JP3257127B2 - Polyetheresteramide elastomer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a block copolymer having a polyether chain as a soft segment and a hard segment as an aromatic polyamide. The block copolymer of the present invention can be used as a coating or coating material in various automobile and industrial parts requiring electric and heat resistance and oil resistance, and in the electric and electronic fields.

[0002]

2. Description of the Related Art There are various types of thermoplastic elastomers (hereinafter, referred to as TPEs) which have been industrially known. In particular, polyester-based TPEs are known as heat-resistant special TPEs. Has been developed. However, it has been pointed out that polyester-based TPE is inferior in dynamic heat resistance to general-purpose crosslinked rubber, that is, has a problem in creep property. In fact, even in polyester-based TPE, which is said to have the highest heat resistance, the continuous usable temperature under a dynamic environment is 100 ° C. or less,
Does not have the heat resistance to withstand crosslinked rubber.

[0003] In view of these facts, recently, heat-resistant TP
Research has been conducted to produce E. For example,
JP-A-4-293923 discloses a technique in which an aromatic dicarboxylic acid dichloride is reacted with polytetramethylene glycol in an amide solvent, and then an aromatic diamine compound is reacted. However, in the TPE obtained by this method, the polymer structure is not regulated and the sequence of the monomer is not controlled, so that the aromatic polyamide segment forming the hard segment has a distribution, which causes a problem in melt moldability. . In addition, since solution polymerization is used as a manufacturing process, additional facilities such as polymer isolation are required, and an increase in polymer manufacturing cost is unavoidable. Also, JP-A-63-15
No. 9432 discloses a method for producing a polyesteramide elastomer by reacting an aliphatic dicarboxylic acid such as an aromatic dicarboxylic acid ester, adipic acid or glutaric acid with a low molecular weight diol at a high temperature of 280 to 297 ° C. However, according to this method, a polymer having a high molecular weight cannot be obtained depending on the structure of the polymer, and only a polymer having low strength is obtained. Further, since the aliphatic polyester is used as a soft segment, there is a problem in low-temperature characteristics. Further, the hard segment is essentially a polymer of a low molecular weight diol and an aromatic dicarboxylic acid ester or the aromatic dicarboxylic acid itself, and the sequence of the monomer is not controlled. Therefore, in some cases, the melting behavior of the polymer becomes complicated, and a problem remains in the moldability.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an elastomer having excellent strength and moldability.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, have found that in melt-polycondensing a dialkyl diamide dicarboxylic acid compound with poly (alkylene oxide) glycol. The present inventors have found that a high-molecular-weight polyetheresteramide can be obtained by adding a specific solvent at an early stage of the polymerization, removing the solvent during the polymerization, and performing bulk melt polymerization.

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

[0007]

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Wherein Z represents an aromatic dicarboxylic acid residue and G represents a poly (alkylene oxide) glycol residue having a number average molecular weight of 250 to 8000.
The Z average molecular weight is 1.0 × 10 ⁵ to 2 in terms of polystyrene.
0.0 a × 10 ^5, polyetheresteramide elastomers and aromatic diamide dicarboxylic acid ester compound (a) and the number average molecular weight of 250 to 8000 poly (alkylene oxide) glycol Mz / Mw is from 3 to 20 ( b) is a polyetheresteramide elastomer produced by reacting the ester compound (a) and / or the ester compound (a) with the glycol (b).
Dissolve 0.01 g / ml or more at 5 ° C, and have a boiling point of 1 at normal pressure.
The present invention relates to a method for producing a polyetheresteramide elastomer, which comprises reacting in the presence of a solvent at 40 to 290 ° C. to obtain a prepolymer having a number average molecular weight of 10,000 or less, and then removing the solvent to carry out bulk melt polymerization. .

The present invention will be described in detail below.

The elastomer of the present invention is obtained by controlling the sequence of a monomer comprising a repeating unit of an aromatic diamide dicarboxylic acid ester and a poly (alkylene oxide) glycol as shown in the general formula (1), Shows excellent moldability. Further, since the Z-average molecular weight is high and Mz / Mw is high, it is an elastomer having excellent strength.

The aromatic diamide dicarboxylic acid diester compound (a) used in the present invention is represented by the following general formula (2):

[0012]

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(Wherein R and R 'each independently represent an aliphatic alkyl group having 1 to 13 carbon atoms, and Z represents an aromatic dicarboxylic acid residue). ,
Specifically, the following compounds

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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(Where R and R ′ each independently represent an aliphatic alkyl group having 1 to 13 carbon atoms), but are not limited thereto.

