WO2010081632A1 - Procédé de fabrication de particules de caoutchouc pourvues d'un enrobage multicouche et particules de caoutchouc pourvues d'un enrobage multicouche - Google Patents

Procédé de fabrication de particules de caoutchouc pourvues d'un enrobage multicouche et particules de caoutchouc pourvues d'un enrobage multicouche Download PDF

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Publication number
WO2010081632A1
WO2010081632A1 PCT/EP2009/067978 EP2009067978W WO2010081632A1 WO 2010081632 A1 WO2010081632 A1 WO 2010081632A1 EP 2009067978 W EP2009067978 W EP 2009067978W WO 2010081632 A1 WO2010081632 A1 WO 2010081632A1
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WO
WIPO (PCT)
Prior art keywords
rubber particles
coating
granules
coated rubber
coated
Prior art date
Application number
PCT/EP2009/067978
Other languages
German (de)
English (en)
Inventor
Andreas Berlineanu
Kirsten Luce
Margit Bukohl
Nicole Dudek
Siegfried Jittenmeier
Marisa Cruz
Rainer Fuchs
Frank Dieter Kuhn
Original Assignee
Evonik Degussa Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Evonik Degussa Gmbh filed Critical Evonik Degussa Gmbh
Publication of WO2010081632A1 publication Critical patent/WO2010081632A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
    • E01C13/08—Surfaces simulating grass ; Grass-grown sports grounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D113/00—Coating compositions based on rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
    • E01C13/06—Pavings made in situ, e.g. for sand grounds, clay courts E01C13/003
    • E01C13/065—Pavings made in situ, e.g. for sand grounds, clay courts E01C13/003 at least one in situ layer consisting of or including bitumen, rubber or plastics
    • 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

Definitions

  • the invention relates to a process for the coating of rubber particles, manufactured from used tires, the coating agent, the coating method and the coated rubber particles and its use as bedding in artificial turf or for other floor coverings, for example in sports facilities.
  • the coating of rubber surfaces is also possible.
  • EP 1 416 009 (Mülsener Recycling and Trading Company mbH) describes a loose, free-flowing rubber granulate which is coated with a polyurethane-based binder.
  • the binder can optionally also be dyed.
  • the diameter of the rubber particles is between 0.5 mm and 2.5 mm, the average layer thickness of the coating is 5 microns to 20 microns, in some places, the layer may be up to 35 microns thick.
  • Mechanical or chemical properties of the coated rubber particles are not disclosed. In the coating is not paid attention to a special type of addition of the paint, such as single and / or multiple coating. It is coated so that an allegedly complete wrapping of the used tire granulate takes place, concrete technical measures are not described.
  • DE 196 31 251 (ContiTech Holding) describes a rubber granulate body coated with a flame retardant binder coating.
  • the binder used is a rubber, as a flame retardant inorganic flame retardants, such as magnesium hydroxide or aluminum hydroxide used.
  • the rubber granulate bodies provided with the flame-retardant coating are processed into flame-retardant rubber workpieces.
  • DE 21 10 327 (Allworld) describes a manufacturing method for elastic sports floors made of used tire granules and binder. Granules and binders are mixed and harden to the ground.
  • a granular, free-flowing product that could be used as bedding for artificial turf is not described in the four last-mentioned patent publications, but is the networking of the resulting coated particles to a massive flooring in the foreground of efforts.
  • Rubber granules and a binder wherein an epoxy resin or a (meth) acrylate resin is used as the binder.
  • WO 2002/18706 (Fieldturf Inc.) describes a portable, modular synthetic turf element of turf surface element and base element and litter into the turf surface element.
  • the litter may consist of unspecified rubber particles, sand or a mixture of sand and rubber particles. A coating of the rubber particles is not mentioned.
  • WO 2002/060290 (Groundsape Technologies LLC) describes a material of vulcanized rubber particles, a first colored coating layer covering the vulcanized rubber particles, and a second coating layer protecting the colored coating layer from abrasion.
  • the second coating layer has as binder a polyacrylate, a polyurethane or a styrene / butadiene rubber.
  • US 2002/0128366 (Coffey) describes a process for the preparation of colored particles of vulcanized rubber, comprising the following steps: An aqueous pigment dispersion is added to the still undyed vulcanized rubber particles and mix the two ingredients until the rubber particles are colored, then add an elastomeric latex, mix again and allow the latex to set.
  • the elastomer used is either a styrene / butadiene rubber or a polybutadiene rubber.
  • the cited prior art has the disadvantage that no manufacturing conditions of coated granules of rubber have been given, in which a particularly effective use of the paint is carried out by a targeted, multi-layer job.
  • the filling materials must have a certain resistance to humidification and the resulting leaching of particular heavy metal-containing aqueous solutions, since the DIN V 18035-7 (pre-standard) provides that to improve the sport and protective functional properties and to reduce the wear a possibility for moistening the artificial turf surface can be provided.
  • the objects are achieved by a multicomponent system for coating rubber granules in a fluidized bed apparatus, a solids mixer or in a drum mixer and a method for producing the coating.
  • This system consists of an epoxy resin based binder component and an anhydride hardener.
  • the crosslinking reaction can be carried out with different catalysts.
  • the curing of the coating takes place in a temperature range of 60 degrees Celsius to 150 degrees Celsius, preferably in a temperature range of 80 degrees Celsius to 120 degrees Celsius.
  • the addition of the paint to the rubber granulate is carried out so that in a mixer granules are coated with a first portion of paint, then carried out a curing step or a waiting period is met, then a further subset of paint is added, carried out a curing step or a waiting period is met , etc. After the last Lackzugabe suits still a curing step is performed or a waiting period observed, then filled the granules.
  • the waiting time between the individual steps is between 5 and 50 minutes, preferably between 5 and 20 minutes and most preferably between 5 and 15 minutes.
  • the curing step at the end of the coating process lasts between 5 and 60 minutes, preferably between 5 and 50 minutes and most preferably between 5 and 40 minutes.
  • the first subset of the paint is about 1/3 of the total amount of paint
  • the second subset of the paint is also about 1/3 of the total amount of paint
  • the third subset of the paint is also about 1/3 of the total amount of paint, with this information are to be understood as a rough guideline.
  • Paint formulation and particles can also be done by infrared emitters. Heating by infrared radiators may e.g. take place in one step after the mixing of paint with the particles to be coated.
  • infrared radiators may e.g. take place in one step after the mixing of paint with the particles to be coated.
  • rubber particles not only rubber particles, but also rubber surfaces or rubber coatings can be coated with the method according to the invention and the mixture according to the invention.
  • the coating of the granules takes place in several layers.
  • a cross-linking step is in each case installed (keeping the temperature as for the paint addition for a certain time, or keeping a temperature higher than the temperature for paint addition for a certain time).
  • the color measurement is based on DIN 5033.
  • the quick test for attrition after irradiation according to the invention comprises the steps of
  • i.) determines the abrasion of a granulate before the irradiation, ii.) irradiating the granules, iii.) determining the abrasion of the irradiated granules.
  • the determination of abrasion resistance includes the following steps:
  • a cutting mill is used in the context of the present invention, which usually consists of a horizontally or vertically arranged rotor, which is equipped with knives, which operate in the context of a first particularly preferred embodiment of the present invention against anchored in the mill housing knife.
  • a schematic sketch of such a mill is shown in Römpp Lexikon Chemie, publisher: J. Falbe, M. Regitz, 10th edition, Georg Thieme Verlag, Stuttgart, New York, 1998, volume: 4, keyword: "Mill", page 2770 For further details reference is therefore made to this document and the cited references.
  • the housing of the mill does not comprise anchored knives, so that the ground granules can be more easily removed from the housing.
  • the working principle of the granulator is preferably cutting / impact.
  • the intensity of the grinding can be controlled via the energy emitted by the mill.
  • the rotational speed of the granulator is preferably in the range of 100 / min to 30,000 / min, in particular in the range of 1,000 / min to 25,000 / min.
  • the peripheral speed of the granulator is preferably in the range of 10 m / s to 100 m / s, in particular in the range of 20 m / s to 80 m / s.
  • the dimensioning of the mill can basically be chosen freely and adapted to the requirements of the case.
  • the grinding chamber of the cutting mill during milling to at least 10%, based on the maximum useful volume of the granulator filled.
  • the cutting mill and the cutting tool are preferably made of a harder material than the granules to be examined.
  • the material to be ground is preferably placed in the chamber of the cutting mill and sheared by a stainless steel racket within a predetermined loading time ("grinding time"), whereby rubbing, crushing and cutting occur
  • Granules or layers on the granules Due to the massive and complex nature of the shears, rapid testing of the abrasion stability of granules, in particular of coated plastic granules, is achieved.
  • the results of the test are mainly influenced by the following variables:
  • ⁇ the degree of adhesion of the coating to the particle. ⁇ Size of the particles. ⁇ Size distribution of the particles.
  • the duration of milling also influences the results.
  • milling times in the range from 5 seconds to 10 minutes, in particular in the range from 5 seconds to 150 seconds, are preferably selected.
  • the action of the grinding power of the granulator can be continuous or discontinuous.
  • An approach has proven particularly useful in which the grinding power is preferably not varied during the grinding.
  • the grinding chamber of the cutting mill can be tempered during the grinding, in particular heated or cooled, to gain knowledge about the abrasion behavior of the granules at other temperatures.
  • Purpose is preferably a suitable, tempered liquid, such.
  • Cutting mills suitable for the purposes of the present invention are commercially available. The following mill has proven particularly successful:
  • the partial size distribution of the ground product is determined by sieve analysis, which is preferably followed by reference to DIN 53 477 (November 1992).
  • sieves Preferably round test sieves (called sieves for short) are used, the screen frame of which preferably consists of metal.
  • the sieves preferably have a nominal diameter of 200 mm.
  • the sieve lid, all sieve frames and the sieve pan preferably fit sealingly on or into one another.
  • the sieves are preferably covered with metal wire mesh according to DIN ISO 3310 Part 1.
  • a sieve set of 6 sieves with metal wire mesh (mesh size: 63 ⁇ m, 125 ⁇ m, 250 ⁇ m, 500 ⁇ m, 1mm, 2mm) is sufficient.
  • it is particularly preferred to use a sieve set comprising a 500 ⁇ m sieve and a bottom.
  • the separation is preferably achieved by a horizontal, circular movement of the sieve set with a rotational frequency of preferably 300 + - 30 min "1 and an amplitude of 15 mm.
  • the intervals are preferably the same length and are expediently 1 minute to 5 minutes, in particular 3 minutes, long.
  • the screening is preferably interrupted and then restarted again. This can possibly be programmed on the screening machine.
  • the determination of the particle size distribution is carried out in a known manner by weighing the sieves.
  • the result of the sieve analysis is compared with at least one reference value in order to classify the abrasion of the investigated granulate.
  • the determined particle size distribution of the ground product is preferably compared with the result of at least one other granulate in order to classify the attrition of the investigated granulate in comparison to the other granules.
  • the determined particle size distribution of the milled product is compared with the particle size distribution of the unmilled starting material in order to classify the attrition of the investigated granulate.
  • the determined particle size distribution of the milled product is compared with at least one predetermined limit value in order to classify the abrasion of the investigated granulate.
  • the proportion of particles smaller than 500 ⁇ m has proven to be a particularly suitable criterion for assessing the attrition of the particles.
  • the walls are tested after grinding for possible deposits, which were caused by the shear stress of the granules in the granulator.
  • optical comparison e.g., with appropriate reference samples, references, reference scales
  • the granules are arranged in a sample container and irradiated with an irradiation lamp, the granules being periodically mixed during the irradiation, so that different surfaces of the granules are irradiated.
  • periodic in this context refers to a regularly recurring activity at regular intervals (here the mixing), in the present case a repetition of at least 2 operations, preferably of at least 5 operations, in particular of at least 10 operations, is preferred.
  • the repetition rate of the activity is preferably at least 1 process per minute, preferably at least 5 processes per minute, in particular at least 10 processes per minute.
  • a continuous mixing takes place during the irradiation.
  • the term "thorough mixing” denotes a thorough mixing of the granules, which preferably leads to a change in the three-dimensional orientation of at least two granules, preferably at least 5 granules, in particular at least 10 granules two granules, preferably of at least 5 granules, in particular of at least 10 granules, relative to each other changed.
  • the granules are mixed in such a way that at least two different, preferably at least three different, surfaces of the granules are irradiated successively, each of these surfaces being irradiated at least twice, preferably at least five times, in particular at least 10 times ,
  • the irradiation method according to the invention differs from the known irradiation methods, in which the granules are dispersed during the irradiation process Irradiation not mixed and irradiated only one surface of the granules continuously.
  • the inventive method leads to a very uniform irradiation of the entire surface of the granules.
  • the irradiation is preferably carried out in such a way that the difference between the shortest irradiation time of a surface of the granules and the longest irradiation time of a surface of the granules is at most 100%, preferably at most 50%, in particular at most 20%, of the longest irradiation time of a surface of the granules.
  • Irradiation simulates the influence of light, especially sunlight, on the granules.
  • the light therefore preferably comprises components of natural sunlight; the irradiation is preferably carried out with a wavelength in the range of 1 nm to 1000 nm, preferably with a wavelength in the range of 200 nm to 400 nm (so-called near UV radiation), in particular with a wavelength in the range of 295 nm to 315 nm (so-called UV-B radiation).
  • a device according to the invention for the irradiation of granules is particularly advantageous.
  • This device includes
  • sample container is connected to a drive, so that the sample container during the irradiation moves and the granules can be mixed.
  • the position of the irradiation lamp relative to the sample container can in principle be chosen freely, wherein the irradiation lamp is preferably arranged inside the sample container. However, it can also be arranged outside the sample container, although this variant is less preferred.
  • the irradiation lamp is preferably sheathed with an inert gas purge, which is preferably arranged between the irradiation lamp and the sample container.
  • Inert gases particularly suitable for the purposes of the present invention include, in particular, nitrogen as well as all noble gases, such as helium and neon.
  • a rinsing of the granules in the sample space with at least one gas and / or at least one liquid is furthermore provided in order to examine the influence of the gas and / or the liquids on the properties of the granules during the irradiation.
  • Particularly suitable for this purpose are air, water vapor, acidic steam, acid rain and water.
  • the irradiation lamp is preferably provided with a filter which at least partially filters out IR radiation (780 nm to 1 mm) from the radiation spectrum of the irradiation lamp.
  • the irradiation lamp is preferably sheathed with a quenching space which comprises an IR quenching liquid and preferably between the
  • Irradiation lamp and the sample container more preferably between the inert gas and the sample container is arranged.
  • IR quench liquids include all liquids which are used in the
  • Examination conditions are liquid and absorb at least partially in the range of 780 nm to 1 mm light.
  • sample container is also not particularly limited. However, sample containers having a region which comprises a straight cylindrical shape have proven particularly useful, the irradiation lamp preferably being arranged centered in the middle of the cylinder.
  • the irradiation lamp has an elongated shape, wherein the orientation of the irradiation lamp is preferably the main axis of the
  • Sample container in particular the main axis of a straight cylindrical portion of the sample container corresponds.
  • the inner walls of the sample container preferably comprise a reflective material to absorb the light, which e.g. B. the granules are not has hit or passed, after reflection on the granules. In this way, the effectiveness of the irradiation can be significantly increased.
  • particularly suitable reflective materials lead to a reflection of at least 5%, preferably at least 25%, particularly preferably at least 50%, of the incident radiation.
  • a particularly suitable material for this purpose is steel.
  • At least 80% of the entire inner surface of the sample container is coated with and / or consists of the reflective material.
  • the sample container further comprises a material having a high thermal conductivity, a thermal conductivity preferably greater than 1 W / (m ⁇ K), in particular greater than 3 W / (m ⁇ K), measured at 25 ° C.
  • At least 80% of the sample container is made of a material having a high thermal conductivity.
  • the device of the present invention preferably comprises at least one tempering element, preferably a heating or cooling element, in particular a cooling element, which allows the irradiation of the plastic particles at fixed temperature conditions or in predetermined temperature ranges.
  • at least one tempering element preferably a heating or cooling element, in particular a cooling element, which allows the irradiation of the plastic particles at fixed temperature conditions or in predetermined temperature ranges.
  • the sample container preferably further comprises at least one mixing element for mixing the granules during the irradiation.
  • at least one mixing element for mixing the granules during the irradiation.
  • flow breakers which at least partially divert the movement of the granules during a rotation of the container along its main axis have proven particularly useful.
  • the head and / or the foot end, particularly preferably the head and foot ends, of the sample container are chamfered in order to agitate the granules even more during the irradiation. It takes the inner diameter of the
  • Sample container in the direction of the tapered end preferably from.
  • sample container is of minor importance.
  • sample container is dimensioned such that it can accommodate between 10 g and 500 kg of granules.
  • particularly suitable sample containers have a capacity in the range of 1 kg to 10 kg.
  • the sample container is preferably filled with granules to 0.1% to 10%, preferably to 0.5% to 5%, based on the total volume of the sample container.
  • the sample container is preferably rotated in order to achieve thorough mixing of the granules.
  • the rotation is preferably carried out about a main axis of the container, wherein the irradiation lamp is preferably also positioned along this major axis.
  • the rotational speed is preferably in the range of 1 rpm to 500 rpm.
  • FIG. 2 The structure of an irradiation apparatus particularly suitable for the purposes of the present invention is shown schematically in FIG. It comprises an irradiation lamp (3) and a sample container (2), the irradiation lamp (3) being elongated and centered along the main axis of the sample container (2).
  • the sample container (2) has a straight cylindrical shape with bevelled head and foot ends (7), wherein the inner diameter of the sample container (2) decreases in the direction of the tapered ends (7).
  • the sample container (2) is preferably made of a thermally conductive steel which reflects at least 5% of the incident radiation.
  • the irradiation lamp is sheathed with an inert gas purge (4) which is arranged between the irradiation lamp (3) and the sample container (2).
  • the irradiation lamp (3) is sheathed with a quenching space (5) which comprises an IR quenching liquid and is arranged between the inert gas purge (4) and the sample container (2).
  • the device comprises a tempering element (1), preferably a cooling water bath, for tempering the sample container (2) during the course of the irradiation.
  • a tempering element (1) preferably a cooling water bath
  • the sample container (2) is preferably rotated continuously about the main axis of the sample container (3) by means of the drive, along which the irradiation lamp (3) is positioned.
  • the temperature during the irradiation can in principle be chosen freely and in particular adapted to the conditions that are to be simulated or readjusted. However, for the purposes of the present invention, the temperature is preferably in the range from 0 0 C to 95 ° C.
  • the intensity of the irradiation of the granules can be controlled.
  • the irradiation preferably takes place for a time in the range from 1 h to 1000 h, in particular in the range from 24 h to 500 h.
  • the irradiation of the granules is preferably carried out with an irradiance in the UV-B range in the range of 1 W / m 2 to 10,000 W / m 2 , in particular in the range of 100 W / m 2 to 1000 W / m 2 .
  • the color properties of the granulate before and after the irradiation are furthermore investigated.
  • the color measurement is preferably carried out in accordance with DIN 5033.
  • the Zinkeluation of the granules is examined before and after the irradiation.
  • the measurement of the Zinkeluation is preferably carried out in accordance with the pre-standard DIN V 18035-7, 6.11.3 (sports fields, Part 7: artificial turf surfaces). In particular, the following procedure has proved particularly useful:
  • the water retention capacity of the granules before the irradiation is examined. Furthermore, the determination of the water retention capacity of the granules after the irradiation is particularly preferred.
  • the binder component may consist of one or more epoxy resins.
  • Solid resins can be usefully dissolved in reactive diluents, such as, for example, aliphatic monoglycidyl ethers, cresyl glycidyl ethers, p-tert-butylphenol glycidyl ethers, butanediol diglycidyl ethers, hexanediol diglycidyl ethers, thymethylolpropane thglycidyl ethers, etc., and low-viscosity, liquid epoxy resins.
  • This binder component may be a mixture of the substances mentioned, but also pigments, fillers, such as, for example, finely ground silicon dioxide (quartz powder, for example Sikron SF 800 from the company
  • Quarzwerke GmbH is preferably the quartz sand silanized such as Silbond FW 600 EST) in order to achieve a better connection to the polymer matrix, such as with Glycidyloxymethylpropylthmethoxythoxysilan, manufactured and sold by Evonik Degussa GmbH under the brand DYNASYLAN ® GLYMO), additives, anti-aging agents, UV Absorber, solvents, leveling agents, catalysts.
  • a cycloaliphatic epoxy resin with the designation Epikote ® Resin 760 from the company. Hexion is used.
  • the anhydride can be modified with maleic anhydride polymers of different chemical base and or or or
  • Methylhexahydrophthal Acidanhydrid (Epikure ® Curing Agent 868, Hexion), Methyltetrahydrophthal Acidanhydrid (Epikure ® Curing Agent 866, Hexion) included.
  • maleic anhydride modified polymers are meant polyalkenylenes, preferably based on 1,3-butadiene, isoprene, 2,3-dimethylbutadiene-1.3 and chloroprene.
  • the polyalkenylenes may be 1, 4 or 1, 2 linked. However, it is also possible for mixtures of 1, 2 and 1, 4 linkages to be present, it being possible for the 1, 4 linkage to occupy both cis and trans arrangements. Very particular preference is given to using a polybutadiene having about 75% of 1,4-cis, about 24% of 1, 4 of trans and about 1% of 1,2-double bonds (polyole Degussa).
  • polyalkenylenes which consist of at least one of the above-mentioned. monomeric dienes and one or more vinyl compounds and / or AI kenen are constructed.
  • Suitable vinyl compounds are, for.
  • styrenes or substituted styrenes vinyl ethers or acrylic or methacrylic acid esters.
  • Suitable alkenes are for. Ethene, propene, butene or isobutene.
  • natural oils such as coconut oil, palm oil, castor oil, olive oil, peanut oil, rapeseed oil, soybean oil, sunflower oil, poppy oil, linseed oil, wood oil, etc. can be modified with maleic anhydride.
  • the maleic anhydride modified polymers may contain 1 to 20 weight percent maleic anhydride.
  • the preferred one is
  • Maleic anhydride content is between 7 and 14 weight percent.
  • POLYVEST ® EP OC For example, as with maleic anhydride modified polymer of the product POLYVEST ® OC 800 S used.
  • POLYVEST ® OC 800 S represents a maleic anhydride - modified Polyöl 110 from Evonik Degussa GmbH and is available under this name from Evonik Degussa GmbH.
  • POLYVEST OC ® 800 S, POLYVEST ® EP 1000 S OC and OC POLYVEST ® EP 1200 S contain randomly distributed succinic anhydride. The originally apolar polybutadiene becomes more polar and accessible to various chemical reactions. POLYVEST OC ® 800 S, POLYVEST ® EP 1000 S OC and OC POLYVEST ® EP 1200 S have good electrical insulating properties and low temperature properties. POLYVEST OC ® 800 S, POLYVEST ® EP 1000 S OC and OC POLYVEST ® EP 1200 S are soluble in aliphatics, aromatics, ethers, and compatible with long-oil alkyds, rosin, rosin esters and zinc resinates. It can be used as a crosslinking component in 2K systems, as a polymeric chalk activator for rubber, in particular for EPDM mixtures and for water-soluble, oxidatively drying binders.
  • Hardening and / or binder component can be formulated either solvent-free or solvent-containing as clear coat or filled system.
  • the hardener component can optionally also organic and / or inorganic pigments, wetting agents, dispersants, lubricants, organic and / or inorganic fillers, antioxidants, UV absorbers, UV stabilizers, IR absorbers, flow aids, release agents or leveling agents are added ,
  • Solvents which can be used in the paint industry are customary solvents, for example esters of organic carboxylic acids and aliphatic alcohols, for example ethyl acetate, propyl acetate, butyl acetate or methoxypropyl acetate.
  • catalysts can be added as a third component of the mixture of binder and hardener component prior to application. Some catalysts can be added already in the production of the respective hardener or binder component.
  • An admixture to the binder or hardener component is also possible.
  • Tertiary amines such as, for example, thethylamine, cyclohexyldimethylamine, benzyldimethylamine, N-methylimidazole, organic titanates, zirconates, zinc and bismuth carboxylates can be used as catalysts.
  • the particles to be coated rubber particles are used, which are preferably obtained by reprocessing used tires.
  • the size of the rubber particles is between 0.1 mm and 10 mm, preferably between 0.5 mm and 7.5 mm and particularly preferably between 0.4 mm and 4 mm.
  • the thickness of the coating is between 1 ⁇ m and 100 ⁇ m, preferably between 2 ⁇ m and 50 ⁇ m, and very particularly preferably between 5 ⁇ m and 25 ⁇ m.
  • the components can be premixed or via a
  • Multi-component mixing plant such as a 2K mixing and spraying system can be applied.
  • the coating material necessary for the coating consisting of A, B and catalyst component, is applied in several steps. After the task of each individual layer, a crosslinking step (time, heating) is interposed. At the end of the addition of the last lacquer layer, a crosslinking step (time, heating) is carried out.
  • Cycloaliphatic epoxy resin wherein between 10% and 80% by weight of cycloaliphatic epoxy resin, preferably between 15% by weight and 70% by weight of cycloaliphatic epoxy resin and most preferably between 20 and 50% by weight of cycloaliphatic epoxy resin are used,
  • Silicone oil in amounts between 0.1% and 5.9% by weight,
  • a wetting and dispersing agent in amounts between 0.1% and 2.9% by weight is provided.
  • an antioxidant barium sulfate wherein between 1% and 60% by weight barium sulphate, preferably between 20% and 50% barium sulphate by weight and most preferably between 30% and 45% barium sulphate by weight, •
  • barium sulphate quartz powder and silane-modified quartz powder can be used in the quantities indicated above.
  • pigments optionally a solvent, about 0% by weight to 20% by weight (the other components supplement to 100% by weight),
  • Aliphatic anhydride wherein between 1% by weight and 50% by weight of aliphatic anhydride, preferably between 5% by weight and 40% by weight of aliphatic anhydride and most preferably between 5% by weight and 30% by weight of aliphatic anhydride are used, and
  • MSA-modified polybutadiene wherein between 99% and 50% by weight MSA-modified polybutadiene, preferably between 90% and 65% MSA-modified polybutadiene and most preferably between 70 and 85% MSA by weight modified polybutadiene can be used
  • the coating is mixed in a drum mixer with the rubber granules.
  • the amount of catalyst is between 0.5 wt .-% and 5 wt .-%, based on the sum of B and A. It is also possible to adjust other mixing ratios and to dispense with the premixing of the coating components and at the same time to the Admit submitted rubber granules.
  • the preferred mixing ratios are given in the table.
  • the coating of the granules takes place in several layers.
