JPS5852348A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent chemical and mechanical properties and heat resistance and improved moldability, consisting of a polyether amide and a linear polyarylene polyether. CONSTITUTION:A thermoplastic resin compsn. consists of a polyether amide contg. a repeating unit of formulaI(wherein R1-R4 are each H, lower alkyl, alkoxy, Cl, Br; R5, R6 are each H, methyl, ethyl, trichloromethyl; Ar is p-or m-phenylene, naphthylene) and a linear polyarylene polyether contg. a repeating unit of formula II (wherein E is a bivalent phenol redidue; E' is a residue of a benzenoid compd. having an inactive electron attractive group at ortho and/or para positions with respect to the valence bond, each residue being attached through an arom. carbon atom to an ether oxygen) such as polysulfone having a repeating unit of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin composition, and more particularly, a composition comprising a polyether amide and a polyaryle/polyether. Excellent formability, chemical properties,
The present invention relates to a novel thermoplastic resin composition having mechanical properties and heat resistance.

Polyether amide produced from aromatic digroup rIIIt or functional derivatives thereof and diamine containing an ether bond or functional n4 form thereof is 1%.
It is publicly known from Publication No. 198 and the like. Such polyether and.

It has excellent electrical properties such as various mechanical strengths, arc resistance, and electric loss rate, as well as chemical resistance, flammability, abrasion resistance, fatigue resistance, and dimensional stability. However, one of its weaknesses is that molding this resin requires a high temperature of around 350° C., which is close to its decomposition temperature, and the temperature range in the working space is wide.

On the other hand, although polyarylene polyether has excellent properties such as one-dimensional stability, heat resistance, and flame retardancy, its application fields are limited due to insufficient water resistance and fatigue resistance. home.

Therefore, the inventors of the present invention have made repeated studies to improve these problems and have come up with the present invention.

An object of the present invention is to provide a novel resin composition having excellent properties and greatly improved moldability.

That is, the present invention is based on ■] General formula (11 (In general formula (1), R1-R4 represent hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine, and may be the same, rarely or different from each other) Good.Rs and R- are hydrogen, methyl group, and ethyl group.

Trifluoromethyl group, preceded by trichloromethyl group9. They may be the same and rarely true. Azt
'19 Polyether amide having a repeating unit represented by phenylene group, m-phenylene group, oxydiphenylene group, sulfonyldiphenylene group, biphenylene group) and CB) General formula (I) 10- E-0-B'± (i[) (In the general formula (厘), E is the residue of dihydric phenol,
E' is a residue of a benzenoid compound which is formed into a valence bond and has an inert electron-withdrawing group in at least one ortho or baro position, and both the ortho groups are linked to an ether via an aromatic and longitudinal atom. It is a thermoplastic resin composition similar to a powdered polyarylene polyether having a repeating unit represented by (bonded to oxygen).

The polyether amide having a backbone unit, which is represented by the general formula +1) used in the present invention, is:

Aromatic dibasic acids, their functional derivatives and general formula ([
1 (in the general formula (during the term, R1''& is the same as that in the general formula [)) and 2, which is the same as that in the general formula [), is inserted to cause a condensation reaction.

The dibasic acids and their functional derivatives used here include terephthalic acid, ino-7-taloxydianic acid, biphenyldicarboxylic acid, 7-tale dicarboxylic acid, diphenylsulfonedicarboxylic acid, and their dichlorides. .

These include their digromides, their alkyl esters, and their aryl esters.

