JPH02268129A - 4,4'''-dihydroxyquarterphenyl derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A 4,4'''-dihydroxyquarterphenyl derivative expressed by formula I (R is alkylene; m and n are integer of >=0, provided that m and n are not simultaneously O). EXAMPLE:A compound expressed by formula II. USE:A monomer for a chemically and physically excellent organic high polymer compound, e.g. polyester resin, polyurethane resin, polyether resin, polycarbonate resin or liquid crystal resin, having high performance such as high heat resistance, flame-retardant, solvent resistance or weather resistance and further, additive having excellent modification ability to other high polymer compound. PREPARATION:4,4'''-Dihydroxyquarterphenyl expressed by formula III is reacted with an alkylene oxide, alkylene carbonate or haloalkanol to provide the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a 4.4#-dihydroxyquaterphenyl derivative and a method for producing the same. The compound provided by the present invention has attracted much attention as a monomer for high-performance organic polymer compounds and as an additive for conventional polymer compounds having excellent modifying ability.

[Conventional technology]

Conventional diol components of organic polymer compounds include aliphatic compounds such as ethylene glycol, delpylene glycol, hexamethylene dalycol, and cyclohexane dimetatool;
Alicyclic diols, hydroquinone, resorcy, 1
．． 5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bisphenol, bisphenol F, bisphenol S.

Aromatic diols such as 4.4'-dihydroxypiphenyl and their ethylene oxide or depyrene oxide addition compounds are listed. These are used as constituent components of polyester resins, polyurethane resins, polycarbonate resins, polyether resins, and the like.

[Problem that the invention seeks to solve]

In recent years, there has been a demand for higher performance in the organic polymer compounds described above, and particularly high quality in terms of heat resistance, durability, chemical resistance, etc. has come to be desired.

[Ninth Means and Effects for Solving the Problem] The present inventors have conducted various studies to meet these demands, and as a result, have arrived at the present invention.

That is, according to the present invention, - Formula (I) [wherein R represents an alkylene group, and m and 1 represent an integer of 0 or 1 or more. However, m and n are never O at the same time. ] 4,4#-di and droxyquaterphenyl derivatives represented by the formula (n), and 4,4'-dihydroxyquaterphenyl represented by the formula (n) and alkylene oxide, alkylene car is reacted with haloalkanol. General formula (I
) A method for producing a 4,P-dihydroxyfortalphenyl derivative is provided.

Especially R2>1-CH2-CH2- group or -CH-CH2
-Group, CH3 mW nl! A compound represented by the general formula (1) and a method for producing the same are provided.

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

4,/-dihydroxyquaterphenyl (hereinafter abbreviated as DOQ) represented by the formula (tilt) is 4-bromo-4'-
By heating and dimerizing methoxybiphenyl in the presence of copper powder and then demethylating it, 9 (J, C, S,

1940, pp. 1379-1382), or by dimerizing 4-bromo-4/codroxybiphenyl in the presence of a palladium catalyst (method of the invention filed by the applicant). can.

→(II) DOQ 'i, hydroxyethylating agent, e.g. ethylene/'7-? $-), ethylene oxide or 2-haloethanol in the presence of a suitable catalyst or acid scavenger to form di(human tetraxyethyl)-DOQ (hereinafter DOQ).
-abbreviated as EO) is produced.

Similarly, DOQ can be substituted with a hydroxybromolizing agent, e.g.
U propylene carnate, propylene oxide,
Alternatively, by reacting with 2-haloethanol in the presence of a suitable catalyst or acid scavenger, zo(hydroxypropyl)-DO
Q (hereinafter abbreviated as DOQ-PO) is manufactured.

Their reaction formulas are shown below: Catalyst 1 ---→DOQ-EO+(m+n)CO2 Catalyst 0Q-EO DOQ-KO+(m+n)A-HX H3 Catalyst DOQ-PO+(m+n)CO2 Catalyst 1→DOQ-PO In (reaction formulas 3) and 6), X is a halogen atom, AFiI!
Represents a capture agent) 1) The reaction of formula 1) will be described later. The reaction of formula 2) is usually carried out by heating DOQ and 2 or more moles of ethylene oxide in an inert solvent in a closed reactor in the presence of a catalyst (organic or inorganic base).

