CA2291131C - Abs molding materials with enhanced working properties - Google Patents
Abs molding materials with enhanced working properties Download PDFInfo
- Publication number
- CA2291131C CA2291131C CA002291131A CA2291131A CA2291131C CA 2291131 C CA2291131 C CA 2291131C CA 002291131 A CA002291131 A CA 002291131A CA 2291131 A CA2291131 A CA 2291131A CA 2291131 C CA2291131 C CA 2291131C
- Authority
- CA
- Canada
- Prior art keywords
- acrylonitrile
- value
- incorporated
- moulding compositions
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08L51/04—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 rubbers
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- 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
- C08L51/08—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 otherwise than 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Landscapes
- 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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to thermoplastic resin ABS-type moulding material s characterized in that the polymer constituent which is soluble in dichloromethane has an average incorporated acrylonitrile structural unit content (c50 value ) of.gtoreq.28 wt.% and an incorporated acrylonitrile chemical distribution (c90-c10 value) of .gtoreq.5 wt.%.
Description
.. CA 02291131 1999-11-24 LeA 32 440 ABS moulding compositions with irgproved processabilitv Thermoplastic resins of the ABS type have been used for many years for the production of all kinds of moulded parts (see e.g. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A21, pages 652-653, VCH, Weinheim, 1992).
Apart from injection moulding, a common form of processing for such thermoplastic resins is extrusion, the extrusion stage (e.g. production of sheets) often being followed by a thermoforming stage (production of three-dimensional moulded parts).
Materials used for processing by extrusion and thermoforming are required to have good melt elasticity whilst maintaining a good surface finish and good mechanical properties (e.g. toughness) of the thermoformed parts.
Moreover, it is important that the appropriate materials are easily obtainable (production without great technical complexity) and have an uncomplicated constitution (no components that are expensive or difficult to obtain).
Thermoplastic resin moulding compositions of the ABS type have now been found which have the required properties and meet the requirements mentioned in that they have a special content of incorporated acrylonitrile and, in particular, a special chemical distribution of the incorporated acrylonitrile.
The present invention provides thermoplastic resin moulding compositions of the ABS
type, characterised in that the polymer proportion soluble in dichloromethane has an average content (cue value) of incorporated acrylonitrile structural units of ?28 wt.%, preferably 30 to 40 wt.% and particularly 32 to 35 wt.% and a chemical distribution of the acrylonitrile incorporated therein (cue c,o value) of >_5, preferably 6 to 25, particularly 7.5 to 20 and more particularly 10 to 15 wt.%.
. CA 02291131 1999-11-24 LeA 32 440 The invention also provides moulding compositions of the ABS type containing at least one polymer component selected from A) a graft rubber prepared by polymerisation of Al) 25 to 70 parts by wt., preferably 35 to 65 parts by wt. of one or more monomers, wherein acrylonitrile must be contained as the monomer component, onto A2) 30 to 75 parts by wt., preferably 35 to 65 parts by wt. of one or more rubber bases with a glass transition temperature of <_0°C with an average content (c5o value) of acrylonitrile units incorporated in the graft envelope of >_30 wt.%, preferably 31 to 40 wt.% and particularly 32 to 35 wt.% (based on the total graft envelope in each case) and with a chemical distribution of the acrylonitrile incorporated therein (c9o-c,o value) of >_5, preferably 6 to 25, particularly 7.5 to 20 and more particularly 10 to 15 wt.%, and B) a rubber-free thermoplastic vinyl resin, obtained by radical polymerisation of acrylonitrile and styrene and/or a-methylstyrene with an average content (cso value) of incorporated acrylonitrile units of >_28 wt.%, preferably 30 to 40 wt.%, and particularly 32 to 35 wt.% and with a chemical distribution of the acrylonitrile incorporated in the polymer resin (c9o coo value) of >_5, preferably 6 to 25. particularly 7.5 to 20 and more particularly 10 to 15 wt.%.
The moulding compositions according to the invention are characterised by improved processability by extrusion and thermoforming compared with well known moulding compositions of the ABS type.
Particularly preferred ABS moulding compositions according to the invention are those which. apart from conventional graft rubbers, contain thermoplastic resin component B in proportions of 35 to 90 wt.%, preferably 45 to 80 wt.%.
LeA 32 440 Graft rubbers A) within the meaning of the invention are the products obtained during the graft polymerisation of monomers A.1 ) in the presence of rubber A.2), whereby the above-mentioned chemical distribution of the incorporated acrylonitrile must be maintained.
Monomers A.1 ) are preferably mixtures of A.1.1 ) 50 to 99 parts by wt. of vinyl aromatics and/or vinyl aromatics substituted on the nucleus (such as, for example, styrene, a-methylstyrene, p-methylstyrene, p-chlorostyrene) and/or methacrylic acid (C,-C4) alkyl esters (such as, e.g., methylmethacrylate, ethylmethacrylate) and A.1.2) 1 to 50 parts by wt. of vinyl cyanides (unsaturated rutriles such as acrylonitrile and methacrylonitrile) and optionally (meth)acrylic acid (C,-C8) alkyl esters (such as, e.g. methylmethacrylate, n-butylacrylate, t-butylacrylate) and/or unsaturated carboxylic acids (such as malefic acid) and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example, malefic anhydride and N-phenylmaleinimide).
Preferred monomers A.1.1 ) are styrene, a-methylstyrene and methylmethacrylate, preferred monomers A.1.2) are acrylonitrile, malefic anhydride, N-phenylmaleinimide and methylmethacrylate, whereby acrylonitrile must necessarily be used as a monomer component in graft polymerisation.
Particularly preferred monomers are A.1.1) styrene and A.1.2) acrylonitrile.
Rubber bases A.2) suitable for graft polymers A) are, for example, dime rubbers, EPM
and EPDM rubbers, i.e. composed of ethylene/propylene and optionally small quantities of a non-conjugated diene (such as norbornene, norbornadiene), acrylate, polyurethane, silicone, chloroprene, and ethylene/vinyl acetate rubbers, provided said ~
LeA 32 440 rubbers are in the emulsion form.
Preferred rubber bases A.2) are dime rubbers (e.g. based on butadiene, isoprene etc.) or mixtures of dime rubbers or copolymers of dime rubbers or mixtures thereof with S other copolymerisable monomers (e.g. according to A.1.1) and A.1.2)), provided that their glass transition temperatures are below 0°C.
Pure polybutadiene rubber and butadiene/styrene copolymer rubbers and butadiene/acrylonitrile copolymer rubbers are particularly preferred.
