CS232308B1 - Light-current material of polyphenylene oxide-based electrotechnics - Google Patents

Abstract

The invention relates to materials for low-current electrical engineering based on polyphenylene oxide and its mixtures with other polymers, stabilizers, flame retardants or lubricants and other processing additives. The material contains 0.1 to 3 parts by weight of nitrogen bases such as amines, diamines, piperidines or piperazines and 0.5 parts by weight of metal oxides such as zinc oxide, magnesium oxide or titanium dioxide, or mixtures thereof. The material has excellent electrical properties, especially the dissipation factor.

Description

(54) Material for low-current electrical engineering based on polyphenylene oxide

The invention relates to polyphenylene oxide-based low voltage electrical engineering materials and mixtures thereof with other polymers, stabilizers, flame retardants or lubricants and other processing additives.

The material comprises 0.1 to 3 parts by weight of nitrogenous bases such as amines, diamines, piperidines or piperazines and 0.5 parts by weight of metal oxides such as zinc, magnesium or titanium dioxide, or mixtures thereof. The material has excellent electrical properties, especially loss factor.

232308 2

The invention relates to a polyphenylene oxide-based light-current electrical material and a mixture thereof with other polycores with the addition of a stabilizer, flame retardants and other electrical-enhanced additives. properties. Pure poly (2,6-dimethyl-1,4-phenylene oxide) is characterized by excellent electrical properties in a wide temperature and frequency range, very good dimensional stability, considerable heat resistance and good mechanical strength, which together with excellent resistance to moisture, acids, and alcohols predestines it for use in the electrical industry. However, its use in pure form is very limited due to the high viscosity of the melt. A common solution to this problem is the blending of polyphenylene oxide and other polymers, most commonly of which clear or tough polystyrene is used in combination with fewer rubbers and polyolefins. These blends have very good flow and mechanical properties, but the addition of other polymers reduces thermo-oxidative stability, and high levels of polystyrene in the blends also cause material flammability, which means adding flame retardants in addition to stabilizers for most applications.

The stabilizers cause a significant deterioration of the electrical properties, in particular the loss factor at room temperature, while at temperatures above 100 ° C their positive effect is already evident. The presence of retarders in the stabilized compositions results in a further significant increase in the value of the loss factor over a temperature range of from 20 to 150 [deg.] C., which is generally possible in practice. It follows that self-flame retardant material with good processing and mechanical properties is not suitable for demanding applications in low-current electrical engineering.

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It has now been found that the deterioration of the electrical properties of stabilized and possibly retarded compositions in which the basic polyphenylene oxide is inhibited against undesirable changes in nitrogen base treatment properties such as amines, diamines, piperidines or piperszines can be prevented by the addition of certain metal oxides.

SUMMARY OF THE INVENTION The present invention relates to a low-current electrical polyphenylene oxide based material and mixtures thereof with other polymers, stabilizers, flame retardants and optionally lubricants and other processing aids containing 0.1 to 3 parts by weight of nitrogen bases such as amines, diamines, piperidines or piperazines. 5 to 5 parts by weight of metal oxides such as zinc, magnesium or titanium dioxide or mixtures thereof.

Polyphenylene oxide means poly (2,6-dimethyl-1,4-phenylene oxide), the other component of the mixture may be any of the following polymers, or combinations thereof: styrene plastic, for example clear polystyrene, tough polystyrene or terpolymer of acrylonitrile, butadiene and styrene; polyolefins, for example polyethylene, polypropylene, ethylene-propylene copolymer (having thermoplastic or elastomer properties), polyisobutylene, further ethylene-propylene diane rubber or butyl rubber. The total content of these modifying polymers may range from 1 to 70% by weight, based on the mixture with the polyphenylene oxide. The material further comprises 0.05 to 3% by weight of nitrogen bases such as amines, diamines, piperidines or piperazines suppressing unwanted changes in the polyphenylene oxide processing properties described in U.S. Pat. AO 159 032, thermo-oxidizing stabilizers (e.g. according to AO 175 876 or other phosphorous acid esters), additives to improve resistance to atmospheric aging and optionally 0.5 to 20% by weight of conventional types of flame retardants with sufficiently high decomposition temperature, such as compounds phosphorus (from the group of triarylphosphates), elemental red phosphorus or halogenated compounds alone or in combination with antimony trioxide. In addition, other additives, for example lubricants and the like, may also be present in the mixture.

