JPH08253580A - Production of high-molecular-weight ester amide copolymer - Google Patents

Abstract

PURPOSE: To produce a high-molecular-weight ester amide copolymer by reacting a specified aromatic oligoester amide with a specified polyglycol and a dicarboxylic acid ester in an amide solvent to form a prepolymer and melt- polymerizing this prepolymer in vacuo. CONSTITUTION: A process for producing a high-molecular-weight ester amide copolymer comprising 10-90wt.% aromatic oligoester amide of the formula (wherein R is a 1-10 C alkyl; and Ar1 and Ar2 are each a 6-30 C aromatic group), 90-10wt.% poly(alkylene oxide) glycol of a number-average molecular weight of 500-10000 and 0-20wt.% dicarboxylic acid ester, which comprises reacting the above components at 200-210 deg.C for 30min to 1hr in an amide solvent to form a prepolymer having a degree of transesterification of 95% or above and a weight-average molecular weight of 10000 or above and melt-polymerizing this prepolymer at 220-250 deg.C in a vacuum of 1mmHg or below. The above aromatic oligoester amide can be obtained by reacting e.g. aminobenzoic acid with a dichloride of e.g. terephthalic acid. This copolymer obtained is a thermoplastic elastomer excellent in heat-resistance and processability.

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 high molecular weight ester amide copolymer which has properties as a thermoplastic elastomer and is excellent in heat resistance, cold resistance, mechanical properties and moldability.

[0002]

BACKGROUND OF THE INVENTION Aliphatic aminocarboxylic acids such as 6 nylon and 66 nylon make up the hard segment,
Esteramide-type block copolymers in which polytetramethylene glycol and polycaprolactone form soft segments are used as automotive elastomers, electrical / electronic parts, mechanical parts, etc. as thermoplastic elastomers with excellent heat resistance and mechanical properties. There is.

However, such an esteramide block copolymer is excellent in molding processability because it is composed of an aliphatic aminocarboxylic acid and an aliphatic glycol, but it does not have sufficient heat resistance and has a high hardness and rubber elasticity. Lack.

In order to improve heat resistance, a poly (ester amide) in which an aromatic amide unit composed of a combination selected from aromatic diamine, aromatic dicarboxylic acid and aromatic aminocarboxylic acid constitutes a hard segment is proposed. (Japanese Patent Laid-Open No. 4-293923). However, since this poly (ester amide) is solution-polymerized, the aromatic amide units are not uniform and the moldability is poor. Generally, when heat resistance is improved, moldability decreases. Further, an elastomer obtained by melt-polymerizing a compound selected from aromatic amides, dicarboxylic acids, glycols and diamines has been proposed (Japanese Patent Laid-Open No. 63-159432). This elastomer has a low molecular weight and does not show good mechanical properties.

[0005]

The present invention has been made to solve these problems, and its object is to provide a high molecular weight ester excellent in heat resistance, cold resistance, mechanical properties and processability. It is to provide a method for producing an amide copolymer.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a novel method for producing an ester amide copolymer and completed the present invention. . That is, the invention is 10 to 90% by weight of an aromatic oligoesteramide represented by the following general formula (I):

[0007]

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(In the formula, R represents an alkyl group having 1 to 10 carbon atoms, Ar ₁ and Ar ₂ each independently represent a divalent aromatic group having 6 to 30 carbon atoms.) Number average molecular weight 500 to 10,000 90% to 20% by weight of polyalkylene oxide glycol and 0 to 20% by weight of dicarboxylic acid ester are reacted at a temperature of 200 to 210 ° C. in an amide solvent in the presence of an ester catalyst to obtain a transesterification reaction rate of 95% or more and a weight. A prepolymer having an average molecular weight of 10,000 or more is produced, and the pressure is reduced to 1 mmHg or less.
A method for producing a high molecular weight ester amide copolymer, which comprises melt-polymerizing at a temperature of 220 to 250 ° C.

The aromatic oligoester amide which is the raw material of the present invention can be produced by reacting an aromatic aminocarboxylic acid ester with an aromatic dicarboxylic acid dichloride. Examples of the aromatic aminocarboxylic acid ester include aminobenzoic acids such as 4-aminobenzoic acid and 3-aminobenzoic acid, 4-amino-4′-carboxybiphenyl, 4-amino-4′-carboxybiphenyl ether and 4-amino. -4'-carboxybiphenyl sulfide, 4-amino-4'-carboxybiphenyl sulfone and other biphenylaminocarboxylic acids, 3-amino-3'-carboxybenzophenone, 4-amino-4 '
-Aminocarboxyphenones such as carboxybenzophenone, 1-amino-4-carboxynaphthalene, 2-
Examples thereof include methyl, ethyl, propyl and butyl esters of aminocarboxynaphthalenes such as amino-6-carboxynaphthalene.

