WO2000063284A1 - Compositions de stabilisateurs exemptes de poussiere pour matieres synthetiques, et leur procede de production - Google Patents

Compositions de stabilisateurs exemptes de poussiere pour matieres synthetiques, et leur procede de production Download PDF

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Publication number
WO2000063284A1
WO2000063284A1 PCT/EP2000/003253 EP0003253W WO0063284A1 WO 2000063284 A1 WO2000063284 A1 WO 2000063284A1 EP 0003253 W EP0003253 W EP 0003253W WO 0063284 A1 WO0063284 A1 WO 0063284A1
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WO
WIPO (PCT)
Prior art keywords
stabilizer composition
stabilizer
mixer
plastics
binder
Prior art date
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PCT/EP2000/003253
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German (de)
English (en)
Inventor
Bernhard Bartnick
Hermann Hupe
Original Assignee
Cognis Deutschland Gmbh
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Publication date
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Publication of WO2000063284A1 publication Critical patent/WO2000063284A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the invention relates to dust-free stabilizer compositions for plastics, in particular polyvinyl chloride (PVC), in granular form, the composition preferably being free of the plastics for which it is intended.
  • PVC polyvinyl chloride
  • Stabilizers are added to plastics in thermoplastic processing to increase durability. These can be lead, cadmium, barium, calcium, tin and zinc compounds, in particular salts and metal soaps, and others.
  • the stabilizer compositions also consist of lubricants, such as fatty acid esters, waxes, paraffins, etc., and fillers, such as chalk, kaolin, titanium dioxide, etc. Further auxiliaries such as flow modifiers can also be contained in the stabilizer compositions.
  • the stabilizer compositions are mixed in powder form into the plastics, which are likewise in powder form or as very fine-grained granules.
  • Stabilizer compositions is favorable in order to obtain a mixture which is as uniform and homogeneous as possible.
  • the stabilizer compositions are provided as a powder for mixing into the plastics, there are serious disadvantages. Since the stabilizer compositions often contain, as can be seen from the examples given above, harmful components which should not be inhaled, the processing of such powdered stabilizer Compositions for special occupational safety measures. Fully encapsulated systems are therefore known which enable the powdery stabilizer composition to be processed completely dust-free from delivery to the finished mixture of plastic and stabilizer composition and beyond. However, the systems are very expensive both in terms of acquisition costs and ongoing maintenance.
  • powdered stabilizer compositions Another disadvantage of powdered stabilizer compositions is their risk of explosion, since the compositions contain a not insignificant proportion of organic compounds. Special measures to avoid dust explosions are therefore necessary.
  • granules are produced from the stabilizer compositions, which the user processes in a special apparatus.
  • the granules are placed together with the plastic powder in a hot-cooling powder mixer with a vertical axis of rotation, in which agitator blades rotate at high rotational speed, typically 2000 rpm.
  • the stirrer breaks the stabilizer granules into fine powder and simultaneously mixes it with the plastic powder.
  • About 2 to 8 parts by weight of the stabilizer compositions are mixed with 100 parts by weight of plastic powder in this way. Due to the mechanical comminution, the temperature in this mixer rises quickly, so care must be taken not to exceed a certain mixing time, because otherwise the plastic is plasticized, so that a caked block is obtained instead of the desired solid powder mixture.
  • the mixture falls into a tubular, horizontally arranged cooler with an agitator shaft arranged in the longitudinal axis, that is to say also horizontally, on which agitator blades are attached.
  • the powder mixture is cooled to around 30 to 40 ° C and then directly processed further or transported to a storage silo.
  • the temperatures given relate to the most common application in which PVC powder is mixed with a stabilizer composition.
  • processing e.g. B. in an extruder or in a plastic injection molding machine, one then works with processing temperatures of 145 to 210 ° C.
  • the typical plasticizing temperature which must not be exceeded in the powder mixer, is around 140 ° C.
  • the stabilizer compositions can be compacted cold into pressure into pellets.
  • high pressures are advantageous in order to obtain particularly dust-free compositions.
  • the high density then achieved leads to poor dispersibility in the plastic.
