DE2025467A1 - Thermoplastic resin compn with good flow - Google Patents

Abstract

Thermoplastic synthetic resin compn. contains (a) 10-90 parts by wt. of a linear thermoplastic polyarylene-polyether-polysol phone resin. (b) 90-10 p.b.w. of an acrylonitrile/butediene/styrene polymer per 100 p.b.w. of (a) + (b)

Description

Synthetic, thermoplastic resin mixture made from polysulfone and ABS.

Additional application to patent (German patent application P 17 94 171.8).

The invention relates to synthetic, thermoplastic resin fencing. In particular, the invention relates to resins which, when physically blending a thermoplastic polysulfone resin with an APS polymer.

ABS resins of the type used in the present invention are for example U.S. Patents 2,439,202, 2,600,024, 2,820,773, 3,111,501, 3,198,853 and 3,261,887.

Thermoplastic polysulfone resins of the type used according to the invention are for example in U.S. Patent 3,264,536 in British Patent 1,060,546 as well as in the simultaneously filed US patent application with the serial Number described4 are mixtures of ABS with various other polymers known, but not with thermoplastic polysulfone resins. So are for example Blends of ABS with polycarbonate resins in U.S. Patent 3,130,177 described.

Mixtures of thermosetting polysulfone resins with thermosetting phenolic resins are known, for example, from US Pat. No. 3,245,947 and 3,256,361; however, such mixtures differ from the mixtures according to the invention.

There is a need for inexpensive, high temperature resistant Plastic compounds that have good flow properties and good impact strength at the same time exhibit. According to the invention, such a mass is in the form of a mixture of lo to 90 parts (all quantities here and below refer to the weight) of a thermoplastic polysulfone synthetic resin and correspond to 90 to 10 parts of an ABS resin provided. The mixtures obtained have unexpected thermoplastic properties including improved flowability, Heat distortion temperature, impact resistance and flexural strength.

The invention is explained in more detail below with reference to the drawings: In detail: FIG. 1 shows a picture based on an electron microscope, purely schematic representation of the morphology of a typical ABS resin; FIG. 2 shows a corresponding representation of the morphology of the polysulfone synthetic resin; figure 3 shows a corresponding illustration of the mixture of ABS with polysulfone; and figures 4, 5 and 7 graphs showing the changes in heat distortion temperature, Impact strength and viscosity at a certain speed gradient (apparent viscosity) with the percentage amount of polysulfone resin in the inventive Mixtures emerges.

The term "ABS synthetic resin" or "ABS resin" is used here and in The following is used in its usual meaning and stands for a thermoplastic Synthetic resin compound that contains a combination of acrylonitrile, butadiene and styrene. In a manner known to the person skilled in the art, the ABS resin can be made from a graft copolymer, consist of a physical mixture (polyblend) or a combination of both. The usual ABS graft copolymers are polymerized by graft resin-forming monomers, namely styrene and acrylonitrile, on a preformed polybutadiene rubber backbone or a butadiene / styrene mix polymerized rubber framework is produced. By doing The finished graft copolymer is partly made up of the resin portion and the rubber portion (typically 40-70%) chemically combined with one another. The graft copolymer can be made by an emulsion polymerization technique in which a previously prepared Latex of a polybutadiene or similar rubber, which is used as a framework or backbone serves, under appropriate conditions, with a monomeric mixture of styrene and acrylonitrile emulsified therein is emulsion-polymerized. on the other hand the graft copolymer can also by solution polymerization methods or by the so-called mass bead polymerisation technique (wet-bead teohnique) will.

On the other hand, the ABS exists in the form of a physical one Mixture typically of a mixture of a butadiene / acrylonitrile rubber with a separately produced styrene / acrylonitrile resin. In some cases this becomes a Graft polymer existing ABS resin with another, separately produced Styrene / acrylonitrile resins and / or a butadiene / acrylonitrile rubber @mixed. All derwartig @ ABS resins are, according to their invention, suitable for mixing with the thermal pla @ tables Polysulfone resin. In addition @@@@@@@@@@@@@@@ if other monomers, such as alpha - @@@@@@@@@@@@ with acrylonitrile, ethyl acrylate, methyl - @@@@@@@@@@@@@@@@ The same partially or fully step @@@@@@@@@@@@@ des styrene or acrylonitrile.

