JP2556899B2 - 4-hydroxy-p-quaterphenyl derivative and aliphatic polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a p-quaterphenyl derivative for providing an aliphatic polyester with improved heat resistance, and a p-quaterphenyl derivative thereof.
-The present invention relates to an aliphatic polyester having a quaterphenyl derivative as a constituent component, and according to the present invention, an aliphatic polyester suitable for use as a material for various molded articles can be provided.

(Prior Art) Generally, in order for a material to exhibit rubber elasticity, it is necessary that an amorphous polymer whose molecular chain can easily rotate is partially crosslinked. For example, in elastic rubber, sulfur molecules form a network structure by bridging the molecular chains by chemical bonds. In addition to rubber, materials in which various polymer compounds and a crosslinking agent are combined have been proposed. Cross-linking materials cannot be molded by injection molding or extrusion because they require a cross-linking step to mold these materials and do not exhibit thermoplasticity after being chemically cross-linked.

In recent years, a thermoplastic elastomer that exhibits rubber elasticity at room temperature and is plasticized at high temperature has been developed, and various types of thermoplastic elastomers are manufactured and marketed. This thermoplastic elastomer does not require a long-time cross-linking step unlike the conventional rubber, and can be molded by injection molding or extrusion molding. A characteristic of the molecular structure of thermoplastic elastomers is a system that applies cross-linking that does not rely on strong chemical bonds, that is, some type of polymer constraint that is effective only at around room temperature, and is a polymer assembly composed of soft and hard segments. That is the typical structure of a thermoplastic elastomer. The soft segment and the hard segment have different chemical structures from each other, and in the hybrid composition of the two, the homogeneous portions are aggregated, and the heterogeneous portions are phase-separated from each other to form a microscopic imbalanced structure.
At that time, the agglomerated portion of the hard segment exhibits a binding action between the molecules.

Examples of the thermoplastic elastomer include styrene type, olefin type, urethane type, ester type and amide type. In the styrene series, polystyrene forms a frozen phase as a hard segment and binds between molecular chains, resulting in rubber elasticity. In the olefin system, the polypropylene crystal phase acts as a hard segment. In the urethane type, the polyurethane segment causes physical crosslinks between molecular chains by hydrogen bonds. Further, the ester-based polybutylene terephthalate chain acts as a hard segment, and the amide-based nylon chain such as 6-nylon or 6,6-nylon acts as a hard segment.

(Problems to be Solved by the Invention) As described above, since the thermoplastic elastomer exhibits rubber elasticity at room temperature and can be molded, it is widely used for automobile parts and various industrial products. However, conventional thermoplastic elastomers have lower heat resistance due to the restriction of the softening and melting point of the part because the crosslinking is performed by physical restraint than that of the cross-linking type rubber, and the creep special property is also inferior. Was becoming. For example, the melting point of Perprene S-9001 manufactured by Toyobo Co., Ltd., which is known as the ester type with the highest heat resistance among thermoplastic elastomers,
223 ℃, heat distortion temperature (low load) 146 ℃, even in the urethane system, its softening point is at most 140 ℃.

The present invention has been made in view of such circumstances, and is intended to provide a polymer compound having properties as a thermoplastic elastomer, excellent heat resistance and mechanical properties, and excellent in moldability. The purpose is to provide a 4-hydroxy-p-quaterphenyl derivative as its constituent component. Another object of the present invention is to provide an aliphatic polyester which has properties as a thermoplastic elastomer, is excellent in heat resistance and mechanical properties, and is also excellent in molding processability.

(Means for Solving the Problems) The 4-hydroxy-p-quaterphenyl derivative of the present invention has the general formula [II] (In the formula, R ² represents an alkylene group, and l is 0 or 1.), whereby the above object is achieved.

The aliphatic polyester of the present invention comprises a monohydroxy compound represented by the general formula [II] below, an aliphatic dicarboxylic acid represented by the general formula [III] below, and an aliphatic diol. , It is the main constituent, and the above purpose is achieved by that.

(In the formula, R ² represents an alkylene group, and l is 0 or 1.) HOOC- (CH ₂ ) m-COOH [III] (In the formula, m is an integer of 0 to 10) The above 4-hydroxy- The p-quaterphenyl derivative is a group of compounds represented by the above formula [I], and specifically, 4-hydroxy-p-quaterphenyl, 4- (2-
Hydroxyethoxy) -p-quaterphenyl, 4-
Typical examples include monohydroxy compounds such as (3-hydroxypropoxy) -p-quaterphenyl, monoalkoxy compounds such as 4-methoxy-p-quaterphenyl and 4-ethoxy-p-quaterphenyl, and 4-acetoxy-p-quaterphenyl. Examples thereof include monoacyloxy compounds.

