JPH093189A - Method for producing polyesteramide elastomer - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing a polyesteramide elastomer having a simplified production process. [Structure] An amino group terminal compound having a specific structure is activated by reacting it in the presence of an amino group activator, and then reacted with an aromatic dicarboxylic acid compound having a specific structure. Method for producing polyesteramide elastomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The polyesteramide elastomer of the present invention has a high softening temperature, excellent low-temperature characteristics, oil resistance, and excellent hysteresis characteristics. Therefore, it is a sealing material, gasket, packing, hose, tube. Or, it can be used for boots, and other automobile parts,
It can be used for a wide range of applications such as industrial parts, electric / electronic parts, and structural materials.

[0002]

2. Description of the Related Art Conventionally, a thermoplastic elastomer has a problem that its softening temperature is lower than that of a cross-linkable elastomer, and deformation at a high temperature has been a problem in use. As a means for solving this problem, the present inventors have found that the polyether ester amide elastomer produced from a specific aromatic ester amide compound and polyether in JP-A-6-279583 has a high softening temperature which has not been found in the past. Is disclosed.

[0003]

The method for producing the polyether ester amide elastomer is a highly pure aromatic alkyl ester amide compound having reactivity from an aminobenzoic acid alkyl ester compound and an aromatic acid chloride compound. After the production, a two-stage production method is employed in which a polyether glycol having hydroxyl groups at both ends is reacted to carry out polymerization. Then, depending on the structure of the aromatic alkyl ester amide compound, an amide-based solvent having a high boiling point may be added as a polymerization solvent because it exhibits almost no meltability, and the added polymerization solvent is removed in the polymerization step. In the final stage of, the solvent-free state is adopted, and a complicated manufacturing method of extracting the polymer in a molten state is adopted.

It is an object of the present invention to provide a simplified and improved process for making polyesteramide elastomers.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and as a result, it has been found that an amino group terminal compound having a specific structure and an aromatic dicarboxylic acid can be used as a starting material. Further, they have found that a polyesteramide elastomer can be produced, and have completed the present invention.

That is, the present invention is represented by the following general formula (1)

[0007]

Embedded image

(Wherein G represents a residue of a diol compound) is activated by reacting an amino group terminal compound in the presence of an amino group activator, and then the following general formula ( 2)

[0009]

Embedded image

The present invention relates to a method for producing a polyesteramide elastomer, which comprises reacting with a compound represented by the formula (wherein A represents a divalent aromatic group having 6 to 18 carbon atoms).

Hereinafter, the present invention will be described in detail.

As the amino group-terminated compound used in the present invention, the 4-aminophenyl group and / or the 3-aminophenyl group represented by the general formula (1) are used at both ends and G
As the compound, any compound having a residue of the diol compound can be used. Examples of G include a polyalkylene oxide glycol residue, a polyester glycol residue, a polyolefin glycol residue, and a polysiloxane glycol residue.