@@@@@@@@@@@@@@@@@@@ both a rubber component @@@@@@@@@@@@ polybutadiene or a butadiene / styrene - @@@@@@@@@@@@@@@@ st or a butadiene / acrylonitrile - @@@@@@@@@@@@@@@@@@) as well as a hars fraction (styrene / @@@@@@@@@@@@@@@@@@ can thus be called "gummiharsarti - @@ @@@ @@@@@@ @@@@@@@@@@@ @@ @@@@ @@@@@@@@@ @@@@@@ @@@ @ @@@ @@ @ @@@@@@@@ @@ @@@ @@@@ @@@@@@ à @ @@ @@@@ @ @@@ @@@ nitrile, 5 to 65% butadiene and 25 to 85% styrene.

The polysulfone resin content of the mixture according to the invention can be described as a linear, thermoplastic polyarylene polyether-polysulfone in which the arylene units of ether and sulfone bonds are thermoset. These resins can be duroh reaction of an alkali metal double salt of a dihydric phenol and a bensoid compound containing two halogens (dihalobenzenoid compound), one or both of which have a sulfone bond "SO2" - intermediate aryl groups for the incorporation of sulfone units into the polymer chain in addition to arylene and ether units (t ) (en) produce.

The polysulfone polymer has a basic structure that is made up of repeating Units of the formula: -O-E-O-E '- where: E denotes the remainder of the dihydric phenol and E 'the remainder of the benzoid compound with an inert, electron withdrawing one Group, such as a sulfone, carbonyl, vinyl, sulfoxide, azo or saturated hydrocarbon group in at least one of the ortho and para positions to the valence bonds, it being the case that both radicals have aromatic carbon atoms are bound to the ether oxygen atoms by means of a valence bond and at least one of the radicals (E or E 'or both) is a sulfone bond between aromatic carbon atoms has, composed. Such polysulfones belong to the in the Prepared US Patent 9,264,536 class of polyarylene described Polyether resins.

Reference is now made to said US patent specification for a more detailed description and explanation of E and E ', including the preferred forms of E which differ from dinuclear phenols of the following structure: derived, referred to. In the structural formula given, the individual radicals have the meanings given in US Pat. No. 3,264,536. However, it should be taken into account here that E or E ′ are selected from the meanings given for E and or E in the cited patent in such a way that they contain a sulfone bond for incorporation of sulfone units into the finished polymer chain. Thus, if E is selected so that it does not contain a sulfone bond, then Q E 'must be selected from one of the forms which have the sulfone bond.

If E1 is selected so that it does not contain a sulfone bond, then E must be selected from one of the forms having a sulfone bond. Of course, both E and E 'can contain sulfone bonds if desired. Typical preferred polymers consist of recurring units of the formula: as indicated in US Pat. No. 3,264,536, but with the proviso that at least one of the radicals R and 2 'must be -SO2-. In the formula given, Y and Y1 can have the same or different inert substituents, such as alkyl groups with 1 to 4 carbon atoms, halogen atoms (ie fluorine, chlorine, bromine or iodine atoms) or alkoxy rusts with 1 to 4 carbon atoms, and r and z are whole numbers from zero to four egg @ schliesslier bedonson. In @@@@ - R stands for sine Bix @@@ g @@ isch @@@@@@ tischen carbonfto @ @@@@@@@@@@@@@@@@@@@@ @@@@@ - gen connecting @@@@ @@@@@@@@@@@@@@@@@ means means R @@@@@@@@@@@@@@@@@ means means R @@@@@@@@@@@@@@@@@ @@@@@@@@@@@@@@ carbon atoms @@ Noc @@@ enr preferred are the thermoplastic polyarylene polysulfones of the given formula, in which r and z are 0, R is a divalent connecting radical of the formula: where R ″, as indicated in the US Pat.

Typical examples are the reaction products from 2,2-bis- (4-hydroxyphenyl) Propane (supplier for remainder E) with 4,4'-dichlorodiphenyl sulfone (supplier for the radical E ') and equivalent reaction products, for example those from 4,4'-dichlorodiphenylsulfone with the bisphenol of benzophenone (4,4'-dihydroxydiphenyl ketone), or the bisphenol of acetophenone [1,1-bis (4-hydroxyphenyl) ethane], or the bisphenol of vinylcyclohexane [1-ethyl-1- (4-hydroxyphenyl) -3- (4-hydroxyphenylcyclohexane)], or 4,4'-dihydroxydiphenyl sulfone (compare Examples 1, 3, 4, 5 and 7 of US Pat. No. 3,264,536) or alpha, alpha'-bis (4-hydroxyphenyl) -p-diisopropylbenzene (see also submitted at the same time US patent application with the serial number).

Another suitable explanation of those which can be used according to the invention Polysulfone resins can be found in the aforementioned British patent 1 060 546.

As a rule, at least about 10% and preferably at least about 20% of the bonds between the arylene groups are sulfonic groups Apart from the ether and sulfone bonds, the arylene groups can be bonded directly to one another or separated from one another by inert groups, for example alkylidene groups, such as isopropylidene groups.

The last groups appear in the chain when at the Production of the polysulfone Bisphenol A E2,2-bis (4-hydroxyphenyl) propanej is used will.

To produce the mixture according to the invention, the two Starting polymers, namely the ABS material and the thermoplastic polysulfone resin by means of a suitable mixing device, as is usually used for mixing of rubbers or synthetic resins is used, for example by means of a Differential mixing roller or by means of a BaFbury mixer, together into the desired Quantities mixed. To facilitate complete mixing of the polymers and the desired improvement in the combination of physical properties bring about, the Mieoh process takes place at elevated temperatures that are sufficient to soften the polymers so that they are completely dispersed in one another and are mixed in.

The mixing temperature usually changes - only after each used ABS and the special polysulfone.

As a rule, the polysulfone will soften at a higher temperature determine the respective mixing temperature.

Mixing is continued until a smooth mixture is obtained.

A preferred range for the amount of polysulfone resin in the mixture is 40 to 70 parts by weight, while correspondingly 60 to 30 parts by weight of ABS -Material are available. Other preferred ranges are 40 to 80, 40 to 60 and parts by weight of polysulfone with corresponding amounts of ABS - Gum @ ihars. In As a rule, the mixture contains at least 48 parts by weight of the polyaulfone resin. Of the the main preferred range is about 48 to 60 parts.

The resin mixture according to the invention, which when mixing a thermoplastic Polysulfone with ABS synthetic resin is obtained, has a synergistic effect in the Flow area; i.e. the results of rheological studies on the inventive Mixtures surprisingly reveal their ability to actually be better (easier) to flow as either the pure ABS used in the blends or the in pure polysulfone used in the mixtures. This is immensely practical Meaning. The main advantages of such improved flowability are in lower treatment temperatures, shorter operations, complicated capabilities To be able to cast molded parts with less deformation under load (lower molded in stress) in a better surface quality of the molded parts and in a simpler configuration of the casting molds. All of these advantages are based on the fluidity. Each of these benefits may be the main benefit depending on the circumstances mean.

A particularly unexpected feature of the invention is that the improved flow properties in combination with the considerably higher Heat deformation temperature can be obtained. In the range of 40 to 60% polysulfone (mixed with correspondingly 60 to 40% ABS) is the behavior of the heat distortion temperature particularly noteworthy. So takes the heat distortion temperature the mixture slowly increases with increasing percentage of polysulfone until the 4O% have been reached0 Over 40% polysulion, the heat deformation temperature rises with it the percentage increase in polysulfone rapidly. This is surprisingly one area excellent flow properties in the mixture. With a share of 40% one special, commercially available polysulfone is the heat distortion temperature of the Mixture at 59.50 C below that of pure polysulfone.

With a 60% polysulfone content, the difference is only 11.70 C. In other words, a 20 goats increase in concentration of this polysulfone, based on the total weight of the mixture, is the heat distortion temperature of the mixture by 71.6% of the heat distortion temperature differential between the pure polysulfone and pure ABS. rise.

In addition to the unexpected combination of flow properties and heat deformation temperature The inventive mixtures of polysulfone and ABS have other valuable ones Properties. These properties consist of, for example, excellent Impact strength and high flexural strength.