  • the corresponding metal soaps are produced from the metal oxides and fatty acids in a melting reactor at temperatures of 130 to 150 ° C. These metal soaps often have an indefinable composition. After the addition of meltable and non-meltable additives, a tough, 140 ° C hot melt is obtained, which is applied to a flaking roller in order to obtain flakes.
  • the scales have a non-uniform shape and are also mechanically relatively unstable, so that a product is obtained with an undesirable dust content that should not be neglected.
  • pastilles It is therefore cheaper to produce pastilles from the melt instead of flakes.
  • drops of the hot melt are applied to a cooling bed using a stamp, which can be a cooled steel strip.
  • the pastilles have the advantage of being almost completely dust-free and better dispersed in the plastic powder, since no mechanical pressure has been applied to produce the pastilles.
  • the pastilles have a diameter of about 3 to 4 mm.
  • the pastilles have the advantage of being dust-free and easy to process, but stabilizer compositions with high metal contents, in particular special lead salt contents, such as z. B. are required for cable plastics, can not be made as pastilles, because such stabilizer compositions are very difficult to melt.
  • Plastics intended for sheathing electrical cables require stabilizer compositions with 50 to 70% by weight, even up to 75% by weight of lead sulfate.
  • fatty alcohols e.g. B. 5 to 10 wt .-%
  • the stabilizer compositions are added so that the composition is pastilizable.
  • a content of fatty alcohols is undesirable for cable masses and even incompatible for soft PVC.
  • the problems with the meltability of the stabilizer composition do not occur with lead contents of less than 50% by weight, so that the addition of fatty alcohols is not necessary here.
  • DE-A-34 29 766 also discloses a granular stabilizer for PVC and a process for its production.
  • a powdery stabilizer mixture and an organic solid binder are assumed.
  • the proportion of the binder is 2 to 15 parts by weight per 100 parts by weight of the powdery stabilizer composition.
  • the binder can also be a common component of the stabilizer mixture, e.g. B. pencil stearate, or a low melting wax. It is important that the binder is added in an amount which is less than the "critical liquid absorption" of the powdery stabilizer composition defined in this document.
  • the powdery stabilizer mixture is comminuted into so-called "primary particles", with no information being given about their grain size. From the devices used for comminution, e.g. B. high-speed mills, however, it can be concluded that the grain sizes are in the nanometer range. Simultaneously with the comminution, the powdery stabilizer mixture is mixed with the binder mentioned in the dry state or with the addition of solvents, so that the surface of the primary particles is covered by the binder.
  • the coated primary particles obtained optionally after removal of the solvent, by melting the surface layer, that is at a temperature higher than the melting point of the binder, granulated to particle sizes of 0.1 to 2 mm.
  • the result is a granulate, but each granulate is made up of several primary particles, which in turn are individually covered by the binder.
  • the disadvantage here is the high expenditure for the strong comminution.
  • typical components of the stabilizer mixture e.g. B. pencilearate, used as a binder, as is proposed in this document, the effort to avoid explosions of the highly dusting powder is disadvantageous.
  • the primary particles are also prone to dust explosions, against which suitable measures are necessary.
  • the starting materials could be comminuted in primary particles with the addition of a solvent, but this has the disadvantage that the solvent must be removed by distillation in a further step after this process step before the primary particles are granulated.
  • the invention has for its object to produce a stabilizer composition for plastics, in particular PVC, which is dust-free during transport and delivery, as well as powdery compositions are dispersible in the plastic and enables high inorganic lead salt contents without the addition of fatty alcohols.
  • the composition should easily disintegrate into powder, which can then be mixed into the plastic without dispersion problems.
  • each granulate consists of several particles of the stabilizer composition and is encased in a binder which contains the lowest melting component of the stabilizer composition.
  • the invention relates to dust-free stabilizer compositions for plastics in granular form, the composition being essentially free of the plastics for which it is intended, each Granules consist of several particles of the stabilizer composition and are encased by a binder which contains the lowest melting component of the stabilizer composition.
  • the plastic used is polyvinyl chloride.
  • the starting materials for the stabilizer composition it is not necessary to comminute the starting materials for the stabilizer composition into primary particles in a first step.
