JPH02212449A - 4,4"-dihydroxy-3-phenyl-p-terphenyl derivative and polyester - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 and R2 are CH3, group of formula II or formula III (R' is alkylene; n is 0 or integer of >=1)]. EXAMPLE:4,4'',-Diacetoxy-3-phenyl-p-terphenyl. USE:Monomer for organic polymer compounds or additive for polymeric compounds such as polyester, polyurethane, polyether, polycarbonate or liquid crystal resin having the structural unit of formula IV and useful as a molding material for molded article, film, fiber, etc. A polymeric compound having excellent heat-resistance and mechanical strength, exhibiting melt anisotropy and having good moldability can be produced from the above compound. PREPARATION:A compound of formula I wherein R1 and R2 are CH3 can be produced by the Grignard coupling reaction of the compound of formula V with the compound of formula VI in a solvent in the presence of a Ni catalyst such as NiCI2(bisdiphenylphosphino)-propane. The compound can be converted to another compound of formula I wherein R1 and R2 are OH by reacting with BBr3 or HBr.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to 4.4"-dihydro, xy-3-phenyl-ρ
-Relates to a terphenyl derivative and a polyester produced using the compound as a constituent component.

The novel compound provided by the present invention is attracting much attention as a high-performance organic polymer compound and as having excellent modifying ability as an additive for conventional polymer compounds. be.

Moreover, polyester, which is an example of a polymer compound obtained using the compound as a constituent component, is specifically useful as a resin for coatings, molded products, or fibers, which has a high degree of heat resistance and moldability.

(Prior art) A dibasic acid such as terephthalic acid, isophthalic acid or carbonic acid and bisphenol A (2,2-propylidene-4,4'
-biphenol), bisphenol S (4,4'-dihydroxydiphenylsulfone) or 4.4°-dihydroxybiphenyl are called polyesters or wholly aromatic polyesters, and have already been It has been put into practical use.

On the other hand, aromatic polyester, which is a homopolycondensate of aromatic hydroxycarboxylic acids, especially parahydroxybenzoic acid, was already known to have extremely high heat resistance and mechanical strength, but practical molding processing is difficult. Due to the difficulty, it was not widely put into practical use.

However, recently, when parahydroxybenzoic acid is copolymerized with a component that lowers the melting point of the polycondensate in an appropriate ratio, it exhibits anisotropy (thermotropic liquid crystallinity) when melted, making it difficult to mold and process. It has been discovered that not only is this process easier, but also that the polymer chains are oriented in the direction of flow, making it possible to obtain a polyester with high elastic modulus and mechanical strength. and.

Practical use of these melt-anisotropic polyesters has just begun, and future technological developments are expected.

(Problem to be solved by the invention) The object of the present invention is to have excellent heat resistance and mechanical strength.

A polymer compound having melt anisotropy and good moldability can be obtained. 4,4-dihydroxy- as its constituent
An object of the present invention is to provide a 3-phenyl-p-terphenyl derivative and a polyester.

(Means for solving the problems) 4.4"-dihydroxy-3-phenyl-p- of the present invention
Terphenyl derivatives are represented by -maximum (1), thereby achieving the above objective.

Moreover, 1 polyester of the present invention is 1 formula (^)-phenyl,
4.4"-dimethoxy-3-phenyl-p-terphenyl, 4,4-diacetoxy-3-7enyl-p-terphenyl, di(hydroxyalkyl)ated 4.4"-dihydroxy-3-phenyl-p- Terphenyl etc.

4,4''-dimethoxy-3-phenyl-p-terphenyl (hereinafter abbreviated as PT-DMe) represented by the following formula (n) has a structural unit represented by 9, thereby achieving the above object. Ru.

Specifically, the compound represented by the general formula (I) of the present invention is a 4.4''-dihydroxy-3-phenyl-p-taNi catalyst (for example, N1CL2(dppp)) (dPP
I): bis(d+phenylphosphino)
propane) by carrying out a Grignard coupling reaction.

(Compound a) (Compound b) The above PT-DH is reacted with acetic anhydride to produce 4,4-diacetoxy-3-phenyl-p-terphenyl (hereinafter referred to as PT-DH).
(abbreviated as OAc) is obtained (formula (■) below).

