DE4122427C2 - Mixtures of polyaryl ether ketone with alkaline earth titanates - Google Patents

Description

The present invention relates to blends of high performance polymers such as Polyaryl ether ketones (PAEK) with alkaline earth titanates, furthermore the use of these Titanate to increase the mechanical strength with the same Elongation at break.

It is known that fillers based on alkali and alkaline earth titanates Toughness properties in molded articles made from polyphenylene ether and Polystyrene resins deteriorate. For this reason, the molding compositions 2 to 30% by weight of an OH-terminated polyester based on adipic acid was added. Shaped bodies from these mixtures then have increased impact and Tensile strength values (US-A 4,073,765).

The aim of the present invention is to increase the mechanical strength of PAEK increase, the elongation at break should remain unchanged. The increased stability causes their while largely maintaining the high strength values of PAEK Use in areas where increased safety limits are required be, e.g. B. when used in the automotive engine sector and in aircraft construction.

The invention therefore relates to a polyether ketone mixture consisting of

• a) a polyaryl ether ketone with repeating units of the general formula
  (-O-Ar (-L-Ar) _x -O-Ar-CO - (- Ar-M) _y -Ar -) - (I)
  in which Ar is an aromatic radical having 6 to 12 carbon atoms, L or M are each independently of one another -O-, or -CO-, x and y are each zero or an integer 1, 2, 3 or 4, and which has a melt flowability (MVI 400/5) of 2 to 250 cm ³ / (10 min) and
• b) an alkaline earth titanate.

In the polyaryl ether ketones that can be used according to the invention, Ar is preferably a phenylene, diphenyl or naphthylene group. PEEKK is preferably used. The polyaryl ether ketones that come into question according to the invention have volume melt indices according to DIN 53 735 of MVI (400/5) = 2 to 250, preferably 2 to 100 cm ³ / (10 min). Their inherent viscosities are at least about 0.5, preferably 0.7 to 1.5 and particularly preferably 0.8 to 1.2, and their molecular weights (number average) are 5,000 to 2,000,000, preferably 10,000 to 1,000,000.

Polymers of this type have glass transition temperatures of 130 to 180 ° C and Melting points from 330 to 400 ° C. Your high thermal Transition temperatures are the reason for the high heat resistance of these materials.

The polyether ketones used are admixed with alkaline earth titanate, e.g. B. Calcium titanate stabilized.

The stabilized polyaryl ether ketones according to the invention have an increased mechanical strength against non-stabilized polymers, and one each improved solvent crack resistance and chemical resistance. The The presence of these properties in polyaryl ether ketones enables their Use not only in engine and mechanical engineering, but also in such Areas of application in which high demands on the thermal and mechanical properties of the polymers are provided, for. B. in automotive engineering, in mechanical engineering, in electrical engineering and electronics and in household appliances. You can also for the production of molded parts in electrolysis technology such. B.  Electrolysis frames are used where known high mechanical Property values are needed. The mixtures according to the invention have for example, very good resistance to elevated temperatures Bases such as potassium hydroxide. So z. B. Moldings from the mixtures stable up to 150 ° C.

The polyaryl ether ketones to be used according to the invention can be prepared in in a known manner z. B. for the polyether ether ketone (PEEKK) nucleophilic condensation from hydroquinone and 1,4-bis- (4'-chlorobenzoyl) -benzene or 1,4-bis (4'-fluorobenzoyl) benzene (EP-PS 0 143 407).

Another possibility for the preparation of polyaryl ether ketones of the formula (I) consists in the reaction of diacyl halides with aromatic compounds at least two hydrogen atoms in the presence of a Friedel catalyst Crafts (DE 16 45 153, US 3,953,400 and US 3,965,240). typical Starting materials for the production of polyaryl ether ketones using Friedel Crafts acylation are terephthaloyl chloride or phosgene and diphenyl ether, optionally diphenoxybiphenyl, diphenoxybenzene or p-phenoxy benzoyl chloride.

According to the invention, alkaline earth titanates are used, but preferably Calcium.

The particle size of the titanates used is generally ≦ 50 μm, it is preferably in the range from 15 to 40 μm.

Examples

• 1. 1.a) 7.708 kg of hydroquinone, 15.3 kg of sodium hydrogen carbonate and 70 kg of diphenyl sulfone were placed in a stirred kettle. The air was displaced by nitrogen and the mixture was heated to 140 ° C. The mixture was then stirred at 140-150 ° C and heated to 210 ° C after the evolution of gas had ceased. 22.45 kg of 1,4-bis (4-fluorobenzoyl) benzene (BFB) was added. The temperature was raised to 310 ° C. within one hour. After a further 20 minutes, the reaction mixture was cooled, comminuted and washed alternately with water and sulfuric acid and with acetone to remove salts and diphenyl sulfone. The polymer powder was dried in a drying cabinet at 120 ° C./100 mbar and had a melting temperature T _m of 366 ° C. and a glass transition temperature T _g of 160 ° C.
• 2. 1.b.1) PEEKK polymer from Example 1.a) was mixed with 20% by weight of calcium titanate (CaTiO ₃ ) with an average particle size of 35 μm and in a double-shaft kneader from Leistritz (Nuremberg, Federal Republic of Germany) compounded and granulated at cylinder temperatures of 360 to 390 ° C. The granules had a melting temperature T _m of 366 ° C and a glass temperature T _g of 166 ° C.
• 3. 1.b.2) Analogously to Example 1.b.1), the PEEKK polymer from Example 1.a) was without Additive compounded and granulated (comparison).
• 4. 1.c) Testing the mechanical properties

The granules according to Examples 1.b.1) and 1.b.2) were dried (24 Hours, 160 ° C) and then to standard shoulder and batons injection molded (cylinder temperature 370-390 ° C, mold temperature 200 ° C). On The test specimens obtained were the property values listed in the table determined:  

table

2) Chemical resistance

With a storage time of more than 2 months in 40% potassium hydroxide solution at 150 ° C there were no signs of an attack on the test specimens according to Example 1.b.1, while the comparison showed clear signs of attack.

Claims (5)

1. Polyaryl ether ketone mixture consisting of

• a) a polyaryl ether ketone with repeating units of the general formula
  (-O-Ar (-L-Ar) _x -O-Ar-CO - (- Ar-M) _y -Ar -) - (I)
  in which Ar is an aromatic radical having 6 to 12 carbon atoms, L or M are each independently of one another -O-, or -CO-, x and y are each zero or an integer 1, 2, 3 or 4, and which has a melt flowability (MVI 400/5) of 2 to 250 cm ³ / (10 min) and
• b) an alkaline earth titanate.

2. Mixture according to claim 1, characterized in that the Component b) is calcium titanate. 3. Mixture according to claim 1, characterized in that the Alkaline earth titanate an average particle size of ≦ 50 microns, preferably of 15 to 40 microns. 4. Mixture according to one or more of claims 1 to 3, characterized characterized in that the polyaryl ether ketone is polyether ether ketone ketone.   5. Use of the mixture according to claim 1 in the automotive engine sector, in Aircraft construction and in electrolysis technology.