JPS58147420A - Preparation of aromatic polyester amide - Google Patents

Abstract

PURPOSE:To obtain the titled novel and useful amide having various kinds of characteristics and improved molding and processing properties, by reacting an aromatic diamine having a specific structure with a dihydric phenol having a specified structure and an aromatic dibasic acid dihalide. CONSTITUTION:The desired amide is obtained by subjecting (A) a diamine consisting essentially of an aromatic diamine{e.g., 2,2-bis[4-(4-aminophenoxy) phenyl]propane, etc.}shown by the formulaI(R1-R4 are H, lower alkyl, lower alkoxy, etc.; R5 and R6 are H, methyl, ethyl, trifluoromethyl, etc.), (B) a dihydric phenol (e.g., bisphenol A, etc.) shown by the formula II (R1'-R4' and R1''-R4'' are H or lower alkyl, lower alkoxy, etc.; Y is O, S, SO2, etc.) and (C) an aromatic dibasic acid dihalide (preferably terephthalic acid dihalide, etc.) to dehydrohalogenation in such a way that the amount of the component C is 0.97-1.03 equivalent based on 1 equivalent of the total amounts of the component A and the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful method for producing aromatic polyesteramides.

Aromatic polyether amide produced from aromatic dibasic acids, functional derivatives thereof, and diamines containing ether bonds/or functional derivatives thereof is 9%.
No. 198, etc., are publicly known. Such aromatic polyetheramides have 9 different mechanical strengths, arc resistance, Ws
In addition to electrical properties such as electrical loss rate, chemical resistance, 1m flammability,
It has excellent wear resistance and dimensional stability. However, molding this resin requires a high temperature of around 350° C., which is close to its decomposition temperature, and one of its weaknesses is that the allowable temperature range for operation is narrow.

On the other hand, Telef! Aromatic dibases such as fluoric acid and isophthalic acid 1
Aromatic polyesters produced from 1h and its functional derivatives, dihydric phenols, and silica have excellent properties such as peck resistance and flame resistance, but their water resistance is poor, and their application fields are limited. I was restricted.

Therefore, the inventors of the present invention have made extensive studies to remedy these problems and have come up with 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 shape processability.

That is, the present invention provides the general formula CI) ((However, in the 2 formulas, R1, R1, Rs and R4 are hydrogen.

It represents a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different. R5
and R- is hydrogen or a methyl group.

A diamine whose main component is an aromatic diamine represented by an ethyl group, a trifluoromethyl group, and a trichloromethyl group, which may be the same or rarely different.

General formula (II) represents an alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different. Yt;t
O, S, Box, Co, CHz, C(
The present invention relates to a method for producing an aromatic polyester amide, which involves reacting (dehydrohalogenation reaction) a dihydric phenol represented by CH3)2 or jd C(CFs)z) with an aromatic dibasic acid cybaride (dehydrohalogenation reaction).

As the aromatic diamine represented by the general formula +1), R
2-bis(4-(4-aminophenoxy)phenyl)clopane, λ2-bis[3-methyl-4-(4-aminophenoxy)phenyl]glopane, λ2-bis[3-chloro-4-(4-7i [7-di)phenyl]propane, λ2-bis[3-promo4-(4-aminophenoxy)phenyl]propane, 2,2-his[3-ethyl-
4-(4-aminophenoxy)phenyl]furopane, λ
2-bis(3-propyl-4-(4-aminophenoxy)phenyl)propane, 2-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]propane,
2゜2-bis[3-butyl-4-(4-aminophenoxy)phenyl]propane, λ2-bis[3-sec -
Butyl-4-(4-aminophenoxy)phenyl]propane, λ2-bis[3-methoxy-4-(4-aminophenoxy)phenyl]propane, λ2-bis[3-ethoxy-4-(4-aminophenoxy) phenyl]furopane, λ2-bis[5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[tortoise5-
Dichloro-4-(4-aminophenoxy)phenyl]propane, 2-bis(&5-dibromo4-(4-aminophenoxy)phenyl)propane, 2.2-bis[
&5-dimethoxy7-4-(4-aminophenoxy)phenyl]propane, 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, l,1-bis[3-promo 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-aminophenoxy7)phenyl]ethane, 1,1-bis [3-Butyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis(3-5ec-
Butyl-4-(4-aminophenoxy)phenyl]emene, 1,1-bis[3-methoxy-4-(4-aminophenoxy)phenyl]ethane, Ll-bis[3-ethoxy-4-(4-amino phenoxy]phenyl]ethane,
Ll-bis(&5-dimethyl-4-(4-aminophenoxy)7enyl]ethane, 1,1-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]ethane, Ll-bis[ 3,5-dibromo-4-(4-aminophenoxy)phenyl]ethane, 1.1-bis[tortoise 5-dimethoxy-4-(4-aminophenoxy)phenyl]ethane, 1.1-bis[3-chloro -4-(4-aminophenoxy)phenyl-5-methylphenyl]ethane, bis[4-(4-aminophenoxy)phenylcomethane.

