CA1249685A - Ageing-resistant polyamide blends - Google Patents
Ageing-resistant polyamide blendsInfo
- Publication number
- CA1249685A CA1249685A CA000491212A CA491212A CA1249685A CA 1249685 A CA1249685 A CA 1249685A CA 000491212 A CA000491212 A CA 000491212A CA 491212 A CA491212 A CA 491212A CA 1249685 A CA1249685 A CA 1249685A
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- graft
- weight
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- rubber
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
"Ageing-resistant polyamide blends"
A B S T R A C T
The invention relates to moulding compositions of ageing-resistant polyamide blends consisting of polyamides and grafted acrylates.
A B S T R A C T
The invention relates to moulding compositions of ageing-resistant polyamide blends consisting of polyamides and grafted acrylates.
Description
"Ageing-resistant polyamide blends'i This invention relates to moulding compositions of polyamides and grafted acrylates.
Polyamide moulding compositions are distinguished by the valuable technological properties thereof, such as rigidity, toughness, resistance to stress corrosion and to solvents. Unfortunately, the toughness and, in particular the impact strength of the mouldings obtained from poly-amide moulding compositions under multiaxial load are inadequate for numerous applications.
It is known from DE-OS 2,742,176 that the notched impact strength of polyamides may be considerably increased by the addition of from 5 to 40%, by weight, of a cross-linked graft polymer. Cross-linked polybutadienes grafted with esters of methacrylic acid are recommended as the graft polymers. The graft polymers are dispersed in the polyamide moulding with a particle size of greater than 0.1 ~m, preferably greater than 0.2 ~m.
Graft polymers of polybutadiene as the graft base degrade on account of the reactive double bonds. Although polyacrylate-based graft polymers do not have this disadvan-tage, they are difficult to disperse. Polyamide mouldings in which the graft polymers are present in particle sizes of mainly greater than 3 ~m do not show adequate toughness.
Although better dispersion may be obtained by applying in-tense shear forces, there is a risk in that case of partial degradation of the polyamide which in turn leads to deter-ioration of the properties.
In addition, it is known that a rubber homogenously dispersed in a polyamide matrix tends to agglomerate during thermoplastic processing, a phenomenon which is more pronoun-ced in polyacrylate rubbers than in polybutadiene rubbers.
Accordingly, an object of the present invention is not only to provide mixtures of substantially non-agglomer-ating polyacrylates characterized by ready dispersibility Le A 22 987-US
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Polyamide moulding compositions are distinguished by the valuable technological properties thereof, such as rigidity, toughness, resistance to stress corrosion and to solvents. Unfortunately, the toughness and, in particular the impact strength of the mouldings obtained from poly-amide moulding compositions under multiaxial load are inadequate for numerous applications.
It is known from DE-OS 2,742,176 that the notched impact strength of polyamides may be considerably increased by the addition of from 5 to 40%, by weight, of a cross-linked graft polymer. Cross-linked polybutadienes grafted with esters of methacrylic acid are recommended as the graft polymers. The graft polymers are dispersed in the polyamide moulding with a particle size of greater than 0.1 ~m, preferably greater than 0.2 ~m.
Graft polymers of polybutadiene as the graft base degrade on account of the reactive double bonds. Although polyacrylate-based graft polymers do not have this disadvan-tage, they are difficult to disperse. Polyamide mouldings in which the graft polymers are present in particle sizes of mainly greater than 3 ~m do not show adequate toughness.
Although better dispersion may be obtained by applying in-tense shear forces, there is a risk in that case of partial degradation of the polyamide which in turn leads to deter-ioration of the properties.
In addition, it is known that a rubber homogenously dispersed in a polyamide matrix tends to agglomerate during thermoplastic processing, a phenomenon which is more pronoun-ced in polyacrylate rubbers than in polybutadiene rubbers.
Accordingly, an object of the present invention is not only to provide mixtures of substantially non-agglomer-ating polyacrylates characterized by ready dispersibility Le A 22 987-US
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-2-in polyamides, but also to find graft products of which the particles are capable of withstanding even relatively long processing times at elevated temperature, as may occur, for example, during compounding in extruders and in the injection-moulding of glass-fibre-containing compositions, without an increase in the size of the particles beyond 3 ~m. This desirable property is hereinafter referred to in short as "processing stability".
The mixtures of polyamide and elastomeric polyacrylate-based graft polymers known from DE-OS 3,200,070 and DE-OS
2,144,528 do not show the desired range of properties.
It has now surprisingly been found that, by graft polymerization of monomers in the absence of suspending agents onto the completely broken latex of an acrylate rubber suspended in water, a powder-form graft polymer is obtained which may not only be dispersed extremely finely in poly-amides in the conventional way without particle enlargement, it also withstands even relatively long processing times at elevated temperature without particle enlargement.
The expression "dispersed extremely finely or extremely small particle size" means that the number, shape and size of the graft polymer particles to be used are still largely identical with the number, shape and size of the graft polymer particles introduced into the molten polyamide, even after homogenization.
Accordingly, the present invention relates to mixtures comprising:
(A) from 55 to 99%, by weight, preferably from 70 to 98%, by weight, more preferably from 75 to 97%, by weight, p~r~,a~onctrh~ehs/ufm; of components (A) and (B) of a B ~ polyamlde; an tB) from 1 to 45%, by weight, preferably from 2 to 30%, by weight, more preferably from 3 to 25%, by weight, based on the sum of components ~A~ and ~B), of a powder-form graft polymer comprising:
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The mixtures of polyamide and elastomeric polyacrylate-based graft polymers known from DE-OS 3,200,070 and DE-OS
2,144,528 do not show the desired range of properties.
It has now surprisingly been found that, by graft polymerization of monomers in the absence of suspending agents onto the completely broken latex of an acrylate rubber suspended in water, a powder-form graft polymer is obtained which may not only be dispersed extremely finely in poly-amides in the conventional way without particle enlargement, it also withstands even relatively long processing times at elevated temperature without particle enlargement.
The expression "dispersed extremely finely or extremely small particle size" means that the number, shape and size of the graft polymer particles to be used are still largely identical with the number, shape and size of the graft polymer particles introduced into the molten polyamide, even after homogenization.
