JP3135427B2 - Method for producing polyesteramide elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyesteramide elastomer having excellent mechanical strength, chemical resistance and transparency at temperatures ranging from room temperature to high temperature.

[0002]

2. Description of the Related Art In recent years, materials having excellent oil resistance, chemical resistance, and flexibility have been demanded in the fields of automobiles and industry. In particular, there is a strong demand for materials for hoses or tubes having excellent oil resistance and gasoline resistance.

At present, for such applications, butadiene-
Vulcanized rubber such as acrylonitrile copolymer rubber (NBR) and plasticized nylon are used. However, in recent years, environmental problems have become serious and recyclable materials have been heavily used and the use of non-recyclable materials has been evaded.In addition, there is a risk of environmental pollution in the manufacturing and processing processes. Is not preferred.

[0004] Plasticized nylon is disclosed, for example, in Japanese Patent Application Laid-Open No. 60-173047, but its physical properties are changed by extraction of the plasticizer in a solvent having a strong affinity for the plasticizer. In addition, there is a limit to plasticization, and it is not appropriate when more flexibility is required, and furthermore, the low temperature properties are inferior because the nylon material has a substantially high glass transition temperature. There is.

A polyamide elastomer has been proposed as a material which has the same degree of chemical resistance as nylon and is required to have flexibility (Japanese Patent Application Laid-Open No. 61-247732).
However, this is a polyether amide in which the hard segment is made of nylon and the soft segment is made of polyether, and contains a significant proportion of polyether segments, so that the chemical resistance is reduced, and the chemical resistance is reduced. Cannot be used for applications that require it.

[0006] In addition to the above polyamide elastomer, a polyesteramide elastomer has been proposed as a material having both chemical resistance and flexibility. Polyester amide elastomer is a material already known as having excellent chemical resistance and being more flexible than plasticized nylon.

A method for producing a polyesteramide elastomer is disclosed, for example, in Japanese Patent Publication No. 36858/1986. According to this method, it is necessary to use a saturated dimer fatty acid and the reaction time is long. This method is not preferable as a method for industrially obtaining a polyesteramide elastomer.

Further, Japanese Patent Publication No. 46-2268 discloses that
A method for producing a copolymer comprising a polyamide and a polyester is disclosed. Poly-2,2-dimethyl-1,3-propanediol sebacate is proposed as a suitable polyester in this method. However, when a polyesteramide elastomer is produced using sebacic acid as a main component, the polyesteramide elastomer has a disadvantage that it easily swells in solvents such as oil and gasoline, and has a disadvantage that chemical resistance is reduced. However, they have a problem that they are more expensive than fatty acids. Also, when adipic acid is used instead of sebacic acid to form a polyester with 2,2-dimethyl-1,3-propanediol, the reactivity decreases and the polymerization takes time. There is a disadvantage that it is difficult to block.

Furthermore, most of the nylons used in this method are of low molecular weight, and when a polyesteramide elastomer is produced by using such a low molecular weight nylon, high-temperature properties, particularly high-temperature strength, are inferior. ing.

[0010]

As described above, although polyesteramide elastomers have been receiving attention as a material having excellent chemical resistance and flexibility, a method for efficiently producing the same has not been established. Therefore, there has been no application development utilizing the excellent properties of polyesteramide. In view of the above, an object of the present invention is to efficiently provide a polyesteramide elastomer having excellent chemical resistance and flexibility and having sufficient mechanical strength.

[0011]

Means for Solving the Problems The present inventors dissolve a polyamide having a constant molecular weight in a polyester component shown below and polymerize it in a uniform state, thereby achieving excellent chemical resistance and mechanical strength. The present inventors have found that a polyesteramide elastomer can be obtained and completed the present invention.

SUMMARY OF THE INVENTIONIs composed mainly of adipic acid
Aliphatic dicarboxylic acids and ethylene glycol and butyrate
At least one selected from the group consisting of
And one combined with neopentyl glycol
Consists of aliphatic diol as the main componentPolyester composition
100 parts by weight of ingredientsToThe reduced viscosity is 1.8 to 7.0 (1 g
/ DL 98% sulfuric acid solution, 20 ° C)
Not less than 25 parts by weightIs dissolved here,3-6 pieces
Hydroxyl-containing polyol, 3-4 carboxyls
Group-containing polycarboxylic acid, and hydroxyl group and carboxy
And an oxyacid having 3 to 6 groups.
At least one selected from the group
Branching agent(However, if two or more components are selected,
A branching agent mainly composed of two or more components)
Of 0.1 to 2. per 100 moles of aliphatic dicarboxylic acid.
5 molDissolve,Esterification of polyester component
The reaction was performed at 150-230 ° C.rear,The resulting transparent homogeneous solution
The liquid is polymerized under reduced pressure at 200 to 260 ° C.Specially
For the production of polyester amide elastomers
is there.

