JPH03131623A - Polyarylate resin having improved hydrolytic resistance and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject resin having an improved hydrolytic stability without reducing heat resistance, moldability, etc., by using respectively specified bisphenol ester and carboxylic acid in a specified ratio. CONSTITUTION:In a reaction between (A) a bisphenol ester compound of formula I (X is SO2, S or 1-10C alkylidene; R is 1-6C alkyl or phenyl) and (B) a dicarboxylic acid compound of formula II (Ar is formulae III-VI), the objective resin composed of structural components of formulae IX and X and blocked by a group of formula XI is obtained by using the component (A) in an excess amount to the stoichiometric amount so that the ratio of a group of formula VII in the component (A) to a group of formula VIII in the component (B) may satisfy a relation represented by 1.005-1.10 molar ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a polyarylate resin with improved hydrolysis resistance.

(Prior art) Linear aromatic polyester (hereinafter referred to as polyarylate resin) synthesized from aromatic dicarboxylic acids and bisphenols is used as a material suitable for injection molding, extrusion molding, blow molding, compression molding, etc. It is well known. In particular, the polyarylate resin comprising terephthalic acid and/or isophthalic acid and 2,2-bis(4-hydroxyphenyl)propane (bisphenol 8) disclosed in U.S. Patent No. 3,216,970 etc. is heat-resistant. It has excellent properties such as strength, mechanical strength, flame retardancy, electrical properties, dimensional stability, and transparency, and is useful as a material for precision machine parts, films, various equipment cases, etc.

(Problems to be Solved by the Invention) Although the polyarylate resin has excellent initial physical and chemical properties,
When used for a long time in a high temperature and humid atmosphere, it undergoes significant deterioration and its properties are significantly reduced. One of the main causes of this deterioration is a decrease in molecular weight due to hydrolysis of ester bonds.

Molecular weight reduction due to hydrolysis is also observed in polycarbonate resins and other polyester resins, but polyarylate resins often exhibit a significantly more rapid tendency to deterioration and embrittlement than these. As described above, sensitivity to moisture is an important problem of polyarylate resins, which severely limits their use in high-temperature, humid atmospheres and significantly reduces their commercial value.

The following methods have been proposed as methods for improving the hydrolysis resistance of polyarylate resins.

One method is to copolymerize special monomers to impart hydrolytic stability. Examples of such monomers include tetramethylsulfone (Japanese Patent Application Laid-Open No. 60-212423
(Japanese Unexamined Patent Publication No. 1983), tetramethylbisphenols (Japanese Unexamined Patent Publication No. 1983
-42539), aromatic trinuclear bisphenols (JP-A-61-42532), Mihara bisphenols (JP-A-61-42533), and the like. However, the method of copolymerizing such monomers generally requires high raw material costs, and also requires high heat resistance, moldability,
Mechanical strength also decreases slightly.

Another method is to seal the ends of the polymer. Generally, it is widely known that end-capping is performed to improve the hydrolyzability of polyester, and epoxy compounds, substituted phenols, carbodiimides, etc. are being investigated as sealants (for example, Kaisho 64-168
62, JP-A-63-317546),
.

In the case of bisphenol polyarylate, the molding temperature is higher than that of normal polyesters (300°C).
~380°C), among the sealants, an epoxy compound,
Carbodiimide compounds have the problem of thermal decomposition or coloring during molding. Therefore, for bisphenol polyarylates, end-capping agents with excellent thermal stability are mainly being studied.

JP-A-53-8696 discloses end-capping of polyarylate resin with a -valent phenol compound. This method is applied only to a solution polymerization method in which a polyarylate resin is synthesized using diacyl aromatic A halides and a bisphenol compound as raw materials. That is, p-ter
By carrying out the reaction in the presence of m phenol compounds such as t-butylphenol, the terminal halogenated acyl group of the polyarylate is capped with a substituted phenyl ester,
It reduces the hydrolysis catalytic effect of the terminal group. The polyarylate resin produced by this method has improved hydrolysis resistance without reducing thermal stability during molding. However, this method requires a solution polymerization process, which means that expensive aromatic diacyl halides must be used as raw materials, and a solvent (usually a halogenated hydrocarbon) is used, which can be recovered and reused. This process requires high manufacturing costs.

