DE1260135B - Impact-resistant thermoplastic molding compounds - Google Patents
Impact-resistant thermoplastic molding compoundsInfo
- Publication number
- DE1260135B DE1260135B DE1965B0079984 DEB0079984A DE1260135B DE 1260135 B DE1260135 B DE 1260135B DE 1965B0079984 DE1965B0079984 DE 1965B0079984 DE B0079984 A DEB0079984 A DE B0079984A DE 1260135 B DE1260135 B DE 1260135B
- Authority
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- Germany
- Prior art keywords
- parts
- styrene
- weight
- acrylonitrile
- copolymer
- 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.)
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. Cl.:Int. Cl .:
C08fC08f
Nummer: 1260135Number: 1260135
Aktenzeichen: B 79984IV c/39 bFile number: B 79984IV c / 39 b
Anmeldetag: 5. Januar 1965Filing date: January 5, 1965
Auslegetag: 1. Februar 1968Open date: February 1, 1968
Polymerisate auf der Basis von Styrol oder Copolymerisaten aus Styrol und Acrylnitril sind seit langem bekannt. Polystyrol und auch Copolymerisate aus Styrol und Acrylnitril sind glasklar, und die Polymerisate aus Styrol—Acrylnitril haben eine gute Oberflächenhärte. Beiden Polymerisaten fehlt jedoch die Resistenz gegen Schockbeanspruchung. Sie sind nicht schlagfest, und Formkörper, die aus diesen Polymerisaten hergestellt werden, können bei harter Beanspruchung zerbrechen.Polymers based on styrene or copolymers of styrene and acrylonitrile have been around since known for a long time. Polystyrene and copolymers of styrene and acrylonitrile are crystal clear, and the Polymers made from styrene-acrylonitrile have good properties Surface hardness. However, both polymers lack resistance to shock stress. they are not impact-resistant, and moldings that are made from these polymers can with hard Breaking stress.
Es ist auch schon lange bekannt, daß man in diese harten und spröden Polymerisate bzw. Mischpolymerisate weiche, kautschukelastische Polymerisate einarbeiten kann, um dadurch die Schlagfestigkeit zu erzielen. Dadurch geht die Transparenz allerdings verloren. Zur Erzielung von homogenen Mischungen der kautschukelastischen Komponente mit dem harten und spröden Polymerisat auf der Basis von Styrol oder Styrol—Acrylnitril ist es erforderlich, daß die weiche und die harte Komponente miteinander verträglich sind. Um dies zu erreichen, wurden schon verschiedene Vorschläge gemacht. So hat man die kautschukelastische weiche Komponente mit Styrol oder Styrol—Acrylnitril gepfropft, oder man stellte kautschukelastische Copolymerisate her, bei deren Herstellung Monomere mitverwendet wurden, die eine gewisse Verwandtschaft zu der harten und spröden Komponente hatten.It has also long been known that these hard and brittle polymers or copolymers can be used soft, rubber-elastic polymers can be incorporated, thereby increasing the impact resistance to achieve. However, this means that transparency is lost. To achieve homogeneous mixtures the rubber-elastic component with the hard and brittle polymer based on styrene or styrene-acrylonitrile, it is necessary that the soft and hard components are compatible with one another. To achieve this, we have been made various suggestions. So you have the rubber-elastic soft component with styrene or styrene-acrylonitrile grafted, or put rubber-elastic copolymers produced, in the production of which monomers were also used, the had a certain affinity to the hard and brittle component.