Further, as specific examples of diamines represented by the general formula (bright), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-methyl-
4-(4-aminophenokidinphenyl)propane, 2
+2-bis[3-chloro-4-(4-aminophenoxy)enyl]glopane, 2.2-bis[3-promo 4
-(4-aminophenoquine)phenyl]furopane, λ2
-bis[3-ethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-hyx[3-norobyl-4-
(4-aminophenoxy)phenyl]glopane, 2.
2-bisCB-ingrovir-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-butyl-4-(4-aminophenoxy)phenyl]furopane,
2゜2-bis(3-5ec-butyl-4-(4-7minophenoxy)phenyl]propa7.42-bis[3-methoxy-4-(4-'7minophenoxy7)phenyl cogloba/1212-bis [3-ethoxy-4-(4-aminophenox7)phenyl]furopane, 42-bis[:,
%5-dimedel-4-(4-aminoneenoxy)phenyl]gpan, 42-bis[formula 5-diku1=1=4
('-aminophenol)phenyl]glopane,
&2-bis[3,5-dibromo-4-(4-aminophenoxydinphenyl)]propane, 2-bis[tortoise 5-dimethoxy-4-(4-aminophenoxy7)phenyl]propane, 2,2-bis [3-chloro-4-(4-azunophenoxy]-5-methylphenyl]noropane, 1.l-
Bis[4-(4-aminophenoxy)phenyl]ethane.

1.1-bis[3-methyl-4-(4-aminophenoxy)7monyl]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-gloryl-4-(4-aminophenoxy)phenyl]ethane, l
, l-bis [3-1 improbi/le-4-(4-fi/7
-1-/xinphenyl]ethane, l,1-bis[3-
Butyl-4-(4-aminophenoxy)phenyl]ethane, 1.1-bis(3-5ec-butyl-4-(4-aminoenoxy)phenyl)ethane, 1.1-bis[3
-methoxy-4-(4-aminophenoxy)phenyl]
Ethane, 1.1-ni's [3-r-) + C4-(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)phenylcomethane, bis[3-methyl-4-(4-aminophenoxyolipophenylcomethane), bis[3-chloro-4-(4-aminophenoxy]phenyl]methane, bis[ 3-bromo4- (
4-aminophenoxy)phenylcomethane, bis[3-
Ethyl-4-(4-aminophenoxy)phenylcomethane, bis[3-propyl-4-(4-aminophenoxy)phenylcomethane, bis[3-impropyl-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]phenyl]
Methane, Bis[45-dimethyl-4-(4-aminophenoxy)phenylcomethane, Bis[Turtle 5-dichloro-4
-(4-Aquinonephenoxy)phenylcomethane, bis(
3,5-dibromo-4-(4-aminophenoxy)phenylcomethane.

Bis[5-dimethoxy-4-(4-aminophenoxy)phenylcomethane, bis[3-chloro-4-(4-aminophenoxy]-5-methylphenyl]methane, 1
,1,1,3,3.3-hexafluoro-2,2-bis[4-(4-aminophenol?cy) 7x2h]7'o
Ha/, 1, 1, 1, 3. a3-hexachloro-2,2
-bis[4-(4-aminophenoxy)phenyl],'
I=1 pan, a, 3-his(4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,1.l, 3
, 3.3-hexafluoro-2,2-bis(a5-dimethyl-4-(4-aminophenoxy)phenyl)propane+ L L 1+ :A 3.3-he#fria
* -Q, 3-His[3,5-dimethyl-4-(
4-aminephenoxy)phenyl]propane, 3-bis[5-dimethyl-4-(4-aminophenoxy)phenyl]pentane, 1,1-bis(3,5-dimethyl-
4-(4-7minophenoxy)phenyl]propane, 1
,1,1,3,3.3-hexafluoro-42-bis[
Tortoise 5-dibromo-4-(4-aminophenoxy)phenyl pan, 1,1,1. Compound-hexachloro-42
-Bis(&5-dibromo4-(4-aminophenoxy)phenyl)probane, Kame8-bis(35-sifromo-4-(4-aminophenoxy)phenyl)pentane.

1.1-bis[tortoise-5-dibromo-4-(4-aminophenoxy)phenyl]propane, 2-bis(4-(4-
Aminophenoxy7) Phenylcobutane, 42-bis[3
-Methyl-4-(4-a is in nopheno)phenylcobutane, 2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenylcobutane, 2,2-bis[turtle 5 -dibromo-4-(4-aminophenoxy)7enyl]butane, 1,1,1. &&3-hexafluoro-4
2-bis[3-methyl-4-(4-aminophenoxy)
phenyl]propane, etc.

Among these, 2,2-bis(4-(4-aminophenoxy)phenyl)propane is a typical example.A If necessary, two or more of the above siat7-s can be used in combination, or other It is also possible to use known aromatic diamines or aliphatic diamines in combination. Therefore, the [A] acid component polyether amide may contain repeating units other than repeating units represented by general formula (1). May be included.

Here, examples of other aromatic diamino include m-phenylene diamine, p-7 22 diamino 7,4,4'-diaminodiphenylmethane, 44'-diaminodiphenyl ether 144'-sifj nodiphenyl sulfone, 44
'-cyaminodiphenylpropane-&2.4'・4'
-Cyaminodiphenyl sulfide, 1,5-diannonaphthalene, 44'-diaminodiphenylethane, m-)
Luylene diamine, p-tolylene diamine, 3.4'
- diannopenzanilide, 1,4-diaminona7tali/, 3'-dichloroa-44'-cya,
Benzidine* 44'-Schiff i / diphenylamine, 44'-diaminodiphenyl-N-methylanne, 44'-diaminodiphenyl-N-phenylamane,
3.3'-cyanodiphenylsulfone, 44'-diaminodiphenyl silane, 4.4'-diaminodiphenylsilane, 4.4'-di(p-aminophenoxy)diphenylsulfone, 44'-di(m -aminophenoxy) diphenyl sulfone, and at least one of these is used. These are 5 in aromatic diamine.
Preferably, it is used at 0 molar or less.

If the amount exceeds 50 mol, moldability tends to deteriorate.

9. Known aliphatic diane/diane such as piperazine and hexamethylene diamine.

Hegtamethylene diamine, octamethylene/diamine, nonamethylene diamine, decamethylene diamine, p-xylylene diamine, m-xylylene diamine, tetramethylene cyanone. Examples include dodecamethylene diamine, 44-dimethylhbutamethylenediamine, 3-methylhbutamethylenediamine, 411-cya ni nododeca/, 1,12-diaminooctadeca 7, and the like. These are preferably used in an amount of 30 moles or less, preferably 2%, preferably 10 moles or less, of the total diamine component.

For the reaction of the above-mentioned diamine and aromatic dibasic acid (fs4), the method already used for the reaction between an amine and an acid can be adopted, and the various conditions, etc. This can be achieved by, but not limited to, an interfacial polycondensation method, a bath liquid polycondensation method, or the like. When aromatic dicarboxylic acid cybalide is used, a known water-soluble neutralizing agent described below is used in the interfacial polycondensation reaction, and triethylamine is used in the solution polymerization method.

A neutralizing agent consisting of a known tertiary amine such as pyridine, tributylamine, pyridine, etc. is used. In the interfacial polycondensation method and the solution polycondensation method, a reaction f# rope is used, and the solvent used is a diamine or an aromatic dibasic acid whose main component is aromatic cyanide, or the like*@vI4 form (preferably aromatic (group dicarboxylic acid di-I-tude).

At least one of them should be able to be understood, preferably both. Cyclohexanone is an effective reaction medium for use in the present invention. Some of the other compounds that can be used include methylene chloride, trichlene, perchlorene, nitride ethane, nitrobenzene, chloroform, carbon tetrachloride, cynobutyl ketone, acetophenone, p-methylacetophenone,
N,N-dimethylformamide.

N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide.

N,N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolid/.

For pyridine, dimethyl sulfone, hexamethyl phosphoric acid, tetramethylene sulfone, and dimethyl reaction solvent, solve #1 in 1! If necessary, two or more types can be mixed and used for ease of use.

9. In order to obtain 4 with as high a molecular weight as possible, the solvent for dissolving the aromatic dicarbo/acid dihanide should be dehydrated to a high degree of paJ and 1% N, N- When performing solution polycondensation using a polar solvent such as dimethylformand, N,N-dimethylacedoide, and N-methyl-2-pyrrolidone.

5 to 10 wt. of lithium chloride as co-solvent.

Synthesis by adding calcium chloride, calcium rhodan, etc. is advantageous as it significantly increases solubility.

In addition to this co-solvent, all other known co-solvents as described below are effective. Furthermore, according to the research conducted by the present inventors, the following effective reaction method was discovered.

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

Unlike the method of dissolving diamine in alkaline aqueous solution,
Disperse diamine in alkaline aqueous solution.

This is a method in which a bath solution containing an aromatic dicarboxylic acid di-ride in an organic solvent is added to react. By polymerizing in this method, the resulting aqueous chloride is neutralized with a neutralizing agent and becomes a metal chloride, dissolved in water, and precipitated from the organic phase.If the polymer is precipitated from the organic phase, Since no hydrochloric acid or neutralizing agent remains, it will give favorable results to various properties of the polymer. In this case, the amount of alkali used is at least 1 equivalent to the aromatic dicarboxylic acid/-ride.
．． Preferably, it is 3 equivalents or less, and preferably iL< is 1.0 to 1.1 equivalents. Here, the neutralizing agent used is hydroxide which is soluble in water) I) Rum.

Examples include, but are not limited to, potassium hydroxide, sodium carbonate, and sodium bicarbonate.

In addition, for water children, it is sufficient for us that the above-mentioned neutralizing agent is sufficiently dissolved at room temperature. Of course, even if more than that is used, it will not interfere with one reaction, and the reaction temperature is such that water is liquid.

That is, it is in the range of 0 to 100°C, preferably 5 to 60°C. The above polycondensation method can be carried out, for example, by the following procedure. first.

Dissolve the neutralizing agent in a total equivalent amount of water, and add the aromatic diamine to this. Furthermore, aromatic dicarboxylic acid halide t is added to the organic solvent.
- Add the dissolved solution and allow to react. At this time, it is preferable to carry out the reaction in a state where the aromatic diamine is dispersed in the alkaline water bath liquid by stirring. Then only the organic phase is separated.

The polymer is precipitated by pouring it into an organic solvent that does not dissolve the polymer and is easily compatible with the reaction dissection. By filtering this, an aromatic polyether ad resin is obtained.

In the present invention, the aforementioned various aromatic diamines and aliphatic diamines can be used as neutralizing agents. In this case, the amount may be increased at a rate of 1 equivalent or less (an amount not involved in the reaction).

In addition, known boriaodide-forming reactions between an amide-forming conductor other than aromatic dicarboxylic acid cybalide and a diamine whose main component is an aromatic diamine represented by the general formula An aromatic polyetheramide resin having a repeating unit represented by the general formula (11) can also be obtained by an exchange method or the like.

The polyarylene polyether used in the present invention is a linear thermofluorescent polymer having repeating units represented by the general formula (II).

In the general formula +1), E is preferably a dinuclear phenol residue (nine residues excluding the aromatic water group) having the structure of the following general formula (3).

In the formula, Ar is an aromatic group, preferably a phenylene group, and Y and Y' are inert substituents such as an alkyl group having 1 to 4' carbon atoms or a halogen atom, even if they are the same. May be different, r and lu are 0 and nine are 1 to 4
Must be an integer.

B represents a bond between aromatic carbon atoms, as in dihydroxydiphenyl, or the parent is CO, O.

8, -8-8-, inorganic groups such as SOs, alkylene groups, alkylidene groups, cycloaliphatic groups,
alkylene substituted with an alkyl group, an aryl group or a similar group thereof; a similarly substituted letter alkyrite;
It represents a divalent group such as a divalent organic hydrocarbon type 1 with a ring fused to a cycloaliphatic group substituted with the same type, an alkyl-substituted aliphatic group, an alkaline group, an aromatic group, or an Ar group.

Examples of specific divalent polynuclear phenols include, among others, bis-(hydroxyphenyl)alkanes M, 2,2-bis-(4-hydroxyphenyl)/'U haf,
2, t, hydroxydiphenylmethane, bis(2
-hydroxyphenyl)methane.

Bis-(4-hydroxyphenyl)methane, bis-(4
-Hydroxy-46-dimethyl-3-methoxyphenylonmethane, 1,1-bis-(4-hydroxyphenyl)
-ethane, 1,2-bis-(4-hydroxyphenyl)
Ethane, 1.1-bis-(4-hydroxy-2-chlorophenyl)ethane, 1.1-bis-(3-methyl-4-
hydroxyphenyl)propane, 1,3-his-(3-
)f-4-hydroxyphenyl)propane.

1.3-bis-(3-methyl-4-hydroxyphenyl)gukpan, a2-bis-(3-phenyl-4-?:)
'roxyphenyl)propane + 22=bis-(3-improvil-4-hydroxyphenyl)propane, 2.
2-bis-(2-innorovir-4-hydrokyfufu=
le) Clopin.

2.2-bis-(4-hydro-17-naphthyl) gummy huff
, g 2-bis-(4-hydroxyphenyl)pentane, 3.3-bis-(4-hydroxy7enyl)pentane, 2-bis-(4-hydroxyphenyl)heptane, bis-('4- Hydroxyphenyl)phenylmethane+'a2-bis-(4-hydroxyphenyl)-1-phenylg0pan, 2-bis-(4-hydroxyphenyl)Ll, 1. :1,3-hexafluoropropane etc.;
Di(hydroxyphel)sulfone example, thapi x-(
4-hydroxyphenyl) sulfone, s4'-dihydroxydiphenyl sulfone, 5'-talol-λ4'-dihydrocydiphenyl sulfone.

5'-chloro-4,4'-dihydroquine diphenylsulfone; di(hydroxyphenyl) ether example, bis-(4-hydroxyphenyl) ether, 4.3'
-, 4,2'-, 2,2'-, 2,3'-dihydroxy diphenyl ether, 44'-dihydroxy-2,6-
dimethyl diphenyl ether, bis-(4-hydroxy-3-inbutylphenyl) ether, bis-(4-hydroxy-3-isopropylphenyl) ether, bis-(4-hydroxy-3-chlorophenyl) ether,
Bis-(4-hydroxy-3-fluorophenyl) ether, bis-(4-hydroxy-3-promphenyl ether, bis-(4-hydroxynaphthyl ether, bis-(4-hydroxy-3-chlornaphthyl) ) ether, bis-(2-hydroxyphether, 4.4'-
3,6-Simethoxydiphenyl ether in dihydro.

4.4'-dihydroquine-λ5-jethoxydiphenyl ether and analogs.

In the present invention, mixtures of two or more different dihydric phenols can be used to achieve similar objectives.

Thus, in the above explanation, when there is an -E- group in the polymer structure, it is actually the same or a different aromatic residue.
get it.

Next, E/ is a residue of a dino-lobenzenoid compound having an electron-withdrawing group in at least 4 positions that are ortho or para to the two no-rogen atoms bonded to the benzene nucleus and the nucleus no-rogen atom ( )・-9 residues excluding the gen atom)
I'll go.

Dihalobenzenoid compound B, as long as there is an electron-withdrawing group in the ortho or bara position of the be/ze/()' nucleus, p is also mononuclear with a halogen bonded to the same be/zenoid nucleus, and no.11 It may be multinucleated, with different genes bonding to benzenoid nuclei. Therefore, Bl can also mean the same residue as E.

Examples of electron-withdrawing groups include those classified into 9-order dyads.

A 2) Ofi, phenylsulfoyt al-+rusulfone, cyano, trinorolmethyl.

Monovalent group activating one or more halogens such as heteronitrogen such as nitroso and viridi/azo group -N=N-, saturated fluorocarbon group 1 CFmCF-1 organic oxidized phosphine group - P- [in the above formula, a is a swelling hydrogen group], ethylidene group X-C-X (
In the above formula, X is hydrogen or C-halogen.
In 5- or 1,8-difluoroanthraquinone, E' is of course a divalent group capable of activating four or more dino-logons, and E' is a divalent group capable of activating two or more dino-logons (a mixture of two or more dino-logons). It can also mean a group.

The following formula (B
) Polymers having a repeating unit (commonly called 1-polysulfone) and having repeating units represented by the following formula (C) are commonly called "polyethersulfone". Polymers include polymers having repeating units represented by the following formula.

The polyarylene polyether of the present invention can be used, for example, as disclosed in Japanese Patent Publication No. 42-7799. Such polyarylene polyether can be produced by the method disclosed in Mosquito Gazette.

In the present invention, the blending ratio of polyether amide (a) and polyarylene polyether (b) can be freely set within the range of (a)/(b) from 9575 to 5/9s by weight. , # of 80/20 to 20/80! The 11-fat composition of the present invention is preferably made of a resin composition of the present invention. What is the method of heating aromatic polyether amide and polyamide?

Both components are not limited as long as they can be dispersed qualitatively uniformly (for example, they may be mixed in solid form or melted). This is not preferable because the mechanical performance of the molded product is impaired.

Furthermore, the resin composition of the present invention may contain a thermal decomposition inhibitor, an antioxidant, or an ultraviolet absorber in order to improve its heat resistance and weather resistance. In addition, a fixing agent, an I14 additive, a lubricant, etc. may be added.

The resin composition of the present invention can be molded into powder, chips, or other shapes, and can be press molded or injection molded.

It is molded using generally known plastic molding methods such as extrusion molding under milder conditions than aromatic polyetheramide. The molded product is.

It has impact strength, tensile strength, bending strength, abrasion resistance, and excellent flammability in electrical properties. Therefore, this resin composition is useful as engineering plastics, and is used in the manufacture of various products that require superior performance, such as gears, bearings, and electrical component containers.

Next, the present invention will be specifically explained with reference to some examples.

Example 1 (3) Production of aromatic polyether adduct 1548 t of sodium hydroxide was dissolved in 800 ILl of water and charged into the prepared reactor. Next, λ2-bis[4-(4-aminophenoxy)phenyl]prono (7656?) was added to cyclohexanone and
At 4:00, dissolve and add to the reactor and cool to -2°C.

on the other hand.

Terephthalic acid dichloride 164? and isophthalic acid dichloride 164? A solution prepared by dissolving 2.4I14 of cyclohexanone is added dropwise while keeping the temperature of the liquid in the container below 10°C. 3 hours after starting under m, benzoyl chloride 1 yield 9? Cyclohexanone 500? To 11! Unravel and add. After another 2 hours, the reaction solution was poured into methanol.

Separate the polymer.

(B) Nythyl P-1700 (manufactured by Union Carbide, USA, polysulfone) was mixed with the nine-aromatic polyether amide pellets obtained by the above procedure at the weight ratio shown in Table 1, and the mixture was extruded using a 40 φ extruder. using die temperature 3
It was granulated at 00°C.

Incidentally, the polysal 7one has the following repeating unit.

A 45 oz pellet of this WMII product was molded using an in-line screw type injection molding machine.

It was molded into a predetermined test piece and a characteristic test was conducted.

The resulting 9-glue is shown in j119. Therefore, the injection molding pressure is 1
．． LOOW4/cm-.

Margin below All of the compositions mentioned above had good fatigue resistance.

Example 2 Production method of polyether amide copolymer composite
Stirring rod in separable flask, @! Degree needle.

Set the dropping funnel and add 80% of the water
114 and put it in a flask. next.

2. 2-bis-(4-(4-aminophenoxy)phenyl]propane 594f and U4,4'-cyaminodiphenyl ether 66)'i Dissolve in cyclohedoniasanone 3.4 ~ and pour into the previous flask. .

Cool to -2°C. On the other hand, terephthalic acid dichloride 182F and isophthalic acid dichloride 182? is dissolved in dichlorohexanone 244. This acid chloride solution is added dropwise from one to one, and at this time, 9 reaction sources are added to 10
Do not exceed ℃. 8 hours after the start of dropping, 1&l' of benzoyl chloride was added to 500 ml of cyclohexanone. Dissolve and add. After a further 2 hours, one reaction solution was poured into methanol to isolate the polymer.

(B) Obtained by said prisoner d'9! Guiktrex 200 for Beret of P-sho group Posuni-Teru-i-do.
P (commonly known as polyether sulfone 9 manufactured by Imperial Kencal Ltd. in the UK) was mixed in the weight ratio shown in Table 11, and Example 1
Characteristic tests were conducted in the same manner. Note that the polyether sulfone has a primary repeating unit.

Second machine test results Example 3 Production of aromatic polyether amide Powder of aromatic polyether amide was obtained in the same manner as in Example H~ using raw materials having the following composition.

CB) Polyarylene polyether production stirrer,
(44'-dihydroxydiphenyl)methane lOα2? was placed in a 7-fusco equipped with a thermometer, a water-cooled co/de/cer, a benzene-filled water trap, and a water trap. (α5 page), 411
11 caustic potash solution 131? (1 mol KOH), dimethyl sulfoxide 500117. Charge Penze/60dk, purge the system with nitrogen to keep the reaction mixture in an inert atmosphere, and run the mixture in situ for 3-4 hours.

The water contained in the reaction mixture as a be/ze 10 azeotrope is continuously removed and the benzene is optically distilled off to bring the drifting mixture to 130-135°C. The place tIL mixture is (4
An essentially water-free mixture of dipotassium salt of 4'-dihydroxydiphenyl)methane and dimethyl sulfoxide, 4,4'-dichlorodiphenylsul7one 14a &) 5 mol) and then 409d of anhydrous dimethyl sulfoxide. All of these steps are carried out under nitrogen pressure. The hot metal was heated to 130°C and kept at 130-135°C for 7 hours with good stirring.The viscous orange solution was poured into 300ml of water with rapid circulation in a Waring Brenta.
The separated white electrolyte is filtered and then dried in a vacuum oven at 110° C. for 16 hours.

The nine-polyarylene polyneedle thus obtained has the following repeat unit.

(C) Aromatic polyether amine obtained in the above-mentioned manner
Super Me? After uniformly mixing using a mixer, a 40 mm diameter extruder was used.

It was granulated at a die temperature of 300°C.

The obtained composition was injection molded to prepare test pieces, and physical property tests were conducted.The obtained results are shown in Table 3.

M2S test results In the above, the creep bone properties were determined by measuring the change in deformation over time when a constant bending stress (fulcrum spacing 80 cm) was applied at a constant temperature using a creep testing machine manufactured by Takasugi Seisakusho. The measured value was determined to be good for dates when the time was shorter than that for polyether sulfone alone in Example 2.

In addition, fatigue resistance was measured using a Takasugi Seisakusho-1 fatigue testing machine, and measured the number of times the casing would break when a constant tensile stress was repeatedly applied (one-sided digging). is measured, the tensile stress is plotted against the number of times, and the tensile p stress, which is considered to be broken only when io'U<f), is interpolated to find the circle.

The ff number was also good when the interpolated tensile p stress was large for both the polyarylene polyether of Examples 1 and 3 alone.

As is clear from the above, the resin derivatives according to Ippon@mei exhibit excellent acid processability and fatigue resistance, and are also excellent in other properties.

Claims (1)

[Claims] LCA) General formula (1) (In general formula (1), R1-R4 are hydrogen, a lower alkyl group, a lower alkoxy group, chlorine and 9 represent bromine, and even if they are the same, they are different) Rs and R sense are water bulk, methyl group, ethyl group, trifluoromethyl group, or trifluoromethyl group, which may be the same or different from each other. Ar is p-7 enylene group, m-phenylene group, oxydiphenylene group, sulfonyldiphenylene group (representing a biphenylene group or a 7-tyrene group) and having a repeating unit and CB) General formula (If) +o-E -0-r-) (general formula +1), B is a residue of dihydric phenol, C,
E' is a residue of a benzenoid compound having an inert electron-withdrawing group in at least one position (or) or para to the valence bond, and both of the residues are bonded to an ether oxygen via an aromatic carbon atom. A thermoplastic resin composition consisting of a linear polyarylene polyether having a repeating unit represented by