4. Reacting PT-OMe with 88r or Her.
4-dihydroxy-3-phenyl-p-terphenyl (
(hereinafter abbreviated as PT-DH) is obtained (formula (■) below).

(III) Di(hydroxyalkylated)-PT-OH is obtained by reacting the above PT-OH in the presence of a hydroxyalkylating agent and a suitable catalyst or acid scavenger. here.

The alkyl group is preferably a lower alkyl group, more preferably an ethyl group or a propyl group, and may be straight or branched.

For example, di(hydroxyethyl)-PT-OH (hereinafter referred to as PT
−ε0) is obtained.

Similarly, PT-0)1 was used as a hydroxypropylating agent.

For example, propylene carbonate, propylene oxide,
or 2-halopropanol in the presence of a suitable catalyst or acid scavenger to form di(hydroxypropyl)-
PT-OH (hereinafter abbreviated as PT-PO) is obtained.

Their reaction formulas are shown below.

catalyst FT-80+ (+n+n)CD.

The reaction of formula (1) is usually carried out by heating FT-OH and 2 moles or more of ethylene carbonate in the presence of a catalyst in an inert solvent. The reaction in equation (2) is.

This is usually carried out by heating PT-0)1 and 2 moles 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 formula (3) is usually carried out by heating PT-Ko and 2 moles or more of 2-haloethanol in an inert solvent in a closed reactor in the presence of an acid scavenger (organic or inorganic base). It will be done. The reaction of formula (4) is usually carried out by heating PT-Oll and 2 or more moles of propylene carbonate in the presence of a catalyst (organic or inorganic base) in an inert solvent. The reaction of formula (5) is usually carried out by heating PT-0) 1 and 2 or more moles of propylene oxide in the presence of a catalyst (organic or inorganic base) in an inert solvent. The reaction of formula (6) is usually carried out by heating PT-OH and 2 moles or more of 2-halopropanol in an inert solvent in the presence of an acid scavenger (organic or inorganic base) in a closed reactor. This is done by

Among the above six types of reactions, it is difficult to control the number of moles of ethylene oxide added in the reaction of formula (2), and the reaction of formula (3) and (
The reaction of formula 6) has a slow reaction rate, and side reactions (especially CH3X-CH2Cl, OH, XJH, CH, OH (7)
The occurrence of self-polymerization reaction of ffl or 1 is large. On the other hand, the reactions of formulas (1), (4) and (5) have a fast reaction rate and the number of moles added is easy to control, especially when m=n=l
PT-EO, that is, the following formula (I a), and PT
−PO, that is, the following formula (I b) ・ ・ ・ ・ ・ (
Suitable for the preparation of compounds of I a).

The polyester of the present invention contains the above compound (I) as a constituent component and has a structural unit represented by the formula (A). That is, the polyester of the present invention consists of a dihydroxy compound and a dicarboxylic acid.

Alternatively, in a polycondensate containing these two and a hydroxycarboxylic acid as main components, a tetracyclic aromatic dihydroxy compound represented by the above formula (I) is used as one component of the dihydroxy compound.

Other constituent components of the dihydroxy compound include aromatic dihydroxy compounds and aliphatic dihydroxy compounds other than the compound (1), and examples of the dicarboxylic acids include aromatic dicarboxylic acids and aliphatic dicarboxylic acids; Examples of hydroxydicarboxylic acids include aromatic hydroxycarboxylic acids and aliphatic hydroxycarboxylic acids.

Aromatic dihydroxy compounds other than the above-mentioned maximum (I) include resorcinol, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone (2,5-dihydroxybiphenyl), methoxyhydroquinone, phenoxyhydroquinone, 4.4
'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether.

4.4°-dihydroxydiphenyl sulfide, 4°4′-dihydroxydiphenyl sulfone, 4.4'-dihydroxybenzophenone, 4.4'-dihydroxydiphenylmethane, bisphenol A, 1.1-di(4-
hydroxyphenyl)cyclohexane, 1,2-bis(
Examples include 4-hydroxyphenoxy)ethane, 1,4-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

The aromatic dicarboxylic acids include metal salts of terephthalic acid, isophthalic acid, 5-sulfoisophthalic acid, 4.4"
-Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4°-dicarboxydiphenyl sulfide, 4,4'-dicarboxydiphenyl sulfone, 4,4'-dicarboxybenzophenone, 1.2
-bis(4-carboxyphenoxy)ethane, 1.4-
Examples include dicarboxynaphthalene and 2,6-dicarboxynaphthalene.

Examples of the aromatic hydroxycarboxylic acids include metahydroxybenzoic acid and parahydroxybenzoic acid.

3-chloro-4-hydroxybenzoic acid, 3-bromo-4
-Hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid M, 3
-methoxy-4-hydroxybenzoic acid, 4-hydroxy-4°-carboxybiphenyl or 2-hydroxy-6
-carboxynaphthalene, etc.

Examples of the aliphatic dihydroxy compounds include alkylene glycols represented by the maximum HD-((:H2), -0)1 (n is an integer of 2 to 10), such as ethylene glycol, propylene glycol, butylene glycol, and the like.

Examples include propylene-1,2-diol, butane-1,2-diol, butane-1,3-diol, neopentyl glycol, polyethylene glycol, polypropylene glycol, and the like.

The aliphatic dicarboxylic acid mentioned above is oxalic acid.

Dicarboxylic acids represented by maximum H QC' (CL), -COOH (n is an integer of 0 to 10) such as malonic acid, succinic acid, glutaric acid, adipic acid, methyl group, ethyl group.

Alkyl groups such as n-propyl group and iso-propyl group.

Examples include aliphatic dicarboxylic acids substituted with alkoxy groups such as methoxy groups and ethoxy groups, and halogen groups such as bromine groups.

Among these components, polycondensation of large amounts of aromatic dicarboxylic acids and aromatic hydroxycarboxylic acids yields high-strength polyesters with excellent crystallinity and heat resistance. If a large amount of polycondensation is carried out, a flexible polyester will be obtained although the heat resistance will decrease slightly.

Among the constituent components of the polycondensate described above, the dihydroxy compound and dicarboxylic acid form a substantially equal molar ratio, and the hydroxycarboxylic acid forms a high molecular weight polycondensate at an arbitrary molar ratio.

It is difficult to polycondensate each component by heating it as it is, so it is usually preferable to acetylate the hydroxyl groups of the components before carrying out the polycondensation reaction. The polycondensation reaction can be carried out at a temperature of 200°C to 350°C. The acetic acid produced by the polycondensation reaction is preferably removed from the reaction system first under normal pressure and finally under reduced pressure. If the reaction system is particularly crystalline and non-uniform, removing the acetic acid under pressure and finally reducing the pressure will make the system more homogeneous and give better results. The molecular weight of the polycondensate can also be adjusted by adjusting the molar ratio of the constituent dihydroxy compound and dicarboxylic acid, but good results can be obtained when the molecular weight is relatively low. In a high molecular weight range, a method is used to adjust the molecular weight by conducting the reaction while using the melt viscosity of the zero-polycondensate as a guide.

When the above-mentioned highly crystalline compound (I) is incorporated into the constituent components of the polyester of the present invention, the single polycondensate often becomes melt anisotropic. Melt anisotropy can be confirmed by polarization techniques using conventional polarization microscopy.

More specifically, a test piece prepared to a thickness of 1 mm or less was placed on a heating stage and heated at 5°C under a nitrogen atmosphere.
This can be easily confirmed by heating at a temperature increase rate of 1/min and observing at 40x or 100x magnification using a polarizing microscope with the polarizers orthogonal to each other.

The polyester of the present invention is used to improve heat resistance, rigidity, etc. within a range that does not impair its practicality.

Reinforcements such as glass fiber, carbon fiber, whisker wollastonite, etc. may be added. In addition, as crystallization accelerators, inorganic substances such as talc, barium sulfate, alumina, and silicon oxide, higher fatty acid salts such as sodium stearate, barium stearate, and sodium valmitate, and benzyl alcohol.

An organic compound such as benzophenone or a known nucleating agent such as highly crystallized polyethylene terephthalate or polytrans-cyclohexane dimetatool terephthalate may be added. Furthermore, stabilizers such as phosphites, heat retardants, antistatic agents, mold release agents, etc. may be added as desired.

The polyester of the present invention is optimal as a molding material for various molded products. It can also be used in films, m-fibers, adhesives, paints, etc. moreover.

The polyester of the present invention can be mixed with other thermoplastic resins such as polyolefin, modified polyolefin, polystyrene, polyamide, polycarbonate, polysulfone, polyester, etc., or mixed with a rubber component to modify its properties. Good too.

(Example) Next, one embodiment of the present invention will be explained based on an example.

In addition, NjCh (dppp> is derived from Bul
Letin oftl〕e Chemical
5ociety of JAPAN
49(7), 1958-1969 (1976).

Example 1 3.16 g of Grignard magnesium in a 300i three-turn flask equipped with an isobaric funnel and Jim v-) type condenser.
(130 nouol) was activated by heating with a Y5 ear under vacuum. Set the system to a nitrogen atmosphere.

The above compound (a) 28.94 g (1
50ml 1f trihydrofuran (T
About 1 m of HF') solution! ! dripped. I tried stirring with a magnetic stirrer tip, but it was difficult for the reaction to proceed, so I added a spoonful of iodine to a spatula.
The reaction was started. After adding the entire amount of the T-rich solution dropwise over about 1 hour, stirring was continued for another 3 hours to continue one reaction.

Another 500- with isobaric funnel, Dimroth type cooler
The Mitsuro flask was placed in a nitrogen atmosphere, and the above compound (b) 2
6Jl g (100mmol) and THF150m
Enter f.

The mixture was stirred with a magnetic stirrer and heated slightly to dissolve it. To this, N 1c12 (dppp) o, 11
g was added.

The system turned into a red transparent solution, and the Grignard reagent was quantitatively transferred to an isobaric funnel. The Grignard reagent was added dropwise over a period of about 30 minutes, but the appearance of the system changed as the dropwise addition progressed: red transparent solution - yellow transparent solution - yellow opaque solution (with precipitate) - brown opaque solution (same as on the left). After dropping the entire amount, it was heated in a water bath at 80°C and heated under reflux for 1 hour.
The reaction was carried out for 5 hours.

After cooling the reaction mixture, it was filtered with suction and washed with THF.

After further washing with water, drying under reduced pressure at 100°C for about 2 hours yields white crystals 21. , 8g (59mmol) was obtained. The melting point of this white crystal was 194° C. The single element analysis values were as follows.

Elemental analysis value (as C2g8220g) In addition, the infrared absorption spectrum by the Nujol method of this crystal shown in Figure 1 and the 'If-NMR shown in Figure 2
Subectal identified this substance as PT-OLIa.

'H-NMR (DMSO-da, 270M)lz)
δ=3.82 (s, 6)1.0CR5)=7,
03 (d, 2H,)la)=7.21 (d,
IH, Hb) =7.30~? , 90 (+n, 13)1. aro
matic) Example 2 A 300-meter Mitsuro flask equipped with an isobaric funnel and a Dimroth type condenser was placed in a nitrogen atmosphere, and FT-OMe 0.1
615 g (25 mmol) was added. To this C) +2
c12100- was added. BBrs 8 for isobaric funnel
．． A solution of 4 g (33 mmol) of 30 ml CLct was charged. The entire [:LC12 solution of BBr] was added dropwise over about 1 hour while stirring with a magnetic stirrer tip. Thereafter, the mixture was heated to 40 to 50°C in a water bath, and the reaction was continued for 6 hours under reflux. As the reaction progressed, the system, which was a white opaque solution, turned into a pale purple opaque solution. After the reaction mixture was allowed to cool.

It was poured into a large amount of pure water and the white precipitate was isolated by suction filtration. After washing with water, it was dried under reduced pressure at 100°C for about 2 hours. White powder? , l1g (21 mmol) was obtained.

This white powder had a melting point of 185° C. The single element analysis values were as follows.