Als kautschukartige Komponenten werden bei der bekannten Herstellung von schlagfesten Polystyrolen oder sogenannten ABS-Polymerisaten natürliche oder synthetische Kautschuke verwendet. Als synthetische Kautschuke wurden für diesen Zweck insbesondere Butadien-Homo- und Copolymerisate eingesetzt. Daneben sind auch schon kautschukartige Polymerisate, die wenig oder keine Doppelbindungen mehr enthalten, insbesondere solche auf der Basis von Acrylsäureestern, Vinyläthern und Isobutylen, beschrieben worden. Dadurch, daß wenig oder keine Doppelbindungen in den kautschukelastischen Polymerisaten enthalten sind, wurde neben der Schlagfestigkeit eine gute Alterungsbeständigkeit erreicht.The rubber-like components used in the known production of impact-resistant polystyrenes or so-called ABS polymers, natural or synthetic rubbers are used. as Synthetic rubbers, in particular, butadiene homo- and copolymers were used for this purpose used. In addition, there are already rubber-like polymers that have little or no double bonds contain more, especially those based on acrylic acid esters, vinyl ethers and isobutylene, has been described. The fact that little or no double bonds in the rubber-elastic Polymers are contained, in addition to the impact resistance, a good aging resistance achieved.
Schließlich ist bekannt, daß man schlagfeste Formmassen herstellen kann, die neben einem Copolymerisat aus Styrol und Acrylnitril ein Pfropfcopolymerisat enthalten, das durch Pfropfen eines Polymerisats eines Acrylsäureesters eines Alkohols mit 4 bis 8 Kohlenstoffatomen mit einem Gemisch aus Styrol und Acrylnitril hergestellt ist. Aus solchen Formmassen hergestellte Spritzgußartikel haben jedoch schlechte Eigenschaften; unter anderem sind Schlagfeste thermoplastische FormmassenFinally, it is known that impact-resistant molding compositions can be produced in addition to a copolymer from styrene and acrylonitrile contain a graft copolymer which is formed by grafting a polymer an acrylic acid ester of an alcohol having 4 to 8 carbon atoms with a mixture of Styrene and acrylonitrile is made. Injection molded articles produced from such molding compositions have, however bad qualities; among others are impact-resistant thermoplastic molding compounds
Anmelder:Applicant:
Badische Anilin- & Soda-FabrikAniline & Soda Factory in Baden
Aktiengesellschaft, 6700 LudwigshafenAktiengesellschaft, 6700 Ludwigshafen
Als Erfinder benannt:Named as inventor:
Dr. Herbert Willersinn,Dr. Herbert Willersinn,
Dr. Hans-Werner Otto,Dr. Hans-Werner Otto,
Dr. Paul Raff,Dr. Paul Raff,
Dr. Ludwig Schuster, 6700 LudwigshafenDr. Ludwig Schuster, 6700 Ludwigshafen
sie häufig inhomogen und bilden daher schlechte Strukturen aus.they are often inhomogeneous and therefore form poor structures.
Schlagfeste Polystyrole mit guten Schlagzähigkeitswerten bei tiefen Temperaturen kann man erhalten, wenn als kautschukelastische Komponente Butadienpolymerisate, insbesondere solche, die 1,4-cis-Konfiguration aufweisen, verwendet werden. Ein bevorzugtes Polymerisat dieser Art ist 1,4-cis-Polybutadien. Mit der erzielten guten Schlagzähigkeit bei tiefen Temperaturen wird allerdings eine Verschlechterung der Alterungsbeständigkeit erkauft, weil in den weichen Komponenten noch in der Kette enthaltene Doppelbindungen den oxydativen und thermischen Abbau begünstigen.Impact-resistant polystyrenes with good impact strength values at low temperatures can be obtained, if the elastomeric component is butadiene polymers, especially those with the 1,4-cis configuration have to be used. A preferred polymer of this type is 1,4-cis-polybutadiene. With the achieved good impact strength at low temperatures, however, there is a deterioration at the cost of aging resistance because the soft components still contain double bonds in the chain promote oxidative and thermal degradation.
Es ist weiter bekannt, als kautschukelastische Komponente Pfropfcopolymerisate, die erhalten worden sind durch Aufpolymerisieren von Acrylsäureestern auf niedermolekulare Polybutadiene und auf die anschließend Styrol und Acrylnitril aufgepfropft wurde, zu verwenden. Aber auch bei diesem Kautschuk verbleiben in der Hauptkette nach der Pfropfreaktion noch Doppelbindungen.It is also known as rubber-elastic component graft copolymers that have been obtained are by polymerizing acrylic acid esters on low molecular weight polybutadienes and on which was then grafted with styrene and acrylonitrile to use. But also with this rubber double bonds still remain in the main chain after the grafting reaction.