As the aromatic dicarboxylic acid dichloride, phthalic acids such as terephthalic acid and isophthalic acid,
Biphenyldicarboxylic acids such as 4,4'-dicarboxybiphenyl, 4,4'-dicarboxybiphenyl ether, 4,4'-dicarboxybiphenyl sulfide and 4,4'-dicarboxybiphenyl sulfone, 3,3 '
-Dicarboxybenzophenones, 4,4'-dicarboxybenzophenones, dicarboxyphenones such as 1,2-bis (4-carboxyphenoxy) ethane, 1,4-
Examples thereof include dicarboxynaphthalenes and dichlorides of dicarboxynaphthalenes such as 2,6-dicarboxynaphthalene.

Then, the above-mentioned both compounds are replaced with aromatic dicarboxylic acid dichloride / aromatic aminocarboxylic acid ester = 1.
/ 2 to 1/5, preferably 1/2 to 1/3, at a reaction temperature of -20 ° C or higher, preferably 0 to 100 ° C.

At this time, the reaction solvent used is an organic solvent inert to the aromatic dicarboxylic acid dichloride, for example,
Methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, diethyl ether, dioxane, benzene, toluene, chlorobenzene, o-dichlorobenzene, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-acetyl-2. -Pyrrolidone,
N, N'-dimethylformamide, N, N'-dimethylacetamide, N, N'-diethylacetamide, N,
There are N'-dimethylpropionic acid amide, N, N'-diethylpropionic acid amide, tetramethylurea, tetraethylurea, hexamethylphosphortriamide, N-methylcaprolactam and the like, but especially N-methyl-2-pyrrolidone, N -Ethyl-2-pyrrolidone, N-acetyl-
2-pyrrolidone, N, N'-dimethylformamide,
N, N'-dimethylacetamide, N, N'-diethylacetamide, N, N'-dimethylpropionic acid amide, N, N'-diethylpropionic acid amide, tetramethylurea, tetraethylurea, hexamethylphosphortriamide, N An amide solvent such as methylcaprolactam is preferred. In the synthesis of aromatic oligoester amides, N, N'-dimethylaniline, N,
N'-diethylaniline, N, N'-dimethylmorpholine, pyridine or the like is used. The sizing agent is preferably used in 2 to 3 times the molar amount of the aromatic dicarboxylic acid dichloride.

Examples of the poly (alkylene oxide) glycol used in the method of the present invention include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol and ethylene oxide. And a propylene oxide copolymer, an ethylene oxide / tetrahydrofuran copolymer, a poly (propylene oxide) glycol ethylene oxide addition polymer, and the like. You may use these individually or in mixture of 2 or more. Among these, poly (tetramethylene oxide) is especially preferred because of its mechanical strength and moldability.
Ethylene oxide addition polymers of glycol and poly (propylene oxide) glycol are preferred.

The optimum number average molecular weight of poly (alkylene oxide) glycol varies depending on its chemical structure, the kind of aromatic oligoesteramide and the copolymerization ratio.
It is from 00 to 10,000, preferably from 650 to 5,000. If the number average molecular weight is less than 500, the melting point of the obtained ester amide copolymer is high and the moldability is poor, and if the number average molecular weight exceeds 10,000, the reaction rate decreases due to phase separation of the polymer during polymerization, which is not preferable.

The copolymerization amount of poly (alkylene oxide) glycol is 90 due to heat resistance, mechanical strength and molding processability.
It is necessary to be in the range of 10 to 10% by weight, preferably 85 to 15% by weight. If it exceeds 90% by weight, the crystallinity is low and the moldability is poor, and if it is less than 10% by weight, the flexibility and rubber elasticity may be insufficient.

In the method of the present invention, phthalic acid diesters such as terephthalic acid and isophthalic acid, and aliphatic carboxylic acid diesters such as succinic acid, glutaric acid and adipic acid are copolymerized in order to adjust the hardness of the ester amide copolymer. It may be polymerized.

