JPH0246606B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aromatic polyester comprising terephthalic acid, isophthalic acid and divalent phenol. More specifically, terephthalic acid,
An aromatic polyester consisting of isophthalic acid (terephthalic acid, isophthalic acid molar ratio of about 3:7 to about 7:3) and divalent phenol and having a specific amount of acid anhydride bonds, at 25°C, 1 g/ The values of the logarithmic viscosity (abbreviated as ηT) in tetrachloroethane measured by dl and the logarithmic viscosity (abbreviated as ηN) in a mixed solvent of phenol/tetrachloroethane (6/4 weight ratio) in the presence of an alkali. This relates to aromatic polyesters with a difference in the range of 0.02 to 1.0 and (ηT in the range of 0.3 to 1.5.) Aromatic polyesters consisting of terephthalic acid, isophthalic acid, and dihydric phenols have been known for a long time. It is also known that such aromatic polyesters are widely used as molded products for injection molding, extrusion molding, etc. due to their excellent mechanical properties, electrical properties, high heat distortion temperature, etc. The production methods include a melt polymerization method that heats and mixes terephthalic acid, diphenyl ester of isophthalic acid, and divalent phenol, a melt polymerization method that heats and mixes diacetate of divalent phenol, terephthalic acid, and isophthalic acid, and terephthalic acid and isophthalic acid. A solution polymerization method in which an acid dihalide and a divalent phenol are reacted in a solution, and an interfacial polymerization method in which an organic solvent solution of terephthalic acid or isophthalic acid dihalide and an alkaline solution of a divalent phenol are mixed are known.Their production Among the methods, the melt polymerization method is
We focused on the case where the obtained aromatic polyester is heated at high temperature for a long period of time, and it becomes difficult to completely remove volatile components generated as the polymerization reaction progresses. For this reason, solution polymerization methods or interfacial polymerization methods are said to be superior in obtaining aromatic polyesters with less coloring. Such aromatic polyesters can be mixed with other resins and extruded, taking advantage of their high heat distortion temperature and mechanical properties.
It is often used as a resin composition. Examples of resins that can be mixed include polyethylene, polypropylene, polystyrene, ABS, styrene/acrylonitrile copolymer, SBR, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polycapramide, polysulfone, polyphenylene sulfide, polyoxymethylene, and polyphenylene terephthalate. Examples include ionomers of nylene oxide, polymethyl methacrylate, polyacrylonitrile, polyvinyl chloride, acrylic acid copolymerized olefin, or mixtures thereof. Compositions made of aromatic polyester and these resins have the following characteristics: aromatic polyester's high heat distortion temperature, mechanical properties, weather resistance, flame retardance, transparency,
New compositions that take advantage of characteristics such as chemical properties and electrical properties are expected. However, it is generally considered that it is often difficult to develop the physical properties of a resin composition formed by mixing different types of resins by taking advantage of the characteristics of the resins before mixing. Even in the case of aromatic polyesters made of terephthalic acid, isophthalic acid, and divalent phenols, they have poor compatibility with other resins and often cause phase separation, resulting in unsatisfactory mechanical strength and mechanical strength. It has been desired to investigate a method for producing an excellent resin composition without any problems. The present inventors have developed an interfacial polymerization method in which an organic solvent solution of terephthalic acid dihalide or isophthalic acid dihalide and an alkaline aqueous solution of divalent phenol are mixed and stirred, or terephthalic acid dihalide or isophthalic acid dihalide and divalent phenol are mixed and stirred in the presence of a base. As a result of various studies on resin compositions using aromatic polyesters produced by solution polymerization in organic solvents, we found that they have a specific amount of acid anhydride bonds, and that ηT and ηN have a specific relationship. The present inventors have discovered that when an aromatic polyester having ηT within a specific range is used, a resin composition having good compatibility with other resins and improved physical properties can be obtained, leading to the present invention. That is, the present invention provides the following repeating unit (I),