Erfindungsgegenstand sind thermoplastische Formmassen aus:The subject of the invention are thermoplastic molding compounds made of:
A. 15 bis 50 Gewichtsteilen eines Pfropfcopolymerisates von 10 bis 50 Gewichtsprozent eines Gemisches aus Styrol und Acrylnitril im Verhältnis 60:40 bis 90:10, auf 50 bis 90 Gewichtsprozent eines 98 bis 80 Gewichtsprozent mindestens eines Acrylsäureesters eines Alkohols mit 4 bis 8 Kohlenstoffatomen enthaltenden Copolymerisates undA. 15 to 50 parts by weight of a graft copolymer from 10 to 50 percent by weight of a mixture of styrene and acrylonitrile in a ratio of 60:40 to 90:10, to 50 to 90 percent by weight 98 to 80 percent by weight of at least one acrylic acid ester of an alcohol having 4 to 8 carbon atoms containing copolymer and
B. 50 bis 85 Gewichtsteile eines Copolymerisates aus Styrol und Acrylnitril im Verhältnis 50:50 bis 90:10,B. 50 to 85 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 50:50 until 90:10,
709 747/095709 747/095
dadurch gekennzeichnet, daß das Copolymerisat der Auf das Copolymerisat aus den verschiedenencharacterized in that the copolymer is the on the copolymer from the different
Komponente A unter Verwendung von 2 bis 20 Ge- Acrylsäureestern wird dann ein Gemisch aus Styrol wichtsprozent des Acrylsäureesters des Tricyclode- und Acrylnitril aufpolymerisiert. Dabei werden 10 cenylalkohols als copolymerisierbares Monomeres bis 50 Gewichtsprozent, bezogen auf das endgültige hergestellt worden ist. 5 Pfropfpolymerisat, eines Gemisches aus Styrol undComponent A using 2 to 20 Ge acrylic acid esters then becomes a mixture of styrene weight percent of the acrylic acid ester of tricycloditrile and acrylonitrile polymerized. There are 10 cenyl alcohol as copolymerizable monomer up to 50 percent by weight, based on the final has been made. 5 graft polymer, a mixture of styrene and
Die erfindungsgemäßen Formmassen weisen gute Acrylnitril verwendet. Das Gemisch aus Styrol und Schlagzähigkeiten bei tiefen Temperaturen, verbunden Acrylnitril muß ein Mischungsverhältnis zwischen mit einer guten Alterungsbeständigkeit, auf. 60:40 bis 90:10 haben. Die Copolymerisation derThe molding compositions according to the invention have good acrylonitrile used. The mixture of styrene and Impact strength at low temperatures, connected acrylonitrile must have a mixing ratio between with good aging resistance. 60:40 to 90:10. The copolymerization of the
Die erfindungsgemäßen Formmassen bestehen also Acrylsäureester und das anschließende Aufpfropfen aus einem Gemisch der Komponenten A und B, io des Styrol-Acrylnitril-Gemisches wird vorzugsweise wobei A die kautschukelastische Komponente und B in wäßriger Emulsion vorgenommen. Dabei werden die harte und spröde Polymerisate enthaltende Korn- die üblichen Polymerisationshilfsmittel, wie Katalyponente darstellt. Die Komponente A ist ein Pfropf- satoren, Regler und Emulgatoren, und auch die copolymerisat, bei dem auf ein Copolymerisat zweier üblichen Polymerisationsbedingungen, Temperaturverschiedener Acrylsäureester ein Gemisch aus Styrol 15 bereiche u.dgl. angewendet. The molding compositions according to the invention therefore consist of acrylic acid esters and the subsequent grafting from a mixture of components A and B, io of the styrene-acrylonitrile mixture is preferred where A is the rubber-elastic component and B is made in an aqueous emulsion. Be there the grains containing hard and brittle polymers - the usual polymerization auxiliaries, such as catalyst components represents. Component A is a grafting agent, regulator and emulsifier, and also the copolymer in which a mixture of styrene 15 areas and the like is applied to a copolymer of two customary polymerization conditions, temperature of different acrylic acid esters.