  • the grain size of the components of the stabilizer composition that is usually supplied ensures good dispersibility in the plastic. Since the stabilizer composition does not need to be melted, as in the known process for the production of pastilles, high levels of lead salt can also be present in the composition. Dust-free is achieved by coating the granules with the lowest melting component of the stabilizer composition.
  • each granule is completely covered by the binder.
  • Another advantage of the stabilizer composition according to the invention is that an additional binder is not used for the granulation, but rather that the proportions by weight of the components in the stabilizer composition are not changed by the granulation.
  • the lowest melting component preferably has a proportion of 1 to 20% by weight, in particular 5 to 10% by weight, in the stabilizer composition. The optimal value depends in individual cases on the other proportions in the stabilizer composition. It is also suggested that the lowest melting component has a melting point below 100 ° C. Therefore, only low temperatures are required for the granulation. The low melting point of the component enveloping the granules also means that when the granules are mixed with the plastic, they break down into the starting particles at relatively low temperatures, which can be dispersed very well in the plastic due to their small particle size. It is also proposed that the binder contain a lubricant for plastics processing. However, other low-melting components of the stabilizer composition can also be used as binders for the granules according to the invention.
  • the binder be a lubricant made from fatty acids with 8 to 24 carbon atoms, fatty alcohols with 12 to 24 carbon atoms, esters from fatty acids with 8 to 24 carbon atoms and fatty alcohols with 6 to 24 carbon atoms, Contains esters of fatty acids with 8 to 24 carbon atoms and polyhydric alcohols with 4 to 6 hydroxyl groups and hydroxystearic acid esters.
  • the compounds mentioned can be used both individually and in a mixture with one another.
  • Both fatty and synthetic straight-chain saturated compounds of this class of substances can be considered as fatty acids with 8 to 24 carbon atoms. If fatty acid mixtures are used, they can contain minor amounts of unsaturated fatty acids, provided that the melting point of such mixtures is in any case above 25 ° C.
  • fatty acids which can be used as a meltable component are caprylic, capric, lauric, tridecane, myristic, pentadecanoic, palmitic, margaric, stearic, behenic and lignoceric acids.
  • Fatty acids containing hydroxyl groups, such as 12-hydroxystearic acid, are also suitable here.
  • Such fatty acids can be obtained from naturally occurring fats and oils, for example via fat cleavage at elevated temperature and pressure and subsequent separation of the fatty acid mixtures obtained, optionally hydrogenation of the double bonds present.
  • Technical fatty acids are preferably used here, which as a rule represent mixtures of different fatty acids of a certain chain length range with a fatty acid as the main constituent.
  • Fatty acids with 12 to 18 carbon atoms are preferably used here.
  • the fatty alcohols with 12 to 24 carbon atoms which are considered as fusible components are straight-chain saturated representatives of this class of substances which, without exception, have a melting point above 25 ° C.
  • Corresponding fatty alcohols can be obtained from naturally occurring sources Fats and oils can be obtained via the transesterification with methanol, subsequent catalytic hydrogenation of the methyl ester obtained and fractional distillation.
  • synthetic fatty alcohols such as those obtained via oxo and Ziegler synthesis, can also be used. Examples of such fatty alcohols are lauryl, myristyl, cetyl, stearyl and behenyl alcohol. These compounds can be used individually and in a mixture with one another.
  • Technical fatty alcohols are preferably used, which normally represent mixtures of different fatty alcohols of a limited chain length range, in each of which a fatty alcohol is present as the main constituent.
  • Fatty alcohols with 12 to 18 carbon atoms are preferably used here.
  • esters from fatty acids with 8 to 24 C atoms and fatty alcohols with 6 to 24 C atoms should in turn meet the condition that their melting point is above 25 ° C.
  • Suitable starting materials for the production of such fatty alcohol fatty acid esters are the fatty acids and fatty alcohols already described in detail above, fatty acids with 6 to 11 carbon atoms, for example n-hexanol, n-octanol and n-decanol, also being used in such esters. may be present as an alcohol component.