The blends retain most of the desirable properties from polysulfone and also achieve a special synergistic improvement in the impact strength, which is mainly due to the ABS content in the mixture is. The mixtures are cheaper than the pure polysulfone and therefore offer an economical way to provide a desirable one Combination of high bottom toughness, high heat deformation temperature and good flow and treatment properties. If the proportion of polysulfone in the mixture is So% or is more, the mixtures extinguish by themselves, i.e. they retain a combustion not upright.

In addition to the essential polysulfone resin and ABS material, the mixtures according to the invention, optionally other modifying constituents, such as pigments or fillers, a glass reinforcement in flake, powder or fiber form, Stabilizers, processing aids, lubricants, mold release agents or others Common modifiers contain. The mixtures can also contain blowing agents mixed to produce foams. The mixtures based on "ABS graft copolymers" are particularly preferred from the standpoint of impact resistance, though also those based on "ABS polyblends" (in the form of a physical blend) Compared to a plastic such as PVC, blends have considerable impact strength exhibit. While not intending to apply the invention in any special way Establishing labor theory, it seems possible that certain unusual properties of the mixtures according to the invention at least partially the consequence of an unusual, unique morphology in the field of technically usable thermoplastics of the mixes are. Based on an electron microscopic examination of the mixtures it was concluded that the mixtures are basically continuous Polysulfone phase and a continuous ABS - composite phase (composite phase).

In Figure 1 of the drawings is the morphology of a typical ABS shown in which the graft rubber balls (dark pleke) in a continuous SAN - Harphase are dispersed. Figure 2 shows the homogeneous nature of the polysulfone phase. In Figure 3, the mixture according to the invention is shown in cross section, the continuous nABS composite phase "(spotted areas) and the continuous Polysulfone resin phase (gray areas) can be seen. The two continuous phases in the mixture are evident for the high heat distortion temperature and the good flow behavior is responsible. When the mixture is heated, the Polysulfone phase (since it is continuous) soften before the heat distortion temperature is reached. The continuous ABS composite phase takes effect during the flow probably as a lubricant, the morphology being clearly anisotropic.

This unusual morphology is also likely to be responsible for the synergistic To be responsible for impact resistance.

The presence of 2 continuous phases was evident not yet described for other thermoplastic material mixtures.

The following examples are intended to illustrate the invention in more detail.

In this example, the ABS used contained 22.2% acrylonitrile, 26.5% butadiene and 51.3% styrene and was made by mixing 53 parts of a graft copolymer with 47 parts of a separately prepared Styrene / acrylonitrile resin. The graft copolymer consisted of one Graft copolymer of 34 parts of styrene and 16 parts of acrylonitrile per 50 parts Polybutadiene. The styrene / acrylonitrile resin contained 71% styrene and 29% acrylonitrile.

A commercially available polysulfone with recurring units of the structural formula was used as the thermoplastic polysulfone: which was prepared, for example, in the manner described in Example 1 of U.S. Patent 3,264,536.

Mixtures of the ABS and polysulfone in various amounts, such as from Table 1 below, follow by mixing for 2 minutes both materials in a Banbury ° mixer at the temperature of 237.80 to C (460 ° F).

These mixtures were then operated at 190.60.degree Roll pulled out into sheets and then cut into cubes.

In order to determine the flow properties of the mixtures, the Viscosity at a certain speed gradient (apparent viscosity) with a commercially available rheometer, for example with an Instron capillary rheometer, Model TTC, MCR measured. For this purpose, injection molding was done from the test material test rods with a size of 127 by 9.5 mm produced. Everyone The rod was heated to a temperature of 232.20 o in the barrel of the rheometer. A plunger was then pressed down on the upper surface of the heated test stick, the rod for flowing through a capillary 1.52 mm in diameter, the length of which to the diameter measer ratio was 33.

The plunger descended at a constant rate of o, 254 mm per minute. The force that had to be used was measured to extrude the rod through the capillary. The applied plunger speed was so great that apparent shear rates were generated that were roughly correspond to those of a Mooney viscometer, the one with 2 revolutions per minute is operated at a temperature of 232.20 C.

The results compiled in Table I below leave recognize that the ABS / polysulfone blends were more flowable than both the pure ABS used in the mixtures as well as the pure polysulfone for itself alone.