Further particularly preferred rubber bases A.2) are acrylate rubbers, preferably - polymers of acrylic acid alkyl esters, optionally with up to 40 wt.% (based on A.2) of other polymerisable ethylenically unsaturated monomers. The preferred polymerisable acrylates include C,-C8 alkyl esters, for example, methyl-, ethyl-, butyl-, n-octyl and 2 ethylhexyl esters; halogen alkyl esters, preferably halogen C,-Cg alkyl esters, such as chloroethylacrylate, and mixtures of said monomers.
For the purpose of cross-linking, monomers with more than one polymerisable double bond may be copolymerised. Preferred examples of cross-linking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as, e.g., ethylene glycol dimethacrylate, allylmethacrylate;
polyunsaturated heterocyclic compounds such as, e.g., trivinyl- and triallylcyanurate;
polyfunctional vinyl compounds, such as di- and trivinylbenzenes; and also triallyl phosphate and diallylphthalate.
Preferred crosslixlking monomers are allylmethacrylate, ethylene glycol dimethacrylate, diallylphthalate and heterocyclic compounds containing at least 3 ethylenically unsaturated groups.
Particularly preferred crosslinking monomers are the cyclic monomers LeA 32 440 triallylcyanurate, triallylisocyanurate, trivinylcyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. The quantity of crosslinking monomers is preferably 0.02 to 5, particularly 0.05 to 2 wt.%. based on the graft base A.2).
5 In the case of cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the quantity to less than 1 wt.% of the graft base A.2).
Preferred "other" polymerisable ethylenically unsaturated monomers, apart from the acrylates, which may be used optionally for the preparation of the graft base A.2), are e.g. acrylonitrile, styrene, oc-methylstyrene, acrylamides, vinyl C,-C6 alkyl ethers, methylmethacrylate, butadiene. Acrylate rubbers preferred as graft base A.2) are emulsion polymers having a gel content of at least 50 wt.%.
Further suitable graft bases according to A.2) are silicone rubbers with graft-active sites such as those described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 361 539.
The geI content of graft base A.2) is 30 to 95 wt.%, preferably 40 to 90 wt.%
and particularly 45 to 85 wt.% (measured according to the wire cage method in toluene, compare Houben-Weyl, Methoden der Organischen Chemie, Makromolekulare Stoffe, part 1, page 307 ( 1961 ), Thieme Verlag Stuttgart).
The average particle diameter d5° of the rubber base A.2) is generally 100 to 600 nm, preferably 150 to 500 nm and particularly 200 to 400 nm.
The average particle diameter d5° is the diameter above and below which 50 wt.% of the particles lie in each case. It may be determined by an ultracentrifuge measurement (W. Scholtan, H. Large, Kolloid Z. a Z. Polymere 250 (1972), pages 782 to 796).
The graft rubbers A are prepared preferably by radical emulsion polymerisation.
LeA 32 440 T'he compounds normally used as molecular weight regulators, such as, e.g.
mercaptans or terpinols or dimeric a-methylstyrene, may be used in the preparation of the graft rubbers A.
Practically all types of emulsifier (anionic, cationic and nonionic emulsifiers) are suitable as emulsifiers, anionic emulsifiers being used in preference.
Suitable anionic emulsifiers are, for example, sodium, potassium or ammonium salts of long-chain fatty acids with 10 to 20 carbon atoms, e.g. potassium oleate, salts of the disproportionated abietic acid, salts of long-chain benzene sulfonates, salts of long-chain sulfonic acids, e.g. the sodium salts of C9-C,g alkylsulfonic acid mixtures and salts of dicarboxylic acids based on cyclic hydrocarbon frameworks according to DE-OS 3 639 904 and DE-OS 3 913 509.
- -The reaction temperatures selected may be any temperatures at which the initiator compounds used yield radicals to a sufficient extent for initiating and maintaining the polymerisation reaction. This temperature range is approximately between 30°C and 120°C, preferably between 45°C and 100°C and particularly between 50 and 90°C.
Suitable initiators for the preparation of A) and B) are all the substances acting as radical formers. Examples thereof are inorganic and organic peroxides, e.g.
HzO,, di-tert.-butylperoxide, cumene hydroperoxide, dicyclohexyl percarbonate, tert.-butylhydroperoxide, p-menthane hydroperoxide, azo initiators such as, e.g., ?5 azobisisobutyronitrile, inorganic persalts such as ammonium, sodium or potassium persulfate, potassium perphosphate, sodium perborate and redox systems which are composed of a normally organic oxidising agent and a reducing agent, heavy metal ions preferably also being present in the reaction medium (see H. Logemann in Houben-Weyl, Methoden der organischen Chemie, volume 14/1, pages 263-297).
Preferred initiators are ammonium, sodium or potassium persulfate and redox systems LeA 32 440 of an organic peroxide and an organic reducing agent. Particularly preferred initiators are potassium persulfate or redox systems of cumene hydroperoxide and/or tert.-butylhydroperoxide and ascorbic acid and/or ascorbic acid salt.
The non-homogenous incorporation of the acrylonitrile monomer units into the graft envelope required according to the invention (broad chemical distribution) is known in principle. It may be achieved, e.g., if, during the graft polymerisation reaction, the value for the monomer ratio required for a homogeneous constitution on account of copolymerisation parameters is not maintained throughout the reaction period.
The rubber-free thermoplastic vinyl resin component B) includes one or more specially constituted polymers obtained by radical polymerisation of monomer mixtures of styrene and acrylonitrile, a-methylstyrene and acrylonitrile or of styrene, a methylstyrene and acrylonitrile, whereby these may contain further comonomers in smaller quantities (up to about 15 wt.%).
Suitable monomers of such kind are, for example, acrylic acid (C,-Cg) alkyl esters (e.g.
n-butylacrylate, tert.-butylacrylate, ethylhexylacrylate), methacrylic acid (C,-C8) alkylesters (e.g. methylmethacrylate, ethylmethacrylate), unsaturated carboxylic acids including their derivatives (such as anhydrides or imides) (e.g. acrylic acid, methacrylic acid, malefic acid, malefic anhydride, N-phenylmaleinimide).
In order to obtain the improvement in processability according to the invention by extrusion and thermoforming, the thermoplastic vinyl resin component B) must have a special constitution in terms of the chemical uniformity to the effect that the acrylonitrile monomer units are not incorporated homogeneously, but the resins have a broad chemical distribution.
Vinyl resins of such a constitution are known, in principle. They are obtained e.g. if, during polymerisation of the resins, the value for the monomer ratio required for a homogeneous constitution on account of copolymerisation parameters is not LeA 32 440 maintained throughout the reaction period.
Particularly suitable vinyl resins B) according to the invention are those in the preparation of which the monomers styrene (a) and acrylonitrile (b) or a-methylstyrene (a) and acrylonitrile (b), or styrene (aj and a-methylstyrene (a) and acrylonitrile (b) are metered into the reaction zone of at least one reactor in such a way that the weight ratio (a) : (b) during the course of the co- or terpolymerisation reaction assumes an increasing or a decreasing value, but not a constant value.