Accordingly, the present invention relates to mixtures comprising:
(A) from 55 to 99%, by weight, preferably from 70 to 98%, by weight, more preferably from 75 to 97%, by weight, p~r~,a~onctrh~ehs/ufm; of components (A) and (B) of a B ~ polyamlde; an tB) from 1 to 45%, by weight, preferably from 2 to 30%, by weight, more preferably from 3 to 25%, by weight, based on the sum of components ~A~ and ~B), of a powder-form graft polymer comprising:
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-3-(a) from 60 to 98%, by weight, preferably from 70 to 95%, by weight, based on (B), of an acrylate rubber having a glass transition temperature below 0C, as determined by shear modulus measurements, as the graft base; and (b) from 2 to 40%, by weight, preferably from 5 to 30%, by weight, based on (B), of at least one ethylenically unsaturated monomer of which the homo- or co-polymer(s) formed in the absence of (a) have a glass transition temperature above 25C, as the graft monomer;
characterized in that the graft polymer (B) is obtained by grafting graft monomers (b) onto the completely broken latex of (a) suspended in water in the absence of suspending agents.
The powder-form graft polymer (B) obtained may then be dried and homogenized in the desired ratio with polyamide (A) in such a way that the average particle size of (B) in (A) is from 0.05 to 3 ~m, preferably from 0.1 to 2 ~m, more preferably from 0.1 to 1 ~m.
Suitable polyamides (A) are thermoplastic polyamides~
-partially crystalline polyamides. Particularly suitable partially crystalline polyamides are polyamides of which the acid component consists completely or partially of terephthalic acid andJor isophthalic acid and/or suberic acid andJor sebacic acid and/or azelaic acid and/or adipic acid and/or cyclohexane dicarboxylic acid and of which the diamine component consists completely or partially of m-and/or p- xylylene diamine and/or hexamethylene diamine andJ
or 2,2,4-trimethylhexamethylene diamine andJor 2,4,4-trimethyl-hexamethylene diàmine and/or isophorone diamine and of which the composition is known.
Other suitable polyamides are polyamides produced completely or partially from C6-C12 lactams, optionally using one or more of the above-mentioned starting components.
Particularly preferred partially crystalline poly-amides are polyamide-6, polyamide-66 and corresponding Le A 22 987-US
characterized in that the graft polymer (B) is obtained by grafting graft monomers (b) onto the completely broken latex of (a) suspended in water in the absence of suspending agents.
The powder-form graft polymer (B) obtained may then be dried and homogenized in the desired ratio with polyamide (A) in such a way that the average particle size of (B) in (A) is from 0.05 to 3 ~m, preferably from 0.1 to 2 ~m, more preferably from 0.1 to 1 ~m.
Suitable polyamides (A) are thermoplastic polyamides~
-partially crystalline polyamides. Particularly suitable partially crystalline polyamides are polyamides of which the acid component consists completely or partially of terephthalic acid andJor isophthalic acid and/or suberic acid andJor sebacic acid and/or azelaic acid and/or adipic acid and/or cyclohexane dicarboxylic acid and of which the diamine component consists completely or partially of m-and/or p- xylylene diamine and/or hexamethylene diamine andJ
or 2,2,4-trimethylhexamethylene diamine andJor 2,4,4-trimethyl-hexamethylene diàmine and/or isophorone diamine and of which the composition is known.
Other suitable polyamides are polyamides produced completely or partially from C6-C12 lactams, optionally using one or more of the above-mentioned starting components.
Particularly preferred partially crystalline poly-amides are polyamide-6, polyamide-66 and corresponding Le A 22 987-US
-4-copolyamides.
The polyamides should preferably have a relative viscosity (as measured using a 1%, by weight, solution in _-cresol at 25C) of from 2.0 to 5.0, more preferably from 2.5 to 4.0 The acrylate rubbers (B) (a) are preferably polymers of acrylates, optionallv containing up to 40%, by weight, of other polymerizable, ethylenically unsaturated monomers. If the acrylate rubbers used as the graft base (a) are themselves graft products containing a diene rubber core, the diene rubber core is not included in the calcul-ation of that percentage. Preferred polymerizable acrylates include C1-C8 alkyl esters, for example methyl, ethyl, butyl, octyl and 2-ethyl hexyl esters; halogenated alkyl esters, preferably halogen C1-C8 alkyl esters, such as chloroethylacrylate, and aromatic esters, such as benzylacrylate and phenylethylacrylate. They may be used either individually or in admixture.
The acrylate rubbers (a) may be uncross-linked, cross-linked and, preferably, partially cross-linked.
Monomers c.ontaining more than one polymerizable double bond may be copolymerized for cross-linking.
Preferred examples of cross-linking monomers are esters of unsaturated monocarboxylic acids containing from 3 to 8 carbon atoms and unsaturated monohydric alcohols containing from 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 dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate and isocyanurate, tris-acrylol-s-triazines, more especially triallyl cyanurate;
polyfunctional vinyl compounds, such as di- and tri-vinyl benzenes; and also triallyl phosphate and diallyl phthalate.
Preferred cross-linking monomers are allyl meth-acrylate, ethylene glycol dimethacrylate, diallyl phthalate Le A 22 987-US
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,5,
The polyamides should preferably have a relative viscosity (as measured using a 1%, by weight, solution in _-cresol at 25C) of from 2.0 to 5.0, more preferably from 2.5 to 4.0 The acrylate rubbers (B) (a) are preferably polymers of acrylates, optionallv containing up to 40%, by weight, of other polymerizable, ethylenically unsaturated monomers. If the acrylate rubbers used as the graft base (a) are themselves graft products containing a diene rubber core, the diene rubber core is not included in the calcul-ation of that percentage. Preferred polymerizable acrylates include C1-C8 alkyl esters, for example methyl, ethyl, butyl, octyl and 2-ethyl hexyl esters; halogenated alkyl esters, preferably halogen C1-C8 alkyl esters, such as chloroethylacrylate, and aromatic esters, such as benzylacrylate and phenylethylacrylate. They may be used either individually or in admixture.
The acrylate rubbers (a) may be uncross-linked, cross-linked and, preferably, partially cross-linked.
Monomers c.ontaining more than one polymerizable double bond may be copolymerized for cross-linking.
Preferred examples of cross-linking monomers are esters of unsaturated monocarboxylic acids containing from 3 to 8 carbon atoms and unsaturated monohydric alcohols containing from 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 dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate and isocyanurate, tris-acrylol-s-triazines, more especially triallyl cyanurate;
polyfunctional vinyl compounds, such as di- and tri-vinyl benzenes; and also triallyl phosphate and diallyl phthalate.
Preferred cross-linking monomers are allyl meth-acrylate, ethylene glycol dimethacrylate, diallyl phthalate Le A 22 987-US
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,5,
-5-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, tri-allyl benzenes.