und Acrylnitril aufpolymerisiert wird, so daß das Das auf diese übliche Weise erhaltene Pfropf-and acrylonitrile is polymerized, so that the graft obtained in this usual way
Gemisch aus Styrol und Acrylnitril auf das Copoly- copolymerisat A stellt bereits für sich unter Ummerisat der beiden Acrylsäureester aufgepfropft wird. ständen ein Gemisch verschiedener Polymerisate dar. Die Komponente A wird wie folgt üblicherweise Dieses Gemisch besteht dann aus dem Pfropfcopolyhergestellt: 20 merisat aus Styrol—Acrylnitril auf dem Acrylsäure-Mixture of styrene and acrylonitrile on the copolymers A is already under conversion of the two acrylic acid esters is grafted on. would be a mixture of different polymers. Component A is usually produced as follows: This mixture then consists of the graft copoly: 20 merisate of styrene-acrylonitrile on the acrylic acid
Zunächst muß man als Stamm das Copolymerisat estercopolymerisat als Rückgratpolymeres und geverschiedener Acrylsäureester herstellen. Als Acryl- gebenenfalls dem Copolymerisat aus Styrol und säureester kommen einerseits solche von Alkoholen Acrylnitril.First, you have to use the copolymer ester copolymer as a backbone polymer and different as a trunk Manufacture acrylic acid esters. As acrylic, optionally the copolymer of styrene and acid esters come on the one hand those of alcohols acrylonitrile.
mit 4 bis 8 Kohlenstoffatomen, beispielsweise Acryl- Die kautschukelastische Komponente A wird mitwith 4 to 8 carbon atoms, for example acrylic- The rubber-elastic component A is with
säurebutylester oder Acrylsäureäthylhexylester, in 25 der harten Komponente B vermischt. Die Kompo-Frage und andererseits der Acrylsäureester des Tri- nente B besteht aus einem Copolymerisat aus Styrol cyclodecenylalkohols I. und Acrylnitril. Das Copolymerisat aus Styrol undbutyl acid or ethylhexyl acrylate, mixed in 25 of the hard component B. The compo question and on the other hand the acrylic acid ester of trinent B consists of a copolymer of styrene cyclodecenyl alcohol I. and acrylonitrile. The copolymer of styrene and
Acrylnitril, wobei Styrol—Acrylnitril im Verhältnis 50: 50 bis 90:10 einpolymerisiert wurden, wird nach 30 den herkömmlichen Methoden erhalten. Herkömm- * liehe Methoden sind insbesondere die Substanzpolymerisation in Abwesenheit von wesentlichen Mengen von Verdünnungsmitteln oder auch die Emulsionspolymerisation. Das Copolymerisat aus 35 Styrol und Acrylnitril kann auch durch Polymeri-Acrylonitrile, with styrene-acrylonitrile in the ratio 50:50 to 90:10 were polymerized, is after 30 the conventional methods. Conventional * borrowed methods are in particular bulk polymerization in the absence of substantial amounts of diluents or emulsion polymerization. The copolymer from 35 Styrene and acrylonitrile can also be obtained by polymer
Ein Acrylsäureester dieser allgemeinen Formel kann sation in methanolischer Suspension in bekannter bekannterweise z. B. hergestellt sein wie folgt: Weise hergestellt werden.An acrylic acid ester of this general formula can be sation in methanolic suspension in a known manner known z. B. be made as follows: way to be made.