The present invention will be described in detail below. The monomers constituting the polyester of the polyesteramide elastomer of the present invention are aliphatic dicarboxylic acids and aliphatic diols.

As the aliphatic dicarboxylic acid according to the present invention,
In addition to adipic acid, various aliphatic dicarboxylic acids can be used as long as the physical properties of a molded article obtained from the resulting polyesteramide are not impaired. Such materials include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, suberic acid, sebacic acid and the like.

The aliphatic diol according to the present invention includes, in addition to ethylene glycol, butylene glycol and neopentyl glycol, other glycols and polyalkylene oxides as long as the physical properties of the molded product obtained from the resulting polyesteramide are not impaired. Can be used.

As such glycols, for example, propylene glycol, trimethylene glycol, 1,3
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,7-heptanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like. .

Examples of such polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide and the like.

In the present invention, the preferred range of the amount of neopentyl glycol charged is 90 to 20 of the diol component.
Mol%. If it exceeds 90 mol%, the blocking property decreases and the strength at high temperatures decreases. If the amount is less than 20 mol%, the polymerization time is increased due to a decrease in the polymerization rate, the blocking property is reduced, and the high temperature properties are reduced. If the amount is less than 20 mol%, crystallization of the polyester component occurs,
Lack of rubbery properties.

In the present invention, the mixing ratio of the aliphatic dicarboxylic acid and the aliphatic diol, which are the constituent components of the polyester, can be appropriately determined within the range in which the effects of the present invention can be obtained. Such a mixing ratio may be, for example, 100 parts by weight of the aliphatic dicarboxylic acid and 15 parts of the aliphatic diol.
0 to 160 parts by weight, etc., but not particularly limited thereto.

As the branching agent used in the present invention,
In order to increase the molecular weight of the polyesteramide, increase the viscosity, and improve the mechanical strength, a polyol having 3 to 4 hydroxyl groups, a polycarboxylic acid having 3 to 4 carboxylic acids, and a hydroxyl group and a carboxylic acid are used. Has a radix of 3 to 6
At least one of the oxyacids is added.

Examples of such polyols include glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakishydroxymethylcyclohexane, tris (2-hydroxyethyl ) Isocyanurate, dipentaerythritol and the like.

Further, as such a polycarboxylic acid,
For example, hemi-mellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid and the like can be mentioned.

Examples of such oxyacids include citric acid, tartaric acid, 3-hydroxyglutaric acid, trihydroxyglutaric acid and 4-β-hydroxyethylphthalic acid.

These branching agents include aliphatic dicarboxylic acids 10
0.1 to 2.5 mol is added per 0 mol. 0.1
When the amount is less than the mole, the molecular weight of the obtained polyesteramide elastomer does not increase, and an elastomer having excellent mechanical strength cannot be obtained. When the amount exceeds 2.5 mol, gelation occurs, so that the amount is limited to this range.

The polyamide used in the present invention is:
It has an amide bond in the polymer main chain and has a reduced viscosity of 1.8 to 7.0 (in a 1 g / dL 98% sulfuric acid solution,
20 ° C.), which can be heated and melted, and whose swelling degree with respect to a toluene / isooctane mixed solvent (weight ratio 1/1) is preferably not more than 5.0% by weight change rate.

As such a polyamide, for example,
4-nylon, 6-nylon, 6,6-nylon, 11
Nylon, 12-nylon, 6,10-nylon,
Aliphatic nylons such as 6,12-nylon, isophthalic acid, terephthalic acid, meta-xylylenediamine, 2,2-
Bis (paraaminocyclohexyl) propane, 4,4 '
Polyamides obtained by polymerizing aromatic, alicyclic or side-chain substituted aliphatic monomers such as -diaminodicyclohexylmethane, 2,2,4- or 2,4,4-trimethylhexamethylenediamine.