(), (), (), (V) (However, R is represented by the following formula. The molar ratio of (I), (), (), (), and (V) is in the relationship of the following formulas () and (), and the logarithm of 1 g/dl in tetrachloroethane at 25 ° C. Viscosity (ηT) and 1 g/1 g in phenol/tetrachloroethane mixed solvent (6/4 weight ratio) in the presence of alkali
dl, the logarithmic viscosity (ηN) at 25℃ is as follows (), ()
The gist is an aromatic polyester that satisfies the conditions of the formula at the same time. 0.999＞(I)+()/(I)+()+()+(
) + (V) > 0.95 () 0.7 > (I) / (I) + () > 0.3 () 1.0 > ηT - ηN > 0.02 () 1.5 > ηT > 0.3 () It has been found that the compounds have good compatibility and, when used as one component of a resin composition, provide a resin composition with excellent characteristics. Although such aromatic polyesters are suitable for producing resin compositions, they are used not only as a component of the composition, but also by themselves, and have high heat distortion temperatures, mechanical strength, electrical properties, etc. It can also be used as a plastic with special characteristics. The aromatic polyester of the present invention can be produced by mixing and stirring an organic solvent solution of a mixture of terephthalic acid dihalide and isophthalic acid dihalide with an alkaline aqueous solution of divalent phenol, or by mixing and stirring a mixture of terephthalic acid dihalide and isophthalic acid dihalide and divalent phenol with a base. It is produced by mixing and stirring in an organic solvent in the presence of organic solvents. The mixing molar ratio of terephthalic acid and isophthalic acid is selected from a range of approximately 3:7 to 7:3. Terephthalic acid dihalide,
As the isophthalic acid dihalide, dichloride and dibromide are preferable. As an organic solvent solution, it does not react with terephthalic acid dihalide and isophthalic acid dihalide, and is a good solvent for both the terephthalic acid dihalide and isophthalic acid dihalide mixture and the aromatic polyester produced, and an alkaline aqueous solution of divalent phenol. In the interfacial polymerization method in which the material is mixed and stirred with water, it is desirable to use a material that is completely incompatible with water. Examples of such organic solvents include halogenated hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, etc. Specific examples include methylene chloride, chloroform, tetrachloroethane, tetrachloroethane,
Chlorobenzene, dichlorobenzene, benzene,
Examples include toluene, xylene, methyl ethyl ketone, ethyl acetate, butyl acetate, dioxane, and tetrahydrofuran. The concentration of terephthalic acid dihalide and isophthalic acid dihalide in the organic solvent is 1 to 20% by weight, preferably 5 to 15% by weight.
used in As the divalent phenol, for example, 2,2-bis-(4'-hydroxyphenyl)-propane or the like is used. In the interfacial polymerization method in which an alkaline aqueous solution of divalent phenol is mixed and stirred with an organic solvent solution of terephthalic acid dihalide or isophthalic acid dihalide, it is desirable to use caustic soda or caustic potash as the alkali. The concentration of divalent phenol in the alkaline aqueous solution is 1 to 1.
20% by weight, preferably 4 to 15% by weight. The amount of alkali used in the aqueous alkali solution is in the range of 1 to 2 equivalents, preferably 1.02 to 1.1 times the equivalent of the hydroxyl group of the dihydric phenol. In an interfacial polymerization method in which an organic solvent solution of terephthalic acid dihalide or isophthalic acid dihalide and an alkaline aqueous solution of divalent phenol are mixed and stirred, terephthalic acid dihalide, isophthalic acid dihalide, and divalent phenol are reacted at near stoichiometric equivalents. is desirable. The volume ratio of the organic solvent solution to the alkaline aqueous solution is preferably such that the organic phase volume/aqueous phase volume ratio is approximately 1 to 0.5 in order to facilitate separation and cleaning after completion of the interfacial polymerization reaction. The temperature of the interfacial polymerization reaction is controlled at 5 to 50°C, preferably 10 to 30°C. In order to proceed smoothly with the polymerization reaction, tertiary amines or quaternary ammonium salts are added to divalent phenols.
It is desirable to use 0.1 to 5 parts by weight per 100 parts by weight. Examples of the tertiary amine include triethylamine and trimethylamine, and examples of the quaternary ammonium salt include trimethylbenzylammonium chloride and triethylbenzylammonium chloride. In order to control the degree of polymerization of the resulting aromatic polyester, 0.01 to 10% of monofunctional phenol or monofunctional carboxylic acid halide is added to 1 mole of dihydric phenol.
