JPH03255124A - Aromatic polyester-amide copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the title copolymer having excellent physical and mechanical properties, especially high-temp. durability by polycondensing a specified amide compound with usual polyester-forming monomers. CONSTITUTION:An aromatic polyester-amide copolymer having a nitrogen content of 0.001-5wt.% is obtained by polycondensing amid compounds of formulas I and/or II (wherein A is a bivalent organic radical; R1 is a 2-10C aliphatic or alicyclic bivalent radical; and R2 is H or a 1-10C aliphatic or aromatic radical) with mainly an aromatic dicarboxylic acid or its esterifiable derivative and mainly an aliphatic glycol or its esterifiable derivative. This polyester-amide has excellent mechanical strengths, impact resistance and flexibility, undergoes less deterioration in properties (especially flexibility) even when it is kept at high temperatures for a long time, and has a promising use as electrical and electronic components and automobile parts, for example, connectors, switches and coating materials (for, e.g. wires) which are used at high temperatures.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel aromatic polyesteramide copolymer and a method for producing the same, which have excellent physical and mechanical properties and are particularly durable for long periods of time at high temperatures. The object of the present invention is to provide a material that has high temperature durability without deteriorating its physical properties when used.

[Prior art and its problems] Thermoplastic polyester resins, especially polyalkylene terephthalate resins such as polyethylene terephthalate or polybutylene terephthalate, have excellent mechanical properties, electrical properties, and other physical and chemical properties, and are easy to process. Because of its good properties, it is used in a wide range of applications such as automobiles, electrical and electronic parts, etc. as fibers and engineering plastics.

On the other hand, polyamides represented by nylon 6 and nylon 6.6 also have excellent mechanical strength and are widely used in the field of molded products as films and engineering plastics.

However, each of these resins has drawbacks, and attempts have been made for a long time to combine both ester bonds and amide bonds from the viewpoint of polymer molecular structure in order to improve these drawbacks and take advantage of the advantages of both. For example, a polyamide component is copolymerized to give polyester dyeability and impact resistance, or conversely, a polyester component is copolymerized to improve physical property changes and low rigidity caused by the hygroscopicity of boria straw. It is intended to be polymerized.

However, although the physical properties of such polyesteramides have been improved, they are still insufficient for some uses, particularly in terms of high temperature durability.

[Means for Solving the Problems] As a result of intensive studies to obtain a polyester amide that has a high molecular weight, maintains excellent physical properties, and particularly has excellent high-temperature durability, the present inventor has developed a specific ester-forming ashort compound. By polycondensing a specific amount of polyester with a regular polyester-forming monomer, the mechanical strength, impact resistance, heat resistance, hydrolysis resistance, etc. can be improved without losing the excellent properties of polyester.
We discovered that it is possible to obtain a highly practical polyester resin that has flexibility, solvent resistance, and particularly excellent high-temperature durability.
The present invention has now been fully developed.

That is, the present invention provides: (1) Ado compound represented by the general formula (A) and/or (B) [II] Mainly an aromatic dicarboxylic acid or an ester-forming derivative thereof [III] Mainly an aliphatic glycol or an ester thereof Nitrogen content 0 obtained by polycondensation reaction of forming derivatives
．． 001 to 5% by weight aromatic polyester amide and its manufacturing method.

The polyester amide obtained by the present invention has a small amount of amide units represented by the following general formula (A゛) and/or (B゛) in the main chain mainly composed of polyester units represented by the following general formula (C). It is an aromatic polyesteramide copolymer with an introduced structure.

(In the formula, A and R4 correspond to those of formula (A) and (B), Ar is an aromatic (for example, aromatic having 6 to 22 carbon atoms) divalent radical corresponding to [II], R3 is [III]
shows an aliphatic divalent radical corresponding to ) Hereinafter, the constituent components used in the production of the polyesteramide copolymer of the present invention will be specifically described in detail.

First, the terminal-reactive amide derivative [III] will be explained.

In formulas (A) and (B), ^ is a divalent organic radical,
For example, an alkylene group having 1 to 10 carbon atoms, 6 to 15 carbon atoms
arylene group, a cycloalkylene group having 5 to 12 carbon atoms, and the like. More specifically, alkylene groups include methylene, ethylene, propylene, butylene, bentylene, hexamethylene, octamethylene, nonamethylene, decamethylene, dimethylmethylene, etc., and arylene groups include phenylene, naphthylene, diphenylene, etc. Examples include cyclohexylene as a cycloalkylene group.

Preferably it is an arylene group, especially a phenylene group.

R1 in formulas (A) and (B) represents an aliphatic or alicyclic divalent radical having 2 to 10 carbon atoms.

Specifically, examples of aliphatic divalent radicals include ethylene, propylene, butylene, pentylene, hexamethylene, octamethylene, nonamethylene, decamethylene, dimethylmethylene, and substituted products thereof, and examples of alicyclic divalent radicals include cyclohexylene. and substituted products thereof. Among these, as R, in formula (B), ethylene and propylene are particularly preferred from an economical point of view, and Rt is hydrogen, an aliphatic monovalent radical having 1 to 10 carbon atoms, or an aromatic radical. More specifically, examples of aliphatic radicals include methyl, ethyl, propyl, butyl, pentyl, etc., and examples of aromatic radicals include phenyl group and its derivatives.

Among these, hydrogen, methyl,
Ethyl and phenyl are particularly preferred.

Specific examples of the siad compound represented by the general formula (A) include N,N'-bis(2-hydroxyethyl)malonamide, N,N'-bis(2-hydroxyethyl)succiamide, NjJ''-bis (2-hydroxyethyl)
Glutaramide, N,N'-bis(2-hydroxyethyl)adipinamide, NN'-bis(2-hydroxyethyl)isophthalamide, N,N'-bis(2-hydroxyethyl)terephthalamide, N,N '-Bis(3
-hydroxypropyl)malonamide, N,N'-bis(3-hydroxypropyl)succiamide, N,N'-bis(3-hydroxypropyl)glutaranamide, N,N
'-bis(3-hydroxypropyl)adipinamide,
N,N'-bis(3-hydroxypropyl)isophthalamide, N,N''-bis(3-hydroxypropyl)terephthalamide, 2,6-bis([(2-hydroxyethyl)7trillionococarbonyl)naphthalene, Examples include 2.7-bis[[(2-hydroxyethyl)aξnococarbonyl]naphthalene, 4.4'-bis[[(2-hydroxyethyl)aξno]carbonyl]biphenyl, etc. The compounds may be used alone or in combination of two or more.

Among these compounds, preferred are those in which 8 is an aromatic group, and more preferred is a phenylene group. Particularly preferred are N,N'-bis(2-hydroxyethyl)terephthalamide, N,N"-bis(2-hydroxyethyl)isophthalamide, N,N'-bis(3-hydroxypropyl)terephthalamide, N , N
”-bis(3-hydroxypropyl)isophthalamide.

Specific examples of the monoamide compound represented by m formula (B) include 2-([(2-hydroxyethyl)amino]carbonyl]acetic acid, 3-([(2hydroxyethyl)amino]
carbonyl]propanoic acid, 4-([(2-hydroxyethyl)amino]carbonyl]butanoic acid, 5-([(2-
hydroxyethyl)amino]carbonyl]pentanoic acid,
6-[[(2-hydroxyethyl)amino]carbonyl]hexanoic acid, 2-[[(3hydroxypropyl)amino]carbonyl]acetic acid, 3-([(3-hydroxypropyl)a≧no]carbonyl]propanoic acid ,4-([(3
-Hydroxypropyl)ano]carbonyl]butanoic acid, 5-([(3-hydroxypropyl)aminococarbonyl)pentanoic acid, 6-([(3-hydroxypropyl)amino]carbonyl]hexanoic acid, 4- ([(2-hydroxyethyl)amino]carbonyl]benzoic acid, 3-
([(2-hydroxyethyl)amino]carbonyl]benzoic M, 4-([(3-hydroxypropyl)amino]
carbonyl]benzoic acid, 3-([(3-hydroxypropyl)amino]carbonyl]benzoic acid, 6-([(2-
Examples include hydroxyethyl)amino]carbonyl]-2-naphthoic acid, 6[(3-hydroxypropyl)amino]carbonyl]-2-naphthoic acid, and alkyl esters thereof, particularly methyl ester derivatives.

Particularly preferred are 4-([(2-hydroxyethyl)amino]carbonyl]benzoic acid, 3-([(2-hydroxyethyl)aminococarbonyl)benzoic acid, 4-(
[(3-hydroxypropyl)amino]carbonyl]benzoic acid, 3-([(3-hydroxypropyl)amino]
[carbonyl]benzoic acid and their methyl ester derivatives.

Here, the compounds of formula (A) and formula (B), which are the characteristic constituent components (1) of the present invention, are a dicarboxylic acid derivative represented by the following general formula (D) and an alkanol represented by the general formula (E). It is obtained by reacting with an amine, and by selecting the molar ratio, it can be obtained as a single amide compound of only (A) or (B), or a mixed amide compound of (A) and (B). .

(A and R8 in formulas (D) and (E) are equivalent to formulas (A) and (B). Also, X in formula (D) is
Indicates active leaving groups such as hydroxyl, chlorine, alkoxy, and phenoxy. ) Typical examples of compounds represented by the general formula (D) include malonic acid, succinic acid, glutaric acid, adipic acid, terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 1
．． 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2.2"-biphenylene dicarboxylic acid, 4
, 4'-biphenylenedicarboxylic acid, their acid chlorides, their monoalkyl esters, especially monomethyl esters, their dialkyl esters, especially their dimethyl esters, and their diphenyl esters.

Representative examples of the alkanolamine compound represented by the general formula (E) include 2-amino-1-ethanol, 3-amino-1-propanol, 4-amino-1-butanol,
5-amino-1-pentanol, 2-amino-1-propatol, NHz-R, -OH(E) 2-amino-1-butanol, 2-agono 2-methyl-1-propatol, 2 -amino-3methyl-1-butanol, 2-amino-1-pentanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-
Examples include propatool, 2,2-dimethyl-3-72 nolobanol, 4-aminocyclohexanol, and the like.

Here, whether to obtain a compound of formula (A) or a compound of formula (B) is approximately determined by the mixing molar ratio of (D) and (E). That is, the mixing molar ratio of (D) and (E) is [(E)]
/[(D)]≧2, shear 5d (A) is selectively generated.

On the other hand, when 1 < [(E)]/[(D)] < 2, a mixture of chiagod (A) and monoamide (B) is produced.

Furthermore, if [(E)]/[(D)] ≦1, mainly (
B) is generated.

This synthetic reaction can be carried out without a solvent or in a solvent, and component (II
If the reaction is carried out using [) as a solvent, the entire reaction system can be used for the polycondensation reaction, which is convenient.

Next, the components [I[) and (I[I] constituting the aromatic polyester portion of the copolymer of the present invention will be explained. Component (If) mainly consists of an aromatic dicarboxylic acid or an ester-forming derivative thereof.

Representative substances include terephthalic acid, 2,6 naphthalene dicarboxylic acid, or derivatives thereof, and in some cases, dicarboxylic acids such as isophthalic acid and phenylene dicarboxylic acid or derivatives thereof, adipic acid,
Dicarboxylic acids or ester-forming derivatives thereof such as sebacic acid and succinic acid, and aromatic hydroxycarboxylic acids or ester-forming derivatives thereof such as hydroxybenzoic acid and hydroxynaphthoic acid are used.

Next, component [III] for constituting the polyester copolymer of the present invention mainly consists of aliphatic glycol or its ester-forming derivative.

Typical substances include low molecular weight glycols ranging from C2 to CII, such as ethylene glycol, I+4-butylene glycol, 1,3-propanediol, and 1,4-
butynediol, 1.6-hexanediol, 1.8-
Examples include diols such as octanediol. Also,
In addition to these low molecular weight glycols, high molecular weight glycols such as polyalkylene oxide glycols, such as polyethylene oxide glycol, polybutylene oxide glycol, etc., can also be used in combination.

In addition, the component (I [ It is also possible to use alkylene oxide adduct alcohols such as a 2-mole propylene oxide adduct of ^, polyhydroxy compounds such as glycerin, pentaerythritol, or ester-forming derivatives thereof.

In general, the polyesteramide copolymer of the present invention often has a colored product and has a low molecular weight when a large amount of amide groups is introduced. On the other hand, when the amount is small, the improvement effect due to the introduction of the amide group is small.

Therefore, the nitrogen content in the aromatic polyesteramide copolymer of the present invention is suitably 0.001 to 5% by weight, preferably 0.005 to 2% by weight.

This nitrogen content is determined by (A) and (B) in all monomer components.
It can be adjusted by adjusting the amount of component (I) used according to the formula.

The method for producing the polyester amide of the present invention can be carried out in accordance with the conventional method for producing polyester. That is, for example, [I] is added to [■] and [III], heated to about 150 to 300°C in the presence of a catalyst to perform an esterification or transesterification reaction, and then the excess monomer or eliminated component is removed under reduced pressure. A copolymer is obtained by performing polycondensation while distilling off.

The proportion of each component used in this polycondensation is component (n)
Component (I) is 90 to 300 mol, preferably 95 to 250 mol, and component (I) is 0.01 mol per 100 mol.
-30 mol, preferably 0.04-15 mol. In this case, the catalysts used are tetraalkoxytitanium such as tetrabutoxytitanium, titanium oxalate metal salts such as potassium titanium oxalate, tin compounds such as dibutyltin oxide or dibutyltin laurate, zinc acetate, lead acetate, manganese acetate, Alternatively, known catalysts generally useful in polyester polycondensation reactions, such as metal acetates such as calcium acetate and antimony compounds such as antimony dioxide, may be used alone or in combination of two or more.

In addition, the timing of addition of component [III] in the polycondensation reaction is arbitrary, and may be at any time during the progress of the esterification reaction or transesterification reaction of components (n) and [■], or during the subsequent polycondensation reaction. The process may proceed at a point when a polyester having a considerable molecular weight has been produced.

In order to increase the molecular weight of the polymer (including oligomers) obtained by melt polymerization or solution polymerization in the present invention, it is preferable to further perform solid phase polymerization. Solid phase polymerization may be carried out in accordance with the method generally used for polyesters, and may be carried out in a vacuum or inert gas at a high temperature within a range that does not cause particles to fuse together for a required period of time. Thus, the polyesteramide of the present invention can have an intrinsic viscosity of 0.4 to 3.0, and has excellent properties as described above.

In addition, when the polymer of the present invention is used, in order to further impart desired properties according to its purpose, known substances generally added to thermoplastic resins, thermosetting resins, etc., such as antioxidants and ultraviolet absorbers, may be added. stabilizers such as antistatic agents, flame retardants, flame retardant aids, colorants such as dyes and pigments, lubricants,
Of course, it is also possible to use a composition in which a mold release agent, a plasticizer, a crystallization accelerator, a crystal nucleating agent, an inorganic filler, etc. are added during polymerization or after polymerization and before molding.

Examples of inorganic fillers include glass fiber, carbon fiber, ceramic fiber, boron fiber, potassium titanate fiber, general inorganic fibrous substances such as asbestos, calcium carbonate, highly dispersed silicates, alumina, aluminum hydroxide, talc, and clay. , mica, glass flakes, glass powder, glass peas, quartz powder, silica sand, wollastonite, carbon black, barium sulfate, calcined gypsum, silicon carbide, alumina, boron nitride, silicon nitride, etc. This includes inorganic compounds such as whiskers.

These inorganic fillers can be used singly or in a combination of two or more as needed, and among them, glass fiber is a typical filler, and it may be preferable to use other powdery or plate-like fillers in combination. many.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Example 1 970 parts by weight of dimethyl terephthalate as component [II], 513 parts by weight of 1,4-butanediol as component [III]
N, N'- belonging to formula (A) as part by weight and component [I]
7111 parts by weight of bis(2-hydroxyethyl)terephthal and 0.7 parts by weight of tetrabutoxytitanium as a catalyst were charged into a reactor equipped with a stirrer, a nitrogen inlet tube and a distillation tube, and stirred at 160°C for 130 minutes under a nitrogen stream. did. The temperature was gradually raised from 200°C to 250°C, and the mixture was heated and stirred for 2 hours. Next, after stopping the introduction of nitrogen, the pressure in the reactor was gradually reduced, and after 30 minutes, the pressure was lowered to 0.3 mm/g, and the mixture was stirred at this pressure for 3 hours. The obtained polymer exhibited an intrinsic viscosity of 1.2 and a nitrogen content of o, oio wt%. Typical physical properties are shown in Table-1.

Example 2 N,N'-bis(2) belonging to formula (A) as component (1)
The same procedure as in Example 1 was carried out except that 5 parts by weight of -hydroxyethyl)isophthalamide was used. The obtained polymer had an intrinsic viscosity of 1.1 and a nitrogen content of 0.
．． It was 0.051% by weight. (See Physical Properties Table 2-1) Example 3 Component (1) includes N, N' to bis(3) belonging to formula (A).
The entire procedure was the same as in Example 1 except that 5 parts by weight of -hydroxypropyl) terephthalamide was used. The obtained polymer had an intrinsic viscosity of 1.1 and a nitrogen content of 0.
．． It was 0.045% by weight.

(Refer to Physical Properties Table 2-1) Example 4 As component (1), N, N'-bis(
The same procedure as in Example 1 was carried out except that 3 parts by weight of 2-hydroxyethyl)adipinamide was used. The obtained polymer had an intrinsic viscosity of 1.0 and a nitrogen content of 0.
It was 0.033% by weight.

(See Physical Properties Table 2-1) Example 5 Same as Example 1 except that 10 parts by weight of 4-1:[(2hydroxyethyl)amino]carbonyl]benzoic acid belonging to formula (B) was used as component (I). Exactly the same operation was performed. The obtained polymer had an intrinsic viscosity of 0.8 and a nitrogen content of 0.060% by weight. (Physical properties: see Table 1) Example 6 N,N'-bis(2) belonging to formula (A) as component (I)
-Additional amount of (hydroxyethyl) isophthalamide 10
The operation was performed in exactly the same manner as in Example 2 except that the amount was 0 parts by weight.

The obtained polymer had an intrinsic viscosity of 0.7 and a nitrogen content of 0.962% by weight. (Refer to Physical Properties Table 2-1) Example 7 N, N'-bis(
The same procedure as in Example 1 was carried out, except that a mixture of 2-hydroxyethyl)isophthalamide and methyl 3-(((2-hydroxyethyl)amino]carbonyl]benzoate belonging to formula CB) was used. Component (I) used in this example was prepared by heating 3 parts by weight of a mixture of 1.0 mol of methyl isophthalate and 1.5 mol of ethanolamine at 120°C for 2 hours using 1.4-butanediol as a solvent. This is the reaction product obtained.The obtained polymer exhibited an intrinsic viscosity of 1.1 and a nitrogen content of 0.020% by weight.

(See Physical Properties Table 2-1) Example 8 Component [■]: 970 parts by weight of dimethyl terephthalate;
730 parts by weight of ethylene glycol as component (I [ .6 parts by weight was charged into a reactor equipped with a stirrer, a nitrogen inlet tube, and a distillation tube, and stirred at 180° C. for 160 minutes under a nitrogen stream. The temperature was gradually raised to 200°C, and the mixture was further heated and stirred for 2 hours. Next, the temperature was raised to 220'C to distill off excess ethylene glycol. Next, the temperature was gradually raised to 280°C, and the introduction of nitrogen was stopped, and the pressure inside the reactor was gradually reduced. After 30 minutes, the pressure was lowered to 0.3 mmHH, and stirring was carried out at this pressure for 3 hours.

The obtained polymer exhibited an intrinsic viscosity of 1.2 and a nitrogen content of 0.058% by weight. (See Physical Properties Table 2-1) Comparative Example 1 The same operation as in Example 1 was performed except for component (1). The intrinsic viscosity of the obtained polymer was 0.8.
(See Physical Properties Table 2-1) Comparative Example 2 The same operation as in Example 8 was performed except for component (I). The intrinsic viscosity of the obtained polymer was 0.9. (
Physical Properties (See Table 1) The measuring methods used to evaluate the physical properties of the polymer molded articles of each example are as follows.

■ Tensile strength and elongation In accordance with ASTM D-638 (test piece ASTM type ■ type: thickness 1 mm), initial strength and elongation, and 120°
The elongation after heating at C for 500 hours was measured.

(2) Izont impact strength Notched Izont impact strength was measured in accordance with ASTM D-256.

〔Effect of the invention〕

The aromatic polyester amide of the present invention has superior mechanical strength, impact resistance, and flexibility compared to conventional polyester, and has physical properties (especially flexibility) when kept at high temperatures for a long time.
It is a promising material for use in electrical/electronic parts, automobile parts, etc. that are used at high temperatures, such as connectors, switches, and coating materials (for wiring, etc.) because of their low deterioration in temperature.

Claims (1)

[Claims] 1. [I] An amide compound represented by the general formula (A) and/or (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) In the formula, A represents a divalent organic radical. R_1 represents an aliphatic or alicyclic divalent radical having 2 to 10 carbon atoms. R_2 represents hydrogen or an aliphatic or aromatic radical having 1 to 10 carbon atoms. [II] Primarily aromatic dicarboxylic acid or its ester-forming derivative [III] Nitrogen content 0 obtained by polycondensation reaction of mainly aliphatic glycol or its ester-forming derivative
．． 001-5% by weight of aromatic polyesteramide copolymer. 2. The aromatic polyester amide copolymer according to claim 1, wherein A in the amide compound represented by the general formula (A) and/or (B) is an arylene group having 6 to 15 carbon atoms. 3. The aromatic polyester according to claim 1, wherein A of the amide compound represented by the general formula (A) and/or (B) is an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms. Amide copolymer. 4. Claim 1 in which R_1 of the amide compound represented by the general formula (A) and/or (B) is an alkylene group having 2 to 10 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms.
The aromatic polyesteramide copolymer according to any one of items 1 to 3. 5. The aromatic polyesteramide copolymer according to claim 1, wherein the amide compound [I] represented by the general formula (A) and/or (B) is a reaction product of a dicarboxylic acid or a derivative thereof and an alkanolamine. 6. [II] The aromatic dicarboxylic acid or its ester-forming derivative is one or two selected from terephthalic acid or its derivative, isophthalic acid or its derivative, naphthalene dicarboxylic acid or its derivative, and biphenylene dicarboxylic acid or its derivative. The aromatic polyesteramide copolymer according to any one of claims 1 to 5, which is the above dibasic acid compound. 7. Any one of claims 1 to 6, wherein the aliphatic glycol or ester-forming derivative thereof in [III] is one or more diol compounds selected from aliphatic glycols having 8 or less carbon atoms or derivatives thereof. Aromatic polyesteramide copolymer according to item 1. 8. Add the amide compound [I] represented by the general formula (A) and/or (B) to the monomers [II] and [III], and heat the mixture to 150 to 300°C in the presence of a catalyst. A method for producing an aromatic polyesteramide copolymer, which comprises carrying out an esterification reaction, and then carrying out a polycondensation reaction while distilling off excess monomers or eliminated components under reduced pressure.