The cross-linking monomers are preferably used in quantities of from 0.02 to 5%, by weight, more preferably from 0.05 to 2%, by weight, based on the graft base (a).
Cyclic cross-linking monomers containing at least three ethylenically unsaturated groups are advantageously used in quantities of less than 1%, by weight, based on the graft base (a).
Preferred "other" polymerizable ethylenically unsaturated monomers which may optionally be used in addition to the acrylates in the production of the graft base (a) are, for example, acrylonitrile, styrene, a-methylstyrene, acrylamides, vinyl C1-C6 alkyl ethers.
Preferred acrylate rubbers as the graft base (a) are emulsion polymers which have a gel content of >,60%, by weight.
The gel content of the graft base (a) is determined in dimethyl formamide at 25C (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme Verlag, Stuttgart 1977).
The graft base (a) may also be an acrylate rubber which accumulates in the form of an aqueous emulsion (latex) and of which the latex particles contain from 1 to 20%, by weight, preferably from 1 to 10%, by weight, based on (a), of monomers already grafted on in aqueous emulsion of which the homo- or co-polymers have glass temperatures above 0C.
Preferred monomers such as these to be grafted on are alkyl acrylates, alkyl methacrylates, styrene, acryl-onitrile, a-methylstyrene and/or vinyl acetate.
The graft bases (a) are produced, for example, by emulsion polymerization or emulsion graft polymerization.
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Particularly preferred cross-linking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloyl hexahydro-s-triazine, tri-allyl benzenes.
The cross-linking monomers are preferably used in quantities of from 0.02 to 5%, by weight, more preferably from 0.05 to 2%, by weight, based on the graft base (a).
Cyclic cross-linking monomers containing at least three ethylenically unsaturated groups are advantageously used in quantities of less than 1%, by weight, based on the graft base (a).
Preferred "other" polymerizable ethylenically unsaturated monomers which may optionally be used in addition to the acrylates in the production of the graft base (a) are, for example, acrylonitrile, styrene, a-methylstyrene, acrylamides, vinyl C1-C6 alkyl ethers.
Preferred acrylate rubbers as the graft base (a) are emulsion polymers which have a gel content of >,60%, by weight.
The gel content of the graft base (a) is determined in dimethyl formamide at 25C (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme Verlag, Stuttgart 1977).
The graft base (a) may also be an acrylate rubber which accumulates in the form of an aqueous emulsion (latex) and of which the latex particles contain from 1 to 20%, by weight, preferably from 1 to 10%, by weight, based on (a), of monomers already grafted on in aqueous emulsion of which the homo- or co-polymers have glass temperatures above 0C.
Preferred monomers such as these to be grafted on are alkyl acrylates, alkyl methacrylates, styrene, acryl-onitrile, a-methylstyrene and/or vinyl acetate.
The graft bases (a) are produced, for example, by emulsion polymerization or emulsion graft polymerization.
Le A 22 987-US
-6-However, they may also be obtained by preparing an acrylate rubber by solution or mass polymerization, subsequently grafting on the graft monomers and then converting these rubbers into an aqueous emulsion which is suitable for further grafting processes.
Acrylate rubbers as the graft base (a) may also be products which contain a cross-linked diene rubber of one or more conjugated dienes, such as polybutadiene, or a copolymer of a conjugated diene with an ethylenically unsaturated monomer, such as styrene and/or acrylonitrile, as core.
The graft base (a) may contain from 0.1 to 80%, by weight, preferably from 10 to 50%, by weight, based on (a), of the polybutadiene core. The shell and core of the graft base, independently of one another, may be uncross-linked, partially cross-linked or highly cross-lin~ed.
Accordingly, preferred graft bases (a) are acrylate rubbers containing at least 20%, by weight, of acrylate units which may be selected from the following:
20 (1) polyacrylate homo- and copolymers;
(2) polyacrylate homo- and copolymers containing a diene rubber core;
(3) emulsion graft polymers of polyacrylate homo- or copolymers optionally containing a diene rubber core and ethylenically unsaturated polymerizable monomers.
The grafting yield, i.e. the quotient of the quantity of monomer (b) grafted on and the quantity of graft monomer (b) used, generally amounts to from 20 to 80%, by weight.
The grafting yield may be determined as described in M.
Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik, Vol. 1, Georg Thieme Verlag, Stuttgart 1977.
Preferred graft monomers (b) are ~-methyl styrene, styrene, acrylonitrile, methyl methacrylate or mixtures of these monomers. Preferred graft monomer mixtures are mixtures of styrene and acrylonitrile in a ratio, by weight, Le A 22 987-US
-
Acrylate rubbers as the graft base (a) may also be products which contain a cross-linked diene rubber of one or more conjugated dienes, such as polybutadiene, or a copolymer of a conjugated diene with an ethylenically unsaturated monomer, such as styrene and/or acrylonitrile, as core.
The graft base (a) may contain from 0.1 to 80%, by weight, preferably from 10 to 50%, by weight, based on (a), of the polybutadiene core. The shell and core of the graft base, independently of one another, may be uncross-linked, partially cross-linked or highly cross-lin~ed.
Accordingly, preferred graft bases (a) are acrylate rubbers containing at least 20%, by weight, of acrylate units which may be selected from the following:
20 (1) polyacrylate homo- and copolymers;
(2) polyacrylate homo- and copolymers containing a diene rubber core;
(3) emulsion graft polymers of polyacrylate homo- or copolymers optionally containing a diene rubber core and ethylenically unsaturated polymerizable monomers.
The grafting yield, i.e. the quotient of the quantity of monomer (b) grafted on and the quantity of graft monomer (b) used, generally amounts to from 20 to 80%, by weight.
The grafting yield may be determined as described in M.
Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik, Vol. 1, Georg Thieme Verlag, Stuttgart 1977.
Preferred graft monomers (b) are ~-methyl styrene, styrene, acrylonitrile, methyl methacrylate or mixtures of these monomers. Preferred graft monomer mixtures are mixtures of styrene and acrylonitrile in a ratio, by weight, Le A 22 987-US
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-7-of from 90:10 to 50:50. The preferred graft monomer is methyl methacrylate.
The powder-form graft polymers (B) may be prepared as follows:
First, the monomers of the graft base (a) are polymer-ized in emulsion in known manner in the presence of radical-forming initiators so that particles having an average particle diameter d50 of from 0.05 to 3 ~m are formed. The monomer mixture may be introduced into the polymerization system continuously or semi-continuously at the beginning of or during the polymerization process.
If a cross-linked acrylate rubber containing a cross-linked diene rubber as core is to be used as the graft base (a), the diene rubber is first prepared in latex form by emulsion polymerization of a conjugated diene. The graft monomers are then emulsified in the diene rubber latex, again in aqueous emulsion, and the resulting emulsion polymerized in known manner in the presence of radical-forming initiators. The thus-formed acrylate rubber shell may be cross-linked by using cross-linking monomers during the actual production process.
In this production of a graft base (a) already partially grafted in emulsion, the formation of new particles must be prevented as far as possible. An emulsion stabilizer must be present in a quantity sufficient to cover the surface of the particles. The size of these particles may be varied within wide limits according to the conduct of the reaction. If an agglomerated latex is used as the polydiene core to obtain large particles, the acrylate rubber particles may contain several diene rubber cores. Polymerization of the acrylate rubber may also be controlled in such a way that acrylate rubber particles with and without a diene rubber core are formed alongside one another. In certain circumstances, mixtures of the type in question may also be used as the graft base (a).
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The powder-form graft polymers (B) may be prepared as follows:
First, the monomers of the graft base (a) are polymer-ized in emulsion in known manner in the presence of radical-forming initiators so that particles having an average particle diameter d50 of from 0.05 to 3 ~m are formed. The monomer mixture may be introduced into the polymerization system continuously or semi-continuously at the beginning of or during the polymerization process.
If a cross-linked acrylate rubber containing a cross-linked diene rubber as core is to be used as the graft base (a), the diene rubber is first prepared in latex form by emulsion polymerization of a conjugated diene. The graft monomers are then emulsified in the diene rubber latex, again in aqueous emulsion, and the resulting emulsion polymerized in known manner in the presence of radical-forming initiators. The thus-formed acrylate rubber shell may be cross-linked by using cross-linking monomers during the actual production process.
In this production of a graft base (a) already partially grafted in emulsion, the formation of new particles must be prevented as far as possible. An emulsion stabilizer must be present in a quantity sufficient to cover the surface of the particles. The size of these particles may be varied within wide limits according to the conduct of the reaction. If an agglomerated latex is used as the polydiene core to obtain large particles, the acrylate rubber particles may contain several diene rubber cores. Polymerization of the acrylate rubber may also be controlled in such a way that acrylate rubber particles with and without a diene rubber core are formed alongside one another. In certain circumstances, mixtures of the type in question may also be used as the graft base (a).
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-8-If an already grafted rubber is to be used as the graft base (a) an aqueous suspension of that graf`ted rubber must first be prepared.
After preparation of the graft base (a), the emulsion is completely broken or coagulated, i.e. by electrolytes, acids, bases, mechanical forces or temperature. It is preferred to use aqueous solutions of acids and/or salts at elevated temperatures, more especially at temperatures of from 30 to 100C. A heterogeneous suspension of the polymer in the form of discrete polymer particles of different shape and size in aqueous phase is obtained in this way. The particle characteristics may be influenced in the coagulation medium by variation of the precipitation parameters.
The process is favourably influenced by stirring the suspensions.
After preparation of the polymer suspension in the aqueous coagulation medium, the graft monomers (b), option-ally in combination with regulators, radical initiators (more especially water-soluble persulphates) or antioxidants are introduced into the stirred polymer suspension, preferably at temperatures of from 30 to 100C, and radically polymerized. The addition of suspension media should be avoided. The graft polymer (B) is then isolated, for example by filtration or centrifugation, and subsequently dried. The process is suitable for batch, semi-continuous or fully continuous operation.
After isolation and drying, the graft polymers (B) are storable, free-flowing, non-sticking powders which may readily be metered by conventional powder metering units for mixing with the polyamides (A). One particular advantage lies in the fact that the graft products (B) may readily be dispersed in the molten polyamide (A) without a need for intense shear forces to be applied.
If the graft polymers (B) used in accordance with the present invention contain fractions of polymer formed by Le A 22 987-US
12~685 _9_ polymerization of ungrafted parts of the graft monomers (b), the expression "graft polymer (B)", irrespective of the degree of grafting, is to be understood to ~ean the sum of the reaction products formed by polymerization of the graft monomers (b) in the presence of the graft base (a).
The average particle size d50 is the diameter above which 50%, by weight, and below which 50%, by weight, of the dispersed particles lie. It may be determined by ultra-centrifuge measurements (W. Scholtan, H. Lange, Kolloid. Z.
and Z. Polymere 250 (1972), 782 - 796) or by electron microscopy and subsequent particle counting (G. Kampf, H.
Schuster, Angew. Makromolekulare Chemie 14, (1970), 111 -129) or by light scattering measurements.
The expression "in the absence of suspending agents"
used herein means the absence of substances which are able, depending on quantity and type, to suspend the graft monomers (b) in the aqueous phase. This definition does not exclude the presence of substances which may have had a suspend~nE effect, for example in the production of a grafted graft base (a). In such cases, the coagulant or precipitant used to break the latex (a) has to be used in a quantity which compensates the suspending effect of the substances used in the initial stage. In other words, it is important in accordance with the present invention to ensure that the graft monomers (b) do not form a (stable) emulsion in the aqueous phase.
The moulding compositions according to the present invention may contain conventional additives, such as lubricants and mould release agents, nucleating agents, stabilizers, fillers and reinforcing materials, flameproof-ing 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.
Preferred reinforcing materials are glass fibres. Preferred Le A 22 987-US
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fillers, which may also have a reinforcing effect, are glass beads, mica, silicates, feldspar, quartz, talcum, titanium dioxide, wollastonite.
The flameproofed moulding compositions contain flameproofing agents in a concentration of generally less than 30%, by weight, based on the flameproofed moulding compositions.
The flameproofing agents used may be various known flameproofing agents, such as cyclic chlorine compounds, melamine and its salts, such as melamine cyanurate or melamine sulphate, red phosphorus.
The mixtures of polyamide (A) and graft rubber (B) may be prepared in conventional mixing units, such as mixing rolls, kneaders, single-screw and multi-screw extruders. The temperature prevailing during preparation of the mixtures should be at least 10C and preferably at most 90C above the melting point of the polyamide.
Even with low contents of graft polymer (B), the mixtures according to the present invention are distin-guished by a considerable improvement in impact strengthunder multiaxial load, even where polyamides of relatively low molecular weight are used. Another surprising property of the mixtures is the high flow line resistance thereof.
In addition, they are distinguished by high dimensional stability under heat and by surprisingly high resistance to ageing in hot air.
Commensurate with this range of properties, the mixtures according to the present invention may be used anywhere in the injection moulding and extrusion field where high multiaxial toughness in combination with high dimensional stability under heat and resistance to hot air is required, as is the case for example with parts of mechanical and electrical units in the engine compartment of motor vehicles and with temperature-stressed domestic appliances.
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In the following Examples, the parts are parts, by weight, and the percentages percentages, by weight.
EXAMPLES
1. Production of the graft base (a) 1.1 Production of a polybutadiene latex In a reactor, the following emulsion was polymerized while stirring at 65C until the monomers had reacted almost completely (approx. 22 hours):
100 parts of butadiene 1.8 parts of the sodium salt of disproportionated abietic acid, 0.257 part of sodium hydroxide, 0.3 part of n-dodecyl mercaptan, 1.029 parts of sodium ethylene diamine tetraacetate, 0.023 part of potassium persulphate and 176 parts of water.
A latex is obtained which contains polybutadiene particles having an average diameter (d50) of 0.1 ~m in a concen-tration of approx. 36%.
1.2 Production of acrylate rubber containing polydiene cores The following mixture is introduced into a reactor with stirring at 63C:
200 parts of latex 1.1, 5000 parts of water, 14 parts of potassium persulphate, 0.0124 part of triallyl cyanurate and 30 399.09 part of n-butylacrylate.
The following mixtures are separately introduced into the reactor over a period of 5 hours at 63C:
Mixture 1: 90 parts of sodium C14-C18 alkyl sulphonate and 11900 parts of water.
Le A 22 987-US
lZ49685 Mixture 2: 23.09 parts of triallyl cyanurate and 10101 parts of n-butylacrylate.
Polymerization is then completed over a period of 2 hours at 65C. The polymers formed have gel contents of from 85 to 95% and average particle diameters (d50) of 0.5 ~m (polymer content in the latex: 38%).
2. Production of the graft polymers (B) 2.1 Graft polymer of 80% of acrylate rubber 1.2 and 20% of methyl methacrylate 18800 parts of water and 245 parts of magnesium sulphate (MgS04 . xH20) are introduced into a reactor at 70C. 11200 parts of latex 1.2 are then run into the reactor with stirring over a period of 2 hours.
After this addition, 1 part of potassium persulphate is introduced into the reactor. 1276 parts of methyl methacrylate are then uniformly introduced with stirring over a period a 1 hour. Thereafter, the suspension is stirred for 1 hour at 90C. The polymer may then be isolated (graft polymer K).
3. Production of the graft polymers (B) containing remains of monomers (b) grafted both in emulsion and also in suspension 3.1 Production of the emulsion graft polymers 3.1.1 Emulsion graft polymer of 80% of acrylate rubber 1.2 and 20% of methyl methacrylate.
30 2926 parts of latex 1.2, 1.5 parts of potassium persulphate and 90 parts of water are introduced into a reactor. The following mixtures are separately introduced into the reactor at 65C:
Mixture 1: 278 parts of methyl methacrylate Le A 22 987-US
Mixture 2: 150 parts of water and 4 parts of sodium C~4 C18 alkyl sulphonate Polymerization is then completed over a period of 4 hours at 65C (graft polymer L). Polymer content in the latex: 37.8%.
3.1. 2 Emulsion graft polymer of 80% of acrylate rubber 1.2, 14.4% of styrene and 5. 6% of acrylonitrile The prodcedure is as in Example 3.1.1, except that a mixture of 77 parts of acrylonitrile and 201 parts of styrene is introduced as mixture 1 instead of methyl methacrylate (graft polymer M) 3.2 Production of the graft polymers (B) from the emulsion graft polymers 3. 2.1 Graft polymer of 70% of acrylate rubber and 30% of methyl methacrylate 20 18800 parts of water and 240 parts of magnesium sulphate are introduced into a reactor at 70C. 11200 parts of latex 3.1.1 (graft polymer L) are run into the reactor with 25 stirring over a period of 2 hours. After the addition, 1 part of potassium persulphate is introduced into the reactor. 529 parts of methyl methacrylate are then uniformly introduced with stirring over a period of 1 hour, after which the suspension is stirred for 1 hour at 90~C.
30 The polymer is then isolated (graft polymer ~).
3.2.2 Graft product of 70% of acrylate rubber, 21.6% of styrene and 8.4% of acrylonitrile Le A 22 987-US
The procedure is as in Example 3.2.1, except that latex 3.1.2 containing graft polymer ~ is used instead of latex - 3.1.1 and a mixture of :
148 parts of acrylonitrile and 381 parts of styrene is incorporated instead of methyl methacrylate (graft polymer 0).
4. Production of comparison graft polymers Graft polymer, type NP
A copolymer of a graft base of :
69.45 parts of n-butylacrylate, 0.35 part of 1,3-butylene diacrylate and 0.28 part of allyl methacrylate and a graft shell of 19.95 parts of methyl methacrylate and
After preparation of the graft base (a), the emulsion is completely broken or coagulated, i.e. by electrolytes, acids, bases, mechanical forces or temperature. It is preferred to use aqueous solutions of acids and/or salts at elevated temperatures, more especially at temperatures of from 30 to 100C. A heterogeneous suspension of the polymer in the form of discrete polymer particles of different shape and size in aqueous phase is obtained in this way. The particle characteristics may be influenced in the coagulation medium by variation of the precipitation parameters.
The process is favourably influenced by stirring the suspensions.
After preparation of the polymer suspension in the aqueous coagulation medium, the graft monomers (b), option-ally in combination with regulators, radical initiators (more especially water-soluble persulphates) or antioxidants are introduced into the stirred polymer suspension, preferably at temperatures of from 30 to 100C, and radically polymerized. The addition of suspension media should be avoided. The graft polymer (B) is then isolated, for example by filtration or centrifugation, and subsequently dried. The process is suitable for batch, semi-continuous or fully continuous operation.
After isolation and drying, the graft polymers (B) are storable, free-flowing, non-sticking powders which may readily be metered by conventional powder metering units for mixing with the polyamides (A). One particular advantage lies in the fact that the graft products (B) may readily be dispersed in the molten polyamide (A) without a need for intense shear forces to be applied.
If the graft polymers (B) used in accordance with the present invention contain fractions of polymer formed by Le A 22 987-US
12~685 _9_ polymerization of ungrafted parts of the graft monomers (b), the expression "graft polymer (B)", irrespective of the degree of grafting, is to be understood to ~ean the sum of the reaction products formed by polymerization of the graft monomers (b) in the presence of the graft base (a).
The average particle size d50 is the diameter above which 50%, by weight, and below which 50%, by weight, of the dispersed particles lie. It may be determined by ultra-centrifuge measurements (W. Scholtan, H. Lange, Kolloid. Z.
and Z. Polymere 250 (1972), 782 - 796) or by electron microscopy and subsequent particle counting (G. Kampf, H.
Schuster, Angew. Makromolekulare Chemie 14, (1970), 111 -129) or by light scattering measurements.
The expression "in the absence of suspending agents"
used herein means the absence of substances which are able, depending on quantity and type, to suspend the graft monomers (b) in the aqueous phase. This definition does not exclude the presence of substances which may have had a suspend~nE effect, for example in the production of a grafted graft base (a). In such cases, the coagulant or precipitant used to break the latex (a) has to be used in a quantity which compensates the suspending effect of the substances used in the initial stage. In other words, it is important in accordance with the present invention to ensure that the graft monomers (b) do not form a (stable) emulsion in the aqueous phase.
The moulding compositions according to the present invention may contain conventional additives, such as lubricants and mould release agents, nucleating agents, stabilizers, fillers and reinforcing materials, flameproof-ing 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.
Preferred reinforcing materials are glass fibres. Preferred Le A 22 987-US
12~968S
fillers, which may also have a reinforcing effect, are glass beads, mica, silicates, feldspar, quartz, talcum, titanium dioxide, wollastonite.
The flameproofed moulding compositions contain flameproofing agents in a concentration of generally less than 30%, by weight, based on the flameproofed moulding compositions.
The flameproofing agents used may be various known flameproofing agents, such as cyclic chlorine compounds, melamine and its salts, such as melamine cyanurate or melamine sulphate, red phosphorus.
The mixtures of polyamide (A) and graft rubber (B) may be prepared in conventional mixing units, such as mixing rolls, kneaders, single-screw and multi-screw extruders. The temperature prevailing during preparation of the mixtures should be at least 10C and preferably at most 90C above the melting point of the polyamide.
Even with low contents of graft polymer (B), the mixtures according to the present invention are distin-guished by a considerable improvement in impact strengthunder multiaxial load, even where polyamides of relatively low molecular weight are used. Another surprising property of the mixtures is the high flow line resistance thereof.
In addition, they are distinguished by high dimensional stability under heat and by surprisingly high resistance to ageing in hot air.
Commensurate with this range of properties, the mixtures according to the present invention may be used anywhere in the injection moulding and extrusion field where high multiaxial toughness in combination with high dimensional stability under heat and resistance to hot air is required, as is the case for example with parts of mechanical and electrical units in the engine compartment of motor vehicles and with temperature-stressed domestic appliances.
Le A 22 987-US
"
In the following Examples, the parts are parts, by weight, and the percentages percentages, by weight.
EXAMPLES
1. Production of the graft base (a) 1.1 Production of a polybutadiene latex In a reactor, the following emulsion was polymerized while stirring at 65C until the monomers had reacted almost completely (approx. 22 hours):
100 parts of butadiene 1.8 parts of the sodium salt of disproportionated abietic acid, 0.257 part of sodium hydroxide, 0.3 part of n-dodecyl mercaptan, 1.029 parts of sodium ethylene diamine tetraacetate, 0.023 part of potassium persulphate and 176 parts of water.
A latex is obtained which contains polybutadiene particles having an average diameter (d50) of 0.1 ~m in a concen-tration of approx. 36%.
1.2 Production of acrylate rubber containing polydiene cores The following mixture is introduced into a reactor with stirring at 63C:
200 parts of latex 1.1, 5000 parts of water, 14 parts of potassium persulphate, 0.0124 part of triallyl cyanurate and 30 399.09 part of n-butylacrylate.
The following mixtures are separately introduced into the reactor over a period of 5 hours at 63C:
Mixture 1: 90 parts of sodium C14-C18 alkyl sulphonate and 11900 parts of water.
Le A 22 987-US
lZ49685 Mixture 2: 23.09 parts of triallyl cyanurate and 10101 parts of n-butylacrylate.
Polymerization is then completed over a period of 2 hours at 65C. The polymers formed have gel contents of from 85 to 95% and average particle diameters (d50) of 0.5 ~m (polymer content in the latex: 38%).
2. Production of the graft polymers (B) 2.1 Graft polymer of 80% of acrylate rubber 1.2 and 20% of methyl methacrylate 18800 parts of water and 245 parts of magnesium sulphate (MgS04 . xH20) are introduced into a reactor at 70C. 11200 parts of latex 1.2 are then run into the reactor with stirring over a period of 2 hours.
After this addition, 1 part of potassium persulphate is introduced into the reactor. 1276 parts of methyl methacrylate are then uniformly introduced with stirring over a period a 1 hour. Thereafter, the suspension is stirred for 1 hour at 90C. The polymer may then be isolated (graft polymer K).
3. Production of the graft polymers (B) containing remains of monomers (b) grafted both in emulsion and also in suspension 3.1 Production of the emulsion graft polymers 3.1.1 Emulsion graft polymer of 80% of acrylate rubber 1.2 and 20% of methyl methacrylate.
30 2926 parts of latex 1.2, 1.5 parts of potassium persulphate and 90 parts of water are introduced into a reactor. The following mixtures are separately introduced into the reactor at 65C:
Mixture 1: 278 parts of methyl methacrylate Le A 22 987-US
Mixture 2: 150 parts of water and 4 parts of sodium C~4 C18 alkyl sulphonate Polymerization is then completed over a period of 4 hours at 65C (graft polymer L). Polymer content in the latex: 37.8%.
3.1. 2 Emulsion graft polymer of 80% of acrylate rubber 1.2, 14.4% of styrene and 5. 6% of acrylonitrile The prodcedure is as in Example 3.1.1, except that a mixture of 77 parts of acrylonitrile and 201 parts of styrene is introduced as mixture 1 instead of methyl methacrylate (graft polymer M) 3.2 Production of the graft polymers (B) from the emulsion graft polymers 3. 2.1 Graft polymer of 70% of acrylate rubber and 30% of methyl methacrylate 20 18800 parts of water and 240 parts of magnesium sulphate are introduced into a reactor at 70C. 11200 parts of latex 3.1.1 (graft polymer L) are run into the reactor with 25 stirring over a period of 2 hours. After the addition, 1 part of potassium persulphate is introduced into the reactor. 529 parts of methyl methacrylate are then uniformly introduced with stirring over a period of 1 hour, after which the suspension is stirred for 1 hour at 90~C.
