JPH08245465A - Bisphenols for polymer raw material and production thereof - Google Patents

Abstract

PURPOSE: To obtain a bisphenol for polymers, capable of minimizing yellowing in polymerization or molding process by adding a specific amount of a specific phenol to 4,4'-bisphenol. CONSTITUTION: This bisphenol comprises 4,4'-bisphenol of formula I (X is a difunctional group) (such as; bisphenol-A) containing 50-100000ppm(wt) of phenol selected from 2,4'-bisphenols of formula II (such as; 2,4'-bisphenol-A), trisphenols of formula III and alkyl substituted 4,4'-bisphenols of formula IV (R,R' are each an alkyl of more than IC; n is 0,1) (such as 3-methylbisphenol-A). When the total content of bisphenols of the formula II-IV is less than 50ppm(wt) in 4,4'-bisphenol, 4,4'-bisphenol containing a large amount of above-noted bisphenols is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to 4,4'-bisphenols useful as a raw material for producing various transparent polymers and a method for producing the same, and more particularly to 4,4'-bisphenols.
TECHNICAL FIELD The present invention relates to a bisphenol for polymer raw material capable of preventing coloring of a polymer produced from bisphenol as a raw material as much as possible, and a method for producing the same.

[0002]

2. Description of the Related Art For example, bisphenol A, which is one of typical 4,4'-bisphenols, is generally prepared by reacting acetone with an excess of phenol in the presence of an acidic catalyst to prepare a reaction mixture obtained from the reaction mixture. After removing water, acetone and / or a catalyst, this is cooled to precipitate adduct crystals of bisphenol A and phenol, and the crystals are separated from the mother liquor, followed by dephenol treatment.

When the bisphenol A is used in applications requiring high purity, for example, as a raw material for producing transparent polymers such as polycarbonate, polyester, polyether and epoxy resin, the content of impurities is simply small. Not only that, it is also required to have an excellent hue such as no coloring.

Therefore, conventionally, in order to produce bisphenol A which is excellent in hue without coloring, bisphenol A is decolorized by acid treatment with thioglycolic acid or the like (Japanese Patent Publication No. 47-43937), phosphorus. A method of adding acid alkaline earth metal salt or the like for treatment (Japanese Patent Publication No. 37-1
No. 0788), a method of recrystallizing an adduct of bisphenol A and phenol with water or an aromatic hydrocarbon solvent (JP-A-5-294871), bisphenol A.
When removing phenol from the adduct of phenol and phenol with a centrifugal thin film evaporator, the centrifugal thin film evaporator is maintained at a predetermined pressure and washed with phenol (JP-A-5-294).
No. 877) and the like have been proposed.

However, even if bisphenol A which is highly pure and has an excellent hue without coloring is produced by such a method, a transparent polymer having a severe hue requirement such as an optical polycarbonate is produced using this bisphenol A. When molded by, the polymer produced and molded may yellow due to the heat history at that time.

[0006]

Therefore, the present inventors have examined 4,4'-bisphenols which can prevent the occurrence of coloration such as yellowing during polymer production or molding. As a result, they have found that the object can be achieved by allowing a predetermined phenolic compound to be present in the 4,4′-bisphenols at a predetermined ratio, and have reached the present invention.

Therefore, an object of the present invention is to provide bisphenols for polymer raw materials, which are produced from 4,4'-bisphenols as raw materials and which can prevent coloring of molded polymers as much as possible. Especially. Another object of the present invention is to provide a method for producing such a bisphenol for polymer raw material.

[0008]

That is, the present invention provides the following general formula (1):

[Chemical 6] (However, X is a divalent group in the formula) 4,4 '
-In bisphenols, the following general formula (2)

[Chemical 7] (Wherein, X is a divalent group in the formula)
-Bisphenols, the following general formula (3)

Embedded image (However, in the formula, X is a divalent group) and a trisphenol represented by the following general formula (4)

[Chemical 9] (However, in the formula, X is a divalent group, R and R'are alkyl groups having 1 or more carbon atoms, and n is an integer of 0 or 1.) Alkyl-substituted 4,4'- It is a bisphenol for polymer raw material which contains at least one phenolic compound selected from bisphenols in a total amount of 50 to 10,000 ppm by weight.

The present invention also provides bisphenols having at least one substituent at the ortho position for one hydroxyl group and no substituent at the ortho position for other hydroxyl groups. 50 to 10 relative to 4'-bisphenols,
The following general formula (1) added in the range of 000 ppm by weight

[Chemical 10] (In the formula, X is a divalent group) and is a bisphenol for polymer raw material.

In producing such bisphenols for polymer raw materials, 4,4 'represented by the general formula (1)
-The total content of the phenolic compounds represented by the general formulas (2), (3) and (4) in the bisphenols is measured, and when the total content is lower than 50 ppm by weight, the phenolic compound is Either mixed with 4,4'-bisphenols (1) having a high total content of (2), (3) and (4), or recovered in the purification step during production of 4,4'-bisphenols (1) Phenolic compound (2),
A by-product having a large total content of (3) and (4) is added, or at least one compound selected from the separately synthesized phenolic compounds (2), (3) and (4) is added. However, when the total content is more than 10,000 ppm by weight, it is further purified, or 4,4′-with a small total content of the phenolic compounds (2), (3) and (4). For polymer raw material which is mixed with bisphenols (1) to adjust the total content of the phenolic compounds represented by the general formulas (2), (3) and (4) within the range of 50 to 10,000 ppm by weight. It is a method for producing bisphenols.

In the above general formulas (1) to (4), divalent
The group X of is, for example, -C (CH ₃)₂-, -CH
(CH₃)-,-SO₂-, -CH₂C (CH₃)
₂-, -O-, and the like, and preferably benze
Next to the ring is -C (CH₃)₂-Or-SO₂As bulky
It is desirable to be high.

In the present invention, the 4,4'-bisphenols represented by the general formula (1) are specifically bisphenol A, bisphenol F, bis (hydroxyphenyl) ethane, dihydroxybiphenyl, bis (hydroxy). Examples thereof include phenyl) trimethylcyclohexane, bis (hydroxyphenyl) butane, bis (hydroxyphenyl) sulfide, bis (hydroxyphenyl) sulfone, and bis (hydroxyphenyl) ketone.

As the phenolic compound to be present in the 4,4'-bisphenols, 2,4'-bisphenols represented by the general formula (2) and tris represented by the general formula (3). Phenols and general formula (4)
Is any one or more of the alkyl-substituted 4,4′-bisphenols represented by Then, "bisphenol having at least one substituent at the ortho position with respect to the hydroxyl group of 1 and having no substituent at the ortho position with respect to other hydroxyl groups is added to the 4,4'-bisphenols. Examples of the “class” include, but are not limited to, the phenolic compound represented by the general formula (2) or the general formula (4). Examples of the substituent at the ortho position include an alkyl group and an aryl group, and X in the general formula (1).
Also appears as this substituent.

The 2,4'-bisphenols represented by the general formula (2) include 2,4'-bisphenol A,
2,4'-bis (hydroxyphenyl) sulfone and the like. In the case of such a compound, it is preferable that the divalent group X adjacent to the 2-position OH group is bulky.

Since a compound such as 2,4'-bisphenol A is obtained as a by-product in the production of 4,4'-bisphenol A and the like, it is contained in a predetermined amount by controlling the degree of purification. However, it is disadvantageous to unnecessarily reduce the degree of purification, because the property deteriorates due to the simultaneous increase in the amount of other impurities. In the purification step of 4,4′-bisphenol A and the like,
Since there are filtrates and fractions in which compounds such as 2,4′-bisphenol A are discharged as impurities at a high concentration, it is advantageous to purify them as necessary and add them in a predetermined amount. Of course, it is also suitable to add a predetermined amount of a separately obtained compound such as 2,4′-bisphenol A.

The trisphenols represented by the general formula (3) include bisphenol and phenol.
There are compounds obtained by reacting with acetone. And
In the general formula of this trisphenol, the substitution position of the OH group is the 2-position or 4-position. Since such trisphenols are also obtained as a by-product in producing 4,4′-bisphenol A and the like, it is preferable to add a predetermined amount in the same manner as above.

Further, since the phenolic compound represented by the general formula (4) can be obtained as a by-product in 4,4'-bisphenols in the same manner as above, a predetermined amount is added in the same manner as above. Is good. Further, as a method of making this positively exist, the following general formula (5) is used as a part of the phenol raw material during the production of 4,4′-bisphenols.

[Chemical 11] (However, in the formula, R and R ′ are an alkyl group having 1 or more carbon atoms, and n is an integer of 0 or 1), and a predetermined amount of the alkylphenol may be added.

The alkylphenol is typically 2-tert-butylphenol, 2-tert-butyl-6-methylphenol, 2,6-ditertiarybutylphenol, o-cresol, o-ethylphenol, 2,6-. Examples include xylenol and the like.
Regarding the proportion of such alkylphenol added, for example, if 1% by weight is added to the phenol raw material, about 1% by weight of the 4,4′-bisphenol produced will be represented by the general formula (4). Since a phenolic compound is produced, the phenolic compound may be added to 4,4′-bisphenol so that it is produced within the range of 50 to 10,000 ppm by weight, and, for example, 4,
4,4'-bisphenols having a high purity of 4,4 'were added to the 4'-bisphenols so that the phenolic compound of the general formula (4) was produced in excess of 10,000 ppm by weight. -Mixing with bisphenols to give a total content of phenolic compounds of 50-10,000 ppm by weight
You may make it adjust in the range of.

The ratio of the phenolic compounds represented by the above general formulas (2), (3) and (4) to be present in 4,4'-bisphenols is usually 50 to 10,0.
00ppm, preferably 200-3000ppm, less than 50ppm may be produced using such 4,4'-bisphenols, the coloring such as yellowing may occur in the molded polymer, on the contrary, 10,0
If it is more than 00 ppm, the 4,4′-bisphenols themselves may be colored.

Then, these phenolic compounds are
There is no particular limitation on the method of allowing the 4'-bisphenol to be present, but the following method is preferable.

That is, first, the general formulas (2) and (3) in the 4,4'-bisphenol represented by the general formula (1) are described.
And the total content of the phenolic compounds represented by (4) is measured.

When the measured total content is lower than 50 ppm by weight, 4,4 'having a large total content of the phenolic compounds (2), (3) and (4).
-Mixed with bisphenols (1) or 4,4'-
A phenolic compound (2), (3) and (4) with a high total content by-product recovered in the purification step during the production of the bisphenol (1) was added, or the phenolic compound was synthesized separately. Adding at least one compound selected from (2), (3) and (4),
The total content of the phenolic compounds represented by the general formulas (2), (3) and (4) is 50 to 10,000 ppm by weight.
Adjust within the range of. The same applies when the above-mentioned "bisphenol having at least one substituent at the ortho position for the hydroxyl group of 1 and having no substituent at the ortho position for the other hydroxyl group" is added. .

The total content measured is 10,000
When it is more than 0 ppm by weight, it is further purified or mixed with 4,4′-bisphenols (1) having a small total content of the phenolic compounds (2), (3) and (4), The total content of the phenolic compounds represented by the general formulas (2), (3) and (4) is 50 to 1
Adjust within the range of 10,000 ppm by weight.

The bisphenols for polymer raw material according to the present invention can prevent coloring of the polymer produced and molded from the bisphenol as a raw material as much as possible, so that it is excellent in hue such as being transparent and not colored. Polymers such as polycarbonates, polyesters, polyethers for optical applications,
It can be suitably used as a raw material for producing an epoxy resin or the like.

As a method for producing the above-mentioned polycarbonate, polyester, polyether, epoxy resin, polyetheretherketone and the like using the bisphenols for polymer raw material of the present invention, a conventionally known method can be directly adopted.

[0026]

According to the present invention, the phenolic compound in 4,4'-bisphenol used as a polymer raw material acts as a heat stabilizer at the time of polymer production and molding, and is produced and molded by this. It is considered that the polymer can be prevented from being colored as much as possible.

The coloring of the polymer during molding is due to the thermal deterioration of the polymer. The phenolic compound (ArOH), which prevents this thermal deterioration, donates a hydrogen atom to the radical (R.) from the polymer, as shown by the following formula, and becomes a stable phenoxy type radical (ArO.). Exerts the function of stopping the radical chain. R · + ArOH → RH + ArO · To confirm the function of the phenolic compound as a thermal stabilizer by observing this stable phenoxy type radical (ArO ·) by electron spin resonance (ESR) method. You can Therefore, there is a large correlation between the ESR value and the coloring of the resin.

[0028]

EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples.

Example 1 Acetone and phenol were reacted with a strongly acidic cation exchange resin as a catalyst, low boiling point substances such as water were separated from the resulting reaction mixture, and this was cooled to obtain a mixture of bisphenol A and phenol. The adduct was precipitated, and the obtained adduct was separated and recrystallized with phenol to obtain a purified adduct crystal. This refined adduct (bisphenol A about 60
% By weight and about 40% by weight of phenol) were charged into a thin film evaporator, and phenol was evaporated at a vacuum degree of 1.5 to 3 Torr and a temperature of 200 ° C. to obtain bisphenol A.

The type and concentration of impurities of the obtained bisphenol A were measured. The result is residual phenol 10p
pm, 2,4-bisphenol A [general formula (2)] 24
ppm, trisphenols [general formula (3)] 4 pp
m, 3-methyl substituted bisphenol A [general formula (4)]
The total amount of impurities was 401 ppm, and the total content of general formulas (2), (3) and (4) was 36 ppm.

Bisphenol A thus obtained
Was added separately to 1000 ppm of 2,4-bisphenol A [general formula (2)],
A bisphenol A for polymer raw material having a total content of (3) and (4) of 1036 ppm was produced.

Next, 22.3 g of this polymer raw material bisphenol A and 21.4 g of diphenyl carbonate were polymerized by a melting method and then reprecipitated and purified with chloroform / methanol to produce a polycarbonate powder. With respect to the obtained polycarbonate powder, the presence of stable radicals, which serves as an index for heat stabilization of the resin, was measured by ESR.

In this ESR measurement, 0.15 g of polycarbonate powder was added to a quartz tube for ESR measurement (inner diameter 3.75 mm,
After putting it in an outer diameter of 5.0 mm and replacing it with nitrogen, before heating it, the measurement conditions (magnetic field 323.5 ± 7.5 mT,
Magnetic field modulation frequency 100 kHz, magnetic field modulation width 0.32 m
T, time constant of amplifier circuit 0.1 sec, microwave output 8 m
W, room temperature). As a result, the ESR signal could not be observed. This indicates that there is no radical before heating.

Next, after heating at 250 to 330 ° C.,
After cooling, ESR measurement was performed in the same manner as above. The result is g
Value 2.0042, ΔH _pp (peak-to-peak line width)
A stable phenoxy type radical ESR signal showing a 14.4 G singlet was observed.

Comparative Example 1 A polycarbonate was produced in the same manner as in Example 1 except that bisphenol A having a total content of the general formulas (2), (3) and (4) produced in Example 1 was 36 ppm. For this polycarbonate, the ESR before and after heating was measured in the same manner as in Example 1. As a result, no ESR signal was observed before and after heating.

Example 2 Bisphenol A1 produced in the above Example 1 having a total content of the general formulas (2), (3) and (4) of 36 ppm.
General formulas (2) and (3) separately prepared in the same manner as
And 10 g of bisphenol A having a total content of 1164 ppm of (1) and (4) were uniformly mixed to prepare 20 g of bisphenol A for a polymer raw material having a total content of general formulas (2), (3) and (4) of 1200 ppm.

