JPH0662747B2 - Method for producing polyester carbonate - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyester carbonate by a transesterification method. More specifically, a dihydric phenol and a carbonic acid diester are used as catalysts in the presence of an aromatic dicarboxylic acid ester to form a fourth catalyst.
A salt of a primary nitrogen compound was allowed to be present in an amount of 10 ^-1 to 10 ^-4 mol% with respect to a divalent phenol, and transesterification followed by polycondensation reaction was carried out, so that the relative solution viscosity of the polymer reached 1.15 or more. At this point, a phosphite compound and a hindered phenol compound are added to the total amount of the polymer to complete the polymerization, thereby producing a polyester carbonate having excellent thermal stability, hue, and hydrolysis stability.

[0002]

2. Description of the Related Art Hitherto, many proposals have been made on how to obtain a high-molecular weight polycarbonate having a good hue by making the reaction conditions mild when producing a polycarbonate by a transesterification method.

For example, in Japanese Examined Patent Publication No. 47-14742, an initial condensate is prepared from an aromatic dioxy compound and a diaryl carbonate in the presence of a basic catalyst, and then a quaternary ammonium compound is allowed to exist to carry out a post-condensation reaction of the initial condensate. It has been shown that a polycarbonate having an excellent heat stability and a hue can be obtained by aging. In continuation of Japanese Patent Publication No. 47-14743, a polycarbonate having a similar hue is obtained from an aromatic dioxy compound and diallyl carbonate using a quaternary ammonium hydroxide as a transesterification catalyst. According to USP 4,363,905, a high-molecular weight polycarbonate having a good hue is obtained by using a phase transfer catalyst together with a basic reaction condition containing a basic catalyst.
It indicates that hydroxide and tetraethylphosphonium hydroxide are used.

[0004]

However, even if the transesterification reaction is carried out using such a quaternary ammonium compound, deterioration of the hue can be avoided if the polycondensation time is long in order to obtain a high molecular weight polycarbonate. Absent.
Further, from the viewpoint of heat resistance and hydrolysis resistance, it is essentially insufficient as shown in Comparative Examples.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve these problems, and as a result, have arrived at the method for producing a polyester carbonate proposed herein.

That is, the present invention uses a salt of a quaternary nitrogen compound as a catalyst for producing a polyester carbonate from a dihydric phenol and a carbonic acid diester in the presence of an aromatic dicarboxylic acid ester by a transesterification reaction.
To 10 ^-1 no relative valent phenols ^10-4 allowed to exist mole percent perform transesterification, after a relative solution viscosity (polymer concentration 0.5 g / dl, 20 ° C. for entering the polycondensation reaction polymer, methylene chloride solution (Measured in step 1) above 1.15, the phosphonite compound (I) was added to the total amount of the polymer at any time.
0.1% by weight or more and 0.5% by weight or less, and the hindered phenolic compound (II) is added so that the total amount of (I) and (II) is 0.5% by weight or less and (I )
Relates to a method for producing a polyester carbonate, characterized in that at least 0.1% by weight, based on the total amount of the polymer, comprises a compound represented by formula (I).

[0007]

[Chemical 3]

Examples of the divalent phenols used in the present invention include bisphenol type compounds represented by the formula (V), singly or as a mixture. Also, with these compounds as the main components, some of them are dihydroxybenzene,
Dihydroxy naphthalene or its derivative, etc.
It may be replaced with an aromatic compound containing two phenolic hydroxyl groups.

[0009]

[Chemical 4]

(R ¹ and R ² are hydrogen, a methyl group, a chloro group or a bromine group, and R ¹ and R ² may be the same or different; X is

[0011]

[Chemical 5]

