JPH0749507B2 - Polyester composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a polyester composition exhibiting a property as a thermoplastic elastomer with an increased degree of polymerization when melt-molded.

(Prior Art) An aliphatic polyester having a dihydroxy or monohydroxy compound having a p-terphenyl or p-quaterphenyl skeleton as a constituent component is a polyester having properties as a thermoplastic elastomer. Such an aliphatic polyester is usually produced by melt polycondensation, but since it is necessary to suppress decomposition, the polymerization temperature has an upper limit, and the capacity of the apparatus is also limited. It's not easy to get.

As a method of increasing the melt viscosity of a resin, a solid phase polymerization method, a method of blending an ionomer, etc. have been conventionally known. The solid phase polymerization method is not economical because it requires a long reaction time to obtain a resin having a sufficient viscosity. In the method of blending an ionomer, a polyester having a sufficient viscosity cannot be obtained because of poor compatibility between the polyester and the ionomer.

(Problems to be Solved by the Invention) The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyester composition capable of increasing the degree of polymerization by melt molding. It is in.

(Means for Solving the Problem) The present inventors have studied a method for obtaining a polyester having a high degree of polymerization by melt-molding without particularly raising the production temperature. As a result, the dicarboxylic acid anhydride and 2
It has been found that it is very effective to mix a predetermined amount of functional oxazoline with the polyester, and the present invention has been completed.

That is, the polyester composition of the present invention comprises an aliphatic dicarboxylic acid represented by the following formula [I]; an aliphatic diol; and a dihydroxy compound represented by the following formula [II] and a below formula [III]. A polyester composition containing a polyester having at least one of the monohydroxy compounds represented by as a constituent component, a dicarboxylic acid anhydride, and a bifunctional or higher functional oxazoline, wherein 100 parts by weight of the polyester is used. The dicarboxylic acid anhydride is contained in an amount of 0.05 to 10 parts by weight, and the oxazoline compound is contained in an amount of 0.1 to 10 parts by weight, whereby the above object is achieved.

HOOC- (CH ₂₎ n-COOH (I) (wherein, n represents an integer of 0.) (In the formula, R ¹ and R ² independently represent an alkylene group, and p is 3
Or 4, and q and r each independently represent 0 or an integer of 1 or more. ) (In the formula, R ³ represents an alkylene group, l is 2 or 3, and m represents an integer of 0 or 1 or more.) In the above aliphatic dicarboxylic acid, when a dicarboxylic acid having more than 10 carbon atoms is used, , The physical properties of the molded product obtained from the polyester are deteriorated. As the dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glataric acid, adipic acid, suberic acid, and sebacic acid are preferably used.

Examples of the aliphatic diol include glycol and polyolylene 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-
Examples thereof include diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like, which may be used alone or in combination of two or more kinds. .

Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide, and the like.
These may be used alone or in combination of two or more. The number average molecular weight of polyalkylene oxide is
When it becomes smaller, the ability to impart flexibility to the resulting polyester decreases, and when it becomes too large, physical properties such as thermal stability of the obtained polyester decrease, so 100 to 20,000 is preferable, and 500 to 5,000 is more preferable. .

The dihydroxy compound represented by the above formula [II] is a low molecular weight compound exhibiting liquid crystallinity, the alkylene groups R ¹ and R ² are preferably ethylene groups or propylene groups, and q and r are 0.
Or, 1 is preferred, and 4,4 ″ -dihydroxy-p-ta-phenyl, 4,4-dihydroxy-p-quaterphenyl, 4,4-di (2-hydroxyethoxy) -p-quaterphenyl and the like are preferably used. To be done.

The crystalline to liquid crystalline transition temperature of 4,4 "-dihydroxy-p-ta-phenyl is 260 ° C, that of 4,4-dihydroxy-p-quarterphenyl is 336 ° C, and 4,4"-
That of -di (2-hydroxyethoxy) -p-quaterphenyl is 403 ° C. 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 [II] may be used alone or in combination.

Liquid crystal molecules generally have high crystallinity, and as described above, 4,
4 ″ -dihydroxy-p-ta-phenyl, 4,4-dihydroxy-p-quaterphenyl and 4,4-di (2-
(Hydroxyethoxy) -p-quaterphenyl has a high transition point from the crystal to the liquid crystal state, and therefore, when these dihydroxy compounds [II] are incorporated into the polymer chain, the polymer shows unique properties.

That is, the dihydroxy compound [II] shows crystallinity,
Moreover, because of its high transition point, dihydroxy compounds [I
Even when the compounding amount of I] is small, a strong and heat-resistant physical crosslink is formed. 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.

The monohydroxy compound represented by the above formula [III] is a rigid low-molecular compound having a paraphenylene skeleton,
The melting points of these compounds are extremely high, reflecting their characteristic molecular structures. Further, 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). Is shown. Therefore, the above monohydroxy compound [II
When [I] is incorporated into the polymer terminal, it brings about very strong physical crosslinks with high heat resistance and produces a thermoplastic elastomer having excellent heat resistance.

In the monohydroxy compound represented by the above formula [III], R ³ is preferably an ethylene group or a propylene group, and n
Is preferably 0 or 1. Examples of the monohydroxy compound include 4-hydroxy-p-terphenyl,
4-hydroxy-p-quaterphenyl, 4- (2-
Hydroxyethoxy) -p-terphenyl, 4- (2-
Hydroxyethoxy) -p-quarterphenyl and the like. The monohydroxy compounds [III] may be used alone or in combination.

Polysilcone, lactone, and aromatic having two hydroxyl groups in a polyester composed of at least one of the above aliphatic dicarboxylic acid [I], aliphatic diol and dihydroxy compound [II], and monohydroxy compound [III] A hydroxycarboxylic acid may be included as a constituent component.

The above-mentioned poly-silicone has two hydroxyl groups, and a poly-silicone having two hydroxyl groups at the molecular ends is preferable. For example, dimethyl polysiloxane having two hydroxyl groups at both ends of the molecule, diethyl polysiloxane,
Examples thereof include diphenylpolysiloxane. When the number average molecular weight of the polysilicone is small, the ability to impart flexibility to the polyester produced is reduced, and when it is large, it becomes difficult to produce the polyester.
It is preferably 0, more preferably 500 to 5,000.

The lactone is one that opens a ring and reacts with an acid and a hydroxyl group to add an aliphatic chain, imparts flexibility to the polyester, and has 4 or more carbon atoms in the ring. Is preferred, and more 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, and 3-bromo-4-hydroxy. Benzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-4'-carboxy Biphenyl and the like can be mentioned, with preference given to parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid and 4-hydroxy-4'-carboxybiphenyl.

Further, the above polyester may contain an aromatic diol other than the dihydroxy compound [II] 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) Examples thereof include ethane, 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-
Examples thereof include dicarboxynaphthalene and 2,6-dicarboxynaphthalene.

The polyester comprising the hydroxy compound [II], an aliphatic diol and an aliphatic dicarboxylic acid has a dihydroxy compound [II] content of which the heat resistance is decreased when the content is low, the elastic modulus is increased when the content is high, and the flexibility is decreased, Since it becomes unsuitable as a thermoplastic elastomer, the content of the dihydroxy compound [II] is preferably 0.1 to 30 mol% in all the monomers constituting the polyester, more preferably 0.5 to 20 mol%, and It is preferably 1.0 to 10 mol%. When polyalkylene oxide or polysilicone is used as a diol other than aromatic, its constituent unit is counted as one monomer. That is, polyethylene oxide having a degree of polymerization of 10 is counted as 10 monomers.

Further, in the polyester consisting of the monohydroxy compound [III], the aliphatic diol and the aliphatic dicarboxylic acid, the heat resistance is lowered when the content of the monohydroxy compound [III] is decreased, and when the content is increased, the molecular weight of the polyester is sufficiently increased. However, since it is inferior in physical properties, it is preferably 0.1 to 20 mol% based on all monomers constituting the polyester.

The polyester composed of the dihydroxy compound [II], the monohydroxy compound [III], the aliphatic diol and the aliphatic dicarboxylic acid has a content of the hydroxy compound obtained by combining the dihydroxy compound [II] and the monohydroxy compound [III]. When the amount is small, the heat resistance is lowered, and when it is large, the flexibility is not lowered and the sufficient molecular weight is not increased. Therefore, it is preferably 0.1 to 30 mol% in all the monomers constituting the polyester. In this case, the ratio of the dihydroxy compound [II] and the monohydroxy compound [III] is preferably in the range satisfying 0 <[III] / [II] + [III] <2/3.

The polyester composed of the above constituents can be produced by any of the following generally known polycondensation methods.

A method of directly reacting a dicarboxylic acid with a diol component (which includes an aliphatic diol, a dihydroxy compound, a monohydroxy compound and the like).

A method of reacting a lower ester of dicarboxylic acid and a diol component by transesterification.

A method of reacting a dicarboxylic acid halide and a diol component in a suitable solvent such as pyridine.

A method of reacting a metal alcoholate of a diol component with a dicarboxylic acid halide.

A method of reacting an acetylated diol component and a dicarboxylic acid by transesterification.