Further, JP-A-62-218418 discloses terminal-capping with phenyl benzoate. This method is
It is applied to melt polymerization methods that synthesize polyarylate resins using diaryl esters of dicarboxylic acids and bisphenol compounds as raw materials. The melt polymerization method does not require the use of a solvent, thus solving the above-mentioned production cost problem. However, when end-capping is performed with phenyl benzoate, the polymer ends lose their polymerization ability, so if phenyl benzoate is present from the early stage of the reaction, polymerization may be inhibited.
There is a problem that the molecular weight distribution widens. In order to overcome such drawbacks, a method may be considered in which phenyl benzoate is added after the polyarylate resin reaches a sufficient degree of polymerization in the above method, but such a polyarylate resin with a high degree of polymerization Since the melting temperature and viscosity are high, uniform kneading is impossible, and therefore it is difficult to completely seal the ends.

As described above, in this technical field, problems remain in all methods, and it is desired to develop a technology that solves all of these problems.

SUMMARY OF THE INVENTION An object of the present invention is to overcome all of the above problems and provide a bisphenol polyarylate resin having improved hydrolytic stability and a method for producing the same.

(Means for Solving the Problems) In order to achieve the above object, the polyarylate resin of the present invention has the following general formula: (13(Ill'@◎', X is Oz-S-10-1 or represents an alkylidene group having 1 to 10 carbon atoms, and component (I) and component (n) may each be a single component or two or more components, and this polymer Both ends of the chain have the following formula, (R in the formula represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, -8O□--S--C-, an alkydene group having 1 to 110 carbon atoms) ) is characterized by being sealed with a group represented by.

Further, the present invention uses a bisphenol ester compound represented by the following general formula (wherein X and R are the same as those described above) as a raw material, and the following general formula, (Ar in the formula is the same as above.) When reacting with the dicarboxylic acid compound represented by The present invention relates to a method for producing the polyarylate resin with improved hydrolysis resistance, characterized in that the polyarylate resin is used in excess of the stoichiometric amount.

The polyarylate resin of the present invention has the following general formula, (I)
(II) (nu) (total in the formula,
X indicates the same as above. ), and each of the components (1) to (III) may be a single component or two or more components.
0 mol% or less, and both ends of the polymer chain are capped with groups represented by the following formula (in which R and X are the same as above); The general formula is 0 (1) (II) 0 (Ar and X in the formula are the same as above.)
CI), (II) and [■] component may each be a single component or two or more kinds of components, [■] acid component is 25 mol% or less, and this Those in which both ends of the polymer chain are capped with groups represented by the following formula (R and X in the formula are the same as above), and further the following general formula, (1) ( n) (I[[) 0 (IV) (Ar and X in the formula are the same as above.)
The components ([) to (■) may each be a single component or two or more components, and the molar fractions of these components (1) component and (H) component are Both are 30 mol% or more, (I [I) component is 30 mol% or less, (IV)
The component is 25 mol% or less, and both ends of the polymer chain are capped with a group represented by the following formula, (in which R and X are the same as above). It can be done.

In the manufacturing method of these polyarylate resins as well, the following general formula is used as a raw material: 0 (X and R in the formula are the same as above.)
A bisphenol ester compound represented by the following general formula, (Ar in the formula is the same as above.) A dicarboxylic acid compound represented by the following general formula, 0 (Ar in the formula is the same as above.) is the same as the above.) and the following general formula, R'(C-Ar-C-0-CH,CI, O+R"I
II 0 (iv) (In the formula, the sum is the same as above, and 1 is the same as above, and 1 is used depending on the final target product, and when reacting, the ratio with the group is the following formula in molar ratio) It is characterized in that the raw material (i) is used in excess of the chemical amount so as to satisfy the relationship expressed by , .

(Function) The polyarylate resin of the present invention is a bisphenol polyarylate resin having a component selected from the following repeating positions (I) to (■); +0-Ar-C+ (III)0.

