JP3409346B2 - 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 esteramide copolymer having properties as a thermoplastic elastomer and excellent in heat resistance, cold resistance and moldability, and a method for producing the same.

[0002]

2. Description of the Related Art Esteramide type block copolymers in which aliphatic aminocarboxylic acids such as 6-nylon and 6,6-nylon compose hard segments and polytetramethylene glycol and polycaprolactone compose soft segments are known. It is used as a thermoplastic elastomer with excellent heat resistance and mechanical properties for automobile parts, electric / electronic parts, mechanical parts, etc.

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 high hardness and rubber elasticity. Is lacking in.

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, this poly (ester amide) is produced by solution polymerization, and the aromatic amide units are not uniform, resulting in poor moldability. Generally, when heat resistance is improved, moldability decreases.

[0005]

The present invention has been made to solve these problems, and an object thereof is to provide an ester amide copolymer excellent in heat resistance, cold resistance and processability. To do.

[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 have completed the present invention. . That is, the present invention provides a monoalkyl ester chloride of an aromatic dicarboxylic acid compound (provided that
The alkyl group is an alkyl group having 1 to 4 carbon atoms. The present invention relates to an ester amide copolymer obtained by melt-reacting an aromatic oligoamide composed of an aromatic diamine compound, an aliphatic diol, and a dicarboxylic acid diester, and a method for producing the same.

Aromatic oligosaccharides used in the present invention
Mido is a monoalkyl ester of an aromatic dicarboxylic acid compound.
Terchloride (however, the alkyl group has 1 to 4 carbon atoms)
It is an alkyl group. ) And consists aromatic diamine compound, as the methods for their synthesis, for example, aromatic diamine compounds / aromatic dicarboxylic acid monoalkyl ester chloride = 1 / 2-1 / 5, moles of preferably 1 / 2-1 / 3 The reaction temperature is -20 ° C or higher, preferably 0 to 30 ° C.
And the like. In this case, as the reaction solvent inert organic solvent an aromatic dicarboxylic acid monoalkyl ester chloride, in particular amide solvent is preferably used.

The ester amide copolymer of the present invention is produced by a melt reaction. That is, the aromatic o
Rigoamido aliphatic Geo - le or aromatic oligoamides,
It is produced by a method of directly polycondensing a carboxylic acid diester and an aliphatic diol in the presence of a catalyst, and specifically, the above raw materials are present in the presence of an esterification catalyst in a nitrogen stream under atmospheric pressure at about 150 to 240 ° C. The method of carrying out the transesterification reaction in (1) to allow methanol to flow out, and further polycondensate at about 150 to 300 ° C. under a reduced pressure of 5 mmHg or less can be mentioned.

Examples of the esterification catalyst used in the above method include titanium compounds such as tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium, and tetrabutoxy titanium, di-n-butyltin dilaurate, Examples thereof include tin compounds such as di-n-butyltin oxide and di-n-butyltin diacetate, and mixtures of antimony oxide with acetates such as magnesium, calcium and zinc. Among them, good catalysts are organic titanium compounds. These catalysts
It is 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 processability can be obtained.

The aromatic diamine compound used in the present invention includes p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-diaminobenzidine, 2,4-bis (β-amino-t-butyl) toluene, bis (p-amino-t-butylphenyl) benzene, 1,3-diamino-4-isopropylbenzene, m-xylenediamine, 2,4-diamino Examples thereof include toluene and 2,6-diaminotoluene.

Further, the aromatic dicarboxylic acid compound monoamine
Rualkyl ester chloride (However, the alkyl group is carbon
It is an alkyl group of the numbers 1 to 4. ) Are phthalic acids such as terephthalic acid and isophthalic acid, 4,4′-dicarboxybiphenyl, 4,4′-dicarboxybiphenyl ether, 4,4′-dicarboxybiphenyl sulfide, 4,4′-dicarboxyl Biphenyl dicarboxylic acids such as biphenyl sulfone, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy)
Examples include dicarboxyphenones such as ethane, methyl, ethyl, propyl and butyl ester chlorides of dicarboxynaphthalenes such as 1,4-dicarboxynaphthalene and 2,6-dicarboxynaphthalene.

As the organic solvent used in the reaction, solvents such as methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, diethyl ether, dioxane, benzene, toluene, chlorobenzene, o-dichlorobenzene and the like can be used. N-methyl-2
-Pyrrolidone, N-ethyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, N, N'-diethylacetamide, N, N'-dimethylpropione Amide solvents such as acid amide, N, N′-diethylpropionic acid amide, tetramethylurea, tetraethylurea, hexamethylphosphortriamide, and N-methylcaprolactam are preferable.

Further, in the synthesis of aromatic oligoamides , N, N'-dimethylaniline, N, N'-diethylaniline, as a scavenger for hydrogen chloride produced by the reaction of monoalkyl ester chloride of dicarboxylic acid and diamine, N, N'-dimethylmorpholine, pyridine or the like is used. The sizing agent is a monoalkyl dicarboxylic acid .
It is preferable to use 2 to 3 times the molar amount of the ester chloride .

Aromatic oligos in ester amide copolymers
The copolymerization amount of amide is in the range of 10 to 90% by weight, preferably 15 to 85% by weight, from the viewpoint of heat resistance, mechanical strength and moldability of the obtained copolymer.

As the aliphatic diol used in the present invention, poly (alkylene oxide) glycol is preferably used, and specifically, poly (ethylene oxide) is used.
Glycol, poly (propylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and tetrahydrofuran, and ethylene oxide addition polymers of poly (propylene oxide) glycol. You may use these individually or in mixture of 2 or more. Among these, from the viewpoint of mechanical strength and molding processability of the resulting copolymer, an ethylene oxide addition polymer of poly (tetramethylene oxide) glycol or poly (propylene oxide) glycol is more preferably used.

Further, aliphatic Geo used - the number-average molecular weight of Le, the optimum value differs depending on the type and copolymerization ratio of the chemical structure and used aromatic oligoamide, 500-100
00 is preferable, and more preferably 650 to 4000. When the number average molecular weight is less than 500, heat resistance and molding processability are poor, and when 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 copolymerized depends on the heat resistance, mechanical strength and molding processability of the resulting copolymer.
It is necessary to be 0 to 10% by weight, preferably 85 to
It is in the range of 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.

Examples of dicarboxylic acid diesters used in the method of the present invention include 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 dicarboxylic acid diester is preferably 0 to 20% by weight.

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

[0020]

[Chemical 2]

(In the above formula, R ¹ and R ² have 6 to 30 carbon atoms.
Represents a divalent aromatic group. ) Number average molecular weight 500 to 1
90 to 10% by weight of polyalkylene oxide chain of 0000
And a number average molecular weight consisting of 0 to 20% by weight of dicarboxylic acid unit is 5,000 to 500,000, and a melting point of 100 to
The ester amide copolymer of the present invention having a temperature of 300 ° C. is obtained.

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

A stabilizer may be added to the ester amide copolymer of the present invention during or after the polymerization in order to improve heat resistance, especially thermochromic property. Examples of the stabilizer include phosphoric acid, Phosphorous acid, hypophosphorous acid derivative, phenylphosphinic acid, polyphosphonate, phosphorus compounds such as dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite, hindered phenol compounds, thioethers, dithioates, mercaptobenzimidazoles , Thiocarbanilide compounds, sulfur-containing compounds such as thiodipropionic acid esters, tin compounds such as tin malate and dibutyltin monoxide are used. The amount of these stabilizers added is 0.01 to 2.0 with respect to 100 parts by weight of the ester amide copolymer.
It is preferably part by weight.

Further, in order to improve the moldability of the esteramide copolymer of the present invention, a lubricant such as stearates of calcium, barium, aluminum or the like, stearic acid ester, silicone oil, waxes, ethylenebisstearylamide or the like is added. May be, the amount of addition of these,
0.05 based on 100 parts by weight of ester amide copolymer
The range of up to 5.0 parts by weight is preferred.

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. It doesn't matter if the agent is added.

[0026]

EXAMPLES Next, the present invention will be described in detail with reference to Examples. The measuring instruments and methods used for the analysis of the esteramide copolymer obtained in the present invention are as follows.

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

(2) The ¹³ C-NMR spectrum was measured by using JNM-GSX270 type manufactured by JEOL Ltd. in hexafluoroisopropanol under the conditions of 45 ° C. and the number of integrations of 18,000.

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

(4) Dynamic viscoelastic behavior is based on rheology
Using a DVE-V4 FT Rheospectr, the frequency was 11 Hz and the measurement was performed in the range of -100 to 300 ° C.

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

(7) The molecular weight of the polymer is S manufactured by Tosoh Corporation.
C-8010, polystyrene gel on column GMHXL
And G2500H8 connected column system GPC were used, the flow rate was 1.0 ml / min, the eluent was N-methyl-2-pyrrolidone / LiCl, and the column temperature was 40 ° C.

(8) Elemental analysis was carried out by Carlo Ebal Co. 1
Carbon type, hydrogen, and nitrogen were quantified by a dynamic combustion method using Model 106.

(9) The hardness was measured with a micro rubber hardness meter manufactured by Kobunshi Keiki Co., Ltd. using a press sheet having a thickness of 1 mm.

(10) Mechanical properties (breaking strength, breaking elongation)
Was measured by Shimadzu Autograph DCS-100 using a press sheet having a thickness of 1 mm.

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 replaced with nitrogen, and then terephthalic acid monomethyl chloride [MMC was used. ] 99.32 g (0.
5 mol) and dehydrated N-methyl-2-pyrrolidone [NM
P] 300 ml was charged. MMC was dissolved in NMP and ice-cooled (0 to 5 ° C). Then NMP 200 ml
To m-phenylenediamine [m-PDA] 21.65 g
A solution in which (0.2 mol) was dissolved was added. After reacting at 0 to 5 ° C for 6 hours, it was precipitated in methanol, washed with acetone, and recrystallized from NMP / toluene. Melting point 31
Oligoamides having the 2 ℃ [a] 54.03g (yield 62
%) Was obtained. 1H-NM of the obtained oligoamide [a]
The R measurement result is shown in FIG. 1, the 13 C-NMR measurement result is shown in FIG.
The infrared absorption spectrum is shown in FIG.

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 replaced with nitrogen, and then MMC5 was used.
9.59 g (0.3 mol) and dehydrated NMP 100 ml
Was charged. Dissolve MMC in NMP and ice-cool (0-5
℃). Then, 22.61 g (0.1%) of bis (4-amino-3-methylphenyl) methane was added to 100 ml of NMP.
Mol) was dissolved in the solution. 6 hours at 0-5 ° C,
After reacting for one day at room temperature, it was precipitated in methanol, washed with acetone, and recrystallized with NMP / toluene. It was obtained oligoamides having a melting point of 246 ℃ [b] 33.72g (69 % yield).

Reference Example 3 (Synthesis of Aromatic Oligoamide [c]) A 1-liter four-necked flask equipped with a nitrogen inlet tube and a magnetic stirring blade was completely dried and replaced with nitrogen, and then MMC5.
9.58 g (0.3 mol) and dehydrated NMP 100 ml
Was charged. Dissolve MMC in NMP and ice-cool (0-5
℃). Then, 25.41 g of bis (4-amino-3,5-dimethylphenyl) methane in 100 ml of NMP
A solution in which (0.1 mol) was dissolved was added. After reacting at 0 to 5 ° C. for 6 hours at room temperature for one day and night, it was precipitated in methanol, washed with acetone, and recrystallized with NMP / toluene. Oligoamide [c] 27.7 having a melting point of 284 ° C.
8 g (yield 45%) was obtained.

Example 1 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.
Oligoamic [a] 17.30 g (0.04 mol), polytetramethylene glycol (PTMG; number average molecular weight Mn = 1009) 40.39g (0.04 mol) and Irganox 1010 (phenolic stabilizer available from Ciba-Geigy ) 0.06 g was charged. After sufficiently substituting with nitrogen, 0.15 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 methanol was flown out in 4 hours. 230
The mixture was reacted under reduced pressure of ° C / 1 mmHg for 2 hours, further heated to 270 ° C and reacted for 1 hour. As a result, 50.92 g (yield: 92%) of an ester amide copolymer having good rubber elasticity was obtained.
1 H-NMR and 13 C-NMR of this polymer are shown in FIG. 4 and FIG. 5, respectively. Further, FIG. 6 shows the dynamic viscoelastic behavior. The molecular weight, glass transition temperature (Tg), melting point (T
m) and elemental analysis results are shown in Table 1. The mechanical properties of the obtained ester amide copolymer are hardness (Hs = 91 JIS
-A), breaking strength (TB = 218 kg / cm 2) and breaking elongation (EB = 1000%).

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.
Oligoamic [a] 17.32g (0.04 mol), P
80.73 g (0.08 mol) of TMG (Mn = 1009), 7.72 g (0.04 mol) of dimethyl terephthalate and 0.08 g of Irganox 1010 were charged. After sufficiently substituting with nitrogen, 0.21 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 220 ° C. in 1 hour, and a predetermined amount of methanol was flown out in 4 hours. The mixture was reacted under reduced pressure of 220 ° C./1 mmHg for 2 hours, further heated to 260 ° C. and reacted for 1 hour. 95.63 g of ester amide copolymer showing good rubber elasticity
(Yield 95%) was obtained. The molecular weight of this polymer, T
The g, Tm and elemental analysis results are shown in Table 1.

Example 3 In a 500 ml four-neck separable flask equipped with a nitrogen introducing tube, a temperature sensor, a magnetic stirring blade, and a distilling tube,
Oligoamic [b] 11.01g (0.02 mol), P
20.06 g (0.02 mol) of TMG (Mn = 1002) and 0.02 g of Irganox 1010 were charged. After sufficiently substituting with nitrogen, 0.07 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 200 ° C. in 1 hour, and a predetermined amount of methanol was flown out in 4 hours. The temperature was raised to 240 ° C. and the reaction was performed for 2 hours under reduced pressure of 1 mmHg or less. 27.4 g (yield 92%) of an ester amide copolymer showing good rubber elasticity was obtained. The molecular weight, Tg, Tm and elemental analysis results of this polymer are shown in Table 1.

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.
Oligoamic [c] 11.56g (0.02 mol), P
20.06 g (0.02 mol) of TMG (Mn = 1002) and 0.02 g of Irganox 1010 were charged. After sufficiently substituting with nitrogen, 0.07 g of tetrabutoxytitanium (catalyst) was added. Under a nitrogen stream, the temperature was raised from room temperature to 200 ° C. in 1 hour, and a predetermined amount of methanol was flown out in 4 hours. The temperature was raised to 240 ° C. and the reaction was performed for 2 hours under reduced pressure of 1 mmHg or less. 27.6 g (yield 91%) of an ester amide copolymer having good rubber elasticity was obtained. The molecular weight, Tg, Tm and elemental analysis results of this polymer are shown in Table 1.

Comparative Example 1 A 1-liter four-necked flask equipped with a nitrogen inlet tube and a magnetic stirring blade was completely dried, and after substituting with nitrogen, 20.34 g (0.1 mol) of terephthalic acid dichloride [TPC] was added.
Then, 50 ml of dehydrated NMP was charged. NMP to TPC
Was dissolved and ice-cooled (0 to 5 ° C.). Then NMP5
PTMG (Mn = 1009) 5 fully dried to 0 ml
A solution in which 0.19 g (0.05 mol) was dissolved was slowly added dropwise. After overnight reaction at room temperature, m-PDA8.42
A solution in which g (0.05 mol) was dissolved was added. 0-5
After reacting at ℃ for 6 hours, it was precipitated in methanol, washed, and dried under reduced pressure. 59.63 g (yield 87%) of an ester amide copolymer having good rubber elasticity was obtained. The ¹ H-NMR and ¹³ C-NMR of this polymer are shown in FIG. 7 and FIG. 8, respectively. Further, FIG. 9 shows the dynamic viscoelastic behavior. The molecular weight, Tg, Tm and elemental analysis results of this polymer are shown in Table 1. The mechanical properties of the obtained ester amide copolymer are hardness (Hs = 82 JIS-A) and breaking strength (T _B = 240).
kg / cm ² ) and elongation at break (E _B = 630%).

[0044]

[Table 1]

[0045]

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

[Brief description of 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 diagram showing an infrared absorption spectrum of oligoamide [a].

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

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

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

FIG. 7: 1H- of the esteramide copolymer of Comparative Example 1
It is a figure which shows NMR.

FIG. 8: 13 C- of the ester amide copolymer of Comparative Example 1
It is a figure which shows NMR.

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

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 69/44 C08G 69/40

Claims (3)

(57) [Claims] 1. A monoalkyl of an aromatic dicarboxylic acid compound.
Ester chloride (However, the alkyl group has 1 to 1 carbon atoms.
4 is an alkyl group. ) And method for producing an ester amide copolymer characterized by melt reacting an aromatic oligoamide and aliphatic diols consisting of an aromatic diamine compound. 2. A monoalkyl of an aromatic dicarboxylic acid compound.
Ester chloride (However, the alkyl group has 1 to 1 carbon atoms.
4 is an alkyl group. ) And an aromatic oligodiamine compound, an aromatic oligoamide , a dicarboxylic acid diester, and an aliphatic diol are melt-reacted to produce an esteramide copolymer. 3. An aromatic amide represented by the following general formula (I)
Block chain 10 to 90% by weight, (In the above formula, R ¹ and R ² represent a divalent aromatic group having 6 to 30 carbon atoms.) 90 to 10% by weight of polyalkylene oxide chain having a number average molecular weight of 500 to 10,000 and 0 of dicarboxylic acid unit Number average molecular weight consisting of -20% by weight is 500
An ester amide copolymer having a melting point of 0 to 500000 and a melting point of 100 to 300 ° C.