Cycloalkylene group having 4 to 15 carbon atoms,-(CH
_{2) n -, - CO -} , - O -, - S -, - SO -, - SO 2 - a divalent group represented by. R ₃ and R ₄ represent hydrogen, methyl group, ethyl group, n-propyl group, si-propyl group, n-butyl group, i-butyl group and phenyl group, and R ₃ and R ₄ are the same or different. Good. Further, n is an integer of 1 to 3. ) Specific examples of the bisphenol type compound include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-1,2-ethane, 4,4'-dihydroxydiphenyl-1,1-ethane, 4 , 4'-dihydroxydiphenyl-1,
1-butane, 4,4'-dihydroxydiphenyl-1,1-
Isobutane, 4,4'-dihydroxydiphenyl-2,2-
Propane, 4,4'-dihydroxydiphenyl-2,2-butane, 4,4'-dihydroxydiphenyl-2,2-pentane, 4,4'-dihydroxydiphenyl-2,2- (4-methylpentane ), 4,4'-dihydroxydiphenyl-diphenylmethane, 4,4'-dihydroxydiphenylphenylmethylmethane, 4,4'-dihydroxydiphenyl-1,
1-cyclopentane, 4,4'-dihydroxydiphenyl-1,1-cyclohexane, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxy-diphenyl sulfide, 4 ,Four'
-Dihydroxy diphenyl sulfoxide, 4,4'-
Examples thereof include dihydroxy / diphenyl sulfone and the like, and their nucleus-substituted derivatives of methyl group, chloro group and bromine group.

The carbonic acid diester used in the present invention includes diphenyl carbonate, bis (p-chlorophenyl) carbonate, bis (o-chlorophenyl) carbonate, bis (p-nitrophenyl) carbonate and bis (o-nitro). Examples include diaryl carbonates having unsubstituted and nuclear substituents such as phenyl) carbonate and ditolyl carbonate.

The polyester carbonate as referred to in the present invention is specifically an aromatic polyester carbonate, and when an aromatic polyester carbonate is produced by a transesterification reaction, the presence of an aromatic dicarboxylic acid ester is required. Aromatic dicarboxylic acid esters include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, dimethyl ester such as p, p'-diphenyl dicarboxylic acid, and diphenyl ester. . In the case of producing a polyester carbonate, the transesterification reaction is carried out by allowing these aromatic dicarboxylic acid esters to coexist with dihydric phenols and carbonic acid diesters.

The quaternary nitrogen compound salts used in the present invention include various quaternary ammonium salts, quaternary pyridinium salts, quaternary picolinium salts, quaternary quinolinium salts and quaternary isoquinolinium salts. , Etc., but particularly preferable results are obtained when the quaternary ammonium halogenide represented by the formula (III) and / or the quaternary pyridinium halogenide represented by the formula (IV) is used.

[0016]

[Chemical 6]

(Wherein R ¹ , R ² , R ³ and R ⁴ represent the same or different alkyl groups, aralkyl groups, cycloalkyl groups and aryl groups, and R ⁵ represents an alkyl group and an aralkyl group.
Indicates chlorine or bromine. ) Specifically, tetramethyl
Ammonium chloride, tetramethyl ammonium bromide, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, trimethyl Phenylammonium chloride, trimethylphenylammonium bromide, triethylphenylammonium chloride,
Triethylphenyl ammonium bromide, trimethyl benzyl ammonium chloride, trimethyl benzyl ammonium bromide, triethyl benzyl ammonium chloride, triethyl
Benzyl ammonium bromide, tributyl benzyl ammonium chloride, tributyl benzyl ammonium bromide, dimethyl benzyl phenyl ammonium chloride, dimethyl benzyl phenyl ammonium bromide, tetrabenzyl ammonium chloride, tetrabenzyl ammonium・ Bromide, tribenzyl phenyl ammonium chloride, tribenzyl phenyl ammonium bromide, trimethyl cyclohexyl
Ammonium chloride, trimethyl cyclohexyl ammonium bromide, tributyl cyclohexyl ammonium chloride, tributyl cyclohexyl ammonium bromide, trioctyl
Methyl ammonium chloride, trioctyl methyl ammonium bromide, N-lauryl pyridinium chloride, N-lauryl pyridinium
Examples thereof include bromide, N-stearyl pyridinium chloride and N-stearyl pyridinium bromide.

