JPH03252451A - Aliphatic polyester composition - Google Patents

Abstract

PURPOSE:To obtain an aliphatic polyester composition having high melt viscosity by mixing an aliphatic polyester comprising a specific constituting component with a specific amount of epoxy compound. CONSTITUTION:(B) 5-100mmol diepoxy compound is mixed into (A) 1kg aliphatic polyester composed of A1: an aliphatic dicarboxylic acid expressed by formula I (n is 0-10) is reacted with A2: aliphatic diol and A3: a dihydroxy compound expressed by formula II (R<1> and R<2> are alkylene; p is 3 or 4; q and r are 0 or >=1) and/or a monohydroxy compound expressed by formula III (R<3> is alkylene; l is 2 or 3; m is 0 or >=1). Contained amount of a compound expressed by formula II in the polyester is 0.1-30mol%, amount of a compound expressed by formula III is 0.1-20mol% and an amount in a case of co-using the both is 0.1-30mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a composition having properties as a thermoplastic elastomer, and in particular to a composition capable of obtaining a high melt viscosity (one aliphatic boone ester).

(Prior Art) Thermoplastic elastomers exhibit rubber elasticity at room temperature and can be molded, so they are widely used in various industrial products. In particular, V5 group polyesters containing dihydroxy or monohydroquine compounds having p-terphenyl or +ip mil-quaterphenyl can provide thermoplastic elastomers with excellent mechanical properties, and the applicant has An invention relating to aliphatic polyester has already been filed (for example, Japanese Patent Application No. 1-263476).

(Problems to be Solved by the Invention) Such aliphatic polyesters are usually produced by melt polycondensation, but there is an upper limit to the polymerization temperature due to the need to suppress decomposition, and there is also a limit to the capacity of the equipment. It is not easy to obtain aliphatic polyesters with high melt viscosity.

As a method of increasing the melt viscosity of a resin, a solid phase polymerization method, a method of blending an ionomer, etc. are known. The solid phase polymerization method requires a long reaction time in order to obtain a resin with sufficient viscosity, which is not economical. In the method of blending ionomers, it is not possible to obtain a product with sufficient viscosity due to poor compatibility between polyester and ionomer.

The present invention has been made in view of the above-mentioned circumstances, and its purpose is to provide an aliphatic polyester composition that can be obtained with a high melt viscosity without particularly raising the production temperature.

(Means for Solving the Problems) As a result of studying a method for obtaining a high-viscosity aliphatic polyester without particularly raising the production temperature, the present inventors found that a predetermined amount of a jepoxy compound is mixed into the aliphatic polyester. We have found that this is very effective, leading to the present invention.

That is, the aliphatic polyester composition of the present invention comprises an aliphatic dicarboxylic acid whose general formula is represented by the following formula (1); an aliphatic diol: and a dihydroxy compound whose general formula is represented by the following formula [■]; and a dihydroxy compound whose general formula is represented by the following formula [■]. (2) An aliphatic polyester composition containing an aliphatic polyester containing at least one of the monohydroxy compounds represented by 5~
It is contained in a proportion of 100 mmol, thereby achieving the above object.

HOOC-(CH2)n-Coon (I)(
(In the formula, n represents an integer of 0 to 10) (In the formula, R1 and R2 independently represent an alkylene group, and p
is 3 or 4, and q%r independently represents an integer of 0 or 1 or more. The aliphatic polyester used in the present invention has properties as a thermoplastic elastomer, has excellent heat resistance and mechanical properties, and is also excellent in moldability.

Among the above aliphatic dicarboxylic acids, when a dicarboxylic acid having a carbon number exceeding 10 is used, the physical properties of the molded article obtained from the aliphatic polynistyl deteriorate. As the dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, speric acid, and cepatic acid are preferably used.

Examples of the aliphatic diols include glycols and polyalkylene oxides. The above-mentioned glycols include ethylene glycol, fluoropylene glycol, trimethylene glycol, 1.4-flutanediol, 1.3
-butanediol, 1,5-bentanediol, 1,6
-hebotanediol, 1,7-hebutanediol, 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-diol Examples include dimethatol, and 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, etc.
These may be used alone or in combination of two or more. The number average molecular weight of polyalkylene oxide is
If it becomes too small, the ability to impart flexibility to the aliphatic polyester produced will decrease, and if it becomes too large, the physical properties such as thermal stability of the aliphatic polyester obtained will decrease.
00 to 20.000 is preferable, more preferably 500
~s, ooo.

