JP3324171B2 - Method for producing ester amide copolymer - Google Patents

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 an ester amide copolymer having properties as a thermoplastic elastomer and having excellent heat resistance, cold resistance and moldability.

[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 excellent in molding workability because it is composed of an aliphatic aminocarboxylic acid and an aliphatic glycol, but has insufficient heat resistance and high hardness. It lacks elasticity.

Therefore, in order to improve heat resistance, an aromatic amide unit composed of a combination selected from aromatic diamine, aromatic dicarboxylic acid, and aromatic aminocarboxylic acid constitutes a hard segment of poly (ester amide). Has been proposed (JP-A-4-293923). However, since this poly (ester amide) is obtained by solution polymerization, aromatic amide units are not uniform, and molding processability is poor. 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 produce an ester amide copolymer excellent in heat resistance, cold resistance and workability. It is to provide a method.

[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 is characterized in that the terminal of poly (alkylene oxide) glycol is substituted with an aromatic aminocarboxylic acid compound and then reacted with an aromatic dicarboxylic acid dichloride in an organic solvent.

[0007]

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(However, R1 and R2 each have 6 to 3 carbon atoms.)
Shows zero divalent aromatic groups. ) Aromatic ori
Goamide chain 10-90 % by weight and number average molecular weight 500-1
90 to 10% by weight of polyalkylene oxide chains of 0000
And a method for producing an ester amide copolymer having a number average molecular weight of 5,000 to 500,000.

The aromatic aminocarboxylic acid compound used in the method of the present invention includes, for example, aminobenzoic acids such as 4-aminobenzoic acid and 3-aminobenzoic acid;
Amino-4'-carboxybiphenyl, 4-amino-4
'-Carboxybiphenyl ether, 4-amino-4'
-Carboxybiphenyl sulfide, 4-amino-4
Biphenylaminocarboxylic acids such as'-carboxybiphenylsulfone; aminocarboxyphenones such as 3-amino-3'-carboxybenzophenone and 4-amino-4'-carboxybenzophenone; 1-amino-4-
Methyl of aminocarboxynaphthalenes such as carboxynaphthalene and 2-amino-6-carboxynaphthalene;
Ethyl, propyl and butyl esters and the like.

The poly (alkylene oxide) glycol used in the method of the present invention includes, for example, poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) Glycol, a copolymer of ethylene oxide and propylene oxide, 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 these, in view of the mechanical strength and moldability of the obtained ester amide copolymer, it is particularly preferable to use an ethylene oxide addition polymer of poly (tetramethylene oxide) glycol or poly (propylene oxide) glycol. preferable. Further, the number average molecular weight of the poly (alkylene oxide) glycol used varies depending on its chemical structure, but is preferably from 500 to 10000, more preferably from 650 to 4000. When the number average molecular weight is less than 500, the heat resistance and moldability of the obtained ester amide copolymer are inferior, 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 aromatic dicarboxylic acid dichloride used in the method of the present invention includes phthalic acids such as terephthalic acid and isophthalic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxybiphenyl ether, 4,4 Biphenyldicarboxylic acids such as' -dicarboxybiphenylsulfide, 4,4'-dicarboxybiphenylsulfone, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ) Dicarboxyphenones such as ethane, and dichlorides of dicarboxynaphthalenes such as 1,4-dicarboxynaphthalene and 2,6-dicarboxynaphthalene.

In the present invention, the terminal of the above-mentioned poly (alkylene oxide) glycol is substituted with an aromatic aminocarboxylic acid. As a specific method, for example, a poly (alkylene oxide) glycol is used in the presence of a transesterification catalyst. The aromatic aminocarboxylic acid ester is used in an amount of at least 2 times the amount of the glycol, and in a nitrogen stream under atmospheric pressure, about 150 times.
The transesterification reaction is carried out at ~ 240 ° C to allow butanol to flow out.
A method of reacting at 0 ° C. is exemplified. The esterification catalyst used here includes titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, di-n-butyltin dilaurate, di-n -Butyltin oxide, tin compounds such as di-n-butyltin diacetate, magnesium, calcium,
Examples include a combination of an acetate such as zinc and an oxide such as antimony oxide and germanium oxide. Among them, a good catalyst is an organic titanium compound.

