CA1196130A - High-impact polyamide moulding compositions - Google Patents
High-impact polyamide moulding compositionsInfo
- Publication number
- CA1196130A CA1196130A CA000418879A CA418879A CA1196130A CA 1196130 A CA1196130 A CA 1196130A CA 000418879 A CA000418879 A CA 000418879A CA 418879 A CA418879 A CA 418879A CA 1196130 A CA1196130 A CA 1196130A
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- weight
- moulding composition
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Classifications
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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
-
- 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
Abstract
High-impact polyamide moulding compositions Abstract of the Disclosure High-impact moulding compositions of polyamides and particulate graft polymers of a diene rubber as the core surrounded by a crosslinked acrylate rubber as the first, respectively inside shell and by a homopolymer or co-polymer of (.alpha.-methyl) styrene and/or a (meth)acrylic acid derviative as the second,respectively outside shell.
Description
~6~
~i~h-impact polyamide moulding compositions This invention relates to high-impact ~esistant ~xtures of polyamides and graft copolymers comprising a diene rubber as the core surrounded by at least two different shells.
Polyamides are of importance in the production of fibres and mouldings by virtue of their valuable technological properties, for example, their stiffness and toughness, their resistance to corrosion caused by stress crazing and their solvent resistance. However, their toughness and, in particular, their impact strength under multiaxial stressing are inadequate for many applications 9 particularly for components having large surface areas.
There are numerous proposals for increasing the toughness of polyamides by the addition of other polymers, particularly those based on modified elastomers and polyolefins. Unfortunately, this improvement in toughness is generally obtained at the expense of a significant deterioration in the flow of the polyamides.
In addition, multiaxial impact strength is not achieved to the required extent.
~ -OS No. 24 35 266 des~ribes filled moulding composi-tions of polyamides, fillers and ~raft copolymers havin~ increased impac-t ~ in the dry state and a-t low temperatures coupled with improved toughness under multiaxial stressing, the graft copolymer having been produced by grafting styrene and~or methacrylic acid esters onto a copolymer of acrylate and a comonomer containing two non-conjugated olefinic double bonds.
Although this DE-OS describes polyamide moulding compositions~having improved multiaxial impact strength, the flow of the moulding compositions in question is unsatisfactory. However, it is precisely the combination of high multiaxial impact strength and good flow properties which is important in t'ne production of impact-st~essed large-surface mouldings.
Le A 21 318 . ~
l3~
-DE-OS NoO 21 44 528 describes polyamides contain-ing as high-impact modifier a so-called "multiphase polymer" in which the first phase is an elastorneric phase obtained by the polymerisation of a monomer system of an alkyl acrylate, butadiene or ethylene, a crosslinking monomer and a graft-crosslinking monomer, and a final, hard thermoplastic phase containing amine-reactive carboxyl groups.
Unfortunately, the multiaxial impact strength of these moulding compositions is inadequate.
Surprisingly, it is now possible to improve the multiaxial impact strength of polyamides by the addition of particulate graft products of a highly crosslinked diene rubber as the core and graft substra-te surrounded by a first shell of crosslinked acrylate rubber and a second or outer shell of a polymer or copolymer derived from the group of monomers comprising styrene,~ -met~yl styrene, acrylo~itrile, methacr~loni-trile, acrylates, methacryla-tes or mixtures thereof, without any adverse effect upon the flow of the unmodified polyamide.
Accordingly, the present invention provides moulding compositions having improved multiaxial impact strength comprising 1. from 40 to 99% by weight, preferably from 60 to 98%
by weight and, more particularly, from 70 to 97% by weight, based on the total moulding composition, of a polyamide and
~i~h-impact polyamide moulding compositions This invention relates to high-impact ~esistant ~xtures of polyamides and graft copolymers comprising a diene rubber as the core surrounded by at least two different shells.
Polyamides are of importance in the production of fibres and mouldings by virtue of their valuable technological properties, for example, their stiffness and toughness, their resistance to corrosion caused by stress crazing and their solvent resistance. However, their toughness and, in particular, their impact strength under multiaxial stressing are inadequate for many applications 9 particularly for components having large surface areas.
There are numerous proposals for increasing the toughness of polyamides by the addition of other polymers, particularly those based on modified elastomers and polyolefins. Unfortunately, this improvement in toughness is generally obtained at the expense of a significant deterioration in the flow of the polyamides.
In addition, multiaxial impact strength is not achieved to the required extent.
~ -OS No. 24 35 266 des~ribes filled moulding composi-tions of polyamides, fillers and ~raft copolymers havin~ increased impac-t ~ in the dry state and a-t low temperatures coupled with improved toughness under multiaxial stressing, the graft copolymer having been produced by grafting styrene and~or methacrylic acid esters onto a copolymer of acrylate and a comonomer containing two non-conjugated olefinic double bonds.
Although this DE-OS describes polyamide moulding compositions~having improved multiaxial impact strength, the flow of the moulding compositions in question is unsatisfactory. However, it is precisely the combination of high multiaxial impact strength and good flow properties which is important in t'ne production of impact-st~essed large-surface mouldings.
Le A 21 318 . ~
l3~
-DE-OS NoO 21 44 528 describes polyamides contain-ing as high-impact modifier a so-called "multiphase polymer" in which the first phase is an elastorneric phase obtained by the polymerisation of a monomer system of an alkyl acrylate, butadiene or ethylene, a crosslinking monomer and a graft-crosslinking monomer, and a final, hard thermoplastic phase containing amine-reactive carboxyl groups.
Unfortunately, the multiaxial impact strength of these moulding compositions is inadequate.
Surprisingly, it is now possible to improve the multiaxial impact strength of polyamides by the addition of particulate graft products of a highly crosslinked diene rubber as the core and graft substra-te surrounded by a first shell of crosslinked acrylate rubber and a second or outer shell of a polymer or copolymer derived from the group of monomers comprising styrene,~ -met~yl styrene, acrylo~itrile, methacr~loni-trile, acrylates, methacryla-tes or mixtures thereof, without any adverse effect upon the flow of the unmodified polyamide.
Accordingly, the present invention provides moulding compositions having improved multiaxial impact strength comprising 1. from 40 to 99% by weight, preferably from 60 to 98%
by weight and, more particularly, from 70 to 97% by weight, based on the total moulding composition, of a polyamide and
2. from 1 to 60% by weight, preferably from 2 to L10% by weight and, mor~ particularly, from 3 to 30% by weight, based on the total moulding composition, of a graEt product of (I) a crosslinked diene rubber as the core and graf`t substrate, (II) a crosslinked acrylate rubber as the first shell and (III) a homopolymer or copolymer of styrene, (~-methyl styrene and/or a (me~h)acrylic acid Le A 21 318
3~
~ 3 --derivative, preferably acrylonitrile, methacrylonitrile, acrylates , me-~acrylates or mix~res there~f as -the second or outer shell.
The quantitative ratio of the core (I) to the first shell (~I) is fromO.1:99O9 to 80:20 parts by weight and preferably from 0 4:99.6 to 20:80 parts by weight. The proportion of the second shell (III) in the total graft product(2)amounts to between 10 and 80% by weight and preferably to between 20 and 50% by wei~ht base~ on the gra:Et product(2). The graft products (2) according to the inven~ion have average particle di~meters (d50) of from 0 05 to 3 llm and preferably from 0.1 to 2 ~m. Particularly preferred particle diameters are in the range from 0.2 to 1 ~m The average particle diameter d50 is the diameter above which 50% by weight and below which the other 50%
by weight of the particles lie. It may be deter~ined by ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid Z. und Z. ~olymere 250 (1972), (782-296) or by electron microscopy and subse~uent counting of the particles (G.
Kampf, ~. Schuster, Angew. ~akromolekulare Chemie 14, (1970), 111-129) or by light scattering measurements.
The constituent material of the core (I) is a crosslinked rubber of one or more conjugated dienes, such as butadiene, or of a copolymer of a conjugated diene with an ~ unsaturated monomer, such as styrene and/or acrylonitrile.
The first shell (II) preferably consists of a crosslinked acrylate rubber. In particular, it consists of a crosslinked polymer of acrylic acid alkyl esters, optionally copolymerised with up to 40% by weight of other vinyl monom~s. Suitable acrylic acid esters, which may optionally be substituted by halogen atoms, such asCï or Br, include C1-C8-alkyl esters, for example methyl, ethyl, butyl, octyl and 2-echyl hexyl ester, haloalkyl esters, preferably C1-C8-haloalkyl esters, such as chloroethyl acrylate, and aromatic~aliphatic esters, such as benzyl acrylate and phenyl ethyl acrylate. They may be used Le A 21 318 .. ..
3~
D, _ either indivi~ually or in admixture.
The monomers copolymerised for crosslinking are preferably polyfunctional monomers and, more preferably, at least trifunctional monomers, for example esters of a, ~ -unsaturated monocarboxylic acids with a polyol preferably containing from 2 to 20 carbon atoms in the ester moiety, such as ethylene glycol di(meth)acrylate;
esters of polycarboxylic acids with mono-unsaturated alcohols, preferably containing from 8 to 30 carbon atoms in the ester moiety; triallyl compounds, such as triallyl cyanurate, triallyl isocyanurate; divinyl compounds, such as divinyl benzene; esters of~ un-saturated monocarboxylic acids with mono-unsaturated alcohols preferably containing from 6 to 12 carbon atoms in the ester moiety, such as allyl methacrylate;
phosphoric acid esters with monounsaturated alcohols, for example triallyl phosphate; 1,3,5-triacryloyl hexahydro-s-triazine and also diallyl phthalate.
Preferred polyfunctional monomers are allyl methacrylate, ethylene glycol dimethacrylate 7 diallyl phthalate and cyclic compounds containing at least 3 ethylenically unsaturated groups.
Particularly preferred polyfunctional nmonomers are the cyclic monomers such as triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, 1,3,5-triacryloyl hexahydro-s-triazine, trivinyl benzenes and triallyl benzenes.
The polyfunctional monomers are used in quantities of preferably from 0.05 to 10% by weight and, more preferably, in quantities of frorn 0.1 to 5% by ,~
weight, based on the total quantity of the first shell (II), for crosslinking. The elastomer of the first shell II may additonally contain a copolymerisable monomer or several such monomers of the vinyl or vinylidene type, for example acrylonitrile, styrene, ~-methyl styrene, acrylamides, vinyl alkyl ethers, Le A 21 318 in co-polymerised form. Th?se comonomers may be copoly-merised in quantities of up to 30% by weight, based on the first shell (II).
The second shell III is grafted on by the polymerisation of monomers, such as~-methyl styrene, styrene t acrylonitrile, methyl methacrylate or mixtures thereof.
Copolymers of styrene and acrylonitrile in a ratio by weight of from 90:10 to 50:50 and also polymethyl methacrylate are preferred.
The graft p~oducts 2 may be prepare~ in aqueous emulsion as follows:
The diene rubber for the core (I) is first prepared in latex form by the emulsion polymerisation of a conju-gated diene in known manner. The acrylate rubber for the first shell (II) is then prepared in the presence of the diene rubber latex, again in aqueous ernulsion, by emulsifying the monomer(s) in the latex and polymerising the resulting emulsion in known manner in the presence of radical-forming initiators. The acrylate rubber polymerises onto the diene rubber. It may even be cross-linked at the production stage by using polyfunctional monomers.
During the graft copolymerisation of the first shell II, the formation of new particles should be ~ompletely suppressed. Accordingly, an emulsion stabiliser should be present in a quantity sufficient to cover the surface of the particles. The size of the particle may be varied within wide limits according to how the reaction is carried out. If an agglomerated latex is used as the core I in order to obtain large particles, these particles may contain several diene rubber particles. Polymerisation of the first shell (II) may also be carried out in such a way that particles having a diene rubber core and particles of pure crosslinked acrylate rubber are obtained simultan-eously. In special cases, mixtures of this type mayalso be used for producing the moulding compositions according to the invention.
Le A ~1 318 On completion of graft copolymerisation of the acrylate rubber a vinyl monomer or a mixture of vinyl monomers of the type mentioned is preferably polymerised preferably in emulsion onto the latex obtained. This ylelds the gra~t products 2 under formation of ~ne second shell (III). ~uring this graf`t copolymerisation which is known E~ se:~ an.d is normally carried out in the presence of radical initiators for example water-soluble initiators, emulsifiers and or complexing agents/graft activators and regulators, homo-or copolymers of he monorners forming the second shell (III) are also generally formed to a certain e~-tent ~es..cles the graft copolymer. . The quantity of this ungrafted polymer may be characterised by the degree of grafting or the grafting yield which is determined inter _lia by the polymerisation conditions the composition of the first shell (II), the size of the particles to be grafted and the quantity of grafted acrylate rubber.
In the context of this invention therefore graft product 2 is the product which is obtained by the polymerisation of vinyl monomers in the presence of the rubber latex and which may represent a mixture of graft copolymer and homo(co)polymers of the graft monomers.
The graft products 2 thus produced may be worked ~5 up by known methods for example by coagulation of the latices with electrolytes (salts acids or mixtures thereof) followed by purification and drying or by so-called spray drying.
Suit~le polyamides are any thermoplastic poly-amides, preferably par-tially crystalline polyamides. Thus, polyamide-6, polyamide-6,6 and copolymers of these two components may be used as ~artially crystalline polyamides for the moulding compositions according to the invention.
It is also possible to use partially crystalline polyami~es of which the acid component consists either completely or partly of terephthalic acid and/or isophthalic acid Le A 21 318 3~3 and/or suberic acid and/or sebacic and~or azelaic acid and/or adipic acid and/or cyclohexane dicarboxylic acid, of which the diamine component consists either completely or partly of m- and/or p-xylylene diamine and/or hexamethylene diamine and/or 2,2,4-trimethylhexamethylene diamine and/or 2,4,4-trimethyl hexamethylene diamine and/or isophorone diamine and~or diamino cyclohexyl alkanes and of` which the composition is known from the prior art.
Furthermore, it is possible to use polyamides produced completely or partly from lactams containing at least 5 ring members, optionally in conjunction with one or more of the above mentioned starting materials.
Particularly preferred partially crystalline poly-amides are polyamide-6 and polyamlde-6,6.
The polyamides should preferably have a relative viscosity of from 2.0 to 5.0 and, more preferably, from 2.5 to 4.5, as measured on a 1% by weight solution in m-cresol at 25C.
The polyamide moulding compositions according to the present invention may contain usual known addi-tlves, such as lubricants and mould release agents~ nucleating agents, stabilisers, fillers and reinforcing materials, flameproofing agents and dyes.
The polyamide moulding compositions according to the invention may contain up to 60% by weight, based on the rrloulding compositions, of fillers and~or reinforcing materials. Preferred reinforcing materials are glass fibres. Preferred fillers, which may also have a reinforcing effect, are glass beads, mica, silicates, quartz, talcu~, titanium dioxide, wollastonite, kaolin, calcined kaolin, feld spar.
The moulding compositions according to the inven'cion may be produced in the usual mixing units, such as kneaders, single-screw and multi-screw extruders.
Le A ~1 318 ;~ 3~
Twin-screw extruders are particularly suitable.
The moulding compositions may be produced in the above-mentioned mixing units by melting and homogenising the two components 1 and 2 together or by working the graft product 2 in~o a melt of the polyamide 1.
The temperature at which the moulding compositions are produced should be below 320C an~ preferably in the range from 260 to 300C.
In one advantageous process, a mixture of from 35 to 95 % by weight and preferably from 50 to 90 % by weight (based on components 1 and 2) of graft product 2 and from 5 to 65 % by weight and preferably f'rom 10 to 50%
by weight (based on components 1 and 2) of polyamide 1 is prepared in a first step in one of the above-mentioned mixing units and, in a second step, processed with more polyamide 1 to form the moulding compositions according to the invention.
The polyamide moulding compositions according to the invention are characterised by a considerable improvement in multiaxial impact strength, even where they have low contents of graft product 2. The good flow properties of the mixtures is also surprising. In addition, the moulding compositions according to the invention are characterised by t'neir high dimensional stability under heat and by their high resistance to ageing in hot air.
Commensurate with their good properties, the moulding compositions according to the invention may be used 3~ anywhere in ~e injection moulding and extrusion fields where high multiaxial impact strength, high thermal stability and high resistance to hot air are essential requirements, as or the production of par~s of cars.
EXAMPLES
1. Production of the polydiene latices (core I) a) The following emulsion is polymerised with stirring in Le A 21 318 . . .
1~9~
l a reactor at 65C until the monomers have reac-ted substantially completely (which takes approximately 22 hours):
lO0 parts by weight of butadiene, 1.8 parts by weight of the Na-salt of disproportion-ated abietic acid 0.257 part by weight of sodium hydroxide 0.3 part by weight of N-dodecyl mercaptan 1O029 parts by weigh-t of Na-ethylene diamine tetraacetate 0.023 part by weight of potassium persulfate 760 parts by weight of water The latex obtained contains polybutadiene par-ticles having an average diameter (d50) of 0.1 ~m in a concentration oE approximately 35 to 36% (latex la).
b) The following emulsion is polymerised for about llO hours at 60 to 58C in the same way as described in la):
100.0 parts by weight of butadiene 70 parts by weight of water 1.146 parts by weight of the Na-salt of disproportion-ated abietic acid 0.055 part by weight of Na-ethylene diamine tetraacetate 0.137 part by weight of sodium hydroxide 0.028 part by weight of sodium hydrogen carbonate 0.282 part by we:;ght of potassium persulfate The latex obtained contains polybutadiene particles having an average diameter (d50) of 0.4 ~m in a concentration of approximately 58% (latex lb).
2. Production of acrylate rubber particles containing poly-butadiene cores (core I with first shell II) a) The following mixture is introduced into a reactor with stirring at ~3C:
200 parts by weight of latex la 5000 parts by weight of water 14 parts by weight of potassium persulfate 0.9124 parts by weight of triallyl cyanurate 399.09 par-ts by weight of n-butyl acrylate Le A 21 318 -1 The following mix-tures are separately introduced into the reactor over a period of 5 hours at 63C:
Mixture A:90 parts by weigh-t of Na-sulfonate of Cl4-C18-hydrocarbons 11,900 parts by weight of water Mixture B:23.09 par-ts by weight of triallyl cyanurate 10,101 parts by weight of n-butyl acrylate The mixtures are polymerised for 3 hours at 63C. The polymers formed have gel contents of from 85 to 95~ by weight, as measured in dime-thyl formamide at 2SC (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I
and II, Georg Thieme Verlag, Stuttgart 1977) and average particle diameters d50 of 0-5 ~m (latex 2a).
b) The following mixture is introduced into a reactor at 65C:
2168 parts by weight of latex lb 9500 parts by weight of water 27 parts by weight of potassium persulfate 1700 parts by weight of water The following mixtures are separately introduced into the reactor over a period of 4 hours at 65C:
Mixture C: 9214 parts by weigh-t of n-bu-tylacrylate 15 parts by weight of tri.allyl cyanurate Mixture D: 6600 parts by weight of water 156 parts by weight of Na-sulfonate of C14-C18--hydrocarbons.
The two mixtures are polymerlsed for 4 h~urs at 65C. The polymers formed have a gel content of 91~ by weight (as measured in dimethyl formamide at 25C, cfo M.
Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme Verlag Stuttgart, 1977), a degree of swelling of 6.5, as measured in dimethyl formamide at 25C (loc. Clt.) and a distribution of the particle diameters of 0.2 to 0.9 ~m (latex 2b)~ ~s determined by ultracentrifuge measurements~
Le A 21 318 3~
l 3. Production of the graft produc-ts 2 a parts by weigh-t of latex 2a) respectively of latex 2b) are introduced into a reactor and heated to 65C. Polymerisation is initiated by the addition of a mixture of b parts by weight of potassium persulfate and c parts by weight of water.