The salts of these quaternary nitrogen compounds are 10 ^-1 to 10 ^-4 mol%, preferably 10 ^-4 mol%, based on the divalent phenols.
A transesterification reaction is carried out after completely adding nitrogen to the reaction system so that the concentration becomes 10 ^-2 to 10 ^-4 mol%. That is, the transesterification reaction is started from 150 to 180 ° C, and at the same time, in the presence of an aromatic monooxy compound and an aromatic dicarboxylic acid ester, an aromatic monooxy compound or an aliphatic monooxy compound is generated, so the temperature is gradually raised to 200 to 200 ° C. The temperature of the reaction system was raised to 220 ° C and the pressure of the reaction system was 100 mmHg.
To 20 mmHg to produce these monooxy compounds by distillation from the reaction system to complete the transesterification reaction and at the same time obtain an initial condensate. During this time, a reaction of 2 hours or more is required. Subsequently, the temperature is further raised, and at the same time, the reaction system is put under high vacuum to proceed with the polycondensation reaction and finally the reaction system is heated to 270 to 290
At a temperature of several mmHg or less, preferably 1 mmHg or less, a high molecular weight polymer is obtained. In the polycondensation reaction stage in the latter half of this reaction, the relative solution viscosity of the reaction system polymer (measured at a polymer concentration of 0.5 g / dl and methylene chloride solution at 20 ° C) reached 1.15 or more A hindered phenolic compound is added to the reaction system, and the torque measured with a torque meter attached to the stirring shaft of the reaction vessel and a methylene chloride solution having a polymer concentration of 0.5 g / dl of the polymer are prepared in advance. If a graph showing the relationship between relative solution viscosities obtained by measurement at 20 ° C. is created, the addition timing can be easily known by reading the torque applied to the stirring shaft.

The ratio of the total amount of the carbonic acid diester and the aromatic dicarboxylic acid ester to the dihydric phenol in the reaction should theoretically be equimolar so that a high molecular weight polymer can be obtained. In order to prevent collapse and to allow dihydric phenols that are relatively susceptible to thermal decomposition to undergo rapid initial condensation reaction with carbonic acid diester to obtain an intermediate that is relatively stable against thermal decomposition and to proceed the reaction A slight excess of stoichiometric amount of carbonic acid diester and aromatic dicarboxylic acid ester is used. The ratio of carbonic acid diester to aromatic dicarboxylic acid ester is 5 in molar ratio.
It can be carried out in the range of / 95 to 95/5.

Next, the amount of the phosphonite compound added at any time when the relative solution viscosity of the polymer reaches 1.15 or more is 0.1 to 0.5% by weight based on the total amount of the polymer. Of the knight compounds, at least 0.1% by weight based on the total amount of polymer is tetrakis (2,4-di-tert-butylphenyl 4,4'-biphenylene phosphonite) represented by the following formula.

[0021]

[Chemical 7]

It is necessary that it is (commercially available as Irgaphos (registered trademark) P.EPQ manufactured by Ciba-Geigy Co., Ltd.), and other commercially available various phosphonite compounds as long as 0.1% by weight or more is added. And / or it may be used in combination with a hindered phenol compound. A great many types of these hindered phenol compounds are commercially available, for example, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate]. Methane (Irganox (registered trademark) 1010 manufactured by Ciba-Geigy) or 1,3,5 trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene (Ionox (registered trademark) 330 manufactured by Shell Co.) and the like can be mentioned. However, the total addition amount is required to be 0.5% by weight or less with respect to the total amount of the polymer, and if it exceeds 0.5% by weight, the mechanical properties of the polymer are affected, which is not preferable.

These phosphonite compounds and hindered phenol compounds are added at any time when the relative viscosity of the polymer in the reaction system reaches 1.15 or more, but at a time when the relative viscosity is much lower than 1.15. When added, it obviously affects the condensation reaction and makes it difficult to obtain a high molecular weight polymer, but when added at any time when it reaches 1.15 or higher, there is virtually no effect on the molecular weight and heat is not observed. A polyester carbonate having excellent stability, hue and hydrolysis stability can be obtained.

The polyester carbonate obtained in this manner is used as a general engineering plastic material, but especially for outdoor applications such as outdoor lighting equipment, window glass, fences, microwave ovens, dishes, tanks, transportation pipes, etc. Suitable as a material for applications exposed to the bottom.

It is also applicable to heat-sensitive elements such as electric blankets and carpets, various hoses, tubes and hot melt adhesives.

[0026]

EXAMPLES Next, specific contents will be described with reference to examples.

Example 1 228 g (1.00 mol) of bisphenol A, 207 g (0.97 mol) of diphenyl carbonate, 32 g of diphenyl terephthalate
(0.10 mol) was placed in a 1-liter autoclave, and the autoclave was purged with nitrogen, and then melted at 150 to 160 ° C. Here, trimethylbenzylammonium bromide was added at 10 ^-3 mol% with respect to bisphenol A, and the temperature was gradually raised to 220 ° C. in about 3 hours. At the same time pressure 100mmH
It was lowered from g to 20 mmHg and about 175 ml of phenol was distilled.
After that, the temperature was gradually raised to 250 ° C and the pressure in the system was also lowered to reach 2 mmHg.・ EPQ) 0.75 g was added, and the estimated relative solution viscosity (polymer concentration: 0.5 g / 100 ml, 20 ° C., methylene chloride solvent) obtained from the stirring torque at this addition was 1.17, and some polymer was The relative solution viscosity obtained by measuring a small amount of sample was 1.18.
Met. Then, the temperature was raised and the reaction was carried out at 270 ° C. and 0.5 mmHg for 2 hours to obtain a polymer. It was considered that diphenyl terephthalate added to the reaction system was involved in the reaction because a part of the polymer was crushed and an acetone extraction was tried, but an acetone extract was not substantially obtained. This polymer is almost colorless and transparent, and the intrinsic viscosity [η] measured at 20 ° C in a methylene chloride solution [η] = 1.11 × 10 ^-4 M ^0.82 (Enc
yclopedia of Polymer Science and Technology Vol 10
P732: John Wiley & Sons Inc (1969)) The average molecular weight calculated using the formula was 26800. Further, as an evaluation of heat resistance, thermal decomposition behavior was measured with a differential thermogravimetric analyzer (manufactured by Rigaku Denki Co., Ltd.) in a nitrogen stream at a temperature rising rate of 10 ° C./min. Decomposition start temperature (T _d ) is 432 ℃, weight loss is 5
% (T ₅ ) reached 482 ° C., and temperature (T ₁₀ ) reached 10% weight loss was 508 ° C. To evaluate the hydrolysis resistance, a 50 mm x 50 mm x 0.6 mm thick sheet was prepared by hot pressing and suspended in a constant temperature and humidity chamber at 90 ° C and 100% RH to measure the molecular weight reduction due to hydrolysis. 90 ° C, 100%
After 30 days under the condition of RH (relative humidity), the molecular weight retention against the initial molecular weight was 92.0%, the appearance of the sheet was colorless and transparent, and no abnormality was observed. These results are summarized in Table 1 together with other examples and comparative examples.

Example 2 Diphenyl isophthalate was used in place of diphenyl terephthalate in Example 1, and N-stearyl pyridinium chloride was used as a catalyst in place of trimethylbenzylammonium bromide at 10 ^-4 mol% based on bisphenol A. The relative solution viscosity of the polymer is
When 1.19 was reached, 0.25 g of Irgaphos P.EPQ (manufactured by Ciba-Geigy) and 0.25 g of Irganox 1010 (manufactured by Ciba-Geigy) were added to carry out the reaction. Table 1 shows the hue, average molecular weight, thermal decomposition behavior and hydrolysis behavior of the obtained polymer.

Comparative Example 1 For the purpose of comparison in Example 1, lithium hydroxide, which is an alkali metal hydroxide, was used as a known catalyst for comparison with bisphenol A in an amount of 10 ⁻³ mol%, especially diphenyl terephthalate, Irgaphos P.EPQ ( The reaction was carried out without the addition of Ciba Geigy). The obtained polymer had a high average molecular weight of 26500, but it was pale yellow, and thermal decomposition started at 375 ° C and showed a 10% weight loss at 430 ° C. In a hydrolysis test at 90 ° C and 100% RH, the retention of the average molecular weight remained at 65.3% after 30 days, and the test sheet became cloudy and at the same time many small white spots (including some voids) were generated on the entire surface, causing embrittlement. It was remarkable. These results are shown in Table 1.
It was shown to.

Comparative Example 2 In Comparative Example 1, using 10 ^-3 mol% of lithium carbonate which is a carbonate of an alkali metal as a catalyst with respect to bisphenol A, when the relative solution viscosity of the polymer reached 1.16, Irgaphos P.EPQ was used. The reaction was carried out by adding 0.5 g (manufactured by Ciba Geigy) and 0.25 g of Irganox 1010 (manufactured by Ciba Geigy). The obtained polymer was pale yellow and the thermal decomposition behavior was slightly improved as shown in Table 1. However, the result of the hydrolysis test was inferior to that of the example of the present invention, and the hydrolysis test result was also in terms of the molecular weight retention and the appearance. On the other hand, no improvement was seen.

Comparative Example 3 In Comparative Example 1, tetrabutyl ammonium bromide was used as a catalyst, and 0.50 g of Irganox 1010 (manufactured by Ciba-Geigy) was added at the point that the relative solution viscosity of the polymer reached 1.18 as a stabilizer. A polymer was obtained. As shown in the results in Table 1, although the appearance after the hydrolysis test was improved, the molecular weight retention rate and the thermal decomposition behavior were not improved.

Comparative Example 4 In Comparative Example 3, diphenyl terephthalate and diphenyl isophthalate were added, and the reaction was carried out without adding Irganox 1010 (manufactured by Ciba Geigy). The polymer obtained was pale yellow and the thermal decomposition behavior was improved as shown in Table 1, but no improvement was observed in the retention of the molecular weight of the hydrolyzed product.

[0033]

[Table 1]

* 1 0.5g / 100ml concentration, 20 ° C, methylene
Value measured with chloride * 2 20 ° C, value calculated from the intrinsic viscosity measured with a methylene chloride solution using the formula [η] = 1.11 x 10 ^-4 M ^0.82 * 3 Increase of 10 ° C / min in N ₂ gas stream Measured at temperature rate T _d is the weight loss start temperature, T ₅ is the temperature at the time of weight loss of 5%,
T ₁₀ indicates the temperature at the time of weight loss of 10%.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 67/00 KKD 8933-4J 69/00 KKJ 9363-4J

Claims (2)

[Claims] 1. A process for producing a polyester carbonate from a divalent phenol and a carbonic acid diester in the presence of an aromatic dicarboxylic acid ester by a transesterification reaction, wherein a salt of a quaternary nitrogen compound is used as a catalyst. Transesterification is carried out in the presence of 10 ^-1 to 10 ^-4 mol% with respect to phenols, and the post-polycondensation reaction enters and the relative solution viscosity of the polymer (polymer concentration 0.5 g / dl, 20 ° C, measured with methylene chloride solution) ) Reached 1.15 or more, the phosphonite compound (I) was added in an amount of 0.1% by weight or more and 0.5% by weight or less and the hindered phenolic compound (II) was added in an amount of 0.5% by weight or less with respect to the total amount of the polymer. The total amount of (I) and (II)
0.5% by weight or less is added, and the phosphonite compound (I) is characterized in that at least 0.1% by weight is composed of a compound represented by the formula (I) with respect to the total amount of the polymer. Method for producing polyester carbonate. [Chemical 1] 2. A quaternary ammonium halogenide represented by formula (III) and / or a quaternary pyridinium halogenide represented by formula (IV) is used as a salt of a quaternary nitrogen compound. The manufacturing method according to claim 1. [Chemical 2] (However, R ¹ , R ² , R ³ , and R ⁴ are the same or different alkyl groups,
An aralkyl group, a cycloalkyl group, an aryl group,
R ⁵ represents an alkyl group or an aralkyl group. X represents chlorine or bromine. )