The synthetic method of 4-hydroxy-p-quaterphenyl derivative is shown below.

(1) Synthesis of 4-hydroxy-p-quaterphenyl (in the formula [I], R ¹ = H) (In the formula [I], R ¹ = H) First, 4-bromo-4′-hydroxybiphenyl is reacted with a methylating agent such as dimethylsulfate to synthesize a corresponding methoxy derivative. This methoxy form is treated with anhydrous THF
In (tetrahydrofuran), it reacts with 1.1 equivalents of metallic magnesium to lead to the corresponding Grignard reagent, which is present in the presence of NiCl ₂ (dppp) (dppp represents 1,3-bis (diphenylphosphino) propane) catalyst Then, by performing a cross-coupling reaction with 4-bromobiphenyl,
-Methoxy-p-quaterphenyl can be obtained. This methoxy compound can be demethylated by the action of boron tribromide to obtain the corresponding monohydroxy compound.

(2) Synthesis of monoalkoxy compound Starting from 4-hydroxy-p-quaterphenyl obtained by the reaction formula (1) as a starting material, K in an aprotic polar solvent such as DMSO (dimethyl sulfoxide) or DMF (dimethylformamide). It can be easily obtained by reacting with an alkyl halide in the presence of an inorganic base such as ₂ CO ₃ , Na ₂ CO ₃ (reaction formula (2) -1). K ₂ CO ₃ , Na ₂ C
It is also possible to generate a phenolate anion in advance by using NaH instead of an inorganic base such as O _{3 and then} react with an alkyl halide (reaction formula (2) -2). Each reaction formula is shown below.

(3) Synthesis of monoacyloxy compound Obtained easily by reacting 4-hydroxy-p-quaterphenyl obtained by the reaction formula (1) as a starting material with an acid halide in a basic solvent such as pyridine or picoline. be able to.

It can also be obtained by a reaction with an acid anhydride, for example, 4-acetoxy-p-quaterphenyl is produced by a reaction with acetic anhydride.

(4) Synthesis of monohydroxy compound By using 4-hydroxy-p-quaterphenyl obtained by the reaction formula (1) as a starting material and reacting it with a hydroxyalkylating agent in the presence of a suitable catalyst or acid scavenger 4- (Hydroxyalkyl) -p-quaterphenyl can be obtained.

For example, there are the following methods for hydroxyethylation.

When the hydroxyethylation reactions ~ are compared, each has the following characteristics.

It is carried out by heating 4-hydroxy-p-quaterphenyl and an equimolar amount or more of 2-haloethanol in the presence of an acid scavenger (organic or inorganic base) in an inert solvent. Since this reaction is accompanied by side reactions such as ring closing or self-polymerization of X-CH ₂ CH ₂ -OH, the following reaction using halogenated acetaldehyde is more preferable.

It is a reaction of 4-hydroxy-p-quaterphenyl with ethylene oxide in the presence of a base in an inert solvent. Although the number of added moles can be controlled by changing the amount of ethylene oxide, it is difficult to obtain only the target hydroxyethoxy compound because the number of added moles has a distribution.

It is a reaction of 4-hydroxy-p-quaterphenyl and ethylene carbonate in the presence of a base in an inert solvent. Since the reaction rate is high and the number of added moles is easy to control, it is the most suitable method for this purpose.

As described above, the above-mentioned hydroxyethylation reactions have advantages and disadvantages, respectively, but 4- (2-hydroxyethoxy) -p-quaterphenyl can be obtained by any method.

Similarly, by reacting with a hydroxypropylating agent, the corresponding 4- (2-hydroxypropoxy)
-P-quaterphenyl can be obtained.

In the reaction of 4-hydroxy-p-quaterphenyl with ethylene oxide, it is possible to lengthen the chain composed of ethylene glycol units by making the amount of ethylene oxide introduced excessive. (Under formula) The 4-hydroxy-p-quaterphenyl derivative [I] obtained by the present invention is a low molecular compound having rigidity, and the melting point of these compounds is around 300 ° C. or higher, reflecting its characteristic structure. Extremely high at.
Therefore, when these are incorporated into the polymer chain, the heat resistance is remarkably improved.

When the 4-hydroxy-p-quarterphenyl skeleton obtained by the present invention is introduced at the terminal of the aliphatic polyester obtained by copolymerization with an aliphatic dicarboxylic acid and a diol, a thermoplastic elastomer having excellent heat resistance can be obtained. That is, since the main skeleton brings about very strong physical crosslinks with high heat resistance, it is possible to synthesize a high heat resistant elastomer which is difficult to obtain by the conventional method.