As the compound represented by the structural formula (1),
For example, polytetramethylene oxide glycol-α, ω
-Bis (4-aminobenzoate), poly (3-methyltetrahydrofuran) -α, ω-bis- (4-aminobenzoate), polyoxyethylene glycol-α, ω
-Bis (4-aminobenzoate), polyoxypropylene glycol-α, ω-bis (4-aminobenzoate), α, ω-bis (4-aminobenzoate) ester of ethylene oxide-tetrahydrofuran random copolymer, propylene oxide- Tetrahydrofuran random copolymer α, ω-bis (4-aminobenzoate) ester, ethylene oxide-propylene oxide random copolymer α, ω-bis (4-aminobenzoate) ester, polytetramethylene oxide glycol-α, ω -Bis (3-aminobenzoate), polyoxyethylene glycol-α, ω-bis (3-aminobenzoate), polyoxypropylene glycol-α,
ω-bis (3-aminobenzoate), ethylene oxide-tetrahydrofuran random copolymer α, ω-bis (3-aminobenzoate) ester, propylene oxide-tetrahydrofuran random copolymer α, ω
-Bis (3-aminobenzoate) ester, α of ethylene oxide-propylene oxide random copolymer,
α, ω-bis (aminobenzoate) esters of polyoxyalkylene glycols such as ω-bis (3-aminobenzoate) ester; α, ω-bis (4- of polyoxyethylene-polytetramethylene oxide block copolymer) Aminobenzoate) ester, polyoxyethylene-polyoxypropylene block copolymer α, ω
-Bis (4-aminobenzoate) ester, α-ω of polyethylene-polyoxypropylene block copolymer
-Bis (4-aminobenzoate) ester and other polyoxyalkylene block copolymer α, ω-bis (4-
Aminobenzoate) esters; polyoxy (3-methyltetramethylene) -oxytetramethylene glycol α, ω-bis (4-aminobenzoate) ester, polyoxyethylene-oxytetramethylene glycol α, ω-bis (4- Α, ω-bis (4-aminobenzoate) esters of polyalkylene glycol diblock copolymers such as aminobenzoate) esters;
Α, ω-bis (4-aminobenzoate) ester of polyoxyethylene-polyoxytetramethylene-polyoxyethylene triblock copolymer, α of polyoxypropylene-polyoxytetramethylene-polyoxypropylene triblock copolymer , Ω-bis (4-aminobenzoate) ester, poly (oxy-3-methyltetrahydrofuran) -polyoxytetramethylene glycol-poly (oxy-3-methyltetrahydrofuran)
Polyblocks such as α, ω-bis (4-aminobenzoate) ester of triblock copolymer and α, ω-bis (4-aminobenzoate) ester of propylene-polyoxytetramethylene-polyoxypropylene triblock copolymer Alkylene glycol triblock copolymer α,
ω-bis (4-aminobenzoate) ester; α, ω-bis (3-aminobenzoate) ester of polyoxyethylene-polytetramethylene oxide block copolymer, of polyoxyethylene-polyoxypropylene block copolymer α, ω-bis (3-aminobenzoate) esters, α, ω-bis (of polyoxyalkylene block copolymers such as α, ω-bis (3-aminobenzoate) esters of polyethylene-polyoxypropylene block copolymers 3-Aminobenzoate) esters; α, ω-bis (3-aminobenzoate) ester of polyoxy (3-methyltetramethylene) -oxytetramethylene glycol, α, ω-bis (of polyoxyethylene-oxytetramethylene glycol 3-aminobenzoate) ester etc. Α, ω-bis (3-aminobenzoate) esters of a polyalkylene glycol diblock copolymer; α, ω-bis (3-amino of a polyoxyethylene-polyoxytetramethylene-polyoxyethylene triblock copolymer Benzoate) ester, α of polyoxypropylene-polyoxytetramethylene-polyoxypropylene triblock copolymer,
ω-bis (3-aminobenzoate) ester, α, ω of poly (oxy-3-methyltetrahydrofuran) -polyoxytetramethylene glycol-poly (oxy-3-methyltetrahydrofuran) triblock copolymer
-Bis (3-aminobenzoate) ester, propylene-polyoxytetramethylene-polyoxypropylene triblock copolymer α, ω-bis (3-aminobenzoate) ester and other polyoxyalkylene glycol triblock copolymer α, ω-bis (3-aminobenzoate) esters; hydrogenated polyisoprene diol-α, ω-bis (4-aminobenzoate), hydrogenated polybutadiene diol-α, ω-bis (4-aminobenzoate), hydrogen Added polyisoprene diol-
α, ω-bis (3-aminobenzoate), hydrogenated polybutadiene diol-α, ω-bis (aminobenzoate) esters of polyolefin diol such as α, ω-bis (3-aminobenzoate); polydimethylsiloxane diol- α, ω-bis (4-aminobenzoate), polymethylphenylsiloxanediol-α, ω
-Bis (4-aminobenzoate), polymethylvinylsiloxane diol-α, ω-bis (4-aminobenzoate), polydimethylsiloxane diol-α, ω-
Bis (3-aminobenzoate), polymethylphenylsiloxanediol-α, ω-bis (3-aminobenzoate), polymethylvinylsiloxanediol-α,
α, ω-bis (aminobenzoate) esters of polysiloxane diol such as ω-bis (3-aminobenzoate); poly (butylene adipate) diol-α, ω
-Bis (4-aminobenzoate), poly (hexanediol adipate) diol-α, ω-bis (4-aminobenzoate), poly (3-methylpentanediol adipate) diol-α, ω-bis (4-aminobenzoate) ), Poly (caprolactone) diol-α,
ω-bis (4-aminobenzoate), poly (butylene adipate) diol-α, ω-bis (3-aminobenzoate), poly (hexanediol adipate) diol-α, ω-bis (3-aminobenzoate), poly Α, ω-bis (of polyester diols such as (3-methylpentanediol adipate) diol-α, ω-bis (3-aminobenzoate) and poly (caprolactone) diol-α, ω-bis (3-aminobenzoate). Aminobenzoate) esters can be used, and these compounds can be used in combination of two or more kinds. In addition, polyoxytetramethylene glycol-α, ω-bis (4-aminobenzoate), polyoxypropylene glycol-is particularly excellent in polycondensation reactivity, thermal stability, and mechanical strength of the elastomer after polymerization.
It is preferable to use α, ω-bis (4-aminobenzoate) and polydimethylsiloxanediol-α, ω-bis (4-aminobenzoate).