Table I Physical properties of the polysulfone / ABS blends % Polysulfone 0 10 20 30 40 50 60 70 80 90 100% ABS, SAN plug type 100 90 80 70 60 50 40 30 20 10 0 1/4 inch (Izod) impact strength in ft.lb.

per inch notch 7 6.2 6.0 5.7 5.5 4.2 3.9 3.1 2.7 2.2 1.1 heat distortion temperature, 18.5 kg / cm2 (264 psi) ° C 100 102.2 100 102.8 107.2 135.6 155 157.2 162.8 157.8 166.7 ° F 212 216 212 217 225 276 311 315 325 316 332 Flexural Strength kg / cm 537 573 634 682 714 798 879 891 945 - 1069 (psi) 7650 8150 9016 9700 10150 11350 12750 12670 13440 - 15200 Viscosity at a certain speed gradient at 232.2 ° C (450 ° F) in poises x 105 7.6 7.3 7.4 7.2 7.6 6.7 6.9 8.2 17.0 15.2 25.6 fortunes, of to extinguish yourself no no no no no yes yes yes yes yes yes Tabel I also shows that the mixtures according to the invention have high impact strength and have good flexural strength. The "Capability" contained in Table I, by itself extinguishing was determined by the test method ASTM D635-63.

In the graph of Figure 4 of the drawings Heat distortion temperature (measured according to ASTM test method D648-56 from 1961) plotted as a function of increasing polysulfone resin content in the mixture. FIG. 6 shows the change in viscosity at a certain speed gradient with the polysulfone resin content (for this example and Examples 2 and 3).

Example 2 In Table II are the physical properties composed of an ABS / polysulfone mixture which, using an ABS - Poly mix (physikallsoho mix) was made. The ABS was made by mixing of 67% styrene / acrylonitrile resin with 33% butadiene / acrylonitrile rubber. The individual monomers in ABS can be put together as follows: Styrene: 49 % Butadiene: 19% Acrylonitrile: 32% The polysulfone used in this example and the appropriate method used to prepare the mixture Polysulfone or the procedure of Example 1. The pleat properties were in the same Way as determined in Example 1.

Table II Physical properties of the polysulfone / ABS blends % Polysulfone 0 10 30 40 50 60 70 90 100% ABS (SAN-Nitril- 100 90 70 60 50 40 30 10 10 rubber type) heat distortion temperature at a pressure of 18.5 kg / cm2 ° C 92.8 93.3 95.6 98.9 106.1 133.9 155 165.6 166.7 ° F 199 200 204 210 223 273 311 330 332 Flexural Strength kg / cm 432 486 587 648 715 837 864 1053 1069 (psi) 6140 6912 8356 9216 10176 11904 12288 15000 15200 Viscosity at a certain speed gradient at 232.22 ° C (450 ° F) in poises x 105 9.75 9.30 8.84 8.85 8.89 8.85 10.5 16.1 25.6 The It can be seen from the values in Table II that the viscosity at a certain speed gradient of the mixtures at a content roughly equivalent to or below pure ABS remains relatively constant until a content of 90% polysulfone is reached and that even with a 90% polysulfone content it is still far below the corresponding one Viscosity of pure polysulfone is (Figure 6).

It can also be seen from the table that the heat distortion temperature of the mixtures increases with increasing polysulfone resin content, although this slope increases is not as significant as in Example 1.

The flexural strength also increases with increasing polysulfone content.

