JPS62148563A - Aromatic polyamide fiber-reinforced polybiphenylene ether ketone resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition useful as raw materials with high heat distortion temperature, small strain and outstanding mechanical properties for use in the aerospace industry, by incorporating aromatic polyamide fiber in a polybiphenylene ether ketone constituted by specific recurring unit. CONSTITUTION:The objective composition can be obtained by incorporating (A) 30-99wt% of a crystalline thermoplastic polybiphenylene ether ketone constituted by recurring unit of formula with an intrinsic viscosity IV 0.7-2.5 (pref. 0.8-1.8) prepared by polycondensation between 4,4'-dihydroxydiphenyl(p,p'- biphenol) and 4,4'-dihalobenzophenone in the presence of an aromatic sulfone solvent with (B) 1-70(pref. 5-40)wt% of aromatic polyamide fiber with a fiber length 0.1-10mm carrying p-phenylene group.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is an aromatic polyamide fiber-reinforced polybiphenylene ether ketone resin that has excellent heat resistance as represented by heat distortion temperature and mechanical properties as represented by flexural modulus. The present invention relates to a composition.

<Prior Art> A thermoplastic aromatic polyether ether ketone composed of a repeating unit represented by the following formula (n) has excellent chemical resistance, steam resistance, etc., and is also excellent in heat resistance.

However, since the glass transition temperature is as low as 143°C, the heat distortion temperature is also as low as 152°C.

Therefore, in order to increase the heat distortion temperature, a resin composition in which glass fiber or carbon fiber is blended with the thermoplastic aromatic polyether ether ketone is disclosed in JP-A-56-92952.

This resin composition is attracting attention as a material with excellent heat resistance.

On the other hand, JP-A-58-109554 discloses 1! of thermoplastic polyether aromatic ketone! Lubricating resin compositions containing fluororesins and aromatic polyamide fibers have been reported for the purpose of improving dynamic properties.

<Problems to be Solved by the Invention> However, all of the resin compositions are still insufficient as materials for the aerospace industry in terms of heat resistance and other aircraft surface characteristics.

As a result of further studies aimed at obtaining a resin composition with a higher heat distortion temperature and less distortion, the present invention combines polybiphenylene ether ketone, a new polymer previously proposed by the present inventors, with aromatic polyamide fibers. It was discovered that this problem could be solved by doing so.

Means for Solving the Problems> That is, the present invention provides (A) a crystalline thermoplastic polybiphenylene ether ketone 3Q to 99% by weight consisting of repeating units represented by the following formula (I>) and (B) an aromatic This is an aromatic polyamide fiber-reinforced polybiphenylene ether ketone resin composition comprising 1 to 70% by weight of group polyamide fibers.

The crystalline thermoplastic polybiphenylene etherketone (A) used in the present invention is a crystalline thermoplastic polybiphenylene etherketone consisting of repeating units represented by the above formula (I>).

Further, the crystalline thermoplastic polybiphenylene ether ketone can contain repeating units thereof to the extent that its original properties are not impaired.

Other repeating units include -C>302-00-, preferably -
〇sa c Q o-.

It is considered that the original properties of the crystalline thermoplastic polybiphenylene ether ketone will not be impaired if the content of these is approximately 15% by weight or less.

The crystalline thermoplastic polybiphenylene ether ketone of the present invention preferably has an intrinsic viscosity Iv of 0.7 to 2.5, particularly 0.
．． 8 to 1.8 is preferred.

When IV is less than 0.7, the polymer tends to become brittle, and when it exceeds 2.5, blending with aromatic polyamide fiber tends to become difficult.

In addition, the intrinsic viscosity IV here refers to a polymer solution in concentrated sulfuric acid with a density of 1.849/d containing 0.59 polymer per 100 units of solution. Intrinsic viscosity measured at 25°C. A viscometer with a flow time of about 2 minutes was used to measure IV. When the outflow time of concentrated sulfuric acid is to and the outflow time of the polymer solution is t, the intrinsic viscosity IV is IV = (In t
/1o) 10.5te is expressed.

