JPH06239980A - Polyester and molded form using the same - Google Patents

Abstract

PURPOSE:To obtain a polyester high in crystallization rate, excellent in heat resistance and molding processability, useful for liquid crystal polymers etc., made up of each specific quaterphenyldicarboxylic acid and diol as the main constituents. CONSTITUTION:This polyester is made up of, as the main constituents, (A) a dicarboxylic acid such as 4,4'''-quaterphenyldicarboxylic acid of the formula I and (B) a dial of formula II ((h) is 1-4) such as 4,4''-dihydroxyterphenyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester preferably used as a material for various molded articles, fibers, films, sheets, paints, adhesives and the like, and a molded article using the same. More specifically, the present invention relates to a polyester that is applied as a thermoplastic elastomer or a liquid crystal polymer to materials such as various molded products, and a molded product obtained by molding the polyester.

[0002]

BACKGROUND OF THE INVENTION Polyester is a polycondensate containing diols, dicarboxylic acids, hydroxycarboxylic acids and the like as its constituent components. Among these polyesters, a polymer aggregate composed of a soft segment and a hard segment having different chemical structures from each other is known as a thermoplastic elastomer, shows a liquid crystallinity, and is a polycondensate containing an aromatic main chain. Known as a liquid crystal polymer.

Thermoplastic elastomers are polymeric materials which exhibit rubber elasticity at room temperature and have the property of being plasticized at high temperatures, and various types are commercially available. Generally, molding of a thermoplastic elastomer does not require a long-time cross-linking step unlike rubber, and can be carried out by injection molding or extrusion molding. This is because a thermoplastic elastomer has a strong chemical structure because of its molecular structure. This is because it has a physical cross-linking that does not rely on a physical bond, that is, it has a system that effectively constrains the polymer only at around room temperature. As described above, the thermoplastic elastomer is a polymer aggregate composed of soft segments and hard segments, and has a microscopic unbalanced structure in which homogeneous portions of these segments are aggregated and heterogeneous portions are phase-separated from each other. However, at that time, the aggregated portion of the hard segment exerts a binding action between the polymers.

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. But,
Conventional thermoplastic elastomers have a problem that they have low heat resistance and poor creep properties because they restrain the molecules by physical cross-linking rather than chemical cross-linking like rubber. For example, Perprene (registered trademark) S-9001 (manufactured by Toyobo Co., Ltd.), which is known to have the highest heat resistance among thermoplastic elastomers, has a melting point of 223 ° C. and a heat distortion temperature (JIS K7207, B method). Deflection temperature under load, HDT) is 146 ° C.

Further, in order to improve the heat resistance of the thermoplastic elastomer, it has been conventionally practiced to increase the proportion of hard segments. However, in this case, since the hardness of the molded product inevitably increases at room temperature and low temperature, parts requiring flexibility over a wide range of temperatures, such as tubes, hoses, belts, packing, electric wires, and sports. It has not been preferably used for articles and automobile parts. Therefore, it has been desired to obtain a polyester having excellent heat resistance as a thermoplastic elastomer without increasing the proportion of hard segments.

On the other hand, the liquid crystal polymer has a higher fluidity than a normal polymer in a molten state due to the liquid crystallinity based on the hydroxycarboxylic acid as described above. In particular, a liquid crystal polymer composed of para-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid is known as Vectra (registered trademark, Celanese Co.), and has good moldability such as injection molding (Japanese Patent Publication No. 57-24407).

However, the conventional liquid crystal polymer has a problem that it is difficult to improve both heat resistance and molding processability.

First, in order to improve moldability as a liquid crystal polymer, it is generally necessary to lower the melt viscosity of polyester. In that case, a method of reducing the molecular weight of polyester or a process for producing polyester Then, a method of adding a plasticizer, a processing aid and the like can be considered. However, the former method has a drawback that mechanical properties such as strength and impact resistance and heat resistance of the obtained molded article are lowered, and the latter method has a drawback that heat resistance is lowered.

On the other hand, as a method for improving the heat resistance of the liquid crystal polymer, there has been proposed a method of blending a reinforcing fiber such as glass fiber with polyester, or a method of increasing the molecular weight of polyester or increasing the crosslink density. .

However, in the above method, there is a problem that the molding processability of the polyester is lowered and the surface condition of the obtained molded product is deteriorated. 10 mg to 10 g
In the case of molding a component having a moderate mass, a component having a thin portion with a wall thickness of 1 mm or less, or a component having a sharp edge portion such as a gear, the fluidity of the glass fiber in the thin portion or the sharp corner portion Since it is insufficient, sufficient effect cannot be obtained by the glass fiber in this portion, and anisotropy or warpage occurs due to the orientation of the glass fiber, which makes precise molding impossible. In the above method, there is a problem that the melting temperature of the polyester is raised and the moldability is lowered.