When a polyamide having a reduced viscosity of less than 1.8 is used, the resulting polyesteramide has insufficient mechanical strength at high temperatures. If it is larger than 7.0, the solubility of nylon in the polyester constituents decreases, so that the synthesis of polyesteramide becomes difficult.

The proportion of the polyamide used in the present invention is at least 5 parts by weight and less than 25 parts by weight based on 100 parts by weight of the polyester component. When the charge ratio is less than 5 parts by weight, the mechanical strength of the molded product obtained from the produced polyesteramide becomes insufficient, and when the charge ratio is 25 parts by weight or more, an elastomer having good rubber elasticity is obtained. Unsuitable for

In the present invention, it is necessary to dissolve the polyamide in the polyester component to form a transparent and homogeneous solution. In a heterogeneous state, the reaction does not proceed efficiently. The melting temperature is preferably from 150 to 230C. Fifteen
When the temperature is lower than 0 ° C., it is difficult to dissolve the polyamide. If the temperature is higher than 230 degrees, a decomposition reaction may occur, which is not preferable.

The transparent homogeneous solution in which the polyamide obtained as described above is dissolved is subjected to an esterification reaction at 150 to 230 ° C. Next, polymerization is performed, and the polymerization is performed under reduced pressure, preferably at 1 mmHg or less at 200 to 260 ° C. When the temperature is lower than 200 ° C., the reaction rate is low and the polymerization viscosity is high, so that efficient polymerization becomes difficult. When the temperature is higher than 260 ° C., decomposition reaction and coloring occur, which is not preferable.

In the polymerization, a catalyst generally used for producing a polyester can be used. Such catalysts include, for example, lithium, sodium, potassium, cesium, magnesium, calcium, barium,
Metals such as strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, zirconium, their organometallic compounds, organic acid salts, metal alkoxides, metal oxides, etc. No.

Particularly preferred catalysts are tetrabutoxytitanium, calcium acetate, stannous diacyl, stannous tetraacyl, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyl Titanate, tetrapropoxytitanate, titanium (oxy) acetylacetonate, germanium dioxide, tungstic acid, antimony trioxide, and the like can be mentioned. Two or more of these catalysts may be used in combination.

In the above polymerization, a stabilizer may be used. Examples of such a stabilizer include 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) -propionyloxy] -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane and other hindered phenolic antioxidants; 4-di-t-butylphenyl) phosphite, trilauryl phosphite, 2-t
-Butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipro Heat stabilizers such as pionate, pentaerythryltetrakis (3-laurylthiopropionate), and ditridecyl 3,3'-thiodipropionate are exemplified.

The polyester amide according to the present invention is obtained by the above series of operations. In o-chlorophenol, the intrinsic viscosity of the polyesteramide at 30 ° C. is
0.9 or more is preferable. When it is less than 0.9, the mechanical strength of the obtained molded product is insufficient.

The polyesteramide elastomer according to the present invention can be molded by press molding, extrusion molding, injection molding, blow molding, etc., and is suitable for automobile parts, electric / electronic parts, industrial parts, sporting goods, medical supplies and the like. Used for Examples of the automobile parts include boots such as constant velocity joint boots and rack and opinion boots, ball joint seals, safety belt parts, bumper fascias, emblems, moldings, and the like.
Examples of the electric / electronic parts include wire covering materials, gears, rubber switches, membrane switches, tact switches, O-rings, and the like. As industrial parts,
For example, a hydraulic hose, a coil tube, a sealing material, a packing, a V-belt, a roll, an anti-vibration / vibration control material, a shock absorber, a coupling, a diaphragm and the like can be mentioned. Examples of sporting goods include shoe soles and ball balls. As medical supplies, for example,
Examples include a medical tube, an infusion bag, and a catheter. In addition, elastic fibers, elastic sheets, composite sheets,
Has a wide range of applications in industrial fields such as hot melt adhesives and materials for alloying with other resins.