Examples of the esterification catalyst used in the present invention include titanium compounds such as tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium and tetrabutoxy titanium, and di-n.
Examples include tin compounds such as -butyltin dilaurate, di-n-butyltin oxide and di-n-butyltin diacetate, acetates such as magnesium, calcium and zinc, and antimony chloride. Among them, good catalysts are organic titanium compounds. These catalysts are preferably used in an amount of 0.002 to 0.8% by weight based on the total copolymer produced.

The amide solvent used in the present invention is N-
Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylacetamide, N, N'-dimethylacetamide, N, N'-diethylacetamide, N, N '
-Dimethylformamide, N, N'-dimethylpropionic acid amide, N, N'-diethylpropionic acid amide,
N, N'-dimethyl methoxyacetamide etc. are mentioned. The amide solvent is used in an amount of 1 to 50% by weight, preferably 20 to 40% by weight, based on the total amount of the aromatic oligoester amide, poly (alkylene oxide) glycol and carboxylic acid diester.

A method for producing an ester amide copolymer includes aromatic oligoester amide, poly (alkylene oxide) glycol and carboxylic acid diester in the presence of an esterification catalyst in an amide solvent under a nitrogen stream at atmospheric pressure. A transesterification reaction is carried out at 200 to 210 ° C., the alcohol produced as a by-product is discharged, and a prepolymer is produced. The transesterification rate must be 95% or more, and the weight average molecular weight of the prepolymer must be 10,000 or more. If the transesterification rate and the weight average molecular weight of the prepolymer are low, a high molecular weight polymer cannot be obtained. After separating the solvent, a high molecular weight ester amide copolymer is obtained by further melt polycondensation at 220 to 250 ° C. under reduced pressure of 1 mmHg or less. At this time, if it is lower than 220 ° C, the molten state is not uniform, and if it exceeds 250 ° C, a high molecular weight polymer cannot be obtained.

By the above method, a high molecular weight esteramide copolymer having excellent heat resistance, cold resistance, mechanical properties and processability can be obtained.

To improve the heat aging resistance of the ester amide copolymer, a stabilizer is added during or after the polymerization. As these stabilizers, hindered phenol anti-aging agents, phosphorus anti-aging agents, sulfur anti-aging agents, amine anti-aging agents are used. The addition amount of these antioxidants is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the ester amide copolymer.

In order to improve the moldability of the ester-amide copolymer obtained in the present invention, stearates such as calcium, barium and aluminum, stearates,
Lubricants such as silicone oil, waxes and ethylenebisstearylamide can be added. The addition amount of these is preferably in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the ester amide copolymer.

Further, known compounds such as dyes, pigments, inorganic reinforcing agents, plasticizers, hindered amine light stabilizers, ultraviolet absorbers, foaming agents, epoxy compounds and isocyanate compounds are used for the ester amide copolymer obtained in the present invention. Additives can be added.

[0024]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these. The equipment and method used for the analysis of the esteramide copolymer obtained in the present invention are as follows.

(1) The molecular weight of the prepolymer is HLC-802A manufactured by Tosoh Corporation for high performance liquid chromatography, and polystyrene gel G4000HXL, G3000H for column.
Using a measuring instrument connected to XL, G2000HXL and G1000HXL, flow rate 1.0 ml / min, TH as eluent
It was measured at a column temperature of 40 ° C. using F.

The transesterification rate was calculated from the amount of unreacted aromatic oligoesteramide.

(2) The molecular weight of the polymer was measured by Toso CP-8000 for high performance liquid chromatography, a measuring instrument with two polystyrene gel GMHHR connected to the column, a flow rate of 1.0 ml / min, and an eluent of N-methyl. It was measured at a column temperature of 40 ° C. using 2-pyrrolidone / LiCl.

(3) Melt indexer [MI] is a melt indexer L244, X416 manufactured by Takara Kogyo,
Measured at 230 ° C. under low load (2.01 kg).

(4) The glass transition temperature and melting point were determined by using DSC200 manufactured by Seiko Denshi Kogyo Co.
Min, measured in the range of -100 to 300 ° C.

(5) The thermal decomposition temperature is TG-DTA200 manufactured by Seiko Denshi Kogyo Co., Ltd., and the heating rate is 20 ° C./min.
It was measured in the range of ˜650 ° C.

