CA1182236A - Thermoplastic moulding compositions of aromatic polycarbonate and graft polymer of o,o,o',o' tetra- methyl bisphenol polycarbonate and a graft polymer with an acrylate rubber base - Google Patents
Thermoplastic moulding compositions of aromatic polycarbonate and graft polymer of o,o,o',o' tetra- methyl bisphenol polycarbonate and a graft polymer with an acrylate rubber baseInfo
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- CA1182236A CA1182236A CA000402688A CA402688A CA1182236A CA 1182236 A CA1182236 A CA 1182236A CA 000402688 A CA000402688 A CA 000402688A CA 402688 A CA402688 A CA 402688A CA 1182236 A CA1182236 A CA 1182236A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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Abstract
ABSTRACT
Thermoplastic moulding compositions of aromatic polycarbonate and graft polymer Moulding compositions of aromatic polycarbonate consisting at least partly of o,o,o',o'-tetramethyl bisphenol polycarbonate may be processed after the addition of certain graft polymer to form mouldings having high multiaxial impact strength.
Thermoplastic moulding compositions of aromatic polycarbonate and graft polymer Moulding compositions of aromatic polycarbonate consisting at least partly of o,o,o',o'-tetramethyl bisphenol polycarbonate may be processed after the addition of certain graft polymer to form mouldings having high multiaxial impact strength.
Description
~2;~36 This invention relates to thermoplastic moulding compositions containing o,o,o',o'-tetramethyl bisphenol polycarbon-ate and a particular graft polymer.
Thermoplastic moulding compositions of from 10 to 95%, by weight, of aroma-tic polycarbonates, at least 50 mole percent of the bisphenol units of which are o,o,o',o'-tetramethyl bisphenol units, and from 5 to 90%, by weight, of an optionally modified rubber are known (cf. DE-OS No. 2,329,585 _ US-PS No. ~,172,103).
They are characterised by high resistance to hydrolysis, high dimensional stability to heat, high impac-t strength, high notched impact strength, high tracking resistance and high resistance to stress crazing. However, the impact strength thereof in the event of multiaxial stressing, which is very important, for example for parts of housings that are subjected to impact, is not always entirely satisfactory.
The present invention relates to thermoplastic moulding compositions comprising:
(A) 100 parts, by weigh-t, of aromatic polycarbonate; and (s) from 1 to 30 parts, by weight, of a graft polymer having a glass transition temperature below -20C, characterised in that the aromatic polycarbonate (A) consists at least partly of o,o,o',o' tetramethyl bisphenol polycarbonate and in that the graft polymer (B) is a graft polymer of:
(a) from 25 to 98%, by weight, preferably from 85 to 98%, by weight, based on the graft polymer, of an acrylate rubber having a glass transition -temperature below -20C as the graft base; and (b) from 2 to 75%, by weight preferably from 2 to 20%, i, . ,,~ -- 1 --~2~Z3~
by weight, based on the graft polymer, of at least one polymerisable ethylenically unsatura-ted monomer of which the homo- or co-polymer(s) formed in the absence of (a) would have a glass transition tempera-ture above 25C, as the graft monomer;
monomer (b) preferably having been grafted onto the completely broken latex of (a), suspended in water, in the absence of suspendlng agents.
In the context of -the present invention, aromatic polycarbonates (~) are to be understood to be homopolycarbonates, copolycarbonates and mixtures of these polycarbonates which are based, for example, on at least one of the following diphenols:
hydroquinone, resorcinol, dihydroxy diphenyls, bis-(hydroxyphenyl)-alkanes, bis-
Thermoplastic moulding compositions of from 10 to 95%, by weight, of aroma-tic polycarbonates, at least 50 mole percent of the bisphenol units of which are o,o,o',o'-tetramethyl bisphenol units, and from 5 to 90%, by weight, of an optionally modified rubber are known (cf. DE-OS No. 2,329,585 _ US-PS No. ~,172,103).
They are characterised by high resistance to hydrolysis, high dimensional stability to heat, high impac-t strength, high notched impact strength, high tracking resistance and high resistance to stress crazing. However, the impact strength thereof in the event of multiaxial stressing, which is very important, for example for parts of housings that are subjected to impact, is not always entirely satisfactory.
The present invention relates to thermoplastic moulding compositions comprising:
(A) 100 parts, by weigh-t, of aromatic polycarbonate; and (s) from 1 to 30 parts, by weight, of a graft polymer having a glass transition temperature below -20C, characterised in that the aromatic polycarbonate (A) consists at least partly of o,o,o',o' tetramethyl bisphenol polycarbonate and in that the graft polymer (B) is a graft polymer of:
(a) from 25 to 98%, by weight, preferably from 85 to 98%, by weight, based on the graft polymer, of an acrylate rubber having a glass transition -temperature below -20C as the graft base; and (b) from 2 to 75%, by weight preferably from 2 to 20%, i, . ,,~ -- 1 --~2~Z3~
by weight, based on the graft polymer, of at least one polymerisable ethylenically unsatura-ted monomer of which the homo- or co-polymer(s) formed in the absence of (a) would have a glass transition tempera-ture above 25C, as the graft monomer;
monomer (b) preferably having been grafted onto the completely broken latex of (a), suspended in water, in the absence of suspendlng agents.