30 The polymer is then isolated (graft polymer ~).
3.2.2 Graft product of 70% of acrylate rubber, 21.6% of styrene and 8.4% of acrylonitrile Le A 22 987-US
The procedure is as in Example 3.2.1, except that latex 3.1.2 containing graft polymer ~ is used instead of latex - 3.1.1 and a mixture of :
148 parts of acrylonitrile and 381 parts of styrene is incorporated instead of methyl methacrylate (graft polymer 0).
4. Production of comparison graft polymers Graft polymer, type NP
A copolymer of a graft base of :
69.45 parts of n-butylacrylate, 0.35 part of 1,3-butylene diacrylate and 0.28 part of allyl methacrylate and a graft shell of 19.95 parts of methyl methacrylate and
9.97 parts o~ allyl methacrylate (corresponding to DE-OS 2,726,256).
5. Production of the mixtures The following polyamides were melted in a Werner &
Pfleiderer continuous-action twin-screw extruder:
Type Q: polyamide-6 having a relative viscosity (as measured using a 1%, by weight, solution in m-cresol at 25C) of 3.5 Type R: polyamide-66 having a relative viscosity (as measured using a 1%, by weight, solution in m-cresol at 25C) of 3.5.
The graft polymer (B) was introduced into the polyamide melt under nitrogen through a second feed inlet and homo-geneously dispersed in the melt. (It may be advantageous to degas the melt before it issues from the die.) The barrel temperatures were selected in such a way that a melt Le A 22 987-US
-i249685 temperature of 275 C was guaranteed. The melt strand of the mixtures according to the present invention was cooled in water, granulated and dried. Standard small test bars tcorresponding to DIN 53 453) and plates measuring 3 x 60 x 60 mm were produced from the granulate in a conventional injection moulding machine at mould temperatures of 80C.
The test specimens were used for testing impact strength and notched impact strength (in accordance with DIN 53 543), ball indentation hardness (in accordance with DIN 53 456), Vicat dimensional stability under heat (in accordance with DIN 53 460) and also impact strength under multi-axial load using the so-called EFDR test (according to DIN 53 443, page 2, penetration of a 3 x 60 x 60 mm plate under a weight of 35 kg by a spherically tipped spike 20 mm in diameter dropped from a height of 1 m). Flow line resistance was tested in accordance with DIN 52 455 (tension test) using tension bars injected at either end. The results are shown in the following Table.
Le A 22 987-US
lZ~9685 ~1 ~ o\ ~
o-- X
a)~ ooo~ooo1~ ooo r~ O o a~ ~ o o o ~ ~Q
U~
~0 ~; U~ L~7 0 0 0 U~ O rl ~ o ~ o 14 3 ~ ~ ~ a~
~ --~a ~ In O U~ O O O U~ O ~ ~
.,1 0 CO OG 00 ) 1-- ~ ~ ~ O 00 ~ ~, -- ~ ~ ~ ~ ~ ~ ~
a~ 0~o o o o o~ ~ In o In o o co o o o -- - U~
~:: 3 ~ ~ ~ ~ o N _ Q E~ ~ O
o ~ o n o ~ ~
~: .Y ~ O 3 o u s~ ~ ~ o ~
s~ ~ ~o ~ In O In ~ o o u~ 3 ~ O ~ ~
Q~ P~ P~ O~ ~ a~
ZZ~ZZZZZ I ZZ
~ ~ Q, Lf~ ~ ~ o ~
O u~ tn ,~
~ ~ ~ ~ 1 a) Q) rl d~ U7 0 U~ 1~ O O U~ 1-- 0 In ul ~ o ~ ~1 ~1 c~ o ~ O .
''I ~ ~
O ~ 1 ~ Q rl ~1 ~ 3 z m ~ -' 3 3 .-~ ~f ~ N ~7 ~r ~ O ~1 Q X O S S ~
:, , ~ .
5. Production of the mixtures The following polyamides were melted in a Werner &
Pfleiderer continuous-action twin-screw extruder:
Type Q: polyamide-6 having a relative viscosity (as measured using a 1%, by weight, solution in m-cresol at 25C) of 3.5 Type R: polyamide-66 having a relative viscosity (as measured using a 1%, by weight, solution in m-cresol at 25C) of 3.5.
The graft polymer (B) was introduced into the polyamide melt under nitrogen through a second feed inlet and homo-geneously dispersed in the melt. (It may be advantageous to degas the melt before it issues from the die.) The barrel temperatures were selected in such a way that a melt Le A 22 987-US
-i249685 temperature of 275 C was guaranteed. The melt strand of the mixtures according to the present invention was cooled in water, granulated and dried. Standard small test bars tcorresponding to DIN 53 453) and plates measuring 3 x 60 x 60 mm were produced from the granulate in a conventional injection moulding machine at mould temperatures of 80C.
The test specimens were used for testing impact strength and notched impact strength (in accordance with DIN 53 543), ball indentation hardness (in accordance with DIN 53 456), Vicat dimensional stability under heat (in accordance with DIN 53 460) and also impact strength under multi-axial load using the so-called EFDR test (according to DIN 53 443, page 2, penetration of a 3 x 60 x 60 mm plate under a weight of 35 kg by a spherically tipped spike 20 mm in diameter dropped from a height of 1 m). Flow line resistance was tested in accordance with DIN 52 455 (tension test) using tension bars injected at either end. The results are shown in the following Table.
Le A 22 987-US
lZ~9685 ~1 ~ o\ ~
o-- X
a)~ ooo~ooo1~ ooo r~ O o a~ ~ o o o ~ ~Q
U~
~0 ~; U~ L~7 0 0 0 U~ O rl ~ o ~ o 14 3 ~ ~ ~ a~
~ --~a ~ In O U~ O O O U~ O ~ ~
.,1 0 CO OG 00 ) 1-- ~ ~ ~ O 00 ~ ~, -- ~ ~ ~ ~ ~ ~ ~
a~ 0~o o o o o~ ~ In o In o o co o o o -- - U~
~:: 3 ~ ~ ~ ~ o N _ Q E~ ~ O
o ~ o n o ~ ~
~: .Y ~ O 3 o u s~ ~ ~ o ~
s~ ~ ~o ~ In O In ~ o o u~ 3 ~ O ~ ~
Q~ P~ P~ O~ ~ a~
ZZ~ZZZZZ I ZZ
~ ~ Q, Lf~ ~ ~ o ~
O u~ tn ,~
~ ~ ~ ~ 1 a) Q) rl d~ U7 0 U~ 1~ O O U~ 1-- 0 In ul ~ o ~ ~1 ~1 c~ o ~ O .