The polybiphenylene ether ketone used in the present invention is prepared by combining 4,4-dibidroxydiphenyl (p, p=-biphenol) and 4,4-- in the presence of an aromatic sulfone solvent.
By polycondensation with dihalobenzophenone′! A can be built.

A mixture of 4,4'-dihydroxydiphenyl and 4,4-dihalobenzophenone in substantially equimolar amounts is added under substantially anhydrous conditions to an alkali metal per mole of said 4,4-dihydroxydiphenyl. In the presence of an alkali metal carbonate (polycondensation agent) in an amount equivalent to 2 gram atoms or more, the following formula (Y represents a direct bond, an oxygen atom, or two hydrogens bonded to each benzene ring, Z and Z- hydrogen or phenyl group) in the aromatic sulfone, 150 to 45
It can be produced by polycondensation at 0'C and raising the final temperature high enough to keep the final polymer in the molten state.

The 4,4-dihalobenzophenone used in the polymerization reaction is 4,4-difluorobenzophenone or 4,4-dihalobenzophenone.
4-dichlorobenzophenone is preferred, and a mixture of both may be used.

Further, the alkali metal carbonate used as the polycondensation agent is preferably potassium carbonate or sodium carbonate, and a mixture of both may be used.

The amount used is preferably 2.0 to 2.20 moles of alkali metal ion per mole of 4,4-dihydroxydiphenyl.

In addition, if generation of gelled products is observed, adding a small amount of anhydrous sodium sulfate to polymerize can suppress the generation of gelled products.

The polycondensation reaction is carried out in the above aromatic sulfone solvent,
Examples of such aromatic sulfone include diphenyl sulfone, dibenzothiophene dioxide, and phenoxathiine dioxide, with diphenyl sulfone being preferred.

The polycondensation temperature is 150 to 450'C, but the temperature is raised continuously or stepwise from a low temperature until the final temperature is 380'C.
It is preferable to set it near 'C.

The intrinsic viscosity of the polybiphenylene ether ketone used in the present invention is 4.4-1 dihydroxydiphenyl or 4.
, 4--dihalobenzophenone in slight excess. In this case, it is preferable to use 4,4'-dihalobenzophenone in excess of 5 mol % or less, since heat stability tends to be better if the polymer ends are halide ends rather than phenol ends.

Another method involves adding a polymerization terminator once the desired molecular weight level is reached.

As the polymerization terminator, a halobenzenoid compound having an electron-withdrawing group at at least one position ortho or para to the halogen is preferred.

The number of halogen atoms may be any number, but one or two are preferred, and examples include 4-fluorophenylsulfonylbenzene, 4,4'-didifluoropenzophenone, and 4,4'-dichlorodiphenylsulfone. It will be done.

The aromatic polyamide fiber used in the present invention is -NH-A
It has a repeating unit represented by r1-NH-Co-Ar2-Co-. Here, Ar1 and Ar2 are divalent aromatic residues, and among these, p-phenylene group is preferred. The fiber length is preferably 0.1 to 10 m, but roving can also be used. Further, aromatic polyamide fibers do not necessarily require fiber convergence treatment using epoxy resin or the like, but may be applied depending on the purpose, such as better adhesion to resin and workability.

Between the aromatic polyamide fibers in the composition according to the invention,
The amount is 1 to 70% by weight, preferably 5 to 40% by weight in the composition. If it is less than 1% by weight, no increase in heating deformation temperature or improvement in flexural modulus will be observed, and if it exceeds 70%,
This is not preferable because the polybiphenylene ether ketone is not sufficiently dispersed between the aromatic polyamide fibers, making it impossible to obtain a uniform composition.