The obtained bisphenol A for polymer raw material
10.2 g, 10.2 g of a mixture of terephthalic acid chloride / isophthalic acid chloride 1: 1, 0.76 g of p-tertiarybutylphenol, calcium hydroxide 11.
Using 1 g and triethylamine 0.1 ml, 1,2-
After reaction in dichloroethane, reprecipitation purification was carried out to produce wholly aromatic polyester powder.

With respect to the wholly aromatic polyester powder thus obtained, the ESR before and after heating was measured in the same manner as in Example 1 above. As a result, no ESR signal was observed before heating, but an ESR signal was observed after heating.

Comparative Example 2 A wholly aromatic polyester was prepared in the same manner as in Example 2 except that bisphenol A having a total content of the general formulas (2), (3) and (4) produced in Example 1 was 36 ppm. A powder was produced, and ESR before and after heating was measured for this wholly aromatic polyester powder in the same manner as in Example 1 above. As a result, no ESR signal was observed before and after heating.

[0040]

The bisphenols for polymer raw material of the present invention can prevent coloring of the polymer produced and molded by using the bisphenol as a raw material as much as possible. It is useful as a raw material for producing a transparent polymer required for optical applications. Also,
The method of the present invention is suitable as a method for producing such bisphenols for polymer raw materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 315/06 C07C 315/06 317/22 7419-4H 317/22 319/26 319/26 323 / 20 7419-4H 323/20 C09K 15/08 C09K 15/08 15/14 15/14 // C08G 59/06 NGZ C08G 59/06 NGZ 63/195 NNC 63/195 NNC 64/04 NPT 64/04 NPT 65 / 44 NQX 65/44 NQX (72) Inventor Yoshio Sugiyama 1618 Ida, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Advanced Technology Research Laboratories, Nippon Steel Corporation (72) Masatsugu Matsuo Nakai, Kokurakita-ku, Kitakyushu City, Fukuoka Prefecture 4-10-3 (72) Inventor Katsuhiko Sakura 4-6-1-14 Nakai Nakai, Kokurakita-ku, Kitakyushu City, Fukuoka Prefecture

Claims (3)

[Claims] 1. The following general formula (1): (However, X is a divalent group in the formula) 4,4 '
-In bisphenols, the following general formula (2): (Wherein, X is a divalent group in the formula)
-Bisphenols, the following general formula (3): (Wherein, X is a divalent group) and a trisphenol represented by the following general formula (4): (However, in the formula, X is a divalent group, R and R'are alkyl groups having 1 or more carbon atoms, and n is an integer of 0 or 1.) Alkyl-substituted 4,4'- A bisphenol for a polymer raw material, which contains at least one phenolic compound selected from bisphenols in a total amount of 50 to 10,000 ppm by weight. 2. A bisphenol which has at least one substituent at the ortho position with respect to the hydroxyl group of 1, and has no substituent at the ortho position with respect to other hydroxyl groups,
50-10,000 weight pp for bisphenols
The following general formula (1) is characterized by being added in the range of m. (However, X is a divalent group in the formula.) A bisphenol for polymer raw material. 3. When producing the bisphenol for polymer raw material according to claim 1, the general formulas (2) and (3) in the 4,4′-bisphenol represented by the general formula (1).
And the total content of the phenolic compounds represented by (4) is measured, and when the total content is less than 50 ppm by weight, the total content of the phenolic compounds (2), (3) and (4) Phenolic compound (2), which is mixed with a large amount of 4,4′-bisphenol (1) or recovered in the purification step during the production of 4,4′-bisphenol (1),
A by-product having a large total content of (3) and (4) is added, or at least one compound selected from the separately synthesized phenolic compounds (2), (3) and (4) is added. However, when the total content is more than 10,000 ppm by weight, it is further purified, or 4,4′-with a small total content of the phenolic compounds (2), (3) and (4). It is mixed with bisphenols (1), and the total content of the phenolic compounds represented by the general formulas (2), (3) and (4) is adjusted within the range of 50 to 10,000 ppm by weight. And a method for producing bisphenols for polymer raw materials.