The use of aromatic dicarboxylic acids and diols as copolymerization components makes it possible to synthesize polymers with high heat resistance and high strength. For example, an aromatic rigid liquid crystal polymer is one application example.

Further, the 4-hydroxy-p-quaterphenyl derivative [I] obtained by the present invention can remarkably improve its fluidity by adding a small amount to engineering plastics such as PES, PEEK, and polyarylate. , It can be used as an easy-molding agent for engineering plastics.

 Next, the aliphatic polyester of the present invention will be described.

The monohydroxy compound represented by the above formula [II] is a rigid low-molecular compound having a paraphenylene skeleton, and the melting point of these compounds is extremely high at 250 ° C. or higher, reflecting the characteristic molecular structure. Furthermore, the paraphenylene skeleton is known to be effective as a mesogen for low-molecular liquid crystal compounds, and it has a strong cohesive force not only in the solid state but also in the high temperature state (molten state). It means that. Therefore, when the above-mentioned monohydroxy compound [II] is incorporated at the polymer end, it brings about very strong physical crosslinks with high heat resistance,
It is presumed that a thermoplastic elastomer having excellent heat resistance is produced.

In the monohydroxy compound [II], the alkylene group R ² is preferably an ethylene group or a propylene group, l is 0 or 1, and 4-hydroxy-p-quaterphenyl, 4- (2
-Hydroxyethoxy) -p-quaterphenyl is preferably used. The method for synthesizing 4-hydroxy-p-quaterphenyl and 4- (2-hydroxyethoxy) -p-quaterphenyl is as described above.

The above monohydroxy compounds [II] may be used alone or in combination.

Polyester is obtained by polycondensing equimolar amounts of dicarboxylic acid and diol. In the aliphatic polyester of the present invention, in addition to the above monohydroxy compound [II], the kind of compound as a constituent component and the compounding ratio of the compound By changing, the properties of the aliphatic polyester and the physical properties of the molded product obtained from the aliphatic polyester can be freely changed.

An aliphatic polyester suitable as a thermoplastic elastomer contains a monohydroxy compound [II], the above-mentioned aliphatic dicarboxylic acid [III], and an aliphatic diol as main constituent components.

Examples of the aliphatic dicarboxylic acids of the general formula _{HOOC- (CH 2) m-COOH} (m is an integer of 0) is a dicarboxylic acid represented by, the use of dicarboxylic acids in which the carbon number exceeds 10, polyester The physical properties such as rubber elasticity of the molded product obtained from are deteriorated. As the dicarboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid are preferably used.

Examples of the aliphatic diol include glycol and / or polyalkylene oxide.

Examples of the glycol include ethylene glycol, propylene glycol, trimethylene glycol,
1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol,
1,10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, etc. These may be used alone or in combination of two or more.

Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide and the like, and these may be used alone or in combination of two or more kinds.

The number average molecular weight of the polyalkylene oxide is preferably 100 to 20,000, because the ability to impart flexibility to the resulting polyester decreases as the number average molecular weight decreases, and the physical properties such as thermal stability of the resulting polyester decrease when the number average molecular weight becomes too large. ，
It is more preferably 500 to 5,000.

The aliphatic polyester of the present invention may further contain a dihydroxy compound represented by the above formula [IV] as a constituent component. These two types of rigid monomers [II]
In the aliphatic polyester in which [IV] and (IV) are introduced into the polymer chain and at the polymer terminal, more physical crosslinks are formed, and the properties as a heat-resistant thermoplastic elastomer are remarkably improved.

If you expect the outstanding effects described above, [IV]
At least 3 benzene rings are required. Furthermore, although the number of benzene rings increases and the physical crosslinks become stronger and the melting point rises significantly, the number of benzene rings in [IV] is 3 considering the ease of handling during polymerization and the difficulty of synthesis.
Or 4, ie paraterphenyl or paraquaterphenyl skeletons are used.

The dihydroxy compound represented by the above formula [IV] is a low molecular weight compound exhibiting liquid crystallinity, the alkylene groups R ³ and R ⁴ are preferably ethylene groups or propylene groups, and q and r are 0 or 1, 4,4 "-dihydroxy-p-terphenyl represented by the formula [A] and 4,4-" represented by the following formula [B]
Dihydroxy-p-quaterphenyl and the following formula [C]
4,4-di (2-hydroxyethoxy) -p represented by
-Quarterphenyl and the like are preferably used.

The transition temperature of 4,4 "-dihydroxy-p-terphenyl [A] from the crystalline state to the liquid crystal state is about 260 ° C, 4,4-
Dihydroxy-p-quaterphenyl [B] is
336 ° C, that of 4,4-di (2-hydroxyethoxy) -p-quaterphenyl [C] is 403 ° C. Further, the liquid crystal state means a state in which the compound is in a molten state and the molecules maintain the alignment state.