The following mixtures are run into the reactor with stirring over a period of 4 hours at 65C:
Mixture E: d parts by weight of monomer l e parts by weight of monomer 2 Mixture F: f parts by weight of water g parts by weight of Na-sulfonate of C14C18-hydrocarbons Table 1 shows the composition of the graft products 2, types K, L and M.
Le A 21 318 Table 1: Composition of the graft products (2) w Graft product (2) Type l~ex typer a b c d e r g K 2a 3088 3.5 145 273 MMA - 880 5 h 2a 3088 3.5 145 76.4 A~ 196.6 S 880 5 M 2b 13000 18 1400 311 AN 799 S 1200 22 Quantities of a to g in parts by weight MMA = methyl methacrylate AN = acrylonitrile S = styrene a 3~3 l Polymerisation is then completed over a period of 4 hours at 65C.
Followi.ng the addition of an aqueous stabiliser dispersion corresponding to between 0.25 and l part by weight of a phenolic oxidation inhibitor per 100 parts by weight of latex dye, the graft product latices K to M are coagulated by the addition of an electrolyte or acid. The resulting powders are dried in vacuo at 70C.
~ 3 --derivative, preferably acrylonitrile, methacrylonitrile, acrylates , me-~acrylates or mix~res there~f as -the second or outer shell.
The quantitative ratio of the core (I) to the first shell (~I) is fromO.1:99O9 to 80:20 parts by weight and preferably from 0 4:99.6 to 20:80 parts by weight. The proportion of the second shell (III) in the total graft product(2)amounts to between 10 and 80% by weight and preferably to between 20 and 50% by wei~ht base~ on the gra:Et product(2). The graft products (2) according to the inven~ion have average particle di~meters (d50) of from 0 05 to 3 llm and preferably from 0.1 to 2 ~m. Particularly preferred particle diameters are in the range from 0.2 to 1 ~m The average particle diameter d50 is the diameter above which 50% by weight and below which the other 50%
by weight of the particles lie. It may be deter~ined by ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid Z. und Z. ~olymere 250 (1972), (782-296) or by electron microscopy and subse~uent counting of the particles (G.
Kampf, ~. Schuster, Angew. ~akromolekulare Chemie 14, (1970), 111-129) or by light scattering measurements.
The constituent material of the core (I) is a crosslinked rubber of one or more conjugated dienes, such as butadiene, or of a copolymer of a conjugated diene with an ~ unsaturated monomer, such as styrene and/or acrylonitrile.
The first shell (II) preferably consists of a crosslinked acrylate rubber. In particular, it consists of a crosslinked polymer of acrylic acid alkyl esters, optionally copolymerised with up to 40% by weight of other vinyl monom~s. Suitable acrylic acid esters, which may optionally be substituted by halogen atoms, such asCï or Br, include C1-C8-alkyl esters, for example methyl, ethyl, butyl, octyl and 2-echyl hexyl ester, haloalkyl esters, preferably C1-C8-haloalkyl esters, such as chloroethyl acrylate, and aromatic~aliphatic esters, such as benzyl acrylate and phenyl ethyl acrylate. They may be used Le A 21 318 .. ..
3~
D, _ either indivi~ually or in admixture.
The monomers copolymerised for crosslinking are preferably polyfunctional monomers and, more preferably, at least trifunctional monomers, for example esters of a, ~ -unsaturated monocarboxylic acids with a polyol preferably containing from 2 to 20 carbon atoms in the ester moiety, such as ethylene glycol di(meth)acrylate;
esters of polycarboxylic acids with mono-unsaturated alcohols, preferably containing from 8 to 30 carbon atoms in the ester moiety; triallyl compounds, such as triallyl cyanurate, triallyl isocyanurate; divinyl compounds, such as divinyl benzene; esters of~ un-saturated monocarboxylic acids with mono-unsaturated alcohols preferably containing from 6 to 12 carbon atoms in the ester moiety, such as allyl methacrylate;
phosphoric acid esters with monounsaturated alcohols, for example triallyl phosphate; 1,3,5-triacryloyl hexahydro-s-triazine and also diallyl phthalate.
Preferred polyfunctional monomers are allyl methacrylate, ethylene glycol dimethacrylate 7 diallyl phthalate and cyclic compounds containing at least 3 ethylenically unsaturated groups.
Particularly preferred polyfunctional nmonomers are the cyclic monomers such as triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, 1,3,5-triacryloyl hexahydro-s-triazine, trivinyl benzenes and triallyl benzenes.
The polyfunctional monomers are used in quantities of preferably from 0.05 to 10% by weight and, more preferably, in quantities of frorn 0.1 to 5% by ,~
weight, based on the total quantity of the first shell (II), for crosslinking. The elastomer of the first shell II may additonally contain a copolymerisable monomer or several such monomers of the vinyl or vinylidene type, for example acrylonitrile, styrene, ~-methyl styrene, acrylamides, vinyl alkyl ethers, Le A 21 318 in co-polymerised form. Th?se comonomers may be copoly-merised in quantities of up to 30% by weight, based on the first shell (II).
The second shell III is grafted on by the polymerisation of monomers, such as~-methyl styrene, styrene t acrylonitrile, methyl methacrylate or mixtures thereof.
Copolymers of styrene and acrylonitrile in a ratio by weight of from 90:10 to 50:50 and also polymethyl methacrylate are preferred.
The graft p~oducts 2 may be prepare~ in aqueous emulsion as follows:
The diene rubber for the core (I) is first prepared in latex form by the emulsion polymerisation of a conju-gated diene in known manner. The acrylate rubber for the first shell (II) is then prepared in the presence of the diene rubber latex, again in aqueous ernulsion, by emulsifying the monomer(s) in the latex and polymerising the resulting emulsion in known manner in the presence of radical-forming initiators. The acrylate rubber polymerises onto the diene rubber. It may even be cross-linked at the production stage by using polyfunctional monomers.
During the graft copolymerisation of the first shell II, the formation of new particles should be ~ompletely suppressed. Accordingly, an emulsion stabiliser should be present in a quantity sufficient to cover the surface of the particles. The size of the particle may be varied within wide limits according to how the reaction is carried out. If an agglomerated latex is used as the core I in order to obtain large particles, these particles may contain several diene rubber particles. Polymerisation of the first shell (II) may also be carried out in such a way that particles having a diene rubber core and particles of pure crosslinked acrylate rubber are obtained simultan-eously. In special cases, mixtures of this type mayalso be used for producing the moulding compositions according to the invention.
Le A ~1 318 On completion of graft copolymerisation of the acrylate rubber a vinyl monomer or a mixture of vinyl monomers of the type mentioned is preferably polymerised preferably in emulsion onto the latex obtained. This ylelds the gra~t products 2 under formation of ~ne second shell (III). ~uring this graf`t copolymerisation which is known E~ se:~ an.d is normally carried out in the presence of radical initiators for example water-soluble initiators, emulsifiers and or complexing agents/graft activators and regulators, homo-or copolymers of he monorners forming the second shell (III) are also generally formed to a certain e~-tent ~es..cles the graft copolymer. . The quantity of this ungrafted polymer may be characterised by the degree of grafting or the grafting yield which is determined inter _lia by the polymerisation conditions the composition of the first shell (II), the size of the particles to be grafted and the quantity of grafted acrylate rubber.
In the context of this invention therefore graft product 2 is the product which is obtained by the polymerisation of vinyl monomers in the presence of the rubber latex and which may represent a mixture of graft copolymer and homo(co)polymers of the graft monomers.
The graft products 2 thus produced may be worked ~5 up by known methods for example by coagulation of the latices with electrolytes (salts acids or mixtures thereof) followed by purification and drying or by so-called spray drying.
Suit~le polyamides are any thermoplastic poly-amides, preferably par-tially crystalline polyamides. Thus, polyamide-6, polyamide-6,6 and copolymers of these two components may be used as ~artially crystalline polyamides for the moulding compositions according to the invention.
It is also possible to use partially crystalline polyami~es of which the acid component consists either completely or partly of terephthalic acid and/or isophthalic acid Le A 21 318 3~3 and/or suberic acid and/or sebacic and~or azelaic acid and/or adipic acid and/or cyclohexane dicarboxylic acid, of which the diamine component consists either completely or partly of m- and/or p-xylylene diamine and/or hexamethylene diamine and/or 2,2,4-trimethylhexamethylene diamine and/or 2,4,4-trimethyl hexamethylene diamine and/or isophorone diamine and~or diamino cyclohexyl alkanes and of` which the composition is known from the prior art.
Furthermore, it is possible to use polyamides produced completely or partly from lactams containing at least 5 ring members, optionally in conjunction with one or more of the above mentioned starting materials.
Particularly preferred partially crystalline poly-amides are polyamide-6 and polyamlde-6,6.
The polyamides should preferably have a relative viscosity of from 2.0 to 5.0 and, more preferably, from 2.5 to 4.5, as measured on a 1% by weight solution in m-cresol at 25C.
The polyamide moulding compositions according to the present invention may contain usual known addi-tlves, such as lubricants and mould release agents~ nucleating agents, stabilisers, fillers and reinforcing materials, flameproofing agents and dyes.
The polyamide moulding compositions according to the invention may contain up to 60% by weight, based on the rrloulding compositions, of fillers and~or reinforcing materials. Preferred reinforcing materials are glass fibres. Preferred fillers, which may also have a reinforcing effect, are glass beads, mica, silicates, quartz, talcu~, titanium dioxide, wollastonite, kaolin, calcined kaolin, feld spar.
The moulding compositions according to the inven'cion may be produced in the usual mixing units, such as kneaders, single-screw and multi-screw extruders.
Le A ~1 318 ;~ 3~
Twin-screw extruders are particularly suitable.
The moulding compositions may be produced in the above-mentioned mixing units by melting and homogenising the two components 1 and 2 together or by working the graft product 2 in~o a melt of the polyamide 1.
The temperature at which the moulding compositions are produced should be below 320C an~ preferably in the range from 260 to 300C.
In one advantageous process, a mixture of from 35 to 95 % by weight and preferably from 50 to 90 % by weight (based on components 1 and 2) of graft product 2 and from 5 to 65 % by weight and preferably f'rom 10 to 50%
by weight (based on components 1 and 2) of polyamide 1 is prepared in a first step in one of the above-mentioned mixing units and, in a second step, processed with more polyamide 1 to form the moulding compositions according to the invention.
The polyamide moulding compositions according to the invention are characterised by a considerable improvement in multiaxial impact strength, even where they have low contents of graft product 2. The good flow properties of the mixtures is also surprising. In addition, the moulding compositions according to the invention are characterised by t'neir high dimensional stability under heat and by their high resistance to ageing in hot air.
Commensurate with their good properties, the moulding compositions according to the invention may be used 3~ anywhere in ~e injection moulding and extrusion fields where high multiaxial impact strength, high thermal stability and high resistance to hot air are essential requirements, as or the production of par~s of cars.
EXAMPLES
1. Production of the polydiene latices (core I) a) The following emulsion is polymerised with stirring in Le A 21 318 . . .
1~9~
l a reactor at 65C until the monomers have reac-ted substantially completely (which takes approximately 22 hours):
lO0 parts by weight of butadiene, 1.8 parts by weight of the Na-salt of disproportion-ated abietic acid 0.257 part by weight of sodium hydroxide 0.3 part by weight of N-dodecyl mercaptan 1O029 parts by weigh-t of Na-ethylene diamine tetraacetate 0.023 part by weight of potassium persulfate 760 parts by weight of water The latex obtained contains polybutadiene par-ticles having an average diameter (d50) of 0.1 ~m in a concentration oE approximately 35 to 36% (latex la).
b) The following emulsion is polymerised for about llO hours at 60 to 58C in the same way as described in la):
100.0 parts by weight of butadiene 70 parts by weight of water 1.146 parts by weight of the Na-salt of disproportion-ated abietic acid 0.055 part by weight of Na-ethylene diamine tetraacetate 0.137 part by weight of sodium hydroxide 0.028 part by weight of sodium hydrogen carbonate 0.282 part by we:;ght of potassium persulfate The latex obtained contains polybutadiene particles having an average diameter (d50) of 0.4 ~m in a concentration of approximately 58% (latex lb).
2. Production of acrylate rubber particles containing poly-butadiene cores (core I with first shell II) a) The following mixture is introduced into a reactor with stirring at ~3C:
200 parts by weight of latex la 5000 parts by weight of water 14 parts by weight of potassium persulfate 0.9124 parts by weight of triallyl cyanurate 399.09 par-ts by weight of n-butyl acrylate Le A 21 318 -1 The following mix-tures are separately introduced into the reactor over a period of 5 hours at 63C:
Mixture A:90 parts by weigh-t of Na-sulfonate of Cl4-C18-hydrocarbons 11,900 parts by weight of water Mixture B:23.09 par-ts by weight of triallyl cyanurate 10,101 parts by weight of n-butyl acrylate The mixtures are polymerised for 3 hours at 63C. The polymers formed have gel contents of from 85 to 95~ by weight, as measured in dime-thyl formamide at 2SC (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I
and II, Georg Thieme Verlag, Stuttgart 1977) and average particle diameters d50 of 0-5 ~m (latex 2a).
b) The following mixture is introduced into a reactor at 65C:
2168 parts by weight of latex lb 9500 parts by weight of water 27 parts by weight of potassium persulfate 1700 parts by weight of water The following mixtures are separately introduced into the reactor over a period of 4 hours at 65C:
Mixture C: 9214 parts by weigh-t of n-bu-tylacrylate 15 parts by weight of tri.allyl cyanurate Mixture D: 6600 parts by weight of water 156 parts by weight of Na-sulfonate of C14-C18--hydrocarbons.