As a mixing method for obtaining the composition of the present invention, polybiphenylene ether ketone and aromatic polyamide fiber are tri-blended using a mixer such as a Henschel mixer or a super mixer, and then melt-kneaded using a single-screw or multi-screw extruder. The most common method is to extrude the strands and turn them into pellets using a cutter.

In addition, when using roving, it is supplied from the vent groove of the extruder, and the feeding speed of the roving is adjusted so that the blending ratio with the crystalline thermoplastic polybiphenylene ether ketone supplied from the hopper is appropriate. Can be mixed in any way.

The present invention will be explained below with reference to Examples.

<Example> Reference example Production of crystalline thermoplastic polybiphenylene ether ketone 4,4'-dichlorobenzophenone 251.1
! ? (1.0 mol), 4.4-dihydroxydiphenyl 186.2y (1 mol), anhydrous potassium carbonate 143.
7! IF (1,04 mol), anhydrous sodium sulfate 309
and diphenylsulfone 6003 were charged, and the inside of the reaction vessel was replaced with N2. The reaction vessel was heated to 180'C under a stream of N2 and stirred slowly. Rewarm for 30 minutes, 1.5
250℃ for 1 hour, then 250-270℃ for 1.5 hours.
'C held. The temperature was continued to be gradually raised to 380° C. for about 2 hours, and after stirring at this temperature for 1 hour, stirring was stopped and the mixture was cooled. After cooling, take out the contents and crush them,
The powder was made into a powder with a diameter of 00 μm or less.

Diphenylsulfone was removed by extracting and washing this with 31 g of acetone and refluxing and washing in roughly 3 g of ethanol. After this, wash with plenty of water and remove
The a-salt was removed and dried in vacuo at 150°C overnight.

The IV of the polymer was 0.95. The melting point measured by a differential scanning calorimeter was 387°C, and the glass transition point obtained from the temperature dependence curve of dynamic viscoelasticity was 175°C.

Examples 1-2 Comparative Examples 1-5 Crystalline thermoplastic polybiphenylene ether ketone (hereinafter abbreviated as PBEK) or polyether ether ketone ("Victor" manufactured by ICI) manufactured in the above reference example
x PE E K” > (hereinafter abbreviated as PEEK) Two aromatic polyamide fibers (Pakeblar “49” manufactured by DuPont) having a basic structure of T-NH-QNtf-CO-o-CO- @b extruder (extrusion temperature: PB
EK: 420-440'C, PEEK; 360
The mixture was uniformly blended at ~380'C) and pelletized.

These pellets were then molded into samples using a 3 oz injection molding machine (temperature conditions are shown in Table 1).

Table 1 The sample size is 215.9 mm x 12.70 mm, which is suitable for measuring the flexural modulus according to ASTM-D790.
trtmX3.17mm. Furthermore, from this sample A
A sample having a size of 100 m x 12.70 m x 3.17 # suitable for measuring heat distortion temperature was prepared in accordance with STM-D648.

Table 2 shows the amount of aromatic polyamide fibers, heat distortion temperature, and measurement results of flexural modulus.

As shown in Table 2, the composition consisting of polybiphenylene ether ketone and aromatic polyamide fiber has a high heat distortion temperature, and the heat distortion temperature of #120% aromatic polyamide fiber is 300°C.
significantly exceeded.

Moreover, the bending elastic modulus also shows a large value.

<Effects of the Invention> The present invention has produced an aromatic polyamide fiber-reinforced polyester material that is promising for use as a material for the aerospace industry and has excellent heat resistance as represented by heat distortion temperature and mechanical properties as represented by flexural modulus. A biphenylene ether ketone resin composition is now available.

Claims (1)

[Scope of Claims] (A) Crystalline thermoplastic polybiphenylene ether ketone 30-99 consisting of a repeating unit represented by the following formula (I)
(B) Aromatic polyamide fiber-reinforced polybiphenylene ether ketone resin composition consisting of 1 to 70% by weight of aromatic polyamide fibers