About 0.05 mol can be used. Examples of monofunctional monophenols include ortho-phenylphenol,
Examples of the monofunctional carboxylic acid halide include paracumylphenol, paratertiary butylphenol, and methoquinone, and examples of the monofunctional carboxylic acid halide include benzoyl chloride. In such a polymerization reaction, the aromatic polyester of the present invention can be obtained by appropriately combining the water content of the organic solvent used as the acid halide solution and the polymerization conditions. Stirring a solution of terephthalic acid dihalide dissolved in a solvent and an alkaline aqueous solution of divalent phenol, the required power is 3KW/ ^m3 or less,
Preferably 1KW/ ^m3 or less, more preferably
It is obtained by continuing stirring for 1 to 30 hours under gentle stirring conditions of 0.5 KW/m ³ or less. Such stirring methods include stirring using propeller blades consisting of several blades, stirring using paddle blades,
Although any method such as circulation stirring using a pump can be adopted, it is not preferable that the power required for stirring is applied locally. In solution polymerization in which a mixture of terephthalic acid dihalide and isophthalic acid dihalide is reacted with divalent phenol in an organic solvent in the presence of a base, a tertiary amine such as pyridine is used as a base. Aromatic polyester is produced by dissolving phthalic acid halide in an organic solvent with a water content of 50 ppm or more, preferably 100 ppm or more, more preferably 300 ppm or more, and then mixing and reacting with divalent phenol in a solvent with a water content in the same range. That's what you get. The type of organic solvent, concentration of terephthalic acid dihalide and isophthalic acid dihalide mixture, type and amount of molecular weight regulator, molar ratio of terephthalic acid dihalide, isophthalic acid dihalide and dihydric phenol, polymerization time, etc. are almost the same as in the case of interfacial polymerization. It's the same. The polymerization temperature used is a temperature up to the boiling point of the organic solvent. After the polymerization reaction is completed, the organic solvent phase containing the polymer is filtered and washed with water, and then the organic solvent is distilled off under heating or a non-solvent is added to obtain an aromatic polyester. In the polymerization for obtaining the aromatic polyester of the present invention, repeating units (I) and () are produced in the main reaction, and repeating units (), (), and (V) are produced in the side reactions.
That is, in both the interfacial polymerization method and the solution polymerization method, when a certain amount of water is contained in the organic solvent used, repeating units (), (), and (V) are produced as by-products. In this case, when the water content of the organic solvent is high, the amount of the above-mentioned by-products is large, while when the water content is low, the amount of by-products is small.
Furthermore, in the case of the interfacial polymerization method, if the required power for stirring is small, the number of repeating units (), (), and (V) increases. Therefore, in the case of interfacial polymerization method, by adjusting the water content of the organic solvent and selecting the required stirring power, and in the case of solution polymerization method, by adjusting the water content of the organic solvent, formula () can be obtained. An aromatic polyester that satisfies the following can be obtained. In other words, in the case of interfacial polymerization, the water content of the organic solvent is
By selecting the required stirring power in the range of 50 ppm or more and 3 KW/ ^m3 or less, and in the case of solution polymerization method, by selecting the water content of the organic solvent in the range of 50 ppm or more, the aroma that satisfies the formula () can be obtained. A group polyester is obtained. Additionally, 1 g/dl in tetrachloroethane at 25°C.
The logarithmic viscosity (ηT) of is the repetition unit (I),
(), (), (), (V), so the amount of monofunctional phenol, etc. to control the degree of polymerization, that is, the amount of molecular weight regulator, is determined by the amount of divalent phenol. By adjusting the amount within the range of 0.01 to 0.05 mol per mol, formula () is satisfied. Furthermore, in a phenol/tetrachloroethane mixed solvent (6/4 weight ratio) in the presence of an alkali.
The logarithmic viscosity (ηN) at 1 g/dl and 25°C is the viscosity caused only by the repeating units (I) + () generated by the main reaction, and as mentioned above, the water content of the organic solvent and the required stirring power By selecting and adjusting the amount of the molecular weight regulator, the above logarithmic viscosity (ηN)
Adjust so that the above formula () is satisfied. Such an aromatic polyester consists of repeating units (I), (), (), (), and (V), and the ratio of (I) and () in the aromatic polyester is
In the range of 99.9% to 95%, and at the same time (I), ()
The proportion of (I) in this is about 30 to 70%. The abundance of repeating units (), (), (V) is measured by infrared absorption spectrum. Aromatic polyesters containing acid anhydride bonds (), (), and (V) exhibit an absorption peak at 1806 cm ^-1 in the infrared absorption spectrum due to the acid anhydride bonds, and are repeatedly unit(),
The abundance of () and (V) can be measured. First, an aromatic polyester film containing repeating units (), (), and (V) (with a thickness of approximately
10 μm) and repeating units for controls (), (),
An aromatic polyester film (about 10 μm thick) containing no (V) is prepared. The aromatic polyester not containing the repeating units (), (), (V) is prepared by phenol decomposition of the aromatic polyester containing the repeating units (), (), (V) with phenol/caustic soda. Measure the absorption spectra at 1806 cm ^-1 of the above film and the control film, find the difference between the two absorption spectra, and use the following formula to determine the concentration c of repeating units (), (), and (V).