The poly (alkylene oxide) glycol (b) used in the present invention may be a poly (alkylene oxide) such as poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol. Poly (alkylene oxide) copolymer such as copolymer of ethylene oxide and propylene oxide, copolymer of ethylene oxide and tetrahydrofuran, and poly (alkylene oxide) such as poly (tetramethylene oxide) glycol and polyethylene oxide block copolymer Block copolymers and the like are exemplified, and those having a molecular weight of 250 to 8000 can be used. Among them, in order to obtain an elastomer having particularly excellent low-temperature characteristics, a molecular weight of 500 to 2 is preferred.
It is preferable to use poly (tetramethylene oxide) glycol having a molecular weight of 500 to 1
600 are more preferably used.

In the present invention, the charged molar ratio of the reaction between the aromatic diamide dicarboxylic acid ester (a) and the poly (alkylene oxide) glycol (b) is usually 0.8:
1.0 to 1.0: 0.8, but preferably 0.1 to 1.0.
95: 1.0 to 1.0: 0.95, more preferably 0.995: 1.0 to 1.0: 0.995.

In the present invention, the ester compound (a) and / or the polyetheresteramide elastomer formed by the reaction of the ester compound (a) with the glycol (b) may be used at 25 ° C. in an amount of 0.01 g / ml or more. A solvent that dissolves and has a boiling point at normal pressure of 140 to 290 ° C is used. Such solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylacetamide, N, N'-dimethylacetamide, N, N '
-Diethylacetamide, N, N'-dimethylformamide, N, N'-dimethylpropionamide,
N′-dimethylmethoxyacetamide, N, N′-diethylpropionamide, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, sulfolane,
Examples include amide solvents such as γ-butyrolactone, tetramethylurea, tetraethylurea, hexamethylphosphortriamide, N-methylcaprolactam and the like.

The above solvent is usually used in an amount of 1 to 5 with respect to the total charged amount of the aromatic diamide dicarboxylic acid ester compound (a) and the poly (alkylene oxide) glycol (b).
It is used in an amount of about 0% by weight, preferably 1 to 40% by weight, more preferably 1 to 30% by weight.

In the production method of the present invention, the above-mentioned ester compound (a) and glycol (b) are reacted in the presence of the above-mentioned solvent to obtain a prepolymer having a number-average molecular weight of 10,000 or less. Removal is performed by bulk melt polymerization, whereby an elastomer having a high Z-average molecular weight and excellent strength can be obtained. Specifically, the above-mentioned solvent, aromatic diamide dicarboxylic acid ester and poly (alkylene oxide) glycol are simultaneously charged in the initial stage of polymerization, and then a polymerization catalyst is added and uniformly stirred and mixed. The mixture is reacted for a predetermined time under pressure to produce a prepolymer. At this time, the reaction temperature was 14
The reaction is carried out at 0 to 220 ° C, preferably 160 to 210 ° C, more preferably 170 to 200 ° C, and the reaction time is 2 to 6 hours, preferably 2 to 4 hours, more preferably 2 to 3 hours.

After the preparation of the prepolymer, the solvent is gradually distilled off under reduced pressure over 30 to 60 minutes to make a transition to a bulk molten state, and at a reduced pressure of 0.1 to 2 mmHg at 210 to 270 ° C.
A high molecular weight elastomer can be obtained by carrying out the reaction at preferably 220 to 260 ° C. for 2 to 6 hours, preferably 3 to 4 hours.

Examples of the catalyst used in the above reaction include titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetra (n-propyl) titanate, tetraisopropyl titanate and tetrabutyl titanate, and di (n-butyl) tin dilaurate. ,
Dialkyltin compounds such as di (n-butyl) tin oxide and di (n-butyl) tin diacetate; oxides such as magnesium, calcium, germanium, zinc and antimony;
Acetates and sulfates are exemplified, and among them, metal alkoxides are preferably used. In addition, the amount of the catalyst to be added is usually 0.0005 to the total weight of the charged monomers.
It is used in a range of 1.0% by weight and is not particularly limited.

[0033]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The analytical instruments and methods used for analyzing the block copolymer of the present invention are as follows.

(1) GPC measurement was performed by Tosoh Corporation C
P-8000 and column with polystyrene gel 2000H
8, using a column system connected to GMHXL, flow rate 1.0
ml / min, N eluted with 20 mM lithium chloride
-Methyl-2-pyrrolidone, column temperature 40 ° C
Was measured.

(2) ¹ H-NMR spectrum and ¹³ C-
The NMR spectrum was measured by JEOL JNM-GSX270.
Using a mold, in hexafluoroisopropanol, 45
The measurement was carried out under the conditions of ° C, 400 times of integration and 18,000 times.

Reference Example 1 (Synthesis of diamide dicarboxylic acid ester [a]) A 1-liter four-necked flask equipped with a nitrogen inlet tube and a magnetic stirring blade was completely dried and purged with nitrogen, and then butyl aminobenzoate [ BAB] 99.65 g (0.5 mol) and dehydrated N-methyl-2-pyrrolidone [NMP] 200 m
l was charged. Dissolve BAB in NMP and cool on ice (0 ~
5 ° C). Next, a solution in which 40.60 g (0.2 mol) of terephthalic acid dichloride [TPC] was dissolved in 200 ml of NMP was added. After reacting at 0 to 5 ° C. for 6 hours and at room temperature for 24 hours, it was precipitated in methanol, washed with acetone, and recrystallized with NMP / toluene. Melting point 305
Diamide dicarboxylic acid ester [a] at 78.5 ° C.
1 g (76% yield) was obtained.