Further, there are many conventional polyesters using ethylene glycol or the like as a diol, but in a liquid crystal polymer made of such a polyester, the crystallization rate of the polymer is slow and molding such as injection molding is required. There is a problem that the dimensional stability of the resulting molded product is poor and the surface condition of the molded product is poor because the crystallization during the process does not proceed sufficiently. In order to solve this problem, a liquid crystal polymer made of polyester using an aromatic diol as a diol is disclosed in JP-A-2-276817.
It is disclosed in the publication. Since this polyester has a high crystallization rate and excellent heat resistance, a liquid crystal polymer which is a hard engineering plastic can be obtained.
However, this polyester has a problem that it has a very high melting temperature, is difficult to be melt-molded, and has lower mechanical properties such as impact resistance.

[0012]

As described above, heat resistance is a problem in conventional thermoplastic elastomers, and in liquid crystal polymers, heat resistance, moldability, crystallinity and mechanical properties of the polymer. There was a problem that we couldn't get everything that satisfied all of the above.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a polyester, which is a thermoplastic elastomer having excellent heat resistance, and a molded article using the same. Another object of the present invention is to provide a polyester, which is a liquid crystal polymer having good heat resistance and molding processability, excellent mechanical properties, and a high crystallization rate, and a molded product using the same. It is in.

[0014]

The polyester of the present invention is a polyester mainly composed of a dicarboxylic acid and a diol, and the dicarboxylic acid is represented by the following formula [I]: 4,4 "' It is characterized in that it contains a quarter phenyl dicarboxylic acid, and the diol contains a dihydroxy compound represented by the following general formula [II], whereby the above object is achieved.

[0015]

[Chemical 4]

[0016]

[Chemical 5]

(In the formula, n represents an integer of 1 to 4).

In one embodiment of the present invention, the diol contains a dihydroxy compound [II] and a diol other than an aromatic diol. In this case, the polyester becomes a thermoplastic elastomer.

In another embodiment of the present invention, the diol comprises a dihydroxy compound [II] and an aromatic diol. In this case, the polyester is a liquid crystal polymer.

The present invention will be described in detail below.

The polyester of the present invention mainly comprises a dicarboxylic acid containing a dicarboxy compound represented by the above formula [I] and a diol containing a dihydroxy compound represented by the above general formula [II]. Polyester is obtained by polycondensing equimolar amounts of dicarboxylic acid and diol. In the polyester of the present invention, by changing the types of dicarboxylic acid component, diol component and other constituent components and the content ratio thereof, the polyester It is possible to freely change the properties and the physical properties of the molded product using the same. In this case, the polyester whose diol contains a dihydroxy compound [II] and a diol other than an aromatic diol becomes a thermoplastic elastomer, and the polyester whose diol consists of a dihydroxy compound [II] and an aromatic diol becomes a liquid crystal polymer. .

First, the polyester which is a thermoplastic elastomer (hereinafter referred to as polyester (A)) will be described.

The dicarboxylic acid which is a constituent of the polyester (A) contains 4,4 ′ ″-quaterphenyldicarboxylic acid represented by the above formula [I].

The 4,4 ′ ″-quaterphenyldicarboxylic acid represented by the above formula [I] is a low molecular weight compound having liquid crystallinity, and its melting point is 482 ° C. Here, the liquid crystal state means a state in which the compound is in a liquid state and the molecules are aligned to maintain optical anisotropy. In general, liquid crystal molecules have high crystallinity, and especially 4,4 ′ ″-quaterphenyldicarboxylic acid [I] has a high transition temperature, and therefore, when incorporated in a polymer chain, the polymer is unique. It comes to show the property.

The 4,4 '''-quaterphenyldicarboxylic acid [I] can be produced by any method.
The method described in 39147 publication, that is, the following general formula [IV]

[0026]

[Chemical 6]

4-halogenobiphenyl-4'-carboxylic acid represented by the formula (wherein X is a halogen atom) is treated with an alkali metal or alkaline earth metal hydroxide and / or an alkali metal in an alcohol. It can be produced by dehalogenating dimerization using metallic palladium as a catalyst in the presence of the alcoholate. In this case, X in the general formula [IV] is preferably a chlorine atom, a bromine atom and an iodine atom, and the alcohol is preferably methanol, ethylene glycol or the like. The hydroxide is preferably sodium hydroxide or potassium hydroxide,
Sodium methylate is preferred as the alcoholate. In addition, 4,4 "'-quaterphenyldicarboxylic acid [I] is 4,4"'-quaterphenyldicarboxylic acid dimethyl ester, before being polycondensed with the diol contained in the polyester (A). It may be converted to an ester such as 4,4 ′ ″-quaterphenyldicarboxylic acid diethyl ester and 4,4 ′ ″-quaterphenyldicarboxylic acid diphenyl ester.

The diol which is a constituent of the polyester (A) contains the dihydroxy compound represented by the above general formula [II].

The above dihydroxy compound [II] is a low molecular weight compound exhibiting liquid crystallinity and has a high crystal-to-liquid crystal transition temperature. For example, the transition temperature of 4,4 ″ ′-dihydroxyquaterphenyl is 336 ° C. Therefore, a polyester mainly composed of a dicarboxylic acid containing 4,4 '''-quaterphenyldicarboxylic acid [I] and a diol containing the dihydroxy compound [II] is a thermoplastic elastomer excellent in heat resistance. Become. 4,4 '''-quaterphenyldicarboxylic acid [I] and the above dihydroxy compound [I
[I] exhibits crystallinity and has a high crystal-to-liquid crystal transition point, so that even if the content is small, a strong and heat-resistant physical crosslink is formed. further,
When synthesizing the polyester of the present invention by melt polycondensation, a high temperature of about 300 ° C. is required, so that thermal decomposition or thermal deterioration during the reaction of the polymer may become a problem. II] can act effectively as a stabilizer for preventing such thermal decomposition or thermal deterioration.

As the above-mentioned dihydroxy compound [II],
Examples thereof include 4,4 ″ -dihydroxyterphenyl and 4,4 ′ ″-dihydroxyquaterphenyl. Further, the dihydroxy compound [II] can be produced by any method, for example 4,4 '''-dihydroxyquaterphenyl is the method described in Journal of Chemical Society, 1379-85 (1940), 4- Method of synthesizing dimer by reacting hydroxy-4'-bromobiphenyl by heating and pressurizing with a palladium catalyst in the presence of alkali, and then acid precipitation (JP-A-2-25)
56434) and the like.

The total amount of 4,4 '''-quaterphenyldicarboxylic acid [I] and the above dihydroxy compound [II] is 0.
1 to 30 mol% is preferable, and more preferably 0.5 to 2
It is 0 mol%, and most preferably 1.0 to 10 mol%. When the content is less than 0.1 mol%, the heat resistance of the obtained polyester (A) may be lowered, and when the content exceeds 30 mol%, the obtained polyester (A) 2) has a high elastic modulus and lowers flexibility, and may be unsuitable as a thermoplastic elastomer.

By the way, the polyester (A) in which the above dicarboxylic acid is composed of 4,4 '''-quaterphenyldicarboxylic acid [I] alone is very hard and brittle, and the melting temperature becomes very high. There is a risk of deterioration in sex. Therefore, the dicarboxylic acid preferably contains a dicarboxylic acid other than the aromatic dicarboxylic acid in addition to the 4,4 ′ ″-quaterphenyldicarboxylic acid [I], and the polyester (A) obtained thereby Moldability can be improved while maintaining heat resistance.

As the dicarboxylic acid other than the aromatic dicarboxylic acid, an aliphatic dicarboxylic acid represented by the following general formula [III] is preferable.

[0034]

[Chemical 7]

(In the formula, n is an integer of 0 to 10).

When n exceeds 10 in the above formula [III], physical properties such as rubber elasticity of the molded product obtained from the polyester (A) may be deteriorated.

Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid and sebacic acid. These may be contained alone or in combination of two or more.

On the other hand, the diol preferably contains a diol other than the aromatic diol in order to impart flexibility to the polyester (A) in addition to the dihydroxy compound [II].

The diol other than the aromatic diol is selected from at least one selected from the group consisting of glycol, polyalkylene oxide and polysilicone having two hydroxyl groups in the molecule. When polyalkylene oxide or polysilicon is selected as the diol, the constitutional unit is counted as one monomer. For example, polyethylene oxide having a degree of polymerization of 10 is counted as 10 monomers.

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-
Examples thereof include 1,3-diol, cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol. These may be contained alone or in combination of two or more.

Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide,
And polyhexamethylene oxide, which may be contained alone,
Moreover, you may contain 2 or more types. The number average molecular weight of the polyalkylene oxide is preferably 100 to 20,000, more preferably 500 to 5,000. When the number average molecular weight is less than 100, the resulting polyester (A)
When the number average molecular weight exceeds 20,000, physical properties such as heat stability of the obtained polyester (A) may be deteriorated.

Examples of the above-mentioned polysilicone include dimethylpolysiloxane, diethylpolysiloxane, diphenylpolysiloxane and the like having two hydroxyl groups at the molecular ends. The number average molecular weight of the polysilicone is preferably 100 to 20,000, more preferably 500 to 5,000.
Is. When the number average molecular weight is less than 100, the resulting polyester (A) may have a reduced ability to impart flexibility, and when the number average molecular weight is more than 20,000, the polyester (A) It can be difficult to generate.

The above-mentioned 4,4 '''-quaterphenyldicarboxylic acid [I], the above dihydroxy compound [II],
When a compound having a soft segment such as an aliphatic dicarboxylic acid [III] or a diol other than an aromatic diol is used as the main constituent component of the polyester, the flexibility derived from the soft segment is not impaired and heat resistance is improved. It is presumed that an excellent thermoplastic elastomer can be obtained.

The polyester (A) may further contain a lactone and / or an aromatic hydroxycarboxylic acid as a constituent in addition to the above-mentioned constituents.

The lactone is a compound that opens the ring and reacts with the carboxyl group of the dicarboxylic acid and the hydroxyl group of the diol to add an aliphatic chain, thereby further imparting flexibility to the polyester (A). It The lactone preferably has 4 or more carbon atoms, and more preferably has a 5- to 8-membered ring. For example, ε-caprolactone, δ-valerolactone, γ-butyrolactone and the like can be mentioned. These may be contained alone,
Further, two or more kinds may be contained.

The content of the lactone may be appropriately determined depending on the properties of the target polyester (A), but it is 90 mol% in all monomers constituting the polyester (A).
It is preferably the following or less, more preferably 75 mol% or less. When the above content exceeds 90 mol%,
The molecular weight of the polyester (A) does not increase and elasticity tends to decrease.

The above-mentioned aromatic hydroxycarboxylic acid imparts rigidity to the polyester (A), and examples thereof include salicylic acid, metahydroxybenzoic acid, parahydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid and 3-bromo. -Four-
Hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-4'- Carboxybiphenyl etc. are mentioned. Preferably, para-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid and 4-hydroxy-4'-carboxybiphenyl are contained. These may be contained alone or in combination of two or more.

The content of the aromatic hydroxycarboxylic acid can be appropriately determined depending on the properties of the target polyester (A), but it is preferably 30 mol% or less in all the monomers constituting the polyester (A), And 4,4 '''-
The total amount with quarter phenyl dicarboxylic acid [I] is preferably 0.1 to 30 mol%. When the content in all the monomers is more than 30 mol%, the resulting polyester (A) has a high rigidity and a low flexibility, and may be unsuitable as a thermoplastic elastomer.

In addition to the above-mentioned constituents, the polyester (A) is used as a diol in order to improve the mechanical properties of the polyester (A).
Other than aromatic diols and dicarboxylic acids 4,4 '''-
An aromatic dicarboxylic acid other than quarter phenyl dicarboxylic acid [I] may be contained.

Examples of the aromatic diol include resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenylsulfide, 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, 2,6-dihydroxynaphthalene, and 4,4 ″ -di (2-hydroxyethoxy) -p-ter Examples include phenyl and the like. These may be contained alone or in combination of two or more.

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'-dicarboxylic acid. Carboxydiphenyl sulfide, 4,4'-dicarboxydiphenyl sulfone,
3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy)
Examples thereof include ethane, 1,4-dicarboxynaphthalene and 2,6-dicarboxynaphthalene. These may be contained alone or in combination of two or more.

The total amount of the aromatic diol and the aromatic dicarboxylic acid is preferably 30 mol% or less, more preferably 25 mol% or less, based on all the polymers constituting the polyester (A). preferable. When the total amount exceeds 30 mol%, the flexibility of the obtained polyester (A) may be reduced. Further, the total amount of the above aromatic diol, the above aromatic dicarboxylic acid, 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and the above dihydroxy compound [II] is preferably 0.2 to 40 mol%, More preferably, it is 0.5 to 30 mol%.

The polyester (A) comprising the above constituents can be produced by any of the following generally known polycondensation methods.

A method in which a dicarboxylic acid component and a diol component are directly reacted, a method in which a lower ester of a dicarboxylic acid and a diol component are reacted by transesterification, and a halide of the dicarboxylic acid and a diol component are appropriately selected from pyridine and the like. A method of reacting in a different solvent, a method of reacting a metal alcoholate of a diol component with a halide of a dicarboxylic acid, and a method of reacting an acetylated product of a diol component with a dicarboxylic acid by transesterification.

It is also possible to control the structure of the obtained polyester by changing the addition order of 4,4 '''-quaterphenyldicarboxylic acid [I] during polycondensation. For example, when 4,4 '''-quaterphenyldicarboxylic acid [I] is charged together with a diol component and another dicarboxylic acid component, a random copolymer is easily obtained, but 4,4' When ″ -quaterphenyldicarboxylic acid [I] is charged in the latter stage of polycondensation, a block copolymer is easily obtained. In addition, polyester synthesized in advance was kneaded with 4,4 '''-quaterphenyldicarboxylic acid [I] or 4,4'''-quaterphenyldicarboxylic acid [I] ester under reduced pressure heating, and by transesterification reaction. It is also possible to introduce a segment based on 4,4 ′ ″-quaterphenyldicarboxylic acid [I] into the molecular chain.

In the polycondensation, a catalyst generally used in producing polyester may be used. For example, lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium,
Metals such as zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium and manganese, their organometallic compounds,
Examples thereof include organic acid salts, metal alkoxides and metal oxides.

Particularly preferred catalysts are calcium acetate, diacyl stannous tin, tetraacyl stannic tin, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
Tin dioctanoate, tin tetraacetate, triisobutyl aluminum, tetrabutyl titanate, germanium dioxide, and antimony trioxide. Two or more kinds of these catalysts may be used in combination.

Further, in order to efficiently distill off water, alcohol, glycol and the like, which are by-produced during the polymerization, to obtain the high molecular weight polyester (A), the reaction system is depressurized to 1 mmHg or less in the latter stage of polycondensation. It is preferable.
The reaction temperature is generally 150 to 350 ° C.

Further, the following additives may be added during or after the production within a range not impairing the practical use: (i) Inorganic fiber: glass fiber, carbon fiber, boron fiber, silicon carbide fiber, alumina fiber , Amorphous fiber, silicone-titanium-carbon fiber, etc. (ii) organic fiber: aramid fiber, etc. (iii) inorganic filler: calcium carbonate, titanium oxide, mica, talc, etc. (iv) flame retardant: hexabromocyclo Dodecane, Tris-
(2,3-dichloropropyl) phosphate, pentabromophenylallyl ether, etc., (v) heat stabilizer: triphenylphosphite, trilaurylphosphite, trisnonylphenylphosphite,
2-tert-butyl-α- (3-tert-butyl-4-hydroxyphenyl-p-cumenylbis (p-nonylphenyl) phosphite, etc. (vi) Antistatic agent: N, N-bis (hydroxyethyl) alkyl (Vii) Inorganic powder: barium sulfate, alumina, silicon oxide, etc. (viii) higher fatty acid salt: sodium stearate, barium stearate, sodium palmitate, etc. (ix) UV absorber: p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,
4,5-Trihydroxybutyrophenone, etc. (x) Antioxidants: butylhydroxyanisole, butylhydroxytoluene, distearylthiodipropionate, dilaurylthiodipropionate, hindered phenyl antioxidants, etc. (xi) Organic compound: benzyl alcohol, benzophenone, etc., (xii) Crystallization accelerator: Highly crystallized polyethylene terephthalate, polytrans-cyclohexanedimethanol terephthalate, etc.

Further, the polyester (A) may be another thermoplastic resin such as polyolefin, modified polyolefin,
It may be used by mixing with polystyrene, polyamide, polycarbonate, polysulfone, polyester or the like, or by mixing with a rubber component to modify its properties.

The polyester (A) is formed into a molded product by press molding, extrusion molding, injection molding, blow molding, etc., and its physical properties can be arbitrarily changed depending on the constituent components and the content ratio thereof. When the polyester (A) is prepared as a thermoplastic elastomer, the molded product is preferably used for flexible molded products such as automobile parts, hoses, packings, belts, paints and adhesives.

Next, the polyester which is a liquid crystal polymer (hereinafter referred to as polyester (B)) will be described.

The dicarboxylic acid which is a constituent component of the polyester (B) contains 4,4 ′ ″-quaterphenyldicarboxylic acid [I], like the polyester (A). This 4,
The 4 '''-quaterphenyldicarboxylic acid [I] can be produced by the same method as described for the polyester (A).

The diol which is a constituent component of the polyester (B) contains a dihydroxy compound [II] as in the polyester (A). This dihydroxy compound [II] can be produced in the same manner as the polyester (A).

Dicarboxylic acids including 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and the above dihydroxy compounds [I]
The polyester (B) containing a diol containing I] as a main constituent becomes a liquid crystal polymer having a high crystallization rate and excellent heat resistance. It contains 4,4 '''-quaterphenyldicarboxylic acid [I] and the dihydroxy compound [I
This is because [I] exhibits crystallinity and the transition point from the crystals to the liquid crystal is high. Furthermore, when synthesizing the polyester of the present invention by melt polycondensation, a high temperature of about 300 ° C. is required, so that thermal decomposition or thermal deterioration during the reaction of the polymer may become a problem. The compound [II] can effectively act also as a stabilizer for preventing such thermal decomposition or thermal deterioration.

The above-mentioned dicarboxylic acid contains an aromatic dicarboxylic acid other than 4,4 ″ ″-quaterphenyldicarboxylic acid [I] in addition to 4,4 ′ ″-quaterphenyldicarboxylic acid [I]. May be. For example, 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,
Examples thereof include 1,2-bis (4-carboxyphenoxy) ethane, 1,4-dicarboxynaphthalene and 2,6-dicarboxynaphthalene.

When the above dicarboxylic acid consists of 4,4 '''-quaterphenyldicarboxylic acid [I] alone, or
When 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and an aromatic dicarboxylic acid are used, the resulting polyester (B) has excellent heat resistance and mechanical strength, but has the drawback of being brittle. Similarly, the polyester (B) further containing an aromatic hydroxycarboxylic acid, which will be described later, becomes brittle. Although this drawback is slightly improved in toughness by further containing a lactone described later as a constituent component, it has a drawback that the melting temperature becomes high and thermoforming becomes difficult.

In order to improve such drawbacks, the dicarboxylic acid preferably contains a dicarboxylic acid other than the aromatic dicarboxylic acid in addition to 4,4 ′ ″-quaterphenyldicarboxylic acid [I]. .

As the dicarboxylic acid other than the above aromatic dicarboxylic acid, an aliphatic dicarboxylic acid represented by the following general formula [III] is preferable as in the polyester (A).

[0070]

[Chemical 8]

(In the formula, n is an integer of 0 to 10).

Examples of the above aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid and sebacic acid. These may be contained alone or in combination of two or more. By containing the above aliphatic dicarboxylic acid [III] as a dicarboxylic acid together with 4,4 ′ ″-quaterphenyldicarboxylic acid [I], while maintaining the heat resistance and mechanical properties of the polyester (B), Molding processability can be improved.

When the aliphatic dicarboxylic acid [III] is contained in the polyester (B), the total amount of the 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and the dihydroxy compound [II] is the polyester ( It is preferably 0.1 to 20 mol% in all monomers constituting B). When the content is less than 0.1 mol%, the effect of improving the heat resistance and mechanical properties of the obtained polyester (B) may be reduced, and when the content exceeds 20 mol%. In this case, the melting temperature of the polyester (B) becomes very high, and there is a risk that it will decompose before melting.

On the other hand, the diol preferably contains an aromatic diol in addition to the dihydroxy compound [II] in order to further impart rigidity to the polyester (B). By doing so, the ratio of the aromatic monomer in all the monomers constituting the polymer (B) increases, so that a liquid crystal polymer that is a hard engineering plastic can be obtained.

Examples of the aromatic diol include resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenylsulfide, 4, 4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1,1-di (4-
Examples thereof include hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. These may be contained alone or in combination of two or more.

The above-mentioned 4,4 ′ ″-quaterphenyldicarboxylic acid [I], the above dihydroxy compound [II],
A main constituent component of the polyester (B) is a compound having a hard segment such as an aromatic dicarboxylic acid other than 4,4 '''-quaterphenyldicarboxylic acid [I] and an aromatic diol other than the dihydroxy compound [II]. In such a case, a liquid crystal polymer having a high crystallization rate and excellent heat resistance and mechanical properties can be obtained. Further, by containing 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and aliphatic dicarboxylic acid [III] as the dicarboxylic acid of the polyester (B), the melting temperature of the polyester (B) is lowered. Forming processability is improved.

Like the polyester (A), the polyester (B) may further contain a lactone and / or an aromatic hydroxycarboxylic acid as a constituent in addition to the above-mentioned constituents.

The lactone may be the same as in the case of the polyester (A), and its content is 75 mol% in all the monomers constituting the polyester (B).
The following is preferable. If the above content exceeds 75 mol%, the polyester (B) may become flexible, and mechanical strength, heat resistance, etc. may decrease.

As the aromatic hydroxycarboxylic acid, the same ones as in the case of the polyester (A) can be mentioned, and the content thereof is 85 mol% or less in all the monomers constituting the polyester (B). Is preferred,
It is more preferably 75 mol%. When the content exceeds 85 mol%, the resulting polyester (B) has a large amount of aromatic groups, and heat resistance and liquid crystallinity are improved,
There is a risk that melt molding may not be possible. The total amount of the aromatic hydroxycarboxylic acid, 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and the dihydroxy compound [II] is 0. 2-95 mol% is preferable, and 1.0-60 mol% is more preferable.

The polyester (B) composed of the above-mentioned constituents can be produced by the same method as described for the polyester (A).

Further, 4,4 '''-quaterphenyldicarboxylic acid [I] is added to the polyester (B) produced in advance.
Or 4,4 '''-quaterphenyldicarboxylic acid [I]
The acetylated compound was kneaded under reduced pressure and depolymerized into ethylene glycol or transesterified to give 4,4 '''-
It is also possible to introduce a segment based on quarterphenyldicarboxylic acid [I].

In the polycondensation, a catalyst generally used in the production of polyester may be used, and in this case, the same catalysts as mentioned in the polyester (A) can be used.

Further, in order to efficiently distill off water, alcohol, glycol and the like, which are by-produced during the polymerization, to obtain the high molecular weight polyester (B), the reaction system is depressurized to 1 mmHg or less in the latter stage of polycondensation. It is preferable.
The reaction temperature is generally 150 to 350 ° C.

Further, during or after the production, the same additives as those mentioned for the polyester (B) may be added within the range not impairing the practicality.

Further, the polyester (B) may be another thermoplastic resin such as polyolefin, modified polyolefin,
It may be used by mixing with polystyrene, polyamide, polycarbonate, polysulfone, polyester or the like, or by mixing with a rubber component to modify its properties.

The polyester (B) is formed into a molded product by press molding, extrusion molding, injection molding, blow molding, etc., and its physical properties can be arbitrarily changed depending on the constituent components and the content ratio thereof. When the polyester (B) is prepared as a liquid crystal polymer, the molded product is suitably used for a mechanical component such as a pipe having rigidity, an electronic component, a molded product such as a fiber, a film, a sheet, a coating material, an adhesive agent and the like. .

[0087]

EXAMPLES The present invention will be described below based on examples.
The properties of the polyesters obtained in the following examples were measured according to the following methods.

[Tensile Breaking Strength, Tensile Breaking Elongation and Tensile Elastic Modulus] Samples (polyesters obtained in Examples) were 10
Dry at 0 ° C for 6 hours or more, and use an injection molding device (TOSHIBA MACHINE, IS 30 EPN) to make the cylinder temperature 20.
A JISK63013 dumbbell was produced at 0 to 250 ° C, a nozzle temperature of 200 to 250 ° C, and a mold temperature of 50 to 100 ° C. About this No. 3 dumbbell, ASTM D638
A tensile test was carried out with a Shimadzu Autograph AGB-5000 according to the above, and the tensile breaking strength, the tensile breaking elongation and the tensile elastic modulus were determined.

[Shore D Hardness] Shore D hardness was measured with a D type durometer according to JIS K7215.

Example 1 Synthesis of 4,4 ′ ″-quaterphenyldicarboxylic acid isobutyl ester A glass reaction flask (capacity 100 ml) was equipped with a stirrer, a water cooling tube and a thermometer, and anhydrous nickel chloride (0.58 g).
And N, N'-dimethylacetamide (15 g) were charged and dissolved in a nitrogen atmosphere at 40 ° C., triphenylphosphine (5 g) and zinc powder (4 g) were added thereto, and reddish brown tetrakistriphenylphosphine- A nickel complex was formed. 4'-Brombiphenyl-4-carboxylic acid isobutyl ester (15 g) dissolved in N, N'-dimethylacetamide (30 g) was added dropwise thereto, and the reaction was carried out at 70 ° C for 2 hours. Crystals of the target substance began to precipitate during the reaction. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solid matter (4,4 '''-quaterphenyldicarboxylic acid isobutyl ester and unreacted zinc powder) was collected by filtration, sufficiently washed with isopropyl alcohol, and dried. Subsequently, xylene (10
0 g) was added and heated under stirring to perform hot filtration. afterwards,
The filtrate was cooled and the precipitate was collected by filtration, washed with xylene, and dried to give 4,4 ′ ″-quaterphenyldicarboxylic acid isobutyl ester as white scale crystals (8.3 g, yield).
72.8%, melting point 202 ° C).

Elemental analysis value (%): theoretical value as C ₃₄ H ₃₄ O ₄ C, 80.60: H, 6.76 actual measurement value C, 80.38: H, 6.71 polyester production Stirrer, thermometer , 4,4 '''-dihydroxyquaterphenyl (16.9 g, 0.05 mol) was placed in a glass flask (content: 1 L) equipped with a gas injection port and a distillation port, 4,4'''-obtained above. Quarter phenyl dicarboxylic acid isobutyl ester (25.3g, 0.05mol), dimethyl adipate (348.4g, 2mol), ethylene glycol (4.8mol),
Calcium acetate and a small amount of germanium dioxide as a catalyst 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. As the reaction proceeded, methanol and isobutyl alcohol were distilled from the flask. The flask was further heated to 300 ° C. and reacted in this state for 2 hours. Next, the distillation port was connected to a vacuum device, and the reaction was carried out for 1 hour while the pressure inside the flask was reduced to 1 mmHg or less. With the progress of the reaction, ethylene glycol was distilled out, and an extremely viscous liquid polyester was produced in the flask. With respect to the polyester thus obtained, the tensile breaking strength, the tensile breaking elongation, the tensile elastic modulus and the Shore D hardness were measured. The results are shown in Table 1.

(Example 2) In Example 1, 4,4 '''-
33.8 g (0.10 mol) of dihydroxy quarterphenyl,
A polyester was produced in the same manner as in Example 1 except that 4,4 ′ ″-quaterphenyldicarboxylic acid isobutyl ester was 50.7 g (0.10 mol), and the tensile strength at break, tensile elongation at break, and tensile elastic modulus were measured. And Shore D hardness was measured.
The results are shown in Table 1.

(Example 3) In Example 1, 4,4 '''-
50.8 g (0.15 mol) of dihydroxy quarterphenyl,
Polyester was produced in the same manner as in Example 1 except that 7,4 g (0.15 mol) of 4,4 ′ ″-quaterphenyldicarboxylic acid isobutyl ester was used, and the tensile breaking strength, tensile breaking elongation, and tensile elastic modulus were measured. And Shore D hardness was measured.
The results are shown in Table 1.

[0094]

[Table 1]

[0095]

As is apparent from the above description, one polyester of the present invention has excellent heat resistance and is suitable as a thermoplastic elastomer. Molded articles using such polyesters have elasticity and are very useful as various molded articles. Further, the other polyester of the present invention is suitable as a liquid crystal polymer because it has excellent heat resistance and mechanical properties, has a high crystallization rate, and has a low melting temperature and good moldability. A molded product using such a polyester has rigidity and is very useful as various molded products.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Toranosuke Saito, 5-17-21 Yamatedai, Ibaraki City, Osaka Prefecture (72) Inventor Hiroki Tsunomachi, 1-11-3 Minami Kasugaoka, Ibaraki City, Osaka Prefecture (72) Inventor Daishiro Kishimoto 2-24-23 Mishimaoka, Ibaraki City, Osaka Sun Heights Mishimaoka 306

Claims (23)

[Claims] 1. A polyester mainly composed of a dicarboxylic acid and a diol, wherein the dicarboxylic acid contains 4,4 ″ ′-quaterphenyldicarboxylic acid represented by the following formula [I]: And a polyester in which the diol contains a dihydroxy compound represented by the following general formula [II]. [Chemical 1] [Chemical 2] (In the formula, n represents an integer of 1 to 4). 2. The diol contains the dihydroxy compound [II] and a diol other than an aromatic diol.
The polyester according to claim 1. 3. A diol other than the aromatic diol,
The polyester according to claim 2, which is at least one selected from the group consisting of glycols, polyalkylene oxides, and silicones having two hydroxyl groups in the molecule. 4. The glycol is 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 ,
From the group consisting of 10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol The polyester according to claim 3, which is at least one selected. 5. The polyethylene oxide, wherein the polyalkylene oxide has a number average molecular weight of 100 to 20,000.
The polyester according to claim 3, which is at least one selected from the group consisting of polypropylene oxide, polytetramethylene oxide, and polyhexamethylene oxide. 6. The polyester according to claim 1, wherein the diol is composed of the dihydroxy compound [II] and an aromatic diol. 7. The aromatic diol is resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4′-dihydroxydiphenylether, 4,4′-dihydroxydiphenylsulfide, 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 and 2,6 -The polyester according to claim 6, which is at least one selected from the group consisting of dihydroxynaphthalene. 8. The polyester according to claim 2, wherein the dicarboxylic acid contains 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and a dicarboxylic acid other than the aromatic dicarboxylic acid. 9. The polyester according to claim 8, wherein the dicarboxylic acid other than the aromatic dicarboxylic acid is an aliphatic dicarboxylic acid represented by the following general formula [III]. [Chemical 3] (In formula, n is an integer of 0-10). 10. The aliphatic dicarboxylic acid [III] is at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid and sebacic acid. The polyester described in. 11. The total amount of 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and the dihydroxy compound [II] is 0.1% of all monomers constituting the polyester.
The polyester according to claim 2, which is -30 mol%. 12. The dicarboxylic acid contains 4,4 ′ ″-quaterphenyldicarboxylic acid [I] and an aromatic dicarboxylic acid other than 4,4 ′ ″-quaterphenyldicarboxylic acid [I]. The polyester according to claim 6. 13. The dicarboxylic acid further comprises:
Containing an aliphatic dicarboxylic acid [III] according to, and 4,
The polyester according to claim 6 or 12, wherein the total amount of 4 '''-quaterphenyldicarboxylic acid [I] and the dihydroxy compound [II] is 0.1 to 20 mol% in all monomers constituting the polyester. . 14. The polyester according to claim 2, further comprising lactone as a constituent component. 15. The polyester according to claim 14, wherein the lactone is at least one selected from the group consisting of ε-caprolactone, δ-valerolactone and γ-butyrolactone. 16. The polyester according to claim 2, which further contains an aromatic hydroxycarboxylic acid as a constituent component. 17. A total amount of 4,4 ′ ″-quaterphenyldicarboxylic acid [I], the dihydroxy compound [II] and the aromatic hydroxycarboxylic acid, which further contains aromatic hydroxycarboxylic acid as a constituent component. Is 0.1 to 30 mol% with respect to all monomers constituting the polyester
The polyester according to claim 2, which is 18. An aromatic hydroxycarboxylic acid as a constituent component, wherein the content of the aromatic hydroxycarboxylic acid is 8 in all monomers constituting the polyester.
5 mol% or less, and the total amount of 4,4 ′ ″-quaterphenyldicarboxylic acid [I], the dihydroxy compound [II] and the aromatic hydroxycarboxylic acid is 0.2 to
The polyester according to claim 6, which is 95 mol%. 19. The aromatic hydroxycarboxylic acid is
The polyester according to claim 16, which is at least one selected from the group consisting of para-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and 4-hydroxy-4'-carboxybiphenyl. 20. A thermoplastic elastomer comprising the polyester according to claim 2. 21. An elastic molded body made of the thermoplastic elastomer according to claim 20. 22. A liquid crystal polymer comprising the polyester according to claim 6. 23. A molded article having rigidity, which is made of the liquid crystal polymer according to claim 22.