The above dihydroxy compounds [IV] may be used alone or in combination. 4,4-dihydroxy-p-quaterphenyl [B] is, for example,
The method described in Journal of Chemical Society, 1379-85 (1940), or 4-hydroxy-4'-bromobiphenyl was reacted by heating and pressurizing with a palladium catalyst in the presence of alkali to synthesize a dimer, and then acid precipitation Can be synthesized by the method described above. 4,4-Di (2-hydroxyethoxy) -p-quaterphenyl [C] can be obtained by adding ethylene oxide to 4,4-dihydroxy-p-quaterphenyl [B]. Also, 4,4-dihydroxy-p-quaterphenyl [B] and 4,4
-Di (2-hydroxyethoxy) -p-quaterphenyl [C] is acetylated when it is polycondensed with dicarboxylic acid to give polyester, and 4,4-diacetoxy-p-quaterphenyl and 4,4 It may also be used as -di (2-acetoxyethoxy) -p-quaterphenyl.

Liquid crystal molecules generally have high crystallinity, and as described above,
4,4 "-dihydroxy-p-terphenyl [A], 4,4
-Dihydroxy-p-quaterphenyl [B] and 4,
Since 4-di (2-hydroxyethoxy) -p-quarterphenyl [C] has a high transition point from its crystal to a liquid crystal state, when these dihydroxy compounds [IV] are incorporated in the polymer chain, Polymers show unique properties.

That is, the dihydroxy compound [IV] exhibits crystallinity,
Moreover, because of its high transition point, dihydroxy compounds [I
It forms a strong and heat-resistant physical crosslink even when the compounding amount of V] is small. As a result, it is presumed that a thermoplastic elastomer having high heat resistance can be obtained without impairing the flexibility derived from the soft segment.

Further, a three-component aliphatic polyester comprising the above monohydroxy compound [II], an aliphatic diol and an aliphatic dicarboxylic acid [III], or a monohydroxy compound [II], a dihydroxy compound [IV], an aliphatic diol and a fat A four-component aliphatic polyester composed of a group dicarboxylic acid [III] may contain other reaction components, for example, a poly-silicone having two hydroxyl groups, a lactone, or an aromatic hydroxycarboxylic acid as a constituent component. .

The above-mentioned polysilicone has two hydroxyl groups, and dimethylpolysiloxane, diethylpolysiloxane, diphenylpolysiloxane having two hydroxyl groups at the molecular ends are preferable. The number average molecular weight of polysilicone is
When it becomes smaller, the ability to impart flexibility to the polyester produced decreases, and when it becomes larger, it becomes difficult to produce the polyester, so 100 to 20,000 is preferable, and 500 to 5,000 is more preferable.

The lactone is a compound that opens a ring and reacts with an acid and a hydroxyl group to add an aliphatic chain, which imparts flexibility to the polyester, and which has 4 or more carbon atoms in the ring. It is preferably a 5-membered to 8-membered ring, and examples thereof include ε-caprolactone, δ-valerolactone, γ-butyrolactone and the like.

The aromatic hydroxycarboxylic acid imparts rigidity and liquid crystallinity to the polyester, and includes salicylic acid, metahydroxybenzoic acid, parahydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxyl. Benzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3-
Methyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-
Examples thereof include hydroxy-4′-carboxybiphenyl, and preferred are parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and 4-hydroxy-4′-carboxybiphenyl.

Further, the above aliphatic polyester may contain an aromatic diol other than the dihydroxy compound [IV] or an aromatic dicarboxylic acid as a constituent component in order to improve the mechanical properties of the polyester.

Examples of the aromatic diol include hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, 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, Examples thereof include 1,4-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.

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, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane, 1,4-dicarboxynaphthalene, Alternatively, 2,6-dicarboxynaphthalene and the like can be mentioned.

The monohydroxy compound [II] used in the present invention is introduced at the polymer terminal, and its content is preferably 0.1 to 20 mol% in the hydroxy component used. Here, the hydroxy component includes an aliphatic diol, a monohydroxy compound, and optionally a dihydroxy compound. The molar ratio of the monohydroxy compound [II] is
If it is less than 0.1 mol%, physical cross-linking by the hard segment will be insufficient and sufficient physical properties and heat resistance will not be reached. On the other hand, if it exceeds 20 mol%, the molecular weight does not rise sufficiently, and only those with inferior physical properties are obtained. When the monohydroxy compound [II], the aliphatic diol, and the dihydroxy compound [IV] are used as the hydroxy components, the monohydroxy compound [II] and the dihydroxy compound [IV] among the hydroxy components are used. ], The molar ratio of the hydroxy compound is preferably 0.1 to 30 mol% in the total hydroxy component.
The molar ratio of [II] + [IV] in the hydroxy component is 0.
If it is less than 1 mol%, physical cross-linking by the hard segment will be insufficient, and sufficient physical properties and heat resistance will be difficult to develop. Further, when the molar ratio of the hydroxy compound [II] + [IV] in the hydroxy component exceeds 30 mol%, the elastic modulus of the aliphatic polyester tends to be high and the elastomer tends to be unsuitable. However, this has high heat resistance and can be suitably used as a thermoplastic resin having excellent mechanical properties.