The following compounds are exemplified as the aromatic dicarboxylic acid used in the present invention, but other dicarboxylic acids can be similarly used in combination without departing from the object of the present invention.

[0015]

Embedded image

In the polyesteramide elastomer obtained by the method of the present invention, the melting point of the obtained elastomer changes depending on the kind of the aromatic dicarboxylic acid. The melting point of the elastomer affects the molding conditions during processing and the softening temperature of the obtained elastomer. Then, terephthalic acid and / or isophthalic acid is preferably used as a material that can obtain a polyesteramide elastomer having a balance between processability and physical properties (softening temperature).

It is also possible to use two or more kinds of dicarboxylic acids for the purpose of controlling the characteristics such as the melting point of the polymer.

The amounts of the amino group-terminated compound represented by the general formula (1) and the dicarboxylic acid compound used in the present invention are not particularly limited as long as a high molecular weight polyesteramide elastomer can be obtained. . Since the high-molecular-weight polyesteramide elastomer can be obtained efficiently, the dicarboxylic acid compound is added in an amount of 0.95 to 1.30 moles per mole of the amino group terminal compound represented by the general formula (1). It is preferable to use.

In the production method of the present invention, a so-called amino group activator capable of activating the amino group of the amino group terminal compound represented by the above general formula (1) is used. As such an amino group activator, any one can be used as long as it can activate an amino group, and for example, acetic anhydride or chlorosilanes such as trialkylchlorosilane and triarylchlorosilane are preferable. Used. Then, economically, acetic anhydride is preferably used.

The addition amount of these amino group activators is not particularly limited as long as a high molecular weight polyesteramide elastomer can be obtained. Since a high molecular weight polyesteramide elastomer is efficiently obtained, 0.9 to 1.5 times mol is used with respect to the number of moles of amino groups of the amino group terminal compound represented by the general formula (1). Further, since it is unlikely that an unreacted amino group activator remains in the obtained high molecular weight polyesteramide elastomer, it is particularly preferably 0.95 to 1.3 times by mole.

The method for adding the amino group activator is not particularly limited, but when the amino group is activated, a considerable amount of heat is generated, so that the amino group activator represented by the above general formula (1) is dividedly added or added. Dropping is preferred.

As the method for producing the polyesteramide elastomer of the present invention, any polymerization method may be used without departing from the object of the present invention. Examples of such a polymerization method include melt polycondensation method, solution polycondensation method, An interfacial polycondensation method and the like can be mentioned. The melt polycondensation method is preferable because a polyesteramide elastomer can be obtained with good production efficiency. Further, in the melt polycondensation method, it is particularly preferable to use the two-step polymerization method because it is possible to easily attain a high molecular weight. Further, in the present invention, the above general formula (1)
After charging the amino group terminal compound represented by and the amino group activator and activating the amino group, the above dicarboxylic acid compound may be added to cause a polymerization reaction, or may be represented by the above general formula (1). In the state where the amino group terminal compound and the above dicarboxylic acid compound are present, an amino group activator may be charged to activate the amino group to cause a polymerization reaction.
In the present invention, since the production efficiency is excellent, an amino group activator is charged in the presence of the amino group terminal compound represented by the general formula (1) and the dicarboxylic acid compound to activate the amino group. It is preferable to carry out the polymerization reaction after that.

An example of the method for producing a polyesteramide elastomer by the melt polycondensation method is shown below, but the production method of the present invention is not limited to this. First, the amino group terminal compound represented by the general formula (1), the dicarboxylic acid compound and the amino group activator are charged to activate the amino group, and then prepolymerization for synthesizing a prepolymer is performed. As the polymerization reaction conditions for the first-stage polymerization, a polymerization temperature of 100 to 210 ° C. and a polymerization time of 0.5 to 6 hours are preferable as the polymerization reaction is likely to proceed and decomposition of the prepolymer is unlikely to occur. Then, after that, second-stage polymerization is performed to further increase the molecular weight. In the second-stage polymerization, a polymerization temperature of 170 to 27 is used as a polymerization condition in which a high molecular weight is possible and decomposition does not easily occur.
The polymerization time is preferably 0 ° C. and 0.5 to 6 hours. Further, during the second-stage polymerization, it is preferable to gradually reduce the pressure in order to more easily achieve a higher molecular weight, and it is preferable to perform the polymerization under a reduced pressure of 0.1 to 2 mmHg as the final degree of reduced pressure.

Further, a phenol-based antioxidant commonly used for the purpose of suppressing the decomposition of the polyesteramide elastomer during polymerization may be added alone or in combination as an antioxidant. It is preferably 0.05 to 2% by weight based on the total weight of the charged monomers.

The polyesteramide elastomer obtained by the production method of the present invention comprises a hindered phenol antioxidant, an aromatic amine antioxidant, a sulfur antioxidant and / or a phosphorus antioxidant as an antioxidant. Etc. can be usually added in combination.

As the flame retardant, one or more organic or inorganic flame retardants of bromine compound, aluminum compound or phosphorus compound can be added in combination.

Inorganic compounds such as silica, carbon black, calcium carbonate, and glass fibers, or inorganic fibers can be added for the purpose of maintaining rigidity at high temperatures.

[0028]

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

The test equipment and test methods used to evaluate polyesteramide elastomers in the examples are described below.

-Tensile Test- Using an Autograph DCS-100 (manufactured by Shimadzu Corporation) and a JIS No. 3 dumbbell in accordance with JIS K-6301, a tensile speed of 200 mm / min. The tensile strength test (TB) and the elongation at break (EB) were measured.

-MI (melt index)-Density correction is performed by using melt indexers L244 and X416 (manufactured by Takara Kogyo Co., Ltd.) under the conditions of 230 ° C., load 2.01 kg, die diameter 2.095 mm, and L / D = 4. It was measured.

-Hardness (Hs) -Thickness of 2 mm measured by a micro rubber hardness meter (made by Kobunshi Keiki Co., Ltd.)
The press-molded product of No. 1 was used to measure the hardness on the JIS-A hardness scale.

Example 1 Polyoxytetramethylene glycol-α, ω-bis (4-aminobenzoate) (number average molecular weight; 124
5) 4200 g (3.37 mol), terephthalic acid 630
g (3.70 mol) and 0.4 g of phenolic antioxidant (manufactured by Ciba Geigy, trade name Irganox 1330)
Was charged into a 15 l autoclave. After uniformly stirring the contents, 723 g (7.08 mol) of acetic anhydride was gradually added. At that time, although the internal temperature rose due to the activation of the amino group, it was not cooled and was heated up to 210 ° C. over 2 hours. After that, the reaction is continued for 1 hour, and the internal temperature is 235 ° C.
The temperature was raised to 30 minutes, and the reaction was carried out while removing the acetic acid produced. The pressure in the system was gradually reduced from the time when the outflow of acetic acid was no longer observed, and the degree of pressure reduction was finally 0.5 mmHg.
Was reacted for 30 minutes. Then, nitrogen was introduced into the reaction system and the system was pressurized, and the molten polyesteramide elastomer was introduced into the water tank from the lower part of the polymerization vessel and extracted in a strand form. The yield of the obtained polyesteramide elastomer was 4520 g.

The evaluation results of the obtained polyesteramide elastomer are shown in Table 1.

Examples 2 to 7 The same method as in Example 1 except that the molecular weight, kind and addition amount of the residue of the diol compound used, addition amounts of terephthalic acid and acetic anhydride were changed as shown in Table 1. To produce a polyesteramide elastomer.

The evaluation results are shown in Table 1.

[0037]

[Table 1]

[0038]

According to the present invention, it is possible to provide a method for producing a polyesteramide elastomer having a simplified production process.

Claims (1)

[Claims] (1) The following general formula (1): (Wherein G represents a residue of a diol compound) is activated by reacting with an amino group terminal compound represented by the following general formula (2): Chemical 2] (Here, A represents a divalent aromatic group having 6 to 18 carbon atoms.) A method for producing a polyesteramide elastomer, which comprises reacting with a compound represented by the formula: