JPS58149944A - Aromatic polyether-amide resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent mechanical properties, flow characteristics and moldability, by blending a polyfluorinted polymer to a specified arom. polyther-amide. CONSTITUTION:One equivalent of an arom. diamine of formulaI(wherein R1- R4 are each H, lower alkyl, lower alkoxy, Cl, Br; R5, R6 are each methyl, ethyl, trifluoromethyl, trichloromethyl) and 0.9-1.2 equivalents of an arom. dicarboxylic acid halide having an ether linkage of formula II (wherein Ar is p- or m-phenylene, dishenylene ether, diphenylene sulfone, diphenylene, naphthylene, X is Cl, Br) are subjected to a polycondensation reaction of obtain an arom. polyether-amide (A) having a repeating unit of formula III and a reduced viscosity of 0.3-1.5dl/g. Then 1-50pts.wt. polyfluorinated polymer (B) having an MW of 100,000-1,000,000 such as tetrafluoroethylene resin is blended with 100pts.wt. component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to aromatic polyetheramides, polyfluorinated addition polymers, and resin compositions having improved moldability and chemical and material properties.

In the general formula (representing an alkoxy group, chlorine or bromine, one stone and a) are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group.

They may be the same or different. ) is disclosed in Japanese Unexamined Patent Publication No. 52-23198 and US Pat.
5 (known in the specification of No. 1288, etc.).

By the way, the aromatic polyether amide obtained from such special diamines has mechanical properties such as tensile strength, crushing strength *impact strength, thermal properties such as heat distortion temperature and thermal decomposition, and arc resistance. It maintains excellent properties in terms of electrical properties such as dielectric constant and dielectric loss, flame resistance, and dimensional stability. is expected to have a wide range of uses. However, a drawback of this type of aromatic polyether amide is that it has poor moldability. In general, the evaluation of moldability is extremely important for plastics, and even if the plastic itself has inherently excellent properties, if the moldability is poor, it will not be possible to economically manufacture the product. Not only that, but it is also important to make full use of its excellent properties in products. For example, if a product is made by injection molding using a polymer with a high softening temperature (low temperature), it requires a high layering temperature, high injection pressure, high mold temperature, etc. In addition to causing high costs, high layering temperatures can cause thermal decomposition of the polymer, and high injection pressures can cause extreme distortion. If such strict conditions are not met,
Appearance defects such as short shots, sink marks, and flow marks may occur, and mechanical properties may deteriorate. For this reason, improvements in moldability have also been made for aromatic polyetheramides.

The inventors of the present invention have conducted extensive research and research to improve the fluidity of the resin while maintaining the excellent properties of aromatic polyether amide.
As a result, the present invention was completed.

That is, one object of the present invention is to provide a resin composition in which the fluidity of aromatic polyether amide is increased and, moreover, excellent properties such as mechanical properties are maintained.

However, one book - I#jFi, general formula (summer) """ (1) (However, in formula (1), approximately 1.-, ru and ru are hydrogen.

You can stay there. & and ordinary are water volume, methyl group, engineering, etc.)
1 part by weight of polyfluorinated addition polymer per 100 parts by weight of aromatic polyetheramide resin having repeating units represented by
-50 parts by weight of an aromatic polyetheramide resin composition.

This shield is 111JI with improved moldability.
In addition to providing the I composition, it is also possible to provide a resin composition with excellent abrasion resistance and impact resistance.

The polyfluorinated addition polymer used in the present invention includes ethylene tetrafluoride, trifluorochloride: t-fl/7°t or vinylidene fluoride, and unsaturated fluorine-containing hexamer.
It is produced by addition polymerization using 1 m or more of 50 mol or more of two or more types, and the molecular weight is usually 100,000 to 1,000,000 O. Polyfluorinated addition polymers include tetrafluorinated ethylene resin, fluorinated ethylene/propylene copolymer 111r, barfluoroalkoxy resin (polymer of perfluoroalkyl vinyl ether or copolymer of the ether and tetrafluorinated ethylene, etc.), Ethylene/1a77 modified tyrene copolymer resin,
Trifluorochloroethylene resin, vinyl fluoride resin, vinylidene fluoride resin, etc. can be used.

In the present invention, there are no particular limitations on the method of warming the polyfluorinated addition polymer with the aromatic polyetheramide. For example, it is possible to use a known method such as a roll extruder or a Banbury mixer 1 extruder.

If the amount of the polyfluorinated addition polymer added is too small, the effect will not be recognized, and if it is too large, the dispersion tends to become non-uniform. Therefore, the blending amount of the polyfluorinated addition polymer is as follows: aromatic polyether amide 1
It is practical to use 1 to 50 parts by weight, preferably 2 to 30 parts by weight.

The aromatic polyetheramide used in the present invention has a repeating unit represented by the general formula (11), and in the general formula (1), R1゜Ra, Rs and R4 are hydrogen. , and a repeating unit in which the stone and B. Aromatic polyetheramides having nine repeating units (bonded to the benzene nucleus at the Kl position) are preferably used.

When the aromatic polyether amide is an aromatic polyether amide consisting of repeating units represented by It is most preferable that the ratio of the former is 80 to 20% and the latter is 20 to goqk.

The aromatic polyetheramide resin used in the present invention is, for example, an aromatic diamine represented by the above-mentioned general formula (set) and an aromatic dicarboxylic acid dino Sride represented by the following general formula (1).

It is obtained by polycondensation reaction of XC0-Ar-C0X =...(l[) (in formula 9, one r represents a p-phenylene group or a m-phen group, and X represents chlorine or bromine).

The aromatic diamide represented by general formula (II) is,
λ2-bis(4-(4-aminophenoxy)phenyl)
Propane, λ2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, λ2-bis[3-chloro-4-(4-aminophenoxy)phenyl]pronokun, λ2-bis[3- Promo 4-(4-aminophenoxy)phenyl]propane, z2-bis[3-ethyl-4-(4-aminophenoxy)phenyl]propane,
12-bis(3-7' lobi-4-(4-aminophenoxy)phenyl]prono(n, λ2-bis[3-inpropyl-4-(4-7minophenoxy)phenyl)prono(n, λ2-bis[ 3-Butyl-4-(4-aminophenoxy)phenyl]propane, λ2-bis[3-se
c-butyl-4-(4-7minophenoxy)phenyl]
Propane, sous-bis[3-methoxy-4-(4-7minophenoxy)phenyl]propane, λ2-bis[3-
Ethoxy-4-(4-7minophenoxy)phenyl]pronokun, Su-2-bis[3,5-dimethyl-4-(4-
aminophenoxy)phenyl]propane, &2-bis(
! L5-dichloro4-(4-aminophenoxy)phenyl]propane, 2,2-bis[turtle8''-dibromo-4
-(4-aminophenoxy)phenyl]propane, λ2
-bisC3,5-dimethoxy-7-4-(4-aminophenoxy)7enyl]propane, &2-bis[3-chloroE
2-4-(4-7minophenoxy)-5-methylphenyl]propane, Ll-bis(4-(4-aminophenoxy)phenyl)ethane, Ll-bis[3-methyl-4-
(4-aminophenoxy)phenyl]ethane, Ll-bis[3-chloro-4-(4-amino72]enyl)ethane, l,1-bis[3-promo 4-(4-7
minophenoxy)phenyl]ethane, l,1-bis[3
-Ethyl-4-(4-aminophenoxy)phenyl]ethane, Ll-bis[3-propyl-4-(4-aminophenoxy)phenyl]phenol, 1,1-bis[3-inpropyl-4- (4-aminophenoxy)phenyl]ethane, 1.1-bis[3-phthyl-4-(4-aminophenoxy)7enyl]ethane, 1.1-bis(3-5e
c-butyl-4-(4-7minophenoxy)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[&5-dimethyl-4-(4-aminophenoxy)7enyl]ethane, Ll-bis[3,5
-dichloro-4-(4-aminophenoxy)7enyl]
Ethane, 1,1-bis[kame-5-dibromo-4-(4-aminophenoxy)phenyl]ethane, Ll-bis[&5
-dimethoxy4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4-aminophenoxy)7enyl-5-)f-ruphenyl]ethane, bis[4-(4 -aminophenoxy)phenylcomethane.

Bis[3-methyl-4-(4-aminophenoxy)phenylcomethane, bis(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,
BisC3-5ec-butyl-4-(4-aminophenoxy)phenylcomethane, bis[3-methoxy-4-(4
-aminophenoxy)phenylcomethane, bis[3-ethoxy-4-(4-aminophenoxy)phenylcomethane, bis[&5-dimethyl-4-(4-aminophenoxy)phenylcomethane.

Bis(35-dichloro-4-(4-aminophenoxy)
Phenylcomethane, bis[turtle 5-dibromo-4-(4-
aminophenoxy) phenylcomethane, bis[&5-dimethoxy4-(4-aminophenoxy)phenylcomethane, bis[3-chloro-4-(4-aminophenoxy)-5-methylphenylcomethane, 1,1, 1. &
&3-hexafluoro-λ2-bis(4-(4-aminophenoxy)phenyl)propa/, 1.1,1゜Denden 3
-hexachloro-&2-bis[4-(4-aminophenoxy)phenyl]propane, &3-bis(4-(4-7
minophenoxy)phenyl]pentane, 1,1-bis(
4-(4-aminophenoxy)phenyl]propane, i
,i,1. a&3-hexafluoro-λ2-bis [Turtle 5
-dimethyl-4-(4-aminophenoxy)phenyl]
Propane, 1.1.1. Turtle & 3-hexachloro-22-
Bis[&5-dimethyl-4-(4-aminophenoxy)
phenyl]propane, 3,5-bis[tortoise 5-dimethyl-
4-(4-7minophenoxy)phenyl]pentane, L
l-bis(35-dimethyl-4-(4-aminophenoxy)7enyl]propane, LLl, &3,3-hexafluoroλ2-bisC&S-dibromo-4(4-7minophenoxy)phenyl]propane, , 1.1゜L electric 3-hexachlorolose 2-bis(3,5-dibromo-
4-(4-aminophenoxy)phenyl]furopane, &
3-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]pentane, Ll-bis[&5-dibromo-4-(4-aminophenoxy)phenyl]propane.

&2-bis(4-(4-aminophenoxy)phenylcobutane, λ2-bis(3-me?4-(4-aminophenoxy)phenylcobutane).

λ2-bis[&5-dimethyl-4-(4-7minophenoxy)phenylcobutane, λ2-bis[3,5-dibromo-4-(4-aminophenoxy)phenylcobutane,
1.1.1. a&3-hexafluoro-2,2-bis[
3-methyl-4-(4-aminophenoxy)phenyl]
There is a propane nato.

All known aromatic dicarboxylic acid cybarides represented by the above general formula (1) are useful. For example, terephthalic acid dichloride, terephthalic acid dibromide, inphthalic acid dichloride, isophthalic acid dibromide, diphenyl ether dicarboxylic acid dichloride-44', diphenyl ether dicarboxylic acid dichloride-4,4', diphenylsulfone dicarboxylic acid dichloride-44', diphenyl sulfone dicarboxylic acid dipromide-4,4', diphenyldicarboxylic acid dichloride-44', di7-dicarboxylic acid dibu pmite-4,4', naphthalene dicarboxylic acid dichloride-1,56 or naphthalene dicarboxylic acid dichloride-1, 5, etc., and at least one of them is used.

The blending ratio of the aromatic diamine and the aromatic dicarboxylic acid civalide is preferably 1 weight of the former to 0.0 weight of the latter.
It is set in the range of 9 to 1.2 equivalents. Outside the above range, a high molecular weight product tends to be obtained, and only an oligomer-like product that does not have a resinous appearance tends to be obtained. Particularly preferably, the latter aromatic dicarboxylic acid civalide is 0.97 to 1.03 per 1 part of the former aromatic diamine.
It is within the reasonable range. When the amount is equivalent to 4IK, the maximum molecular weight of the target aromatic polyetheramide resin can be obtained.

Note that a part of the aromatic diamine can be replaced with other known aromatic diamines.

Its amount is expediently preferably 50 mol, preferably 70 mol (based on the total amount of aromatic diamine).
should be the upper limit. If the amount exceeds 50 mol, molding processability may be impaired. Examples of other aromatic diamines include Example 1/dm-phenylenediamine, p-phenylenediamine, 44'-diaminodiphenylmethane 44'-diaminodiphenyl ether, 44'-diaminodiphenylsulfone, 44'-diaminodiphenylpropane-λ2. 44'-/aminodiphenylsulfide, 1,5-diaminonaphthalene.

44'-/aminodiphenylethane * m") lylene diamine, 9-) lylene diamine &4/-diaminobenzanilide, 1,4-diaminonaphthalene, &3'
-Dichloro44'-diaminodiphenyl, benzidine, 44'-diaminodiphenylamine, 44'-diaminodiphenyl-N-methylamine, 4.4'-diaminodiphenyl-N-phenylamine, 3.3'-diaminodiphenylsulfone 44 / -diaminodiphenylsilane, 4,4'-diaminodiphenylsilane, etc., and at least one of these is used.

Additionally, known aliphatic diamines, such as pibezine,
Hexamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, p-xylylene diamine.

m-xylylene diamine, tetramethylene diamine, dodecamethylene diamine, 44-dimethyl hebutamethylene diamine, 3-methyl hebutamethylene diamine, &11
- Diaminododecane.

1,12-diaminooctadecane and the like can also be used in combination with the above aromatic diamine. The combined use of aliphatic diamine has the effect of further improving the moldability of the target aromatic polyetheramide resin. However, as the amount of the compound increases, the heat resistance gradually decreases, so the amount of the compound should be set so as not to impair the purpose of the present invention.
Preferably Fi 30 mol or less, 411K preferably lO
It is used in combination in the range II of less than molar amount (based on the total amount of diamine). The aliphatic diamine is used alone or in combination with the aromatic diamine represented by the above-mentioned general formula (1).

When the aforementioned various diamines are used in combination, the blending ratio of all the diamine components and the aromatic dicarboxylic acid sybaride can be set on exactly the same basis as described above.

For the reaction, the method already used for the reaction between an amine and an acid can be adopted as is, and even if K such as m conditions are set, *FC@ is not determined. For example, this can be achieved by interfacial polycondensation method, *liquid polycondensation method, #lkl condensation method, etc. In the interfacial polycondensation reaction, a known water-soluble neutralizing agent described below is used. Also,
In the case of solution polymerization, a neutralizing agent consisting of a known tertiary amine such as triethylamine, pyridine, tributylamine, pyridine, etc. is used. In the interfacial polycondensation method and the solution polymerization method, a reaction solvent is used, but this solvent must be capable of dissolving at least one of aromatic diamine and aromatic dicarboxylic acid sybaride, preferably both. No. A typical example of a particularly effective reaction solvent in the interfacial condensation method is cyclohexanone, and some examples of other lacquer ropes that can be used include: , nitrobenzene, chloroform, carbon tetrachloride, diisobutyl ketone, acetophenone.

Examples include p-methylacetophenone. Also, as a reaction solvent used in solution polymerization method.

N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-
Pyrrolidone, pyridine, dimethylsulfone, hexamethylposneramide. Preferred are tetramethylene sulfone, dimethyltetramethylene sulfone, and the like.

The reaction solvent must be used to facilitate the dissolution operation, etc.
It is also possible to use a mixture of more than one species.

In order to obtain a product with as high a molecular weight as possible, it is preferable to use a more dehydrated solvent for dissolving the aromatic dicarbonate. In particular, when lacquer polycondensation is carried out using a W solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone, 5 to 10% by weight of lithium chloride is used as a co-solvent. It is convenient to synthesize by adding calcium chloride, calcium chloride, calcium rhodan, etc., as it significantly increases solubility. As the co-solvent, other known co-solvents such as those described below are also effective.

According to the research of Keiku 3-moto and others, the following method is effective.

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

A method different from the method of dissolving diamine in alkaline aqueous solution,
Disperse diamine in alkaline water III.

This is a method of reacting aromatic dicarboxylic acid cybaride by adding a lacquer solution to an organic solvent. By polymerizing in this method, the nine halogenated water moat produced is neutralized with a neutralizing agent and becomes water and metal halide, which dissolves in water.When the polymer is precipitated from the organic phase, the polymer is precipitated with hydrochloric acid or neutralized. Since no agent remains, this gives favorable results to the properties of the polymer. In this case, the amount of alkali used is 1.3 equivalents or more than the aromatic dicarboxylic acid halide.
and preferably 1.0 to 1.1 equivalents. ζThe neutralizing agent used here is sodium hydroxide, which is soluble in water.

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

First, the amount of water is sufficient as long as the above-mentioned neutralizing agent is sufficiently dissolved at room temperature. Of course, even if you use more than that, it will not change to 9 reactions. Also, the reaction temperature is the state where 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 an appropriate amount of water, and add the aromatic diamine to this. Furthermore, a solution of aromatic dicarboxylic acid halide dissolved in an organic solvent is added and reacted. At this time, I would like to express my gratitude to
It is preferable to carry out the reaction while stirring and dispersing the aromatic diamine in the alkaline water droplet. 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 solvent. By filtering this, an aromatic polyetheramide resin is obtained.

The various aromatic diamines and aliphatic diamines mentioned above can act as neutralizing agents. In this case, the amount may be increased at a rate of 1 or less (an amount that does not participate in the reaction).

9. Known polyamide-forming reactions between amide-forming derivatives other than aromatic dicarboxylic acid dihydrides and aromatic diamines represented by the general formula A mido resin represented by the general formula (1) can be obtained.

The aromatic polyetheramide resin of the present invention particularly preferably has a molecular weight of 0.5 to 0.9 dl/P.

o, stu/, the strength decreases, 1.5 dt/P
If it exceeds this value, moldability tends to be poor.

Furthermore, by blending other types of polymers into the resin composition of the present invention, its properties can be improved.
ar? Anti-inflammatory agent, ultraviolet absorber.

By coexisting additives such as lubricants and flame retardants,
Its properties can also be improved.

The aromatic polyetheramide resin composition according to the present invention has excellent mechanical properties such as fluidity and wear resistance.

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited thereto.

Example 1 11i[t, 2
．． 2-bis[:4-(4-aminophenoxy)phenylpropane by contacting and reacting 20 ml of cyclohexanone liquid in the presence of 101 aqueous sodium hydroxide solution,
An aromatic polyether amide was produced. However, the blending ratio of the acid chloride mixture and the aromatic diamine is equimolar. This in dimethylformamide (0.2t/di)
The reduced viscosity of was 0.94 dl/). To 100 parts by weight of this aromatic polyetheramide resin powder, perfluoroalkoxy resin (Mikata Fluorochemical - trade name MP-
Add 10) in the amount shown in 1 and use an extruder to
Pelletization was performed at 320°C. Table 1 shows the fluidity of each pellet and the amount of wear measured using a RIKEN Ohkoshi rapid wear tester. (Constant conditions: two friction distances of 10,011 m and moderate friction of 0.
51m/I, carbon steel, load 12.0It). 300℃ using a Shimadzu flow tester
, ioo~/-.

Table 1 Tofunehiki-Tsurukame Example 2 An acid chloride mixture with a mixing ratio of terephthalic acid dichloride/inphthalic acid dichloride of 4:6 (molar ratio),
An aromatic polyetheramide resin having a reduced viscosity of 0.73 dl/P was obtained from bis(4-(4-aminoneenoxy)phenyl)methane by solution polymerization using N-methylpyrrolidone as a solvent.

To 100 parts by weight of this polymer, 20 parts by weight of ethylene/tetrafluoroethylene copolymer resin (Tefzel 200 manufactured by DuPont) was mixed and pelletized at 300 to 320°C. 3
Fluidity at 00'C, 100 noodles/aIi is 4.8X10
cc/*, and the amount of wear measured with a RIKEN Ohkoshi rapid abrasion tester was 0.29*3.

Example 3 101 Separable flask, stirring bar, temperature needle.

Set the dropping funnel and add 171,8) of NaOH to 80% of water.
0114KII and put into flask. Next, λ2-bis(4-(4-aminophenoxy)phenyl]propane 594F and 44'-diaminodiphenyl ether 66
Dissolve t in cyclohexanone 3.4 noodles, pour into a separate flask, and cool to -2°C. On the other hand, 182t of terephthalic acid dichloride and 182t of inphthalic acid dichloride are dissolved into 2.411KII of cyclohexanone.

Pour the acid chloride** from the dropping funnel, making sure that the reaction temperature does not exceed 10°C. Three hours after the addition, the reaction vessel was poured into methanol to isolate the polymer. 100 parts by weight of the nine-aromatic polyetheramide resin powder obtained by drying was mixed with 10 parts by weight of tetra7tethylene resin (Sankata, produced by Plo Chemical ■, TLP-10), and the mixture was made into a powder of 300 to 320 Pelletized at °C. a
Fluidity at OO℃, 100Kt// is 6.4 x 10
-"ec/s, and the amount of wear measured by II Research Institute Ohkoshi type rapid abrasion tester was 0.33■1.

Claims (1)

[Claims] 1. General formula (1) % formula % (1) (However, in formula 9, R1, Ba, Rs and the mountain represent water volume. Represents a lower alkyl group, a lower alkoxy group, chlorine or dibromine, The arms may be the same or different from each other, and R4 and & represent hydrogen, a methyl group, an ether group, a trifluoromethyl group, or a trichloromethyl group. Based on 100 parts by weight of an aromatic polyether amide having a repeating unit, which may be the same or different, and Ar is a p-phenylene group. An aromatic polyether amide scoop composition comprising 1 to 50 parts by weight of a polyfluorinated addition polymer. 2. Aromatic polyether amide in general formula (1). iLt, R snow# The aromatic polyetheramide resin composition according to claim 1, which is an aromatic polyetheramide having a repeating unit in which Rm and R4 are hydrogen, and Rs and 8. are methyl groups. thing. 3. Aromatic polyether amide in general formula (1). The aromatic polyetheramide resin composition according to claim 1 or claim 2, wherein Ar is an aromatic polyetheramide having repeating units in which Ar is a p-phenylene group and a m-phenylene group. thing. 4. Claim H in which the aromatic polyether amide is an aromatic polyether amide of formula (4) (however, in formula 1, the two carbonyl groups are mutually bonded to the benzene nucleus at the meta or para position) The aromatic polyetheramide resin composition according to item 1, item 2, or item 8.