JP3324170B2 - Ester amide copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ester amide copolymer having properties as a thermoplastic elastomer and having excellent heat resistance, cold resistance and moldability, and a method for producing the same.

[0002]

2. Description of the Related Art An ester amide type block copolymer in which an aliphatic aminocarboxylic acid such as nylon 6 and nylon 6,6 constitutes a hard segment and polytetramethylene glycol or polycaprolactone constitutes a soft segment is known. It is used as a thermoplastic elastomer having excellent heat resistance and mechanical properties in automobile parts, electric / electronic parts, mechanical parts and the like.

[0003] However, such an ester amide block copolymer is composed of an aliphatic aminocarboxylic acid and an aliphatic glycol and thus has excellent moldability, but has insufficient heat resistance and high hardness and rubber elasticity. It lacks.

In order to improve heat resistance, 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. (JP-A-4-293923). However, this poly (ester amide) is produced by solution polymerization, and has no aromatic amide units, and is inferior in moldability. Generally, when heat resistance is improved, moldability decreases.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve these problems, and an object of the present invention is to provide an ester amide copolymer excellent in heat resistance, cold resistance and workability. Is to do.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a novel method for producing an ester amide copolymer, and have completed the present invention. . That is, the present invention relates to an ester amide copolymer obtained by a melt reaction of an aromatic oligoamide comprising an aromatic dicarboxylic acid compound and an aromatic amino carboxylic acid compound, an aliphatic diol and a dicarboxylic acid diester, and a method for producing the same. It is.

Aromatic oligos used in the present invention
The amide is composed of an aromatic dicarboxylic acid compound and an aromatic aminocarboxylic acid compound. For example, aromatic dicarboxylic acid dichloride compound / aromatic aminocarboxylic acid ester = 1
It can be obtained by a method of reacting at a reaction temperature of -20 ° C or higher, preferably 0 to 30 ° C at a molar ratio of 1/2 to 1/5, preferably 1/2 to 1/3. At this time, the reaction solvent used is preferably an organic solvent inert to the aromatic dicarboxylic acid dichloride, particularly an amide solvent.

The ester amide copolymer of the present invention can be produced by a melting reaction of the aromatic oligoamide and the aliphatic diol or a melting reaction of the aromatic oligoamide or aliphatic diol and the dicarboxylic diester. That is, these raw materials can be produced by a method of direct polycondensation in the presence of a catalyst. Specifically, in the presence of an esterification catalyst, the transesterification reaction is carried out at about 150 to 240 ° C. in a nitrogen stream under normal pressure. Run off the methanol and add 5 more
It can be produced by a method of performing polycondensation at about 150 to 300 ° C. under reduced pressure of mmHg or less.

Examples of the esterification catalyst used in the above method include titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium; di-n-butyltin dilaurate; Examples include tin compounds such as di-n-butyltin oxide and di-n-butyltin diacetate, and mixtures of acetates such as magnesium, calcium, and zinc with antimony oxide. Among them, particularly preferred 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. By the above method, the ester amide copolymer of the present invention having excellent heat resistance, cold resistance and workability can be obtained.

The aromatic aminocarboxylic acid compound used in the present invention includes aminobenzoic acids such as 4-aminobenzoic acid and 3-aminobenzoic acid, and 4-amino-4 '.
Biphenylaminocarboxylic acids such as -carboxybiphenyl, 4-amino-4'-carboxybiphenylether, 4-amino-4'-carboxybiphenylsulfide, 4-amino-4'-carboxybiphenylsulfone, 3-amino-3'- Carboxybenzophenone, 4
Aminocarboxyphenones such as -amino-4'-carboxybenzophenone; and methyl, ethyl, propyl and butyl esters of aminocarboxynaphthalenes such as 1-amino-4-carboxynaphthalene and 2-amino-6-carboxynaphthalene. Can be

As the aromatic dicarboxylic acid compound, phthalic acids such as terephthalic acid and isophthalic acid;
Biphenyl dicarboxylic acids such as 4'-dicarboxybiphenyl, 4,4'-dicarboxybiphenyl ether, 4,4'-dicarboxybiphenyl sulfide, 4,4'-dicarboxybiphenyl sulfone, 3,3
Dicarboxyphenones such as' -dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane;
Preferred compounds include dichlorides of dicarboxynaphthalenes such as 4-dicarboxynaphthalene and 2,6-dicarboxynaphthalene.

The organic solvent used in the production method of the present invention includes methylene chloride, chloroform,
Solvents such as 1,2-dichloroethane, tetrahydrofuran, diethyl ether, dioxane, benzene, toluene, chlorobenzene, and o-dichlorobenzene can also be used. N-acetyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, N, N'-diethylacetamide,
Amide solvents such as N, N'-dimethylpropionamide, N, N'-diethylpropionamide, tetramethylurea, tetraethylurea, hexamethylphosphortriamide, N-methylcaprolactam and the like are preferably used.

In the synthesis of aromatic oligoamides , N, N 'is used as a sizing agent for hydrogen chloride produced by the reaction between dicarboxylic acid dichloride and aminocarboxylic acid.
-Dimethylaniline, N, N'-diethylaniline,
N, N'-dimethylmorpholine, pyridine and the like are used. This sizing agent is preferably used in a molar amount of 2 to 3 times the amount of the dicarboxylic acid dichloride.

Further, aromatic compounds in the ester amide copolymer
Copolymerization amount of oligoamide is, the heat resistance of the resulting copolymer, the mechanical strength, 10 to 90 wt% from the viewpoint of moldability, preferably from 15 to 85 wt%.

The aliphatic diol used in the present invention includes poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, and a copolymer of ethylene oxide and propylene oxide. And a copolymer of ethylene oxide and tetrahydrofuran, and an ethylene oxide addition polymer of poly (propylene oxide) glycol. These may be used alone or as a mixture of two or more. Among them, it is particularly preferable to use an ethylene oxide addition polymer of poly (tetramethylene oxide) glycol or poly (propylene oxide) glycol from the viewpoint of mechanical strength and moldability.

The number average molecular weight of the aliphatic diol used is
The optimum value varies depending on the chemical structure and the type and copolymerization ratio of the aromatic oligoamide used, but 500 to 10,000,
Preferably it is 650-4000. Number average molecular weight is 5
If it is less than 00, heat resistance and molding processability are inferior. If the number average molecular weight is more than 10,000, the reaction rate may decrease due to phase separation of the polymer during polymerization.

The amount of the aliphatic diol to be copolymerized is determined according to the heat resistance, mechanical strength, and moldability of the resulting copolymer.
The content is 0 to 10% by weight, preferably 85 to 15% by weight. If it exceeds 90% by weight, the crystallinity is low,
Also, the moldability is poor, and if it is less than 10% by weight, flexibility and rubber elasticity may be insufficient.

The dicarboxylic acid diester used in the present invention includes phthalic acid diesters such as terephthalic acid and isophthalic acid, and aliphatic dicarboxylic acid diesters such as succinic acid, glutaric acid and adipic acid.
The copolymerization amount of the carboxylic acid diester is preferably from 0 to 20% by weight.

In the production method of the present invention, the aromatic oligo
An ester amide copolymer of the present invention having an aromatic ester amide having excellent heat resistance, cold resistance and processability as a hard segment by melt-polymerizing an amide , an aliphatic diol and a dicarboxylic acid diester, that is, the following general formula: 10 to 90% by weight of an aromatic oligoamide chain represented by (I),

[0020]

Embedded image

(Wherein R ¹ and R ^{2 each} have 6 to 30 carbon atoms)
Represents two divalent aromatic groups. ) Number average molecular weight 500-1
90 to 10% by weight of polyalkylene oxide chains of 0000
And an ester amide copolymer having a number average molecular weight of 5,000 to 500,000 and a dicarboxylic acid unit of 0 to 20% by weight.

The ester amide copolymer of the present invention has a number average molecular weight of 5,000 to 500,000, preferably 1,000.
0 to 100,000. If the number average molecular weight is less than 5,000, the mechanical properties are poor, and if it is more than 500,000, there is a problem in processability.

Further, a stabilizer may be added during or after the polymerization in order to improve the heat resistance, particularly the thermochromic property of the ester amide copolymer of the present invention.
Phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphinic acid, polyphosphonates, dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite, hindered phenol compounds, thioethers, dithioates, mercapto Sulfur-containing compounds such as benzimidazoles, thiocarbanilides, and thiodipropionates, and tin-based compounds such as tinmalate and dibutyltin monoxide are used. The addition amount of these stabilizers is preferably 0.01 to 2.0 parts by weight based on 100 parts by weight of the ester amide copolymer.