As the method for polymerizing the aliphatic polyester of the present invention, any method can be adopted. First, the case where the monohydroxy compound [II] is used alone without the dihydroxy compound [IV] is described. For example, after esterifying an aliphatic dicarboxylic acid [III], it is reacted with about 2 molar equivalents of an aliphatic diol at 100 ° C to 250 ° C, and a dealcoholization reaction produces an aliphatic diol adduct of the aliphatic dicarboxylic acid. Then, a method for producing an aliphatic polyester from this adduct and the above monohydroxy compound [II] at 200 ° C to 350 ° C with a dealiphatic diol, after esterifying the aliphatic dicarboxylic acid [III] as a constituent component , A method of reacting with a hydroxy component ([II] + aliphatic diol) and polymerizing by dealcoholization, a halogen compound of an aliphatic dicarboxylic acid [III] and a hydroxy component ([II] + aliphatic diol) such as pyridine. Method of reacting in a suitable solvent, reacting metal salt of hydroxy component ([II] + aliphatic diol) with halide of aliphatic dicarboxylic acid [III] Law, etc., can be obtained aliphatic polyester by reaction of dicarboxylic acids with alcohols of the prior art.

Further, it is possible to control the structure of the aliphatic polyester by changing the addition order of the monohydroxy compound [II] during the polymerization. For example, in the method of (1), since the reaction occurs only at the terminal, it is preferable to add the monohydroxy compound [II] after the reaction between the aliphatic dicarboxylic acid [III] and the aliphatic diol has sufficiently proceeded.

On the other hand, in the case of 1, since the reaction also takes place in the polymer chain, there is no particular limitation on the addition timing of the monohydroxy compound [II], and a polymer having a high degree of polymerization can be obtained. In addition, a pre-synthesized aliphatic polyester is kneaded with a monohydroxy compound [II] or an acetylated product of a monohydroxy compound under reduced pressure heating, and the molecular chain is based on the monohydroxy compound [II] by a dealiphatic diol or transesterification reaction. It is also possible to introduce segments.

Next, the case where the monohydroxy compound [II] and the dihydroxy compound [IV] are used in combination will be described.

The polymerization method of the aliphatic polyester is the same as that described above except that both the monohydroxy compound [II] and the dihydroxy compound [IV] are used instead of the monohydroxy compound [II]. The same procedure as described above except that the dihydroxy compound [IV] is added to the component ([II] + aliphatic diol), the halide of the aliphatic dicarboxylic acid [III] and the hydroxy component (aliphatic diol + [IV]) are added. After reacting in a suitable solvent such as pyridine, and finally reacting with a monohydroxy compound [II], a metal alcoholate of a hydroxy component (aliphatic diol + [IV]) is converted into a halogen of an aliphatic dicarboxylic acid [III]. A dicarboxylic acid, which has been conventionally known, such as a method of reacting a metal alcoholate of a monohydroxy compound [II] after the reaction with a dicarboxylic acid. Aliphatic polyesters can be obtained by reaction with rucor.

Further, the previously synthesized aliphatic polyester is kneaded with the above-mentioned dihydroxy compound, monohydroxy compound or dihydroxy compound, and an acetylated product of the monohydroxy compound under reduced pressure heating, and the aliphatic hydroxy diol or the dihydroxy compound is added to the molecular chain by a transesterification reaction. It is also possible to introduce segments based on monohydroxy compounds.

In the polycondensation, a catalyst generally used in producing polyester may be used. The catalyst includes metals such as lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, and manganese. The organic metal compounds, organic acid salts, metal alkoxides, metal oxides and the like can be mentioned.

Particularly preferred catalysts are calcium acetate, diacyl stannous, tetraacyl stannic tin, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanate, germanium dioxide and trioxide. It is antimony. Two or more of these catalysts may be used in combination. In addition, in order to efficiently distill water, alcohol, glycol, etc., which are by-products of the polymerization, to obtain a high molecular weight polymer, the reaction system should be 1 mmHg at the latter stage of the polymerization.
It is preferable to reduce the pressure below. Reaction temperature is generally 150
~ 350 ° C.