In the context of -the present invention, aromatic polycarbonates (~) are to be understood to be homopolycarbonates, copolycarbonates and mixtures of these polycarbonates which are based, for example, on at least one of the following diphenols:
hydroquinone, resorcinol, dihydroxy diphenyls, bis-(hydroxyphenyl)-alkanes, bis-
- 2 -(hydroxyphenyl)-cycloalkanes~ bis-(hydroxyphenyl)-sulphides, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulphoxides, bis-(hydroxy-phenyl)-sulphones and ~,~'-bis-(hydroxyphenyl)-diisopropyl benzenes, as well as the nucleus-alkylated and nucleus-halogenated derivatives. These and other suitable diphenols are described, for example, in US-PS Nos.
3,028,365; 3,275,601; 3,148,172; 3,062,781; 2,991,273;
3,271,367; 2,999,835; 2,970,131 and 2,999,846; in DE-OS Nos. 1,570,703; 2,063,050, 2,063,052; 2,211,956 and 2,211,957; in FR-PS No. 1,561,518 and in H. ~chnell's book entitled "Chemistry and Physics of Polycarbonates", Interscience Publishers, ~ew York, 1964.
Preferred diphenols are, for example, 4,4'-dihydroxydiphenyl, 2,4-bis~(4-hydroxyphenyl)-2-methyl butane, a,~'-bis-(4-hydroxyphenyl)-p-diisopropyl benzene, 2,2-bis-(3-methyl~4-hydroxyphenyl)-propane and 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane.
Particularly preferred dipheno s are, for example, 2,2-bis-(4-hydroxyphenyl~-propane, 2,2-bis-(3,5-dichloro-
3,271,367; 2,999,835; 2,970,131 and 2,999,846; in DE-OS Nos. 1,570,703; 2,063,050, 2,063,052; 2,211,956 and 2,211,957; in FR-PS No. 1,561,518 and in H. ~chnell's book entitled "Chemistry and Physics of Polycarbonates", Interscience Publishers, ~ew York, 1964.
Preferred diphenols are, for example, 4,4'-dihydroxydiphenyl, 2,4-bis~(4-hydroxyphenyl)-2-methyl butane, a,~'-bis-(4-hydroxyphenyl)-p-diisopropyl benzene, 2,2-bis-(3-methyl~4-hydroxyphenyl)-propane and 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane.
Particularly preferred dipheno s are, for example, 2,2-bis-(4-hydroxyphenyl~-propane, 2,2-bis-(3,5-dichloro-
4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxy-phenyl)~propane and l,l-bis-(4-hydroxyphenyl)-cyclohexane.
Preferred o,o,o'o'-tetramethylbisphenol poly-carbonates are, for example, polycarbonates prepared from the following bisphenols: bis-(3,5-dimethyl-4hydroxy-phenyls), bis-(3,5-dimethyl-4-hydroxyphenyl)-alkanes, bis (3,5-dimethyl-4-hydroxyphenyl)-cycloalkanes, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulphides, bis-(3,5-dimethyl-4-hydroxyphenyl)-ethers, bis-(3,5-dimethyl-4-hydroxy-phenyl)-ketones, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulphoxides, ~,~'-bis-(3,5-dimethyl-4-hydroxyphenyl)-diisopropyl benzenes and the nucleus-halogenated derivatives thereof, more particularly bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxy-phenyl)-propane, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methyl butane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, ~,~'-bis-(3,5-dimethyl-4-hydroxyphenyl)-Le A 21 048 p-diisopropyl benzene and bis-(3,5-dimethyl-~-hydroxy-phenyl)-sulphone.
Particularly preferred o,o,o',o'-tetramethyl bisphenol polycarbonates are those of which the diphenol component consists of 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane; from 0.5 to 20 ~, by weight, preferably from 1 to 7 %, by weight, of this compound may optionally be replaced by 1,1,3,4,6,-pentamethyl-3-(3,5-dimethyl-4-hydroxyphenyl)-indan-5-ol corresponding to the following formula:
CH ~ CH3 (I) The aromatic polycarbonates (A) may be branched by the incorporation of from 0.05 to 2.0 mole percent (based on the diphenols used) of at least trifunctional compounds, for example compounds containing three or more phenolic hydroxy groups.
The aromatic polycarbonates (A) should generally have average molecular weights, Mw, of from lO,000 to more than 200,000, preferably from 20,000 to 80,000, as determined by relative viscosity measurements in di-chloromethane at 25C and using a concentration of 0.5%, by weight.
Small cuantities of low molecular weight poly-carbonates for example having an average degree of polycondensation of from 2 to 20, may also be added to and mixed with the high molecular weight polycarbonates having molecular weights, Mw f from lO,000 to 200,000.
Chain-terminators, such as phenol, halo-phenols or alkyl phenols, may be used in known manner in the calculated quantities for adjusting the molecular weisht Mw, of the polyca~bonates (A).
In general, from ~-~ to 100%, by weight, of the Le A 21 048 "f~3~
aromatic polycarbonates (A) consists of tetramethyl bisphenol carbonate units, based on the sum of all the bisphenol carbonate units; in other words, mixtures and co-condensates are treated the same for calculatory purposes so that a polycarbonate consist-ing of 20%, by weight, of bisphenol-A-carbona-te units and 80%, by weight, of tetramethyl bisphenol-A-carbonate is calculated as a mixture of 20%, by weight, of bisphenol-A-polycarbonate and 80%, by weight, of tetramethyl bisphenol-A-polycarbonate.
Moulding compositions according to the present invention, from 80 -to 100%, by weight, of the aromatic polycarbonates (A) of which consist of tetramethyl bisphenol polycarbonate show particularly high resistance to hydrolysis and solvents and a minimal tendency to crack under stressO
Where the aromatic polycarbonate (A) consists wholly of tetramethyl bisphenol polycarbonate, the moulding compositions according to the present invention contain two resin components.
They preferably consist of:
(A) 100 parts, by weight, of o,o,o',o'-tetramethyl bisphenol polycarbonate, and (B) from 1 to 30 parts, by weight, preferably from 5 to 20 parts, by weight, of a polymer having a glass transition temperature below -20C.
Compared with a moulding composition according to the present invention additionally containing another bisphenol polycarbonate (of which the bisphenol units in the o-position are not methylated), the above-mentioned two-component mixture shows lower impact strength, but greater dimensional stability to heat.
Preferred o,o,o'o'-tetramethylbisphenol poly-carbonates are, for example, polycarbonates prepared from the following bisphenols: bis-(3,5-dimethyl-4hydroxy-phenyls), bis-(3,5-dimethyl-4-hydroxyphenyl)-alkanes, bis (3,5-dimethyl-4-hydroxyphenyl)-cycloalkanes, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulphides, bis-(3,5-dimethyl-4-hydroxyphenyl)-ethers, bis-(3,5-dimethyl-4-hydroxy-phenyl)-ketones, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulphoxides, ~,~'-bis-(3,5-dimethyl-4-hydroxyphenyl)-diisopropyl benzenes and the nucleus-halogenated derivatives thereof, more particularly bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxy-phenyl)-propane, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methyl butane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, ~,~'-bis-(3,5-dimethyl-4-hydroxyphenyl)-Le A 21 048 p-diisopropyl benzene and bis-(3,5-dimethyl-~-hydroxy-phenyl)-sulphone.
Particularly preferred o,o,o',o'-tetramethyl bisphenol polycarbonates are those of which the diphenol component consists of 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane; from 0.5 to 20 ~, by weight, preferably from 1 to 7 %, by weight, of this compound may optionally be replaced by 1,1,3,4,6,-pentamethyl-3-(3,5-dimethyl-4-hydroxyphenyl)-indan-5-ol corresponding to the following formula:
CH ~ CH3 (I) The aromatic polycarbonates (A) may be branched by the incorporation of from 0.05 to 2.0 mole percent (based on the diphenols used) of at least trifunctional compounds, for example compounds containing three or more phenolic hydroxy groups.
The aromatic polycarbonates (A) should generally have average molecular weights, Mw, of from lO,000 to more than 200,000, preferably from 20,000 to 80,000, as determined by relative viscosity measurements in di-chloromethane at 25C and using a concentration of 0.5%, by weight.
Small cuantities of low molecular weight poly-carbonates for example having an average degree of polycondensation of from 2 to 20, may also be added to and mixed with the high molecular weight polycarbonates having molecular weights, Mw f from lO,000 to 200,000.
Chain-terminators, such as phenol, halo-phenols or alkyl phenols, may be used in known manner in the calculated quantities for adjusting the molecular weisht Mw, of the polyca~bonates (A).
In general, from ~-~ to 100%, by weight, of the Le A 21 048 "f~3~
aromatic polycarbonates (A) consists of tetramethyl bisphenol carbonate units, based on the sum of all the bisphenol carbonate units; in other words, mixtures and co-condensates are treated the same for calculatory purposes so that a polycarbonate consist-ing of 20%, by weight, of bisphenol-A-carbona-te units and 80%, by weight, of tetramethyl bisphenol-A-carbonate is calculated as a mixture of 20%, by weight, of bisphenol-A-polycarbonate and 80%, by weight, of tetramethyl bisphenol-A-polycarbonate.
Moulding compositions according to the present invention, from 80 -to 100%, by weight, of the aromatic polycarbonates (A) of which consist of tetramethyl bisphenol polycarbonate show particularly high resistance to hydrolysis and solvents and a minimal tendency to crack under stressO
Where the aromatic polycarbonate (A) consists wholly of tetramethyl bisphenol polycarbonate, the moulding compositions according to the present invention contain two resin components.
They preferably consist of:
(A) 100 parts, by weight, of o,o,o',o'-tetramethyl bisphenol polycarbonate, and (B) from 1 to 30 parts, by weight, preferably from 5 to 20 parts, by weight, of a polymer having a glass transition temperature below -20C.
Compared with a moulding composition according to the present invention additionally containing another bisphenol polycarbonate (of which the bisphenol units in the o-position are not methylated), the above-mentioned two-component mixture shows lower impact strength, but greater dimensional stability to heat.
5 -~2~6 The degree of grafting, G, is the ratio, by weight, between the monomers grafted on and -the graft base and has no dimension. The average particle diame-ter, d50, is that diameter above and below which 50%, by weight, of the particles lie. It may be determined by ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid. Z. and Z. Polymere 250 (1972), 782-796) or by electron microscopy and subsequent counting of the particles (G. Kampf, H. Schuster, Angew. Makromolekulare Chemie 1~, (1970, 111-129) or by light scattering measurements.
The acrylate rubbers (a) of the polymers (s) are preferably the polymers of acrylic acid alkyl esters, optionally con-taining up to 40%, by weight, of other polymerisable, ethylenically unsaturated monomers. Providing the acrylate rubbers used as the graft base (a) are for their part graf-t products having a diene rubber core, as described on page 9, the diene rubber core is not included in the calculation of this percentage. Preferred polymerisable acrylic acid esters include, Cl-C8 alkyl esters, for example, methyl, ethyl, butyl, octyl and 2-ethylhexyl esters; halo-alkyl esters, preferably halo-Cl-C~
alkyl esters, such as chloroethyl acrylate, and aromatic esters, such as benzyl acrylate and phenethyl acrylate. They may be used either individually or in admixture.
The acrylate rubbers (a) may be uncross-linked or cross-linked, preferably partially cross-linked.
Monomers containing more than one polymerisable double bond may be copolymerised for cross~linking. Preferred examples of cross-linking monomers are esters of unsa-turated monocarboxylic acids containing from 3 to 8 carbon atoms and unsaturated monohydric alcohols containing ~rom 3 to 12 carbon atoms or saturated polyols containing from 2 to 4 OH-groups and from 2 to 20 carbon atoms, such as, ethylene glycol dlmethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate and isocyanurate, tris-acryloyl-s-triazines, particularly triallyl cyanurate; polyfunctional vinyl compounds, such as divinyl and trivinyl benzenes, and also triallyl phosphate and diallyl phthalate.
Preferred cross-linking monomers are allyl methacrylate,ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups.
Particularly preferred cross-linking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloyl hexahydro-s-triazine and triallyl benzenes.
The cross-linking monomers are preferably used in quantites of from 0.02 to 5~, by weight, more preferably from 0.05 to 2%, by weight, based on the graft base (a).
In the case of cyclic cross-linking monomers containing at least three ethylenically unsaturated groups, it is advantageous to limit the quantity to <l~, by weight, oE graft base (a).
Preferred "other" polymerisable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, may optionally be used for producing the graft base (a) are, for example, acrylonitrile, styrene, ~-methyl styrene, acrylamides and vinyl-Cl-C6 alkyl ethers.
Preferred acrylate rubbers as the graft base (a) are emulsion polymers having a gel content of >60%, by welght.
The gel content of the graft base (a) is determined in dimethyl formamide at 25C (M. Hoffmann, H. Kromer, ~. Kuhn, Polymeranalytik I and II, Gerog Thieme Verlag, Stuttgart 1977).
Acrylate rubbers as the graft base (a) may also be Le A 21 048 ~8Z~23~
products containing a cross-linked diene rubber of one or more conjugated dienes, such as polybutadiene, or a co-polymer of a conjugated diene with an ethylenically unsaturated monomer, such as gtyrene and/or acrylonitrile as the core.
The proportion of polydiene core in the graft base (a) may amount to from 0.1 to 50%, by weight, preferably from 1 to 10%, by weight, based on (a). The shell and core may be uncross-linked, partially cross-linked or highly cross-linked independently of one another.
Particularly preferred graft bases (a) for graft polymers (B) based on polyacrylic acid esters are summarised once again in the following:
(1) Acrylic acid ester polymers and copolymers without a diene rubber core and (2) acrylic acid ester polymers and copolymers containing a diene rubber core.
The graft yield, i.e. the quotient of the quantity of monomers (b) grafted-on and the quantity of graft monomers (b) used, generally amounts to from 20 to 80%, by weight, and may be determined by the method described by M. Hoffmann, H. Kromer. R. Kuhn in Polymeranalytik, Vol 1, Gerog Thieme Verlag, Stuttgart 1977.
Preferred graft monomers (b) are ~-methyl styrene, styrene, acrylonitrile, methyl methacrylate or mixtures thereof. Preferred graft monomer mixtures are mixtures of styrene and acrylonitrile in a ratio, by weight, of from 90:10 to 50:50.
~ Graft polymers (B)-~f~-t~ are described, for example, in DE-AS No. 2,444,584 (- US-PS No. 4,022,748) and in DE-OS No. 2,726,256 (- US-PS NO. 4,096,202).
Particularly advantageous graft polymers ~f-~-ype--~2~are obtained when from 2 to 20%, by weight, preferably from 3 to 15%, by weight, based on (B) ~, of monomer (b) is grafted onto from 80 to 98%, by weight, preferably from 85 to 97~, by weight, based on (B) ~, of the Le A 21 048 .
2~
-- ~o completely broken latex, suspended in water, of (a) in the absence of suspending agents. The powder-form grat polymer obtained may subsequently be dried and homogenised wi-th the other components in the required ratio under the action of shearing forces in such a way that the average partlcle diame-ter, d50, of (B) in the mixture according to the present invention amounts to from 0.05 to 3, preferably from 0.1 to 2, more preferably from 0.2 to 1 ,um.
The expression "in the absence of suspending agents" means the absence of substances which could be suspended in the aqueous phase, depending on the type and quantity of graft monomers (b). This definition does not exclude the presence of substances which have had a suspending effect, for example in the production of a grafted graft base (a). In such cases, the coagulant or precipitant used for breaking the latex (a) has to be added in a quantity which neutralises the suspending effect of the substances used in the preliminary stage.
In other words, it is important to ensure that the graft monomers (b) do not form a (stable) emulsion in the aqueous phase.
As part of the moulding compositions according to the present invention, a graft polymer (B) produced in this way in the absence of suspending agents may be dispersed in the other resin components to an extremely small particle size which remains substantially un-changed even over prolonged processing times at elevated temperature.
The expression "extremely small particle size"
means that the number, shape and size of the graft polymer particles used still correspond substantially to the number, shape and size of the graft polymer particles introduced into the other, melted resin components, even after homogenisation.
It is also possible to use as the graft base (a) Le A 21 048 23~
acrylate rubbers of the type which accumulate in the form of an aqueous emulsion (latex) and of which the latex particles contain from 1 to 20 %, by weight, preferably already grafted on in aqueous emulsion of which the homopolymers of copolymers would have glass transition temperatures of~ 0C.
Preferred grafted-on monomers of this type are alkyl acrylates, alkyl methacrylates, styrene, acrylo-nltrile, ~-methyl styrene and/or vinyl acetate.
Graft bases (a) of this type are produced, for example, by emulsion polymerisation or by emulsion graft polymerisation. ~owever, they may also be obtained by preparing an acrylate rubber by solution or bulk polyme-risation, subsequently grafting on the graft monomers and then converting the rubbers into an aqueous emulsion which is suitable for further grafting processes.
Accordingly, in addition to the polymers listed on page ~, other suitable graft bases ~a) for acrylate rubbers of this particular embodiment are graft polymers produced in aqueous emulsion, of acrylic acid ester homo-or co-polymers optionally containing a diene rubber core and ethylenically unsaturated polymerisable monomers.
The moulding compositions according to the present invention may contain conventional additives, such as lubricants and mould release agents, nucleating agents, stabilisers, fillers and reinforcing materials, flame-proofing agents and dyes.
The filled or reinforced moulding compositions may contain up to 60~, by weight, based on the reinforced moulding composition, of fillers and/or reinforcing materials. Préferred reinforcing materials are glass fibres. Preferred fillers, which may also have a reinforcing effect, are glass beads, mica, silicates, quartz, talcum, titanium dioxide and wollastonite.
Le A 21 048 The flameproofed polyester moulding compositions generally contain flameproofing agents in a concentration of less than 30~, by weight, based on the flameproofed moulding compositions.
It is possible to use various known flameproofing agents, such as, polyhalogen diphenyl, polyhalogen diphenyl ether, polyhalogen phthalic acid and derivatives thereof and polyhalogen oligocarbonates and polycarbonates, the corresponding bromine compounds being particularly effective. In addition, they generally contain a synergist, such as antimony trioxide.
The moulding compositions may be produced in the conventional mixing units, such as mixing rolls, kneaders, single and multiple-screw extruders.
The parts quoted in the following Examples represent parts, by weight, while the percentages quoted represent percentages, by weight.
Le A 21 048 ~22~
EXAMPLES
COmpQnents used:
I. A polycarbonate of bisphenol-A, phenol and phosgene, relative viscosity 1.285, as measured on a 0.5% solution in dichloromethane at 25C.
II. A polycarbonate of o,o,o',o'-tetramethyl bisphenol-A, phenol and phosgene, relative viscosity 1.29, as measured on a 0.5% solution ln dichloromethane at 25C.
III. A core-shell-type graft polymer having the following composition (expressed in the ratios, by weight, between its constituen-t monomers): n-butyl acrylate/1,3-butane diol diacrylate/diallyl maleate/methyl methacrylate = 79.2:0.4:0.4:20Ø
IV. A graft polymer of 80 parts of cross-linked polybutyl acrylate having a polybutadiene core as the graft base and 20 parts of methyl methacrylate, as the graft monomer.
V. A graft polymer of 90 parts of cross-linked polybutyl acrylate having a polybutadiene core as the graft base and 7.2 parts of styrene and 2.8 parts of acrylonitrile as the graft monomer.
Production of the moulding compositions:
The components (in the ratio shown in the Table) were melted and homogenised under nitrogen in a twin-screw extruder.
The melt strand of the moulding compositions according to the present invention was degassed before leaving the extrusion nozzle, cooled in water, granulated and dried.
Standard small test bars were injection-moulded from the granulate and tested for impact strength and notched impact strength in accordance with DIN 53 453. In addition, plates were produced for testing multiaxial impact strength.
~32Z3~
Multiaxial impact strength was determined by the EFTR (electronic force/travel recording) test according to DIN 53 443, page 2; penetration of a plate measuring 3 x 60 x 60 mm by a 35 kg weight fixed to a spike (spherical point 20 mm in diameter) dropped from a height of 1 metre.
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The acrylate rubbers (a) of the polymers (s) are preferably the polymers of acrylic acid alkyl esters, optionally con-taining up to 40%, by weight, of other polymerisable, ethylenically unsaturated monomers. Providing the acrylate rubbers used as the graft base (a) are for their part graf-t products having a diene rubber core, as described on page 9, the diene rubber core is not included in the calculation of this percentage. Preferred polymerisable acrylic acid esters include, Cl-C8 alkyl esters, for example, methyl, ethyl, butyl, octyl and 2-ethylhexyl esters; halo-alkyl esters, preferably halo-Cl-C~
alkyl esters, such as chloroethyl acrylate, and aromatic esters, such as benzyl acrylate and phenethyl acrylate. They may be used either individually or in admixture.
The acrylate rubbers (a) may be uncross-linked or cross-linked, preferably partially cross-linked.
Monomers containing more than one polymerisable double bond may be copolymerised for cross~linking. Preferred examples of cross-linking monomers are esters of unsa-turated monocarboxylic acids containing from 3 to 8 carbon atoms and unsaturated monohydric alcohols containing ~rom 3 to 12 carbon atoms or saturated polyols containing from 2 to 4 OH-groups and from 2 to 20 carbon atoms, such as, ethylene glycol dlmethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate and isocyanurate, tris-acryloyl-s-triazines, particularly triallyl cyanurate; polyfunctional vinyl compounds, such as divinyl and trivinyl benzenes, and also triallyl phosphate and diallyl phthalate.
Preferred cross-linking monomers are allyl methacrylate,ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups.
Particularly preferred cross-linking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloyl hexahydro-s-triazine and triallyl benzenes.
The cross-linking monomers are preferably used in quantites of from 0.02 to 5~, by weight, more preferably from 0.05 to 2%, by weight, based on the graft base (a).
In the case of cyclic cross-linking monomers containing at least three ethylenically unsaturated groups, it is advantageous to limit the quantity to <l~, by weight, oE graft base (a).
Preferred "other" polymerisable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, may optionally be used for producing the graft base (a) are, for example, acrylonitrile, styrene, ~-methyl styrene, acrylamides and vinyl-Cl-C6 alkyl ethers.
Preferred acrylate rubbers as the graft base (a) are emulsion polymers having a gel content of >60%, by welght.
The gel content of the graft base (a) is determined in dimethyl formamide at 25C (M. Hoffmann, H. Kromer, ~. Kuhn, Polymeranalytik I and II, Gerog Thieme Verlag, Stuttgart 1977).
Acrylate rubbers as the graft base (a) may also be Le A 21 048 ~8Z~23~
products containing a cross-linked diene rubber of one or more conjugated dienes, such as polybutadiene, or a co-polymer of a conjugated diene with an ethylenically unsaturated monomer, such as gtyrene and/or acrylonitrile as the core.
The proportion of polydiene core in the graft base (a) may amount to from 0.1 to 50%, by weight, preferably from 1 to 10%, by weight, based on (a). The shell and core may be uncross-linked, partially cross-linked or highly cross-linked independently of one another.
Particularly preferred graft bases (a) for graft polymers (B) based on polyacrylic acid esters are summarised once again in the following:
(1) Acrylic acid ester polymers and copolymers without a diene rubber core and (2) acrylic acid ester polymers and copolymers containing a diene rubber core.
The graft yield, i.e. the quotient of the quantity of monomers (b) grafted-on and the quantity of graft monomers (b) used, generally amounts to from 20 to 80%, by weight, and may be determined by the method described by M. Hoffmann, H. Kromer. R. Kuhn in Polymeranalytik, Vol 1, Gerog Thieme Verlag, Stuttgart 1977.
Preferred graft monomers (b) are ~-methyl styrene, styrene, acrylonitrile, methyl methacrylate or mixtures thereof. Preferred graft monomer mixtures are mixtures of styrene and acrylonitrile in a ratio, by weight, of from 90:10 to 50:50.
~ Graft polymers (B)-~f~-t~ are described, for example, in DE-AS No. 2,444,584 (- US-PS No. 4,022,748) and in DE-OS No. 2,726,256 (- US-PS NO. 4,096,202).
Particularly advantageous graft polymers ~f-~-ype--~2~are obtained when from 2 to 20%, by weight, preferably from 3 to 15%, by weight, based on (B) ~, of monomer (b) is grafted onto from 80 to 98%, by weight, preferably from 85 to 97~, by weight, based on (B) ~, of the Le A 21 048 .
2~
-- ~o completely broken latex, suspended in water, of (a) in the absence of suspending agents. The powder-form grat polymer obtained may subsequently be dried and homogenised wi-th the other components in the required ratio under the action of shearing forces in such a way that the average partlcle diame-ter, d50, of (B) in the mixture according to the present invention amounts to from 0.05 to 3, preferably from 0.1 to 2, more preferably from 0.2 to 1 ,um.
The expression "in the absence of suspending agents" means the absence of substances which could be suspended in the aqueous phase, depending on the type and quantity of graft monomers (b). This definition does not exclude the presence of substances which have had a suspending effect, for example in the production of a grafted graft base (a). In such cases, the coagulant or precipitant used for breaking the latex (a) has to be added in a quantity which neutralises the suspending effect of the substances used in the preliminary stage.
In other words, it is important to ensure that the graft monomers (b) do not form a (stable) emulsion in the aqueous phase.
As part of the moulding compositions according to the present invention, a graft polymer (B) produced in this way in the absence of suspending agents may be dispersed in the other resin components to an extremely small particle size which remains substantially un-changed even over prolonged processing times at elevated temperature.
The expression "extremely small particle size"
means that the number, shape and size of the graft polymer particles used still correspond substantially to the number, shape and size of the graft polymer particles introduced into the other, melted resin components, even after homogenisation.
It is also possible to use as the graft base (a) Le A 21 048 23~
acrylate rubbers of the type which accumulate in the form of an aqueous emulsion (latex) and of which the latex particles contain from 1 to 20 %, by weight, preferably already grafted on in aqueous emulsion of which the homopolymers of copolymers would have glass transition temperatures of~ 0C.
Preferred grafted-on monomers of this type are alkyl acrylates, alkyl methacrylates, styrene, acrylo-nltrile, ~-methyl styrene and/or vinyl acetate.
Graft bases (a) of this type are produced, for example, by emulsion polymerisation or by emulsion graft polymerisation. ~owever, they may also be obtained by preparing an acrylate rubber by solution or bulk polyme-risation, subsequently grafting on the graft monomers and then converting the rubbers into an aqueous emulsion which is suitable for further grafting processes.
Accordingly, in addition to the polymers listed on page ~, other suitable graft bases ~a) for acrylate rubbers of this particular embodiment are graft polymers produced in aqueous emulsion, of acrylic acid ester homo-or co-polymers optionally containing a diene rubber core and ethylenically unsaturated polymerisable monomers.
The moulding compositions according to the present invention may contain conventional additives, such as lubricants and mould release agents, nucleating agents, stabilisers, fillers and reinforcing materials, flame-proofing agents and dyes.
The filled or reinforced moulding compositions may contain up to 60~, by weight, based on the reinforced moulding composition, of fillers and/or reinforcing materials. Préferred reinforcing materials are glass fibres. Preferred fillers, which may also have a reinforcing effect, are glass beads, mica, silicates, quartz, talcum, titanium dioxide and wollastonite.
Le A 21 048 The flameproofed polyester moulding compositions generally contain flameproofing agents in a concentration of less than 30~, by weight, based on the flameproofed moulding compositions.
It is possible to use various known flameproofing agents, such as, polyhalogen diphenyl, polyhalogen diphenyl ether, polyhalogen phthalic acid and derivatives thereof and polyhalogen oligocarbonates and polycarbonates, the corresponding bromine compounds being particularly effective. In addition, they generally contain a synergist, such as antimony trioxide.
The moulding compositions may be produced in the conventional mixing units, such as mixing rolls, kneaders, single and multiple-screw extruders.
The parts quoted in the following Examples represent parts, by weight, while the percentages quoted represent percentages, by weight.
Le A 21 048 ~22~
EXAMPLES
COmpQnents used:
I. A polycarbonate of bisphenol-A, phenol and phosgene, relative viscosity 1.285, as measured on a 0.5% solution in dichloromethane at 25C.
II. A polycarbonate of o,o,o',o'-tetramethyl bisphenol-A, phenol and phosgene, relative viscosity 1.29, as measured on a 0.5% solution ln dichloromethane at 25C.
III. A core-shell-type graft polymer having the following composition (expressed in the ratios, by weight, between its constituen-t monomers): n-butyl acrylate/1,3-butane diol diacrylate/diallyl maleate/methyl methacrylate = 79.2:0.4:0.4:20Ø
IV. A graft polymer of 80 parts of cross-linked polybutyl acrylate having a polybutadiene core as the graft base and 20 parts of methyl methacrylate, as the graft monomer.
V. A graft polymer of 90 parts of cross-linked polybutyl acrylate having a polybutadiene core as the graft base and 7.2 parts of styrene and 2.8 parts of acrylonitrile as the graft monomer.
Production of the moulding compositions:
The components (in the ratio shown in the Table) were melted and homogenised under nitrogen in a twin-screw extruder.
The melt strand of the moulding compositions according to the present invention was degassed before leaving the extrusion nozzle, cooled in water, granulated and dried.
Standard small test bars were injection-moulded from the granulate and tested for impact strength and notched impact strength in accordance with DIN 53 453. In addition, plates were produced for testing multiaxial impact strength.
~32Z3~
Multiaxial impact strength was determined by the EFTR (electronic force/travel recording) test according to DIN 53 443, page 2; penetration of a plate measuring 3 x 60 x 60 mm by a 35 kg weight fixed to a spike (spherical point 20 mm in diameter) dropped from a height of 1 metre.
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4~
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Z
Claims (6)
PROPERTY OR PRIVILEGE IS CALIMED ARE DEFINED AS FOLLOWS:
1. A thermoplastic moulding composition comprising:
(A) 100 parts, by weight, of aromatic polycarbonate; and (B) from 1 to 30 parts, by weight, of a graft polymer having a glass transition temperature below -20°C;
characterised in that the aromatic polycarbonate (A) consists of 80 to 100% of o,o,o',o'-tetramethyl bisphenol polycarbonate and in that the graft polymer (B) is a graft polymer of:
(a) from 25 to 98%, by weight, based on the graft polymer, of an acrylate rubber having a glass transition temperature below -20°C, as the graft base; and (b) from 2 to 75%, by weight, based on the graft polymer, of at least one polymerisable, ethylenically unsaturated monomer of which the homo- or co-polymer(s) formed in the absence of (a) would have a glass transition temperature above 25°C, as the graft monomer.
(A) 100 parts, by weight, of aromatic polycarbonate; and (B) from 1 to 30 parts, by weight, of a graft polymer having a glass transition temperature below -20°C;
characterised in that the aromatic polycarbonate (A) consists of 80 to 100% of o,o,o',o'-tetramethyl bisphenol polycarbonate and in that the graft polymer (B) is a graft polymer of:
(a) from 25 to 98%, by weight, based on the graft polymer, of an acrylate rubber having a glass transition temperature below -20°C, as the graft base; and (b) from 2 to 75%, by weight, based on the graft polymer, of at least one polymerisable, ethylenically unsaturated monomer of which the homo- or co-polymer(s) formed in the absence of (a) would have a glass transition temperature above 25°C, as the graft monomer.
2. A moulding composition as claimed in Claim 1, character-ised in that the graft polymer (B) is produced from 85 to 97%, by weight, of graft base (a) and from 3 to 15%, by weight, of graft monomer (b).
3. A moulding composition as claimed in Claim 1, character-ised in that, to produce the graft polymer (B), the monomer (b) was grafted onto the completely broken latex of (a), suspended in water, in the absence of suspending agents.
4. A moulding composition as claimed in Claim 1, 2 or 3, characterised in that it contains glass fibre as a reinforcing material.
5. A moulding composition as claimed in Claim 1, 2 or 3, characterised in that the aromatic polycarbonate (A) consists at least partly of 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane polycarbonate.
6. A moulding composition as claimed in Claim 1, 2 or 3, characterised in that the aromatic polycarbonate (A) is a mixture of bisphenol-A- and o,o,o',o'-tetramethyl bisphenol-A-polycarbo-nate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3118861.3 | 1981-05-13 | ||
| DE19813118861 DE3118861A1 (en) | 1981-05-13 | 1981-05-13 | "THERMOPLASTIC MOLDS MADE OF AROMATIC POLYCARBONATE AND GRAFT POLYMERISATE" |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1182236A true CA1182236A (en) | 1985-02-05 |
Family
ID=6132111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000402688A Expired CA1182236A (en) | 1981-05-13 | 1982-05-11 | Thermoplastic moulding compositions of aromatic polycarbonate and graft polymer of o,o,o',o' tetra- methyl bisphenol polycarbonate and a graft polymer with an acrylate rubber base |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0064692B1 (en) |
| JP (1) | JPS57195146A (en) |
| AU (1) | AU8358082A (en) |
| CA (1) | CA1182236A (en) |
| DE (1) | DE3118861A1 (en) |
| ES (1) | ES8307015A1 (en) |
| ZA (1) | ZA823273B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902746A (en) * | 1987-12-22 | 1990-02-20 | Bayer Aktiengesellschaft | Use of mixtures of polycarbonates and styrene polymers as substrates for optical storage media |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515921A (en) * | 1982-07-21 | 1985-05-07 | Mobay Chemical Corporation | Polycarbonate compositions having a high impact strength and melt flow rate |
| DE3245292A1 (en) * | 1982-12-08 | 1984-06-20 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| JPS60501111A (en) * | 1983-04-18 | 1985-07-18 | アモコ、コ−ポレ−ション | Improved polycarbonate blend |
| JPS59221350A (en) * | 1983-06-01 | 1984-12-12 | Daicel Chem Ind Ltd | Heat-resistant and impact-resistant resin composition |
| DE3344101A1 (en) * | 1983-12-07 | 1985-06-13 | Bayer Ag, 5090 Leverkusen | USE OF HALOGEN-FREE POLYCARBONATES BASED ON BIS- (3,5-DIMETHYL-4-HYDROXYPHENYL) METHANE IN COMBINATION WITH POLYMERISATES AS A FLAME RETARDANT |
| DE3436815A1 (en) * | 1984-10-06 | 1986-04-10 | Basf Ag, 6700 Ludwigshafen | SELF-EXTINGUISHING THERMOPLASTIC MOLD |
| DE3436816A1 (en) * | 1984-10-06 | 1986-04-10 | Basf Ag, 6700 Ludwigshafen | SELF-EXTINGUISHING THERMOPLASTIC MOLD |
| US4883841A (en) * | 1988-10-05 | 1989-11-28 | The B.F. Goodrich Company | Polycarbonate compositions having multiple phase impact modifiers therein |
| JPH04136069A (en) * | 1990-09-26 | 1992-05-11 | Kanegafuchi Chem Ind Co Ltd | Resin composition |
| US5384353A (en) * | 1993-05-12 | 1995-01-24 | General Electric Company | Glass reinforced PC/ABS blend with toughness |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2259564C3 (en) * | 1972-12-06 | 1979-07-26 | Bayer Ag, 5090 Leverkusen | Thermoplastic molding compounds |
| DE2329646A1 (en) * | 1973-06-09 | 1975-01-09 | Bayer Ag | TRANSPARENT MOLDINGS |
| DE2329585C2 (en) * | 1973-06-09 | 1984-01-05 | Bayer Ag, 5090 Leverkusen | Polycarbonate molding compounds |
| DE2717165A1 (en) * | 1977-04-19 | 1978-11-02 | Bayer Ag | THERMOPLASTIC MOLDING COMPOUNDS MADE FROM POLYCARBONATE AND ABS POLYMERIZED |
-
1981
- 1981-05-13 DE DE19813118861 patent/DE3118861A1/en not_active Withdrawn
-
1982
- 1982-04-30 EP EP82103699A patent/EP0064692B1/en not_active Expired
- 1982-05-11 CA CA000402688A patent/CA1182236A/en not_active Expired
- 1982-05-11 AU AU83580/82A patent/AU8358082A/en not_active Abandoned
- 1982-05-12 ZA ZA823273A patent/ZA823273B/en unknown
- 1982-05-12 JP JP57078504A patent/JPS57195146A/en active Pending
- 1982-05-12 ES ES512129A patent/ES8307015A1/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4902746A (en) * | 1987-12-22 | 1990-02-20 | Bayer Aktiengesellschaft | Use of mixtures of polycarbonates and styrene polymers as substrates for optical storage media |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0064692B1 (en) | 1986-11-20 |
| JPS57195146A (en) | 1982-11-30 |
| DE3118861A1 (en) | 1982-12-02 |
| AU8358082A (en) | 1982-11-18 |
| ES512129A0 (en) | 1983-06-16 |
| EP0064692A3 (en) | 1983-03-16 |
| ES8307015A1 (en) | 1983-06-16 |
| EP0064692A2 (en) | 1982-11-17 |
| ZA823273B (en) | 1983-03-30 |
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