JPH0229064B2 - JIHIDOROKISHIHOKOZOKUKAABONEETOORIGOMAANOSEIHO - Google Patents

Description

[Detailed description of the invention]

The present invention has a narrow molecular weight distribution and OH at both ends.
This invention relates to a method for producing aromatic carbonate oligomers having groups in high yield. A dihydroxy aromatic carbonate oligomer can be reacted with a dicarboxylic acid or a salt thereof to obtain a polyester carbonate,
Moreover, it can be expected to be used as a resin additive, etc. by itself. Conventionally, the method for producing aromatic carbonate oligomers from divalent phenols has been a transesterification method under vacuum at high temperatures (Japanese Patent Application Laid-Open No. 117893, U.S. Pat.
3510507, U.S. Patent 3655718), solution polycondensation method involving reaction in an organic solvent (JP-A-117893, U.S. Patent 3510507, U.S. Patent 3655718), water and water-immiscible solvent system, presence of basic inorganic compounds under,
Interfacial method for polycondensation (JP-A-51-136690, JP-A-Showa
48-52834, Japanese Patent Application Laid-open No. 52-27746), various methods have been proposed. However, in the above method, the hue of the obtained compound is poor and the polymerization is high, so it is not possible to obtain a compound with a low degree of polymerization, for example, an average degree of polymerization of about 2, and the molecular weight distribution of the obtained oligomer is quite poor. In addition, most of the terminals are terminated, and it is difficult to convert all terminals into hydroxyl groups. In the above method, an aromatic carbonate oligomer is obtained in the presence of a chain terminator in order to suppress the degree of polymerization, but a reactive double-terminated hydroxy aromatic carbonate oligomer cannot be obtained. Further, as the above-mentioned method, the method disclosed in Japanese Patent Application Laid-open No. 1983-1989 limited the divalent phenol to halogenated divalent phenol.
52834 and JP-A No. 52-27746. In the former, a halogenated aromatic carbonate oligomer is obtained in the coexistence of a chain terminator, and in the latter, a halogenated aromatic carbonate oligomer is obtained without using a chain terminator. However, it has a chloroformate group other than an OH group at the end, which requires a complicated operation to convert all ends to an OH group by hydrolyzing it, and the molecular weight distribution of the obtained oligomer is wide. In addition, JP-A-51-136690 describes a method for producing bisphenol A carbonate oligomers of uniform quality using a tubular reactor without using a chain terminator; The resulting oligomer has chloroformate groups at 50% or more of its terminals, has an average molecular weight of 430 to 460, and an average degree of polymerization of 1.5 to 1.7. As described above, with these conventional methods, it is difficult to obtain dihydroxy aromatic carbonate oligomers with a narrow molecular weight distribution in high yield. As a result of intensive research on the above-mentioned interfacial production method, the present inventors determined that the concentration of the divalent phenol compound in the reaction medium was 20 to 100 g/2, the pH was constantly adjusted to 10 to 12, and the specified amount of By adding a condensation catalyst in two stages, we have invented a new method for efficiently producing dihydroxy aromatic carbonate oligomers, which were conventionally thought to be impossible to obtain by interfacial methods, without requiring complicated operations. That is, the present invention provides a reaction medium consisting of water and a water-immiscible solvent, and 20 to 100
After adding the carbonyl halide to the reaction mixture containing g of the divalent phenol compound, adding 1 x 10 ^-5 to 4 x 10 ^-4 mol of a polycondensation catalyst per 1 mol of the divalent phenol, After substantially completing the reaction in the reaction system, a step of additionally adding 1 x 10 ^-4 to 4 x 10 ^-3 mol of a polycondensation catalyst per 1 mol of the dihydric phenol to proceed and complete the reaction. This is a method for producing dihydroxy aromatic carbonate oligomers, which is characterized in that the pH of the reaction system in all steps is always maintained at 10 to 12 by stepwise addition of a basic inorganic compound. In the present invention, as the divalent phenol compound, a bisphenol compound represented by formula (1) is used. A divalent phenol type compound represented by formula (2), are used, and an appropriate one is selected from these groups. In the above general formula, X ₁ and X ₂ are hydrogen atoms,
a chlorine atom, a bromine atom or a lower alkyl group,
Z is a straight chain or branched alkylene group having 9 or less carbon atoms, or -O-, -S-, -CO-, and -SO ₂ -
means a cross-linking group selected from the group represented by Representative examples of compounds represented by these general formulas include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,
2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, bis( 4-
Examples include hydroxyphenyl) sulfone, bis(4-hydroxyphenyl)ketone, hydroquinone, and resorcinol. As the carbonyl halide used in the method of the present invention, for example, phosgene or trichloromethyl chloroformate (Cl ₃ COCOCl) is used, but phosgene is usually used. Phosgene is fed to the aqueous phase containing the divalent phenolic compound or to the aqueous phase and the water-immiscible solvent phase under stirring in gaseous or liquid form or as a solution in a water-immiscible solvent. The water-immiscible solvent used here may be any organic solvent that does not completely dissolve in water when mixed with water and can form two layers by separating at least a portion of the water, and also phosgene. dissolve, and
On the other hand, there are organic solvents which are inert and can dissolve the target dihydroxy aromatic carbonate oligomer. Typical examples include dichloromethane, 1,2-dichloroethane, 1,
Examples include 1,2,2-tetrachloroethane, chloroform, carbon tetrachloride, monochlorobenzene, and dichlorobenzene. The mixing ratio of this water-immiscible solvent and water is preferably in the range of 5/1 to 1/5 by volume. The concentration of the divalent phenol compound in the reaction medium consisting of water and a water-immiscible solvent is 20 to 100, as described above.
g/, particularly preferably 40 to 80 g/.
However, when the carbonyl halide is added as a solution in a water-immiscible solvent, the concentration is adjusted to the above-mentioned level, taking into consideration the amount of the water-immiscible solvent. At the beginning of the process of the present invention is a reaction medium consisting of water and a water-immiscible solvent containing a defined amount of dihydric phenolic compound, and a basic inorganic compound
This is a step in which carbonyl halide is added to the reaction system, which has been adjusted to a value of 10 to 12, with stirring. The carbonyl halide is introduced over a period of several minutes to several tens of minutes, and at this time, the temperature of the reaction system is controlled within the range of 0 to 40°C, preferably 5 to 30°C. Before adding the carbonyl halide, it is effective to add a reducing agent such as sodium hydrosulfite in order to prevent discoloration of the divalent phenol compound and thus of the obtained dihydroxy aromatic carbonate oligomer. , is preferred. In the case of the present invention, the decomposition loss of carbonyl halide is extremely small, so the amount of carbonyl halide added is within 5% excess of the theoretical amount to obtain a dihydroxy aromatic carbonate oligomer with the desired degree of polymerization. It may be added, and the lower the degree of polymerization, the closer to the theoretical amount. For example, when obtaining the target products of the following structural formulas (3) and (4) from bisphenol A and phosgene, the theoretical amount of phosgene is 1 mole of bisphenol A.
Although the amounts are 0.500 mol and 0.667 mol, it is appropriate that the actual amounts added are approximately 0.505 mol and 0.680 mol, respectively. After addition of carbonyl halide, at least 3
After stirring for more than a minute, the first addition of catalyst is carried out. As the polycondensation catalyst, it is preferable to use known tertiary amines, quaternary ammonium salts, and quaternary phosphonium salts. Examples of the tertiary amine include trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline, etc. Examples of quaternary ammonium salts include trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride, and examples of quaternary phosphonium salts include triphenyl n-butylphosphonium bromide and triphenylmethylphosphonium bromide. As mentioned above, the initial amount of the catalyst added is 1×10 ^-5 to 4×10 ^-4 per mole of the divalent phenol compound.
molar, preferably 1.1×10 ⁻⁵ to 2.5×10 ⁻⁴
It is the amount in moles. After the initial addition of the catalyst, the temperature of the system is maintained at 0 to 40°C, preferably 5 to 30°C to carry out the reaction. By adding the catalyst in the first stage, the reaction progresses until more than 90% of the chloroformate ends have reacted. After reaching a stage where the reaction hardly progresses any further, additional catalyst is added. As mentioned above, the additional amount of dihydric phenol is 1
The amount is 1×10 ⁻⁴ to 4×10 ⁻³ mol per mole. This causes the reaction to proceed further. Reaction temperature to 0
The reaction is terminated by maintaining the temperature at ~40°C, preferably 5-30°C. In the present invention, as described above, in the initial reaction system,
The pH is adjusted to 10 to 12, and a basic inorganic compound is added stepwise as needed during the process to adjust the pH within this range. Basic inorganic compounds include potassium hydroxide,
Examples include sodium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, and trisodium phosphate. According to the present invention, oligomers with a high content of dihydroxy aromatic carbonate oligomers having the desired molecular weight, that is, oligomers with a narrow molecular weight distribution, can be obtained in high yield, and the decomposition rate of carbonyl halide can be kept extremely low. . Therefore, the amount of carbonyl halide used can be approximately the same as the theoretical amount. In addition, in order to quantify the terminal chloroformate group of the obtained oligomer, the oligomer was hydrolyzed,