Elemental analysis values (as C,, tl,, O,) Also, from the infrared absorption spectrum of this crystal shown in Figure 3 and the 'H-NMR spectrum shown in Figure 4, this crystal is PT-0) ( It was identified that

IR (Nujol) van=3400cm-'(broad)')l-
NMR (DMSO-d-, 270M) Iz) δ=6.8
7 (d, 2H, Ha) = 7.05 <d, I
H, Hb) = 7.20-7.80 (m, 13H
, aromatic)=9.37 (s, 2)! ,
DH) Example 3 A flask No. 11 equipped with a Dimroth condenser was placed in a nitrogen atmosphere, and 26.5 g (78 mmol) of PT-DH was heated to about 160° C. in a Sulfo 5 400 oil bath, and the reaction was continued for 6 hours under reflux. After allowing the reaction mixture to cool. The precipitate was isolated by suction filtration. After washing with ethanol, it was dried under reduced pressure at 80°C for about 2 hours. White crystal 13. 26g (31
mmol) was obtained.

This white crystal had a melting point of 316° C. The single element analysis values were as follows.

Elemental analysis values (as C., H., (l)) Also, from the infrared absorption spectrum of this crystal shown in Figure 5, it was identified that this crystal was PT-OAc.

IR (Nujol) ν. = 1760cm − ' Example 4 Spiral stirrer. Internal volume 100 mI with thermometer, gas inlet and distillation port! in a hard glass three-loaf flask.

4,4”-diacetoxy-3-phenyl-ρ-ditterenyl (PT-OAc) 8.4496g
(0.02 mol) Terephthalic acid 3.
3226 g (0.02 mol) paraacetoxybenzoic acid 3.6032 g (0.02 n+ol) was charged, the flask was placed in a silicone oil bath, and the temperature of the bath was raised while blowing nitrogen gas through the gas inlet.

When the temperature of the bath rises and the temperature of the contents reaches approximately 240°C, the polycondensation reaction begins.

The acetic acid produced began to distill out from the distillation port. Approximately 3 from now
The temperature of the contents was raised to 300°C over time. 30
After an hour had passed since the temperature reached 0°C, the distillation port was connected to a vacuum vessel, and the pressure inside the flask was gradually reduced to less than 1 mF. After the temperature drops below 1mF. After reacting for another hour, the liquid in flask 6 became extremely viscous. The flask was removed from the bath and allowed to cool. After the product cooled and solidified, the flask was broken and taken out. The resulting product was a light brown, opaque aromatic polyester. When observed with a polarizing microscope, it was found to have melting anisotropy at temperatures of 172°C or higher. or. The heat distortion temperature is 162℃ (JI
Compliant with 7207. 1B, 5kgf/cd).

Melt viscosity at 240°C is 5. 2 X lo'po
It was ise. The melt viscosity was measured using a flow tester under a load of 100 k[f].

Example 5.6 As shown in Table 1. Other than changing the composition of each component of the aromatic polyester. An aromatic polyester was synthesized in the same manner as in Example 1. The obtained aromatic polyester was measured for its liquid crystal transition temperature, heat distortion temperature B, and melt viscosity in the same manner as in Example 1. Table 1 shows the results.
are summarized in

(Blank below) (Effects of the invention) The compound of the present invention is used as an organic polymer compound such as polyester, polyurethane, polyether, polycarbonate, liquid crystal resin, etc., and has high heat resistance,
Providing resin with excellent flame retardancy, solvent resistance, weather resistance, and other chemical and physical properties.

It also exhibits excellent chemical and physical improvement effects when added to other resins.

Further, according to the polyester of the present invention, a polyester having excellent moldability and heat resistance can be provided.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of the compound obtained in Example 1, and Figure 2 shows its 'H-NMR spectrum. 3 shows an infrared absorption spectrum of the compound obtained in Example 2, FIG. 4 shows its 'H-NMR spectrum, and FIG. 5 shows an infrared absorption spectrum of the compound obtained in Example 3. that's all

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, R_1 and R_2 are CH_3-, ▲, respectively]
There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R' represents an alkylene group, and n represents an integer of 0 or 1 or more). , R_1 and R_2 may be the same or different] 4,4''-dihydroxy-3-phenyl-p
-terphenyl derivatives. 2. Formula (A) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼・・・(A) Polyester having the structural unit shown.