JPS6221810B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel and useful method for producing aromatic polyesteramides. Aromatic polyetheramides produced from aromatic dibasic acids or functional derivatives thereof and diamines containing ether bonds or functional derivatives thereof are known from, for example, JP-A-52-23198. Such aromatic polyetheramides have excellent electrical properties such as mechanical strength, arc resistance, and dielectric loss factor, as well as chemical resistance, flame retardance, abrasion resistance, and dimensional stability. There is. However, molding this resin requires high temperatures of around 350°C, which is close to its decomposition temperature, and one of its weaknesses is that the allowable working temperature range is narrow. On the other hand, aromatic polyesters made from aromatic dibasic acids such as terephthalic acid and isophthalic acid, their functional derivatives, and divalent phenols have excellent properties such as impact resistance and flame retardancy.
Due to its poor water resistance, its field of application has been limited. Therefore, the inventors of the present invention have made extensive studies to improve these problems, and have completed the present invention. That is, an object of the present invention is to provide a new and useful method for producing a resin having excellent properties and improved moldability. That is, the present invention provides general formula () (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. _{R 5} and R ₆ is hydrogen, methyl group, ethyl group,
A diamine whose main component is an aromatic diamine represented by a trifluoromethyl group or a trichloromethyl group (which may be the same or different), general formula () (In the formula, R′ ₁ , R′ ₂ , R′ ₃ and R′ ₄ and R″ ₁ ,
R″ ₂ , R″ ₃ and R″ ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. Y is O,
S, _SO2 , CO, _CH2 , C( _CH3 ) ₂ or C
The present invention relates to a method for producing an aromatic polyester amide, which comprises reacting a dihydric phenol represented by (CF ₃ ) ₂ with an aromatic dibasic acid dihalide (dehydrohalogenation reaction). Aromatic diamines represented by the general formula () include 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]
Propane, 2,2-bis[3-chloro-4-(4
-aminophenoxy)phenyl]propane, 2.
2-bis[3-bromo-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-
Ethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-propyl-4
-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-isopropyl-4-(4
-aminophenoxy)phenyl]propane, 2.
2-bis[3-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-
sec-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-methoxy-
4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-
Bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3. 5
-dibromo-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dimethoxy-4-(4-aminophenoxy)phenyl]
Propane, 2,2-bis[3-chloro-4-(4
-aminophenoxy)-5-methylphenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methyl-4-(4-aminophenoxy)phenyl]
Ethane, 1,1-bis[3-chloro-4-(4-
Aminophenoxy)phenyl]ethane, 1,1-
Bis[3-bromo-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-ethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-propyl-4- (4-
Aminophenoxy)phenyl]ethane, 1,1-
Bis[3-isopropyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-
Butyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis(3-sec-butyl-
4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methoxy-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-ethoxy-4-(4-aminophenoxy)phenyl ) ethane, 1,1-bis[3,5-
Dimethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dichloro-
4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dibromo-4-(4
-aminophenoxy)phenyl]ethane, 1.1
-bis[3,5-dimethoxy-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4-aminophenoxy)phenyl-5-methylphenyl]ethane, bis[4-
(4-aminophenoxy)phenyl]methane, bis[3-methyl-4-(4-aminophenoxy)
phenyl]methane, bis(3-chloro-4-(4
-aminophenoxy)phenyl]methane, bis[3-bromo-4-(4-aminophenoxy)phenyl]methane, bis[3-ethyl-4-(4-aminophenoxy)phenyl]methane, bis[3-
Propyl-4-(4-aminophenoxy)phenyl]methane, bis[3-isopropyl-4-(4
-aminophenoxy)phenyl]methane, bis[3-butyl-4-(4-aminophenoxy)phenyl]methane, bis[3-sec-butyl-4-(4
-aminophenoxy)phenyl]methane, bis[3-methoxy-4-(4-aminophenoxy)phenyl]methane, bis[3-ethoxy-4-(4
-aminophenoxy)phenyl]methane, bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]methane, bis[3,5 -dibromo-4-(4-aminophenoxy)phenyl]methane, bis[3,5-
Dimethoxy-4-(4-aminophenoxy)phenyl]methane, bis[3-chloro-4-(4-aminophenoxy)-5-methylphenyl]methane, 1,1,1,3,3,3-hexafluoro-
2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexachloro-2,2-bis[4-(4-aminophenoxy)phenyl]propane, 3. 3-bis[4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1.1.1.3.3.