Suitable resins according to the invention preferably have an average content (cso value) of incorporated acrylonitrile structural units of >_30 wt.%, preferably 31 to 40 wt.% and particularly 32 to 35 wt.%, and a chemical distribution of the acrylonitrile incorporated in the polymer resin such that a (c9o-coo value) (c9°
minus c,o) of >_5, preferably 6 to 25, particularly 7.5 to 20 and more particularly 10 to 15 wt.%
is obtained. _ -The c;° value means the acrylonitrile content in the polymer (in wt.%) above and below which 50 wt.% of the acrylonitrile quantity is incorporated in each case.
Accordingly, the c~ value means the acrylonitrile content in the polymer above and below which 90 wt.% of the acrylonitrile quantity is incorporated.
These values may be determined by HPLC with gradient elution (see, e.g. G.
GlOckner: Gradient HPLC of Copolymers and Chromatographic Cross-Fractionating, Springer Verlag, Berlin-Heidelberg, 1991).
Apart from the chemical non-uniformity described here, the vinyl polymer resins B) preferably have average molecular weights M « (weight-average, determined by light scattering or sedimentation) of 20,000 to 500,000, preferably 50,000 to 400,000 and particularly 60,000 to 300,000.
LeA 32 440 In principle, the vinyl resins B) may be prepared according to all the processes of radical polymerisation such as emulsion, suspension, solution or bulk polymerisation.
The weight ratio A : B is 2 : 1 to 1 : 4, preferably between I : 1 and 1 : 2.
Higher A : B
ratios lead to an insufficient flow behaviour and reduced stiffness, whilst A
: B ratios lower than 1 : 4 bring about an unsatisfactory low temperature toughness.
The moulding compositions according to the invention may also contain further known additives in the conventional or necessary quantities. Without any claim to completeness, mention may be made here of stabilisers (e.g. sterically hindered phenols and thioethers or phosphite compounds as synergists), conventional pigments (carbon black, metal oxides etc.), mould release agents (e.g. pentaerythritol tetrastearate,), flow improvers (ethylene diamine bisstearylamide), fillers and reinforcing agents (e.g. glass fibres and carbon fibres), flame retardants (e.g.
tetrabromobisphenol A), antidrip agents (e.g. tetrafluoroethylene polymers) and antistatic agents (e.g. polyalkylene ethers).
The moulding compositions according to the invention may be prepared by mixing the constituents in a known way and melt-compounding or melt-extrusion at elevated temperatures, preferably at 200 to 260°C, in conventional devices such as internal kneaders, extruders or twin shaft screws. The moulding compositions according to the invention are particularly suitable for the production of parts by extrusion (e.g. sheets and films) followed by thermoforming.
The invention also provides the use of the moulding compositions described for the production of moulded parts by extrusion and by thermoforming.
LeA 32 440 Examples 1. Constituents A.I. Graft rubber prepared by emulsion polymerisation of 30.6 parts by weight of styrene and 14.4 parts by weight of acrylonitrile in the presence of 55 parts by weight (calculated as solid) of a polybutadiene latex produced by a conventional method (average particle diameter d;o = 423 nm, gel content = 81 10 wt.%) with 0.5 parts by weight of potassium persulfate as initiator, the monomers being metered within 4 hours to the rubber latex in such a way that the styrene metering takes place uniformly and continuously (25% of the total quantity per hour in each case) and the acrylonitrile metering takes place in decreasing amounts (40% of the total quantity in the first hour, 30% of the total quantity in the second hour, 2_0% of the total quantity in the thud hour and 10%
of the total quantity in the fourth hour).
Average content of acrylonitrile units in the dichloromethane-soluble polymer proportion (c;o value) = 32.1 wt.%, chemical distribution of the incorporated acrylonitrile (cue-c,° value) = 12.4 wt.%.
A.II (Comparison):
Graft rubber prepared by emulsion polymerisation of 30.6 parts by weight of styrene and 14.4. parts by weight of acrylonitrile in the presence of 55 parts by weight (calculated as solid) of a polybutadiene latex produced by a conventional method (average particle diameter d;o = 423 nm, gel content = 81 wt.%) with 0.5 parts by weight of potassium persulfate as initiator, the monomers being metered uniformly and continuously to the rubber latex within 4 hours (25% of the total quantity of styrene and acrylonitrile in the first, second, third and fourth hour in each case).
LeA 32 440 Average content of acrylonitrile units in the dichloromethane-soluble polymer proportion (cso value) = 32.0 wt.%, chemical distribution of the incorporated acrylonitrile (c9o c,o value) = 3.2 wt.%.
B.I. Styrene/acrylonitrile copolymer with a styrene : acrylonitrile weight ratio of 68 32 and an average molecular weight M W ~ 110,000, prepared by emulsion polymerisation whereby, within 4 hours, 17 parts by weight of styrene and 12.8 parts by weight of acrylonitrile are polymerised in the first hour, 17 parts by IO weight of styrene and 9.6 parts by weight of acrylonitrile within the second hour, 17 parts by weight of styrene and 6.4 parts by weight of acrylonitrile within the third hour, and 17 parts by weight of styrene and 3.2 parts by weight of acrylonitrile within the fourth hour, using potassium persulfate (KzSz08) as initiator.
Average content of acrylonitrile structural units with respect to a dichloromethane solution (c5o value) = 31.9 wt.%, chemical distribution of the incorporated acrylonitrile (cue -c,o value) =
13.7 wt. %.
B.II. (Comparison):
Styrene/acrylonitrile copolymer with a styrene : acrylonitrile weight ratio of 32 and an average molecular weight M W ~ I 12,000, prepared by emulsion polymerisation whereby, within 4 hours, 17 parts by weight of styrene and 8 parts by weight of acrylonitrile are polymerised uniformly in each case, with the use of potassium persulfate (KzS208) as initiator. (Average content of acrylonitrile structural units with respect to a dichloromethane solution (c5o value) = 32.0 wt.%, chemical distribution of the incorporated acrylonitrile (c~o-c,o value) = 2.2 wt.%.
2. Preparation and testing of the moulding compositions according to the LeA 32 440 invention and of the comparison moulding compositions The components A and B are melted and homogenised in the quantities given in Table 1 together with additives (2 parts by weight of pentaerythritol tetrastearate and 0.1 part by weight of silicone oil, in each case per 100 parts by weight of A + B) in an internal kneader at temperatures between 180 and 230°C.
Sheets are prepared from the granules.
As a high melt elasticity is required for good thermoforming properties of ABS
moulding compositions (corresponding to a low loss factor tan 8), the thermoforming behaviour may be determined by determining the loss factor tan S at low frequencies (corresponding to a low shear rate occurring during thermoforming) at a temperature of 170°C (instrument: RDA II from Rheometrics, plate/plate arrangement).
In addition, extruded sheets (30 cm x 26 cm) of some products are thermoformed to a paraboloid, the thermoforming properties and nature of the surface being assessed.
The mechanical properties are assessed by the behaviour during impact.
As can be seen from Table 2, only the moulding compositions according to the invention have a low loss factor tan S at low frequencies (w = 0.02 rad/sec) required for good thermoforming properties; the practical thermoforming behaviour and surface finish of the paraboloids produced are very good for the moulding compositions according to the invention.
The thermoforming properties and the surface of the thermoformed parts are evaluated as follows:
++ very good + good o average poor LeA 32 440 -- very poor Table 1:
Compositions of the moulding compositions examined Examples A.1. A.II B.1. B.II.
(Parts by wt.) (Parts by wt.) (Parts by wt.) (Parts by wt.) 4 (comparison) -- 40 -- 60 7 (comparison) -- 30 -- 70 Table 2:
Evaluation of the moulding compositions Example tan 8 at Behaviour Surface finish Behaviour c~ = 0.02 during of thermo- during impact rad/sec thermoforming formed part 1 1.1 ++ ++ tough 2 1.4 ++ ++ tough 3 1.2 ++ ++ tough 4 (comparison) 1.9 o n.m. tough ~
5 1.5 ++ ++ tough 6 1.6 + ++ tough 7 (comparison) 2.3 - n.m. tough n.m. = not measured
Apart from injection moulding, a common form of processing for such thermoplastic resins is extrusion, the extrusion stage (e.g. production of sheets) often being followed by a thermoforming stage (production of three-dimensional moulded parts).
Materials used for processing by extrusion and thermoforming are required to have good melt elasticity whilst maintaining a good surface finish and good mechanical properties (e.g. toughness) of the thermoformed parts.
Moreover, it is important that the appropriate materials are easily obtainable (production without great technical complexity) and have an uncomplicated constitution (no components that are expensive or difficult to obtain).
Thermoplastic resin moulding compositions of the ABS type have now been found which have the required properties and meet the requirements mentioned in that they have a special content of incorporated acrylonitrile and, in particular, a special chemical distribution of the incorporated acrylonitrile.
The present invention provides thermoplastic resin moulding compositions of the ABS
type, characterised in that the polymer proportion soluble in dichloromethane has an average content (cue value) of incorporated acrylonitrile structural units of ?28 wt.%, preferably 30 to 40 wt.% and particularly 32 to 35 wt.% and a chemical distribution of the acrylonitrile incorporated therein (cue c,o value) of >_5, preferably 6 to 25, particularly 7.5 to 20 and more particularly 10 to 15 wt.%.
. CA 02291131 1999-11-24 LeA 32 440 The invention also provides moulding compositions of the ABS type containing at least one polymer component selected from A) a graft rubber prepared by polymerisation of Al) 25 to 70 parts by wt., preferably 35 to 65 parts by wt. of one or more monomers, wherein acrylonitrile must be contained as the monomer component, onto A2) 30 to 75 parts by wt., preferably 35 to 65 parts by wt. of one or more rubber bases with a glass transition temperature of <_0°C with an average content (c5o value) of acrylonitrile units incorporated in the graft envelope of >_30 wt.%, preferably 31 to 40 wt.% and particularly 32 to 35 wt.% (based on the total graft envelope in each case) and with a chemical distribution of the acrylonitrile incorporated therein (c9o-c,o value) of >_5, preferably 6 to 25, particularly 7.5 to 20 and more particularly 10 to 15 wt.%, and B) a rubber-free thermoplastic vinyl resin, obtained by radical polymerisation of acrylonitrile and styrene and/or a-methylstyrene with an average content (cso value) of incorporated acrylonitrile units of >_28 wt.%, preferably 30 to 40 wt.%, and particularly 32 to 35 wt.% and with a chemical distribution of the acrylonitrile incorporated in the polymer resin (c9o coo value) of >_5, preferably 6 to 25. particularly 7.5 to 20 and more particularly 10 to 15 wt.%.
The moulding compositions according to the invention are characterised by improved processability by extrusion and thermoforming compared with well known moulding compositions of the ABS type.
Particularly preferred ABS moulding compositions according to the invention are those which. apart from conventional graft rubbers, contain thermoplastic resin component B in proportions of 35 to 90 wt.%, preferably 45 to 80 wt.%.
LeA 32 440 Graft rubbers A) within the meaning of the invention are the products obtained during the graft polymerisation of monomers A.1 ) in the presence of rubber A.2), whereby the above-mentioned chemical distribution of the incorporated acrylonitrile must be maintained.
Monomers A.1 ) are preferably mixtures of A.1.1 ) 50 to 99 parts by wt. of vinyl aromatics and/or vinyl aromatics substituted on the nucleus (such as, for example, styrene, a-methylstyrene, p-methylstyrene, p-chlorostyrene) and/or methacrylic acid (C,-C4) alkyl esters (such as, e.g., methylmethacrylate, ethylmethacrylate) and A.1.2) 1 to 50 parts by wt. of vinyl cyanides (unsaturated rutriles such as acrylonitrile and methacrylonitrile) and optionally (meth)acrylic acid (C,-C8) alkyl esters (such as, e.g. methylmethacrylate, n-butylacrylate, t-butylacrylate) and/or unsaturated carboxylic acids (such as malefic acid) and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example, malefic anhydride and N-phenylmaleinimide).
Preferred monomers A.1.1 ) are styrene, a-methylstyrene and methylmethacrylate, preferred monomers A.1.2) are acrylonitrile, malefic anhydride, N-phenylmaleinimide and methylmethacrylate, whereby acrylonitrile must necessarily be used as a monomer component in graft polymerisation.
Particularly preferred monomers are A.1.1) styrene and A.1.2) acrylonitrile.
Rubber bases A.2) suitable for graft polymers A) are, for example, dime rubbers, EPM
and EPDM rubbers, i.e. composed of ethylene/propylene and optionally small quantities of a non-conjugated diene (such as norbornene, norbornadiene), acrylate, polyurethane, silicone, chloroprene, and ethylene/vinyl acetate rubbers, provided said ~
LeA 32 440 rubbers are in the emulsion form.
Preferred rubber bases A.2) are dime rubbers (e.g. based on butadiene, isoprene etc.) or mixtures of dime rubbers or copolymers of dime rubbers or mixtures thereof with S other copolymerisable monomers (e.g. according to A.1.1) and A.1.2)), provided that their glass transition temperatures are below 0°C.
Pure polybutadiene rubber and butadiene/styrene copolymer rubbers and butadiene/acrylonitrile copolymer rubbers are particularly preferred.
Further particularly preferred rubber bases A.2) are acrylate rubbers, preferably - polymers of acrylic acid alkyl esters, optionally with up to 40 wt.% (based on A.2) of other polymerisable ethylenically unsaturated monomers. The preferred polymerisable acrylates include C,-C8 alkyl esters, for example, methyl-, ethyl-, butyl-, n-octyl and 2 ethylhexyl esters; halogen alkyl esters, preferably halogen C,-Cg alkyl esters, such as chloroethylacrylate, and mixtures of said monomers.
For the purpose of cross-linking, monomers with more than one polymerisable double bond may be copolymerised. Preferred examples of cross-linking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as, e.g., ethylene glycol dimethacrylate, allylmethacrylate;
polyunsaturated heterocyclic compounds such as, e.g., trivinyl- and triallylcyanurate;
polyfunctional vinyl compounds, such as di- and trivinylbenzenes; and also triallyl phosphate and diallylphthalate.
Preferred crosslixlking monomers are allylmethacrylate, ethylene glycol dimethacrylate, diallylphthalate and heterocyclic compounds containing at least 3 ethylenically unsaturated groups.
Particularly preferred crosslinking monomers are the cyclic monomers LeA 32 440 triallylcyanurate, triallylisocyanurate, trivinylcyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. The quantity of crosslinking monomers is preferably 0.02 to 5, particularly 0.05 to 2 wt.%. based on the graft base A.2).
5 In the case of cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the quantity to less than 1 wt.% of the graft base A.2).
Preferred "other" polymerisable ethylenically unsaturated monomers, apart from the acrylates, which may be used optionally for the preparation of the graft base A.2), are e.g. acrylonitrile, styrene, oc-methylstyrene, acrylamides, vinyl C,-C6 alkyl ethers, methylmethacrylate, butadiene. Acrylate rubbers preferred as graft base A.2) are emulsion polymers having a gel content of at least 50 wt.%.
Further suitable graft bases according to A.2) are silicone rubbers with graft-active sites such as those described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 361 539.
The geI content of graft base A.2) is 30 to 95 wt.%, preferably 40 to 90 wt.%
and particularly 45 to 85 wt.% (measured according to the wire cage method in toluene, compare Houben-Weyl, Methoden der Organischen Chemie, Makromolekulare Stoffe, part 1, page 307 ( 1961 ), Thieme Verlag Stuttgart).
The average particle diameter d5° of the rubber base A.2) is generally 100 to 600 nm, preferably 150 to 500 nm and particularly 200 to 400 nm.
The average particle diameter d5° is the diameter above and below which 50 wt.% of the particles lie in each case. It may be determined by an ultracentrifuge measurement (W. Scholtan, H. Large, Kolloid Z. a Z. Polymere 250 (1972), pages 782 to 796).
The graft rubbers A are prepared preferably by radical emulsion polymerisation.
LeA 32 440 T'he compounds normally used as molecular weight regulators, such as, e.g.
mercaptans or terpinols or dimeric a-methylstyrene, may be used in the preparation of the graft rubbers A.
Practically all types of emulsifier (anionic, cationic and nonionic emulsifiers) are suitable as emulsifiers, anionic emulsifiers being used in preference.
Suitable anionic emulsifiers are, for example, sodium, potassium or ammonium salts of long-chain fatty acids with 10 to 20 carbon atoms, e.g. potassium oleate, salts of the disproportionated abietic acid, salts of long-chain benzene sulfonates, salts of long-chain sulfonic acids, e.g. the sodium salts of C9-C,g alkylsulfonic acid mixtures and salts of dicarboxylic acids based on cyclic hydrocarbon frameworks according to DE-OS 3 639 904 and DE-OS 3 913 509.
- -The reaction temperatures selected may be any temperatures at which the initiator compounds used yield radicals to a sufficient extent for initiating and maintaining the polymerisation reaction. This temperature range is approximately between 30°C and 120°C, preferably between 45°C and 100°C and particularly between 50 and 90°C.
Suitable initiators for the preparation of A) and B) are all the substances acting as radical formers. Examples thereof are inorganic and organic peroxides, e.g.
HzO,, di-tert.-butylperoxide, cumene hydroperoxide, dicyclohexyl percarbonate, tert.-butylhydroperoxide, p-menthane hydroperoxide, azo initiators such as, e.g., ?5 azobisisobutyronitrile, inorganic persalts such as ammonium, sodium or potassium persulfate, potassium perphosphate, sodium perborate and redox systems which are composed of a normally organic oxidising agent and a reducing agent, heavy metal ions preferably also being present in the reaction medium (see H. Logemann in Houben-Weyl, Methoden der organischen Chemie, volume 14/1, pages 263-297).
Preferred initiators are ammonium, sodium or potassium persulfate and redox systems LeA 32 440 of an organic peroxide and an organic reducing agent. Particularly preferred initiators are potassium persulfate or redox systems of cumene hydroperoxide and/or tert.-butylhydroperoxide and ascorbic acid and/or ascorbic acid salt.
The non-homogenous incorporation of the acrylonitrile monomer units into the graft envelope required according to the invention (broad chemical distribution) is known in principle. It may be achieved, e.g., if, during the graft polymerisation reaction, the value for the monomer ratio required for a homogeneous constitution on account of copolymerisation parameters is not maintained throughout the reaction period.
The rubber-free thermoplastic vinyl resin component B) includes one or more specially constituted polymers obtained by radical polymerisation of monomer mixtures of styrene and acrylonitrile, a-methylstyrene and acrylonitrile or of styrene, a methylstyrene and acrylonitrile, whereby these may contain further comonomers in smaller quantities (up to about 15 wt.%).
Suitable monomers of such kind are, for example, acrylic acid (C,-Cg) alkyl esters (e.g.
n-butylacrylate, tert.-butylacrylate, ethylhexylacrylate), methacrylic acid (C,-C8) alkylesters (e.g. methylmethacrylate, ethylmethacrylate), unsaturated carboxylic acids including their derivatives (such as anhydrides or imides) (e.g. acrylic acid, methacrylic acid, malefic acid, malefic anhydride, N-phenylmaleinimide).
In order to obtain the improvement in processability according to the invention by extrusion and thermoforming, the thermoplastic vinyl resin component B) must have a special constitution in terms of the chemical uniformity to the effect that the acrylonitrile monomer units are not incorporated homogeneously, but the resins have a broad chemical distribution.
Vinyl resins of such a constitution are known, in principle. They are obtained e.g. if, during polymerisation of the resins, the value for the monomer ratio required for a homogeneous constitution on account of copolymerisation parameters is not LeA 32 440 maintained throughout the reaction period.
Particularly suitable vinyl resins B) according to the invention are those in the preparation of which the monomers styrene (a) and acrylonitrile (b) or a-methylstyrene (a) and acrylonitrile (b), or styrene (aj and a-methylstyrene (a) and acrylonitrile (b) are metered into the reaction zone of at least one reactor in such a way that the weight ratio (a) : (b) during the course of the co- or terpolymerisation reaction assumes an increasing or a decreasing value, but not a constant value.
Suitable resins according to the invention preferably have an average content (cso value) of incorporated acrylonitrile structural units of >_30 wt.%, preferably 31 to 40 wt.% and particularly 32 to 35 wt.%, and a chemical distribution of the acrylonitrile incorporated in the polymer resin such that a (c9o-coo value) (c9°
minus c,o) of >_5, preferably 6 to 25, particularly 7.5 to 20 and more particularly 10 to 15 wt.%
is obtained. _ -The c;° value means the acrylonitrile content in the polymer (in wt.%) above and below which 50 wt.% of the acrylonitrile quantity is incorporated in each case.
Accordingly, the c~ value means the acrylonitrile content in the polymer above and below which 90 wt.% of the acrylonitrile quantity is incorporated.
These values may be determined by HPLC with gradient elution (see, e.g. G.
GlOckner: Gradient HPLC of Copolymers and Chromatographic Cross-Fractionating, Springer Verlag, Berlin-Heidelberg, 1991).
Apart from the chemical non-uniformity described here, the vinyl polymer resins B) preferably have average molecular weights M « (weight-average, determined by light scattering or sedimentation) of 20,000 to 500,000, preferably 50,000 to 400,000 and particularly 60,000 to 300,000.
LeA 32 440 In principle, the vinyl resins B) may be prepared according to all the processes of radical polymerisation such as emulsion, suspension, solution or bulk polymerisation.
The weight ratio A : B is 2 : 1 to 1 : 4, preferably between I : 1 and 1 : 2.
Higher A : B
ratios lead to an insufficient flow behaviour and reduced stiffness, whilst A
: B ratios lower than 1 : 4 bring about an unsatisfactory low temperature toughness.
The moulding compositions according to the invention may also contain further known additives in the conventional or necessary quantities. Without any claim to completeness, mention may be made here of stabilisers (e.g. sterically hindered phenols and thioethers or phosphite compounds as synergists), conventional pigments (carbon black, metal oxides etc.), mould release agents (e.g. pentaerythritol tetrastearate,), flow improvers (ethylene diamine bisstearylamide), fillers and reinforcing agents (e.g. glass fibres and carbon fibres), flame retardants (e.g.
tetrabromobisphenol A), antidrip agents (e.g. tetrafluoroethylene polymers) and antistatic agents (e.g. polyalkylene ethers).
The moulding compositions according to the invention may be prepared by mixing the constituents in a known way and melt-compounding or melt-extrusion at elevated temperatures, preferably at 200 to 260°C, in conventional devices such as internal kneaders, extruders or twin shaft screws. The moulding compositions according to the invention are particularly suitable for the production of parts by extrusion (e.g. sheets and films) followed by thermoforming.
The invention also provides the use of the moulding compositions described for the production of moulded parts by extrusion and by thermoforming.
LeA 32 440 Examples 1. Constituents A.I. Graft rubber prepared by emulsion polymerisation of 30.6 parts by weight of styrene and 14.4 parts by weight of acrylonitrile in the presence of 55 parts by weight (calculated as solid) of a polybutadiene latex produced by a conventional method (average particle diameter d;o = 423 nm, gel content = 81 10 wt.%) with 0.5 parts by weight of potassium persulfate as initiator, the monomers being metered within 4 hours to the rubber latex in such a way that the styrene metering takes place uniformly and continuously (25% of the total quantity per hour in each case) and the acrylonitrile metering takes place in decreasing amounts (40% of the total quantity in the first hour, 30% of the total quantity in the second hour, 2_0% of the total quantity in the thud hour and 10%
of the total quantity in the fourth hour).
Average content of acrylonitrile units in the dichloromethane-soluble polymer proportion (c;o value) = 32.1 wt.%, chemical distribution of the incorporated acrylonitrile (cue-c,° value) = 12.4 wt.%.
A.II (Comparison):
Graft rubber prepared by emulsion polymerisation of 30.6 parts by weight of styrene and 14.4. parts by weight of acrylonitrile in the presence of 55 parts by weight (calculated as solid) of a polybutadiene latex produced by a conventional method (average particle diameter d;o = 423 nm, gel content = 81 wt.%) with 0.5 parts by weight of potassium persulfate as initiator, the monomers being metered uniformly and continuously to the rubber latex within 4 hours (25% of the total quantity of styrene and acrylonitrile in the first, second, third and fourth hour in each case).
LeA 32 440 Average content of acrylonitrile units in the dichloromethane-soluble polymer proportion (cso value) = 32.0 wt.%, chemical distribution of the incorporated acrylonitrile (c9o c,o value) = 3.2 wt.%.
B.I. Styrene/acrylonitrile copolymer with a styrene : acrylonitrile weight ratio of 68 32 and an average molecular weight M W ~ 110,000, prepared by emulsion polymerisation whereby, within 4 hours, 17 parts by weight of styrene and 12.8 parts by weight of acrylonitrile are polymerised in the first hour, 17 parts by IO weight of styrene and 9.6 parts by weight of acrylonitrile within the second hour, 17 parts by weight of styrene and 6.4 parts by weight of acrylonitrile within the third hour, and 17 parts by weight of styrene and 3.2 parts by weight of acrylonitrile within the fourth hour, using potassium persulfate (KzSz08) as initiator.
Average content of acrylonitrile structural units with respect to a dichloromethane solution (c5o value) = 31.9 wt.%, chemical distribution of the incorporated acrylonitrile (cue -c,o value) =
13.7 wt. %.
B.II. (Comparison):
Styrene/acrylonitrile copolymer with a styrene : acrylonitrile weight ratio of 32 and an average molecular weight M W ~ I 12,000, prepared by emulsion polymerisation whereby, within 4 hours, 17 parts by weight of styrene and 8 parts by weight of acrylonitrile are polymerised uniformly in each case, with the use of potassium persulfate (KzS208) as initiator. (Average content of acrylonitrile structural units with respect to a dichloromethane solution (c5o value) = 32.0 wt.%, chemical distribution of the incorporated acrylonitrile (c~o-c,o value) = 2.2 wt.%.
2. Preparation and testing of the moulding compositions according to the LeA 32 440 invention and of the comparison moulding compositions The components A and B are melted and homogenised in the quantities given in Table 1 together with additives (2 parts by weight of pentaerythritol tetrastearate and 0.1 part by weight of silicone oil, in each case per 100 parts by weight of A + B) in an internal kneader at temperatures between 180 and 230°C.
Sheets are prepared from the granules.
As a high melt elasticity is required for good thermoforming properties of ABS
moulding compositions (corresponding to a low loss factor tan 8), the thermoforming behaviour may be determined by determining the loss factor tan S at low frequencies (corresponding to a low shear rate occurring during thermoforming) at a temperature of 170°C (instrument: RDA II from Rheometrics, plate/plate arrangement).
In addition, extruded sheets (30 cm x 26 cm) of some products are thermoformed to a paraboloid, the thermoforming properties and nature of the surface being assessed.
The mechanical properties are assessed by the behaviour during impact.
As can be seen from Table 2, only the moulding compositions according to the invention have a low loss factor tan S at low frequencies (w = 0.02 rad/sec) required for good thermoforming properties; the practical thermoforming behaviour and surface finish of the paraboloids produced are very good for the moulding compositions according to the invention.
The thermoforming properties and the surface of the thermoformed parts are evaluated as follows:
++ very good + good o average poor LeA 32 440 -- very poor Table 1:
Compositions of the moulding compositions examined Examples A.1. A.II B.1. B.II.
(Parts by wt.) (Parts by wt.) (Parts by wt.) (Parts by wt.) 4 (comparison) -- 40 -- 60 7 (comparison) -- 30 -- 70 Table 2:
Evaluation of the moulding compositions Example tan 8 at Behaviour Surface finish Behaviour c~ = 0.02 during of thermo- during impact rad/sec thermoforming formed part 1 1.1 ++ ++ tough 2 1.4 ++ ++ tough 3 1.2 ++ ++ tough 4 (comparison) 1.9 o n.m. tough ~
5 1.5 ++ ++ tough 6 1.6 + ++ tough 7 (comparison) 2.3 - n.m. tough n.m. = not measured
Claims (10)
1. Thermoplastic resin moulding compositions of the ABS type, characterised in that the polymer proportion soluble in dichloromethane has an average content (c50 value) of incorporated acrylonitrile structural units of >= 28 wt.%, and a chemical distribution of the incorporated acrylonitrile (c90-c10 value) of >=5 wt.%.
2. Thermoplastic resin moulding compositions according to claim 1, characterised in that the polymer proportion soluble in dichloromethane has an average content (c50 value) of incorporated acrylonitrile structural units of >=30 to 40 wt.% and a chemical distribution of the incorporated acrylonitrile (c90-c10 value) of 6 to 25 wt%.
3. Thermoplastic resin moulding compositions of the ABS type according to claim 1, containing at least one polymer component selected from:
A) a graft rubber prepared by polymerisation of A1) 25 to 70 parts by wt. of one or more monomers, wherein acrylonitrile must be contained as the monomer component, onto A2) 30 to 75 parts by wt. of one or more rubber bases with a glass transition temperature of <=0°C with an average content (c50 value) of acrylonitrile units incorporated in the graft envelope of >=30 wt.%
(based on the total graft envelope in each case) and with a chemical distribution of the acrylonitrile incorporated therein (c90-c10 value) of >=5 wt.%, and B) a rubber-free thermoplastic vinyl resin obtained by radical polymerisation of a monomer combination of acrylonitrile and styrene and/or a methylstyrene with an average content (c50 value) of incorporated acrylonitrile structural units of >= 28 wt.% and a chemical distribution of the acrylonitrile incorporated in the polymer resin (c90-c10 value) of >=5 wt.%.
A) a graft rubber prepared by polymerisation of A1) 25 to 70 parts by wt. of one or more monomers, wherein acrylonitrile must be contained as the monomer component, onto A2) 30 to 75 parts by wt. of one or more rubber bases with a glass transition temperature of <=0°C with an average content (c50 value) of acrylonitrile units incorporated in the graft envelope of >=30 wt.%
(based on the total graft envelope in each case) and with a chemical distribution of the acrylonitrile incorporated therein (c90-c10 value) of >=5 wt.%, and B) a rubber-free thermoplastic vinyl resin obtained by radical polymerisation of a monomer combination of acrylonitrile and styrene and/or a methylstyrene with an average content (c50 value) of incorporated acrylonitrile structural units of >= 28 wt.% and a chemical distribution of the acrylonitrile incorporated in the polymer resin (c90-c10 value) of >=5 wt.%.
4. Thermoplastic resin moulding compositions of the ABS type according to claim 3, containing at least one polymer component selected from:
A) a graft rubber prepared by polymerisation of A1) 35 to 65 parts by wt. of one or more monomers, wherein acrylonitrile must be contained as the monomer component, onto A2) 35 to 65 parts by wt. of one or more rubber bases with a glass transition temperature of <=0°C with an average content (c50 value) of acrylonitrile structural units incorporated in the graft envelope of 31 to 40 wt.%, based on the total graft envelope in each case, and with a chemical distribution of the acrylonitrile incorporated therein (c90-c10 value) of 6 to 25 wt.%, and B) a rubber-free thermoplastic vinyl resin, obtained by radical polymerisation of a monomer combination of acrylonitrile and styrene and/or .alpha.-methylstyrene with an average content (c50 value) of incorporated acrylonitrile structural units of 30 to 40 wt.% and with a chemical distribution of the acrylonitrile incorporated in the polymer resin (c90-c10 value) of 6 to 25 wt.%.
A) a graft rubber prepared by polymerisation of A1) 35 to 65 parts by wt. of one or more monomers, wherein acrylonitrile must be contained as the monomer component, onto A2) 35 to 65 parts by wt. of one or more rubber bases with a glass transition temperature of <=0°C with an average content (c50 value) of acrylonitrile structural units incorporated in the graft envelope of 31 to 40 wt.%, based on the total graft envelope in each case, and with a chemical distribution of the acrylonitrile incorporated therein (c90-c10 value) of 6 to 25 wt.%, and B) a rubber-free thermoplastic vinyl resin, obtained by radical polymerisation of a monomer combination of acrylonitrile and styrene and/or .alpha.-methylstyrene with an average content (c50 value) of incorporated acrylonitrile structural units of 30 to 40 wt.% and with a chemical distribution of the acrylonitrile incorporated in the polymer resin (c90-c10 value) of 6 to 25 wt.%.
5. Thermoplastic resin moulding compositions of the ABS type according to claim 3, containing 10 to 65 wt.% of a graft rubber and 90 to 35 wt.% of at least one rubber-free vinyl resin component B).
6. Moulding compositions according to claim 3, wherein A1) is a mixture of styrene and acrylonitrile.
7. Moulding compositions according to claim 3, wherein A2) is selected from polybutadiene, butadiene/styrene copolymer rubber and butadiene/acrylonitrile copolymer rubber.
8. Moulding compositions according to claim 3, wherein B) is a copolymer of styrene and acrylonitrile.
9. The use of moulding compositions according to any one of claims 1 to 8, for the production of thermoformed moulded parts from extruded sheets.
10. Moulded parts of the moulding compositions according to any one of claims 1 to 8, obtained by thermoforming.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722791.0 | 1997-05-30 | ||
| DE19722791A DE19722791A1 (en) | 1997-05-30 | 1997-05-30 | ABS molding compounds with improved processability |
| PCT/EP1998/002919 WO1998054238A1 (en) | 1997-05-30 | 1998-05-18 | Abs molding materials with enhanced working properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2291131A1 CA2291131A1 (en) | 1998-12-03 |
| CA2291131C true CA2291131C (en) | 2007-04-10 |
Family
ID=7831004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002291131A Expired - Fee Related CA2291131C (en) | 1997-05-30 | 1998-05-18 | Abs molding materials with enhanced working properties |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0984994B1 (en) |
| JP (1) | JP4181642B2 (en) |
| KR (1) | KR100579674B1 (en) |
| CN (1) | CN1140550C (en) |
| AR (1) | AR015836A1 (en) |
| AU (1) | AU7913498A (en) |
| BR (1) | BR9809529A (en) |
| CA (1) | CA2291131C (en) |
| DE (2) | DE19722791A1 (en) |
| ES (1) | ES2178225T3 (en) |
| TW (1) | TW515820B (en) |
| WO (1) | WO1998054238A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6806318B2 (en) * | 1997-05-30 | 2004-10-19 | Bayer Aktiengesellschaft | ABS molding materials with enhanced working properties |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4120851A (en) * | 1977-08-22 | 1978-10-17 | Monsanto Company | Process for polymerizing high nitrile ABS polyblends |
| JPS5937006B2 (en) * | 1978-12-30 | 1984-09-07 | 鐘淵化学工業株式会社 | Manufacturing method of nitrile resin |
| JPS5937007B2 (en) * | 1978-12-30 | 1984-09-07 | 鐘淵化学工業株式会社 | Manufacturing method of high nitrile resin |
| JPS6021689B2 (en) * | 1980-06-13 | 1985-05-29 | 住友ノ−ガタック株式会社 | Polymer manufacturing method |
| KR0182358B1 (en) * | 1995-10-09 | 1999-05-15 | 유현식 | Abs resin compositions having high flowability and good vacuum moldability |
-
1997
- 1997-05-30 DE DE19722791A patent/DE19722791A1/en not_active Withdrawn
-
1998
- 1998-05-07 TW TW087106987A patent/TW515820B/en not_active IP Right Cessation
- 1998-05-18 KR KR1019997011102A patent/KR100579674B1/en not_active IP Right Cessation
- 1998-05-18 CN CNB98805518XA patent/CN1140550C/en not_active Expired - Fee Related
- 1998-05-18 DE DE59804434T patent/DE59804434D1/en not_active Expired - Lifetime
- 1998-05-18 JP JP50017999A patent/JP4181642B2/en not_active Expired - Fee Related
- 1998-05-18 ES ES98929335T patent/ES2178225T3/en not_active Expired - Lifetime
- 1998-05-18 AU AU79134/98A patent/AU7913498A/en not_active Abandoned
- 1998-05-18 WO PCT/EP1998/002919 patent/WO1998054238A1/en active IP Right Grant
- 1998-05-18 EP EP98929335A patent/EP0984994B1/en not_active Expired - Lifetime
- 1998-05-18 CA CA002291131A patent/CA2291131C/en not_active Expired - Fee Related
- 1998-05-18 BR BR9809529-3A patent/BR9809529A/en not_active Application Discontinuation
- 1998-05-29 AR ARP980102532A patent/AR015836A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CA2291131A1 (en) | 1998-12-03 |
| AU7913498A (en) | 1998-12-30 |
| JP2002500689A (en) | 2002-01-08 |
| EP0984994A1 (en) | 2000-03-15 |
| DE19722791A1 (en) | 1998-12-03 |
| CN1140550C (en) | 2004-03-03 |
| ES2178225T3 (en) | 2002-12-16 |
| CN1258304A (en) | 2000-06-28 |
| AR015836A1 (en) | 2001-05-30 |
| EP0984994B1 (en) | 2002-06-12 |
| KR20010013122A (en) | 2001-02-26 |
| TW515820B (en) | 2003-01-01 |
| DE59804434D1 (en) | 2002-07-18 |
| KR100579674B1 (en) | 2006-05-15 |
| WO1998054238A1 (en) | 1998-12-03 |
| BR9809529A (en) | 2000-06-20 |
| JP4181642B2 (en) | 2008-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4605699A (en) | Thermoplastic molding compositions containing polycarbonate and an acrylate graft copolymer | |
| AU738243B2 (en) | Thermoplastic high-gloss moulding compositions of the ABS type | |
| JP2793892B2 (en) | ABS molding material with improved yield stress | |
| US5290859A (en) | Thermoplastic molding materials based on polycarbonates, styrene/acrylonitrile polymers and polyolefins | |
| US5420181A (en) | Composition of polycarbonate, ABS, a basic additive and a carboxylic and compound | |
| US5883190A (en) | Thermoplastic moulding compositions of the ABS type | |
| EP3848414B1 (en) | Thermoplastic resin composition | |
| US5969016A (en) | Molded materials based on polycarbonates | |
| WO2011090200A1 (en) | Resin composition for irregular shape extrusion molding and irregularly shaped extrusion molded resin article | |
| CA2351574C (en) | Abs-moulding compounds with an improved combination of properties | |
| US20090012222A1 (en) | Low individual colour thermoplastic molding composition | |
| US4870131A (en) | Low gloss molding composition | |
| US4778850A (en) | Thermoplastic moulding materials made from vinyl chloride polymers and graft polymers and having improved properties | |
| AU604164B2 (en) | Thermoplastic resin composition | |
| US4603169A (en) | Thermoplastic molding compositions containing polycarbonate and a graft copolymer of resin-forming monomers on a rubber | |
| US5804656A (en) | Compositions of the ABS type for processing by extrusion and deep drawing | |
| CA2291131C (en) | Abs molding materials with enhanced working properties | |
| MX2015001638A (en) | Polymer mixtures with optimized toughness/stiffness ratio and optical properties. | |
| US6656889B2 (en) | Thermoplastic molding compositions containing additive mixtures | |
| US5210135A (en) | ABS moulding compounds with improved yield stress | |
| US6806318B2 (en) | ABS molding materials with enhanced working properties | |
| US6602939B2 (en) | Additive mixtures containing thermoplastic moulding compositions | |
| CA2099480A1 (en) | Thermoplastic moulding compounds | |
| KR20170025866A (en) | Thermoplastic resin composition having paper texture and molded article produced therefrom | |
| JPH0641497B2 (en) | Manufacturing method of weather resistant resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |