JP2636042B2 - 4,4 '""-dihydroxyquarterphenyl derivative and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a 4,4-dihydroxyquarterphenyl derivative and a method for producing the same. The compounds provided by the present invention are of great interest as monomers of high-performance organic polymer compounds and as those having excellent modifying ability as additives of conventional polymer compounds.

[Conventional technology]

Conventionally, as the diol component of the organic polymer, ethylene glycol, propylene glycol, hexamethylene glycol, aliphatic and alicyclic diols such as cyclohexane dimethanol, hydroquinone, resorcinol,
Aromatic diols such as 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxybiphenyl, and ethylene oxide or propylene oxide adducts thereof are listed. . These are used as constituents of polyester resin, polyurethane resin, polycarbonate resin, polyether resin and the like.

[Problems to be solved by the invention]

In recent years, higher performance has been demanded for the organic polymer compounds as described above, and high quality has been particularly required in heat resistance, durability, chemical resistance and the like.

[Means and effects for solving the problem]

The present inventors have conducted various studies to meet such a demand, and as a result, have reached the present invention.

That is, according to the present invention, the compound represented by the general formula (I) [Wherein, R represents an alkylene group, and m and n each represent 0 or an integer of 1 or more. However, m and n are not 0 at the same time. A 4,4-dihydroxyquarterphenyl derivative represented by the formula: Formula (I) obtained by reacting a 4,4-dihydroxyquarterphenyl represented by the formula with an alkylene oxide, an alkylene carbonate or a haloalkanol.
And a method for producing a 4,4-dihydroxyquarterphenyl derivative represented by the formula: In particular R is -CH ₂ -CH ₂ - group, or And a compound represented by the general formula (I) wherein m = n = 1 and a production method thereof are provided.

The compound of the present invention is used as a monomer such as an organic polymer compound such as a polyester resin, a polyurethane resin, a polyether resin, a polycarbonate resin and a liquid crystal resin, and has high heat resistance, flame retardancy, solvent resistance, weather resistance and other chemical properties.
Gives a resin with excellent physical properties, and exerts an excellent effect of improving chemical and physical properties when added to other resins.

4,4-Dihydroxyquarterphenyl (hereinafter abbreviated as DOQ) represented by the formula (II) is 4-bromo-4 '
-Methoxybiphenyl is heated and dimerized in the presence of copper powder and then demethylated (JCS, 1940, pp. 1379-138).
2) Or, by dimerizing 4-bromo-4'-hydroxybiphenyl in the presence of a palladium catalyst, the {method of the invention filed by the present applicant} can be obtained.

DOQ is reacted with a hydroxyethylating agent such as ethylene carbonate, ethylene oxide or 2-haloethanol in the presence of a suitable catalyst or an acid scavenger to give di (hydroxyethyl) -DOQ (hereinafter abbreviated as DOQ-EO). To manufacture.

Similarly, the DOQ is reacted with a hydroxypropylating agent, such as propylene carbonate, propylene oxide, or 2-halopropanol, in the presence of a suitable catalyst or an acid scavenger to form a di (hydroxypropyl) -DOQ.
(Hereinafter abbreviated as DOQ-PO).

 The reaction formulas are shown below.

{In Reaction Formulas 3) and 6), X represents a halogen atom and A represents an acid scavenger. The reaction of Formula 1) will be described later. The reaction of equation 2) is
It is usually carried out by heating DOQ and 2 mol or more of ethylene oxide in an inert solvent in a closed reactor in the presence of a catalyst (organic or inorganic base). The reaction of equation 3) is
Usually an acid scavenger (organic or inorganic base) between DOQ and 2 moles or more of 2-haloethanol in an inert solvent in a closed reactor
This is performed by heating in the presence of For the reaction of formula 4), DOQ and propylene carbonate of 2 mol or more are usually catalyzed in an inert solvent (organic or inorganic base).
By heating in the presence of The reaction of the formula 5) is usually performed in an inert solvent using DOQ and 2 mol or more of propylene oxide in the presence of a catalyst (organic or inorganic base). The reaction of formula 6) is usually carried out by heating DOQ and 2 mol or more of 2-halopropanol in an inert solvent in a closed reactor in the presence of an acid scavenger (organic or inorganic base).