The reaction of formula 3) is usually carried out by combining DOQ and 2 moles or more of 2-haloethanol in an inert solvent in a closed reactor with an acid scavenger (
This is carried out by heating in the presence of an organic or inorganic base. The reaction of formula (4) is usually carried out by heating DOQ and 2 moles or more of globylene cargenate in the presence of a catalyst (organic or inorganic base) in an inert solvent. 5) The reaction of formula is usually carried out in an inert solvent with DO
This is carried out in the presence of Q and 2 or more moles of propylene oxide in the presence of a catalyst (organic or inorganic base). The six-type reaction is usually carried out by heating DOQ and 2 or more moles of 2-no-globanol in an inert solvent in a closed reactor in the presence of an acid scavenger (organic or inorganic base). It is done.

In the reaction of 6111 above, the reaction of formula 2) is difficult to control the number of moles of ethylene oxide added, and the reaction of formula 3) and 6
) reaction has a slow reaction rate, and side reactions (specific H5 include X-CH2CH20kl,
(D ring closure or self-polymerization reaction) occurs to a large extent. On the other hand, the reaction of formula 1) and formulas 4) and 5) has a fast reaction rate, and the number of added moles can be easily controlled, especially when m = n =
1, that is, the following formula (Ia), and D
It is suitable for producing OQ-pQ, that is, a compound represented by the following formula (Ib) (Im).

Next, an embodiment of the production method (reaction of formula I) of the present invention when ethylene carbinate is used will be described.

A reactor equipped with a stirrer, thermometer, reflux condenser, and charge port is charged with DOQ, ethylene carbinate, and inert solvent. The fecal amount of ethylene carnate is determined by the formula (I
) is selected depending on the number of ethylene oxide groups contained in the compound.

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

The numbers m and nO in formula (I) are selected depending on the purpose of use, but are usually up to about 20, and in particular, m−n=1 is widely and advantageously used.

The inert solvent is DOQ 1 part (weight, same below)
100 parts, usually about 3 to 50 parts, is used.

The solvent does not necessarily need to dissolve DOQ and/or DOQ-EO, and the reaction proceeds satisfactorily even in a suspended state.

Examples of inert solvents include ethylene glycol lower alkyl ether, fluoropylene gelyl lower alkyl ether,
Benzene, toluene, xylene, N,N-dimethylacetamide, N,N-trimethylformamide, sulfolane (tetrahydrithio7ene-1,1-dioxide), 1
．． 3-methyl-2-imidazolidinone and the like are listed. Although a solvent is not necessarily required, it is convenient to use one from an operational standpoint.

The above mixture is heated under stirring to reflux temperature or from 130 DEG to 250 DEG C. and the catalyst is added. As the catalyst, a basic compound such as alkali hydroxide or alkali carbonate is used. The amount used is about 0.1 to 10 weight of DOQ.

The reaction is generally carried out at the same temperature for 1 to 15 hours, preferably 4 to 6 hours, but it is advantageous to control the reaction while checking the production status of the target product using a liquid chromatograph.

After the reaction is completed, the reaction mixture is cooled, filtered, and washed to obtain the desired product. In this case, filtration is somewhat difficult, so the reaction mixture is allowed to stand, the supernatant liquid is separated by decanting, a washing liquid is added to the precipitate, and the mixture is stirred, allowed to stand, and after separation, it is filtered or dried as it is. The operation of the washing liquid is appropriately selected depending on the solvent used.

The crude DOQ-EO thus obtained is usually purified by recrystallization. Add 30 to 40 parts of a suitable solvent such as sulfolane to 1 part of crude DOQ-EO, heat to around 150°C to dissolve, add activated carbon if necessary, filter hot, and if necessary cool to 5 to IO'cK. , the precipitate is filtered, washed and dried to obtain a purified product. After purification, the mother liquor is further concentrated (thermal filtration)
, cooled and filtered to obtain a secondary crystallized product and further a tertiary crystallized product. These can usually be recycled for recrystallization.

〔Example〕

Next, examples of the present invention will be described. ◎Example 1 A reactor equipped with a stirrer, a thermometer, a reflux condenser, and a charging port contained DOQ of 67.9, F (0.2 mol), and ethylene cargo (ethylene cargo) 52. 8.9 (0.6 mol) and sulfolane (tetrahydrothiophene-1,1-dioxide) 4
Anhydrous potassium carbonate powder 0.2! i, and an additional 0.2 J after about 30 minutes.
After adding I (0.4.9 in total), the mixture was kept at the same temperature for 30 minutes, and then the temperature was raised to 160° C. for about 3 hours.