Example 3 In this example the ABS portion of the mixture a modified ABS type, in which the styrene in the separately manufactured Styrene / acrylonitrile resin component of ABS, as in the USA patents already mentioned 3,311,501 and 3,198,853 is replaced by alpha-methylstyrene. That ABS used contained 22.58% acrylonitrile, 23.85% butadiene and 53.57% monomers of styrene type (20.67% styrene itself and 32.9% alpha-methylstyrene) and has been through Vernisohen of 53 parts of a graft copolymer with 47 parts of a separately made from alpha-methylstyrene / aorylnitrile harses. The graft copolymer consisted of a copolymer of 34 parts of styrene and 16 parts of acrylonitrile on 50 parts of a butadiene / styrene - Copolymer, which Contained 90% butadiene and lo% styrene. The resin copolymer contained 70% alpha-methylstyrene and 30% acrylonitrile. The thermoplastic polysulfone used corresponded to that of Example 1. Mixtures of ABS and polysulfone resin, in different proportions, were made by mechanically mixing the two materials in one for 3 minutes Banbury mixer manufactured at a temperature of 237.80 0. These mixes were then applied to a roller operated at a temperature of 176.7 ° C Plates pulled out and then cut into cubes. From the various Mixtures were made by spraying using a conventional screw machine Test specimens produced. The physical properties of the mixtures were after ASTM test method determined. The physical properties of the individual recipes are compiled in Table III. The most striking result is the salient one synergistic improvement in impact strength achieved when the ABS content in the mixture is between 70 and 30%.

This can also be seen from the graphical representation of Pigur 5. Furthermore, there is a steep rise in the heat distortion temperature of the mixtures when 50% or more polysulfone is used. The same synergistic Flow properties, as explained in the previous examples, also occur in the mixtures of this example (FIG. 6). Tensile and flexural strength of the mixtures decrease linearly with increasing percentage of polysulfone resin to. The 60 to 30% ABS blends are for both economic reasons and particularly attractive in terms of their properties.

Table III polysulfone / ABS mixture% ABS 100 90 80 70 60 50 40 30 20 10 0% polysulfone 0 10 20 30 40 50 60 70 80 90 100 Rockwell hardness 98 100 104 108 112 114 118 120 123 126 120 # Heat distortion temperature at a pressure of 18.5 kg / cm2 in ° F 216 205 219 230 238 285 300 304 313 313 332 ° C 102.2 96.1 103.9 110.0 114.4 140.6 148.9 151.1 156.1 156.1 166.7 Izod impact strength (ft.lbs / in.) (Notch = 1/4 ") b. 5.3 3.3 4.2 10.5 13.4 13.4 11.2 8.2 3.3 2.1 - (notch = 1/8") RT * 6.7 6.5 9.6 12.1 11.5 10.4 10.6 9.5 8.1 1.9 1.3 (notch = 1/4 ") b.3.4 1.3 1 , 2 1.8 2.2 2.9 3.5 2.3 1.1 1.1 - (notch = 1/8 ") - 28.9 2.7 2.2 3.1 3.6 2.8 2.6 3 , 2 3.6 2.7 1.3 1.2 ° C Tensile strength in psi 5391 5740 6200 6704 7221 7657 8206 8756 @ 9470 10.360 10.200 kg / cm2 379.4 403.8 436.0 471.3 507.5 538.0 576.4 615.9 665.9 728.2 717.0 Flexural strength in psi 6912 7680 8448 8832 9600 10.752 11.520 12.864 13.632 14.592 15.400 kg / cm2 485.8 539.6 593.4 621.2 675.0 755.7 809.4 904.5 958.2 1025.5 1083.0 Tensile modulus in psi x 105 2.6 2.6 2.8 2.9 2.9 3.1 3.2 3.2 3.4 3.7 3.6 kg / cm2x105 0.182 0.182 0.196 0.203 0.203 0.217 0.224 0.224 0.238 0.259 0.252 Flexural modulus in psi x 105 2.5 2.5 2.5 2.5 2.9 2.9 3.3 3.3 3.3 3.3 3.9 kg / cm2x105 0.175 0.175 0.175 0.175 0.203 0.203 0.231 0.231 0.231 0.231 0.237 Viscosity at a certain speed gradient at 232.2 ° C in poise x 105 11.2 9.67 25.6 * RT = room temperature Example 4 In this example the ABS used was the same as in Example 3.

The thermoplastic polysulfone resin used consisted of repeating units of the following structural formula: (See US patent application Serial Number.This polysulfone resin could be prepared as follows: In a 1 liter stainless steel resin vessel, which was equipped with an ice bath, a mechanical stirrer, a gas inlet tube, a Dean-Stark condenser and an addition port , 26 g (0.075 mol) of alpha, alpha'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, -in 100 g of sulfolane and 100 ml of benzene were introduced at room temperature, and the reaction mass was flushed with nitrogen for 30 minutes before 20 g (0.15 mol) of a 42.3% aqueous potassium hydroxide solution were added In order to transfer the potassium hydroxide solution completely into the reaction vessel, a further lo ml of distilled water were used.

The bath temperature was increased to 1300 C and with the azeotropic Removal of water started. The removal of the water took about ten hours.

Before complete removal of the water was achieved the bath temperature increased to 1800 o. The benzene was then distilled off and the remaining anhydrous solution of the dipotassium salt of alpha, alpha'-bis (4-hydroxyphenyl) -p-diisopylbenzene cooled to 70 ° C. in sulfolane. This was followed by the anhydrous solution of the dipotassium salt 215 g of 4,4'-dichlorodiphenyl sulfone (0.075 mol) dissolved in 50 ml of benzene were added. The temperature of the reaction mixture was increased to 2000 C, with increasing Temperature the benzene distilled off.

The polymerization was carried out for 5 hours at a temperature of 2000 C.

The viscous polymer solution obtained was cooled, from which the Polymer was precipitated in methanol.

The polymer was placed in water and in a mixer Finely divided by means of high-speed cutting knives. The finely divided polymer was completely washed with water to remove all of the alkali metal salt. The polysulfone polymer was initially for 14 hours at a temperature of 800 C in the oven and then for 12 hours at a temperature of 120 ° O in a vacuum dried. The glass transition temperature as determined by differential scanning calorimetry (differential scanning calorimetry) was 168.330 C. The reduced viscosity (reduced viscosity) of a 0.45 joint chloroform solution at a temperature of 300 o was o.46. The isolated polymer corresponded to 98% the theory. A chemical analysis showed 5.8% hydrogen, 6.4% sulfur and 75.5% carbon (theoretical 5.7% hydrogen, 5.7% sulfur and 77.1% carbon). The polysulfone possessed an Izod impact strength (3.175 m notch) of 0.85 footpounds a temperature of 22,780 C (730 P); (R) a Rockwell hardness of 124 and its heat distortion temperature of 151.11 ° C at a pressure of 18.5 kg / cm2.

Mixtures of ABS and that produced in the manner described Polyarylsulfonharazes, in various proportions, such as the one from the following table IV appears to have been made by mixing the two materials in a Banbury- Mixer prepared at a temperature of 221.110 C (4300 F )0 The individual mixtures were closed in a roller operated at a temperature of 176.7 ° a (3500 F) Plates pulled out and then cut into cubes. From the diced Material were injected into test specimens in a conventional screw machine. The physical Properties, determined by ASTM test method, of the 50/50 blend are im Comparison with ABS itself is given in Table IV below.

Also in Table IV are the heat distortion temperatures indicated for the individual mixtures. A graph of the heat distortion temperature (Figure 7) shows the sharp increase in heat distortion temperature. The Mooney Results in Table IV show an unexpected, non-linear increase in Melt viscosity. The mixtures of this example based on a polyarylsulfone based, which is from alpha, alpha'-bis (4-hydroxyphenyl) -p-diisopropylbenazole and 4,4'-Dlchlorodiphenylsulfone are characterized by that the clear drop in the Mooney values of the respective mixture in comparison to a 100% polyarylsulfone resin only from a small waste in the Heat distortion temperature is accompanied.

This lower Mooney number is in view of greater versatility important for injection molding applications. The value for the notched impact strength (at a 3.175mm notch) 3.7 footpounds of Izod easily within the range of products dedicated to the manufacture of injection molded parts suitable. Another proof of the improved flowability of the polyarylsulfone resin mixture based on this example in comparison to the mixture of example 3, (at using the polyarylsulfone resin described in Example 1) aich from the lower produced during Brabender mixing (see Table V) Torque (melt viscosity). The values contained in Table V were in a as Brabender Plasticord designated mixing device determined. This mixing device has a small mixing cavity with two rotating miso leaves whose speed changeable. The mixing cavity has a jacket through which heated oil can be circulated. The polymer mixture to be examined is introduced into the cavity; the rotating blades show a torque, which can be measured and depends on the viscosity of the polymer. The one in table Results contained V were with 60 g samples at an oil bath temperature of 2200 C. In the table, the term 11 melting temperature "means the temperature the polymer blend in the mixing cavity.