The addition of metal oxides in the presence of the above-mentioned nitrogen bases results in a significant improvement in the electrical properties, in particular the loss factor at room temperature, while the other properties of the material remain substantially unchanged compared to mixtures not containing said oxides. The effect of oxides on the properties of nitrogen-free mixtures is practically non-existent.

The following examples illustrate the invention. The parts shown in the examples are by weight.

He did

To 50 parts of poly (2,6-dimethyl-1,4-phenylene oxide) powder was added 0.1 parts of 8-phenyloctylaaline-1, 45 parts of clear polystyrene, 5 parts of ethylene-propylene rubber, in the case of B an additional 0.7 parts phosphorous acid tris (- (1 / phenyl) ethylphenyl ester) and, in the case of C, 0.5 parts of titanium dioxide. Mixture D differs from Case C only in that it does not contain an inhibitor of molecular weight gain (i.e. 8-phenyloctylamine-1), which is manifested in particular by a change in the eye properties after repetition. After homogenization, the powder mixtures were remelted on a laboratory screw extruder and the extruded strings were granulated. Plates were pressed from the granulate and test specimens were prepared by mechanical machining to determine the basic mechanical, electrical and thermal properties of 1 thermo-oxidative stability. The results of measurements of some properties of the obtained material are summarized in Table I.

The method of measurement is briefly presented in the table, with thermooxidation stability as follows: 0.5 mm thick samples were exposed at 130 ° C in an air atmosphere. At certain intervals, samples were taken and at room temperature the number of bends needed to break them at 9.8 N and a bend angle of + 30 ° was measured. Thermo-oxidative stability was then defined by the time during which the number of bends required to break the test sample was reduced to half that of the unexposed sample.

Example 2 parts of powdered poly (2,6-diaethyl-1,4-phenylene oxide) were mixed with 2 parts of 5,3-

Claims (1)