After cooling the reaction mixture, it was filtered under suction, washed with water, washed with 500 WL of methanol, and then dried under reduced pressure at 100°C for about 2 hours to give 83.4 g of off-white crystals (crude yield: 98 cm/DOQ).
) was obtained.

The next purified product obtained by recrystallizing this crude DOQ-EO from 25,001 Ll of sulfolane is a white crystal with a melting point of 390°C measured by DTA (412°C by polarized light melting point microscopy).
The purity determined by liquid chromatography was 99.0%.

The elemental analysis value of this item is as follows: - Shipman (I) OR
was found to be a compound (molecular formula 028H2AO4) represented by the Maebutsu formula (Im) where is an ethyl group and m and n are 1.

Elemental analysis value C (%) HC%) Measured value 79.65 6.25 Theoretical value 78.85 6.15 (as 0211H2404) In addition, the infrared absorption spectrum (caritum bromide tablet method) of this product is shown in FIG.

Example 2 DOQ67, 6 was added to a reactor having the same equipment as Example 1.
．． 9 (0,27 l), propylene cargoonate 61.
2 g (0.6 mol) and sulfo2y460F were charged, and 0.2 g (0.6 mol) of anhydrous potassium carbonate powder was added at 130-140°C with stirring.
After adding 21t, approx. 3011 and 0.2g (total of 4.1g), keep at the same temperature for about 30 minutes, then raise the temperature to 160g.
The reaction was carried out at ℃ for about 3 hours.

The reaction mixture was cooled, filtered with suction, washed with water, and diluted with methanol 5
00111 and then drying under reduced pressure at 100'C for about 2 hours to give off-white crystals of 87.1 F (crude yield 96 1/D).
OQ) was obtained.

The purified product obtained by recrystallizing DOQ from 2500+aJ of sulfolane is a white crystal with a melting point of 353°C (DTA
), purity determined by liquid chromatography is 99. It was Ochi. The elemental analysis value of this substance is as follows: - Formula C
The above formula (I) in which R in I) is a groll group and m and n are 1
It was recognized that it was a compound represented by b) (molecular formula 〇3oH3oOn).

Elemental analysis value C (%) H (%) Measured value 78.8 6.57 Theoretical value 79.27 6.65 (as C3CH5004) Also, the infrared absorption spectrum (potassium bromide tablet method) of this product is shown in Figure 2. .

[Brief explanation of drawings]

FIG. 1 shows the purified DOQ-EO obtained in Example 1 (-formula (La) in which R is an ethyl group and m=nxl in formula (I)).
6J in the infrared absorption spectrum of the compound), Figure 2 shows:
Purified DOQ obtained in Example 2 -PO[-formula (I)
So 8 is an inglovir group, Ill! The infrared absorption spectrum of the compound of formula (Ib), which is 71-1, is plotted in Table 1. The horizontal axis shows the wave number (in -') and the vertical axis shows the transmittance (%).

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, R represents an alkylene group, and m and n represent an integer of 0 or 1 or more. However, m and n are never 0 at the same time. ] A 4,4'''-dihydroxyquarterphenyl derivative represented by the formula (I). 2. In the general formula (I), R is a -CH_2-CH_2- group or a ▲ mathematical formula, chemical formula, table, etc. ▼ group, and m
4,4'''-dihydroxyquarterphenyl derivative according to claim 1, where = n = 1. 3. 4,4'''- dihydroxyquarterphenyl derivative represented by formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) The method for producing a dihydroxyquarterphenyl derivative according to claim 1, which comprises reacting dihydroxyquarterphenyl with an alkylene oxide. 4. The manufacturing method according to claim 3, wherein alkylene carbonate is reacted instead of alkylene oxide. 5. The manufacturing method according to claim 3, wherein a haloalkanol is reacted instead of the alkylene oxide. 6. The dihydroxy quarter according to claim 2, wherein 4,4'''-dihydroxy quarter phenyl represented by formula (II) ▲There are numerical formulas, chemical formulas, tables, etc. ▼ (II) is reacted with ethylene carbonate or (iso)propylene carbonate. Method for producing phenyl derivatives.