The repeating unit [■] is an essential component constituting the bisphenol polyarylate and is required to be bundled in the polymer in an amount of 30 mol% or more. If the amount of (1) is less than 30 mol%, impact strength and transparency will decrease. In the method of the present invention, the monomer giving (1) is 0.5 to 0.5 to
A 10 mol% excess must be used. (Specifically, monomers providing N include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)sulfone,
-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and the like. Among these, bisphenol 8 is preferred because of its easy availability.

The repeating unit CI is also an essential component constituting the bisphenol polyarylate. The amount of (II) present is also required to be 30 mol% or more. Examples of the raw material for providing (n) include terephthalic acid, isophthalic acid, 2.6-naphthalene dicarboxylic acid, 2.7-naphthalene dicarboxylic acid, and the like. Preferably, a mixture of terephthalic acid and isophthalic acid is used.

The amount of repeating unit CIII) present is 30 mol% or less, preferably 3 to 15 mol%, based on the total amount of the polyester. The repeating unit (I[I) is added mainly to improve melt dripping properties during combustion, but it is not particularly required to be present in the polyarylate of the present invention.

If the amount of (Ill) exceeds 30 mol%, impact strength and transparency will decrease, which is not preferable. (Raw materials that give [Ill include p-hydroquine benzoic acid, m-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, etc. -Hydroxybenzoic acid, 6-hydroxy-2
-Naphthoic acid is preferred.

The amount of repeating units (TV) is 25% based on the total amount of polymer.
The amount is mol% or less, preferably 3 to 7 mol%.

The repeating unit (IV) is added mainly for the purpose of improving moldability and impact strength, but like component (III), its presence in the polyarylate is not particularly required.

It should be noted that if the amount of (IV) present exceeds 25 mol %, it is not preferable because the heat resistance, which is a characteristic of bisphenol polyarylate, decreases.

Examples of raw materials for providing (IV) include polyethylene terephthalate, polyethylene-2,6-natalate, and the like. Polyethylene terephthalate is preferred because of its ease of availability.

Logarithmic viscosity of the polyarylate resin of the present invention (concentration 0.25
g/d, temperature, 23° C., phenol:tetrachloroethane-6:4 (weight ratio) measured in a solvent) is preferably 0.50 d ff 7 g or more.

Next, the method for producing the polyarylate resin of the present invention will be explained.

In producing the polyarylate resin of the present invention,
The above RC-0- group in raw material (i) and raw material (ii) Q
00=1.00
It is within the range of 5 to 1.10, preferably 1.01 to 1.05. If the excess amount is less than 1,005 in this ratio,
The effect of improving hydrolysis resistance is small, and if the amount exceeds this range, the molecular weight of the final polymer will decrease, making it impossible to obtain a polyarylate resin with sufficient strength. The optimum excess amount varies greatly depending on the polymer composition, reaction conditions, etc., and therefore needs to be considered each time. In order to make the above-mentioned C-〇- groups excessive, raw material 1 (i) may be used in excess.

More specifically, the raw materials (i) and (iii) are represented by the following formula, 0, as described above, and are obtained by acylating the hydroxyl group of the corresponding raw material with an acid anhydride.

Examples of the acid anhydride for acylating monomers (i) and (iii) include acetic anhydride, butyric anhydride, propioic anhydride, and the like. Among these, it is preferable to use acetic anhydride, which provides a methyl group as R, because of its ease of availability. Acylation of monomers (i) and (iii) may be performed in a polymerization vessel immediately before polymerization, or may be synthesized separately, isolated, and subjected to the polymerization reaction.

Next, a melt polymerization method applicable to the present invention will be described.

The reaction is started by putting necessary raw materials and, if necessary, a catalyst into a polymerization container and heating it.

There is no particular limit to the polymerization temperature, but -180 to 4 for boat fishing.
00°C1 Preferably carried out at 200-360'C.

If this temperature is less than 180"C, the reaction will be slow and 4
If the temperature exceeds 00°C, resin coloring and decomposition will occur violently.
Undesirable.

The pressure during the reaction is not particularly limited, but it is preferable to carry out the reaction at around atmospheric pressure at the initial stage and gradually reduce the pressure as the polymerization progresses.

In order to prevent the coloring and decomposition of the resin due to local heating and to facilitate the removal of distillates, it is preferable to carry out the reaction with stirring.In addition, to prevent the oxidative decomposition of the resin due to oxygen, the atmosphere of the reaction system is changed to nitrogen. It is preferable to carry out the test under an inert gas such as argon or the like.