The polyester of the present invention is as described above, and is an inorganic material such as glass fiber, carbon fiber, boron fiber, silicon carbide fiber, alumina fiber, amorphous fiber, silicon-titanium-carbon fiber, etc. within a range not impairing its practicality. Fiber, organic fiber such as aramid fiber, calcium carbonate, titanium oxide,
Inorganic fillers such as mica, talc, triphenylphosphite, trilaurylphosphite, trisnonylphenylphosphite, 2-tert-butyl-α- (3-tert-butyl-4-hydroxyphenyl) -p-cumenylbis ( Heat stabilizers such as p-nonylphenyl) phosphite, flame retardants such as hexabromocyclododecane, tris- (2,3-dichloropropyl) phosphate, pentabromophenylallyl ether, p-tert-butylphenyl salicylate, 2- Hydroxy-4-methoxybenzophenone, 2-
UV absorbers such as hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone, butylhydroxyanisole, butylhydroxytoluene, distearylthiodipropionate, dilaurylthiodipropionate, hinder Antioxidants such as dephenol antioxidants, N, N-bis (hydroxyethyl) alkylamines, alkylallyl sulfonates,
Antistatic agents such as alkylsulphanate, inorganic substances such as barium sulfate, alumina, silicon oxide, higher fatty acid salts such as sodium stearate, barium stearate and sodium palmitate; organic compounds such as benzyl alcohol and benzophenone; high crystallization A crystallization accelerator such as polyethylene terephthalate or polytrans-cyclohexanedimethanol terephthalate may be added. The aliphatic polyester of the present invention is used by mixing it with another thermoplastic resin such as polyolefin, modified polyolefin, polystyrene, polyamide, polycarbonate, polysulfone, polyester, or by mixing with a rubber component to modify its properties. You may.

The aliphatic polyester of the present invention is formed into a molded product by press molding, extrusion molding, injection molding, blow molding or the like. The physical properties of the molded article can be arbitrarily changed depending on its constituent components, its compounding ratio and the like. The molded products are flexible molded products such as automobile parts, hoses, belts, packings, paints,
It is suitable for use as an adhesive.

(Example) Below, this invention is demonstrated based on an Example.

<Synthesis of p-quaterphenyl derivative> (A) 4-Methoxy-p-quaterphenyl Phenyl magnesium 3.6g (150mmol) for a Grignard was placed in a well-dried 500ml three-necked flask, and under a nitrogen atmosphere, 4 was added. -Bromobiphenyl 33.6 g (132 mm
ol) in 150 ml anhydrous tetrahydrofuran (THF) solution was added dropwise little by little. After dropping 20 ml and adding 0.02 g of iodine at room temperature to start the reaction, the whole amount of the THF solution was dropped over about 1 hour. The reaction proceeded exothermically, and the reaction solution turned light brown. Then, the reaction was completed by stirring at room temperature for 2 hours to prepare a Grignard reagent.

In another one-necked 3-neck flask, 4-bromo-4'-methoxybiphenyl 31.5 g (120 mmol) and NiCl ₂ (dppp) 108 mg
(0.2 mmol) (dppp: 1,3-bis (diphenylphosphino) propane) was added, and 500 ml of anhydrous THF was added thereto.
This solution was kept at 0 ° C. under a nitrogen atmosphere, and the Grignard reagent prepared above was added dropwise thereto over about 1 hour. At the same time as the dropping, the orange color of the Ni catalyst disappeared and the solution changed to brown. After completion of the dropping, the mixture was stirred and refluxed for 5 hours to complete the reaction. After the reaction was completed, the white solid formed was collected by filtration, and a small amount of
It was washed with THF. It was recrystallized using sulforane. 30.6 g (yield 76%) of 4-methoxy-p-quaterphenyl (hereinafter referred to as MQ) was obtained. The physical properties of MQ were as follows.

Liquid crystal transition temperature of ^{328 ℃ (DTA) 1 H-} NMR (DMSO-d 6, 270MHz) δ3.81 (S, 3H, OCH 3) 7.05 (d, 2H, o-H to OCH 3) 7.3-7.9 (m, 15H, aromatic H) Mass spectrum m / z 336 (M ⁺ ) Elemental analysis C (%) H (%) Theoretical 89.30 6.00 Measured 89.55 5.92 (B) 4-Hydroxy-p-quarterphenyl 1 3-neck flask MQ synthesized in (A)
25.2 g (75 mmol) was added, 500 ml of methylene chloride was added, and the mixture was stirred. The inside of the flask became suspended. 19.0 g (75 mmol) of boron tribromide was added to this suspension under a nitrogen atmosphere.
0 ml methylene chloride solution was added dropwise over about 30 minutes. afterwards,
The mixture was stirred and refluxed under a nitrogen atmosphere for 10 hours. After completion of the reaction, the flask was cooled, the precipitated solid was collected by filtration, washed with methylene chloride and dried. Recrystallized with dimethylsulfoxide. 21.6 g (yield 89%) of 4-hydroxy-p-quaterphenyl (hereinafter referred to as HQ) was obtained as a white solid. The physical properties of HQ were as follows.

Liquid crystal transition temperature 352 ℃ (DTA) IR (Nujol) ν _OH = 3400cm ^-1 (broad) ¹ H-NMR (DMSO-d ₆ , 270MHz) δ 6.87 (d, 2H, J = 9Hz, o-H to- OH) 7.3-7.8 (m, 15H, aromatic) Mass spectrum m / z 322 (M ⁺ ) Elemental analysis C (%) H (%) Theoretical value 89.41 5.63 Measured value 89.62 5.58 (C) 4- (2-hydroxyethoxy) ) -P-Quarterphenyl 1 was synthesized by the method (B) in a three-necked flask.
HQ was dissolved by adding 19.2 g (60 mmol) of HQ and 500 ml of sulfolane. To this was added 7.92 g (90 mmol) of ethylene carbonate and heated under a nitrogen atmosphere. At the reflux temperature of sulfolane, 0.1 g of K ₂ CO ₃ was added and the stirring reflux was continued for 4 hours. After completion of the reaction, the reaction solution was filtered while hot, and when cooled, the target product was precipitated, and this was collected by filtration and dried. Four
18.38 g (yield 83%) of-(2-hydroxyethoxy) -p-quaterphenyl (hereinafter referred to as HEQ) was obtained as a white solid. The physical properties of HEQ were as follows.

Liquid crystal transition temperature 335 ° C (DTA) IR (Nujol) ν _OH = 3400-3500cm ^-1 (broad) Mass spectrum m / z 367 (M ⁺ ) Elemental analysis C (%) H (%) Theoretical value 84.99 6.03 Measured value 84.12 5.99 (D) 4,4-dihydroxy-p-quaterphenyl 4-hydroxy-4'-bromobiphenyl 60.0 g,
Methanol 100g, 10wt% sodium hydroxide aqueous solution 300g, 5w
The disodium salt of 4,4-dihydroxy-p-quaterphenyl was obtained by adding 13% of t% palladium / carbon and reacting at 120 ° C. and 5 atm for 4 hours. N, N-Dimethylformamide was added to this solid, and the catalyst was separated by heating and filtration, and the filtrate was acidified with dilute sulfuric acid and washed with methanol to give 4,4-dihydroxy-white crystalline powder. p-Quaterphenyl (hereinafter referred to as DHQ) was obtained. The liquid crystal transition temperature of DHQ was 336 ° C.

Examples 1 and 2 <Synthesis of bis (2-hydroxyethyl) adipate (BHEA)> Dimethyl adipate was placed in a glass flask having an inner volume of 1 equipped with a stirrer, a thermometer, a gas blowing port and a distillation port.
87.1g (0.5mol), ethylene glycol 74.4g (1.2mo
l), as a catalyst, calcium acetate and a small amount of antimony trioxide were added. After replacing the inside of the flask with nitrogen, the inside of the flask was heated and reacted at 180 ° C. for 2 hours. Along with the reaction, methanol began to distill from the flask, and bis (2
-Hydroxyethyl) adipate (hereinafter referred to as BHEA)
Was generated.

<Preparation of Aliphatic Polyester> HQ was added to the above flask in a molar ratio shown in Table 1, the temperature of the flask was raised to 300 ° C., and the reaction was performed for about 1 hour in this state. Next, the distillation port was connected to a vacuum device, and the reaction was carried out for 2 hours while the pressure inside the flask was reduced to 1 mmHg or less.
With the reaction, ethylene glycol was distilled out, and an extremely viscous liquid was produced in the flask.

The melting point of the aliphatic polyester thus obtained was measured, and the results are shown in Table 1.

Example 3 Bis (2-hydroxyethyl) sebacate (hereinafter referred to as BHES) was synthesized in the same manner as in Example 1 except that the same mol of sebacic acid was used instead of adipic acid. An aliphatic polyester was obtained in the same manner as in Example 1 except that the obtained BHES was used instead of BHEA. The melting point of the obtained aliphatic polyester is shown in Table 1.

Example 4 Example 1 except that HEQ was used in the same molar ratio instead of HQ.
An aliphatic polyester was obtained in the same manner as in. The melting point of the obtained aliphatic polyester is shown in Table 1.

Example 5 BHEA 149.1 g (0.5 mol), DHQ8.5 g synthesized in Example 1
(0.025mol), HQ8.1g (0.025mol) and add 300
The temperature was raised to 0 ° C., and after reacting for about 1 hour in this state, the distillation port was connected to a vacuum vessel, and the reaction was conducted for 2 hours while the pressure inside the flask was reduced to 1 mmHg or less. Ethylene glycol was distilled out along with the reaction, and an extremely viscous liquid was obtained in the flask.

The melting point of the aliphatic polyester thus obtained was measured, and the results are shown in Table 1.

Example 6 An aliphatic polyester was obtained in the same manner as in Example 5 except that the molar ratio of the constituent components of the aliphatic polyester was changed as shown in Table 1. The melting point of the obtained aliphatic polyester is shown in Table 1.

Example 7 Example 5 except that the same mole of BHES was used instead of BHEA.
An aliphatic polyester was obtained in the same manner as. The melting point of the obtained aliphatic polyester is shown in Table 1.

Comparative Example 1 The melting point of a polymer obtained by polymerizing BHEA alone was measured, and the results are shown in Table 1.

Comparative Examples 2 and 3 Perprene S-9001 commercially available from Toyobo Co., Ltd.
(Comparative Example 2) and Hytrel 7247 manufactured by Toray DuPont
The melting point of (Comparative Example 3) was measured, and the results are shown in Table 1.

From the results shown in Table 1, the aliphatic polyester containing the monohydroxy compound [II] in the molecular chain has a higher melting point and excellent heat resistance than a polymer containing no such compound or a commercially available thermoplastic elastomer. I understand. Further, the melting point can be further increased by including the dihydroxy compound [IV] in the molecular chain. The intrinsic viscosity of the aliphatic polyester obtained above measured by an Ubbelohde viscometer at 30 ° C. using a dilute solution of orthochlorophenol was as follows. Example 1 ... 1.0, Example 2
... 0.9, Example 3 ... 1.0, Example 4 ... 1.1, Example 5 ... 1.1
1.0, Example 7 ... 1.1, Comparative Example 1 ... 0.8.

(Effect of the invention) The 4-hydroxy-p-quaterphenyl derivative of the present invention can be used as a monomer of an organic polymer compound such as polyester, polyurethane, polyether, polycarbonate, liquid crystalline resin, etc. and has high heat resistance. ，
It gives resins with excellent flame retardancy, solvent resistance, weather resistance and other chemical and physical properties, and when added to other resins, exhibits excellent chemical and physical improvement effects.

Further, the aliphatic polyester of the present invention is obtained by introducing a segment based on a dihydroxy compound or a monohydroxy compound having high crystallinity and a high melting point into an aliphatic polyester mainly composed of an aliphatic dicarboxylic acid and an aliphatic diol. Therefore, it has the performance as a thermoplastic elastomer, and also has excellent heat resistance, mechanical properties, and moldability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toranosuke Saito 5-17-21 Yamatedai, Ibaraki-shi, Osaka (72) Inventor Hiroki Tsunomachi 7-20 Otemachi, Ibaraki-shi, Osaka (72) Inventor Daishiro Kishimoto 2-11-20 Mishimaoka, Ibaraki-shi, Osaka Umeyama Mansion 102 (56) Reference JP-A 63-125521 (JP, A) JP-A 2-311525 (JP, A) JP-A 2 -212448 (JP, A) Soviet patent invention 186124 (SU, A) Plastic, 38 [9] (1987) P. 14

Claims (3)

(57) [Claims] 1. General formula [II] (In the formula, R ² represents an alkylene group, and 1 is 0 or 1.) A 4-hydroxy-p-quaterphenyl derivative represented by the following formula. 2. A monohydroxy compound represented by the formula [II] according to claim 1 in the general formula, an aliphatic dicarboxylic acid represented by the following formula [III] in the general formula, and an aliphatic diol. As a main constituent, the content ratio of the monohydroxy compound is 0.1 to 20 mol% in the hydroxy component, and the intrinsic viscosity measured by an Ubbelohde viscometer at 30 ° C. using a dilute solution of orthochlorophenol is 0.4 or more. An aliphatic polyester of 2.0 or less. HOOC- (CH ₂₎ m-COOH [III] (wherein, m is 0-10 integer) 3. A dihydroxy compound represented by the following general formula [IV] as a constituent component, and the content ratio of the hydroxy compound in which the monohydroxy compound and the dihydroxy compound are combined is 0.1 in all hydroxy components. The aliphatic polyester according to claim 2, which is -30 mol%. (In the formula, R ³ and R ⁴ independently represent an alkylene group, and p is 3
Or 4, and q and r are independently 0 or 1. )