  • esters mentioned can be obtained by known methods of organic synthesis, for example by heating stoichiometric amounts of fatty acid and fatty alcohol to 180 to 250 ° C., optionally in the presence of a suitable esterification catalyst such as tin grinding and under a protective gas, and distilling off the water of reaction.
  • a suitable esterification catalyst such as tin grinding and under a protective gas
  • esters which can be used according to the invention are stearyl caprylate, stearyl caprinate, cetyl laurate, cetyl myristrate, cetyl palmitate, n-hexanol stearate, n-octyl stearate, lauryl stearate, stearyl stearate, stearyl behenate, behenyl laurate and behenyl behenate. It should be noted that these esters are normally produced from technical raw materials, which in turn are mixtures of substances, so that the corresponding esters are also mixtures of substances.
  • fatty acids already described above are again suitable as the starting material for the preparation of the abovementioned esters from fatty acids with 8 to 24 carbon atoms and alcohols with 4 to 6 hydroxyl groups.
  • Aliphatic polyols with 4 to 12 carbon atoms are particularly suitable as alcohol components, for example erythritol, pentaerythritol, dipentaerythritol, ditrimethylolpropane, diglycerol, triglycerol, tetraglycerol, mannitol and sorbitol.
  • These polyol esters can be full esters in which all the hydroxyl groups of the polyol are esterified with fatty acid.
  • polyol partial esters are also suitable which have one or more free hydroxyl groups in the molecule.
  • These fatty acid polyol esters can also be obtained by known methods of organic synthesis by esterifying the polyols with stoichiometric or substoichiometric amounts of free fatty acids.
  • polyol fatty acid esters examples include the full stearic acid and full stearic acid / palmitic acid esters of erythritol, pentaerythritol and diglycerol, the dilaurates of dipentaerythritol, ditrimethylolpropane, triglycerol, mannitol and sorbitol, the distearates of erythritol, pentaerythritol and ditentaerythritol, ditroerythritol, ditentaerythritol and dentaerythritol titrite, so-called pentaerythritol and dentaerythritol and dentaerythritol, , Mannits and sorbits, for their preparation one uses 1 mol polyol, 1.5 mol fatty acid, especially palmitic and / or stearic acid.
  • esters of hydroxystearic acid since here compounds are considered in which the hydroxystearic acids are esterified via their carboxyl group with a mono- or polyhydric alcohol, as well as those in which they are esterified with their hydroxyl group with fatty acids.
  • These are preferably derivatives of 12-hydroxystearic acid, which can be obtained, for example, from the fatty acid component of the hydrogenated castor oil.
  • the derivatives of the first-mentioned type include 12-hydroxystearic acid esters of the fatty alcohols described in detail above, as well as full and partial 12-hydroxystearic acid esters with polyols with 2 to 6 hydroxyl groups and 2 to 12 C atoms, in particular those which differ from ethylene glycol, 1, 2- and 1, 3-propylene glycol, the isomeric butylene glycols, 1, 12-dodecanediol, glycerol, trimethylolpropane, erythritol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, diglycerol, triglycerol, tetraglycerol, mannitol and sorbitol.
  • esters examples include the 12-hydroxystearic acid full esters of ethylene glycol, 1, 3-propylene glycol, erythritol and pentaerythritol, the di-12-hydroxystearates of pentaerythritol, dipentaerythritol, diglycerol, tetraglycerol and sorbitol, and the 12-hydroxystearic acid ester of pentaerythritol, dipentaerythritol and mannitol.
  • Hardened castor oil which is known to be a triglyceride mixture with a fatty acid component consisting mainly of 12-hydroxystearic acid, is also regarded as a member of this group.
  • the 12-hydroxystearic acid esters of the second type are esterification products of 12-hydroxystearic acid and fatty acids with 8 to 24 carbon atoms, the latter of which have already been described in more detail above.
  • the esterification product of 12-hydroxystearic acid and behenic acid is of particular importance, since it has the characteristic property of dispersing the particles encased by the binder in plastic melts so well that, when used, the usual amounts used for the other components of the Stabilizer composition can be significantly reduced.