Although the polymerization reaction can be carried out without using a catalyst, a catalyst may be used to accelerate the polymerization reaction.

Such a catalyst may be mixed into the starting JJii feed, or
Alternatively, it may be newly added at the start of the reaction. As a catalyst,
germanium oxide, stannous oxalate, stannous acetate,
Examples include titanium dioxide, titanium alkoxides, sodium acetate, potassium acetate, zinc acetate, aluminum chloride, amines, amides, hydrochloric acid, sulfuric acid, and the like. Preferably, from the viewpoint of catalytic activity, sodium acetate, potassium acetate,
Titanium isopropoxide etc. are good.

Further, a solvent may be added to the reaction system for the purpose of facilitating stirring. The solvent may be any solvent as long as it is inert to the reaction, but preferably one with a boiling point of 200"C or higher. Examples of such solvents include diphenyl ether, silicone resins, substituted naphthalenes, etc. It will be done.

Furthermore, in the polyarylate resin, in the polymerization stage or molding stage, to the extent that hydrolytic stability is not impaired,
Fillers, additives, stabilizers, other resins, etc. can also be added to impart new properties. Such fillers include:
Examples include talc, calcium carbonate, mica, wollastonite, glass fiber, carbon fiber, and organic fiber. Examples of the stabilizer include triaryl phosphites, trialkyl phosphites, hydrogen phosphite diesters, triaryl phosphates, trialkyl phosphates, hindered phenol derivatives, and the like.

In addition, other resins include polyethylene terethalate,
Polybutylene terephthalate, Nine-6, Nylon-
6,6, polyethylene, polyprolene, polystyrene,
Examples include rubber, phenoxy resin, rifhenylene sulfide, polymethyl methacrylate, and the like. In addition, flame retardants such as tetrabromosphenol A2 antimony dioxide,
Plasticizers such as dioctyl phthalate may also be added.

As mentioned above, the present invention can apply a melt polymerization method using an acylated aromatic dicarboxylic acid and bisphenol as raw materials, which is well known to those skilled in the art. However, in general, the polyaryl resin synthesized by this reaction is The poly-terminus is a carboxyl group, as is known in the polymer art.

Since this non-O carboxyl group has weak acidity, it acts as a catalyst for the hydrolysis reaction of the ester bond as shown in the following formula, reducing the hydrolysis resistance (for example, Journal Op Applied Polymer → Jens, Vol. 35, p. 1511, (1988)) Therefore, the present inventors believe that the hydrolyzability of polyarylate resins can be improved by sealing the terminal carboxyl groups in a form that does not exhibit a hydrolysis catalytic effect. As a result of intensive study, we have completed the present invention.

That is, in the present invention, an acylated product of bisphenol (raw material (j)), which is one of the monomers, is used in excess of the stoichiometric ratio (2) relative to the aromatic dicarboxylic acid (raw material (ii)),
One important step is to use this excess amount of monomer to seal the terminal carboxyl groups generated during polymer formation, and in the final step of the reaction to obtain a polyarylate resin represented by the following formula, υ, which does not have terminal carboxyl groups. be.

The advantage of the present invention is that, unlike conventional end-capping methods, terminal carboxyl violence is capped with a reactive functional group.
Even if a capping agent (excess acyloxylated hisphenol) is present in the initial stage of polymerization, there are no drawbacks such as limiting the increase in molecular weight or distorting the molecular weight distribution. Furthermore, since the terminal capping agent is the same as the constituent component of the polymer, the hydrolytic stability is improved without impairing the physical properties inherent to the resin, such as heat resistance, moldability, and mechanical strength.

Conventional polyarylate melt polymerization methods involve careful reaction so that a stoichiometric balance of the constituent units forming ester groups within a polymer chain is achieved. However, if the stoichiometric balance is lost due to volatilization of raw materials during the reaction, an excessive amount of raw material monomer may be used to compensate for the loss.