is calculated, and the abundance of repeating units (), (), and (V) is determined. I/I ₀ = exp (-εlc) I ₀ = Incident light intensity I: Transmitted light intensity ε: Molecular extinction coefficient (/mol x cm) l: Thickness of sample (cm) c: Concentration (mol/) Such aroma After drying the group polyester, it is melt-extruded at 280°C to 350°C to form pellets, and then molded products can be obtained by injection molding, extrusion molding, or other methods. In order to obtain a molded article that maintains mechanical strength and mechanical properties, it is necessary to have a molecular weight above a certain level, and the aromatic polyester of the present invention has a ηT of 0.3 to 1.5, preferably 0.5 to 1.0. , more preferably 0.55 to
0.8 is desirable. If the logarithmic viscosity is too high, a very high molding temperature is required in melt extrusion for pellet production, injection molding from pellets, extrusion molding, etc., which is undesirable as it leads to thermal decomposition discoloration of the resin. The aromatic polyester of the present invention not only has ηT within the above range, but also has the following relationship with ηN. 1.0＞ηT−ηN＞0.02 () Such aromatic polyester has 0.02≧ηT−ηN
Compared to the case where the relationship is as follows, the compatibility with other resins is better, and an excellent resin composition can be provided.
Although the meaning of the formula () is not clear, it is clear that when such an aromatic polyester is used, it has good compatibility with other resins, and the resulting resin composition shows marked improvements in various characteristic values. That's surprising. When ηT−ηN is 1.0 or more, thermal decomposition occurs during the melt extrusion process, which is not preferable. In the measurement of ηN, the alkali present in the mixed solvent is an alkali metal hydroxide such as caustic soda, caustic potassium, or lithium hydroxide, or an alkali metal salt of an organic carboxylic acid, or an alkali metal salt of a monovalent or polyvalent phenol. 50ppm or less
The content is about 10,000 ppm, but in the examples of the present invention, it was measured in the presence of 1,000 ppm of caustic soda. The resin composition consisting of the aromatic polyester of the present invention and other resins is mixed using a mixer such as a tumbler before melting, and then heated at a temperature of 250°C to 350°C for 30 minutes.
It can be obtained by melt extrusion in an extruder with a residence time of seconds to 10 minutes. Needless to say, the aromatic polyester of the present invention is effective as a component of a resin composition, but even when used alone, it has a high heat deformation temperature, mechanical properties,
It can be widely used as a molded product that takes advantage of its characteristics such as electrical properties, transparency, and flame retardancy. In such cases, melt extrusion into pellets and then
Although the difference between the values of logarithmic viscosity ηT and ηN in the melt-molded molded article is considerably smaller than the value before melt extrusion, the value of ηT is still large, and a difference still exists.
Furthermore, the difference between the logarithmic viscosities ηT and ηN still exists, although small, even in compositions with other resins. The carboxyl group content of the aromatic polyester of the present invention satisfying the formulas () and () measured using KOH in aniline is 10 eq/Ton or more, and often exceeds 1000 eq/Ton. A high content of carboxyl groups not only leads to good compatibility when mixed and melted with other resins to create a resin composition, but also causes the resulting resin composition to have exceptionally excellent physical properties. It is possible, but the details are not certain. However, if the carboxyl group content is high, it is likely to cause thermal decomposition during melt extrusion, so the carboxyl group content is preferably in the range of 10 eq/Ton to 300 eq/Ton. The aromatic polyester of the present invention may optionally contain dyes and pigments, antioxidants, mold release agents, weathering agents, moldability improvers, thermal decomposition inhibitors, flame retardants, lubricants, antistatic agents, glass fibers, and inorganic fillers. It is also possible to use a mixture of agents and the like. Next, the present invention will be specifically explained using examples. Example 1 10.1 g of terephthalic acid dihalide and 10.1 g of isophthalic acid dihalide were dissolved in 300 g of methylene chloride having a water content of 150 ppm at 20°C. On the other hand, 8.64 g of caustic soda was added to 600 g of ion-exchanged water, and 2,2-bis-(4'-
22.8 g of (hydroxyphenyl)-propane, 0.4 g of paratertiary butylphenol, and 0.2 g of trimethylbenzylammonium chloride were dissolved at 20°C. While stirring these two liquids using a three-blade propeller type stirring blade with a required stirring power of 0.3KW/ ^m3 ,
The mixture was mixed for 30 seconds and continued stirring for 6 hours. Stop stirring and adjust the separated methylene chloride phase to pH 1.