Example 1 A 100 ml separable flask equipped with a nitrogen inlet tube, a temperature sensor, a stirrer, and a distillation device was charged with a molecular weight of 10
29.935 g of 31 polytetramethylene glycol,
15 g of diamide dicarboxylic acid ester [a], Irga
After 0.1 g of nox1010 was charged, drying was performed at 100 ° C. under reduced pressure. Next, 0.1404 g of tetrabutyl titanate and 7 ml of NMP (13.9% by weight based on glycol and ester used) were charged into the flask, and the content was heated to 190 ° C. and reacted for 3.5 hours. The degree of vacuum was gradually increased, and the temperature was raised to 250 ° C. over one hour to remove the solvent almost completely. In addition, the number average molecular weight of the prepolymer obtained at this time was 4,200. In addition, butanol produced in the reaction was distilled off simultaneously with the removal of the solvent. Thereafter, the mixture was further reacted at 250 ° C. under a reduced pressure of 1 mmHg for 4 hours to produce a high-viscosity pale yellow polymer. When this was taken out under nitrogen, 39.8
g (98% yield) of an elastomeric polymer was obtained. The Z-average molecular weight of the obtained polymer was 55200 in terms of polystyrene by GPC measurement, Mz / Mw was 8.95, and the breaking strength was 105 kg / cm ² . FIG. 1 shows the ¹ H-NMR measurement results of the obtained polymer.
FIG. 2 shows the results of ¹³ C-NMR.

Examples 2 to 4 The reaction was carried out in the same manner as in Example 1 except that the amount of NMP was changed, to obtain polymers shown in Table 1.

Comparative Example 1 A 100 ml separable flask equipped with a nitrogen inlet tube, a temperature sensor, a stirrer, and a distillation device was charged with a molecular weight of 10
29.935 g of 31 polytetramethylene glycol,
15 g of diamide dicarboxylic acid ester [a], Irga
0.1 g of nox1010 and 0.1404 g of tetrabutyl titanate were charged and reacted at 190 ° C. for 3.5 hours. Then, the pressure was gradually increased and the temperature was raised to 250 ° C. over 1 hour. Thereafter, at 250 ° C. under a reduced pressure of 1 mmHg,
When the reaction was carried out for a time, a high-viscosity pale yellow polymer was produced. This was taken out under nitrogen to give 33.9 g (98% yield) of an elastomeric polymer. The Z-average molecular weight of the obtained polymer was 73,000 in terms of polystyrene by GPC measurement, and Mz / Mw was 9.1.
2. The breaking strength was 70 kg / cm ² .

[0041]

[Table 1]

[0042]

As described above, according to the present invention, a polyetheresteramide elastomer having a high molecular weight and a high Mz / Mw can be obtained, and the obtained elastomer has excellent strength. It is possible to apply to various fields.

Further, according to the production method of the present invention, only two kinds of raw materials, an aromatic diamide dicarboxylic acid ester compound and a poly (alkylene oxide) glycol, are used, and the reaction occurs only between the two. The sequence of the monomer is controlled, and an elastomer having excellent moldability can be obtained.

[Brief description of the drawings]

[1] ¹ H-NM elastomer obtained in Example 1
It is a figure showing an R spectrum.

FIG. 2 shows ¹³ C-NM of the elastomer obtained in Example 1.
It is a figure showing an R spectrum.

──────────────────────────────────────────────────の Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 69/44

Claims (2)

(57) [Claims] (1) The following general formula (1): (Wherein, Z represents an aromatic dicarboxylic acid residue, G represents a poly (alkylene oxide) glycol residue having a number average molecular weight of 250 to 8000), and the Z average molecular weight is 1. 0 × 10 ^{5 to} 20.0 × 10 ⁵
And a polyetheresteramide elastomer having an Mz / Mw of 3 to 20. 2. An aromatic diamide dicarboxylic acid ester compound (a) and a poly (alkylene oxide) glycol (b) having a number-average molecular weight of 250 to 8,000 are converted into an ester compound (a) and / or an ester compound (a) and a glycol. The polyetheresteramide elastomer produced by the reaction with (b) is dissolved at 25 ° C in an amount of 0.01 g / ml or more, and reacted in the presence of a solvent having a boiling point at normal pressure of 140 to 290 ° C to obtain a number average molecular weight. A method for producing a polyetheresteramide elastomer, comprising: after obtaining a prepolymer of 10,000 or less, removing a solvent and performing bulk melt polymerization.