However, this method is completely different from the present invention, namely it is aimed at the synthesis of stoichiometrically balanced polymers. Therefore, the present inventors discovered for the first time a method of synthesizing polyarylate resin by intentionally changing the stoichiometric amount of monomers for the purpose of improving hydrolysis resistance, and this method is different from the concept of conventional manufacturing methods. The effect cannot be predicted at all.

(Example) The present invention will be specifically explained below using Examples.

Backyard ± upper torque meter, stirring device with tachometer, argon introduction pipe,
54.0 g of p-acetoxybenzoic acid (M++ 180, 0.30
mol), bisphenol A diacetate 401.
8g (Mw 312.1.288 mol), terephthalic acid 105.8g (Axis 166.0.638 mol)
), isophthalic acid 105.8g (Mw 166.0.6
38 mol), polyethylene terephthalate) 28
．． 8 g (Mw 1920, 150 mof) and 0.09 g of sodium acetate as a catalyst were charged. In this case, CH, C-0-1 contained in throat sphenol diacetate in the raw material, and HO contained in the total of 1 terephthalic acid and isophthalic acid.
The proportion of -C- groups is a molar ratio and has the following relationship.

After the inside of the apparatus was sufficiently purged with argon, the temperature was raised to 300°C over 1 hour while acetic acid was distilled off under an argon stream. Stirring was started when the raw materials were sufficiently melted during the temperature rise. In addition, volatile components adhering to the sides and lid of the reaction vessel were heated with a hair dryer to prevent such adhesion as much as possible.

After reacting at 300"C for 30 minutes, the temperature was raised and the pressure was reduced at the same time to reach a final temperature of 340°C and 0.5 mmtlg.The reaction was carried out at this temperature and pressure for about 50 minutes, and the torque meter showed 10
Polymerization was stopped when the speed was 0 Kgcm/7 rpm.

After injection molding, a hydrolysis test, measurement of molecular weight distribution, and quantitative determination of terminal -CO011 groups were performed using the methods described below.

The results are shown in Table 1 below.

X direction [E1-A polymerization reaction was carried out in the same manner as in Example 1, except that the excess amount of bisphenol A diacetate was adjusted to the value shown in Table 1.

After injection molding, a hydrolysis test, measurement of molecular weight distribution, and quantitative determination of terminal -COOI groups were performed using the methods described below.

The results are shown in Table 1.

Soho L6 Using only bisphenol A diacetate, terephthalic acid, and isophthalic acid as monomers, bisphenol/u
A polymerization reaction was carried out in the same manner as in Example 1, except that the excess amount of A diacetate was adjusted to the value shown in Table 1.

The product was injection molded, and the hydrolysis test molecular weight distribution was measured and the terminal -COOI group was quantified using the method described below.

The results are shown in Table 1.

Only bisphenol A diacetate, terephthalic acid, isophthalic acid, and p-acetoxybenzoic acid were used as additives, and the excess amount of bisphenol A diacetate was
A polymerization reaction was carried out in the same manner as in Example 1 except that the values shown in the table were used.

After injection molding, a hydrolysis test, measurement of molecular weight distribution, and quantitative determination of terminal -COOI groups were performed using the methods described below. The results are shown in Table 1.

1 Polymerization reaction was carried out in the same manner as in Example 1, except that only bisphenol A diacetate, terephthalic acid, isophthalic acid, and polyethylene terephthalate were used as the promoting emomers, and the excess amount of bisphenol A diacetate was adjusted to the value shown in Table 1. I did it.

After injection molding, a hydrolysis test, measurement of molecular weight distribution, and quantitative determination of terminal -COOI groups were performed using the methods described below. The results are shown in Table 1.

The procedure was carried out except that bisphenol A diacetate, terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid were used as the penetrating seven-pointer, and the excess amount of bisphenol A diacetate was adjusted to the value shown in Table 1. A polymerization reaction was carried out in the same manner as in Example 1.

After injection molding, a hydrolysis test, measurement of molecular weight distribution, and quantitative determination of terminal -COOII groups were performed using the methods described below. Results first
Shown in the table.

Monomers listed on the back include bisphenol A diacetate, bis(4-acetoxyphenyl)sulfone, terephthalic acid,
A polymerization reaction was carried out in the same manner as in Example 1, except that isophthalic acid was used, bisphenol A diacetate was used in an excess of 4 mol %, and bis(4-acetoxyphenyl)sulfone was used in excess of 1 mol %.

After injection molding, a hydrolysis test, measurement of molecular weight distribution, and quantitative determination of terminal -COOI (group) were performed using the methods described below.
Shown in the table.

Bisphenol A diacetate, 1.
1-bis(4-acetoxyphenyl)ethane, terephthalic acid, and isophthalic acid were used, except that bisphenol A diacetate was used in excess of 4 mol% and 1,1-bis(4-acetoxyphenyl)ethane was used in excess of 1 mol%. A polymerization reaction was carried out in the same manner as in Example 1.

After injection molding, a hydrolysis test, measurement of molecular weight distribution, and quantitative determination of terminal -COOH,l were performed using the methods described below. Results first
Shown in the table.

The reaction was carried out in the same manner as in Example 1, except that the excess amount of bisphenol A diacetate was adjusted to the values shown in Table 1.

The product was injection molded, and the hydrolysis test molecular weight distribution was measured and the terminal -COOH group was quantified using the method described below. The results are shown in Table 1.

Comparison - Example 3. - The reaction was carried out in the same manner as in Example 5.6, except that the excess amount of raw bisphenol A diacetate was adjusted to the values shown in Table 1.

After injection molding, the hydrolysis test molecular weight distribution was measured and the terminal -C00H group was quantified using the method described below. The results are shown in Table 1.

The reaction was carried out in the same manner as in Example 7, except that the excess amount of bisphenol A diacetate was changed to the value shown in Table 1.

The product was injection molded, and the hydrolysis test molecular weight distribution was measured and terminal -COOH5 was quantified using the method described below. The results are shown in Table 1.

Comparative Example 1 The reaction was carried out in the same manner as in Example 8, except that the excess amount of bisphenol A diacetate was changed to the value shown in Table 1.

The product was injection molded, and the hydrolysis test molecular weight distribution was measured and terminal -COOH5 was quantified using the method described below. The results are shown in Table 1.

The reaction was carried out in the same manner as in Example 9, except that the excess amount of ubisphenol A diacetate was changed to the value shown in Table 1.

The product was injection molded, and the hydrolysis test molecular weight distribution was measured and the terminal -COOH group was quantified using the method described below. The results are shown in Table 1.

Comparative Example - The reaction was carried out in the same manner as in Example 10, except that the excess amounts of bisphenol A diacetate and bis(4-acetoxyphenyl)sulfone were adjusted to the values shown in Table 1.

After injection molding, the hydrolysis test molecular weight distribution was measured and the terminal -COOI (i) was determined using the method described below. The results are shown in Table 1.

Le Comparison 1 Bispheno-/Ca diacetate and 1,1-bis(4
The reaction was carried out in the same manner as in Example 11, except that the excess amount of -acetoxyphenyl)ethane was adjusted to the value shown in Table 1.The reaction was carried out in the same manner as in Example 11.The reaction was carried out in the same manner as in Example 11.The reaction was carried out in the same manner as in Example 11. After injection molding, the hydrolysis test was carried out using the method described below.The molecular weight distribution was measured and the terminal -COOH group was measured. Quantification was performed. The results are shown in Table 1.

When synthesizing polymers having the compositions shown in Comparative Examples 10 to 13 in Table 1, 5 mol of p-tert-butylphenol was added to each dicarboxylic acid component (1:11). %
An amount equivalent to 100% was added at the same time as the raw materials to carry out a polymerization reaction.

After injection molding, a hydrolysis test, measurement of molecular weight distribution, and quantitative determination of terminal -COOH groups were performed using the methods described below.

[Hydrolysis test]

0.32X1.27X12.7cm (1/8 XI/
The initial impact strength and the impact strength after being immersed in hot water at 96°C for 50 hours were measured using a 2 x 5 inch test piece, and the two were compared.

[Izotsu impact strength]

Measurement was performed with a notch according to ASTM D-256.

[Quantitative method of terminal -COOI+ group]

110 g of polymer was accurately weighed and dissolved in 12 DMF by heating. This solution was titrated with a methanol solution of O, IN and NaOIt.

The number of end groups present in 1 kg of polymer is -coon
It is expressed as the number of moles of the group (mol/kg).

[Measurement of molecular weight distribution]

Measurement was performed using a GPC manufactured by Tosoh Corporation under the following conditions.

In addition, Mn and the axis are shown in terms of polystyrene.

Analysis conditions: Column TSK get G 300041 Temperature 30°C Flow rate 1.0 mff1/min Eluent HF From Table 1, it can be seen that the polyarylate resins of Examples have improved hydrolytic stability compared to the corresponding comparative examples. It can be seen that the material has excellent properties and high initial strength. It can also be seen that the number of terminal -COOH groups in the polymer is small and that the terminals are capped.

On the other hand, it can be seen that Comparative Examples 1, 3, 5, 6, 7.8 and 9, which were synthesized in a conventional manner to maintain stoichiometric balance, had significantly low hydrolytic stability. Also, seven months
It can also be seen that Comparative Examples 2 and 4, in which the excess amount of (i) was too large, had poor initial physical properties.

Furthermore, when capping with a monofunctional end capping agent such as t-butylphenol, (Comparative Example 10.11°12, 1
3) As shown in FIG. 1, it takes a considerable amount of time to increase the molecular weight, and furthermore, as shown in Table 1, only polymers with a wide molecular weight distribution can be obtained.

The converted torque in Figure 1 is the torque when the rotational speed is 100 rpm, for example, 100k at 7 rpm.
In the case of g cm, it becomes as follows.

In addition, it can be seen that the initial strength is inferior to that of the polyarylate of the present invention (in Table 1, Example 3, Comparative Example 10,
Comparison of Example 6 and Comparative Example 11, Example 7 and Comparative Example 12, and Example 8 and Comparative Example 13).

(Effects of the Invention) As explained above, in the production method of the present invention, the terminal carboxyl group is capped with an acylated product of bisphenol, which is one of the monomers. Problems such as the spread of the molecular weight distribution and the broadening of the molecular weight distribution are solved. In addition, since the polyarylate resin of the present invention obtained by this method has the same structure as the sealing part of the polymer component, the polyarylate resin can be hydrated without deterioration in heat resistance, moldability, or mechanical strength. Degradation stability is improved.

Therefore, according to the present invention, various mechanical parts, films, and the like with improved long-term moisture resistance than conventional polyarylate molded products,
Cases etc. can be easily obtained.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between increase in torque and polymerization time.

Claims (1)