In einem mit Rührer, Thermometer und Zulauf- Die Komponente A wird bevorzugt mit der Kom-In one with a stirrer, thermometer and feed component A is preferably used with the com-
vorrichtung versehenen Gefäß werden 720 Gewichts- ponente B vermischt, indem man das gepfropfte teile Acrylsäure vorgelegt. Man löst hierauf 3 Ge- 40 und getrocknete Emulsionspolymerisat dem Styrolwichtsteile Hydrochinon in der Acrylsäure und leitet Acrylnitril-Polymerisat zugibt und in der Schmelze unter Rühren 22 Teile Bortrifluorid in das Gefäß ein. mischt. Dies kann beispielsweise in einem Extruder Im Verlauf von 60 Minuten läßt man dann 660 Ge- oder einer anderen Knetvorrichtung vorgenommen wichtsteite Dicyclopentadien zufließen. Durch äußere werden.In the vessel provided with the device, 720 weight components B are mixed by adding the grafted parts acrylic acid submitted. 3 Ge 40 and dried emulsion polymer are then dissolved from the weight of the styrene Hydroquinone in the acrylic acid and conducts acrylonitrile polymer and adds in the melt while stirring 22 parts of boron trifluoride into the vessel. mixes. This can be done in an extruder, for example Then, in the course of 60 minutes, 660 kneading devices or another kneading device are made most important dicyclopentadiene flow. Be by external.
Kühlung wird hierbei die Temperatur bei ungefähr 45 Liegen die Komponenten A und B beide als wäßrige 4O0C gehalten. Hierauf läßt man die Temperatur Emulsionen vor, so kann das Vermischen durch Zuauf 60 bis 70° C ansteigen und hält das Reaktionsge- sammengeben der Emulsionen und gemeinsames Ausmisch während 4 Stunden auf dieser Temperatur. fällen der darin enthaltenen Feststoffe erfolgen. Schließ-Die überschüssige Acrylsäure wird im Vakuum lieh ist es auch möglich, die als Emulsion vorliegende (8 mm Hg) abdestilliert, der Rückstand mit Pentan 5° Komponente A mit der als Lösung vorliegenden aufgenommen und dreimal mit Wasser gewaschen. Komponente B abzumischen und gegebenenfalls nach Durch Waschen mit 10%iger Sodalösung und 5%iger Zugabe von einem Fällungsmittel gemeinsam ausNatronlauge werden die Reste von Säure und Kata- zufallen.Cooling the temperature at about 45 beds is in this case the components A and B maintained both as an aqueous 4O 0 C. The temperature of the emulsions is then left, so the mixing can increase by adding from 60 to 70 ° C. and the reaction mixture of the emulsions and joint mixing is kept at this temperature for 4 hours. The solids contained therein are precipitated. Closing-The excess acrylic acid is borrowed in vacuo, it is also possible to distill off the emulsion present (8 mm Hg), the residue is taken up with pentane 5 ° component A with the present as a solution and washed three times with water. To mix component B and, if necessary, after washing with 10% soda solution and 5% addition of a precipitant together from sodium hydroxide solution, the residues of acid and cata- will fall off.
lysator entfernt. Nach dem Abtrennen der organi- Die erfindungsgemäßen Formmassen zeichnen sichlysator removed. After separating off the organic The molding compositions according to the invention stand out
sehen Schicht wird das Pentan abdestilliert und der 55 durch eine gegenüber butadienhaltigen Produkten Rückstand nach Zugabe von 2 Gewichtsteilen Pheno- verbesserte Alterungsbeständigkeit aus. Die aus diesen thiazin im Vakuum fraktioniert. Man erhält 883 Ge- Massen hergestellten Gebrauchsgegenstände besitzen wichtsteile des Acrylsäureesters. einen guten Oberflächenglanz und eine helle Eigen-see layer, the pentane is distilled off and the 55 through a product containing butadiene Residue after adding 2 parts by weight of pheno- improved aging resistance. The ones from these thiazine fractionated in vacuo. 883 ge masses of manufactured articles of daily use are obtained parts by weight of the acrylic acid ester. a good surface gloss and a light characteristic
Das Verhältnis der beiden verschiedenen Arten farbe.The ratio of the two different types of color.
von Acrylsäureestern soll 2 bis 20 Gewichtsprozent 60 Die im Beispiel genannten Teile sind Gewichtsder cycloaliphatischen Acrylsäureester und entspre- teile. Die Herstellung der Komponenten A und B chend 98 bis 80 Gewichtsprozent des Acrylsäure- ist nicht Gegenstand der Erfindung, esters eines C4- bis Q-Alkohols betragen. Es ist .of acrylic acid esters should be 2 to 20 percent by weight. 60 The parts mentioned in the example are weight of the cycloaliphatic acrylic acid esters and corresponding parts. The preparation of components A and B chend 98 to 80 percent by weight of the acrylic acid is not the subject of the invention, esters of a C 4 - to Q alcohol. It is .
selbstverständlich, daß auch innerhalb der genannten Beispiel 1It goes without saying that within the mentioned example 1
Mengenverhältnisse, wobei sich die Prozente jeweils 65 18 Teile Acrylsäurebutylester und 2 Teile Tricyclozu 100 addieren, verschiedene Acrylsäureester von decenylacrylat werden in 145 Teilen Wasser unter Alkoholen mit 4 bis 8 Kohlenstoffatomen copoly- Zusatz von 1,2 Teilen des Natriumsalzes einer Paraffinmerisiert werden können. sulfonsäure (C12 bis C18) und 0,35 Teilen Kalium-Quantities in which the percentages add 65 to 18 parts of butyl acrylate and 2 parts of tricyclo to 100, various acrylic acid esters of decenyl acrylate are copoly- addition of 1.2 parts of the sodium salt of a paraffin in 145 parts of water under alcohols with 4 to 8 carbon atoms. sulfonic acid (C 12 to C 18 ) and 0.35 parts of potassium
persulfat unter Rühren auf 650C erwärmt. Nach dem Anspringen der Polymerisation gibt man eine Mischung aus 72 Teilen Acrylsäurebutylester und 8 Teilen Tricyclodecenylacrylat innerhalb von 2 Stunden hinzu. Nachdem alle Monomeren zugegeben sind, wird der Polymerisationsansatz noch 1 Stunde bei 65° C weitergerührt. Man erhält eine etwa 40%ige wäßrige Polymerisatdispersion.Persulfate heated to 65 0 C with stirring. After the polymerization has started, a mixture of 72 parts of butyl acrylate and 8 parts of tricyclodecenyl acrylate is added over the course of 2 hours. After all the monomers have been added, the polymerization batch is stirred for a further 1 hour at 65.degree. An approximately 40% strength aqueous polymer dispersion is obtained.
250 Teile dieser Dispersion werden mit 25 Teilen einer Mischung aus Styrol und Acrylnitril im Ge- ϊ0 wichtsverhältnis 70:30 und 37,5 Teilen Wasser gemischt und unter Rühren bei 65° C polymerisiert. Als Polymerisationsinitiator werden 0,05 Teile Kaliumpersulfat und 0,075 Teile Lauroylperoxyd verwendet. Man erhält wiederum eine etwa 40%ige wäßrige Polymerisatdispersion, aus der das Festprodukt durch Zusatz einer 0,75%igen Kalziumchloridlösung ausgefällt, mit Wasser gewaschen und im warmen Luftstrom getrocknet wird.250 parts of this dispersion are mixed with 25 parts of a mixture of styrene and acrylonitrile in a weight ratio of 70:30 and 37.5 parts of water and polymerized at 65 ° C. with stirring. The polymerization initiator used is 0.05 part of potassium persulfate and 0.075 part of lauroyl peroxide. An approximately 40% strength aqueous polymer dispersion is again obtained, from which the solid product is precipitated by adding a 0.75% strength calcium chloride solution, washed with water and dried in a stream of warm air.
30 Teile des getrockneten Polymerisatpulvers A werden mit 70 Teilen eines Copolymerisates aus 70 Teilen Styrol und 30 Teilen Acrylnitril (K-Wert = 65) B bei einer Temperatur von etwa 2200C in einem Schneckenextruder gemischt. Das so hergestellte Produkt läßt sich gut auf den üblichen Spritzgußmaschinen verarbeiten. Es lassen "ch Gebrauchsgegenstände mit hoher Steifigkeit, guter Festigkeit gegen Schockbeanspruchung und glänzender Oberfläche herstellen.30 parts of the dried polymer powder A are mixed with 70 parts of a copolymer composed of 70 parts of styrene and 30 parts of acrylonitrile (K value = 65) B at a temperature of about 220 ° C. in a screw extruder. The product produced in this way can be easily processed on conventional injection molding machines. It can be used to produce objects of daily use with high rigidity, good resistance to shock loads and a shiny surface.
Die Schockfestigkeit wurde als mittlere Bruchenergie bei biaxialer Beanspruchung an 1 mm dicken Prüfplättchen bestimmt. Dieser Test wurde mit einem Fallbolzengerät durchgeführt, das im wesentlichen aus folgenden Teilen besteht: Grundplatte mit Führungsholmen für die Fallbolzen, Auflagering (30 mm Durchmesser) für die Prüfplättchen, mehreren Fallbolzen mit unterschiedlichem Eigengewicht und dazugehörigen Zusatzgewichten. Die Fallbolzenspitzen haben Halbkugelform mit einem Durchmesser von 18 mm.The shock resistance was measured as the mean fracture energy under biaxial loading at 1 mm thick Test platelets determined. This test was performed with a dart drop device which essentially consists of the following parts: base plate with guide bars for the drop bolts, support ring (30 mm Diameter) for the test plates, several drop pins with different dead weights and the associated Additional weights. The dart tips have a hemispherical shape with a diameter of 18 mm.
Die Messung besteht darin, den Bruchanteil bei mehreren Stichproben von jeweils zehn Plättchen bei verschiedenen Energieniveaus, d. h. mit verschiedenem Gewicht der Fallbolzen bei gleichbleibender Fallhöhe, zu bestimmen.The measurement consists of the fraction of fractures in several samples of ten platelets each at different energy levels, d. H. with different weights of the drop pins while remaining the same Height of fall, to be determined.
Man erhält so eine Zuordnung der Bruchhäufigkeit ("/„) zu bestimmten. Energiewerten (cm kp). Trägt man die Bruchhäufigkeit gegen die Energie im Wahrscheinlichkeitsnetz auf, so erhält man in guter Näherung eine Gerade. Der Schnittpunkt dieser Geraden mit der 50%-Linie ergibt den Wert für die mittlere Bruchenergie.This gives an assignment of the breakage frequency ("/") to certain energy values (cm kp). If one plots the fracture frequency against the energy in the probability network, one obtains in a straight line to a good approximation. The intersection of this straight line with the 50% line gives the value for the mean fracture energy.
Das Produkt hat, an gepreßten Rundplättchen gemessen, eine mittlere Bruchenergie von 64 cm kp.Measured on pressed round plates, the product has an average breaking energy of 64 cm kp.
55 Beispiel 255 Example 2
und Vergleichsversuche
a) Vergleichsversuchand comparative tests
a) Comparative experiment
100 Teile Butylacrylat, 50 Teile Emulgator H (20°/oig), 3 Teile Kaliumpersulfat und 1480 Teile destilliertes Wasser werden unter Rühren auf 6O0C erwärmt. Nach dem Anspringen der Polymerisation läßt man 900 Teile Butylacrylat im Verlauf von ~ 1 Stunde zulaufen. Man polymerisiert 2 Stunden nach und erhält eine ~4Oü/oige Polymerisatdispersion (A).100 parts of butyl acrylate, 50 parts of emulsifier, H (20 ° / o solution), 3 parts of potassium persulfate, and 1480 parts of distilled water are heated with stirring to 6O 0 C. After the polymerization has started, 900 parts of butyl acrylate are allowed to run in over the course of ~ 1 hour. Is polymerized 2 hours, and receives a ü ~ 4O / o polymer (A).
