetrahydrofuran, dioxane, etc., and the logarithmic viscosity measured in cyclohexanone was 0.79 dt/f. The infrared absorption spectrum of the film of this polymer shows the N-H group of the amide bond at 3340 cm-', the C=0 group of the ester bond at 1740 cm-'', and the C=O group of the amide bond at 16703-''.
A group-based absorption band was seen, clearly indicating that the polymer was a polyesteramide.

2,2-(4'-hydroxy-
4″-aminodiphenyl)propane and 2゜2-bis(4
An aromatic polyester amide copolymer was obtained by completely reacting a mixture of `-hydroxyphenyl)propane with an aqueous solution of IJium and an organic solvent solution of isophthalic acid dichloride and terephthalic acid dichloride. After the reaction is complete,
Alkaline 96 degrees in the aqueous solution was measured in the same manner as in Example 1. Reaction condition 2 Alkali concentration in the aqueous solution at the end of the reaction,
The yield and logarithmic viscosity of the obtained fc polymer are summarized in the table.

Comparative Examples 1 to 3 Hydroxylation of a mixture of 2,2-(4'-hydroxy-4"-aminodiphenyl)delonogun and 2,2-bis(4'-hydroxyphenyl)propane in the same manner as in Example 1. A sodium aqueous solution and an organic solvent solution of isophthalic acid dichloride and terephthalic acid dichloride were completely reacted.However, the company using IJium (without hydration) specified that the alkali concentration in the aqueous solution at the end of the reaction should be 0.021 equivalent/or more. The reaction conditions and results are summarized in the table as in all Examples 2 to 6.

Claims (1)

[Claims] 2t 2-(4'-Hydroxy-4''-aminodiphenyl)propane and 2,2-bis(4'-hydroxyphenyl)propane in a molar ratio of 1:19 to 19:1 in an aqueous alkaline solution, and isophthalic acid. Mixing and reacting a mixture of acid dichloride and terephthalic acid dichloride in a molar ratio of 1:9 to 9:1 with a non-reactive organic solvent solution,
A method for producing an aromatic ester amide copolymer, wherein the amount of alkali used in the aqueous alkali solution is equal to or more than the equivalent of HCt produced during the reaction, and the alkali concentration at the end of one reaction is 0.02 f'A amount A method for producing an aromatic polyesteramide copolymer, characterized in that / is as follows.