[Claims] 1. The following general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (Ar in the formula is ▲ mathematical formulas, chemical formulas, tables, etc.) There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, X is -SO_2-
, -S-, ▲There are numerical formulas, chemical formulas, tables, etc.▼ or indicates an alkylidene group having 1 to 10 carbon atoms. ), the [I] component and the [II] component may each be a single component or two or more components, and both ends of this polymer chain have the following formula, ▲ mathematical formula, chemical formula, There are tables, etc. ▼ (In the formula, R is an alkyl group with 1 to 6 carbon atoms or a phenyl group, X is -SO_2-, -S-, ▲ Numerical formulas, chemical formulas, tables, etc.) 1. A polyarylate resin with improved hydrolysis resistance, characterized in that it is sealed with a group represented by (representing an alkylidene group). 2. In the method for producing a polyarylate resin with improved hydrolysis resistance according to claim 1, the raw materials include the following general formula, ▲mathematical formula, chemical formula, table, etc.▼(i) (X and R in the formula indicates the same as above.)
A bisphenol ester compound represented by the following, and a dicarboxylic acid represented by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(ii) (Ar in the formula indicates the same as above.) When reacting with a compound, raw material (i)
Inside ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Groups and raw materials (ii
) in ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The ratio with the group is the molar ratio and the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The chemical amount of raw material (i) is A method for producing a polyarylate resin with improved hydrolysis resistance, characterized by using an excess of the stoichiometric amount. 3. The following general formulas, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ II ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ III ] ( Ar is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, X is -SO_2,
-S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or indicates an alkylidene group having 1 to 10 carbon atoms. ), each of [I] to [III] components may be a single component or two or more types of components, and [III] component is 30
mol% or less, and both ends of this polymer chain have the following formula, ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, R is an alkyl group with 1 to 6 carbon atoms or a phenyl group, X is -SO_2-, -S-; polyarylate resin. 4. In the method for producing a polyarylate resin with improved hydrolysis resistance according to claim 3, the following general formula, ▲mathematical formula, chemical formula, table, etc. are used as raw materials▼(i) (X and R in the formula indicates the same as above.)
A bisphenol ester compound represented by the following, and a dicarboxylic acid represented by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(ii) (Ar in the formula indicates the same as above.) When reacting a compound with a carboxylic acid compound represented by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(iii) (Ar in the formula indicates the same as above), ▲Mathematical formulas, chemical formulas, tables, etc. in raw materials (i) ▼Groups and raw materials (ii)
There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ The ratio with the group is the molar ratio and the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The raw material (i) is stoichiometrically A method for producing a polyarylate resin with improved hydrolysis resistance, the method comprising using an excess amount of polyarylate resin. 5. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ IV ] (Ar in the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲There are mathematical formulas, chemical formulas, tables, etc.▼, X is -SO_2-
, -S-, ▲There are numerical formulas, chemical formulas, tables, etc.▼ or indicates an alkylidene group having 1 to 10 carbon atoms. ), [I], [II] and [IV] components may each be a single component or two or more types of components;
V] component is 25 mol% or less, and both ends of this polymer chain have the following formula, ▲ Numerical formula, chemical formula, table, etc. ▼ (R in the formula is an alkyl group or phenyl group having 1 to 6 carbon atoms, is -SO_2-, -S-, ▲ has a mathematical formula, chemical formula, table, etc. ▼ or indicates an alkylidene group having 1 to 10 carbon atoms. Polyarylate resin with improved degradability. 6. In the method for producing a polyarylate resin with improved hydrolysis resistance according to claim 5, the raw materials include the following general formula, ▲ mathematical formula, chemical formula, table, etc. ▼ (i) (X and R in the formula indicates the same as above.)
A bisphenol ester compound represented by the following, and a dicarboxylic acid represented by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(ii) (Ar in the formula indicates the same as above.) There are compounds and the following general formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼(iv) (Ar in the formula is the same as above, R^1 is -OH, ▲mathematical formulas, chemical formulas, tables, etc. ▼,
-OCH_3 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, R^2 is -H or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, p indicates an integer of 2 or more. ) When reacting a polymer represented by Hydrolysis resistance characterized by using raw material (i) in excess of the stoichiometric amount so that the molar ratio satisfies the following formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ An improved method for producing polyarylate resins. 7. The following general formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ II ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ III ] ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ [IV] (Ar in the formula is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, X is -SO_2-
, -S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or 1
~10 represents an alkylidene group. ), each of the components [I] to [IV] may be a single component or two or more types of components, and the molar fraction of these components is [
Both component I] and component [II] are 30 mol% or more, and component [III] is 30% by mole or more.
mol% or less, [IV] component is 25 mol% or less, and both ends of this polymer chain have the following formula, ▲ Numerical formula, chemical formula, table, etc. ▼ (R in the formula is an alkyl group having 1 to 6 carbon atoms. or a phenyl group, A polyarylate resin with improved hydrolysis resistance. 8. In the method for producing a polyarylate resin with improved hydrolysis resistance according to claim 7, the raw materials include the following general formula, ▲ mathematical formula, chemical formula, table, etc. ▼ (i) (X and R in the formula indicates the same as above.)
A bisphenol ester compound represented by the following, and a dicarboxylic acid represented by the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(ii) (Ar in the formula indicates the same as above.) A compound and the following general formula, ▲Mathematical formula, chemical formula, table, etc.▼(iii) (Ar in the formula indicates the same thing as above.) A carboxylic acid compound represented by the following general formula , ▲There are mathematical formulas, chemical formulas, tables, etc.▼(iv) (Ar in the formula is the same as above, R^1 is -OH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
-OCH_3 or -OCCH_3, R^2 is -H or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, p indicates an integer of 2 or more. ) When reacting with a polymer represented by A product with improved hydrolysis resistance characterized by using raw material (i) in excess of the stoichiometric amount so as to satisfy the relationship expressed by the following formula, ▲Mathematical formula, chemical formula, table, etc.▼ Method for producing polyarylate resin.