EP1353974A1 - Method for producing mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile - Google Patents

Method for producing mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile

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Publication number
EP1353974A1
EP1353974A1 EP01999598A EP01999598A EP1353974A1 EP 1353974 A1 EP1353974 A1 EP 1353974A1 EP 01999598 A EP01999598 A EP 01999598A EP 01999598 A EP01999598 A EP 01999598A EP 1353974 A1 EP1353974 A1 EP 1353974A1
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EP
European Patent Office
Prior art keywords
acrylonitrile
polyvinyl chloride
conjugated dienes
mixtures
polymers based
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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.)
Withdrawn
Application number
EP01999598A
Other languages
German (de)
French (fr)
Inventor
Rainer Graefe
Paul Krieger
Hans-Christian Strauch
Hans Magg
Dieter LÖHR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1353974A1 publication Critical patent/EP1353974A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile

Definitions

  • the invention relates to a ner process for the production of hybrids from polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile.
  • ⁇ BR rubbers acrylonitrile and butadiene
  • NBR nitrile rubber
  • PNC polyvinyl chloride
  • the vulcanizates have increased tensile and tear strength.
  • the ⁇ BR bale goods are shredded for dry blend ner driving and mixed with PNC powder in batch ner driving.
  • the mixture is in the kneader or in the
  • the PNC portion is distributed so far in the ⁇ BR phase that no PNC domains can be recognized in the ⁇ BR phase.
  • latex blend ner driving the ⁇ BR latex is mixed with a corresponding PNC latex before it is processed into a solid. The mixture is then coagulated, gelled and thus continuously worked up to the solid product.
  • a disadvantage of the latex blend ner driving is that the PNC latex used still contains a not inconsiderable amount of monomeric vinyl chloride.
  • PNC components For environmental and occupational health and safety reasons (with regard to ninyl chloride see: 1. Hazardous Substances Ordinance, 19th Amendment, 2. Römpp Chemielexikon, Thieme Verlag), it is therefore desirable to use PNC components with a monomeric ninyl chloride content of less than 1 ppm.
  • the use of a PVC latex for the production of the blends mentioned is less economical due to the high water content of the latex, which has a disadvantageous effect on the transport and processing (removal of the aqueous phase).
  • a disadvantage of the dry blend ner driving is in particular that a homogeneous distribution of the components NBR and PVC used in the blend must be maintained, that the components NBR and PVC must be well distributed before gelling and that the NBR bale goods used must be comminuted well beforehand. All of this is associated with a high technical outlay, so that the dry blend process is less economical than the latex blend process.
  • the present invention therefore relates to a method for producing
  • powdery polyvinyl chloride in powder form is mixed with the latex based on conjugated dienes and acrylonitrile.
  • Powdery polyvinyl chloride according to the invention are homopolymers based on the emulsion or suspension or microsuspension process and graft copolymers and copolymers according to the suspension process with an average particle diameter in the range from 5 to 200 ⁇ m and K values (DIN 53726 or ISO 1628) from 40 to 90 Roger that.
  • polyvinyl chloride with the typical residual vinyl chloride content ( ⁇ 1 ppm vinyl chloride) is usually used in the process according to the invention, provided that it satisfies the specification given above.
  • latices based on conjugated dienes and acrylonitrile all latices typical of NBR production can be used, which have a polymer weight fraction in the range from 10 to 50%, fractions from 15 to 30% by weight being preferred.
  • the amount of conjugated dienes and acrylonitrile in the polymers to be used can vary within wide ranges, for example polymers can be used, the proportion of conjugated dienes in the range from 40 to 90, preferably from 55 to 75% by weight, and their proportion of acrylonitrile are in the range from 10 to 60% by weight, preferably from 25 to 45% by weight.
  • 1,3-butadiene and isoprene as well as other conjugated dienes such as 2,3- Dimethyl-l, 3-butadiene, 1,3-pentadiene and piperylene are considered, 1,3-butadiene being preferred.
  • acrylonitrile In addition to acrylonitrile, it is also possible to use its known derivatives, such as ⁇ -chloroacrylonitrile and / or methacrylonitrile.
  • crosslinking polyfunctional monomers known to the person skilled in the art can be used to construct the polymers to be used. These are especially di- and trifunctional monomers. Examples include divinylbenzene, diethylglycol dimethacrylate and trimethylolpropane trimethyl acrylate.
  • the additional monomers for building up the polymers based on the conjugated dienes mentioned and the acrylonitriles can be present in amounts of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total polymer.
  • latices to be used according to the invention based on conjugated dienes and acrylonitriles, optionally with the addition of the additionally mentioned polymerizable monomers, are described in the specialist literature known to the person skilled in the art, and also their method of preparation (for example Ullmann's Encyclopedia of Industrial Chemistry, Vol. A23, p. A23). 239-364).
  • the two components can be mixed in a wide variety of mixing devices.
  • mixing devices for example, agitator kettles with variable kettle geometry with single and multi-shaft agitators and different mixing tools as well as rotor-stator mixers, mixing by pumping with and without the use of rotor-stator dispersing machines or mixing nozzles, jet suction devices,
  • Injectors tumble mixers, planetary mixers, ploughshare mixers with and without knife stirrers, preferably mixing in agitator tanks or jet suction devices, injectors, guide jet mixers, in particular mixing in agitator tanks.
  • the said components are mixed at temperatures in the range from about 10 to 100 ° C., preferably at 15 to 30 ° C.
  • the substances and mixtures of substances which are customary for PVC stabilization can be used as stabilizers, organotin compounds, metal soaps, lead compounds and organic nitrogen compounds are preferred, mixtures of calcium and zinc stearate being particularly preferred.
  • the stabilizers are usually preferred in amounts of 0.2 to 5% by weight
  • the process according to the invention can be carried out by adding the polyvinyl chloride in powder form to the latex based on conjugated dienes and acrylonitrile, with thorough mixing Mixing agitator kettles until a homogeneous mixture of polyvinyl chloride and the polymers mentioned has resulted.
  • the suspension obtained in this way is coagulated.
  • the known precipitants are added to the suspension in a conventional manner (cf. Ullmann's Encyclopedia of Industrial Chemistry, Vol. A23, pp. 260 to 261).
  • a mixture of polyvinyl chloride and the polymers based on conjugated dienes and acrylonitrile in solid form is obtained, which can be further processed in the customary manner to produce all types of vulcanizates, for example for use in hoses.
  • Polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile could be produced by simply mixing powdered polyvinyl chloride with the latices mentioned, since it had to be expected that when the PVC powder was stirred into the latex, the latex would coagulate, so that it would not be possible to obtain the desired homogeneous mixture of the two components.
  • the analytical determination of the organic chloride content in the blend shows that the PVC powder has been completely coagulated with the NBR latex. There is no PVC loss due to washing processes during the refurbishment process.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The invention relates to a method for producing mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile. Powdery polyvinyl chloride is mixed with latices based on conjugated dienes and acrylonitrile and is then coagulated therewith. The inventive method represents a cost-effective and ecological method for producing the cited mixtures, and the physical behaviour of the mixtures obtained does not differ from that of corresponding mixtures produced according to the dry mixing method or the latex mixing method.

Description

Verfahren zur Herstellung von Mischungen aus Polyvinylchlorid und Polymerisaten auf Basis von konjugierten Dienen und AcrylnitrilProcess for the preparation of mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile
Die Erfindung betrifft ein Nerfahren zur Herstellung von Mischlingen aus Polyvinylchlorid und Polymerisaten auf Basis von konjugierten Dienen und Acrylnitril.The invention relates to a ner process for the production of hybrids from polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile.
Mischungen aus Polyvinylchlorid und z.B. Copolymerisaten aus Acrylnitril und Butadien (ΝBR-Kautschuken) sind bekannt und werden in der kautschukverarbei- tenden Industrie geschätzt, da deren Nulkanisate eine sehr gute Ozon- bzw. Witterungsbeständigkeit aufweisen, gekoppelt mit einer hohen Quellbeständigkeit in Ölen bzw. Benzin und einer guten Flammfestigkeit. Außerdem zeichnen sich die Verschnitte von Νitrilkautschuk (NBR) mit Polyvinylchlorid (PNC) gegenüber reinen Nitrilkautschuk-Mischungen durch bessere Nerarbeitungseigenschaften aus. Die Nulkanisate weisen darüberhinaus eine erhöhte Zug- und Weiterreißfestigkeit auf.Mixtures of polyvinyl chloride and e.g. Copolymers of acrylonitrile and butadiene (ΝBR rubbers) are known and are valued in the rubber processing industry because their nulcanizates have very good resistance to ozone and weather, coupled with a high resistance to swelling in oils and petrol and good flame resistance. In addition, the blends of nitrile rubber (NBR) with polyvinyl chloride (PNC) are superior to pure nitrile rubber mixtures due to their better processing properties. In addition, the vulcanizates have increased tensile and tear strength.
Wir verweisen in diesem Zusammenhang auf entsprechende Ausführungen im "Handbuch für die Gummiindustrie" der Bayer AG, 2. Ausgabe von 1991, Seite 90 ff.In this context, we refer to the corresponding statements in the "Handbook for the Rubber Industry" of Bayer AG, 2nd edition from 1991, page 90 ff.
Zur Herstellung der bekannten Mischungen aus NBR und PNC werden in derTo produce the known mixtures of NBR and PNC in the
Gummiindustrie zwei unterschiedliche Nerfahren praktiziert, das sogenannte Trockenblend-Nerfahren und das Latexblend-Nerfahren.Rubber industry practices two different ner driving, the so-called dry blend ner driving and the latex blend ner driving.
Beim Trockenblend-Nerfahren wird die ΝBR-Ballenware zerkleinert und im Batch- Nerfahren mit PNC-Pulver gemischt. Die Mischung wird im Kneter bzw. in derThe ΝBR bale goods are shredded for dry blend ner driving and mixed with PNC powder in batch ner driving. The mixture is in the kneader or in the
Schnecke homogenisiert. Dabei wird der PNC-Anteil soweit in der ΝBR-Phase verteilt, dass man keine PNC-Domänen mehr in der ΝBR-Phase erkennt. Man spricht dann auch von einer Gelierung. Beim Latexblend-Nerfahren wird der ΝBR-Latex vor der Aufarbeitung zum Feststoff mit einem entsprechenden PNC-Latex abgemischt. Die Mischung wird dann koaguliert, geliert und so kontinuierlich zum Festprodukt aufgearbeitet.Homogenized snail. The PNC portion is distributed so far in the ΝBR phase that no PNC domains can be recognized in the ΝBR phase. One then speaks of a gelation. In latex blend ner driving, the ΝBR latex is mixed with a corresponding PNC latex before it is processed into a solid. The mixture is then coagulated, gelled and thus continuously worked up to the solid product.
Nachteilig bei dem Latexblend-Nerfahren ist, dass der eingesetzte PNC-Latex noch eine nicht unbeträchtliche Menge an monomerem Ninylchlorid enthält. Aus Umwelt- und Arbeitsschutz-Gründen (bzgl. Ninylchlorid s. h.: 1. Gefahrstoffverordnung 19. Anpassung, 2. Römpp Chemielexikon, Thieme Verlag), ist es daher wünschenswert, PNC-Komponenten einzusetzen, deren Gehalt an monomerem Ninylchlorid weniger als 1 ppm beträgt. Darüber hinaus ist der Einsatz eines PVC-Latex zur Herstellung der genannten Blends weniger wirtschaftlich aufgrund des hohen Wasseranteils des Latex, was sich nachteilig auf den Transport und auf die Verarbeitung (Entfernung der wässrigen Phase) auswirkt.A disadvantage of the latex blend ner driving is that the PNC latex used still contains a not inconsiderable amount of monomeric vinyl chloride. For environmental and occupational health and safety reasons (with regard to ninyl chloride see: 1. Hazardous Substances Ordinance, 19th Amendment, 2. Römpp Chemielexikon, Thieme Verlag), it is therefore desirable to use PNC components with a monomeric ninyl chloride content of less than 1 ppm. In addition, the use of a PVC latex for the production of the blends mentioned is less economical due to the high water content of the latex, which has a disadvantageous effect on the transport and processing (removal of the aqueous phase).
Nachteilig beim Trockenblend-Nerfahren ist insbesondere, dass eine homogene Verteilung der eingesetzten Komponenten NBR und PVC im Blend gewahrt werden muss, dass die Komponenten NBR und PVC vor der Gelierung gut verteilt sein müssen und das die eingesetzte NBR-Ballenware zuvor gut zerkleinert werden muss. Dies alles ist mit einem hohen technischen Aufwand verbunden, so dass das Trockenblend- Verfahren weniger wirtschaftlich als das Latexblend- Verfahren ist.A disadvantage of the dry blend ner driving is in particular that a homogeneous distribution of the components NBR and PVC used in the blend must be maintained, that the components NBR and PVC must be well distributed before gelling and that the NBR bale goods used must be comminuted well beforehand. All of this is associated with a high technical outlay, so that the dry blend process is less economical than the latex blend process.
Aufgabe der vorliegenden Erfindung war es nun, ein kostengünstiges und umweltfreundliches Verfahren zur Herstellung von Mischungen aus Polyvinylchlorid und Polymerisaten auf Basis von konjugierten Dienen und Acrylnitril zur Verfügung zu stellen, das die oben beschriebenen Nachteile der bisher in der Kautschuktechnologie angewandten Mischungsverfahren vermeidet.It was an object of the present invention to provide an inexpensive and environmentally friendly process for the preparation of mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile, which avoids the disadvantages described above of the mixing processes previously used in rubber technology.
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung vonThe present invention therefore relates to a method for producing
Mischungen aus Polyvinylchlorid und Polymerisaten auf Basis von konjugierten Dienen und Acrylnitril, das dadurch gekennzeichnet ist, dass man pulverförmiges Polyvinylchlorid mit NBR-Latices auf Basis von konjugierten Dienen und Acrylnitril mischt und dann gemeinsam koaguliert.Mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile, which is characterized in that it is powdered Mixes polyvinyl chloride with NBR latices based on conjugated dienes and acrylonitrile and then coagulates together.
Für das erfindungsgemäße Verfahren ist es von Bedeutung, dass das Polyvinyl- chlorid in pulverformiger Form mit dem Latex auf Basis von konjugierten Dienen und Acrylnitril abgemischt wird. Als pulverformiges Polyvinylchlorid werden erfindungsgemäß Homopolymerisate auf Basis des Emulsions- oder Suspensions- oder Mikrosuspensionsverfahrens sowie Pfropfcopolymerisate und Copolymerisate nach dem Suspensionsverfahren mit einem mittleren Teilchendurchmesser im Bereich von 5 bis 200 μm und K- Werten (DIN 53726 bzw. ISO 1628) von 40 bis 90 verstanden.It is important for the process according to the invention that the polyvinyl chloride in powder form is mixed with the latex based on conjugated dienes and acrylonitrile. Powdery polyvinyl chloride according to the invention are homopolymers based on the emulsion or suspension or microsuspension process and graft copolymers and copolymers according to the suspension process with an average particle diameter in the range from 5 to 200 μm and K values (DIN 53726 or ISO 1628) from 40 to 90 Roger that.
Bevorzugt sind dabei pulverförmige Homopolymerisate auf Basis des Emulsionsoder insbesondere des Suspensionsverfahrens mit mittleren Teilchendurchmessern von 40 bis 150 μm und K- Werten von 55 bis 75.Preference is given to pulverulent homopolymers based on the emulsion or, in particular, the suspension process with average particle diameters from 40 to 150 μm and K values from 55 to 75.
In das erfindungsgemäße Verfahren wird üblicherweise handelsübliches Polyvinylchlorid mit dem dafür typischen Rest Vinylchloridgehalt (< 1 ppm Vinylchlorid) eingesetzt, sofern es der oben angegebenen Spezifikation genügt.Commercially available polyvinyl chloride with the typical residual vinyl chloride content (<1 ppm vinyl chloride) is usually used in the process according to the invention, provided that it satisfies the specification given above.
Als Latices auf Basis von konjugierten Dienen und Acrylnitril können alle für die NBR-Produktion typischen Latices eingesetzt werden, die einen Polymergewichtsanteil im Bereich von 10 bis 50 % besitzen, wobei Anteile von 15 bis 30 % Gewichtsprozent bevorzugt sind.As latices based on conjugated dienes and acrylonitrile, all latices typical of NBR production can be used, which have a polymer weight fraction in the range from 10 to 50%, fractions from 15 to 30% by weight being preferred.
Die Menge an konjugierten Dienen und Acrylnitril in den einzusetzenden Polymeri- säten kann in weiten Bereichen schwanken, beispielsweise können Polymerisate eingesetzt werden, deren Anteil an konjugierten Dienen im Bereich von 40 bis 90, bevorzugt von 55 bis 75 Gew.-%, und deren Anteil an Acrylnitril im Bereich von bis 10 bis 60 Gew.-%, bevorzugt von 25 bis 45 Gew.-% liegen.The amount of conjugated dienes and acrylonitrile in the polymers to be used can vary within wide ranges, for example polymers can be used, the proportion of conjugated dienes in the range from 40 to 90, preferably from 55 to 75% by weight, and their proportion of acrylonitrile are in the range from 10 to 60% by weight, preferably from 25 to 45% by weight.
Als konjugierte Diene kommen beispielsweise für die einzusetzenden Polymerisate insbesondere 1,3-Butadien und Isopren sowie andere konjugierte Diene wie 2,3- Dimethyl-l,3-butadien, 1,3-Pentadien und Piperylen in Betracht, bevorzugt ist dabei 1,3 -Butadien.For example, 1,3-butadiene and isoprene as well as other conjugated dienes such as 2,3- Dimethyl-l, 3-butadiene, 1,3-pentadiene and piperylene are considered, 1,3-butadiene being preferred.
Neben Acrylnitril können auch dessen bekannte Abkömmlinge eingesetzt werden wie α-Chloroacrylnitril und/oder Methacrylnitril.In addition to acrylonitrile, it is also possible to use its known derivatives, such as α-chloroacrylonitrile and / or methacrylonitrile.
Selbstverständlich können neben den erwähnten konjugierten Dienen und dem Acrylnitril noch weitere dem Fachmann bekannte Monomere zum Aufbau der einzusetzenden Polymerisate eingesetzt werden. Genannt werden z.B. in diesem Zusammenhang α,ß-ungesättigte Carbonsäuren sowie α,ß -ungesättigte Carbonsäureester. Bevorzugt sind dabei Fumarsäure, Maleinsäure, Acrylsäure, Methacrylsäure sowie Butylacrylat und Butylmethacrylat sowie Ethylhexylacrylat und Ethylhexylmethacrylat.In addition to the conjugated dienes mentioned and the acrylonitrile, it is of course also possible to use other monomers known to the person skilled in the art to build up the polymers to be used. The following are mentioned e.g. in this context, α, β-unsaturated carboxylic acids and α, β-unsaturated carboxylic acid esters. Fumaric acid, maleic acid, acrylic acid, methacrylic acid and butyl acrylate and butyl methacrylate as well as ethylhexyl acrylate and ethylhexyl methacrylate are preferred.
Desweiteren können zum Aufbau der einzusetzenden Polymerisate dem Fachmann bekannte vernetzende polyfunktionelle Monomere verwendet werden. Dabei handelt es sich insbesondere um di- und trifunktionelle Monomere. Beispielhaft seien hier Divinylbenzol, Diethylglykoldimethacrylat und Trimethylolpropantrimethylacrylat genannt.Furthermore, crosslinking polyfunctional monomers known to the person skilled in the art can be used to construct the polymers to be used. These are especially di- and trifunctional monomers. Examples include divinylbenzene, diethylglycol dimethacrylate and trimethylolpropane trimethyl acrylate.
Die zusätzlichen Monomere zum Aufbau der Polymerisate auf Basis der genannten konjugierten Dienen und den Acrylnitrilen können in Mengen von 0,1 bis 40 Gew.-%, bevorzugt 1 bis 30 Gew.-%, bezogen auf das Gesamtpolymer vorliegen.The additional monomers for building up the polymers based on the conjugated dienes mentioned and the acrylonitriles can be present in amounts of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total polymer.
Die erfindungsgemäß einzusetzenden Latices auf Basis von konjugierten Dienen und Acrylnitrilen, gegebenenfalls unter Zusatz der zusätzlich genannten polymerisier- baren Monomeren, sind in der dem Fachmann bekannten Fachliteratur beschrieben, dabei auch ihre Herstellungsweise (z.B. Ullmann's Encyclopedia of Industrial Chemistry, Vol. A23, S.239-364).The latices to be used according to the invention based on conjugated dienes and acrylonitriles, optionally with the addition of the additionally mentioned polymerizable monomers, are described in the specialist literature known to the person skilled in the art, and also their method of preparation (for example Ullmann's Encyclopedia of Industrial Chemistry, Vol. A23, p. A23). 239-364).
Nach dem erfindungsgemäßen Verfahren werden Mischungen aus Polyvinylchlorid und Polymerisaten auf Basis von konjugierten Dienen und Acrylnitrilen, gegebenen- falls unter Zusatz der zusätzlich genannten Monomeren, hergestellt, in denen der Anteil an Polyvinylchlorid in den Mischungen im Bereich von 10 bis 95 Gew.-%, bevorzugt 25 bis 45 Gew.-% liegt, und der Anteil der beschriebenen Kautschuk- Polymerisate 90 bis 5 Gew.-%, bevorzugt 55 bis 75 Gew.-%, beträgt.Mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitriles, if produced with the addition of the additionally mentioned monomers, in which the proportion of polyvinyl chloride in the mixtures is in the range from 10 to 95% by weight, preferably 25 to 45% by weight, and the proportion of the rubber polymers described is 90 to 5% by weight, preferably 55 to 75% by weight.
Das Mischen der beiden Komponenten kann in den verschiedensten Mischvorrichtungen durchgeführt werden. Genannt werden beispielsweise Rührwerkskessel variabler Kesselgeometrie mit Ein- und Mehrwellenrührern und unterschiedlichen Mischwerkzeugen sowie Rotor-Stator-Mischern, Mischen durch Umpumpen mit und ohne Einsatz von Rotor-Stator-Dispergiermaschinen oder Mischdüsen, Strahlsauger,The two components can be mixed in a wide variety of mixing devices. For example, agitator kettles with variable kettle geometry with single and multi-shaft agitators and different mixing tools as well as rotor-stator mixers, mixing by pumping with and without the use of rotor-stator dispersing machines or mixing nozzles, jet suction devices,
Injektoren, Taumelmischer, Planetenmischer, Pflugscharmischer mit und ohne Messerrührer, bevorzugt Mischen in Rührwerkskesseln oder Strahlsaugern, Injektoren, Leitstrahlmischern, insbesondere Mischen in Rührwerkskesseln.Injectors, tumble mixers, planetary mixers, ploughshare mixers with and without knife stirrers, preferably mixing in agitator tanks or jet suction devices, injectors, guide jet mixers, in particular mixing in agitator tanks.
Das Mischen der genannten Komponenten erfolgt erfindungsgemäß bei Temperaturen im Bereich von ca.10 bis 100°C, bevorzugt bei 15 bis 30°C.According to the invention, the said components are mixed at temperatures in the range from about 10 to 100 ° C., preferably at 15 to 30 ° C.
Selbstverständlich ist es möglich, das Mischen der Einsatzkomponenten in Gegenwart von Stabilisatoren durchzuführen. Als Stabilisatoren können erfindungsgemäß die für die PVC Stabilisierung üblichen Substanzen und Substanzgemische verwendet werden, bevorzugt kommen hierbei Organozinnverbindungen, Metallseifen, Bleiverbindungen und Organische Stickstoffverbindungen in Betracht, wobei Gemische von Calcium- und Zinkstearat insbesondere bevorzugt werden.Of course, it is possible to mix the feed components in the presence of stabilizers. According to the invention, the substances and mixtures of substances which are customary for PVC stabilization can be used as stabilizers, organotin compounds, metal soaps, lead compounds and organic nitrogen compounds are preferred, mixtures of calcium and zinc stearate being particularly preferred.
Üblicherweise werden die Stabilisatoren in Mengen von 0,2 bis 5 Gew.-%, bevorzugtThe stabilizers are usually preferred in amounts of 0.2 to 5% by weight
0,4 bis 2 Gew.-% , bezogen auf die Kautschuk PVC Mischung eingesetzt.0.4 to 2 wt .-%, based on the rubber PVC mixture used.
Beispielsweise kann man das erfindungsgemäße Verfahren so durchführen, dass man zu dem vorgelegten Latex auf Basis von konjugierten Dienen und Acrylnitril das Polyvinylchlorid in pulverformiger Form unter intensivem Durchmischen mittels Rührwerkskesseln mischt, bis sich eine homogene Mischung aus Polyvinylchlorid und den genannten Polymerisaten ergeben hat.For example, the process according to the invention can be carried out by adding the polyvinyl chloride in powder form to the latex based on conjugated dienes and acrylonitrile, with thorough mixing Mixing agitator kettles until a homogeneous mixture of polyvinyl chloride and the polymers mentioned has resulted.
Bei dem erfindungsgemäßen Verfahren wird nach dem Mischen des pulverförmigen Polyvinylchlorids mit Latices auf Basis von konjugierten Dienen und Acrylnitril die so erhaltene Suspension koaguliert. Hierzu wird die Suspension in üblicher Weise mit den bekannten Fällungsmitteln versetzt (vgl. hierzu Ullmanns Encyclopedia of Industrial Chemistry, Vol. A23, S. 260 bis 261).In the process according to the invention, after the powdery polyvinyl chloride has been mixed with latices based on conjugated dienes and acrylonitrile, the suspension obtained in this way is coagulated. For this purpose, the known precipitants are added to the suspension in a conventional manner (cf. Ullmann's Encyclopedia of Industrial Chemistry, Vol. A23, pp. 260 to 261).
Erhalten wird eine Mischung aus Polyvinylchlorid und den Polymerisaten auf Basis von konjugierten Dienen und Acrylnitril in fester Form, die in üblicher Weise weiterverarbeitet werden kann zur Herstellung von Vulkanisaten aller Art, beispielsweise für die Verwendung in Schläuchen.A mixture of polyvinyl chloride and the polymers based on conjugated dienes and acrylonitrile in solid form is obtained, which can be further processed in the customary manner to produce all types of vulcanizates, for example for use in hoses.
Es ist überraschend, dass nach dem erfindungsgemäßen Verfahren Mischungen ausIt is surprising that mixtures of
Polyvinylchlorid und Polymerisaten auf Basis von konjugierten Dienen und Acrylnitril hergestellt werden konnten durch einfaches Vermischen von pulverformigem Polyvinylchlorid mit den genannten Latices, da erwartet werden musste, dass es beim Einrühren des PVC-Pulvers in den Latex zur Koagulation des Latex kommen würde, so dass es nicht möglich wäre, die gewünschte homogene Mischung der beiden Komponenten zu erhalten. Weiterhin zeigt die analytische Bestimmung des organischen Chloridanteils in dem Blend an, daß das PVC -Pulver vollständig mit dem NBR- Latex zusammen koaguliert wurde. Ein PVC- Verlust durch Waschvorgänge während des Aufarbeitungsprozesses findet nicht statt. Darüber hinaus war es überraschend, dass unter den Mischungsbedingungen keine Entmischung der Komponenten stattfindet und dass Mischungen erhalten werden, die sich im physikalischen Verhalten nicht von den entsprechenden Mischungen die nach dem Trockenblend-Verfahren oder Latexblend- Verfahren hergestellt werden, unterscheiden. BeispielPolyvinyl chloride and polymers based on conjugated dienes and acrylonitrile could be produced by simply mixing powdered polyvinyl chloride with the latices mentioned, since it had to be expected that when the PVC powder was stirred into the latex, the latex would coagulate, so that it would not be possible to obtain the desired homogeneous mixture of the two components. Furthermore, the analytical determination of the organic chloride content in the blend shows that the PVC powder has been completely coagulated with the NBR latex. There is no PVC loss due to washing processes during the refurbishment process. In addition, it was surprising that no separation of the components takes place under the mixing conditions and that mixtures are obtained which do not differ in physical behavior from the corresponding mixtures which are produced by the dry blend process or latex blend process. example
Unter Rühren werden in eine Vorlage von 70 Teilen eines Perbunan NT 2830 (Fa. Bayer AG) Latex 30 Teile eines Suspensions PVC-Pulvers mit einem K-Wert von 71 (Fa. Solvin) sowie 1 Teil eines Calcium-Zinkstearatgemisches (Fa. Ciba) zugegeben.While stirring, 30 parts of a suspension PVC powder with a K value of 71 (from Solvin) and 1 part of a calcium-zinc stearate mixture (from Ciba.) Are placed in a template of 70 parts of a Perbunan NT 2830 (Bayer AG) latex ) added.
Man läßt 1 h Nachrühren bevor das Gemisch durch Zusatz einer Calciumchlorid- lösung bei 70°C gefallt wird. Der Kautschuk wird filtriert und mit Wasser nachgewaschen. Anschließend wird der Kautschuk getrocknet. Die mikroskopische Untersuchung zeigt eine gleichmäßige Verteilung des PVC-Pulvers im Kautschuk, die Chlorbestimmung liefert den theoretisch berechneten Cl-Gehalt, der eine vollständigeThe mixture is left to stir for 1 h before the mixture is precipitated at 70 ° C. by adding a calcium chloride solution. The rubber is filtered and washed with water. The rubber is then dried. The microscopic examination shows an even distribution of the PVC powder in the rubber, the chlorine determination gives the theoretically calculated Cl content, which is complete
Fällung des PVC-Pulvers mit dem Kautschuk bestätigt. Precipitation of the PVC powder with the rubber confirmed.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Mischungen aus Polyvinylchlorid und Polymerisaten auf Basis von konjugierten Dienen und Acrylnitril, dadurch ge- kennzeichnet, dass man pulverformiges Polyvinylchlorid mit Latices auf1. Process for the preparation of mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile, characterized in that powdered polyvinyl chloride with latices
Basis von konjugierten Dienen und Acrylnitril mischt und dann gemeinsam koaguliert.Mixes the base of conjugated dienes and acrylonitrile and then coagulates together.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man als pulver- formiges Polyvinylchlorid ein Polyvinylchlorid einsetzt, dass einen mittleren2. The method according to claim 1, characterized in that a polyvinyl chloride is used as the powdered polyvinyl chloride that a medium
Teilchendurchmesser im Bereich von 5 bis 200 μm und K- Werte (DIN 53726/ ISO 1628) von 40 bis 90 aufweist.Has particle diameters in the range from 5 to 200 μm and K values (DIN 53726 / ISO 1628) from 40 to 90.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man als Latices auf Basis von konjugierten Dienen und Acrylnitril solche einsetzt, die einen3. The method according to claim 1, characterized in that one uses as latices based on conjugated dienes and acrylonitrile, one
Polymergewichtsanteil im Bereich von 10 bis 50 % besitzen.Have polymer weight fraction in the range of 10 to 50%.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man als Polymerisate auf Basis von konjugierten Dienen und Acrylnitril solche einsetzt, in denen der Anteil an konjugierten Dienen im Bereich von 40 bis 90 Gew.-%, und der Anteil an Acrylnitril im Bereich von 10 bis 60 Gew.-% liegt.4. The method according to claim 1, characterized in that the polymers based on conjugated dienes and acrylonitrile are used in which the proportion of conjugated dienes in the range from 40 to 90% by weight and the proportion of acrylonitrile in the range of 10 to 60 wt .-% is.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man pulverformiges Polyvinylchlorid mit den Latices bei Temperaturen im Bereich von 10°C bis 100°C mischt. 5. The method according to claim 1, characterized in that powdered polyvinyl chloride is mixed with the latices at temperatures in the range from 10 ° C to 100 ° C.
EP01999598A 2000-12-06 2001-11-23 Method for producing mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile Withdrawn EP1353974A1 (en)

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DE10060474A DE10060474A1 (en) 2000-12-06 2000-12-06 Process for the preparation of mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile
DE10060474 2000-12-06
PCT/EP2001/013646 WO2002046274A1 (en) 2000-12-06 2001-11-23 Method for producing mixtures of polyvinyl chloride and polymers based on conjugated dienes and acrylonitrile

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US20060014885A1 (en) * 2004-07-14 2006-01-19 Morgan John J Polyvinyl chloride-based elements for floor cleaninig units
ITMO20040223A1 (en) 2004-09-06 2004-12-06 Gambro Lundia Ab PIPE FOR A PERISTALTIC PUMP.
WO2007018394A1 (en) * 2005-08-11 2007-02-15 Lg Chem, Ltd. Highly elastic polyvinyl chloride composition and products prepared using the same
KR100762838B1 (en) 2005-08-11 2007-10-04 주식회사 엘지화학 High elastic polyvinyl chloride composition and objects prepared by the same

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