3-hexafluoro-2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexachloro-2,2-bis[3, 5-dimethyl-4-
(4-aminophenoxy)phenyl]propane,
3,5-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]pentane, 1,1-
Bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1, 1, 1, 3,
3,3-hexafluoro-2,2-bis[3,5
-dibromo-4(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexachloro-2,2-bis[3,5-dibromo-4-
(4-aminophenoxy)phenyl]propane,
3,3-bis[3,5-dibromo-4-(4-aminophenoxy)phenylpentane, 1,1-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 2,2- Screw [4-
(4-aminophenoxy)phenyl]butane,
2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]butane, 2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]butane, 2,2-bis[ 3.5-
Dibromo-4-(4-aminophenoxy)phenyl]butane, 1,1,1,3,3,3-hexafluoro-2,2-bis[3-methyl-4-(4-
Examples include aminophenoxy)phenyl]propane. As the diamine in the present invention, an aromatic diamine other than the aromatic diamine represented by the above general formula () can be used as a part thereof. Such aromatic diamines have the general formula () (However, in the formula, X is -CH ₂ -,

【formula】

[Formula] -O-, -S- or -SO ₂ -, and the two amine groups are respectively bonded to the benzene nucleus at the meta-position or para-position with respect to X); and There are other aromatic diamines. Examples of aromatic diamines represented by the general formula () include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl methane.
4'-diaminodiphenylpropane-2.2.4.
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenyl sulfone, etc. Other aromatic diamines include m-phenylene diamine, p-phenylene diamine, Nylene diamine, 1,5-diaminonaphthalene,
m-Toluylene diamine, p-Toluylene diamine, 3,4'-diaminobenzanilide, 1,4-
Diaminonaphthalene, 3,3'-dichloro-4,
4′-diaminodiphenyl, benzidine, 4・4′-
Diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, 4,4'-diaminodiphenyl-N-phenylamine, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenyl Examples include enylsilane. As the diamine in the present invention, aliphatic diamine can be used as a part thereof. The aliphatic diamines include piperazine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, p-xylylene diamine, m-xylylene diamine, tetramethylene diamine, dodecamethylene diamine, 4. 4-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 2,11-diaminododecane, 1,12-diaminooctadecane, etc. can be used. As the diamine in the present invention, aromatic diamine (a) represented by the general formula ()
50 to 100 mol%, aromatic diamine (b) other than the aromatic diamine represented by general formula () 0 to 50 mol%, and aliphatic diamine (C) 0 to 30 mol%, making the total 100 mol% It is preferable to use it so that In particular, 70 to 100 mol% of (a), (b)
It is preferable to use 0 to 30 mol% of (c) and 0 to 10 mol% of (c) so that the total amount is 100 mol%. When (a) decreases or (b) increases,
There is a risk that the molding processability will be impaired, and if (c) is used in combination, the molding processability will be further improved, but as the amount increases, the heat resistance will gradually decrease. In addition, as dihydric phenols represented by the general formula (), 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-2,2'-dimethyl-diphenyl ether, 4,4'-dihydroxy -diphenyl sulfide, 4,4'-dihydroxy-diphenyl sulfone, 4,4'-dihydroxy-diphenyl ketone, 4,4'-dihydroxy-diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, etc. However, it is commonly produced, and the representative one is 2,2-bis(4-hydroxyphenyl)propane. Diamine and dihydric phenol are 50 to 98 mol% of the former
The latter is preferably used in an amount of 50 to 2 mol%. If the diamine/dihydric phenol ratio is less than 50/50 (mole ratio), water resistance tends to be poor, and if it exceeds 98/2 (mole ratio), moldability (effect of widening the allowable working temperature range) tends to decrease. . All known aromatic dibasic acid dihalides used in the present invention are useful. For example, terephthalic acid dichloride, terephthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, diphenyl ether dicarboxylic acid dichloride-4,4'-diphenyl ethercarboxylic acid dibromide-4,4',
Diphenylsulfonic acid carboxylic acid dichloride
4,4', diphenylsulfonedicarboxylic acid dibromide-4,4', diphenyldicarboxylic acid dichloride-4,4', diphenyldicarboxylic acid dibromide-4,4'-naphthalenedicarboxylic acid dichloride-1,5 or Naphthalene dicarboxylic acid dibromide-1.5, etc., at least 1
Seeds are used. Among these, terephthalic acid dihalide and isophthalic acid dihalide are preferred in terms of characteristics. It is particularly preferable to use terephthalic acid dihalide and isophthalic acid dihalide in a ratio of 20/80 to 80/20 (molar ratio) from the viewpoint of improving moldability. The mixing ratio of the total amount of the diamine and dihydric phenol to the aromatic dicarboxylic acid dihalide is preferably set in a range of 0.9 to 1.2 equivalents of the latter to 1 equivalent of the former. Outside the above range, it is difficult to obtain a high molecular weight product, and there is a tendency that only a non-resin-like oligomer can be obtained.
Particularly preferably, the amount of the latter aromatic dicarboxylic acid dihalide is in the range of 0.97 to 1.03 equivalents per 1 equivalent of the former. In particular, when the amounts are equal, the target aromatic polyester amide can have the maximum molecular weight. In the present invention, the reaction can be carried out using any known method used for the reaction of an amine or phenol with an acid, and the conditions are not particularly limited.
For example, this can be achieved by a solution polycondensation method, a melt polycondensation method, or the like. In the case of solution polymerization, a neutralizing agent consisting of a known tertiary amine such as triethylamine, pyridine, or tributylamine is used. In the solution polymerization method, a reaction solvent is used, and among diamines, dihydric phenols, or aromatic dicarboxylic acid dihalides,
It must be capable of dissolving at least one, preferably both. Reaction solvents that can be used in the present invention include N/N-dimethylformamide, N/N-dimethylacetamide,
N/N-diethylformamide, N/N-diethylacetamide, N/N-dimethylmethoxyacetamide, dimethyl sulfoxide, N-methyl-
2-pyrrolidone, pyridine, dimethylsulfone,
Examples include hexamethylphosphoramide, tetramethylene sulfone, and dimethyltetramethylene sulfone. Two or more reaction solvents may be used in combination, if necessary, to facilitate the dissolution operation. Furthermore, in order to obtain a product with as high a molecular weight as possible, it is preferable to use a highly dehydrated solvent for dissolving the aromatic dicarboxylic acid dihalide. In particular, N.
When performing solution polymerization using a polar solvent such as N-dimethylformamide, N/N-dimethylacetamide, or N-methyl-2-pyrrolidone, 5 to 10% by weight of lithium chloride, calcium chloride, calcium rhodan, etc. may be used as a co-solvent. It is advantageous to synthesize the compound by adding it, as it significantly increases the solubility. In addition to this co-solvent, all other known co-solvents as described below are effective. Further, according to research by the present inventors, the following reaction method is effective. That is, unlike the usual interfacial polycondensation method in which the diamine and/or divalent phenol is dissolved in an alkaline aqueous solution, the reaction is carried out in an organic solvent that is sparingly soluble in water. A solution obtained by dissolving phenol and a solution obtained by dissolving an aromatic dibasic acid dihalide in an organic solvent that is sparingly soluble in water are mixed and stirred under separation or suspension of an aqueous solution of an inorganic acid acceptor. This is the way to do it. By polymerizing in this way,
The generated hydrogen halide is neutralized with an inorganic acid acceptor, becomes metal halide with water, and dissolves in water. When the polymer is separated from the organic phase, no hydrochloric acid or inorganic acid acceptor remains in the polymer, so the polymer This gives favorable results in terms of various properties. In this case, the amount of the inorganic acid acceptor used is at least 1.3 equivalents of the aromatic dicarboxylic acid dihalide, and
Preferably it is 1.0 to 1.1 equivalent. Examples of the inorganic acid acceptor used here include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, etc. that are soluble in water. Further, the amount of water is sufficient as long as the above-mentioned inorganic acid acceptor is sufficiently dissolved at room temperature. Of course, even if less than that is used, the reaction will not be affected. Further, the reaction temperature is in a state where water is a liquid, that is, in the range of 0 to 100°C, preferably 5 to 60°C. According to this method, it is easy to disperse or suspend the aqueous solution of the inorganic acid acceptor, and since the reaction is uniform, there is no local heat generation.
It is easy to control the reaction temperature. This also has the advantage of reducing variations in quality of produced polymers. In addition, examples of the above-mentioned organic solvents that are poorly soluble in water include cyclohexanone, methylene chloride, trichlene, verkleene, dichloroethane, nitrobenzene, chloroform, carbon tetrachloride, diisobutylketone acetophenone, p-methylacetophenone, etc. are used, with cyclohexanone being particularly preferred. Further, as a reaction method, there is also a method of dispersing diamine and dihydric phenol inorganic acid acceptor in an aqueous solution, adding thereto a solution of aromatic dicarboxylic acid dihalide dissolved in an organic solvent, and causing the reaction. The inorganic acid solvent, its usage amount, reaction temperature, etc. are the same as above. The above polycondensation method can be carried out, for example, by the following procedure. First, an inorganic acid acceptor is dissolved in an appropriate amount of water, and an aromatic diamine is added thereto. Furthermore, a solution of aromatic dicarboxylic acid dihalide dissolved in an organic solvent is added to react. At this time, it is preferable to carry out the reaction while stirring and dispersing the aromatic diamine and dihydric phenol in the aqueous solution of the inorganic acid acceptor. Next, only the organic phase is separated and poured into an organic solvent that does not dissolve the polymer and is easily compatible with the reaction solvent to precipitate the polymer. By filtering this, an aromatic polyesteramide resin is obtained. In order to further improve the heat resistance and weather resistance of the aromatic polyester amide of the present invention, a thermal decomposition inhibitor, an antioxidant, or an ultraviolet absorber may be mixed with the aromatic polyester amide. Others, plasticizers,
Pigments, lubricants, etc. may also be mixed. The aromatic polyester amide of the present invention can be made into powder, chips, or other forms, and can be used to make various useful products using commonly known plastic molding methods such as press molding, injection molding, and extrusion molding. . Examples of such products include gears, bearings, electrical parts containers, etc. Thus, the aromatic polyesteramide of the present invention can be used as an engineering plastic in applications requiring high performance. Next, the present invention will be explained in more detail using Examples, but the present invention is not limited by these. Example 1 10 separable flasks, a stirring bar, a thermometer,
Set the dropping funnel and add 144g of NaOH to 1200ml of water.
Pour the aqueous solution (A) dissolved in (A) into the flask. next,
2,2-bis[4-(4-aminophenoxy)phenyl]propane 371.1g and bisphenol
A solution (B) in which 2.6 g of A was dissolved in 2.4 kg of cyclohexanone was poured into the flask and cooled to -2°C. On the other hand, terephthalic acid dichloride 152.4
g, 152.4g of isophthalic acid dichloride is dissolved in 2.4Kg of cyclohexanone. Pour this acid chloride solution (C) from the dropping funnel, making sure that the reaction temperature does not exceed 10°C. 3 from dripping
After a period of time, the reaction solution is poured into methanol to isolate the polymer. Example 2 Except that the aqueous solution (A), solution (B), and acid chloride solution (C) of Example 1 were replaced with the following aqueous solution (A'), solution (B'), and acid chloride (C'), respectively. was carried out according to Example 1. Aqueous solution (A') NaOH 158.4 g and water 1.2 Solution (B') 2,2-bis[4-(4-aminophenoxy)phenyl]propane 371.1 g 4,4'-diaminodiphenyl ether 30 g Dihydroxydiphenyl sulfone 1125 g and Cyclohexanone 2.4Kg Acid chloride solution (C') Terephthalic acid dichloride 167.6g Isophthalic acid dichloride 167.6g and cyclohexanone 2.4Kg Example 3 The aqueous solution (A), solution (B) and acid chloride solution (C) of Example 1 were prepared, respectively. The procedure was carried out according to Example 1 except that the following aqueous solution (A''), solution (B'') and acid chloride solution (C'') were used. Aqueous solution (A'') 168 g of NaOH and 1.2 g of water Solution (B'') Bis [4-(4-aminophenoxy)-3,5-dimethylphenyl]methane 459.4g Bisphenol A 239.7g and p-methoxyacetophenone 2.4Kg Acid chloride solution (C″) Isophthalic acid dichloride 426.3g and p-methoxy Acetophenone 3.4Kg Table 1 shows the properties of the aromatic polyesteramide resins obtained in Examples 1 to 3.

【table】

Claims (1)

[Claims] 1 General formula () (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. _{R 5} and R ₆ is hydrogen, methyl group, ethyl group,
A diamine whose main component is an aromatic diamine represented by a trifluoromethyl group or a trichloromethyl group (which may be the same or different), general formula () (wherein R′ ₁ , R′ ₂ , R′ ₃ and R′ ₄ and R ₁ ″,
R ₂ ″, R ₃ ″, and R ₄ ″ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine, or bromine, and may be the same or different from each other. Y is O,
S, _SO2 , CO, _CH2 , C( _CH3 ) ₂ or C
A method for producing an aromatic polyester amide, which comprises reacting a dihydric phenol represented by (CF ₃ ) ₂ with an aromatic dibasic acid dihalide (dehydrohalogenation reaction). 2. The reaction is carried out using a solution of diamine and dihydric phenol dissolved in an organic solvent that is sparingly soluble in water, and a solution of aromatic dibasic acid dihalide dissolved in an organic solvent that is sparingly soluble in water. 2. The method for producing an aromatic polyester amide according to claim 1, which is carried out by mixing and stirring an aqueous solution of a receptor in a dispersion or suspension state. 3. The aromatic polyester according to claim 1 or 2, which is formed by blending diamine and divalent phenol in a ratio such that diamine/divalent phenol is in a molar ratio of 50/50 to 98/2. Method for producing amides. 4. The method for producing an aromatic polyester amide according to claim 1 or 2, wherein the aromatic dibasic acid dihalide is at least one compound selected from the group consisting of terephthalic acid dihalide and isophthalic acid dihalide. 5. The aromatic dibasic acid dihalide according to claim 4, wherein the aromatic dibasic acid dihalide is a mixture of terephthalic acid dihalide and isophthalic acid dihalide such that the former/latter (molar ratio) is 20/80 to 80/20. Method for producing polyesteramide. 6 Aromatic diamine whose diamine is represented by the general formula ()
A patent claim in which 50 to 100 mol%, 0 to 50 mol% of an aromatic diamine other than the aromatic diamine represented by the general formula (), and 0 to 30 mol% of an aliphatic diamine are blended so that the total amount is 100 mol%. A method for producing an aromatic polyester amide according to item 1, item 2, or item 3.