JP2520954B2 - 4,4 "-dihydroxy-3,3" -diphenyl-p-terphenyl derivative and polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is 4,4 ″ -dihydroxy-3,3 ″ -diphenyl-
The present invention relates to a p-terphenyl derivative and a polyester produced by using the compound as a constituent component.

The novel compound provided by the present invention has excellent modifying ability as a monomer for a high-performance organic polymer compound and as an additive for a conventional polymer compound.
It is extremely noticeable.

Further, polyester, which is an example of a polymer compound using the compound as a constituent, is specifically useful as a resin for paints, molded articles or fibers having a high degree of heat resistance and moldability.

(Prior Art) Dibasic acids such as terephthalic acid, isophthalic acid or carbonic acid and bisphenol A (2,2-propylidene-4,4'-biphenol), bisphenol S (4.4'-dihydroxydiphenyl sulfone) or 4.4'-dihydroxy. Polycondensates with aromatic dihydroxy compounds such as biphenyl are called polyarylate or wholly aromatic polyester,
It has already been put to practical use. On the other hand, aromatic polyesters, which are homopolycondensates of aromatic hydroxycarboxylic acids, especially parahydroxybenzoic acid, have already been known to have extremely high heat resistance and mechanical strength, but practical molding Due to its difficulty, it was never widely used.

However, recently, when a component that lowers the melting point of the polycondensate is copolymerized with para-hydroxybenzoic acid in an appropriate ratio, it exhibits anisotropy (thermotropic liquid crystallinity) during melting, and the molding process is performed. It has been found that a polyester having a high elastic modulus and mechanical strength can be obtained because the polymer chains are oriented in the flow direction as well as being easy.
The practical application of these melt-anisotropic polyesters has only just begun, and future technological development is expected.

(Problems to be Solved by the Invention) An object of the present invention is to obtain a polymer compound having excellent heat resistance and mechanical strength, melt anisotropy, and good moldability. 4 "-dihydroxy-3,3"
-To provide a diphenyl-p-terphenyl derivative and a polyester.

(Means for Solving the Problems) 4,4 ″ -dihydroxy-3,3 ″ -diphenyl-of the present invention
The p-terphenyl derivative has the general formula (I) The above-mentioned object is achieved.

The polyester of the present invention has the formula (A) And has the structural unit shown in FIG.

The compound represented by the general formula (I) of the present invention is specifically 4,4 ″ -dihydroxy-3,3 ″ -diphenyl-p-terphenyl, 4,4 ″ -dimethoxy-3,3 ″- Diphenyl-p
-Terphenyl, 4,4 "-diacetoxy-3,3" -diphenyl-p-terphenyl, di (hydroxyalkyl)
4,4 ″ -dihydroxy-3,3 ″ -diphenyl-p-terphenyl and the like.

4,4 ″ -dimethoxy-3,3 ″ -diphenyl-p-terphenyl (hereinafter abbreviated as DPT-OMe) represented by the formula (II) is And Ni catalyst (eg NiCl ₂ (dppp)) (dppp: bis (dip
It can be obtained by carrying out a Grignard coupling reaction in the coexistence of henylphosphino) propane).

DPT-OMe is reacted with BBr ₃ or HBr to give 4,4 ″ -dihydroxy-3,3 ″ -diphenyl-p-terphenyl (hereinafter D
PT-OH) is obtained (the following formula (III)).

The above DPT-OH is reacted with acetic anhydride to obtain 4,4 ″ -diacetoxy-3,3 ″ -diphenyl-p-terphenyl (hereinafter referred to as DPT
-OAc) is obtained (the following formula (IV)).

The DPT-OH is reacted with a hydroxyalkylating agent in the presence of a suitable catalyst or acid scavenger to obtain a di (hydroxyalkyl) -ized DPT-OH. Here, the alkyl group is preferably a lower alkyl group, more preferably an ethyl group or a propyl group, and may be linear or branched.

For example, DPT-OH 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 di (hydroxyethyl) -DPT-OH (hereinafter referred to as DPT-OH). -Abbreviated as EO) is obtained.

Similarly, DPT-OH is reacted with a hydroxypropylating agent such as propylene carbonate, propylene oxide, or 2-hy-propanol in the presence of a suitable catalyst or acid scavenger to give di (hydroxypropylated) -DPT-OH.
-OH (hereinafter abbreviated as DPT-PO) is obtained.

 The reaction formulas are shown below.

(In the reaction formulas (3) and (6), X represents a halogen atom and A represents an acid scavenger.) In the reaction of the formula (1), DPT-OH and 2 mol or more of ethylene carbonate are usually catalyzed in an inert solvent. It is carried out by heating in the coexistence of. The reaction of formula (2) is usually carried out by heating DPT-OH 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 the formula (3) is usually carried out by mixing DPT-OH and 2 mol or more of 2-haloethanol in an inert solvent in an enclosed reactor with an acid scavenger (organic or inorganic base).
This is performed by heating in the presence of Also, (4)
The reaction of the formula is usually carried out by heating DPT-OH and 2 mol or more of propylene carbonate in the presence of a catalyst (organic or inorganic base) in an inert solvent. (5)
The reaction of the formula is usually carried out by heating DPT-OH and 2 mol or more 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 DPT-OH 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). Done.

In the above six reactions, it is difficult to control the number of moles of ethylene oxide added in the reaction of the formula (2), the reaction rates of the reactions of the formulas (3) and (6) are slow, and side reactions (especially X-CH
₂ CH ₂ OH, Ring closure or self-polymerization reaction) is large. On the other hand, the reactions of the formulas (1), (4) and (5) have a fast reaction rate and can easily control the number of added moles. In particular, DPT-EO where m = n = 1, that is, the following formula ( Ia), and DPT-PO, that is, the following formula (Ib) It is suitable for producing a compound represented by.

The polyester of the present invention contains the compound (I) as a constituent component and has a structural unit represented by the formula (A). That is, the polyester of the present invention is a pentacyclic aromatic compound represented by the above formula (I) in a polycondensate containing a dihydroxy compound and a dicarboxylic acid, or a polycondensate containing these two and a hydroxycarboxylic acid as main components. A group dihydroxy compound is used as another component of the above dihydroxy compound. Other constituent components of the dihydroxy compound include aromatic dihydroxy compounds and aliphatic dihydroxy compounds other than the compound (I), and examples of the dicarboxylic acid include aromatic dicarboxylic acid and aliphatic dicarboxylic acid, and As the hydroxycarboxylic acid,
Examples thereof include aromatic hydroxycarboxylic acid and aliphatic hydroxycarboxylic acid.

Examples of aromatic dihydroxy compounds other than the above general formula (I) include resorcin, 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 (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene,
Alternatively, 2,6-dihydroxynaphthalene and the like can be mentioned.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, metal salts of 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-dicarboxynaphthalene or
2,6-dicarboxynaphthalene and the like can be mentioned.

Examples of the aromatic hydroxycarboxylic acid include meta-hydroxybenzoic acid, para-hydroxybenzoic acid, 3-chloro-
4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 4-hydroxy- 4'-carboxybiphenyl, 2-hydroxy-6-carboxynaphthalene, etc. are mentioned.

Examples of the aliphatic dihydroxy compounds, ethylene glycol, pro ping Le call, the general formula HO- (CH _{2) n} -OH alkylene glycol (n is an integer of 2 to 10) represented by the butylene glycol, propylene -1, 2-diol, butane-1,2-diol, butane-1,3-diol, neopentyl glycol polyethylene glycol,
Examples include polypropylene glycol and the like.

Examples of the aliphatic dicarboxylic acid include general formulas such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, HOOC.
Dicarboxylic acid represented by — (CH ₂ ) _n —COOH (n is an integer of 0 to 10), alkyl group such as methyl group, ethyl group, n-propyl group, iso-propyl group, methoxy group, alkoxy such as ethoxy group, etc. Group, an aliphatic dicarboxylic acid substituted with a halogen group such as a bromine group, and the like.

Of these constituents, polycondensation of a large amount of aromatic dicarboxylic acid or aromatic hydroxycarboxylic acid results in crystallinity,
A polyester having excellent heat resistance and high strength can be obtained. When a large amount of an aliphatic dicarboxylic acid or an aliphatic hydroxycarboxylic acid is polycondensed, the heat resistance is slightly lowered but a flexible polyester can be obtained.

Among the constituents of the polycondensate described above, the dihydroxy compound and the dicarboxylic acid form a high molecular weight polycondensate at approximately the same molar ratio and the hydroxycarboxylic acid at an arbitrary molar ratio. It is difficult to heat each component as it is for polycondensation, and it is usually preferable to acetylate the hydroxy group of the component before the polycondensation reaction. The polycondensation reaction can be performed at a temperature of 200 ° C to 350 ° C. The acetic acid produced by the polycondensation reaction is preferably first removed from the reaction system at atmospheric pressure and finally at reduced pressure. When the reaction system is particularly crystalline and heterogeneous, acetic acid is taken out under pressure and finally depressurized to obtain a more uniform system, which is a good result. The molecular weight of the polycondensate can be adjusted by adjusting the molar ratio of the constituent dihydroxy compound to the dicarboxylic acid, which gives good results when the molecular weight is relatively low. In the range where the molecular weight is high, a method of controlling the size of the molecular weight by carrying out the reaction while using the melt viscosity of the polycondensate as a guide is adopted.

When the above-mentioned highly crystalline compound (I) is incorporated into the constituent components of the polyester of the present invention, the polycondensate often exhibits melt anisotropy. Melt anisotropy can be confirmed by a polarization technique using an ordinary polarization microscope. More specifically, a test piece prepared to have a thickness of 1 mm or less is placed on a heating stage and heated at a heating rate of 5 ° C./min in a nitrogen atmosphere so that the polarizers are orthogonal to each other. It can be easily confirmed by observing with a polarizing microscope of 40 times or 100 times.

In order to improve heat resistance and rigidity, the polyester of the present invention contains glass fiber,
Reinforcing agents such as carbon fiber, whiskers, wollastonite, etc. may be added. Also, as a crystallization accelerator, talc,
Inorganic substances such as barium sulfate, alumina and silicon oxide, higher fatty acid salts such as sodium stearate, barium stearate and sodium palmitate, organic compounds such as benzyl alcohol and benzophenone, or highly crystallized polyethylene terephthalate, polytrans-cyclohexanediene A known nucleating agent such as methanol terephthalate may be added. Further, a stabilizer such as phosphite, a heat-resistant agent, an antistatic agent, and a release agent may be added as desired.

The polyester of the present invention is most suitable as a molding material for various molded products. It can also be used for films, fibers, adhesives and paints. Further, the polyester of the present invention is used by being mixed with other thermoplastic resin such as polyolefin, modified polyolefin, polystyrene, polyamide, polycarbonate, polysulfone, polyester or the like or by being mixed with a rubber component to modify its properties. You may.

(Example) Next, the present invention will be described based on examples.

NiCl ₂ (dppp) was obtained by Kumada et al., Bulletin of the
Chemical Society of JAPAN 49 (7), 1958-1969
(1976) was referred to.

Example 1 Magnesium for Grignard 4.38 g (180 mm) in a 300 ml three-necked flask equipped with an isobaric funnel and a Dimroth condenser.
ol), and heated with a dryer under vacuum to activate. The system was made a nitrogen atmosphere, and 42.13 g (160 mmol) of the above compound (a) in 20 ml of tetrahydrofuran (T
HF) solution was dropped about 1 ml. The reaction was initiated by stirring with a magnetic stirrer tip. After the total amount of the THF solution was added dropwise over about 1 hour, the reaction was continued for 3 hours with stirring.

Another 500 ml equipped with constant pressure funnel and Dimroth type cooler
The three-necked flask was placed in a nitrogen atmosphere and the above compound (b) 1
6.99 g (72 mmol) and 80 ml of THF were added. The compound (b) was completely dissolved into a colorless transparent solution. NiCl ₂ (d
ppp) 0.11 g was added. The system became a red transparent solution, and the Grignard reagent was quantitatively transferred to an isobaric funnel. Although this Grignard reagent was added dropwise over about 30 minutes, the state of the system changed with the addition of red transparent solution → yellow transparent solution → yellow opaque solution (precipitates were present) → brown opaque solution (same as left). After dropping all the amount, the mixture was heated in a water bath at 80 ° C and reacted under reflux for 15 hours.

After cooling the reaction mixture, suction filtration, washing with THF, washing with water, and drying under reduced pressure at 100 ° C for about 2 hours, white crystals 1
8.4 g (41 mmol) was obtained. The melting point of this white crystal is 206 ℃,
The elemental analysis values were as follows.

Elemental analysis C (%) H (%) Measured value 85.92 5.10 Theoretical value 86.85 5.92 (as C ₃₂ H ₂₆ O ₂ ) Also, the infrared absorption spectrum by Nujol method of this crystal shown in Fig. 1 and Fig. 2 are shown. From the ¹ H-NMR spectrum shown, this was identified as DPT-OMe. ¹ H-NMR (CDCl ₃ , 270 MHz) δ = 3.91 (s, 6H, OCH ₃ ) = 7.12 (d, 2H, Ha) = 7.20 ~ 7.90 (m, 18H, aromatic) Example 2 4,4 ″ -diacetoxy-3,3 ″ -diphenyl-p-terphenyl was placed in a 100 ml hard glass three-necked flask equipped with a spiral stirrer, a thermometer, a gas injection port and a distillation port. (DPT-OAc) 9.9716g (0.02mol) Terephthalic acid 3.3226g (0.02mol) Paraacetoxybenzoic acid 3.6032g (0.02mol) were charged, and the flask was put in a silicone oil bath and the nitrogen gas was blown from the gas inlet into the bath. Raised the temperature. When the temperature of the bath increased and the temperature of the contents reached about 240 ° C, the polycondensation reaction started and the acetic acid produced began to distill from the distillation port. The temperature of the contents was raised to 300 ° C in about 3 hours. One hour after the temperature reached 300 ° C., the distillation port was connected to a vacuum device, and the pressure inside the flask was gradually reduced to 1 Torr or less. When the reaction was continued for 1 hour after the temperature became 1 Torr or less, the inside of the flask became an extremely viscous liquid, so the flask was pulled up from the bath and cooled. After the product cooled and solidified, the flask was broken and taken out. The resulting product was a pale brown, opaque aromatic polyester. Observation with a polarizing microscope 16
It had melt anisotropy at 0 ° C or higher. The heat distortion temperature is 1
The temperature was 51 ° C (according to JIS K7207, 18.5 kg f / cm ² ), and the melt viscosity at 240 ° C was 3.5 × 10 ⁴ poise. The melt viscosity was measured with a flow tester under a load of 100 kgf.

Examples 3 and 4 As shown in Table 1, an aromatic polyester was synthesized in the same manner as in Example 1 except that the composition of each constituent component of the aromatic polyester was changed. With respect to the obtained aromatic polyester, its liquid crystal transition temperature, heat distortion temperature and melt viscosity were measured in the same manner as in Example 1. The results are summarized in Table 1.

(Effects of the Invention) The compound of the present invention is used as a monomer for organic polymer compounds such as polyester, polyurethane, polyether, polycarbonate and liquid crystalline resin, and has high heat resistance, flame retardancy, solvent resistance and weather resistance. It also provides resins with excellent chemical and physical properties, and when added to other resins, exerts excellent chemical and physical improvement effects.

Further, according to the polyester of the present invention, it is possible to provide a polyester having excellent moldability and heat resistance.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an infrared absorption spectrum of the compound obtained in Example 1, and FIG. 2 is its ¹ H-NMR spectrum.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 63/193 NNP C08G 63/193 NNP NPS NPS (72) Inventor Toranosuke Saito Yamatedai, Ibaraki, Osaka 5-17-21 (72) Inventor Hiroki Kadomachi 7-20 Otemachi, Ibaraki-shi, Osaka (72) Inventor Daishiro Kishimoto 2-11-20 Mishimaoka, Ibaraki-shi, Osaka (56) References Special Kai 63-105026 (JP, A) JP 61-261319 (JP, A)

Claims (2)

(57) [Claims] 1. A general formula (I) Represented by 4,4 "-dihydroxy-3,3" -diphenyl-
p-terphenyl derivative. 2. The formula (A) A polyester having a structural unit represented by.