According to the present invention, an ester amide copolymer is obtained by reacting poly (alkylene oxide) glycol, the terminal of which is substituted with an aromatic aminocarboxylic acid, with an aromatic dicarboxylic acid dichloride in an organic solvent. is there. This reaction is preferably carried out at a temperature of −20 ° C. or higher, more preferably 0 to 100 ° C. At this time, since hydrogen chloride is generated by the reaction, it is preferable to use the sizing agent.

As the organic solvent used in the above reaction, for example, solvents such as methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, diethyl ether, dioxane, benzene, toluene, chlorobenzene and o-dichlorobenzene can be used. , Especially N-
Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N′-dimethylformamide, N, N′-dimethylacetamide,
Amide solvents such as N, N'-diethylacetamide, N, N'-dimethylpropionamide, N, N'-diethylpropionamide, tetramethylurea, tetraethylurea, hexamethylphosphortriamide, N-methylcaprolactam It is preferable to use

N, N 'is used as a hydrogen chloride suffixing agent.
-Dimethylaniline, N, N'-diethylaniline,
N, N'-dimethylmorpholine, pyridine and the like are used, and this sizing agent is used for dicarboxylic acid dichloride.
It is preferable to use 2 to 3 times the molar amount.

In the present invention, an aromatic compound represented by the general formula (I)
10 to 90% by weight of oligoamide chains and number average molecular weight of 500
An ester amide copolymer having a number average molecular weight of 5,000 to 500,000 comprising 90 to 10% by weight of a polyalkylene oxide chain having a molecular weight of 10,000 to 10,000 is obtained. It can be appropriately adjusted by the ratio of acid dichloride and the like. The number average molecular weight is 50
If it is less than 00, the ester amide copolymer is inferior in mechanical properties, and if it is more than 500,000, there is a problem in processability. Further, it is more preferable that the ester amide copolymer is produced so that the number average molecular weight is 10,000 to 100,000.

In the present invention, a stabilizer may be added during or after the polymerization in order to improve the heat resistance, particularly the thermochromic property of the obtained ester amide copolymer. Examples of these stabilizers include phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphinic acid, polyphosphonates, dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite, hindered phenol compounds, thioether compounds, Dithioate, mercaptobenzimidazole, thiocarbanilide,
Sulfur-containing compounds such as thiodipropionate,
Tin-based compounds such as tinmalate and dibutyltin monoxide are used, and the amount of these stabilizers is 0.01 to 100 parts by weight of the ester amide copolymer.
It is preferable to use 2.0 parts by weight.

In order to improve the moldability of the ester amide copolymer obtained in the present invention, lubricating agents such as stearic acid salts such as calcium, barium and aluminum, stearic acid ester, silicone oil, waxes and ethylenebisstearyl amide are used. Can be added. The amount of these additives is preferably in the range of 0.05 to 5.0 parts by weight based on 100 parts by weight of the ester amide copolymer.

Further, the ester amide copolymer obtained in the present invention may be added to dyes, pigments, inorganic reinforcing agents, plasticizers, hindered amine light stabilizers, ultraviolet absorbers, foaming agents, flame retardants, epoxy compounds and isocyanate compounds. And other known additives.

[0020]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these 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 type manufactured by JEOL Ltd.

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

(3) The dynamic viscoelastic behavior was measured using a DVE-V4 FT Rheospectral manufactured by Rheology Co., Ltd., at a frequency of 11 Hz and in a range of -100 to 300 ° C.

(4) 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.

(5) The thermal decomposition temperature (Td) was measured using a TG-DTA200 manufactured by Seiko Instruments Inc.
C./min., Measured in the range of 50 to 650.degree.

(6) The molecular weight of the polymer is S
C-8010, polystyrene gel GMHXL in column
And G2500H8 were connected using a column system GPC, flow rate was 1.0 ml / min, N-methyl-2-pyrrolidone / LiCl was used as an eluent, and measurement was performed at a column temperature of 40 ° C.

(7) The hardness was measured by a micro rubber hardness meter manufactured by Kobunshi Keiki Co., Ltd. using a 1 mm-thick press sheet.

(8) Mechanical properties (breaking strength, breaking elongation)
Was measured using an autograph DCS-100 manufactured by Shimadzu Corporation using a 1 mm-thick press sheet.

Example 1 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.
50.48 g (0.05 mol) of polytetramethylene glycol (PTMG) having a number average molecular weight (Mn) of 1009 and 19.35 g of butyl aminobenzoate (BuAB)
(0.10 mol) and sufficiently purged with nitrogen. Then, 0.08 g of tetrabutoxytitanium as a catalyst was added thereto, and the temperature was raised from room temperature to 200 ° C. in 1 hour under a nitrogen stream, and a predetermined amount of butanol was discharged in 2 hours, and the pressure was further reduced to 230 ° C./1 mmHg. The reaction was carried out for 2 hours under. Thereafter, 100 ml of N-methyl-2-pyrrolidone (NMP) was added thereto, and the mixture was kept at an ice temperature, and a solution prepared by dissolving 10.15 g (0.05 mol) of terephthalic acid chloride (TPC) in 100 ml of NMP was added dropwise. Further, 8.55 g of pyridine (0.5.
11 mol), and polymerized at room temperature for one day.

After the polymerization, the obtained polymer is precipitated in methanol, filtered and dried to obtain 58.12 g of an esteramide copolymer exhibiting good rubber elasticity (yield: 85).
%)was gotten. FIG. 1 shows the ¹ H-NMR measurement results of the copolymer, and FIG. 2 shows the ¹³ C-NMR measurement results. FIG. 3 shows the dynamic viscoelastic behavior of the obtained copolymer.
The obtained copolymer has a molecular weight (Mw) of 37000, a glass transition temperature (Tg) of -79 ° C, and a melting point (Tm) of 218.
° C and a thermal decomposition temperature (Td) of 403 ° C. The mechanical properties are as follows: the hardness (Hs) is 91 JIS-A, the breaking strength (T _B ) is 231 kg / cm ² , and the breaking elongation (E _B ) is 6
90%.

Example 2 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 prepared.
100.88 g (0.00.0 g) of PTMG having Mn of 2014
5 mol) and 19.37 g (0.10 mol) of BuAB, sufficiently purged with nitrogen, and then 0.08 g of tetrabutoxytitanium was added as a catalyst. Thereafter, the temperature was raised from room temperature to 200 ° C. in 1 hour under a nitrogen stream, and a predetermined amount of butanol was flowed out in 2 hours.
The reaction was performed under a reduced pressure of 1 mmHg for 2 hours. Then, 200 ml of NMP was added thereto, kept at ice temperature, and TPC10.
A solution prepared by dissolving 16 g (0.05 mol) in 100 ml of NMP was added dropwise, and pyridine was used as a hydrogen chloride scavenger.
95 g (0.10 mol) was added, and polymerization was carried out overnight at room temperature.

After the polymerization, the obtained polymer was precipitated in methanol, filtered and dried to obtain 105.03 g (yield: 88%) of an ester amide copolymer having good rubber elasticity. This copolymer has a Mw of 4100
0, Tg is -859 ° C, Tm is 198 ° C, Td is 401
° C. The mechanical properties of Hs are 78 JIS-A,
T _B is 181kg / cm ^2, E _B was 890%.

[0033]

According to the method of the present invention, an ester amide copolymer having properties as a thermoplastic elastomer, having an aromatic oligoamide chain in a hard segment, and having excellent heat resistance, cold resistance and processability can be obtained. Can be

[Brief description of the drawings]

FIG. 1 is a chart showing ¹ H-NMR measurement results of an ester amide copolymer obtained in Example 1.

FIG. 2 is a diagram showing the results of ¹³ C-NMR measurement of the ester amide copolymer obtained in Example 1.

FIG. 3 is a view showing the dynamic viscoelastic behavior of the ester amide copolymer obtained in Example 1.

Claims (1)

(57) [Claims] 1. A poly (alkylene oxide) glycol having a terminal substituted with an aromatic aminocarboxylic acid compound by a melting reaction and then reacting with an aromatic dicarboxylic acid dichloride in an organic solvent. (I) (However, R1, R2 are each carbon atoms shown. 6-30 divalent aromatic group) aromatic oligoamic chain 1 shown in
A method for producing an ester amide copolymer having a number average molecular weight of 5,000 to 500,000, comprising 0 to 90% by weight and 90 to 10% by weight of a polyalkylene oxide chain having a number average molecular weight of 500 to 10,000.