At times this temperature is higher than the oil bath temperature heat is generated during the mixing process. Table IV Example IV Polyarylsulfone / ABS Blend % ABS 100 70 60 50 40 30 0% polyarylsulfone 0 30 40 50 60 70 100 (Example IV) Rockwell hardness 98 117 124 Heat distortion temperature at a pressure of 18.5 kg / cm2 in ° F 216 208 220 275 292 303 305 ° C 102.2 97.8 104.4 135.0 144.4 150.6 151.7 Notched impact strength according to Izod (ft.lbs / in) (notch = 1/4 ') b.room temp. (RT) 5.3 1.5 - (notch = 1/8 ")" " 6.7 3.7 0.85 (notch = 1/4 ") b. -28.9 ° C 2.4 0.75 - (notch = 1/8") b. -28.9 ° C 2.7 1.1 Tensile strength in psi 5.391 7.152 kg / cm2 379.37 502.64 Flexural strength in psi 6.912 10.368 kg / cm2 485.84 728.25 tensile strength in psi x 105 2.6 3.0 kg / cm2 x 105 0.182 0.210 -flexural strength in psi x 105 2.5 2.9 -kg / cm2 x 105 0.175 0.203 -Mooney number at 232.2 ° C 44 35 68 Table V Brabender Melt Viscosity Values Rpm temperature of the torque in the melt in ° C g / m 50/50 mixture as in example III 50 210 3900 60 220 3250 70 227 2150 80 253 175o 90 236 1400 100 240 1300 50/50 Mixture as in Example IV 50 210 2400 60 215 1900 70 222 1500 80 225 1300 90 230 950 loo 233 700 It can be seen from the previous statements that the inventive mixtures of polysulfones and ABS in numerous fields of application, on which 'a high temperature resistant, self-extinguishing and impact resistant Plastic is needed can be used. The possible uses in the manufacture of housings and in automotive engineering are numerous. The material is suitable for common manufacturing processes, especially for injection molding, although other methods such as extrusion and blow molding have also been used can be.

The mixtures according to the invention are suitable for the production of Driver's cabs for trucks and (camping) caravans or trailer bodies and the like and may, if desired, be in the form of a laminate, inclusive a foamed layer of the material according to the invention can be used.

In the parts produced from the mixtures according to the invention the impact strength depends less on the thickness of the parts than it does for certain parts earlier materials is the rebound.

- patent claims -

Claims (9)

Claims 1. Synthetic, thermoplastic resin composition from a mixture of a linear, thermoplastic polyarylene polyether polysulfone resin and an acrylonitrile / butadiene / styrene rubber synthetic resin according to the patent (German patent application P 17 94 171.8-43), characterized in that the synthetic rubber resin also contains an alpha; Contains methyl styrene / acrylonitrile resin or that the polysulfone resin consists of recurring units of the formula consists. 2. Wet according to claim 1, characterized in that it A) to 10 up to 90 parts by weight of the linear, thermoplastic polyarylene polyether poly sulfone resin and B) 90 to 10 parts by weight of an acrylonitrile / butadiene / styrene polymer, based on 100 parts by weight of A + B. 3. Wet according to one of Claims 1 and 2, characterized in that that at least 10 of the ties between the arylene groups in A consist of sulfonic groups. 4. Mass according to one of claims 1 to 3, characterized in that that component A has alkylidene bonds between arylene groups. 5. i ¢ Iasse according to one of claims 1 to 4, characterized in that that component B, apart from the α-methylstyrene / acrylonitrile resin additive, from a graft copolymer of Styrpl and acrylonitrile on a rubber framework, consisting of polybutadiene or a butadiene / styrene copolymer is. 6. Cup according to one or more of claims 1 to 5, characterized in that that component A 40 to 70 parts and component 1 corresponding to 60 to 30 parts. 7. Composition according to one or more of claims 1 to 5, characterized in that that component A 40 to 60 and component 1 correspondingly 60 to 40 parts matters. 8. Composition according to one or more of claims 1 to 5, characterized in that that component A is at least 48 parts and component B is at least 52 parts or less. 9. Composition according to one or more of claims 1 to 5, characterized in that that component A is about 48 to 60 parts and component B is about accordingly 52 to 40 parts. L e r s e i t e