The two mixtures are polymerlsed for 4 h~urs at 65C. The polymers formed have a gel content of 91~ by weight (as measured in dimethyl formamide at 25C, cfo M.
Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme Verlag Stuttgart, 1977), a degree of swelling of 6.5, as measured in dimethyl formamide at 25C (loc. Clt.) and a distribution of the particle diameters of 0.2 to 0.9 ~m (latex 2b)~ ~s determined by ultracentrifuge measurements~
Le A 21 318 3~
l 3. Production of the graft produc-ts 2 a parts by weigh-t of latex 2a) respectively of latex 2b) are introduced into a reactor and heated to 65C. Polymerisation is initiated by the addition of a mixture of b parts by weight of potassium persulfate and c parts by weight of water.
The following mixtures are run into the reactor with stirring over a period of 4 hours at 65C:
Mixture E: d parts by weight of monomer l e parts by weight of monomer 2 Mixture F: f parts by weight of water g parts by weight of Na-sulfonate of C14C18-hydrocarbons Table 1 shows the composition of the graft products 2, types K, L and M.
Le A 21 318 Table 1: Composition of the graft products (2) w Graft product (2) Type l~ex typer a b c d e r g K 2a 3088 3.5 145 273 MMA - 880 5 h 2a 3088 3.5 145 76.4 A~ 196.6 S 880 5 M 2b 13000 18 1400 311 AN 799 S 1200 22 Quantities of a to g in parts by weight MMA = methyl methacrylate AN = acrylonitrile S = styrene a 3~3 l Polymerisation is then completed over a period of 4 hours at 65C.
Followi.ng the addition of an aqueous stabiliser dispersion corresponding to between 0.25 and l part by weight of a phenolic oxidation inhibitor per 100 parts by weight of latex dye, the graft product latices K to M are coagulated by the addition of an electrolyte or acid. The resulting powders are dried in vacuo at 70C.
4. Production of a comparison graft product Graft product) type N:
Copolymer of a graft base of 57 parts by weight of n~butyl acrylate 13 parts by weight of styrene 0.35part by weight of 1,3-butylene diacrylate and 0.14part by weight of allyl methacrylate and a monomer mixture to be grafted on consisting of 28 parts of methyl methacryla-te, and 2 parts of acrylic acid ~according to DE-OS No. 21 44 528) Graft product, type O~
A copolymer of n-butylacrylate and the acrylic acid ester of tricyclodecenyl alcohol as the graft base and grafted-on units of 75% by weight of styrene anc~ 25~ by weight of acrylonitrile (according to DE-OS No. 2~ 35 266).
Copolymer of a graft base of 57 parts by weight of n~butyl acrylate 13 parts by weight of styrene 0.35part by weight of 1,3-butylene diacrylate and 0.14part by weight of allyl methacrylate and a monomer mixture to be grafted on consisting of 28 parts of methyl methacryla-te, and 2 parts of acrylic acid ~according to DE-OS No. 21 44 528) Graft product, type O~
A copolymer of n-butylacrylate and the acrylic acid ester of tricyclodecenyl alcohol as the graft base and grafted-on units of 75% by weight of styrene anc~ 25~ by weight of acrylonitrile (according to DE-OS No. 2~ 35 266).
5.` Production of the mixtures Graft products K to O are worked into polyamide using a standard commercial continuous twin-screw ex-truder (Werner & Pflei~.lerer type ZSK 32) in which the polyarnide was first me~ted.
The graft product was introduced into the polyamide melt through a second inlet. Blanketing with nitrogen is advisable. The graft product was melted and homogeneously dispersed in the polyamide. It can be of advantage to de-gas the melt before it issues frorn the nozzle. The barrel temperatures were adjusted in such a way that a melt Le A 21 318 L3~
l temperature of 280-290C was guaranteed. The melt strand of the mixture of polyamide and graft product was cooled in water, granulated and dried. Standard small tes-t bars ~according to DIN 53 453) and plates measuring 3 x 60 x 60 mm were injection-moulded from the granulate in a standard injection-moulding machine at the following processing temperatures:
Polyamide-6 mixtures: melt temperture 260C
mould temperature 80C
Polyamide-6,6 mixtures: melt temperature 270C
mould temperature 80C
The freshly injection-moulded test specimens were used for testing notched impact streng-th (in accordance with DIN 53 453)~ flexural strength (in accordance with DIN 53 452) and multiaxial impact strength using the EFDR (electronic force-distance recordin~) test (according to DIN 53 443, page 2,penetration of a 3 x 60 x 60 mm plate by a 35 kg weight fitted with a conically tipped spike 20 mm in diameter dropped from a height of l metre) and the so-called flow length in the flow spiral.
The flow length was determined as Eollows:
Using an injection-moulding machine having a barrel temperature of 260C, the sample to be tested was injected into a special mould kept at 90C under an injection pressure of 72 bars. Particularly free-flowin~ materials are capable of filling the mould under these conditions so that a lO0 cm long spiral can be subsequently removed.
Materials which flow less readily fill the mould only partly under~.~he described conditions, as a result o~ which spirals less than lO0 cm long can only be obtained in consequence of the premature solidification of the melt.
The flow length is the length in cm which was reproduced five times.
3 Le A 21 318 3~
Ln Ln o a r~ ~r ~g .
.-- I I I O
Ln r~ ~ .~ r~ r-- ~ ~ o o rn ~; ~ rrl ~ Ln rY~ r.~ ~ .~ ~ ~ Ln r~
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rn c~ Ln ~ ~ .~ ~ Ln Ln ~r Ln Ln ~r~
x ,~ r-- .~ o r-- ~ ~r ~D r~
w O
Q, r _ O
O
rr~ ~" r-- co Ln .~ .~ Ln 0 cs~ r-- C5~ r.~1 ~ o ~ .,~
o o~ co ~ Ln co o~ o 03~ r-- co r~ ~ r~
O
rn o\o OD Ln 1-- 0~ Ln O Ln Ln ~r ~r o o o ,~
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a ~ o O O O O O O O O O O O a~ ~ r~
~r- d ~ r.~ t~1 t~ ~ r.~l t~l ~ t~ t~l t~ rJ
,, r-~:: t '? ~ ,t, ~ U~ o C? K K :~ K ~ ~ ~ ~ ~ Z Z O I I I ~ t t 0 -~\ Q
,~, ,, O O -I
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un, a ~ L l Ln O Ln Ln u. L~ O orn Ln Ln Ln Ln o o t~ 2 - t~
a?~ ~C ~ r~ ~ Ln r~ t~ r~ r~ r~ r~ tl) ~ t~ t~ r~ Ln r-- Q, ~ ~> ~
t~ ~ ~ tvl tr) ~ ~~ ~ r~ tY rr)r~ r~ ?~ tL~ rn _I ,~ .~ ,1 l? ~ 'a tl) ~ r~) '~ ~ D ~ a) rr~ o ? O ~ Ln t~ 4 P~ rn ~ P~
a tl) ,- - .Y tl?
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Le A 21 318
The graft product was introduced into the polyamide melt through a second inlet. Blanketing with nitrogen is advisable. The graft product was melted and homogeneously dispersed in the polyamide. It can be of advantage to de-gas the melt before it issues frorn the nozzle. The barrel temperatures were adjusted in such a way that a melt Le A 21 318 L3~
l temperature of 280-290C was guaranteed. The melt strand of the mixture of polyamide and graft product was cooled in water, granulated and dried. Standard small tes-t bars ~according to DIN 53 453) and plates measuring 3 x 60 x 60 mm were injection-moulded from the granulate in a standard injection-moulding machine at the following processing temperatures:
Polyamide-6 mixtures: melt temperture 260C
mould temperature 80C
Polyamide-6,6 mixtures: melt temperature 270C
mould temperature 80C
The freshly injection-moulded test specimens were used for testing notched impact streng-th (in accordance with DIN 53 453)~ flexural strength (in accordance with DIN 53 452) and multiaxial impact strength using the EFDR (electronic force-distance recordin~) test (according to DIN 53 443, page 2,penetration of a 3 x 60 x 60 mm plate by a 35 kg weight fitted with a conically tipped spike 20 mm in diameter dropped from a height of l metre) and the so-called flow length in the flow spiral.
The flow length was determined as Eollows:
Using an injection-moulding machine having a barrel temperature of 260C, the sample to be tested was injected into a special mould kept at 90C under an injection pressure of 72 bars. Particularly free-flowin~ materials are capable of filling the mould under these conditions so that a lO0 cm long spiral can be subsequently removed.
Materials which flow less readily fill the mould only partly under~.~he described conditions, as a result o~ which spirals less than lO0 cm long can only be obtained in consequence of the premature solidification of the melt.
The flow length is the length in cm which was reproduced five times.
3 Le A 21 318 3~
Ln Ln o a r~ ~r ~g .
.-- I I I O
Ln r~ ~ .~ r~ r-- ~ ~ o o rn ~; ~ rrl ~ Ln rY~ r.~ ~ .~ ~ ~ Ln r~
r~l~ a, r:Q ~r rl) ~ Ln ~r .
rn c~ Ln ~ ~ .~ ~ Ln Ln ~r Ln Ln ~r~
x ,~ r-- .~ o r-- ~ ~r ~D r~
w O
Q, r _ O
O
rr~ ~" r-- co Ln .~ .~ Ln 0 cs~ r-- C5~ r.~1 ~ o ~ .,~
o o~ co ~ Ln co o~ o 03~ r-- co r~ ~ r~
O
rn o\o OD Ln 1-- 0~ Ln O Ln Ln ~r ~r o o o ,~
Ln 1` C~ ' 1-- ~ ~ r-- ~ Ln ~r ~ ,, rd C O
C~
? .
a ~ o O O O O O O O O O O O a~ ~ r~
~r- d ~ r.~ t~1 t~ ~ r.~l t~l ~ t~ t~l t~ rJ
,, r-~:: t '? ~ ,t, ~ U~ o C? K K :~ K ~ ~ ~ ~ ~ Z Z O I I I ~ t t 0 -~\ Q
,~, ,, O O -I
~ r~ ~ O O O O O O O O U
L~ ~ I, t~ t o~ ro ~ a~ tJ~ r~ rY~ n v O ~
~ ,~ tJ rd v .IJ _ u.
un, a ~ L l Ln O Ln Ln u. L~ O orn Ln Ln Ln Ln o o t~ 2 - t~
a?~ ~C ~ r~ ~ Ln r~ t~ r~ r~ r~ r~ tl) ~ t~ t~ r~ Ln r-- Q, ~ ~> ~
t~ ~ ~ tvl tr) ~ ~~ ~ r~ tY rr)r~ r~ ?~ tL~ rn _I ,~ .~ ,1 l? ~ 'a tl) ~ r~) '~ ~ D ~ a) rr~ o ? O ~ Ln t~ 4 P~ rn ~ P~
a tl) ,- - .Y tl?
,_1 ~^4 J rr~ s~
~? ~ rt5 ~:
E~ ~ Z r~ t~? t~ t~ ~ Ln ~ r~o rJ cn ,~ ,~
~1 t~l r~
Le A 21 318
Claims (10)
1. A high-impact moulding composition comprising 1) from 40 to 99 % by weight, based on components 1) and 2) of a polyamide and 2) from 1 to 60 % by weight, based on components 1) and 23, of a particulate graft product of:
(I) a crosslinked diene rubber as the core, II) a crosslinked acrylate rubber as the first shell, and III) a polymer or copolymer of monomers selected from the group consisting of styrene, .alpha.-methyl styrene, acrylic and methacrylic acid derivatives and mixtures thereof as the second respectively outer shell and 3) optionally one or more additional components selected from standard auxiliaries, additives, fillers and reinforcing materials.
(I) a crosslinked diene rubber as the core, II) a crosslinked acrylate rubber as the first shell, and III) a polymer or copolymer of monomers selected from the group consisting of styrene, .alpha.-methyl styrene, acrylic and methacrylic acid derivatives and mixtures thereof as the second respectively outer shell and 3) optionally one or more additional components selected from standard auxiliaries, additives, fillers and reinforcing materials.
2. A high-impact moulding composition according to claim 1, which comprises from 60 to 98 % by weight of component 1) and from 2 to 40 % by weight of component 2).
3. A high-impact moulding composition according to claim 2, which comprises from 70 to 97 % by weight of component 1) and from 3 to 30 % by weight of component 2).
4. A high-impact moulding composition according to claim 1, wherein the quantitative ratio of the core (I) to the first shell (II) is between 0.1:99.9 and 80:20 parts by weight.
5. A high-impact moulding composition according to claim 1, wherein the proportion of the second shell (III) in the total graft product 2) is between 10 and 80 % by weight.
6. A high-impact moulding composition according to claim 1, wherein the second shell (III) consists of poly-merised styrene, acrylonitrile, methylmethacrylate, acrylate, methacrylonitrile or mixtures thereof.