Bis[3-methyl-4-(4-aminophenoxy)phenylcomethane, bisl:3-chloro-4-(4-aminophenoxy)phenylcomethane.

Bis[3-promo 4-(4-aminophenoxy)phenylcomethane, bis[3-ethyl-4-(4-aminophenoxy)phenylcomethane.

Bis[3-propyl-4-(4-aminophenoxy)phenylcomethane, bis[3-isopropyl-4-(4-
aminophenoxy) phenylcomethane, bis[3-butyl-4-(4-aminophenoxy)phenylcomethane,
Bis(3-5ec-butyl-4-(4-aminophenoxy)phenylcomethane, bis[3-methoxy-4-(4
-aminophenoxy)phenylcomethane, bis(3-ethoxy-4-(4-aminophenoxy)phenylcomethane, bis(3,5-dimethyl-4-(4-aminophenoxy7)phenylcomethane).

Bis[λ5-dichloro4-(4-aminophenogine)
Phenylcomethane, bis[turtle 5-dibromo-4-(4-
Aminophenox 7) Phenylcomethane, bis(,3,5
-dimethoxy-4-(4-aminophenoxy)phenylcomethane, bis(310 rho 4-(4-aminophenoxy)-5-methylphenylcomethane, 1,1,1.λ turtle 3-hexafluorose 2 -bis(4-(4-aminophenoxy)phenyl)propane, 1,1,1° & turtle 3-
Hekitchloro212-bis(4-(4-aminophenoxy)phenyl)pro/syn, &3-bis(4-(4-
aminophenoxy)phenyl]pentane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane,
1, 1, 1. Fluoro λ2-bis [&
5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1.1,1. a&3-hexachloro-λ2
-bis[tortoise-5-dimethyl-4-(4-aminophenoxy)phenyl]propane, &5-bis[tortoise-5-dimethyl-
4-(4-aminophenoxy)phenyl]pentane, 1
．． 1-bis(3,5=dimethyl-4-(4-aminophenoxy)phenyl)propane, 1.LL&3.3-hexachlorolose 2-(s[tortoise 5-dibromo-4(4-aminophenoxy)phenyl]) Prono(n, 1,1゜1,3
．． 3.3-hexachloro-λ2-bis[&5-dibromo4-(4-aminophenoxy)phenyl]propane,
Tortoise 3-bis(&5-dibromo4-(4-aminophenoxy)'phenyl)pentane, 1.1-bis[λ5-dibromo4-(4-aminophenoxy)phenyl]chrono2no,λ2-bis(4- (4-aminophenoxy)phenylcobutane, 2,2-bis[3-methyl-4-(4
-aminophenoxy)phenyl]butane, 2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)tzenyl]butane, 2,2-bis[3,5-dibromo-4
-(4-aminophenolic)phenyl]buta/+1.
L 1. & 313-hexafluoro-λ2-bis[3
-Methyl-4-(4-aminophenoxy)phenyl]gulon(n) and the like are al.