50 parts of powdered poly(2,6-diethyl-1,4-phenylene oxide) were mixed with 2 parts of 5,3-dimethylhexamethylenediamine, 48 parts of high-density polystyrene and 2 parts of polyethylene, in case B a stabilizer was added in the composition: 1.K parts of tris(nonylphenyl phosphite) and 0.2 parts of tert.butyl-4-methylphenol and in case C 5 parts of magnesium oxide. Mixture D does not contain an inhibitor (i.e. N,H*-diethylhexamethylenediamine), the other components are the same as in case C. The material was processed in the same way as in example 1, the properties are summarized in Table II. Example 3 To 65 parts of powdered poly(2,6-diethyl-1,4-phenylene oxide) were added 3 parts of octadecylamine, 33 parts of high-density polystyrene, 2 parts of polyethylene and 1 part of tris[4-(1-phenyl)ethylphenylester] of phosphorous acid as a stabilizer, in case B in addition to the stabilizer also a flame retardant in the composition: 1.75 parts of decabromodiphenyl oxide and 0.75 parts of antimony trioxide, in case C additionally a mixture of 3 parts of zinc oxide and titanium dioxide in a weight ratio of 2:1. Mixture D contains the same components as mixture C except for the molecular weight increase inhibitor (i.e. octadecylamine). The material was processed similarly to the previous examples, the measurement results are given in Table III. Table I. Property Measurement Temperature (°C) Mixture A Mixture B Mixture C Mixture D loss factor, ČSN 34 64 66, 50 Hz 23 7,2.10 ^-4 24.10 ^-4 12.1 O ^-4 20,7.1 O ^- ' dissipation factor, 50 Hz 60 9.5.10 ^-4 15.10 ^-4 12.10 ⁴ 15,8.10' dissipation factor, 50 Hz .40 110.10 ^-4 98.1 O ^-4 105.1 O ^-4 1 02.1 0 ^-4 specific internal resistance, GSN 34 64 60 [íJcm] 23 5,9.10 ¹⁷ 2,8.10 ¹⁷ 3,3.10 ¹⁷ 2,9.10 ¹⁷ tensile strength, [MPa] microbodies with a cross-section of the working part of 1 mm 23 58.1 63.7 61.4 63.6 deformation speed 50 mm/min notch toughness [J/cm ² ] CSN 6406/12, test specimens type 3 23 0.72 0.64 0.83 0.74 thermo-oxidative stability at 130 °C . [h] - 320 510 590 490 melt flow index [g/10min] piston load 230.4 N 270 37 4, 41 31 melt flow index [g/1Ominj after five times processing 270 36 43 40 16 Table II. Property Measurement Temperature (°C) Mixture A Mixture B Mixture C Mixture D dissipation factor, 50 Hz 23 7.5.10 ^-4 31.10 ^-4 16,7.10 ^-4 28,7.1 0 ^- ,' dissipation factor, 50 Hz 60 14.5.10 ^-4 9,1.10 ^-4 9.0.10 ^-4 10,5.10 dissipation factor, 50 Hz 140 290.10 ^-4 70.10 ⁴ 73.10 ^-4 72. 10 ^-4 specific internal resistance [í?cm] 23 2,1.10 ¹⁶ 1,2.10 ¹⁶ 2,4.10 ¹⁶ . 1,6.10 ¹⁶ tensile strength [MPa] 23 55.7 56.5 53.4 59.9 notch toughness [J/cm ² ] 23 0.77 0.96 0.86 0.89 thermo-oxidative stability at 130 °C [h] - 270 700 720 710 melt flow index [g/l0min] piston load 230.4 N 270 28 33 31 27 melt flow index [g/min] 270 28 3, 32 15 after five times processing Table III. Property Measurement Temperature (°C) Mixture A Mixture B Mixture 0 Mixture D dissipation factor, 50 Hz 23 25.1 O ^-4 44.10 ^-4 17.5.10 ^-4 42.3o10 ^- ' dissipation factor, 50 Hz ⁶⁰ 8,7.10 ^-4 38.1 O ^-4 25.10 ^-4 36,2.10"' dissipation factor, 50 Hz 1 40 57.10 ^-4 360.1 0 ^-4 360-10 ⁴ 360.10 ^-4 specific internal resistance [Ocm] 23 1,4.10 ¹⁶ 1.0.10 ¹⁶ 1,8.10 ¹⁶ 1,2.10 ¹⁶ tensile strength [MPa] 23 62.3 63.0 60.7 62.5 2 notch toughness [J/cm ] 23 0.83 0.85 0.75 0.79 thermo-oxidative stability at 130 °0 [h] - 710 360 420 330 flammability according to unsatisfactory of course- of course- of course- Underwriters Laboratories, - it's live live Gray Bull. 94 • V - 1 V - 1 V - 1 melt flow index [g/10min] piston load 230.4 N 270 19 19 17 16 melt flow index [g/10min] after five times processing 270 . 17 19 18 5 P S E D M S. T INVENTION E Z U Material for low-current electrical engineering based on polyphenylene oxide and its mixtures with longer polymers, stabilizers, flame retardants or lubricants and other processing additives, characterized in that it contains 0.1 to 3 parts by weight of nitrogen bases such as amines, diamines, piperidines or piperazines and 0.5 to 5 parts by weight of metal oxides such as zinc oxide, magnesium oxide or titanium dioxide, or mixtures thereof.