[0036]

The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1 161 parts by weight of adipic acid, 119 parts by weight of butylene glycol, and 137 parts by weight of neopentyl glycol (50/5 molar ratio of butylene glycol to neopentyl glycol)
0, the charge ratio of adipic acid component / diol component is 1 / 2.4 in molar ratio), 6-nylon (T85, manufactured by Toyobo Co., Ltd.)
0,98% sulfuric acid, reduced viscosity at 20 ° C 3.5) at 40 ° C, 40 parts by weight, pentaerythritol as a branching agent 0.75 parts by weight (0.5 mole per 100 moles of adipic acid), and tetrabutoxytitanium at 0. 25 parts by weight and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) as a stabilizer
After adding 0.4 parts by weight of benzene and 0.4 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, the temperature of the reaction system was raised to 200 ° C. under nitrogen, and 10 minutes later, nylon was dissolved. , Resulting in a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 1 mmHg or less in 10 minutes. As a result of a polycondensation reaction for 1 hour in this state, a transparent resin was obtained.

The resulting resin was measured for intrinsic viscosity [η], surface hardness (Shore A), melting point, tensile strength at break and tensile elongation at break. Table 1 shows the measurement results. Intrinsic viscosity [η]
Was determined by measuring the sample in an o-chlorophenol solvent at 30 ° C. using an Ubbelohde viscosity tube. The surface hardness was measured using an A type durometer according to ASTM D2240.

The melting point was measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). The tensile strength at break and the tensile elongation at break were measured using a No. 3 dumbbell prepared by injection molding (injection pressure 1500 kgf / cm ² , mold temperature 70 ° C., cylinder temperature 200 ° C.) of the obtained resin according to JIS K-6301. (Room temperature, 2
3 ° C.).

Example 2 The procedure of Example 1 was repeated except that the addition amount of 6-nylon (manufactured by Toyobo Co., Ltd., T850, 98% sulfuric acid, reduced viscosity at 20 ° C. 3.5) was 80 parts by weight. Polymerization was performed to obtain a resin. The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Example 3 A resin was obtained by polymerization in the same manner as in Example 1 except that 1.2 parts by weight (0.8 mol per 100 mol of adipic acid) of a branching agent pentaerythritol was added. The same test as in Example 1 was performed on this resin. Table 1 shows the results
It was shown to.

Example 4 2.5 parts by weight of glycerin (adipic acid 10
Example 1 except that 2.5 mol per 0 mol) was used.
Polymerization was carried out in the same manner as in the above to obtain a resin. The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Example 5 A resin was obtained in the same manner as in Example 1 except that 0.5 parts by weight of 3-hydroxyglutaric acid (0.3 mol per 100 mol of adipic acid) was used as a branching agent. The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Example 6 The procedure of Example 1 was repeated except that 0.7 part by weight of 1,1,2,2-ethanetetracarboxylic acid (0.3 mol per 100 mol of adipic acid) was used as a branching agent. A resin was obtained. The same test as in Example 1 was performed on this resin.
The results are shown in Table 1.

Example 7 As a diol component, 82 parts by weight of ethylene glycol, 137 parts by weight of neopentyl glycol (50/50 molar ratio between ethylene glycol and neopentyl glycol), and the charged ratio of adipic acid component / diol component was 1 in molar ratio. /
A resin was obtained in the same manner as in Example 1 except that the value was changed to 2.4.
The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Example 8 161 parts by weight of adipic acid, 69 parts by weight of butylene glycol, 80 parts by weight of neopentyl glycol (molar ratio of butylene glycol to neopentyl glycol 50/50,
The charge ratio of adipic acid component / diol component is 1 / molar ratio.
A resin was obtained in the same manner as in Example 1 except that 1.4) was used. The same test as in Example 1 was performed on this resin.
The results are shown in Table 1.

Example 9 161 parts by weight of adipic acid, 144 parts by weight of butylene glycol, 166 parts by weight of neopentyl glycol (50/5 molar ratio of butylene glycol to neopentyl glycol)
0, and a resin was obtained in the same manner as in Example 1 except that the charge ratio of the adipic acid component / diol component was 1 / 2.9). The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Example 10 161 parts by weight of adipic acid, 36 parts by weight of butylene glycol, and 233 parts by weight of neopentyl glycol (the molar ratio of butylene glycol to neopentyl glycol is 15/8)
5. A resin was obtained in the same manner as in Example 1 except that the charging ratio of the adipic acid component / diol component was 1 / 2.4) in molar ratio. The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Example 11 161 parts by weight of adipic acid, 178 parts by weight of butylene glycol, 69 parts by weight of neopentyl glycol (75/2 molar ratio of butylene glycol to neopentyl glycol)
5. A resin was obtained in the same manner as in Example 1 except that the charging ratio of the adipic acid component / diol component was 1 / 2.4) in molar ratio. The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Example 12 Instead of 40 parts by weight of 6-nylon (T850, manufactured by Toyobo), 6-nylon (A1050, manufactured by Unitika)
A resin was obtained in the same manner as in Example 1, except that 40 parts by weight of a reduced viscosity at 98 ° C. in 98% sulfuric acid 6.2) was used. The same test as in Example 1 was performed on this resin.
The results are shown in Table 1.