''I ~ ~
O ~ 1 ~ Q rl ~1 ~ 3 z m ~ -' 3 3 .-~ ~f ~ N ~7 ~r ~ O ~1 Q X O S S ~
:, , ~ .
Claims (15)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A composition which comprises:
(A) from 55 to 99%, by weight, based on (A) + (B), of at least one partially crystalline polyamide;
and (B) from 1 to 45%, by weight, based on (A) + (B), of at least one powder-form graft polymer comprising:
(a) as the graft base, from 60 to 98%, by weight, based on (B), of an acrylate rubber having a glass transition temperature below 0°C, and (b) as the graft monomer, from 2-40%, by weight, based on (B), of at least one ethylenically-unsaturated monomer, wherein a polymer prepared from the graft monomer in the absence of (a) would have a glass transition temperature above 25°C; and wherein the graft polymer (B) is produced by first preparing an emulsion containing the graft base, then coagulating the emulsion to form an aqueous suspension containing the graft base and then grafting the graft monomer onto the graft base in the aqueous suspension in the absence of a suspending agent. - 2. A composition as claimed in claim 1 wherein from 70 to 98%, by weight, of (A) and from 2 to 30%, by weight, of (B) are present.
- 3. A composition as claimed in claim 2 wherein from 75 to 97%, by weight, of (A) and from 3 to 25%, by weight, of (B) are present.
- 4. A composition as claimed in claim 1 wherein (B) comprises from 70 to 95%, by weight, of (a) and from 5 to 30%, by weight, of (b).
- 5. A composition as claimed in claim 1 wherein the average particle size d50 of (B) in (A) is 0.05 to 3 µm-
- 6. A composition as claimed in claim 5 wherein the average particle size is from 0.1 to 2 µm.
- 7. A composition as claimed in claim 6 wherein the average particle size is from 0.1 to 1 µm.
- 8. A composition as claimed in claim 1 wherein (A) is selec-ted from polyamide-6, polyamide-66 and corresponding copolyamides.
- 9. A composition as claimed in claim 1 wherein the graft base is a methyl methacrylate rubber.
- 10. A composition as claimed in claim 1 wherein the graft base further comprises up to 40%, by weight, of an ethylenically-unsatu-rated comonomer.
- 11. A composition as claimed in claim 1 wherein the graft base is a graft copolymer containing a diene rubber core.
- 12. A composition as claimed in claim 10 wherein the graft base is prepared by emulsion polymerization.
- 13. A composition as claimed in claim 12 wherein the graft base is a graft copolymer containing a diene rubber core.
- 14. A composition as claimed in claim 12 wherein the graft base is comprised of an acrylonitrile or methyl methacrylate acryla-te rubber and a methylstyrene or styrene ethylenically-unsaturated comonomer.
- 15. A composition as claimed in claim 12 wherein the acrylate rubber is an acrylonitrile rubber and the ethylenically-unsaturated comonomer is styrene in an acrylonitrile to styrene ratio, by weight, or from 10:90 to 50:50.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3434820.4 | 1984-09-22 | ||
| DE19843434820 DE3434820A1 (en) | 1984-09-22 | 1984-09-22 | AGING-RESISTANT POLYAMIDE ALLOYS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1249685A true CA1249685A (en) | 1989-01-31 |
Family
ID=6246058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000491212A Expired CA1249685A (en) | 1984-09-22 | 1985-09-20 | Ageing-resistant polyamide blends |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0176011B1 (en) |
| JP (1) | JPS6185471A (en) |
| CA (1) | CA1249685A (en) |
| DE (2) | DE3434820A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0322560A3 (en) * | 1987-12-30 | 1990-11-07 | General Electric Company | Compositions comprising thermoplastic acrylate-crosslinked vinyl aromatic interpolymer elastomers and polyamides |
| DE4223202A1 (en) * | 1992-07-15 | 1994-01-20 | Basf Ag | Particulate graft copolymer |
| DE102009003034A1 (en) | 2009-05-12 | 2010-11-18 | Henkel Ag & Co. Kgaa | Color protecting detergent or cleaner |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2742176A1 (en) * | 1977-09-20 | 1979-03-29 | Bayer Ag | Impact-resistant polyamide moulding compsns. - contain added butadiene! (co)polymer substrate grafted with (meth)acrylic! acid ester and opt. (meth)acrylaminde! and (meth)acrylonitrile! |
| DE3006804A1 (en) * | 1980-02-23 | 1981-09-10 | Bayer Ag, 5090 Leverkusen | NOTCH IMPACT TOE POLYMERISATE WITH IMPROVED WEATHER RESISTANCE |
| DE3100714A1 (en) * | 1981-01-13 | 1982-08-12 | Bayer Ag, 5090 Leverkusen | RUBBER POWDER |
| DE3100748A1 (en) * | 1981-01-13 | 1982-08-26 | Bayer Ag, 5090 Leverkusen | RUBBER POWDER |
| DE3117052A1 (en) * | 1981-04-29 | 1982-11-18 | Bayer Ag, 5090 Leverkusen | "AGING-RESISTANT, PROCESS-STABLE MIXTURES OF HIGH TOUGHNESS BASED ON THERMOPLASTIC POLYESTER" |
| DE3200070A1 (en) * | 1982-01-05 | 1983-07-14 | Bayer Ag, 5090 Leverkusen | IMPACT TOOL POLYAMIDE MOLDS |
| DE3339000A1 (en) * | 1983-07-09 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC POLYAMIDE MOLDS WITH HIGH TOUGHNESS |
| US4495324A (en) * | 1983-10-24 | 1985-01-22 | Allied Corporation | Glass reinforced polyamide composition containing acrylic core/shell polymer |
-
1984
- 1984-09-22 DE DE19843434820 patent/DE3434820A1/en not_active Withdrawn
-
1985
- 1985-09-12 EP EP85111549A patent/EP0176011B1/en not_active Expired - Lifetime
- 1985-09-12 DE DE8585111549T patent/DE3585253D1/en not_active Expired - Lifetime
- 1985-09-20 JP JP60206750A patent/JPS6185471A/en active Pending
- 1985-09-20 CA CA000491212A patent/CA1249685A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0176011A3 (en) | 1987-06-16 |
| JPS6185471A (en) | 1986-05-01 |
| DE3585253D1 (en) | 1992-03-05 |
| EP0176011B1 (en) | 1992-01-22 |
| DE3434820A1 (en) | 1986-04-03 |
| EP0176011A2 (en) | 1986-04-02 |
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