465 Teile Styrol und 200 Teile Acrylnitril werden in Gegenwart von 2500 Teilen der Dispersion (A), 2 Teile Kaliumpersulfat, 1,33 Teile Laurylperoxyd und 1005 Teile destilliertes Wasser unter Rühren bei 6O0C polymerisiert. Man erhält eine ~40%ige Dispersion, aus der das Festprodukt durch Zusatz einer 0,5%igen Calciumchloridlösung ausgefällt, mit Wasser gewaschen und getrocknet wird.465 parts of styrene and 200 parts of acrylonitrile are polymerized in the presence of 2500 parts of the dispersion (A), 2 parts of potassium persulfate, 1.33 parts Laurylperoxyd and 1005 parts of distilled water with stirring at 6O 0 C. A ~ 40% dispersion is obtained from which the solid product is precipitated by adding a 0.5% calcium chloride solution, washed with water and dried.
1490 Teile des getrockneten Polymerisats werden mit 2090 Teilen eines Copolymerisats aus 68 Teilen Styrol und 32 Teilen Acrylnitril bei ~220cC in einem Schneckenextruder gemischt. Man erhält Polymerisat I.1490 parts of the dried polymer are mixed with 2090 parts of a copolymer composed of 68 parts of styrene and 32 parts of acrylonitrile at ~ 220 ° C. in a screw extruder. Polymer I.
b) Vergleichsversuchb) Comparative experiment
Der Versuch wird unter Einsatz von 980 Teilen Butylacrylat und 20 Teilen Butandioldiacrylat (in der ersten Polymerisationsstufe) völlig analog dem oben beschriebenen durchgeführt. Man erhält Polymerisat Ia.The experiment is carried out using 980 parts of butyl acrylate and 20 parts of butanediol diacrylate (in the first polymerization stage) carried out completely analogously to that described above. Polymer is obtained Yes
c) Beispielc) example
Der Versuch wird unter Einsatz von 980 Teilen Butylacrylat und 20 Teilen des Acrylsäureesters des Tricyclodecenylalkohols (in der ersten Polymerisationsstufe) völlig analog dem oben beschriebenen durchgeführt. Man erhält Polymerisat Ib.The experiment is carried out using 980 parts of butyl acrylate and 20 parts of the acrylic acid ester of Tricyclodecenyl alcohol (in the first polymerization stage) completely analogous to that described above carried out. Polymer Ib is obtained.
Eigenschaften der PolymerisateProperties of the polymers
Mittlere Bruchenergie
GrenzbiegespannungMedium fracture energy
Limit bending stress
DIN 53452 DIN 53452
ErweichungspunktSoftening point
Polymerisat
I Ia IbPolymer
I Ia Ib
6565
Bruch
98fracture
98
7070
Bruch
98fracture
98
Claims (1)
Deutsche Auslegeschrift Nr. 1 182 811;
deutsche Patentschrift Nr. 1 138 921.Considered publications:
German Auslegeschrift No. 1 182 811;
German patent specification No. 1 138 921.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1965B0079984 DE1260135B (en) | 1965-01-05 | 1965-01-05 | Impact-resistant thermoplastic molding compounds |
NL6600058A NL6600058A (en) | 1965-01-05 | 1966-01-04 | |
GB23766A GB1124911A (en) | 1965-01-05 | 1966-01-04 | Impact resistant moulding materials |
FR44771A FR1462788A (en) | 1965-01-05 | 1966-01-04 | Impact resistant molding materials |
BE674765D BE674765A (en) | 1965-01-05 | 1966-01-05 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1965B0079984 DE1260135B (en) | 1965-01-05 | 1965-01-05 | Impact-resistant thermoplastic molding compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1260135B true DE1260135B (en) | 1968-02-01 |
Family
ID=6980540
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE1965B0079984 Pending DE1260135B (en) | 1965-01-05 | 1965-01-05 | Impact-resistant thermoplastic molding compounds |
Country Status (5)
Country | Link |
---|---|
BE (1) | BE674765A (en) |
DE (1) | DE1260135B (en) |
FR (1) | FR1462788A (en) |
GB (1) | GB1124911A (en) |
NL (1) | NL6600058A (en) |
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Also Published As
Publication number | Publication date |
---|---|
FR1462788A (en) | 1966-12-16 |
BE674765A (en) | 1966-07-05 |
NL6600058A (en) | 1966-07-06 |
GB1124911A (en) | 1968-08-21 |
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