Measuring the amount of chlorine in the solution after hydrolysis
It was below 10ppm. This shows that all ends of the oligomer are hydroxyl groups. The present invention is particularly suitable for obtaining a target product containing about 6 or less divalent phenol units with a relatively low degree of polymerization in the sense that it fully exhibits the effect of obtaining a target product with a narrow molecular weight distribution. Of course, it can also be applied to those with a higher degree of polymerization. Next, the method of the present invention will be specifically explained using Examples and Comparative Examples. In addition, in these examples, the degree of polymerization refers to oligomer 1
It refers to the number of divalent phenol compound units present in a molecule, and for example, the degrees of polymerization of the oligomers of formulas (3) and (4) are 2 and 3, respectively. Example 1 3420g (15 mol) of bisphenol A (BPA), 442ml of water, 34ml of methylene chloride, and 5g of sodium hydrosulfite were charged into a 100ml reaction vessel, and the pH of this mixture was maintained at 11.0 to 11.8. ,
Add 750g (7.58mol) of phosgene over 20 minutes,
0.137 g (6.0 × 10 ^-4 mol) of triethylbenzylammonium chloride (TEBAC) was added 5 minutes after the addition was completed, and after 15 minutes while stirring.
Add TEBAC 2.74g (1.2×10 ^-2 mol) and PH
The reaction was completed in about 30 minutes while maintaining the temperature between 11.0 and 11.8. During this period, the pH was adjusted by adding a 35% aqueous solution of caustic soda. After the reaction was completed, a white powder product was obtained from the solvent system. The analytical values of the obtained products are shown.
Shown in 1. Example 2 3420 g (15 moles) of bisphenol A (BPA), 42 moles of water, 34 moles of methylene chloride, and 5 g of sodium hydrosulfite were charged into a 100 g reaction vessel, and the pH of this mixture was maintained at 11.2 to 11.8. ,
Add 750g (7.58mol) of phosgene over 20 minutes,
0.103 g (5.5 x 10 ^-4 mol) of trimethylbenzylammonium chloride (TMBAC) was added 5 minutes after the addition was completed, and after 15 minutes while stirring.
Add 2.30g (1.24×10 ^-2 mol) of TMBAC, and
The reaction was completed in about 30 minutes while maintaining the value between 11.2 and 11.8. During this period, the pH was adjusted by adding a 35% aqueous solution of caustic soda. After the reaction was completed, a white powder product was obtained from the solvent system. The analytical values of the obtained product are shown in Table 1. Example 3 4560g (20mol) of bisphenol A (BPA), 38ml of water, 38ml of methylene chloride, and 6.5g of sodium hydrosulfite were charged into a 100ml reaction vessel, and the pH of this mixture was maintained at 11.0 to 11.8. Then, 1000 g (10.1 mol) of phosgene was added over 20 minutes, and 5 minutes after the addition was complete, triethylamine (TEA) was added.
0.091g (9.0×10 ^-4 mol) was added, and after 15 minutes with further stirring, 1.37g (1.36×10 ^-2 mol) of TEA was added.
about 30 while maintaining the pH between 11.0 and 11.8.
The reaction was completed in minutes. During this period, the pH was adjusted by adding a 35% aqueous solution of caustic soda. After the reaction was completed, a white powder product was obtained from the solvent system. The analytical values of the obtained product are shown in Table 1. Example 4 The procedure described in Example-1 was followed except that phosgene was 1010 g (10.2 mol) and the amount of TEBAC added in the first stage was 0.206 g (9 x 10 ^-4 mol).
The results are shown in Table-1. Example 5 The procedure described in Example 1 was followed except that the amount of phosgene added was 1148 g (11.6 moles) and the amount of TEBAC added in the first stage was 0.274 g (1.2 x 10 ^-3 moles). The results are shown in Table-1. Comparative example 1 The reaction container was set to 50, and the bisphenol A concentration was
The procedure described in Example 1 was followed except that 142 g/(12 water, 12 methylene chloride) was used. The results are shown in Table-1. Comparative Example 2 The procedure described in Example 3 was followed, except that 1.46 g (1.45 x 10 ^-2 mol) of TEA was added all at once. The results are shown in Table-1. Comparative Example 3 Example 5 except that the PH during the reaction was set to 12.4 to 13.0
The procedure described in was followed. The results are shown in Table-1.

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Claims (1)

[Claims] 1. After adding carbonyl halide to a reaction mixture containing a reaction medium consisting of water and a water-immiscible solvent and 20 to 100 g of a dihydric phenol compound per reaction medium, 1 mol of the dihydric phenol is added. After adding 1×10 ^-5 ×4×10 ^-4 mol of polycondensation catalyst to the reaction system and substantially completing the reaction in the reaction system, 1×
It consists of a step of additionally adding 10 ^-4 to 4 x 10 ^-3 mol of a polycondensation catalyst to advance and complete the reaction, and
A method for producing a dihydroxy aromatic carbonate oligomer, characterized in that the pH of the reaction system in all steps is always maintained at 10 to 12 by stepwise addition of a basic inorganic compound.