The dihydroxy compound represented by the above formula [11] is a low molecular compound exhibiting liquid crystallinity, the alkylene groups R1 and R2 are preferably an ethylene group or a propylene group, q and r are preferably 0 or l, and the dihydroxy compound is represented by the following formula [ A] represented by 4, 4
°゛-dihydro-bovine-p-terphenyl, 4,4°''-dihydroxy-p~quaterphenyl represented by the following formula (CB), 4,4°°°-di( represented by the following formula (C)) 2-
Hydroxyethoxy)-p-quarterphenyl and the like are preferably used.

)10 Q Q Q Q 0H CB) 4.4°-dihydrotei-p-terphenyl (A) has a transition temperature from crystalline to liquid crystalline state of 260"C, 4.
．． 4°°゛-dihydroxy-p-quarterphenyl [
B] is 336°C, and 4.4°°°-di(2-
hydroxyethoxy)-p-tert-terphenyl [c]
It is 403℃. Note that the liquid crystal state refers to a state in which the compound is in a molten state and the molecules maintain an arrangement state. Each of the above dihydroxy compounds [■] may be used alone or in combination.

Liquid crystal molecules generally have high crystallinity, and as mentioned above, 4
．． 4°'-dihydroxy-p-terphenyl (A), 4
．． 4°゛'-dihydroxy-p-quarterphenyl (
B) and 4,4°°°-di(2-hydroxyethoxy)
-p-Quarterphenyl CC) has a high transition point from crystal to liquid crystal state, so when these dihydroxy compounds [11] are incorporated into the polymer chain, the polymer exhibits unique properties.

That is, since the dihydroxy compound CIr) exhibits crystallinity and has a high transition point, the dihydroxy compound CIr)
Even when the amount of I[) is small, strong and highly heat-resistant physical crosslinks are formed. As a result, it is presumed that a thermoplastic elastomer with high heat resistance can be obtained without impairing the flexibility derived from the soft segment.

The monohydroxy compounds represented by the above formula (III) are rigid low-molecular compounds having a paraphenylene skeleton, and the melting points of these compounds are extremely high reflecting their characteristic molecular structures. Furthermore, the paraphenylene skeleton is known to be effective as a mesogen for low-molecular liquid crystal compounds, and this is because the skeleton has a strong cohesive force not only in the solid state but also in the high temperature state (molten state). This shows that. Therefore, the above monohydroxy compound (I
When II) is incorporated at the end of a polymer, it results in very strong and heat-resistant physical crosslinking, producing a thermoplastic elastomer with excellent heat resistance.

In the monohydroxy compound represented by the above formula Cm), R3 is preferably an ethylene group or a propylene group, and n
is preferably O or l. Examples of the monohydroquine compound include 4-hydroxy-p-9-phenyl,
4-Hydroquine-p-quarterphenyl, 4-(2
-hydroxyethoxy)-p-terphenyl, 4-(2
-hydroxyethoxy)-p-quarterphenyl and the like. The monohydroxy compounds (m) may be used alone or in combination.

The above aliphatic dicarboxylic acid CI), aliphatic diol and dihydroxy compound (n), and monohydroxy compound (
The aliphatic polyester made of at least one of III) may contain a polysilicone having two hydroxyl groups, a lactone, and an aromatic hydrobodicarboxylic acid as constituent components.

The above polysilicone has two hydroxyl groups, preferably a polysilicone with two hydroxyl groups at the ends of the molecule, such as dimethylpolysiloxane, dimethylpolysiloxane, and dimethylpolysiloxane having two hydroxyl groups at both ends of the molecule.
Examples include diphenyl polysilo hand sanitizer. The number average molecular weight of polysilicone is 100 to 20, because if it is small, the ability to impart flexibility to the polyester produced will be reduced, and if it is large, it will be difficult to produce polyester.
．． 000 is preferable, more preferably 500~s, oo
.

It is.

The above lactone is one that opens the ring and reacts with an acid and a hydroxyl group to add an aliphatic chain, gives flexibility to polyester, and has four or more carbon atoms in the ring. is preferred, and more preferably a 5- to 8-membered ring, such as ε-caprolactone, δ-valerolactone, 7-butyrolactone, and the like.

The above aromatic hydroxycarboxylic acids impart rigidity and liquid crystallinity to polyester, and include salicylic acid, metahydroxybenzoic acid, parahydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, and 3-bromo-4-hydroxybenzoic acid. 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 Examples include piphenyl, and preferred are parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and 4-hydroxy-
4-carboxybiphenyl.

Furthermore, a dihydroxy compound (
Aromatic diols and aromatic dicarboxylic acids other than II) may be contained as constituent components.