  • this esterification product at 60 ° C has such a favorable melting point that the granules according to the invention can be mixed into the plastic at low temperatures. On the other hand, the melting point is high enough to also store the shaped stabilizer composition without caking or exudation
  • the binder contains glycerol monostearate.
  • a stabilizer composition of this type makes it possible to coat the other components with the inexpensive glycerol monostearate at relatively low temperatures.
  • Glycerin monostearate is also a very good lubricant in polyvinyl chloride.
  • glycerol monostearate has strong surface-active properties, so that the other components of the composition are very well covered by the glycerol monostearate.
  • glycerol monostearate is extremely well tolerated by other additives added to polyvinyl chloride.
  • glycerol monostearate includes not only pure glycerol monostearate but also mixtures of different ones Contain amounts of glycerol di and tristearate, depending on the degree of purity of the glycerol monostearate. Typical values are 40 - 50% monostearate, 30 - 43% distearate and 8 - 10% tristearate.
  • stabilizers for the purposes of the disclosure, reference is expressly made to the "stabilizers”, “stabilizer auxiliaries”, “sliding stabilizers”, “lubricants” and “resin modifiers” mentioned in DE-A-34 29 766, which may be contained in the granules according to the invention.
  • the lowest melting component forms the binder for coating the other components of the stabilizer composition.
  • the grain size of the granules according to the invention is 95% at most 4 mm, in particular 0.5 to 2 mm.
  • the invention also relates to a process for the preparation of a dust-free stabilizer composition for plastics, in particular for PVC, the composition being essentially free of the plastics for which it is intended, and wherein the dust-free stabilizer composition is obtained by granulating a mixture of the powdery composition in a Produces temperature equal to or greater than the melting point of the lowest melting component.
  • the above-mentioned object according to the invention is achieved here by granulating a mixture in which each particle consists of only one material.
  • the stabilizer composition is granulated in the process according to the invention without any pretreatment with the binder contained in the composition.
  • At least one of the components of the stabilizer composition preferably has a melting point below 100 ° C.
  • this component serves as a binder for preferably completely encasing the other components.
  • the granulation be carried out in a mixer, in particular a heating / cooling mixer, at temperatures up to 100 ° C., in particular at temperatures from 60 to 80 ° C.
  • a mixer in particular a heating / cooling mixer
  • the optimal time period which also depends on the set granulation temperature, can easily be found out by practical tests.
  • a "heating / cooling mixer” is to be understood here as a mixer or granulator in which one part can be heated and the other part can be cooled. The process is first carried out in a heated mixer, the product obtained there being cooled down to the desired temperature in the cooling section of the mixer.
  • Bisphenol A 2,2-bis (4-hydroxyphenyl) propane (Bayer)
  • Loxiol G 53 tallow fatty alcohol (Henkel)
  • Loxiol G 20 stearic acid (Henkel)
  • Ground pentaerythritol mixture of pentaerythritol and dipentaerythritol (Fa.
  • the 150 l heating mixer used was approximately 80-90% full with a batch size of 75 kg.
  • the mix was heated within the heating mixer without targeted friction only by the jacket heater. At a temperature of 50 - 55 ° C, the high volume of calcium stearate was reduced, which reduced the volume the mixture in the heating mixer by up to 20%. It was found that with a formulation of Example 1, physical compaction took place at a temperature of 50-55 ° C., although the lowest and only wax melting point (5.4% of the total formulation with a volume fraction of 2.5-3%) only at 58 - 62 ° C. This can be due to the fact that the mixture components or impurities create a eutectic mixture within the mixture and thus a physical reduction of the melting point takes place.
  • the desired agglomeration took place at a constant temperature of 61 ° C in the mixer arrangement described.
  • the agglomerated mixture was automatically drained into the cooling mixer as soon as the temperature display had reached a constant 61 ° C; the amp display rose from 10 - 12 amps to approx. 150 amps.
  • the total agglomeration time required to drain into the cooling mixer was between 7 and 10 minutes.
  • the cooling mixer was set by its stirring speed so that the material to be cooled was just moved.
  • the recipe was automatically drained into the cooler and reproduced 10 times in a row without checking wall deposits at a temperature of 61 ° C on the digital display (without cleaning the temperature sensor in the mixer). All batches produced in this way showed identical properties within the tolerance limits (particle size distribution absolutely dust-free, metal content, thermostability due to HCI elimination at 200 ° C, etc.).
  • the dispersion behavior was at least in the order of magnitude of melt compounds and was similar to that of a powder mixture.
  • Example 1 The agglomeration process was carried out analogously to Example 1. At a temperature of 61 ° C was discharged into the cooling mixer as in Example 1. The process and appearance of the granules were identical to the product from Example 1 within tolerance limits. Only the stickiness was lower after reaching the pour point than in Example 1.
  • the example was reproduced 5 times with identical results.
  • This agglomeration process was also carried out analogously to Example 1.
  • the agglomerated material was not discharged into the cooling mixer at a temperature of 61.degree. C., but instead when the automatic stirring speed was reduced from 150 to 110 rpm.
  • it was found that at Inlet of the agglomerates in the cooling mixer (due to the very high wax content) they were still jagged on the surface. Only when the cooling mixer reached the pour point of the waxes was the surface of the agglomerates absolutely smooth and rounded. The mixture is dust-free, wall and tool deposits were negligible. A reproducibility of 5 batches was easy to carry out.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Une composition de stabilisateur selon l'invention se présente sous forme granulaire, chacun des grains étant constitué de plusieurs particules constituées de cette composition et enrobées d'un liant qui contient le composant dont le point de fusion est le plus bas. Une telle composition est très facilement dispersible dans une matière plastique et permet d'avoir une teneur en sel de plomb organique élevée, même sans addition d'alcool gras.
PCT/EP2000/003253 1999-04-21 2000-04-12 Compositions de stabilisateurs exemptes de poussiere pour matieres synthetiques, et leur procede de production WO2000063284A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999117978 DE19917978A1 (de) 1999-04-21 1999-04-21 Staubfreie Stabilisatorzusammensetzungen für Kunststoffe und Verfahren zu deren Herstellung
DE19917978.6 1999-04-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9303151B2 (en) 2010-03-11 2016-04-05 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilizer mixtures for halogen-containing plastics by underwater pelletization

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004007429B4 (de) * 2004-02-16 2006-12-14 Baerlocher Gmbh Granulare Stabilisatorzusammensetzungen für halogenhaltige Polymere, deren Herstellung und Verwendung sowie Polymerzusammensetzungen
DE102005031909A1 (de) * 2005-07-07 2007-01-11 Baerlocher Gmbh Verfahren zur Herstellung granularer Stabilisatorzusammensetzungen für halogenhaltige Polymere in einer Wirbelschicht

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2031445A1 (en) * 1970-06-25 1972-01-13 Metallgesellschaft Ag Polyvinyl halide stabiliser granulate prodn - by injecting molten waxy component into stabiliser dispersion under pressure
GB1467789A (en) * 1974-02-22 1977-03-23 Hoechst Ag Granulate containing red phosphorus and a binder for the flame proofing of plastics
US4230501A (en) * 1978-07-31 1980-10-28 Cities Service Company Pigments dispersible in plastics
WO1987000543A1 (fr) * 1985-07-23 1987-01-29 V.A.M.P. S.R.L. Procede pour la preparation de lots concentres polymeres, et produits ainsi obtenus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2031445A1 (en) * 1970-06-25 1972-01-13 Metallgesellschaft Ag Polyvinyl halide stabiliser granulate prodn - by injecting molten waxy component into stabiliser dispersion under pressure
GB1467789A (en) * 1974-02-22 1977-03-23 Hoechst Ag Granulate containing red phosphorus and a binder for the flame proofing of plastics
US4230501A (en) * 1978-07-31 1980-10-28 Cities Service Company Pigments dispersible in plastics
WO1987000543A1 (fr) * 1985-07-23 1987-01-29 V.A.M.P. S.R.L. Procede pour la preparation de lots concentres polymeres, et produits ainsi obtenus

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9303151B2 (en) 2010-03-11 2016-04-05 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilizer mixtures for halogen-containing plastics by underwater pelletization

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