(6) The hardness was measured with a micro rubber hardness meter manufactured by Kobunshi Keiki Co., Ltd. using an injection-molded sheet having a thickness of 1 mm.

(7) Mechanical properties (breaking strength, breaking elongation)
Is Shimadzu Autograph DCS-100,
The injection-molded sheet having a thickness of 1 mm was measured with a dumbbell punched out according to JIS No.3.

Raw Material Production Example A 10-liter four-neck separable flask equipped with a nitrogen inlet tube, a temperature sensor and a magnetic stirring blade was replaced with nitrogen, and then ethyl aminobenzoate [EAB] 1321.5 g was added.
(8.0 mol) and dehydrated N-methyl-2-pyrrolidone [NMP] 4 l were charged, and EBA was dissolved in NMP. NMP 2l with terephthalic acid dichloride [TP
A solution of 812.1 g (4.0 mol) of C] dissolved therein was added dropwise. With dropping, heat was generated up to 75 ° C. and crystals began to precipitate. Further, 636.3 g (8.0 mol) of pyridine was added. After reacting for 4 hours at room temperature, it was filtered, washed thoroughly with pyridine and acetone, and dried under reduced pressure. Melting point 352 ° C
1677.5 g of aromatic oligoester amide
(Yield 91%) was obtained.

Example 1 A 500 ml four-neck separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distillation tube was placed in
Aromatic oligoesteramide 5 obtained in the raw material production example
9.86 g (0.13 mol), polytetramethylene glycol [PTMG; number average molecular weight (Mn) = 1016]
132.09 g (0.13 mol) and 1,3,5-trimethyl-2, as a hindered phenol anti-aging agent
4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene "Irganox 1330"
0.19 g of [made by Ciba-Gaigi] was charged. 1 at 100 ° C
After vacuum drying for an hour, 82.22 g of NMP and 0.23 g of tetrabutoxytitanium (catalyst) were added. Under a nitrogen stream, the temperature was raised from room temperature to 210 ° C., and a predetermined amount of ethanol was flown out in 30 minutes. Sampling and GPC
Was used to measure the molecular weight of the prepolymer. After removing NMP under reduced pressure, the temperature was raised to 240 ° C., and melt polymerization was performed under reduced pressure of 0.3 mmHg for 1 hour. 174.77 g (yield = 97%) of an ester amide copolymer showing good rubber elasticity was obtained.

Molecular weights [Mn, Mw, Mw / Mn] of the obtained prepolymer and polymer, transesterification rate [E], melt indexer [MI] of polymer, glass transition temperature [Tg], melting point [Tm], Thermal decomposition temperature [T
d], hardness [Hs], the breaking strength [T _B], shown in Table 1 the elongation at break [E _B].

Example 2 A 500 ml four-necked separable flask equipped with a nitrogen introducing tube, a temperature sensor, a magnetic stirring blade, and a distilling tube was used.
Aromatic oligoesteramide 4 obtained in the raw material production example
6.06 g (0.10 mol), PTMG [number average molecular weight (Mn) = 1514] 151.41 g (0.10 mol)
And Irganox 1330 [made by Ciba-Gaigi] 0.20
I charged g.

After drying under reduced pressure at 100 ° C. for 1 hour,
NMP 88.73g and tetrabutoxy titanium (catalyst)
0.24 g was added. Room temperature to 210 ° C under nitrogen stream
The temperature was raised to, and a predetermined amount of ethanol was flown out in 30 minutes. The sample was sampled and the molecular weight of the prepolymer was measured by GPC. After removing NMP under reduced pressure, the temperature was raised to 240 ° C., and melt polymerization was performed under reduced pressure of 0.3 mmHg for 1 hour.
Ester amide copolymer showing good rubber elasticity 178.
29 g (yield = 95%) was obtained.

Molecular weights of the obtained prepolymer and polymer, [E], [MI], [Tg], [Tm], [T]
d], shown in Table 1 [Hs], [T _B] and [E _B].

Example 3 A 500 ml four-neck separable flask equipped with a nitrogen introducing tube, a temperature sensor, a magnetic stirring blade, and a distilling tube was used.
Aromatic oligoesteramide 3 obtained in the raw material production example
6.84 g (0.08 mol), PTMG [number average molecular weight (Mn) = 2097] 167.76 g (0.08 mol)
And Irganox 1330 [made by Ciba-Gaigi] 0.20
I charged g.