The aromatic diols include hydroquinone, resorcinol, chlorohydroquinone, bromohydroquinone, methylhydrogynon, phenylhydroquinone, methoxyhydroquinone, phenoxyhydrogynon, 4,4°-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4, 4°-dihydroxydiphenyl sulfide, 4.4°-dihydroxydiphenyl sulfone, 4
, 4°-dihydroxybenzophenone, 4.4'-dihydrodiphenylmethane, bisphenol A, 1
．． Examples include 1-di(4-hydroxyphenyl)cyclohexane, 1,2-bis(4-hydroxyphenoxy)ethane, 1,4-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

The aromatic dicarboxylic acids include metal salts of terephthalic acid, isophthalic acid, 5-sulfoisophthalic acid, 4.4'
-Dicarboxybiphenyl, 4.4°-dicarboxydiphenyl ether, 4.4'-dicarboxydiphenyl sulfide, 4.4-dicarboxydiphenyl sulfone, 3.3°-dicarboxybenzophenone, 4.4'
-dicarboxybenzophenone, 1,2-bis (4-
Examples include carboxydiphenoxy)ethane, 1,4-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene.

In the aliphatic polyester made of the dihydroxy compound (II), aliphatic diol, and aliphatic dicarboxylic acid, when the content of the dihydroxy compound [■] decreases, the heat resistance decreases, and when the content increases, the elastic modulus increases and the flexibility decreases. The content of the dihydroxy compound [■] is preferably 0.1 to 30 mol%, more preferably 0.5 to 30 mol%, based on the total monomers constituting the polyester. It is 20 mol%, more preferably 1.0 to 10 mol%. In addition, when polyalkylene oxide or polysilicone is used as a diol other than aromatic, the constituent unit thereof is counted as a monomer. That is, polyethylene oxide with a polymerization degree of 1O is 1
Count as 0 monomer.

In addition, in the aliphatic polyester made of the monohydroxy compound Cm), an aliphatic diol, and an aliphatic dicarboxylic acid, the heat resistance decreases when the content of the monohydroxy compound [m) decreases, and when the content increases, the molecular weight of the aliphatic polyester decreases. 0.1 to 2 of the total monomers constituting the aliphatic polyester because it does not increase sufficiently and has poor physical properties.
It is preferable to set it to 0 mol%. In addition, the aliphatic polyester consisting of the dihydroxy compound [■], monohydroxy compound Cm), aliphatic diol, and aliphatic dicarboxylic acid contains a hydroxy compound that is a combination of a dihydroxy compound (n) and a monohydroxy compound (m). If the amount is too small, the heat resistance will be lowered, and if the amount is too much, the flexibility will be reduced and a sufficient increase in molecular weight will not be achieved.

In this case, the ratio of the dihydroxy compound (II) to the monohydroxy compound (m) is preferably in a range that satisfies 0<(m)/(H]+(m)<2/3.

The aliphatic polyester consisting of the above components is
It can be produced using any of the generally known polycondensation methods listed below.

■ A method of directly reacting dicarboxylic acid with a diol component (including aliphatic diols, dihydroxy compounds, monohydroxy compounds, etc.).

■A method in which lower esters of dicarboxylic acids and diol components are reacted using transesterification.

■A method in which a dicarboxylic acid halide and a diol component are reacted in a suitable solvent such as pyridine.

■A method in which a metal alcoholade, which is a diol component, is reacted with a dicarboxylic acid halide.

■A method of reacting an acetylated diol component with a dicarboxylic acid using transesterification.

When performing polycondensation, catalysts that are generally used in producing polyester may be used.

This catalyst includes lithium, sodium, potassium,
Cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt,
germanium, tin, lead, antimony, arsenic, cerium,
Examples include metals such as boron, cadmium, and manganese, their organometallic compounds, organic acid salts, metal alkoxides, and metal oxides.

Particularly preferred catalysts include calcium acetate, diacyltin, tin tetraacyl, dibutyltin dilaurate, dimethyltin maleate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanate, germanium dioxide,
and antimony trioxide. Two or more of these catalysts may be used in combination. In addition, water produced as a by-product during polymerization,
In order to efficiently distill off alcohols, glycols, etc. and obtain high molecular weight polymers, the reaction system must be kept at lm in the late stage of polymerization.
It is preferable to reduce the pressure to below Hg. The reaction temperature is generally 150-350°C.

It is also possible to control the structure of the resulting polyester by changing the order of addition of the dihydroxy compound [■] during polymerization. For example, dihydroxy compound (I
When I) is added together with the dicarboxylic acid and other diol components, a random copolymer is easily obtained,
If dihydroxy compound (II) is added in the late stage of polymerization, a block copolymer can be easily obtained.Also, if the dihydroxy compound (II) or an acetyl compound of the dihydroxy compound is kneaded with the pre-synthesized polyester under reduced pressure and heating. It is also possible to introduce a segment based on the dihydroxy compound (n) into the molecular chain by removing ethylene glycol or transesterification.

The jepoxy compound used in the present invention may have two epoxy groups in the same molecule, and its structure is not particularly limited. Specific examples of the jepoxy compound include compounds represented by the following general formulas (1) and (2).

0 In formula (1) and formula (2), R is an alkylene group, a divalent ring group, a divalent aromatic group, or the general formula: -(RaO
)tRJ is a polyether group represented by (RJ has 2 to 2 carbon atoms)
6 represents an alkylene group or a phenylene group, and t is 1 to 6.
(indicates an integer of 20).

The amount of the jepoxy compound used varies depending on the required melt viscosity value of the aliphatic polyester composition, but if the amount of the jepoxy compound added is as small as 5 mmol per Ikg of aliphatic polyester, it will have an effect of increasing the melt viscosity. However, if the amount is more than 100 mmol, the mechanical properties and the like of the molded article formed from the obtained composition will deteriorate, so the amount is limited to 5 to 100 mmol per Ikg of aliphatic polyester.

The thickening effect in the present invention is thought to be due to the reaction between the terminal end of the aliphatic polyester and the epoxy group of the jepoxy compound. A catalyst may be added to promote the reaction between the jepoxy compound and the aliphatic polyester.

Catalysts used include amine compounds such as ethylenediamine, propylenediamine, diethylenetriamine, triethylenepentamine, p-phenylenediamine, p-phenylenediamine, dicyandiamide, and piperidine, silicic acid, maleic acid, fumaric acid, and maleic anhydride. ,
Organic acids such as phthalic anhydride, succinic acid, etc., with 10 carbon atoms
Examples include metal salts of the above-mentioned monocarboxylic acids or dicarboxylic acids of Group 1-a or Group I-a of the Periodic Table of the Elements. The preferred amount of catalyst added is 1 to 50 mmol per kg of aliphatic polyester. If the amount of the catalyst is more than 50 mmol, the melt viscosity of the resin decreases, and the resin tends to be colored burnt brown.

The following additives may be further added to the aliphatic polyester composition of the present invention within a range that does not impair its practicality. That is, inorganic fillers such as calcium carbonate, titanium oxide, mica, and talc, triphenyl phosphite, trilauryl phosphite, trisnonylphenyl phosphite, 2-tert-butyl-α-(3-tert
Heat stabilizers such as t-butyl-4-hydroxyphenyl)-p-cumenylbis(p-nonylphenyl) phosphite, hexabromocyclododecane, tris-(2,3-dichloropropyl) phosphate, pentabromophenyl allyl ether, etc. UV absorbers such as flame retardants, p-tert-butylphenyl sarinlate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and 2.4.5-trihydroxybutyrophenone. , butyl hydroxyanisole, butyl hydrobovine citoluene, distearyl thiodipropionate, dilauryl thiodipropionate, hindered phenolic antioxidants, etc.
Antistatic agents such as N,N-bis(hydroxyethyl)alkylamines, alkylarylsulfonates, and alkylsulfanates; inorganic substances such as barium sulfate, alumina, and silicon oxide; sodium stearate, barium stearate, and sodium palmitate; Higher fatty acid salts; organic compounds such as benzyl alcohol and benzophenone;
Examples include crystallization accelerators such as highly crystallized polyethylene terephthalate and polytrans-cyclohexane dimetatool terephthalate.

The method for producing the aliphatic polyester composition of the present invention is not particularly limited, and after mixing the aliphatic polyester, the jepoxy compound, and, if necessary, a catalyst, etc., the composition is melt-kneaded using a commonly known method. Ru. For example, there are melt-kneading methods using an extruder, a Banbury mixer roll, a kneader, and the like. The temperature during melting cross-wire is 150 to 280
A range of ``C'' is preferred.

In order to obtain a molded article from the obtained aliphatic polyester composition, melt molding methods such as press molding, extrusion molding, injection molding, and blow molding are employed. Molded products are used for mechanical parts, electronic parts, films, pipes, etc.

(Example) The present invention will be explained below based on examples.

In addition, the intrinsic viscosity of the aliphatic polyester composition obtained in the following examples was measured according to the following method.

Intrinsic viscosity [η]: Measured at 30''C in o-chlorophenol solvent using an Ubbelohde viscosity tube.

Aliphatic polyester was prepared by the following method.

(Synthesis of 4,4'''-dihydroxy-p-quarterphenyl) To 60.0 g of 4-hydroboxy-4-bromobiphenyl,
100 g of methanol, 300 g of 10 wt% aqueous sodium hydroxide solution, and 5 vt% palladium/carbon 1
By adding 3 g of 4.4°゛°-dihydroxy-p-
Disodium salt of quarterphenyl was obtained. After adding N,N-dimethylformamide to this solid and heating and filtering to separate the catalyst, the filtrate was precipitated with dilute sulfuric acid, methanol was washed, and 4.4"' of white congealing powder was obtained. -dihydroxy-p-quarterphenyl (hereinafter referred to as DHQ) was obtained.The liquid crystal transition temperature of DHQ was 336°C.

〈Bis(2-hydroxyethyl)adipate (BFI
Synthesis of EA) In a glass flask with an internal volume of 1a equipped with a stirrer, a thermometer, a gas inlet, and a distillation port, dimethyl adipate 8
7.1 g (0, SO mol), 4.4 g (1,20 mol) of ethylene glycol, and small amounts of calcium acetate and antimony dioxide as catalysts were added. After purging 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 out from the flask, and bis(2-hydroxyethyl) adipate (hereinafter referred to as BFIEA) was produced.

<Preparation of aliphatic polyester> DHQ was added to the above flask at a molar ratio of 10 mol % to BHEA, the temperature of the flask was raised to 300°C, and the reaction was allowed to proceed in this state for about 1 hour. Next, the distillation port was connected to a vacuum vessel, and the flask was reacted for 2 hours while the pressure inside the flask was reduced to 1+wHg. During the reaction, ethylene glycol was distilled out, and an extremely viscous liquid was formed in the flask.

The intrinsic viscosity [η] of the obtained aliphatic polyester is 1.
It was 10.

1 to 4 and ratio 1 to 2 11 [g of the above aliphatic polyester, the amount of the jepoxy compound and catalyst shown in Table 1, and 5 g of Irganox 1010 (phenolic stabilizer, manufactured by Ciba Geigy) The mixture was extruded at 240° C. using a Brabender blastograph extruder, cooled with water, and then cut into pellets. Note that the residence time in the extruder was 4 minutes.

The intrinsic viscosity of the obtained pellet was measured. The results are shown in Table 1. Next, the obtained pellet was heat-treated at 220° C. for 5 hours in an oven purged with nitrogen.

The intrinsic viscosity of the pellet after treatment was measured. The results are shown in Table 1. In addition, as shown in Table 1, in Comparative Example 2,
Gelation occurred when the aliphatic polyester and the jepoxy compound were melt-mixed, and the resulting product did not dissolve in 0-chlorophenol, making it impossible to measure the intrinsic viscosity.

(Margin below) Note 1) Jepoxy compound: Sato Shonin Note 2) Gelation occurred and it did not dissolve into 0-chlorophenol.

(Effects of the Invention) According to the present invention, a polyester with a high melt viscosity can be obtained without particularly raising the melting temperature during production of aliphatic polyester, and the resin does not decompose or deteriorate during production. Group polyesters can be obtained, and expensive equipment is not particularly required.

The aliphatic polyester composition thus obtained is
Segments based on dihydroxy compounds and monohydroxy compounds with high crystallinity and high melting points are introduced into the aliphatic polyester mainly composed of aliphatic dicarboxylic acids and aliphatic diols, resulting in improved heat resistance and mechanical properties. It can be used in various parts as a thermoplastic elastomer with excellent moldability.

that's all

Claims (1)

[Claims] 1. An aliphatic dicarboxylic acid whose general formula is represented by the following formula [I]; an aliphatic diol; and a dihydroxy compound whose general formula is represented by the following formula [II] and a dihydroxy compound represented by the following formula [III]. An aliphatic polyester composition containing an aliphatic polyester having at least one of monohydroxy compounds as a constituent component, and a diepoxy compound, wherein the diepoxy compound is contained in an amount of 5 to 1 kg per 1 kg of the aliphatic polyester. Aliphatic polyester composition containing ~100 mmol: HOOC-(CH_2)_n-COOH [I] (In the formula, n represents an integer from 0 to 10) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼[II] (In the formula, R^1 and R^2 independently represent an alkylene group, p is 3 or 4, and q and r are independently 0 or 1
▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] (In the formula, R^3 represents an alkylene group, and l is 2 or 3.
(where m represents an integer of 0 or 1 or more).