7. A high-impact moulding composition according to claim 1, wherein the core I consists of a crosslinked rubber of polybutadiene optionally containing styrene and/or acrylonitrile units.
8. A high-impact moulding composition according to claim 1, wherein the first shell II is derived from acrylic acid C1-C8-alkyl esters, optionally substituted by halogen atoms and at least trifunctional ?,.beta.-un-saturated monomers and optionally up to 40 % by weight of other vinyl or vinylidene monomers.
9. A moulding composition as claimed in claim 8, wherein the trifunctional monomers are triallyl (iso)-cyanurate, trivinyl cyanurate, 1,3, 5-triacryloyl hexa-hydro-S-triazine, trivinyl or triallyl benzene.
10. A moulding composition as claimed in claim 1, wherein the component 1) is polyamide-6 or polyamide-6,6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823200070 DE3200070A1 (en) | 1982-01-05 | 1982-01-05 | IMPACT TOOL POLYAMIDE MOLDS |
| DEP3200070.7 | 1982-01-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1196130A true CA1196130A (en) | 1985-10-29 |
Family
ID=6152606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000418879A Expired CA1196130A (en) | 1982-01-05 | 1983-01-04 | High-impact polyamide moulding compositions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0083446B1 (en) |
| JP (1) | JPS58120663A (en) |
| CA (1) | CA1196130A (en) |
| DE (2) | DE3200070A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4863977A (en) * | 1983-11-16 | 1989-09-05 | Dentsply Research & Development Corp. | Process for preparing interpenetrating polymer network objects employing rubber-modified polymers |
| US5180786A (en) * | 1988-11-09 | 1993-01-19 | Hitachi Chemical Company, Ltd. | Impact modifier, thermoplastic resin composition using the same and molded article obtained therefrom |
| US5210109A (en) * | 1983-11-16 | 1993-05-11 | Dentsply Research & Development Corp. | Interpenetrating polymer network compositions employing rubber-modified polymers |
| US5212224A (en) * | 1986-04-11 | 1993-05-18 | Bayer Aktiengesellschaft | Free flowing moulding materials based on polyamides containing bisphenols |
| US6458879B1 (en) | 1998-11-24 | 2002-10-01 | Basf Aktiengesellschaft | Thermoplastic materials containing nanocomposites and an additional elastomer |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3313919A1 (en) * | 1983-04-16 | 1984-10-18 | Basf Ag, 6700 Ludwigshafen | IMPACT TOE THERMOPLASTIC MOLDS AND METHOD FOR THEIR PRODUCTION |
| 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 |
| US4711913A (en) * | 1983-11-16 | 1987-12-08 | Dentsply International Inc. | Interpenetrating polymer network compositions employing rubber-modified polymers |
| DE3405532A1 (en) * | 1984-02-16 | 1985-08-22 | Bayer Ag, 5090 Leverkusen | MOLDINGS FROM THERMOPLASTIC POLYAMIDE AND GRAFT RUBBER |
| EP0154037A3 (en) * | 1984-02-29 | 1987-02-04 | The Dow Chemical Company | Blends of aromatic-aliphatic polyamides and impact modifiers |
| DE3434820A1 (en) * | 1984-09-22 | 1986-04-03 | Bayer Ag, 5090 Leverkusen | AGING-RESISTANT POLYAMIDE ALLOYS |
| DE3529240A1 (en) * | 1985-08-16 | 1987-02-26 | Basf Ag | IMPACT POLYAMIDE MOLDING MATERIALS AND THEIR PRODUCTION |
| JPS62181312A (en) | 1986-02-06 | 1987-08-08 | Mitsubishi Rayon Co Ltd | Production of thermoplastic resin composition having improved impact resistance, weather resistance and moldability |
| DE3612159A1 (en) * | 1986-04-11 | 1987-10-22 | Bayer Ag | FLOWABLE MOLDS BASED ON POLYAMIDE |
| JPS62250052A (en) * | 1986-04-23 | 1987-10-30 | Mitsuboshi Belting Ltd | Impact-resistant polyamide composition |
| DE3617720A1 (en) * | 1986-05-27 | 1987-12-03 | Bayer Ag | THERMOPLASTIC Graft Polymers |
| JP5154765B2 (en) * | 2006-04-17 | 2013-02-27 | ユーエムジー・エービーエス株式会社 | Thermoplastic resin composition and molded article thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3668274A (en) * | 1970-09-10 | 1972-06-06 | Rohm & Haas | Acrylic modifiers for polycarbonamides |
| US3796771A (en) * | 1970-09-10 | 1974-03-12 | Rohm & Haas | Acrylic modifiers for polycarbonamides |
| US3985703A (en) * | 1975-06-24 | 1976-10-12 | Rohm And Haas Company | Process for manufacture of acrylic core/shell polymers |
| US4167505A (en) * | 1978-01-12 | 1979-09-11 | Rohm And Haas Company | Impact modified high melt flow polycarbonamide |
| US4306040A (en) * | 1980-11-03 | 1981-12-15 | Monsanto Company | Multiphase core//shell polymers |
-
1982
- 1982-01-05 DE DE19823200070 patent/DE3200070A1/en not_active Withdrawn
- 1982-12-27 JP JP57227206A patent/JPS58120663A/en active Granted
- 1982-12-28 EP EP82112044A patent/EP0083446B1/en not_active Expired
- 1982-12-28 DE DE8282112044T patent/DE3273989D1/en not_active Expired
-
1983
- 1983-01-04 CA CA000418879A patent/CA1196130A/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4863977A (en) * | 1983-11-16 | 1989-09-05 | Dentsply Research & Development Corp. | Process for preparing interpenetrating polymer network objects employing rubber-modified polymers |
| US5210109A (en) * | 1983-11-16 | 1993-05-11 | Dentsply Research & Development Corp. | Interpenetrating polymer network compositions employing rubber-modified polymers |
| US5212224A (en) * | 1986-04-11 | 1993-05-18 | Bayer Aktiengesellschaft | Free flowing moulding materials based on polyamides containing bisphenols |
| US5180786A (en) * | 1988-11-09 | 1993-01-19 | Hitachi Chemical Company, Ltd. | Impact modifier, thermoplastic resin composition using the same and molded article obtained therefrom |
| US6458879B1 (en) | 1998-11-24 | 2002-10-01 | Basf Aktiengesellschaft | Thermoplastic materials containing nanocomposites and an additional elastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58120663A (en) | 1983-07-18 |
| DE3273989D1 (en) | 1986-12-04 |
| JPH047392B2 (en) | 1992-02-10 |
| EP0083446A1 (en) | 1983-07-13 |
| EP0083446B1 (en) | 1986-10-29 |
| DE3200070A1 (en) | 1983-07-14 |
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