In the above six reactions, the reaction of the formula (2) is difficult to control the number of moles of ethylene oxide added, and the reactions of the formulas (3) and (6) are difficult.
The reaction of the formula has a slow reaction rate and side reactions (especially X-CH ₂ CH ₂ O
H, Ring closure or self-polymerization reaction) is large. On the other hand, the reactions of the formulas 1) and 4) and 5) have a high reaction rate and are easy to control the number of moles added. In particular, DOQ-E where m = n = 1
O, ie, the following formula (Ia), and DOQ-PO, ie, the following formula (Ib) Suitable for the production of the compound represented by

Next, an embodiment of the production method of the present invention {1) reaction using ethylene carbonate} when using ethylene carbonate will be described.

A reactor equipped with a stirrer, thermometer, reflux condenser and inlet is charged with DOQ, ethylene carbonate and an inert solvent. The amount of ethylene carbonate used is selected according to the number of ethylene oxide groups contained in the target compound of formula (I).

For example, when m = n = 1 in the formula (I), 2 mol or more (up to about 4 mol) of ethylene carbonate is used per 1 mol of DOQ, and when m = n = 2, 4 mol or more (up to about 8 mol) is used. However, the numbers of m and n are also controlled by the reaction temperature and time, and the amount of catalyst.

Although the number of m and n in the formula (I) is selected depending on the purpose of use, it is usually up to about 20, especially those where m = n = 1 are widely and advantageously used.

Inert solvent is 1 to 100 per part of DOQ (weight, same hereafter)
Parts, usually about 3 to 50 parts. The solvent does not necessarily dissolve DOQ and / or DOQ-EO, and the reaction proceeds sufficiently even in suspension. As the inert solvent, ethylene glycol lower alkyl ether, propylene glycol lower alkyl ether, benzene, toluene, xylene, N, N-dimethylacetamide, N, N-dimethylformamide, sulfolane (tetrahydrothiophene-1,1-
Dioxide), 1,3-dimethyl-2-imidazolidinone and the like. Although a solvent is not always necessary, it is convenient to use it in operation.

The mixture is heated with stirring to reflux temperature or 130 ° -250 ° C. and the catalyst is added. As the catalyst, a basic compound such as an alkali hydroxide or an alkali carbonate is used. The amount used is about 0.1 to 10% by weight of the DOQ.

The reaction is usually carried out at the same temperature for 1 to 15 hours, preferably for 4 to 6 hours, and it is advantageous to control while checking the production state of the desired product by liquid chromatography.

After completion of the reaction, the reaction mixture is cooled, filtered and washed to obtain the desired product. In this case, the reaction is somewhat difficult, so the reaction mixture is allowed to stand, the supernatant is decanted, a washing solution is added to the sediment, and the mixture is stirred, allowed to stand, separated, and then dried or dried as it is.
The operation of the washing solution is appropriately selected depending on the solvent used.

The crude DOQ-EO thus obtained is usually subjected to recrystallization purification. To 1 part of the crude DOQ-EO, add an appropriate solvent, for example, 30 to 40 parts of sulfolane, heat to about 150 ° C., dissolve, add activated carbon if necessary, heat and cool to 5 to 10 ° C. if necessary. Then, the precipitate is washed, washed and dried to obtain a purified product.
After purification, the mother liquor was further concentrated (heated), cooled,
A second crystallized product and further a third crystallized product are obtained. These can usually be recycled for recrystallization.

〔Example〕

 Next, examples of the present invention will be described.

Example 1 In a reactor equipped with a stirrer, thermometer, reflux condenser and inlet, 67.9 g (0.2 mol) of DOQ and 52.8 g of ethylene carbonate were added.
(0.6 mol) and 460 g of sulfolane, 0.2 g of anhydrous potassium carbonate powder was added at 130 ° -140 ° C. with stirring, and 0.2 g (0.4 g in total) was added after about 30 minutes, and the temperature was maintained at the same temperature for 30 minutes. Thereafter, the temperature was raised and the reaction was carried out at 160 ° C. for about 3 hours.

