DE2154445A1 - Impact-resistant, thermoplastic resin compositions with good flow properties and high heat distortion temperatures - Google Patents

Description

OJL? .. ν "yT'.risa.

DIPL-L. .-.: .-.!. i.iüLLSIl

8 MUNICH 80 2154445

iucile-Giahn-Strasse 38

Uniroyal, Inc., 1230 Avenue of the Americas, New York , New York 10020 (V. St. A.)

Impact-resistant, thermoplastic resin compositions with good flow properties and high heat distortion temperatures

The present invention is based on the discovery that mixtures of generally immiscible ABS, Polysulfone and polycarbonate resins unexpectedly high impact strength values with unusual and extraordinary Have flow properties and in addition a remarkable retention of high heat distortion temperatures exhibit.

FIG. 1 shows, in the form of a graph, the changes in the heat distortion temperatures as a function of Content of ABS resins in the mixture again; and

FIG. 2 shows the change in the ratio as a curve from heat distortion temperature to viscosity as a function of the content of ABS resins in the mixture represent.

209819/1109

The ABS resin

The term "ABS resin" is used here in its conventional sense and is intended to designate the known thermoplastic polymer compositions which contain a combination of acrylonitrile, butadiene and styrene and also as "ABS rubber plastics" (gum plastics) or "ABS graft copolymers "are referred to, for example, in U.S. Patent 2,439, issued April 6, 1948 by LE DaIy, in U.S. Patent 2,600,024, issued June 10, 1952 by H. Romeyn Jr. and employee ψ tern in which issued on January 21, 1958 US Patent No. 2,820,773 by CW Childers in which issued on November 18, 1963 US Patent No. 3 St. 501 MS Thompson, in · August I965 issued on 3 USA patent 3 19Ö 853 by RL Bergen jun. and in the on I9. U.S. Patent 3,261,887 to JU Mann, issued July 1966. As is known to those skilled in the art, the ABS plastic can be of the graft copolymers type or of the physical mixture type (polyblends), or it can consist of a combination of both types. The conventional ABS graft copolymers are produced by graft copolymerizing resin-forming monomers, such as styrene and acrylonitrile, on a previously prepared polybutadiene rubber backbone or a butadiene / styrene copolymer rubber backbone; In the finished graft copolymer, the resin-like component and the rubber-like component are then partly in a chemical combination. In practice, the so-called graft copolymer contains some non-grafted resin, ie not all of the resin-forming monomers are grafted onto the rubber-like backbone polymer in the course of the graft polymerization process

209819/1 109

been. The graft copolymer can be produced by emulsion polymerization have been obtained at v / elcher a previously prepared latex of polybutadiene or a analogous rubber, which serves as the backbone, emulsion polymerization conditions with a monomer mixture of styrene and acrylonitrile emulsified therein ivird. The graft copolymer can deviate from this also produced with the help of solution polymerization methods or according to the so-called block suspension technique will. On the other hand, the physical mixture type ABS resin is typically composed of a mixture of a butadiene / acrylonitrile rubber with a separately produced styrene / acrylonitrile resin. Often the ABS material of the graft polymer type additionally contains separately produced styrene / acrylonitrile resin in a mixture with the graft copolymer. Any type of these resins are for blending with the thermoplastic polysulfone resin according to the teaching of suitable for the present invention. In addition, another monomer of the styrene type can be used, if desired (e.g. £ X-methylstyrene) instead of the total amount of styrene itself or a part thereof can be used, and other acrylic monomers (e.g. methacrylonitrile, Ethyl acrylate, methyl methacrylate) instead of the total amount of the monomer of the acrylonitrile type or part of this acrylonitrile are used.

Because the ABS material has both a rubber-like component (e.g. polybutadiene or butadiene / styrene backbone or a butadiene / acrylonitrile copolymer component) and also a resinous component (Styrene / acrylonitrile) so it can be used as a material of type

ir 09819/1109 BATH ORIGINAL

a "rubber plastic". Usually, the content of the rubber component in the ABS material is 5 to 35 % , while the content of the resin is accordingly 95 to 65 % . The total proportion of the monomers of the acrylonitrile, butadiene and styrene type is within the range of amounts: 10 to 40 % acrylonitrile; 5 to 65 % butadiene and 25 to 85 % styrene.

U.S. Patent 3,111,501 to Thompson, referenced above as an example of ABS resins of the type used in the present invention, is directed to the type of ABS materials obtained by blending (X-methylstyrene / acrylonitrile resin with a Graft copolymer of styrene and acrylonitrile on polybutadiene is produced. For example, those compositions can be used in the present invention which are obtained by mixing an δ ( -methylstyrene / acrylonitrile resin (69:31) (US patent by Thompson, column 2 Lines 34-35) with a graft copolymer of styrene / acrylonitrile (ratio 70:30) monomers on a polybutadiene latex (46 % styrene / acrylonitrile and 54 % rubber solids) have been obtained (see the US patent by Thompson, column 3, lines 32 to 37). In the US patent by Thompson it is also described on column 1, lines 68 to 70 that some or all of the styrene in the graft copolymer is replaced by O ( - Methyl styrene can be replaced. Similarly, in U.S. Patent 3,261,887 to Mann, at column 5 * lines 48 and 49; Column 10, tables 6 and 7; and column 11, lines 50, 51, 54 and 55, the use of OC -methylstyrene as a co-monomer for

2 09813/1109 BAD ORIGINAL

the butadiene mentioned for the purpose of producing the CK methyl styrene / butadiene mixed polymer backbone for the grafting process, while in US Patent 3 IJO 177, column 4 lines IJ to 15, the partial or complete replacement of styrene by (X-methylstyrene in the Similarly, in the above-mentioned US Pat. No. 3,198,853 to RL Bergen, Jr. ABS materials are disclosed which are a graft copolymer of styrene and acrylonitrile on polybutadiene in a mixture with a separately prepared resinous copolymer of In the USA patent from Bergen, Jr., on column 2, line 39 to, the mixing of the graft copolymer with a separately prepared resinous copolymer of styrene or α- methylstyrene and acrylonitrile is described United States patent by Bergen, Jr. further discloses at column 4, lines 6 to 12, a mixture of 35 parts of a Pf Ropf copolymer of 50 parts of styrene and acrylonitrile (ratio 70:30) to 50 parts of polybutadiene rubber with 65 parts of a separately prepared resinous copolymer of (X-methylstyrene with acrylonitrile (ratio 69:31) described. All such types of ABS materials can be used in the present invention.

The polysulfone resin

The polysulfone resin component of the blend can be used as a linear, thermoplastic polyarylene-polyether-polysulfone are described in which the arylene units are connected to each other by ether and sulfone bridges. Regarding the description of such resins

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can be referred to that issued on August 7, 1966 U.S. Patent 3,264,536 to H.B. Robinson and co-workers, dating back to 1967 British Patent 1,060 5 ^ 6 from Minnesota Mining Manufacturing Co. and on August 4, 1969 filed U.S. Patent Application Serial No. 847,427 by R.J. Cornell. These resins can be obtained by Reaction of an alkali double salt of a dihydric phenol with a dihalobenzoid compound, wherein either one of these partners or both partners have a sulfone bridge member -SOp- between arylene groups contain sulfone units in addition to the arylene units and ether units in the polymer chain to deliver. The polysulfone polymer has a basic structure, the repeating units of the formula

-OEQE ¹ -

wherein E is the remainder of the dihydric phenol and E ^{f is} the remainder of the benzenoid compound which contains an inert electron withdrawing group in at least one of the ortho and para positions to the valence bonds; Both of these radicals are linked to the ether oxygen atoms via valence bonds through aromatic carbon atoms; at least one of the radicals mentioned (E or E ¹ or both radicals) has a sulfone bridge member between aromatic carbon atoms. Such polysulfones belong to the class of polyarylene polyether resins described in U.S. Patent 3,264,536, cited above, and the contents of which are incorporated by reference into this description of the invention in order to further ^{define the radicals E and E 1} and by suitable representatives as an example

209819/1109

explain, and this includes the preferred forms of the radicals E, those from binuclear phenols originate which of the structural formula

HO

(Ar

Ar)

OH

correspond, as it is defined therein, with the further restriction that either E or E ¹ must be selected from the radicals listed in the cited patent specification so that they contain at least one sulfone bridge member so that the sulfone in the finished polymer chain Units to be delivered. If, therefore, a radical E is selected which does not contain a sulfone bridge member, the radical E ¹ must be selected from one of the forms which contain sulfone bridge members; and if the selection of the radical E * is made so that it does not contain a sulfone bridge member, then the radical E must be selected from one of the forms which have a sulfone bridge member. Of course, both radicals E and E ^{1 can,} if desired, contain sulfone bridging members. The preferred polymers in question are typically composed of units of the formula

which are repetitive units and are described in U.S. Patent to Robinson et al., In particular on column 4, line 69 to column 5, line 3, where it is mentioned

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BATH ORIGINAL

21 5AA45

that R can be a link which consists either of a bond between aromatic carbon atoms or of a divalent connecting radical, and that R ^! a connecting member, for example a sulfon, carbonyl, vinyl, sulfoxide, azo, saturated fluorocarbon, organic phosphine oxide or ethylidene group, while Y and Y ^ can have the same or different meanings and each of these Symbols represents an inert substituent group, for example a halogen atom (fluorine, chlorine, bromine or iodine), an alkyl group with 1 to 4 carbon atoms or a
Alkoxy group with 1 to 4 carbon atoms, and that
r and ζ denote integers from 0 to 4 inclusive, with the further proviso that at least one of the radicals R and R ^{1 stands} for the -SOg group. Typically, R represents a bond between aromatic carbon atoms or a divalent linking radical and R ¹ represents a sulfonic group. Preferably, R represents a bond between aromatic carbon atoms. Even more recommendable are the thermoplastic polyarylene-polysulfones of those indicated above
Formula in which r and ζ are zero, R one
divalent connecting radical of the formula

R "

R "

represents, in the R "according to the definition given in the United States patent by Robinson et al an alkyl group, a low molecular weight aryl group or halogen-substituted derivatives of these groups

09813/1109

and R ^{1 stands} for a sulfonic group.

Typical examples are the reaction products of 2,2-bis- (4-hydroxyphenyl) propane (= source of the radical E) and 4,4 ^f -dichlorodiphenylsulfone (= source of the radical E ¹ ) and equivalent reaction products, for example those from 4,4 ^f -dichlorodiphenyl sulfone and the bisphenol of benzophenone (4,4 ^t -dihydroxydiphenyl ketone) or the bisphenol of acetophenone / fi-phenyl-i, 1-bis- (4-hydroxyphenyl) -ethane_J7 'or the bisphenol of vinyl eyelohexens / Γ'λ- Ethyl -1 - (4-hydroxyphenyl) -j5- (4-hydroxyphenylcyclohexene __ / or 4,4 ^! -Dihydroxydiphenylsulfone (cf. Examples 1, 3, 4, 5 in the US patent by Robinson and co-workers) and 7) or et, < ^f -Bis- (4-hydroxyphenyl) -p-diisopropylbenzene (see co-pending U.S. Patent Application Serial No. 847 to RJ Cornell, referenced above) Another useful description of polysulfone resins that uses can be found in British Patent Specification 1 060 5 ^ 6 referred to above. Typically, at least e about 10 % and preferably at least about 20 % of the bridging members between the arylene groups are sulfonic groups

In addition to ether and sulfone bridges, the Arylene groups can also be bonded directly to one another or they can be separated by inert groups, e.g. by Alkylidene groups such as isopropylidene groups, the latter occur in the chain when bisphenol A / ~ 2,2-bis- (4-

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hydroxyphenyl) propane_J7 in the production of polysulfone is used.

The polycarbonate resin

The polycarbonate resin used in the present invention is also a known material and described, for example, in British Patent issued April 17, 1957 7/2627 of the Borg Warner Corporation, dated April 3, 1962 issued U.S. Patent 3,028,865 to Schnell and Associates, Grabowski U.S. Patent 3,130,177, cited above, and that issued March 4, 19o9 U.S. Patent 3,431,224 to Goldbaum. she can be briefly described as organic carbonate polymer, which is produced by reacting a dihydric phenol, in particular a dihydroxy-diaryl compound with mononuclear aryl radicals, including di- (monohydroxyphenyl) -substituted aliphatic hydrocarbons, for example a bis (4-hydroxyphenyl) alkane, with a Carbonate precursors, such as phosgene, a halogen formate or a carbonic acid ester, can be produced.

Generally speaking, such carbonate may polymerisation W sate type moderately be characterized in that they contain recurring structural units of the formula

have, in which A is a divalent aromatic radical of the dihydric phenol, which in the polymer! sat-generating Reaction is used means. The polycarbonates that are used to produce the resinous mixture according to the invention

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Applications are preferred, have an intrinsic viscosity - measured in p-dioxane in deciliters per gram at JO ⁰ C - of about 0.35 to about 0.75. The dihydric phenols which can be used to obtain such aromatic carbonate polymers are mononuclear or polynuclear aromatic compounds which contain 2 hydroxyl radicals as functional groups, each of which is bonded directly to a carbon atom of an aromatic nucleus. Typical dihydric phenols are 2,2-bis (4-hydroxyphenyl) propane hydroquinone;
Resorcinol;

2,2-bis (4-hydroxyphenyl) pentane; 2,4 * -dihydroxydiphenylmethane; Bi s- (2-hydroxyphenyl) methane; Bis (4-hydroxyphenyl) methane; Bis (4-hydroxy-5-nitrophenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 3,3-bis (4-hydroxyphenyl) pentane; 2,2 * -dihydroxydiphenyl; 2,6-dihydroxynaphthalene; Bis (4-hydroxyphenyl) sulfone; 2,4 ^f -dihydroxydiphenyl sulfone; 5'-chloro-2,4 ¹ -dihydroxydiphenylsulfone; Bis (4-hydroxyphenyl) diphenyl disulfone; 4,4 * -dihydroxydiphenyl ether; 4,4 ¹ -dihydroxy-3,3 ^f -dichlorodiphenyl ether and 4,4 ¹ -dihydroxy-2,5-diethoxydiphenylether. A large number of other dihydric phenols that can be used to obtain such polycarbonates

981371109

are in United States patent issued September 12, 1961 2 999 835. It is natural also possible two or more different dihydric phenols or a dihydric phenol in combination with a glycol, a hydroxyl-terminated polyester or a dibasic acid in the Cases to be used in which a carbonate copolymer and not a homopolymer to produce the inventive Mixtures should be used.

If a carbonic acid ester is used as the carbonate precursor in the polymer-forming reaction, then the materials at temperatures of 100 ° C or above within reaction times that are between 1 hour and 15 hours, implemented. Under these conditions transesterification occurs between the carbonic acid ester and the dihydric phenol used. The transesterification is preferably on the order of about 10 to about 100 mm of mercury and under reduced pressure preferably carried out in an inert atmosphere such as nitrogen or argon.

Although the polymer-forming reaction can be carried out in the absence of a catalyst, customary transesterification catalysts, for example metallic lithium, potassium, calcium or magnesium, can also be used if desired. Further catalysts and modifications of the transesterification methods are described in Groggins' work "Unit Processes in Organic Synthesis" (4th edition, McGraw-Hill Book Company, 1952) on pages 616 to 620. If a catalyst is also used, its amount is usually only small, for example about 0.001 to about 0.1 %, based on the moles of the dihydric phenol used,

209R19 / 110 9

The carbonic acid ester useful in this regard can be aliphatic or aromatic in nature, albeit aromatic esters, e.g., diphenyl carbonate, especially are recommended. More examples of usable Carbonic acid esters are dimethyl carbonate, diethyl carbonate, phenyl methyl carbonate, phenyl tolyl carbonate and di (tolyl) carbonate.

A preferred method of making the carbonate polymers consists in the use of a carbonyl halide, such as phosgene, as a carbonate precursor. These The working method is that you pass gaseous phosgene into a reaction mixture, which the bivalent Phenol and an acid acceptor such as a tertiary amine (e.g. pyridine, dimethylaniline, quinoline, and the like). The acid acceptor can be used undiluted or with inert organic solvents such as methylene chloride, Chlorobenzene or 1,2-dichloroethane, diluted for use reach. Tertiary amines are recommended because they are both good solvents and acid acceptors in the reaction represent.

The temperature at which the reaction with the carbonyl halide going on can be between <0 ° C and 100 ° C or above. The implementation runs with technical Satisfactory rate at temperatures between room temperature (25 ° C) and 50 ° C since the reaction is exothermic takes place, the rate of addition of the phosgene can be used to regulate the reaction temperature. The amount of phosgene required will generally depend on the amount of dihydric phenol present. Generally spoken, one mole of phosgene reacts with one mole

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of the dihydric phenol used to form the polymer and 2 moles of HCl is also used. The 2 moles of HCl in turn are absorbed by the acid acceptor that is present bound. What has been said above relates to stoichiometric or theoretical amounts.

Another method for the production of carbonate polymers consists in the addition of phosgene to an alkaline aqueous suspension of the divalent one used Phenol. This is preferably done in the presence of inert solvents such as methylene chloride, 1,2-dichloroethane, etc. Quaternary ammonium compounds can be used use to catalytically accelerate the conversion.

A fourth method for the production of such carbonate polymers consists in the phosgenation of a stirred suspension of the anhydrous alkali salts of the used dihydric phenol in a non-aqueous medium such as benzene, chlorobenzene or toluene. This implementation is illustrated by the addition of phosgene to a slurry of the sodium salt of 2,2-bis (4-hydroxyphenyl) propane in an inert Polymerisat ™ solvent such as chlorobenzene. The organic solvent should preferably be a polymer dissolver, but does not necessarily need a good solvent for the reactants to be.

Generally speaking, a haloformate such as Bis-haloformate of 2,2-bis (4-hydroxyphenyl) propane, can be used in place of phosgene as the carbonate precursor in any of the methods described above.

209819/1109

In each of the solution-making methods described above the carbonate polymer leaves the reaction either as a real solution or as a pseudo-solution whether an aqueous base or pyridine is used as the acid acceptor. The polymer can precipitated from the solution by adding a nonsolvent for the polymer, such as heptane or isopropanol will. Notwithstanding this, the polymer solution can also be heated in order to add the solvent evaporate.

The mixes

In most cases, the amounts of the ABS material, the polysulfone and the polycarbonate in the blends of the invention are in the range of 10 to 75 % ABS material, 10 to 65 % polysulfone and 10 to 65 % polycarbonate, based on the combined weight of the three resins. The sum of the polysulfone resin content and the polycarbonate resin content is usually 25 to 90 %, the weight ratio of polysulfone to polycarbonate is normally in the range from 10:80 to 80 t 10. The mixtures according to the invention usually have the technically more favorable ones characteristic properties show amounts of 25 to 65 % ABS material, 10 to 45 % polysulfone and 10 to 50 % polycarbonate, the sum of polysulfone plus polycarbonate being 35 to 75 % and the ratio of polysulfone to polycarbonate between 3J5: 67 and 60:40 lies. Even more recommended quantity ranges, which can be selected to accentuate a given property or a combination of properties, can be taken from the numerical values below.

2 0 9819/1109

If desired, more than one ABS material can be used as a polysulfone or more than one polycarbonate resin come into use.

To produce the mixtures according to the invention, the three generally immiscible starting polymers, namely the ABS material, the thermoplastic polyarylene-polysulfone resin and the polycarbonate resin, with or without the addition of other suitable ingredients, are mixed with the aid of any suitable mixing device, such as ψ they are usually used for mixing rubbers or plastics, e.g. differential mixing mills or internal mixers, mixed together. In order to facilitate thorough mixing of the polymers and to achieve the desired improved combination of physical properties, the mixing is carried out at elevated temperatures which are high enough to soften the polymers so that they are thoroughly dispersed and undergo intimate mixing. Mix temperatures will generally vary depending on the particular ABS material, polysulfone, and polycarbonate being used; usually the polysulfone, which is the higher temperature softening material, determines the mixture temperature to be selected. The mixing is carried out until a uniform mixture is obtained. The order of adding the ingredients can be appropriately varied as desired. According to one embodiment for producing the mixtures according to the invention, all ingredients are initially poured into a mixer - for example a Banbury mixer,

.? (19 8 19/1 1 O 9.

2154U5

intensively mixed and then rolled out on a roller mill into a skin and into a suitable one Form, appropriately, e.g. for cutting into cubes, transferred. According to a different way of working two of the resins are first mixed together until flowability is achieved, and then is then the third resin was added and the whole thing mixed further ..

In addition to the essential components of polycarbonate resin, Polysulfone resin and ABS material can be those of the present invention Mixtures, if desired, further modifying Contain ingredients such as pigments or fillers, glass reinforcing agents in the form of flakes, Powders or fibers, stabilizers, processing aids, lubricants, mold release agents or other conventional modifying ingredients. The mixtures can also be combined with propellants, to obtain foamed materials ..

The ternary resin mixture of the present invention obtained when the thermoplastic polysulfone and Polycarbonate is made with the ABS plastic a synergistic effect in the area of flow, i.e. the results of the rheological investigations of the Materials according to the invention surprisingly prove that Ability of the ternary mixtures of the present invention, actually better (i.e., lighter) than either of the individual resins or the binary combinations of any two of them Resins to flow. This is of enormous practical importance. Among the main advantages of improved flow include the lower processing temperatures that this makes possible, shorter cycles, the ability to shape complex parts., a lower one, from deforming

BATH ORIGINAL

21544Λ5

Introduced stress: a better molded part surface finish and simpler form constructions »All of these technical advantages are the improved flow attributable and depend on circumstances / on which each could be the main benefit.

A particularly unexpected result of the present Invention consists in the fact that the improved flow properties in combination with remarkable high heat distortion temperatures occur.

About the unexpected combination of improved flow properties and high heat distortion temperatures embody the mixtures according to the invention Polycarbonate, polysulfone and ABS material are also an outright one dramatic synergistic improvement in impact strength. The mixtures open up an economic one Way of gaining a desired combination of high impact strength, high heat deformation temperature with superior flow and processing properties.

In Tables I, V and VI are certain properties of polycarbonate resins, polysulfone resins and ABS resins put together "on their own and in binary combinations, so as to enable a comparison with the properties of the ternary mixtures according to the invention which are shown in the following embodiments are given; Tables II and III contain the percentages Monomers in the copolymers that are used to build the ABS resins used and listed in Table IV have found application.

209 * 1a / 11Θ9
BAD ORfQINAL

The polycarbonate resin listed in Table I is the polycarbonate of 2,2- (4,4-dihydroxydiphenyl) propane and is made up of recurring units of the structural formula

\ = s

CH-

composed (cf. Simonds "Source Book of New Plastics "Volume 1, page I30 ff., 1959, Reinhold, New York) or it is an equivalent material as specified by aas commercially available resin "Lexan 141-112" the General Electric Co. is embodied. Other polycarbonates can also be used here, e.g. those that in U.S. Patent 3,028,365 to Schnell and coworkers, or in U.S. Patent 3,130 von Grabowski, column 4, lines 20-32. The polysulfone resin of Table I can be prepared as described in Example 1 of the United States patent cited above 3,264,536 manufactured by Robinson et al. and is composed of recurring units the structural formula

'0 9 ft. 1 9. / 1 1 D 9 BAD ORiOiNAL

or it may be an equivalent material such as the commercially available resin "Polysulfone P-1700" of US Pat Union Carbide Corp. The heat distortion temperatures listed in Table I. have been determined according to ASTM regulation D648-56 (196I).

Table I Properties of Polycarbonate and Polysulfone

characteristic

1/4 "notched Izod impact strength, 22.8 ° C (73 ° F) Foot . Pound / inch notch

Rockwell hardness R.

Heat deformation temperature Annealed for 16 hours, 18.5 kg / cm ^ (264 psi)

Viscosity, centipoise x. at 260 ° C 86.5 sec. " ¹

Tensile strength kg / cm '(psi)

Polycarbonate
Lexan 141-112

2.3
118

Polysulfone P-1700

(270 ^c

I6-2O

120

167 ⁰ C °

619
88ΟΟ

(too high to measure) greater than 300

705 10000

In Table II, the weight percent compositions of a styrene / acrylonitrile resin ("E") and of four OC-methylstyrene / acrylonitrile copolymer resins (A, B, C and F) and their intrinsic viscosities in dimethylformamide (DMF) indicated at 30 ° C.

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BATH ORIGINAL

Table II '

Examples of resin copolymer compositions (percent by weight)

Styrene Ck -Methyl s tyr oil Acrylonitrile

Fundamental viscosity number in DMF at JO C

A. B. £ E. F. 71 70 70 70 to 30th 30th 30th 29 30th

1.0 0.8 o, 6

Table III shows the composition of a graft copolymer, expressed in percent by weight, referred to as "D" and conventionally by graft copolymerization of styrene and acrylonitrile in a latex of a butadiene / styrene (weight ratio 90:10) copolymer rubber has been made.

Table III

Composition of the graft copolymer (percent by weight)

Acrylonitrile styrene butadiene

D.
16

38.5 45.5

To obtain the ABS mixtures used in the exemplary embodiments, each of the 5 mixed polymer resins is used A, B, C, E and F of Table II with the graft copolymer D of Table III was mixed in the proportions given in Table IV. The so-

209819/1109

21 544Λ5

Existing 5 mixtures are identified by 2 letters, the first letter indicating the resin copolymer that has been mixed with the graft copolymer (D) in order to obtain the ABS material used; For example, the mixture with the designation AD has been obtained by mixing 47 parts by weight of the copolymer A (Table II, 70 % ! X-methylstyrene, 30 % acrylonitrile) with 53 parts by weight of a graft copolymer D of Table III.

Table IV

(Resin) ABS compounds dd (Weight amounts) ti AD A. I! 47 B. C. E.