As the diamine in the present invention, an aromatic diamine other than the aromatic diamine represented by the above general formula (I) can be used as a part thereof. Such an aromatic diamine has the general formula + ml (in formula 1, X is -CHz
, CH, C-.

Fortune telling.

Aromatic diamines and other aromatic There is diamine. The aromatic diamine represented by the general formula (seal) includes 44'-diaminodiphenylmethane 4 N-diaminodiphenyl ether,
4.4'-diaminodiphenyl sulfone, 44'-diaminodiphenylpropane-2,2,44'-diaminodiphenyl sulfide, 44'-diaminodiphenylethane, 33'-diaminodiphenylsulfone, etc.9. As for other aromatic diamines.

m-phenylenediamine, p-phenylenediamine, 1
．． 5-diaminonaphthalene, m-tolylenediamine,
P-) lylene diamine, 4'-diaminopenzanilide, 1,4-diaminonaphthalene, 3'-dichloro44'-diaminodiphenyl, pentidine, 44'-
Diaminodiphenylamine, 44'-diaminodiphenyl-N-methylamine, 44'-diaminodiphenyl-
Examples include N-phenylamine, 4,4'-diaminodiphenyldiethylsilane, and 44'-diaminodiphenylsilane.

As the diamine in the present invention, aliphatic diamine can be used as a part thereof. Examples of skeleton fatty diamines include piperazine, hexamethylene diamine, hegtamethylene diamine, octamethylene diamine, and nonamethylene diamine.

decamethylene diamine, p-xylylene diamine, m-
Xylylene diamine, tetramethylene diamine, dodecamethylene diamine 7.4. 4-dimethyl hebutamethylene diamine, 3-methyl hebutamethylene diamine, 2.11
-diaminododecane, 1,12-diaminooctadecane, etc. can be used.

The diamine in the present invention includes:

Aromatic diamine (1) represented by general compound I) 50-1
Aromatic diamines other than aromatic diamines (b) 0 to 50 moles and superaliphatic diamines (C) θ to 30 moles, the total is well over 100 moles. It is preferable to use it so that
%, (a) to 70 to Zo.

0 to 30 moles of (b) and 0 to 1 mole of (C)
It is preferable to use the total amount of 100 mol tlIK at a ratio of 0 mol. If 181 decreases or (
If b) increases, there is a risk of impairing moldability, and (
When C) is used in combination, the moldability is further improved, but as the amount increases, the heat resistance gradually decreases.

In addition, dihydric phenols represented by the general formula (t)
li, 44'-dihydroxydiphenyl ether, 44
'-Dihydroxy-22'-dimethyl-diphenyl ether, 44'-dihydroxy-diphenyl sulfide, 44'-dihydroxy-diphenyl sulfone, 44'
-dihydroxy-diphenylketone, 44'-dihydroxy-diphenylmethane, and 2-bis(4-hydroxyphenyl)propane. phenyl)probanethiol.

The diamine and dihydric phenol are preferably used in an amount of 50 to 98 moles for the former and 50 to 2 moles for the latter. If the diamine/dihydric phenol ratio is less than 50,150 (mole ratio), water resistance tends to be poor; if it exceeds 98/2 (mole ratio), moldability (effect of widening the workable temperature range) tends to decrease.

All known aromatic dibasic acid cybarides 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-44'.

diphenyl ether carboxylic acid dipromide-44',
Diphenylsulfone dicarboxylic acid cyclola()''-44
', diphenylsulfone dicarbon al/bromide-
44', diphenyldicarboxylic acid dichloride-44'
, diphenyldicarboxylic acid dibromide-4,4', naphthalene dicarboxylic acid dichloride-1,5, or naphthalene dicarboxylic acid dibromide-1,5, and at least one of them is used. Among these, terephthalic acid cybalide and isophthalic acid cybalide are preferable in terms of characteristics. It is particularly preferable to use terephthalic acid cybaride and isophthalic acid cybaride in a ratio of 20/80 to 80/2G (molar ratio) from the viewpoint of improving moldability.

The total amount of the diamine/dihydric phenol and the blending ratio of the aromatic dicarboxylic acid civalide are as follows.

It is preferable that the amount of the latter is set in a range of 0.9 to 1.2 equivalents per 1 equivalent of the former. If the above-mentioned II8 is exceeded, a high molecular weight product is obtained, and there is a tendency that only a single oligomer that does not exhibit a resinous state is obtained. 41, the latter aromatic dicarboxylic acid cybaride is preferably in the range of α97 to 1.03 equivalents relative to the former la amount. When the amount is equivalent to 41, the maximum molecular weight of the target aromatic polyester amide can be obtained.

For one reaction in the present invention, the known amine removal method used for the reaction of phenol and acid can be employed as is.

There are no particular limitations on the terms and conditions.

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 this solvent must be capable of dissolving at least one of diamine and dihydric phenol, preferably both of the aromatic dicarboxylic acid cybaride. Reaction solvents that can be used in the present invention include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N,N-diethylacetamide.

N,N-dimethylmethquinacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone.

Dimethyltetramethylene sulfone etc. cause irritation.

Two or more reaction solvents may be mixed together if necessary to facilitate the dissolution operation.

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 dicarbonate di-ride. In particular, when solution polymerization is carried out using a polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone, lithium or calcium chloride with a weight ratio of 5 to 10 may be used as a co-solvent. , rhodan calcium, etc., is advantageous because it increases the solubility of 11L. In addition to this co-solvent, all other known co-solvents as described below are effective. According to research conducted by the present inventors, the following reaction method is effective.

That is, it is like the usual interfacial polycondensation method.

Unlike the method of dissolving the diamine and dihydric phenol in an alkaline aqueous solution, the reaction with the previous step d is performed by dissolving the diamine and the dihydric phenol in an organic solvent that is sparingly soluble in water and water. - A solution prepared by dissolving an aromatic dibasic acid cybaride in a soluble organic solvent is mixed under dispersion or suspension of an aqueous solution of an inorganic acid acceptor.

This method involves stirring. By polymerizing K in this way, nine hydrogen halides are produced.

It is neutralized with an inorganic acid acceptor and becomes water and metal halide and becomes water! Therefore, when the polymer is separated from the organic phase, no hydrochloric acid or inorganic acid acceptor remains in the polymer, giving favorable results to the properties of the polymer. in this case,
The amount of the inorganic acid acceptor used is at least 1.3 equivalents and preferably 1.3 equivalents or less relative to the aromatic dicarboxylic acid di-ride.
It is 0 to 1.1 equivalent. Here, examples of the inorganic acid acceptor used include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, etc., which are soluble in water, but are not limited to soybean. 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 more than that is used, it will not be a problem for one reaction.The reaction temperature is the same as when water is a liquid, that is, in the range of 0 to 100°C, preferably 5 to 60°C.

According to such a method, it is easy to disperse or suspend the aqueous solution of the inorganic acid acceptor, and the reaction temperature can be easily adjusted without causing local heat generation in rounding, where a uniform reaction is carried out.

This also has the advantage of reducing variations in quality of produced polymers. In addition.

The organic solvents mentioned above are dissolvable with respect to water.

7 Clohexanone, methylene chloride, trichlene.

Percrene, ethane dichloride, nitrobenzene.

Chloroform, carbon tetrachloride, diisobutylketone acetophenone, p-methylacetophenone, etc. are used, and cyclohexanone is particularly preferred.

As a reaction method, diamine and dihydric phenol are dispersed in an aqueous solution of an inorganic acid acceptor.

There is also a method in which a solution of aromatic dicarboxylic acid cybaride dissolved in an organic solvent is added to the reaction mixture. The inorganic acid acceptor, 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 cybaride dissolved in an organic solvent is added to react. At this time, it is preferable to disperse the aromatic diamine and dihydric phenol in the aqueous solution of the inorganic acid acceptor by stirring, and to react in a good condition.

Next, only the organic phase is separated and poured into an organic solvent that does not dissolve the polymer and is compatible with the reaction solvent to precipitate the polymer. By filtering this, an aromatic polyesteramide resin is obtained.

A thermal decomposition inhibitor to further improve the heat resistance and weather resistance of the aromatic polyester amide of the present invention.

Antioxidants or UV absorbers may be mixed with the aromatic polyesteramide. others.

OT plasticizers, M family, additives, etc. may also be mixed.

The aromatic polyester amide of the present invention is a powder.

It can be made into chips or other shapes, and used to make various useful products by commonly known plastic forming methods such as press molding, injection molding, and extrusion molding. Examples of such products include gears, bearings, electrical parts containers, etc.

As described above, 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 examples.

Example 1 A 1Ol separable flask, a stirring bar, and a temperature needle.

Set the funnel and add 144f of NaOH to 1200ml of water.
Place the aLIK-dissolved aqueous solution (A) into a flask. Next, 2,2-bis(4-(4-aminophenoxy)phenyl)propane 371.IP and bisphenol A10
Solution fB of z6y- dissolved in cyclohexanone 24Q
Pour 1 into the flask.

Cool to -2°C. On the other hand, terephthalic acid dichloride 152,4 SJ isophthalic acid dichloride 1514
Dissolve in 2.4 Kf of clohexanone.

This acid chloride solution (C) is poured from the dropping funnel, making sure that the temperature of one reaction does not exceed 10"C. Three hours after dropping, one reaction solution is poured into methanol,
Isolate the polymer.

Example 2 The aqueous solution (B) and acid chloride solution (C) of Example 1 were each mixed with the following aqueous solution (A' solution (B'
) and acid chloride (C'>), the procedure was carried out according to Example 9.

Aqueous solution (A') fII solution (B') Acid chloride solution (σ) Example 3 The aqueous solution (Bl) and acid chloride solution (C1) of Example 1 were replaced with the following aqueous solution (A'') and solution ('
) and acid chloride solution (σ) were used, except that Example IK was followed.

Aqueous solution (A#) Solution ('') Acid chloride solution (σ) I#I characteristics of the aromatic polyesteramide resins obtained in Examples 1 to 3 are shown in Table 1.

Claims (1)

[Claims] 1. General formula (1) (However, in formula 1, e at w Rs $ RB and R4
represents hydrogen, a lower alkyl group, a lower alkoxy group, chlorine represents bromine, and they may be the same or different. R- and Ra represent a water volume, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, 'L
A diamine whose main component is an aromatic diamine represented by (4) which may be the same or different. General formula (primary alkyl group, lower alkoxy group, chlorine and 9 represent bromine, and may be randomly the same or different. Y is 0
, 8, 80s, CO, CHs. Production of an aromatic polyester amide characterized by reacting (dehydrohalogenation reaction) a dihydric phenol represented by C(CHs)1t7'L is C(CFs)* and an aromatic dibasic acid cybalide. Method. 2. The reaction is carried out by mixing and stirring in a water bath solution of a soluble acid acceptor containing cyanide and dihydric phenol in an organic solvent dissociable with water, while dispersing or suspending the same. A method for producing an aromatic polyester amide according to the scope section. Item 111111111 or 9 of the patent application is an aromatic compound as described in item 2, which is obtained by blending diamine and dihydric phenol in a ratio of diaquine/dihydric phenol in a ratio of 50/50 to 9872 (molar ratio) κ. Method for producing polyester adze. Table Claim 1, wherein the aromatic dibasic acid cybaride is at least one compound selected from the group consisting of terephthalic acid cybaride and isophthalic acid cybaride! The method for producing the aromatic polyester amide described above. 5. The aromatic dibasic acid di-I-ride is composed of terephthalic acid civalide and isophthalic acid dino-ride so that the former/latter (molar ratio) is 20/80 to 80/20. A method for producing an aromatic polyester amide according to claim 4, wherein the diamine is an aromatic diamine represented by the general formula (1) 50 to 100.
Aromatic diamines other than aromatic diamines represented by Molle general formula (11) θ ~ 50 moles and aliphatic diamines θ ~ 30 moles are combined into 1
00 mol.