Example 13 Instead of 40 parts by weight of 6-nylon (manufactured by Toyobo Co., Ltd., T850), 6,6-nylon (manufactured by Unitika, MRAN)
A resin was obtained in the same manner as in Example 1 except that YL A226, reduced viscosity in 98% sulfuric acid at 20 ° C. 2.6) 40 parts by weight was used. The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Comparative Example 1 A resin was obtained in the same manner as in Example 1 except that 20 parts by weight of 6-nylon was used. No increase in viscosity was observed, and an elastomer having good elongation and strength could not be obtained. The same test as in Example 1 was performed on this resin.
The results are shown in Table 1.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that 4.5 parts by weight (3.0 mol per 100 mol of adipic acid) of a branching agent pentaerythritol was added. Because of this, it was difficult to mold the obtained resin. The same test as in Example 1 was performed on this product. The results are shown in Table 1.

Comparative Example 3 As a branching agent, 3.5 parts by weight of glycerin (adipic acid 10
Example 1 except that 3.5 mol per 0 mol) was used.
Polymerization was carried out in the same manner as described above, but it was difficult to mold the obtained resin because gelation occurred during the polymerization.
The same test as in Example 1 was performed on this product. The results are shown in Table 1.

Comparative Example 4 Polymerization was carried out in the same manner as in Example 1 except that 0.1 part by weight of pentaerythritol (0.07 mol per 100 mol of adipic acid) was used as a branching agent. An elastomer having good elongation and good strength could not be obtained. The same test as in Example 1 was performed on this product. The results are shown in Table 1.

Comparative Example 5 Example 1 was repeated except that 40 parts by weight of low molecular weight nylon having a reduced viscosity at 98 ° C. of 1.5 in 98% sulfuric acid was used.
A resin was obtained in the same manner as described above. The same test as in Example 1 was performed on this resin. The results are shown in Table 1.

Comparative Example 6 Pebax 25, a polyetheramide elastomer
33 (manufactured by Toray Industries, Inc.) and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 7 Polymerization was carried out in the same manner as in Example 1 except that only 238 parts by weight of butylene glycol was used as the diol component. However, the product was brittle and had poor rubber-like properties.
The same test as in Example 1 was performed on this product. The results are shown in Table 1.

[0059]

[Table 1]

[0060]

According to the present invention, a polyamide is dissolved in a polyester component consisting of adipic acid and a specific diol and a branching agent under specific conditions and polymerized in a uniform state, whereby the temperature range from room temperature to high temperature is increased. , A polyesteramide elastomer having excellent mechanical strength and excellent flexibility can be easily obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 69/00-69/50 C08G 63/00-63/91

Claims (1)

(57) [Claims] 1. A fat consisting mainly of that combination of at least one neopentyl glycol selected from the group consisting of aliphatic dicarboxylic acids and ethylene glycol and butylene glycol as a main component adipic acid 5 parts by weight or more and less than 25 parts by weight of a polyamide having a reduced viscosity of 1.8 to 7.0 (1 g / dL 98% sulfuric acid solution at 20 ° C.) are dissolved in 100 parts by weight of a polyester component composed of an aromatic diol. A group comprising a polyol having 3 to 6 hydroxyl groups, a polycarboxylic acid having 3 to 4 carboxyl groups, and an oxyacid having 3 to 6 hydroxyl groups and carboxyl groups A branching agent containing at least one component selected from the group consisting of two or more
Is a component mainly composed of two or more of these components.
Release agent) in an amount of 0.1 per 100 moles of aliphatic dicarboxylic acid.
~ 2.5 moles, and the esterification reaction of the polyester constituents was 150 ~ 23.
A method for producing a polyesteramide elastomer, comprising conducting the reaction at 0 ° C., and then polymerizing the obtained transparent homogeneous solution at 200 to 260 ° C. under reduced pressure.