After vacuum drying at 100 ° C. for 1 hour,
NMP100.67g and tetrabutoxy titanium (catalyst)
0.27 g was added. Room temperature to 210 ° C under nitrogen stream
The temperature was raised to, and a predetermined amount of ethanol was flown out in 30 minutes. The sample was sampled and the molecular weight of the prepolymer was measured by GPC. After removing NMP under reduced pressure, the temperature was raised to 240 ° C., and melt polymerization was performed under reduced pressure of 0.3 mmHg for 1 hour.
Ester amide copolymer showing good rubber elasticity 192.
64 g (yield = 98%) was obtained.

Molecular weights of the obtained prepolymer and polymer, [E], [MI], [Tg], [Tm], [T]
d], shown in Table 1 [Hs], [T _B] and [E _B].

Example 4 A 500 ml four-neck separable flask equipped with a nitrogen introducing tube, a temperature sensor, a magnetic stirring blade, and a distilling tube was used.
Aromatic oligoesteramide 2 obtained in the raw material production example
3.03 g (0.05 mol), PTMG [number average molecular weight (Mn) = 1031] 103.13 g (0.10 mol)
And Irganox 1330 [made by Ciba-Gaigi] 0.13
I charged g.

After drying under reduced pressure at 100 ° C. for 1 hour,
NMP57.78g, dimethyl adipate [DMAd]
8.78 g (0.05 mol) and tetrabutoxy titanium (catalyst) 0.17 g were added. 160 ° C under nitrogen stream
The mixture was reacted for 3 hours at 210 ° C. for 30 minutes, and a predetermined amount of ethanol was allowed to flow out. The sample was sampled and the molecular weight of the prepolymer was measured by GPC. After removing NMP under reduced pressure, the temperature was raised to 240 ° C., and melt polymerization was performed under reduced pressure of 0.2 mmHg for 1 hour. 123.68 g (yield = 97%) of an esteramide copolymer having good rubber elasticity was obtained.

Molecular weights of the obtained prepolymer and polymer, [E], [MI], [Tg], [Tm], [T]
d], shown in Table 1 [Hs], [T _B] and [E _B].

Comparative Example 1 A 500 ml four-neck separable flask equipped with a nitrogen introducing tube, a temperature sensor, a magnetic stirring blade, and a distillation tube was used.
Aromatic oligoesteramide 4 obtained in the raw material production example
6.06 g (0.10 mol), PTMG [number average molecular weight (Mn) = 1031] 103.14 g (0.10 mol)
And Irganox 13310 [made by Ciba-Gaigi] 0.1
5g was charged.

After vacuum drying at 100 ° C. for 1 hour,
0.20 g of tetrabutoxy titanium (catalyst) was added.
Under a nitrogen stream, the temperature was raised to 260 ° C. over 1 hour while flowing out ethanol. The sample was sampled and the molecular weight of the prepolymer was measured by GPC. Furthermore, 0.3 mmH
Melt polymerization was performed for 1 hour under reduced pressure of g. 135.77 g (yield = 97) of ester-amide copolymer showing good rubber elasticity
%)was gotten.

Molecular weights of the obtained prepolymer and polymer, [E], [MI], [Tg], [Tm], [T]
d], shown in Table 1 [Hs], [T _B] and [E _B].

[0048]

[Table 1]

[0049]

Industrial Applicability According to the production method of the present invention, a high molecular weight esteramide copolymer can be obtained. This copolymer has the properties of a thermoplastic elastomer and is excellent in heat resistance, cold resistance, mechanical properties and processability.

Claims (1)

[Claims] 1. An aromatic oligoesteramide represented by the following general formula (I): 10 to 90% by weight; (In the formula, R represents an alkyl group having 1 to 10 carbon atoms, Ar ₁ and Ar ₂ each independently represent a divalent aromatic group having 6 to 30 carbon atoms.) Poly (number average molecular weight 500 to 10,000) Alkylene oxide) glycol 90 to 10% by weight and dicarboxylic acid ester 0 to 20% by weight, in the production of an ester amide copolymer, in an amide solvent at 200 to 210 ° C.
At a temperature of 30 minutes to 1 hour to produce a prepolymer having a transesterification rate of 95% or more and a weight average molecular weight of 10,000 or more, and further under reduced pressure of 1 mmHg or less, 220
A method for producing a high molecular weight ester amide copolymer, which comprises melt-polymerizing at a temperature of ˜250 ° C.