JPH03273028A - Halogenated aromatic polyesteramide and its production - Google Patents

Abstract

PURPOSE:To obtain the title polyesteramide improved in flexibility and flame retardancy by polycondensing a specified amino compound with an aromatic dicarboxylic acid (esterifiable derivative), an aliphatic glycol (esterifiable derivative) and a halogenated esterifiable compound. CONSTITUTION:Amide 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) are added to an aromatic dicarboxylic acid (esterifiable derivative) (e.g. terephthalic acid), an aliphatic glycol (esterifiable derivative) (e.g. ethylene glycol) and a halogenated esterifiable compound (e.g. tetrabromobisphenol A), and the obtained mixture is esterified at 150-300 deg.C in the presence of a catalyst and polycondensed while distilling off excessive monomers and the formed by-product components in a vacuum to obtain a halogenated aromatic polyesteramide having a nitrogen content of 0.001-5wt.% and a halogen content of 0.5-30wt.%.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is suitable for use as a coating material for functional parts or electric wires in the fields of electrical and electronic equipment, automobiles, etc., and is particularly suitable for use at high temperatures and for long periods of time. It relates to a material that does not lose its flexibility and has excellent flame retardancy.

[Conventional technology and its issues]

Crystalline thermoplastic polyester resins, such as polyalkylene terephthalate resins, have excellent mechanical properties, electrical properties, and other physical and chemical properties, as well as good processability, so they are used as engineering plastics in automobiles, electrical and electronic parts. It is used for a wide range of purposes such as However, with the expansion and diversification of applications, even more advanced performance and special characteristics are often required. Stability of physical properties (long-term heat resistance) during use is increasingly required.

For example, in the automobile industry and the like, due to safety requirements, it is desired that the material be flame retardant and maintain stability in physical properties even when used for long periods of time at high temperatures.

Polyethylene terephthalate and polybutylene terephthalate have good thin-wall processability and excellent mechanical strength (flexibility, abrasion resistance, etc.), heat resistance, and electrical properties.
If the flame retardance is insufficient (there have been many proposals to add various flame retardants, flame retardant aids, etc. to provide flame retardancy), the addition of these substances will impede the mechanical properties. However, if it is kept at high temperatures for a long time, it may ooze out from the molding material.
This is undesirable as it may decompose the polymer. In addition, attempts have been made to prepare polymers with halogens bonded within the molecule by using halogen-containing monomers in the polycondensation of polyester as in the present invention. Although a polymer is obtained that does not ooze out, the general physical properties of the polymer rapidly deteriorate when it is kept at high temperatures for a long period of time, and it cannot be said that it is a material that can withstand long-term use at high temperatures.

[Means to solve the problem]

In view of the above issues, the present inventor conducted intensive research to obtain a material that does not lose its flexibility due to thermal history, is flame retardant, and has excellent mechanical and electrical properties. The inventors have also discovered that a halogen-containing polyester amide into which a unit having a specific amide bond has been introduced can achieve the object of the present invention, leading to the present invention.

That is, the present invention provides [I] an amide compound represented by the general formula (A) and/or (B) OH 1 R2-0-C-^-C-N-R, -DH(B) (A in the formula
represents a divalent organic radical. R1 represents an aliphatic or ring group divalent radical having 2 to 10 carbon atoms. R2 represents hydrogen or an aliphatic or aromatic radical having 1 to 10 carbon atoms. ) CID mainly aromatic dicarboxylic acid or its ester-forming derivative [■] Mainly aliphatic glycol or its ester-forming derivative [■] Nitrogen content 0 obtained by polycondensation reaction of ester-forming compound containing halogen
．． The present invention relates to a halogen-containing aromatic polyester amide having a halogen content of 0.001 to 5% by weight and a halogen content of 0.5 to 30% by weight, and a method for producing the same.

The polyester amide obtained by the present invention has at least the following format (A゛) and/or (
It is an aromatic polyester amide having a structure in which a small amount of the amide unit represented by B') is introduced, and a halogen-containing divalent organic group (described later) corresponding to [IV) is further introduced.