BD CD ED FD

47

40

F "32

D (graft copolymer) 53 53 53 60 68

Table V shows the properties of the 5 ABS blends, k which have been identified according to their composition in Table IV.

981971109

Table V
Properties of ABS materials

AD BD CD ED FD

1/4 "notched Izod

toughness, 22.8 ° C

(73 ° F) 6.9 5.0 4.5 6.0 2.5

Rockwell hardness R 99 99 99 96 113

Heat deformation terriÄ

temperature, 10.5 kg / enT 104 C 102 ° C 102 ° C 95 ⁰ C 110 C

(264 psi), annealed (220 F) ^ 15 F) (215 ° F) (200 F) (23O P) Viscosity 260 ° C

CP x ICK 25.8 23.1 20.2 24.2 3 &

Tensile strength kg / cm ² 422 401 380 373 492

(psi) 6OOO 5700 5 ^J +00 53OO 7OOO

For comparison with the products of the exemplary embodiments below of the present invention are also binary blends of the ABS material with the polycarbonate resin (PC) or with the polysulfone resin (PS), in the weight ratios that are given at the top of the 5 longitudinal columns in Table VI, and there are also the properties of these binary mixtures was determined to give the results shown in Table VI.

209813/11 (19 BAD ORIGINAL

Table VI

properties ABS / PC of binary mixes 6 "O: 4O PS / PC 33:67 58:52 ABS / PS 127 50:50 126 8.0
118 50:50 1.5
126 1/4 "notched Izod
impact strength,
22.8 ⁰ C (73 F)
Rockwell hardness
R. 8.0
119

Heat distortion
^ temperature *,
P 18.5 kg / cm

(264 psi), tempered

pert 124 ° C l49 ° C 162 C 152 ° C 150 ° C

(255 ° F) (300 ° F) (324 ° F) (305 ° F) (3O2 ° F)

Viscosity -,

260 C, CPxIO ^ 30 58 55 42 30.7

Tensile strength p

kg / cm 570 527 675 668 678 (psi) 8IOO 7500 96ΟΟ 9520 - 9650

The following examples, in which all quantities are weight quantities are intended to explain the practical implementation of the invention in great detail.

Examples 1-5

The polysulfone resin described above in connection with Table I. and the polycarbonate resin are carefully dried in the form of granules and placed in a at 121 ° C (250 F) preheated Banbury mixer filled, and in the 6 different proportions given in Table VII. The back pressure (ram) is lowered to a value of 4.22 kg / cm (60 psi)

2098 19/1109

held, with speed 3 being set. After becoming fluid, the two materials are mixed for 3 minutes. The temperature of the mixture is after completion of mixing at about 193-227 ⁰ C (380 - 44O ° F). The hot mixture is unloaded from the Banbury mixer and quickly rolled into a pellet on a roller mill at 149 ° C (300 ° P) and cut to regain granules. These granules are then used as blending approaches for subsequent blending with the ABS resin using the proportions given in Table VII and following the same procedure in the Banbury mixer to produce the final blends of ABS material, Manufacture polysulfone and polycarbonate. It is of interest to note that the polysulfone and poly-carbonate admixtures exhibit some degree of pearlescent appearance which appears to indicate that the polycarbonate is dispersed in a continuous polysulfone phase. Notwithstanding this, all three resins can also be filled into the Banbury mixer from the beginning in the proportions desired in each case, whereupon the mixture is mixed thoroughly in the manner described above in order to produce the finished mixture in one step. In Table VII, each ABS material used is characterized by a two-letter designation which corresponds to the ABS compositions used for identification in Table IV. The calculated heat distortion temperature given in Table VII is that which can be calculated in advance by adding up the contribution of each polymer.

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2154A

.I ₁ Properties of the mixtures 2 5 .4 17, 5 Table VII 21st 2 32, VJl 45 17, 5 Compositions and 14th 25th 32, 30th LfNP
VO O Example: 65
BD 50 LfNP
CM O 4th 25th
BD 8th, 2 Polysulfon 6, 25th
BD .0 10, 3.4 98 Polycarbonate 113 9 10, 120 123 99
210 ABS (quantity; Be
drawing) ⁰ C 108
( ⁰ F) 227 123 142
288 154
310 117
245 .1 / 4 "notched Izod
impact strength,
22.8 ° C (73 P) ° C 120
(° P) 248 133
272 121
250 3 280 14, 9 Rockwell hardness R. 15th 133
272 2 13, 7.13 373
5300 Heat deformation
temperature 2
(l8.5 kg / cm; ge
annealed) (264 ρsi) 484
6880 11 563
8OIO 614
8730 compute te heat
deformation temperature
rature 519
8240 Viscosity, 260 ^° C
CPx .1 (K
(CP = Centipoise) Tensile strenght "
kg / cm
(psi)

^ (Heat deformation
W temperature viscosity

¥ receipt)

χ 10 "^; 15.1 24.3 21.6 42.5 14.1

From the numerical values in Table VII, in particular the remarkably low viscosities, a certain synergistic effect recognizable in the area of paving. This synergism (reduction in viscosity) surprisingly goes far beyond what you can

$ 20 98t / 1109

in the polymers used or in any combination of two of them, such as can also be seen from Table VIII, in the viscosities and heat deformation temperatures (heat deformation temperature : Viscosity ratios) compared to sina. In Table VIII is the polycarbonate resin through the letters PC "and the polysulfone resin marked with the letters PS.

Table VIII
Comparison of the flow properties

ABS PC PS PS / PC ABS / PC AB S / PS / PC

viscosity

cp χ ick 20-38 16-20 300 30-55 30 7-15

at 260 ° C

relationship
(Heat deformation temperature door: Vis = *
viscosity) x10 ~ ^; '9-11 14-17 about 1 6-10 5-6 15 - ^ 5

More surprisingly, it is found that this ease of flow in the ternary mixture of the present invention is achieved while maintaining a high level of resistance to heat distortion. Thus, in Examples 3 and K of Table VII, the heat distortion temperature actually exceeds the calculated values, illustrating a second synergistic effect. Figure 1 of the drawings also illustrates this point. Figure 1 is a graph of numerical values obtained at various polysulfone resin: polycarbonate resin ratios and ABS resin contents. From Figure 1 it can be seen that a synergistic or unexpected increase in heat consumption

BAD ORfQiNAL

Forming temperature above the calculated values sets in at around 65 parts of ABS material up to around 25 parts ABS material, depending on the composition and the polysulfur resin: polycarbonate resin ratio.

Figure 2 illustrates the behavior of the heat distortion temperature: viscosity ratio and leaves a maximum effect (i.e. high ratio) at 50 to Detect 50 parts of ABS material. In another way Expressed: the compositions according to the invention are characterized by a remarkable improvement in processability excellent without an unduly high reduction in the heat distortion temperature at ratios from ABS material to combined polysulfone resin: polycarbonate resin from about 20:80 to about 6O: 4o ABS: PS-PC connected is.

A third unexpected synergism is in the surprising high impact strength of the ternary Harzmisehungen according to the invention has been determined. Table IX illustrates this by comparing the peak impact strength values of the invention Mixtures with those with the base polymers and with mixtures of two of these polymers have been obtained at once. That used ABS material is the material identified above as Compound AD. The numerical values in Table IX are based on impact strength measurements with a

Inch notch. ■ .-. ■

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Table IX Impact resistance 1/4 "notch

ABS PC PS PS / PC ABS / PC ABS / PS ABS / PC-PS

1/4 "Izod

Notched bar

toughness

22.8 ^D C (73 F) 6.9 2.5 1.3 1.6 8.0 8.0 10.4

Looking at the impact strength values measured with 1/8 inch notches, the same effect as shown in Table X can be seen. The one in Table X for the ABS material specified value is in the range of Impact strength values of ABS polymers such as them used here. The value for the binary ABS / polycarbonate mixture (ABS / PC) is based on published numerical values of a commercially available technical ABS / polycarbonate mixture known under the name "Cycoloy 800" (manufacturer: Borg Warner Co.). U.S. Patent 3,130,177 to U.S. Pat. No. 3,130,177 referenced above Grabowski mentions a range of impact strengths between 3.9 and 13.1. The maximum impact resistance Such binary mixtures are sat at about 80 parts of polycarbonate and about 20 parts of ABS polymer under: ¥ er * using an ABS material with an impact resistance of 8.5 achieved. With an ABS material that has an impact resistance of 3 * 0, the highest impact resistance is which can be obtained in the binary mixture, 8.3j again with a polycarbonate ABS ratio of 80:20.

20981971109

Table X Impact strength, 1/8 inch notch

ABS PC PS PS / PC ABS / PC ABS / PC / PS

1/8 "notched Izod impact strength
22.8 ⁰ C
(73 P) 2.9-2.1 12 1.3 1.0-1.6 10.3 13.0-13

Examples 6 to 8

Table XI shows the numerical values of three mixtures according to the invention in which the same polysulfone and the same polycarbonate were used as before. The ABS used is the BD in Table IV. Looking at the total impact strength values given, the really remarkable fact emerges that, according to the teaching of the invention, it is possible to achieve impact strengths which are higher than that of the polycarbonate alone. The maximum impact strength of the mixtures according to the invention is in the quantity range from 25 to 36 parts of ABS, even with different ratios of polycarbonate to ψ polysulfone.

209819/1109

Table XI Properties of the Mixtures

Example:

Polysulfone

Polycarbonate

SECTION

1/8 "notched Izod impact strength 22.8 ⁰ C (73 ° F)

Heat distortion temperature 6.35 χ 12.7 x 127 mm (1/4 "χ 1/2" χ 5 ") kg / cm ^ (264 psi) rod

6th ' 1 CDI , 2 9, 25th
50
25th 21
36 44
29
27 , 0 8.5 13th , 9 13, , 0 13.1 133 ° C 124 ° C 143 ° C
(272 ° F) (256 ⁰ F) (290 ⁰ F) 11

Viscosity.CP 86.3 sec. " ¹ , 260 ⁰ C

The optimal synergistic effects in terms of flow, impact strength and viscosity in
the compositions according to the invention can occur in more or less separate ranges of quantitative ratios. This fact enables the production of new and technically excellently useful mixtures in each of these three quantity ranges, and it also creates the opportunity to produce materials which are in this way
have coordinated properties that they are able to meet many technical applications.

Particularly recommended mixtures according to the invention from the standpoint of the heat distortion temperature are those which - expressed in percent by weight - contain 10 to 30% ABS material and accordingly 90 to 70 % polysulfone resin plus polycarbonate resin, the ratio of polysulfone resin to

209819/1109

Polycarbonate resin is 50:50 to 6θ: 4θ. In other words, the amounts are 10 to 30 % ABS material, 35 to 54 % polysulfone, and 35 to 36% polycarbonate.

Particularly recommended mixtures according to the invention from the standpoint of the pleating properties are those which - in percent by weight, contain 25 to 45% ABS material and accordingly 75 to 55 % polysulfone resin plus polycarbonate resin, the ratio of polysulfone resin to polycarbonate resin being 33:67 to 60:40 amounts to. In other words, the amounts are 25 to 45 % ABS material, 18 to 45 % polysulfone and 30 to 37 % polycarbonate.

Blends particularly recommended from the standpoint of impact strength are those which - expressed in percent by weight - contain 25 to 45% ABS material and accordingly 75 to 55 % polysulfone resin plus polycarbonate resin, the ratio of polysulfone resin to polycarbonate resin being 33 5 67 to 50:50 . In other words, the amounts are 24 to 45 % ABS material, 18 to 38 % polycarbonate and 37 to 38 % polysulfone.

From the foregoing it can be seen that the invention Mixtures of technical utility are useful for many purposes that require a high temperature resistant, require impact-resistant plastic with good processability and good flow properties. The possible applications in fixture construction, for household purposes' and in automobile manufacturing are numerous. The material can be made according to the conventional manufacturing methods, especially after the injection molding process, although other methods such as extrusion and blow molding

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deform, find application. The mixtures according to the invention can be used for the production of truck driver's cabs, Caravan or truck bodies and the like can be used, if desired also in the form of a Layer material to which a foamed layer of the material according to the invention belongs. In the moldings that have been made from the mixtures according to the invention, the impact strength of the molded part thickness is less than is the case with certain prior art materials.

209819/1109

Claims (1)

Claims 1. Impact-resistant thermoplastic resin compositions with good Flow properties and high heat distortion temperatures, characterized in that they contain (A) 10 to 75 % of a polymeric acrylonitrile / butadiene / styrene material, (B) 10 to 65 % of a thermoplastic, linear polyarylene-polyether-polysulfone resin and (C) 10 to 65 % of a resinous, thermoplastic P see polycarbonates, the repeating structure units of the formula -0 — A — 0- has, in which A is a divalent aromatic radical of a dihydric phenol, the Contains 2 hydroxyl groups, each of which is attached directly to a carbon atom of an aromatic Core is bound, represents the percentages mentioned being percentages by weight and based on the total weight of the constituents (A), (B) and (C) are related. 2. Composition according to claim 1, characterized in that the component (B) consists of repeating units the formula 0 — E — 0 — E * is composed, in which E means the remainder of a benzoid compound, which is an inert 209819/1109 contains electron withdrawing group in at least one of the o- and p-positions to the valence bonds, and both said radicals E and E * are bonded by means of valence bonds to ether oxygen atoms through aromatic carbon atoms and at least one of the radicals E and E ^{1 is} a sulfone bridge member between has aromatic carbon atoms, and the component (C) made of a thermoplastic, resinous polycarbonate of a bis (4-hydroxyphenyl) alkane exists, and the proportions are 25 to 65 % component (A), 10 to 45 % component (B) and 10 to 50 % component (C) amount to. 3 · mass according to claim 2, characterized in that the component (B) made up of recurring units of the formula (Y) _r (Y-,) _z is composed, in which R is either a bond between aromatic carbon atoms or a divalent connecting radical and R ^{1 is} a sulfone, carbonyl, vinyl, sulfoxide, azo, saturated fluorocarbon, organic phosphine oxide or ethylidene group, each of the Symbols Y and Y .. for an inert substituent group consisting of halogen atoms, alkyl groups with 1 to 4 carbon atoms 2G9813 / 1 or alkoxy groups with 1 to 4 carbon atoms, and r and ζ are whole numbers im Values from 0 to 4 inclusive, with the proviso that at least one of the radicals R and R 'are -Sop group means. 4. Mass according to claim 2, characterized in that the component (B) made up of recurring units of the formula and the component (c) from recurring units of the formula YH- 0 C- is composed. Composition according to Claim 2, characterized in that component (A) consists of a graft copolymer of styrene and acrylonitrile on a chewing cheek The backbone consists of polybutadiene or a butadiene / styrene copolymer consists. 209819/1109 2154A45 6. mass according to claim 5. » characterized in that component (A) is a separately produced styrene / Contains acrylonitrile resin. 7 · mass according to claim 5 * characterized in that component (A) is a separately produced oC-methylstyrene / acrylonitrile resin contains. 8. Composition according to claim 1, characterized in that the component (A) is present in an amount of 10 to 30 % and the amount of the components (B) plus (C) accordingly amounts to 90 to 70% , the ratio of the component (B) to the component (C) is 50:50 to 60:40. 9 «Composition according to claim 1, characterized in that the component (A) is present in an amount of 25 to 45 % and the amount of the components (B) plus (C) accordingly amounts to 75 to 55% , the ratio of component (B) to component (C) is 33:67 to 60:40. 10. Composition according to claim 1, characterized in that the component (A) is present in an amount of 25 to 45 % and the amount of the components (B) plus (C) accordingly amounts to 75 to 55% , the ratio of component (B) to component (C) is 33:67 to 50:50. 209819/1109