Further, in order to improve the moldability of the ester amide copolymer of the present invention, lubricating agents such as stearates such as calcium, barium and aluminum, stearic esters, silicone oils, waxes and ethylenebisstearylamide are added. May be. The amount of these additives
0.05 with respect to 100 parts by weight of the ester amide copolymer
The range of -5.0 parts by weight is preferred.

Further, known additives such as dyes, pigments, inorganic reinforcing agents, plasticizers, hindered amine light stabilizers, ultraviolet absorbers, foaming agents, epoxy compounds and isocyanate compounds are added to the ester amide copolymer of the present invention. You can add the agent.

[0026]

EXAMPLES Next, the present invention will be described in detail with reference to examples. The measuring instruments and methods used for analyzing the ester amide copolymer obtained in the present invention are as follows.

(1) The ¹ H-NMR spectrum was measured in hexafluoroisopropanol at 45 ° C. and 400 times of integration using JNM-GSX270 manufactured by JEOL.

(2) The ¹³ C-NMR spectrum was measured in hexafluoroisopropanol at 45 ° C. and 18,000 times of integration using JNM-GSX270 manufactured by JEOL.

(3) The infrared absorption spectrum was obtained from Hitachi
It was measured by KBr tablet method using Model 270-30.

(4) The dynamic viscoelastic behavior was determined by Rheology.
The measurement was performed using a DVE-V4 FT Rheospectler at a frequency of 11 Hz and a range of -100 to 300 ° C.

(5) The glass transition temperature (Tg) and the melting point (Tm) were measured using DSC200 manufactured by Seiko Denshi Kogyo Co., Ltd. at a heating rate of 10 ° C./min and in a range of -100 to 300 ° C. (6) Thermal decomposition temperature (Td) is T
Using G-DTA200, heating rate 20 ° C./min, 50-
It was measured in the range of 650 ° C.

(7) The molecular weight of the polymer is
C-8010, polystyrene gel GMHXL in column
And G2500H8 using a column system GPC, flow rate was measured at 1.0 ml / min, eluent was N-methyl-2-pyrrolidone / LiCl, and column temperature was measured at 40 ° C.

(8) Elemental analysis was performed by Carlo Ebal 1
Carbon, hydrogen and nitrogen were quantified by dynamic combustion using Model 106.

Reference Example 1 (Synthesis of Aromatic Oligoamide [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] ] N-methyl-2-pyrrolidone [NMP] 200 m dehydrated to 99.65 g (0.5 mol)
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
℃ oligoamides having a [a] 78.51g (yield 76
%). 1H-NM of the resulting oligoamide [a]
FIG. 1 shows the R measurement results, and FIG. 2 shows the 13 C-NMR measurement results.
FIG. 3 shows the infrared absorption spectrum.

Reference Example 2 (Synthesis of Aromatic Oligoamide [b]) A 1-liter four-necked flask equipped with a nitrogen inlet tube and a magnetic stirring blade was completely dried and purged with nitrogen.
6.65 g (0.5 mol) of dehydrated NMP 200 ml
Was charged. Dissolve BAB in NMP and cool on ice (0-5
° C). Next, a solution in which 40.61 g (0.2 mol) of isophthalic acid dichloride was dissolved in 100 ml of NMP was added. After reacting at 0 to 5 ° C. for 6 hours and at room temperature overnight, precipitated in methanol, washed with acetone, and washed with NM
Recrystallized from P / toluene. Oli having a melting point of 194 ° C.
45.57 g (44% yield) of goamide [b] 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 distilling tube was placed
Oligoamic [a] 15.50 g (0.03 mol), polytetramethylene glycol (PTMG; number average molecular weight Mn = 1009) 30.28g (0.03 mol) and Irganox 1010 (phenolic stabilizer available from Ciba-Geigy ) 0.05 g was charged. After sufficiently purging with nitrogen, 0.10 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 240 ° C. in 1 hour, and a predetermined amount of butanol was allowed to flow out in 3 hours. 240
The reaction was carried out for 2 hours under a reduced pressure of 1 ° C./1 mmHg and further raised to 280 ° C. for 1 hour. 38.22 g (92% yield) of an ester amide copolymer exhibiting good rubber elasticity was obtained.
FIG. 7 shows 1 H-NMR and FIG. 8 shows 13 C-NMR of this polymer. FIG. 9 shows the dynamic viscoelastic behavior. The molecular weight, glass transition temperature (Tg) and melting point (T
m) and the results of elemental analysis are shown in Table 1.

Example 2 A 500 ml four-necked separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distilling tube was prepared.
Oligoamic [a] 15.51g (0.03 mol), P
60.55 g (0.06 mol) of TMG (Mn = 1009), 5.83 g (0.03 mol) of dimethyl terephthalate, and 0.08 g of Irganox 1010 were charged. After sufficiently purging with nitrogen, 0.21 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 240 ° C. in one hour, and a predetermined amount of butanol was allowed to flow out in three hours. The reaction was carried out at 240 ° C./1 mmHg under reduced pressure for 2 hours, and further heated to 280 ° C. for 1 hour. 72.04 g of ester amide copolymer showing good rubber elasticity
(95% yield). The molecular weight of this polymer, T
Table 1 shows g, Tm, and the results of elemental analysis.

Example 3 A 500 ml four-necked separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distilling tube was prepared.
Oligoamic [a] 15.50g (0.03 mol), P
60.44 g (0.03 mol) of TMG (Mn = 2014) and 0.08 g of Irganox 1010 were charged. After sufficient nitrogen substitution, 0.10 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 230 ° C. in 1 hour, and a predetermined amount of butanol was allowed to flow out in 3 hours. The reaction was performed for 2 hours under a reduced pressure of 230 ° C./1 mmHg or less. 67.63 g (yield 94%) of an ester amide copolymer exhibiting good rubber elasticity was obtained. Table 1 shows the molecular weight, Tg, Tm, and elemental analysis results of this polymer.

Example 4 A 500 ml four-necked separable flask equipped with a nitrogen inlet tube, a temperature sensor, a magnetic stirring blade, and a distilling tube was prepared.
Oligoamic [b] 15.51g (0.03 mol), P
130.28 g (0.03 mol) of TMG (Mn = 1009) and 0.05 g of Irganox 1010 were charged. After sufficient nitrogen substitution, 0.10 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 240 ° C. in 1 hour, and a predetermined amount of butanol was allowed to flow out in 3 hours. The reaction was carried out for 2 hours under a reduced pressure of 240 ° C./1 mmHg or less, and further heated to 280 ° C. for 1 hour. Ester amide copolymer 38.57 showing good rubber elasticity
g (93% yield) was obtained. The molecular weight of this polymer,
Table 1 shows Tg, Tm and the results of elemental analysis.

[0040]

[Table 1]

[0041]

According to the present invention, an ester amide copolymer having properties as a thermoplastic elastomer and having an aromatic oligoamide chain in a hard segment can be obtained. This polymer is excellent in heat resistance, cold resistance and workability.

[Brief description of the drawings]

FIG. 1 is a diagram showing a 1 H-NMR spectrum of oligoamide [a].

FIG. 2 is a diagram showing a 13 C-NMR spectrum of oligoamide [a].

FIG. 3 is a view showing an infrared absorption spectrum of oligoamide [a].

FIG. 4 shows 1H- of the ester amide copolymer of Example 1.
It is a figure which shows NMR.

FIG. 5 shows 13C- of the ester amide copolymer of Example 1.
It is a figure which shows NMR.

FIG. 6 is a diagram showing dynamic viscoelastic behavior of the ester amide copolymer of Example 1.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 69/44 C08G 69/40

Claims (3)

(57) [Claims] 1. A process for producing an ester amide copolymer, comprising melting and reacting an aromatic oligoamide and an aliphatic diol comprising an aromatic dicarboxylic acid compound and an aromatic aminocarboxylic acid compound. 2. A method for producing an ester amide copolymer, comprising melting and reacting an aromatic oligoamide , an aliphatic diol and a dicarboxylic diester, each comprising an aromatic dicarboxylic acid compound and an aromatic aminocarboxylic acid compound. 3. An aromatic oligo represented by the following general formula (I):
10 to 90% by weight of amide chains, (In the above formula, R1 and R2 represent a divalent aromatic group having 6 to 30 carbon atoms.) 90 to 10% by weight of a polyalkylene oxide chain having a number average molecular weight of 500 to 10,000 and a dicarboxylic acid unit of 0 to 20 Number average molecular weight of 5000% by weight
~ 500,000 ester amide copolymer.