After cooling, the reaction mixture was filtered by suction, washed with water, washed with 500 ml of methanol, and dried under reduced pressure at 100 ° C. for about 2 hours to obtain 83.4 g (98% crude yield vs. DOQ) of off-white crystals.

The purified product obtained by recrystallizing the crude DOQ-EO from 2500 ml of sulfolane is a white crystal having a melting point of 390 measured by DTA.
° C (412 ° C by polarizing melting point microscopy) and purity by liquid chromatography was 99.0%. Its elemental analysis values are as follows. A compound represented by the above formula (Ia) in which R in the general formula (I) is an ethyl group and m and n are 1 (molecular formula C ₂₈ H
₂₆ O ₄ ).

Elemental analysis value C (%) H (%) Measurement value 79.65 6.25 Theoretical value 78.85 6.15 (as C ₂₈ H ₂₆ O ₄ ) The infrared absorption spectrum (potassium bromide tablet method) of this is shown in FIG.

Example 2 A reactor having the same apparatus as in Example 1 was charged with 67.6 g of DOQ (0.
2 mol), 61.2 g (0.6 mol) of propylene carbonate and 460 g of sulfolane, 0.2 g of anhydrous potassium carbonate powder at 130 to 140 ° C. under stirring, and 0.2 g after about 30 minutes (0.4 g in total)
After the addition, keep at the same temperature for about 30 minutes, then raise the temperature to 160 ° C
For about 3 hours.

The reaction mixture was cooled, filtered by suction, washed with water, and methanol
After washing with 500 ml, it was dried under reduced pressure at 100 ° C. for about 2 hours to obtain 87.1 g (96% crude yield vs. DOQ) of off-white crystals.

The purified product obtained by recrystallizing this DOQ from 2500 ml of sulfolane was white crystals, the melting point was 353 ° C. (DTA), and the purity by liquid chromatography was 99.0%. Its elemental analysis values are as follows, and the compound of the general formula (I) represented by the formula (Ib) wherein R is a propyl group and m and n are 1 (molecular formula: C ₃₀ H ₃₀ O ₄ ) Was observed.

Elemental analysis value C (%) H (%) Measurement value 78.8 6.57 Theoretical value 79.27 6.65 (as C ₃₀ H ₃₀ O ₄ ) The infrared absorption spectrum (potassium bromide tablet method) of this is shown in FIG.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the purified DOQ-EO obtained in Example 1 (compound of the formula (Ia) wherein R is an ethyl group and m = n = 1 in the general formula (I)). FIG. 2 shows an infrared absorption spectrum of the purified DOQ-PO obtained in Example 2 (a compound of the formula (Ib) in which R is an isopropyl group and m = n = 1 in the general formula (I)). It is an absorption spectrum, a horizontal axis shows a wave number (cm ^-1 ), and a vertical axis shows transmittance (%).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08G 63/66 NNH C08G 63/66 NNH 64/02 NPT 64/02 NPT 64/16 NPT 64/16 NPT 65/38 NQV 65/38 NQV 67/00 NRA 67/00 NRA

Claims (6)

(57) [Claims] 1. The compound of the general formula (I) [Wherein, R represents an alkylene group, and m and n each represent 0 or an integer of 1 or more. However, m and n are not 0 at the same time. The 4,4-dihydroxyquarterphenyl derivative represented by these. 2. In the general formula (I), R represents a --CH ₂ --CH ₂ -group or The 4,4-dihydroxyquarterphenyl derivative according to claim 1, wherein m = n = 1. 3. The formula (II) The method for producing a dihydroxyquarterphenyl derivative according to claim 1, wherein the 4,4-dihydroxyquarterphenyl represented by the formula is reacted with an alkylene oxide. 4. The method according to claim 3, wherein an alkylene carbonate is reacted in place of the alkylene oxide. 5. The process according to claim 3, wherein a haloalkanol is reacted in place of the alkylene oxide. 6. The formula (II) The method for producing a dihydroxyquarterphenyl derivative according to claim 2, wherein the 4,4-dihydroxyquarterphenyl represented by the formula is reacted with ethylene carbonate or (iso) propylene carbonate.