(In the formula, ^ and R1 correspond to those of formulas (A) and (B), and Ar is an aromatic (for example, aromatic having 6 to 20 carbon atoms) divalent dicanope corresponding to [II). R3 represents an aliphatic divalent radical corresponding to [■]. ) Hereinafter, the constituent components used in the production of the halogen-containing aromatic polyester amide of the present invention will be specifically described in detail.

First, the terminal-reactive amide derivative [1] will be explained.

(A> and (B) In the formula, A 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, examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexamethylene, octamethylene, nonamethylene, decamethylene, dimethylmethylene, etc., and examples of arylene groups include phenylene, naphthylene, diphenylene, etc. can be exemplified, and cyclohexylene can be exemplified as the 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, bentylene, hexamethylene, octamethylene, nonamethylene, decamethylene, dimethylmethylene, and substituted products thereof, and examples of alicyclic divalent radicals include cyclohexylene. and substituted products thereof. Among these, ethylene and propylene are particularly preferred as R from an economical point of view.

In formula (B), R2 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, and petinobepentyl, and examples of aromatic radicals include phenyl groups and derivatives thereof.

Among these, hydrogen, methinobethyl, and phenyl are particularly preferred from an economic standpoint.

- Specific examples of diamide compounds represented by format (A) include N,N'-bis(2-hydroxyethyl)malonamide, N,N'-bis(2-hydroxyethyl)succiamide, N,N'-bis (2-Hydroxyethyl)glutaramide, N, N'~bis(2-hydroxyethyl)adipinamide, N.

N'-bis(2-hydroxyethyl)inphthalamide, N,N'-bis(2-hydroxyethyl)terephthalamide, N,N'-bis(3-hydroxypropyl)malonamide, N,N'-bis( 3-hydroxypropyl)succiamide, N,N'-bis(3-hydroxypropyl)glutaramide, N,N'-bis(3-hydroxypropyl)adipinamide, N,N'-bis(3-
hydroxypropyl)isophthalamide, N,N'-bis(3-hydroxypropyl)terephthalamide, 2.
6-HisC[(2-hydroxyethyl)amino]carbonyl]naphthalene, 2,7-bis[[(2-hydroxyethyl)amino]carbonyl]naphthalene, 4.4"-
Bis[[(2-hydroxyethyl)amino]carbonyl]biphenyl, 2I6-bisC[(3-hydroxypropyl)amino]carbonyl]naphthalene, 2,7-bis[: E (3-hydroxypropyl)aminococarbonyl] Examples include naphthalene, 4,4'-bis[[(3-hydroxypropyl)aminococarbonyl]biphenyl, and the like. These 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 general formula (B) include 2-([(2-hydroxyethyl)aminococarbonyl]acetic acid, 3-[[(2-hydroxyethyl)amino]carbonyl]propane[1F , 4-[[(2-hydroxyethyl)amino]carbonyl]butanoic acid, 5-
([(2-hydroxyethyl)amino]carbonyl]pentane 16-[[(2-hydroxyethyl)aminococarbonyl]hexanoic acid, 2-[[(3-hydroxypropyl)amino]carbonyl]acetic acid, 3-([ (3-hydroxypropyl)amino]carbonyl]propane L4-
[[(3-hydroxypropyl)amino]carbonyl]
Butanoic acid, 5-([(3-hydroxypropyl)aminococarbonyl]pentanoic acid, 6-C[(3-hydroxypropyl)amino]carbonyl]hexane 14-[:
[(2-hydroxyethyl)aminococarbonyl]benzoic acid, 3-[[(2-hydroxyethyl)amino]carbonyl]benzoic acid, 4-C[(3-hydroxypropyl)aminococarbonyl]benzoic acid fF? ,3-C[(3
-hydroxypropyl)aminococarbonyl]benzoic acid, 6-[: [(2-hydroxyethyl)amino]carbonyl]-2-naphthoic acid, 6-C[(3-hydroxypropyl)amino]carbonyl]-2-naphthoic acid Mention may be made of acids and their alkyl esters, especially methyl ester derivatives.

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

Here, the compounds of formulas (A) and (B), which are the characteristic constituents [■] 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)). .

11t-12-R, -OH(E) (A and R3 in formulas (D) and (E) are equivalent to formulas (A) and (B). Also, B in formula (0) is hydroxyl group, chlorine, alkoxy, phenoxy, etc.) Typical examples of compounds represented by general formula (D) include malonic acid, succinic acid, glutaric acid, adipic acid, terephthalic acid, isophthalic acid, ,4-naphthalene dicarboxylic acid, 1
, 5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,2'-biphenylene dicarboxylic acid, 4
．． Mention may be made of 4'-biphenylenedicarboxylic acids, their acid chlorides, their monoalkyl esters, especially monomethylesterenope, 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, and 2-amino-1-propanol. -1-propanol, 2-amino-1-butanol, 2-amino-2-methyl-1-propatool, 2-amino-3-methyl-1-butanol, 2-amino-1-pentanol, 1-dimethylamino- 2-probanonope 3-dimethylamine-1-propatol, 2,2-dimethyl-3
-aminopropanol, 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, diamide (A) is selectively produced.

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

Furthermore, if [(E)]/mouth(D)] ≦1, mainly (
B) is generated. This synthetic reaction can be carried out without a solvent or in a solvent, and it is convenient to carry out the reaction using component (III) as a solvent because the entire reaction system can be used for the polycondensation reaction.

Next, the components [In and [III] constituting the aromatic polyester portion of the copolymer of the present invention will be explained. Component CIII consists primarily of aromatic dicarboxylic acids or ester-forming derivatives 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, and sebacin. A dicarboxylic acid such as succinic acid or an ester-forming derivative thereof, an aromatic hydroxycarboxylic acid such as hydroxybenzoic acid or hydroxynaphthoic acid or an ester-forming derivative thereof are used.

Next, the component [■] for constituting the polyester portion of the copolymer of the present invention mainly consists of aliphatic glycol or its ester-forming derivative. Typical substances are C2 to C6 low molecular weight glycols, such as ethylene glycol, 4-7" ethylene glycol 1.1
．． Examples include diols such as 3-7'ropanedionobe 2-butene-1,4-dio-/l/, 1°6-hexanediol, and 1,8-octanediol. In addition to these low molecular weight glycols, high molecular weight glycols such as polyalkylene oxide glycols may be used in combination with polyethylene oxide glycol, polybutylene oxide glycol, and the like.

In addition, as component [I), bisphenol A, 4,4''-dihydroxybiphenyl, aromatic alcohols such as phosphinic acid having an aromatic diol group, 2 moles of ethylene oxide adduct of bisphenol A, bisphenol A alkylene oxide adduct alconobeglycerin such as propylene oxide 2 mole adduct;
Polyhydroxy compounds such as pentaerythritol or ester-forming derivatives thereof can also be used.

Next, the polyesteramide of the present invention is an aromatic compound in which a halogen is introduced into the molecule by using a halogen-containing ester-forming compound [■] as a monomer. It is polyesteramide. Examples of the halogen-containing compound CYV r used for this purpose include the following. Here, bromine is particularly preferred as the halogen.

(5) H[]R3' O0-OR,'0H (X).

(X)7 (8) C)1. X HD-Cf12-C-CH, -0)I CIl,X where CH3 R1', R2": C112-, -C-, -0-,
-3-, -3O2113 R3', R4'; C2H4, CJs'-, -(C
2H40). -1(c3Hso)-X; halogen (X) 7 A, m; 1 to 4 n; represents an integer of 1 or more.

Preferred halogen compounds to be incorporated into the copolymer are those represented by general formulas (1) to (7), and those containing 4 or more halogen atoms in one molecule are particularly preferred. When using bromine as the halogen, an example of -formation (1) is tetrabromobisphenol A1
Tetrabromobisphenolsulfone, examples of (2) include tetrabromobisphenol F, examples of (3) include 2 moles of ethylene oxide adduct to tetrabromobisphenol, 2 moles of propylene oxide adduct of tetrabromobisphenol A, and tetrabromobisphenol F; 2 mole ethylene oxide adduct of bromobisphenol sulfone, 2 mole propylene oxide adduct of tetrabromobisphenol sulfone, tetrabromohydroquinone as an example of (4), 2 mole ethylene oxide adduct of tetrabromohydroquinone as an example of (5), An example of (6) is tetrabromo terephthalic acid, and an example of (7) is polycarbonate of tetrabromobisphenol A.

The nitrogen content in the halogen-containing aromatic polyester amide of the present invention is suitably 0.001 to 5% by weight, preferably 0.003 to 2% by weight.

This nitrogen content is determined by (A) and (B) in the monomer gold component.
It can be adjusted by adjusting the usage amount of component CI) consisting of the following formula.

Generally, when the amount of amide groups introduced is large, the product often becomes colored and has a low molecular weight.

On the other hand, when the amount is small, the improvement effect due to the introduction of the amide group is small.

Further, the content of halogen is 0.5 to 30% by weight, preferably 2 to 20% by weight. This halogen content is the component [
It can be adjusted by adjusting the amount of rV) used. If the content is 0.5% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 30% by weight, the mechanical properties will deteriorate, which is not preferable.

The halogen-containing aromatic polyester amide of the present invention has at least the above [I] to CrV) as essential components, but other components may be added as components constituting the copolymer. It's not a hindrance.

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, CI] as monomer, [ID, CIII) and CI
V) and mixed in the presence of a catalyst to about 150 to 300
A copolymer can be obtained by heating to 0.degree. C. to carry out esterification or transesterification reaction, and then carrying out polycondensation while distilling off excess monomers or eliminated components under reduced pressure.

When producing the polyesteramide of the present invention, the ratio of each monomer is Component 1:II when the ester-forming functional group of the halogen compound of Component [■] is alcohol-based.
:1100 mol, component CIII] + [:lV]
is 90 to 300 mol, preferably 95 to 250 mol. In addition, when the ester-forming functional group of the halogen compound of component [■] is a carboxylic acid type, component Cn) [
lV) For 100 mol, component CIIIE is 90-3
00 monobe is preferably 95 to 250 moles.

The proportion of component [1], which is a characteristic component of the present invention, is 0.01 to 30 moles, preferably 0.04 to 15 moles, per 100 moles of component [■].

If a material with a high oxygen index is required depending on the usage conditions, the halogen content in the polymer can be adjusted by adjusting the content of component CIVI as appropriate to obtain a material that satisfies the desired oxygen index. can.

In this case, the catalysts used include tetraalkoxytitanium such as tetrazo)-oxytitanium, metal salts of titanium oxalate such as potassium titanium oxalate, tin compounds such as dibutyltin oxide or dibutyltin laurate, zinc acetate, lead acetate, manganese acetate, or Known catalysts generally useful in polycondensation reactions of polyesters, such as metal acetates such as calcium acetate and antimony compounds such as antimony trioxide, may be used alone or in combination of two or more.

In addition, the timing of addition of component [1) in the polycondensation reaction is arbitrary, and may be at any time during the progress of the esterification reaction or transesterification reaction of components [II), [■] and S■], or after the addition. The polycondensation reaction may proceed to produce a polyester having a considerable molecular weight.

In the present invention, polymers obtained by melt polymerization or solution polymerization (
In order to increase the molecular weight of the polymers (including oligomers), it is preferable to further carry out 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 has an intrinsic viscosity of 0.4 to 3.
It can have a value of 0, and has excellent characteristics as described above.

In addition, when using the polymer of the present invention, in order to further impart desired properties depending on the purpose, a small amount of other thermoplastic resin may be used as an auxiliary agent, or a known substance generally added to thermoplastic resins may be used. That is, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, colorants such as dyes and pigments, lubricants, mold release agents, plasticizers and crystallization promoters, Of course, it is also possible to use a composition in which a crystal nucleating agent, an inorganic filler, etc. are added during polymerization or after polymerization and before molding.

The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures.

For example, polyamide, ABS, polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, polyether sulfone, polyetherimide, polyether ketone, fluororesin, styrene type, olefin type, vinyl chloride type, urethane type, ester type, amide. Examples include thermoplastic elastomers such as elastomers.

Moreover, these thermoplastic resins can also be used in combination of two or more types.

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. Includes inorganic compounds, whiskers, etc.

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〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 970 parts by weight of dimethyl terephthalate as component CII), 513 parts by weight of 1,4-butanediol as component [IID], tetrabromobisphenol A as component [■]
158 parts by weight of 2 mole adduct of ethylene oxide, component CI), N, N'-bis(2-
1 part by weight of hydroxyethyl) terephthalamide and 0.7 parts by weight of tetrabutoxytitanium as a catalyst were charged into a reactor equipped with a stirrer, a nitrogen inlet pipe and a distillation pipe, and stirred at 160°C for 30 minutes under a nitrogen stream. did. The temperature was gradually raised from 200°C to 250°C, and the mixture was 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 Q, 3 mmHg, and the mixture was stirred at this pressure for 3 hours.

The obtained polymer had an intrinsic viscosity of 1.2, a nitrogen content of 0.009% by weight, and a bromine content of 6.5% by weight. The physical properties are shown in Table 1.

Example 2 As component [1], N, N'-bis(
The same procedure as in Example 1 was carried out except that 5 parts by weight of 2-hydroxyethyl)isophthalamide was used.

The obtained polymer had an intrinsic viscosity of 1.0, a nitrogen content of 0.045% by weight, and a bromine content of 6.5% by weight. The physical properties are shown in Table 1.

Example 3 N, N'-bis(
The same procedure as in Example 1 was carried out except that 5 parts by weight of 3-hydroxypropyl) terephthalamide was used.

The obtained polymer had an intrinsic viscosity of 1.1, a nitrogen content of 0.040% by weight, and a bromine content of 6.5% by weight. The physical properties are shown in Table 1.

Example 4 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 0.9, a nitrogen content of 0.029% by weight, and a bromine content of 6.5% by weight. The physical properties are shown in Table 1.

Example 5 The same procedure as in Example 1 was carried out except that 10 parts by weight of 4-C[(2-hydroxyethyl)amino]carbonyl]benzoic acid belonging to formula (B) was used as component [■].

The obtained polymer had an intrinsic viscosity of 0.9, a nitrogen content of 0.054% by weight, and a bromine content of 6.4% by weight. The physical properties are shown in Table 1.

Example 6 N, N'-bis(
The same procedure as in Example 1 was carried out except that 100 parts by weight of 2-hydroxyethyl)isophthalamide was used.

The obtained polymer had an intrinsic viscosity of 0.8, a nitrogen content of 0.885% by weight, and a bromine content of 6.2% by weight. The physical properties are shown in Table 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-[J(2-and-droxyethyl)amino]carbonyl]benzoate belonging to formula (B) was used.

In addition, component [I] used in this example is methyl isophthalate 1
．． This is a reaction product obtained by heating 3 parts by weight of a mixture of 0 mole of ethanolamine and 1.5 moles of ethanolamine at 120° C. for 2 hours using 10 parts by weight of 1,4-butanediol as a solvent.

The obtained polymer had an intrinsic viscosity of 1.2, a nitrogen content of 0.018% by weight, and a bromine content of 6.5% by weight. The physical properties are shown in Table 1.

Example 8 The same procedure as in Example 2 was carried out, except that 270 parts by weight of a 2-mol adduct of tetrabromobisphenol sulfone with propylene oxide was used as component [■].

The obtained polymer had an intrinsic viscosity of 0.9, a nitrogen content of 0.041% by weight, and a bromine content of 9.5% by weight. The physical properties are shown in Table 1.

Example 9 970 parts by weight of dimethyl terephthalate as component [■],
730 parts by weight of ethylene glycol as component [II[), 158 parts by weight of 2 mole ethylene oxide adduct of tetrabromobisphenol A as component CrVE, component [
[2] 5 parts by weight of N,N'-bis(2-hydroxyethyl)terephthalamide belonging to formula (A), 1.6 parts by weight of calcium acetate as a catalyst, and 0.5 parts by weight of antimony trioxide.
6 parts by weight were charged into a reactor equipped with a stirrer, a nitrogen inlet tube, and a distillation tube, and stirred at 180° C. for 60 minutes under a nitrogen stream. The temperature was gradually raised and the mixture was heated and stirred at 200° C. 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 Q, 3 mmHg, and the mixture was stirred at this pressure for 3 hours.

The obtained polymer had an intrinsic viscosity of 1.3, a nitrogen content of 0.050% by weight, and a bromine content of 7.2% by weight. The physical properties are shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was performed except that component [■] was not added.

The obtained polymer had an intrinsic viscosity of 1.0 and a bromine content of 6.5% by weight. The physical properties are shown in Table 1.

Comparative Example 2 The same operation as in Example 1 was performed except that component [IV] was not added.

The obtained polymer had an intrinsic viscosity of 1.2 and a nitrogen content of 0.010% by weight. The physical properties are shown in Table 1.

Comparative Example 3 12.5 parts by weight of decabromodiphenyl ether was added to 87.5 parts by weight of the polymer obtained in Comparative Example 2, and a test piece was prepared and evaluated. The physical properties are shown in Table 1.

Comparative Example 4 The same operation as in Example 9 was performed except that component [■] was not added.

The obtained polymer had an intrinsic viscosity of 0.9 and a bromine content of 7.2% by weight. The physical properties are shown in Table 1.

The measurement methods used to evaluate the physical properties of the polymer molded articles of each example are as follows.

1) 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 ℃ for 500 hours was measured.

ii) Oxygen index Measured in accordance with JIS K 7201.

[Effect of Hathu]

The halogen-containing aromatic polyester amide of the present invention produces the following superior effects compared to conventional polyester materials.

Because the halogen compound is bonded to the copolymer, it has high flame retardancy and does not ooze out at high temperatures, which is the case with the addition of flame retardants. In addition, the deterioration of physical properties due to thermal history is greatly improved without impairing mechanical and electrical properties, and it has excellent flexibility and can be made thinner, dramatically increasing the effective use of limited space. do. Therefore, it is useful as a coating material for molded products and electric wires as functional parts such as around heat sources, around engines of transportation equipment, around heat-generating parts of electric products, etc.

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. (Indicates a radical.) [II] Primarily aromatic dicarboxylic acids or their ester-forming derivatives [III] Primarily aliphatic glycols or their ester-forming derivatives [IV] By polycondensation reaction of ester-forming compounds containing halogens Nitrogen content obtained: 0
．． 001-5% by weight and a halogen-containing aromatic polyester amide with a halogen content of 0.5-30% by weight. 2 In the amide compound represented by the general formula (A) and/or (B), A is an arylene group having 6 to 15 carbon atoms, and 1 to 1 carbon atoms.
The halogen-containing aromatic polyester amide according to claim 1, which is an alkylene group having 10 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms. 3. Claim 1, wherein 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 halogen-containing aromatic polyester amide according to any one of items 1 to 2. 4. The halogen-containing aromatic polyester amide 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. 5 [II] The aromatic dicarboxylic acid or its ester-forming derivative is one or more 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 halogen-containing aromatic polyester amide according to any one of claims 1 to 4, which is a dibasic acid type compound. 6. Any one of claims 1 to 5, wherein the aliphatic glycol or ester-forming derivative thereof [III] is one or more diol compounds selected from aliphatic glycols having 8 or less carbon atoms or derivatives thereof. The halogen-containing aromatic polyester amide described in . 7. The halogen-containing aromatic polyester amide according to any one of claims 1 to 6, wherein the halogen-containing ester-forming compound [IV] is a bromine-containing aromatic diol, an aromatic dicarboxylic acid, or a derivative thereof. . 8 Add the amide compound [I] represented by the above general formula (A) and/or (B) to the above monomers [II], [III] and [IV], and heat to 150 to 300 °C in the presence of a catalyst. A method for producing a halogen-containing aromatic polyester amide, which comprises reacting to perform an esterification reaction, and then performing a polycondensation reaction while distilling off excess monomers or eliminated components under reduced pressure.