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

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

It is also possible to regulate the structure of the polyester obtained by changing the order of addition of the dihydroxy compound [II] during polymerization. For example, a dihydroxy compound [I
When I] is charged together with the dicarboxylic acid and other diol components, a random copolymer is easily obtained,
When the dihydroxy compound [II] is charged in the latter stage of the polymerization, a block copolymer can be easily obtained. Further, a polyester synthesized in advance is kneaded with the dihydroxy compound [II] or an acetyl compound of the dihydroxy compound under reduced pressure heating, and a segment based on the dihydroxy compound [II] is introduced into the molecular chain by deethylene glycol or transesterification reaction. Is also possible.

The dicarboxylic acid anhydride used in the present invention is an anhydride of dicarboxylic acid having two carboxyl groups in the molecule, and specifically, phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, anhydrous 1 Examples include 2,2-naphthalenedicarboxylic acid, succinic anhydride, and the like. The amount of dicarboxylic acid anhydride added is 0.05 based on 100 parts by weight of polyester.
~ 10 parts by weight. A more preferable addition amount is 0.15 to 7 parts by weight. If it is less than 0.05 parts by weight, there is almost no effect of increasing the viscosity, and if it is more than 10 parts by weight, the long-term thermal stability of the molded article formed of polyester is adversely affected.

The structure of the oxazoline compound used in the present invention is not particularly limited as long as it has two or more oxazoline rings in the same molecule. Specific examples of the oxazoin compound include 2,2 ′-(1,3-phenylene) -bis (2-oxazoline), 2,2 ′-(1,2-ethylene) -bis (2-oxazoline), 2, 2 '-(1,4-butylene)-
Examples thereof include bis (2-oxazoline) and 2,2 '-(1,4-phenylene) -bis (2-oxazoline).

The addition amount of the oxazoline compound is 0.1 to 10 parts by weight based on 100 parts by weight of polyester. If the amount is less than 0.1 parts by weight, the viscosity increasing effect is scarce, and if the amount is more than 10 parts by weight, the mechanical strength such as elongation of the molded article obtained from the polyester is lowered, which is not preferable.

The thickening effect in the present invention is considered to be due to the reaction between the terminal of the polyester and the epoxy group of the oxazoline compound. A catalyst may be added to accelerate the reaction between the oxazoline compound and the polyester.

The catalyst used is an organic phosphite such as triphenyl phosphite, p-toluenesulfonic acid,
Examples include dimethyl sulfate, boron trifluoride etherate, anhydrous aluminum chloride, vanadium trichloride, vanadyl chloride, and organic halides. The addition amount is preferably 2% by weight or less with respect to the polyester.

The order of adding the dicarboxylic acid anhydride and the oxazoline compound may be either first or simultaneously, but first, the dicarboxylic acid anhydride is added to the polyester, and the mixture reaction is performed under melting, and then the oxazoline compound is added. Is preferred. The mixing temperature is preferably in the range of 130 ° C to 80 ° C. As a mixing method, a method of melt mixing using an extruder,
There is no particular limitation as long as it is a method capable of uniformly melt mixing.

The following additives may be further added to the polyester composition of the present invention as long as its practicality is not impaired.

Inorganic filler: calcium carbonate, titanium oxide, mica,
Thermal stabilizers such as talc: triphenyl phosphite, trilauryl phosphite, trisnonyl phenyl phosphite, 2
-Tert-butyl-α- (3-tert-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite etc. Flame retardant: hexabromocyclododecane, tris- (2,
3-dichloropropyl) phosphate, pentabromophenylallyl ether, etc. UV absorbers: p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone, etc. Antioxidants: butylhydroxyanisole, butylhydroxytoluene, distearylthiodipropionate, dilaurylthiodipropionate, hinder Dephenolic antioxidants Antistatic agents: N, N-bis (hydroxyethyl) alkylamines, alkylallyl sulfonates, alkylsulfates, etc. Inorganic substances: barium sulfate, alumina, silicon oxide, etc. Higher fatty acid salts: sodium stearate, Other organic compounds such as barium stearate and sodium palmitate: benzyl alcohol, bezophenone, etc. Crystallization accelerators; highly crystallized polyethylene terephthalate, polytrans-cyclohexanedimethanol terephthalate, etc. Reinforcement Fiber: Glass fiber, carbon fiber, boron fiber, silicon carbide fiber, graphite fiber, alumina fiber, amorphous metal fiber, inorganic fiber such as silicon / titanium / carbon fiber, organic fiber such as aramid fiber, etc. The polyester composition of the present invention To obtain a molded product from, a melt molding method such as press molding, extrusion molding, injection molding or blow molding is adopted. The physical properties of the molded product can be arbitrarily adjusted by the constituent components and the mixing ratio thereof, and for example, when polyester is prepared as a thermoplastic elastomer, the molded product has a film, pipe, hose, belt, packing, etc. It can be suitably used for flexible molded products, automobile parts, paints, adhesives and the like.

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

The intrinsic viscosity of the polyester composition obtained in the following examples was measured according to the following procedure.

Intrinsic viscosity [η]: Measured at 30 ° C in an o-chlorophene solvent using an Ubbelohde viscometer.

<Synthesis of 4,4-dihydroxy-p-quaterphenyl> 60.0 g of 4-hydroxy-4′-bromobiphenyl, 100 g of methanol, 300 g of 10 wt% sodium hydroxide aqueous solution and
13 g of 5 wt% palladium / carbon was added and reacted at 120 ° C. under 5 atmospheric pressure for 4 hours to obtain a disodium salt of 4,4-dihydroxy-p-quaterphenyl. After adding N, N-dimethylformamide to this solid and separating the catalyst by heating and filtering, the filtrate was acidified with dilute sulfuric acid and washed with methanol to give 4,4 of white crystalline powder.
-Dihydroxy-p-quaterphenyl (hereinafter DHQ
I got). The liquid crystal transition temperature of DHQ was 336 ° C.

<Synthesis of bis (2-bidroxyethyl) adipate (BHEA)> After stirring, dimethyl adipate 8 was placed in a glass flask with an internal volume of 1 equipped with a thermometer, a gas blowing port and a distillation port.
7.1g (0.50mol), ethylene glycol 74.4g (1.20mo
l), a small amount of calcium acetate and a small amount of antimony trioxide 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. 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> DHQ was added to the above flask at a molar ratio of 10 mol% with respect to BHEA, 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. With the reaction, ethylene glycol was distilled out, and an extremely viscous liquid was produced in the flask.

The intrinsic viscosity [η] of the obtained aliphatic polyester was 1.05.

Examples 1 and 2 and Comparative Example 100 g of the above aliphatic polyester, 0.592 g of phthalic anhydride and 0.2 g of Irganox 1010 (phenolic stabilizer, manufactured by Ciba-Geiger) were mixed, and this was mixed using a Bravelder Plastograph kneader. After melt-kneading at 230 ° C. for 3 minutes, 2,2 ′-(1,3-phenylene) -bis (2-oxazoline) was added in an amount shown in Table 1 and melt-kneading for 5 minutes. The results of measuring the intrinsic viscosity of the obtained aliphatic polyester composition are shown in Table 1.

Examples 3 and 4 Maleic anhydride 0.39 instead of 0.592 g of phthalic anhydride
An aliphatic polyester composition was obtained by mixing in the same manner as in Example 1 except that 2 g was used. The results of measuring the intrinsic viscosity of the obtained aliphatic polyester composition are shown in Table 2.

(Effects of the Invention) The polyester composition of the present invention is easily crosslinked into a polyester having a high degree of polymerization by melt molding.

The polyester thus obtained has a high crystallinity and a hard segment based on a dihydroxy compound or a monohydroxy compound having a high melting point is introduced into an aliphatic polyester mainly composed of an aliphatic dicarboxylic acid and an aliphatic diol. In addition, since it has a high degree of polymerization, it can be used for various members as a thermoplastic elastomer having excellent heat resistance, mechanical properties, molding processability and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Niki 1-5-16 Jonan-cho, Takatsuki-shi, Osaka Bell Maison 301 (72) Torasuke Saito 5-17-21 Yamatedai, Ibaraki-shi, Osaka (72) ) Inventor Hiroki Kadomachi 1-11-3 Minamikasugaoka, Ibaraki-shi, Osaka (72) Inventor Daishiro Kishimoto 2-11-20 Mishima-oka, Ibaraki, Osaka Umeyama Mansion 102 (56) References 56-18617 (JP, A)

Claims (1)

[Claims] 1. An aliphatic dicarboxylic acid having a general formula represented by the following formula [I]; an aliphatic diol; and a general formula having the following formula [I]:
A polyester containing a dihydroxy compound represented by I] and a monohydroxy compound represented by the following formula [III] as a constituent component, a dicarboxylic acid anhydride, and a bifunctional or higher functional oxazoline. A composition, wherein 0.05 to 10 parts by weight of the dicarboxylic acid anhydride and 100 parts by weight of the polyester, and the oxazoline compound
Polyester composition is contained in a proportion of 0.1 to 10 parts by _{weight: HOOC- (CH 2) n-} COOH (I) (wherein, n represents an integer of 0.) (In the formula, R ¹ and R ² independently represent an alkylene group, and p is 3
Or 4, and q and r each independently represent 0 or an integer of 1 or more. ) (In the formula, R ³ represents an alkylene group, l is 2 or 3, and m is 0 or an integer of 1 or more.).