The mixture was neutralized with hydrochloric acid water, mixed with ion exchange water, and washed with stirring. After washing until the aqueous layer became neutral, the methylene chloride phase was heated and distilled off to obtain a solid aromatic polyester. The ηT of this aromatic polyester is 0.93,
ηN was 0.70, the total proportion of (), (), and (V) in the repeat unit was about 2%, and the carboxyl group content was 65 eq/Ton. After drying and extruding with an extruder at 330°C, the pellet had ηT of 0.85 and ηN of 0.65.
After injection molding using such pellets at 350°C, the molded product had ηT of 0.80 and ηN of 0.63. Also,
The carboxyl group content was 98 eq/Ton. Comparative Example 1 20.3g of terephthalic acid dichloride and isophthalic acid dichloride (mixture of 1:1 molar ratio) with water content
Dissolved in 400 g of 10 ppm methylene chloride at 20°C.
On the other hand, add 8.64g of caustic soda to 700g of ion-exchanged water, 2.
2-bis-(4'-hydroxyphenyl)-propane
22.8g, paratarsia butylphenol 0.45g,
Trimethylbenzylammonium chloride 0.2g
was dissolved at 20°C. The power required to stir these two liquids is
While vigorously stirring with a homomixer at 20 KW/m ³ , the mixture was rapidly mixed, stirring was continued for 20 hours, and the mixture was allowed to stand to separate, and the methylene chloride phase was mixed and stirred with aqueous hydrochloric acid having a pH of 1. Ion-exchanged water was mixed and stirred into the methylene chloride phase separated after being left to stand, and the mixture was left to stand to be separated. After repeating such washing several times, the methylene chloride phase is heated,
The solvent was distilled off to obtain a solid aromatic polyester. ηT of 1g/dl at 25℃ for this aromatic polyester
was 0.70, ηN was 0.69, and the ratio of the total amount of (), (), and (V) in the total repeating unit was 0.1%. After drying, it was melt extruded at 320°C to obtain pellets. Both ηT and ηN of this pellet were 0.67. Using such pellets
Injection molded products were obtained at 350°C. ηT and ηN of molded product
were both 0.65. Example 2 50 parts by weight of the aromatic polyester obtained in Example 1 and Comparative Example 1 before melt extrusion and polycapramide (manufactured by Unitika KK, 98% H ₂ SO ₄ , 1 g/dl, relative viscosity at 25°C 2.90) 100 after blending 50 parts by weight
It was dried at ℃ for 10 hours and melt extruded at 280 ℃. Using the obtained pellets, various test pieces were injection molded at 270°C and their performance was investigated. The results are shown in Table 1.

[Table] As is clear from Table 1, the use of the aromatic polyester of the present invention shown in Example 1 is superior in various physical properties. Example 3 Using 60 parts by weight of the aromatic polyester of Example 1 and Comparative Example 1 before melt extrusion, it was mixed with 40 parts by weight of ABS, dried at 100°C for 10 hours, melt-extruded at 280°C, and further heated at 270°C. Various test pieces were formed by injection molding and their physical properties were investigated. The results are shown in Table 2.

[Table] Example 4 70 parts by weight of the aromatic polyester of Example 1 and Comparative Example 1 before melt extrusion and 30 parts by weight of polycarbonate were mixed, dried at 100°C for 10 hours, melt-extruded at 310°C, and then mixed with 30 parts by weight of polycarbonate. Various test pieces were molded by injection molding at ℃ and their physical properties were investigated. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1. The following repeating units (I), (), (), ()
,
(V) (However, R is represented by the following formula. The molar ratio of (I), (), (), (), and (V) is in the relationship of the following formulas () and (), and 1 g/dl in tetrachloroethane at 25 ° C. Logarithmic viscosity (ηT) and 1 g/1 g in phenol/tetrachloroethane mixed solvent (6/4 weight ratio) in the presence of alkali
dl, the logarithmic viscosity (ηN) at 25℃ is as follows (), ()
Aromatic polyester within the range that simultaneously satisfies the conditions of the formula. 0.999＞(I)+()/(I)+()+()+(
)+(V)＞0.95 () 0.7＞(I)/(I)+()＞0.3 () 1.0＞ηT−ηN＞0.02 () 1.5＞ηT＞0.3 ()