  • a cross-linking step is in each case installed (keeping the temperature as for the paint addition for a certain time, or keeping a temperature higher than the temperature for paint addition for a certain time).
  • the A mixture is prepared and stored under nitrogen. It will be
  • Epikure Curing Agent 868 Adliphatic Anhydride, Hexion
  • the formulations of the invention have excellent properties, such as low abrasion values before and after exposure and weathering, good elasticity before and after exposure and weathering, and are stable to weathering.
  • the formulations of the invention have an excellent color stability Exposure and weathering as well as excellent stability during thermal cycling on and under exposure to high temperatures, for example at 50 degrees Celsius over 4 weeks.
  • granules which have been coated with the formulations according to the invention dry slightly after being sprinkled.
  • the free-flowing particles according to the invention for example on site, can be provided with an adhesive or polymerizing or crosslinking layer, which allows the particles to be poured into an arbitrarily shaped matrix and cured.
  • an adhesive or polymerizing or crosslinking layer which allows the particles to be poured into an arbitrarily shaped matrix and cured.
  • the polymer matrix polyurethane resins or epoxy resins can be used. By different colors of matrix and rubber granulate any color effects can be realized.
  • rubber particles be coated with the blend of the invention and the method of the present invention, but also three-dimensional molded rubber articles or rubber surface articles such as toys, rubber mats or tire outer flanks.
  • finely ground fillers may be added, such as barium sulfate, calcium carbonate, quartz powder, or aluminum trihydroxide. coating tests
  • the coating experiments were carried out in a mixer (manufacturer Lödige, type M5R9) at a speed of 150 revolutions per minute. Introduced into the mixing chamber 1 5 kg rubber granules of the type "fine" (available from Fa. Named groups GmbH) and heated in the mixing chamber with a heating jacket by means of thermal oil at 90 0 C. After the rubber granulate has reached the intended temperature, the mixer (manufacturer Lödige, type M5R9) at a speed of 150 revolutions per minute. Introduced into the mixing chamber 1 5 kg rubber granules of the type "fine" (available from Fa. Named groups GmbH) and heated in the mixing chamber with a heating jacket by means of thermal oil at 90 0 C. After the rubber granulate has reached the intended temperature, the
  • Coating composition (by mixing component A, component B and catalyst) in one portion. Then the coating is cured for about 30 minutes at this temperature.
  • the coating experiments were carried out in a mixer (manufacturer Lödige, type M5R9) at a speed of 150 revolutions per minute. Introduced into the mixing chamber 1 5 kg rubber granules of the type "fine" (available from Fa. Named groups GmbH) and heated in the mixing chamber with a heating jacket by means of thermal oil at 90 0 C. After the rubber granulate has reached the intended temperature, the coating composition is (By mixing component A, component B and catalyst) in three portions, mixing between each addition for 10 minutes at 120 ° C. After addition of the third portion, the coating is cured for about 15 minutes at this temperature.
  • Example 3 Example 3:
  • the coating experiments were carried out in a Drais TD250 mixer at a speed of 23 revolutions / minute.
  • 90 kg of rubber granules of the "fine" type (available from Genanograph GmbH) are introduced into the mixing chamber and heated in the mixing chamber by means of heat transfer oil to 90 ° C.
  • the coating composition (by mixing of component A, component B and catalyst) in three portions, mixing between each addition for 20 minutes at 90 ° C.
  • the coating is cured at 105 ° C. for about 10 minutes.
  • the coating trials were carried out in a Drais TD250 vacuum paddle dryer with a nominal capacity of 250 liters at a speed of 23 revolutions / minute.
  • the mixing chamber 90 kg rubber granules of the type "fine" (available from Fa. Genan
  • the paint formulation used in the experiments according to Example 1-4 is prepared as follows:
  • the A mixture was prepared and stored under nitrogen. In this case, 15 parts by weight of Epikure Curing Agent 868 (Aliphatic Anhydride, Fa.
  • the B-blend was prepared as follows:
  • Epikote Resin 760 (cycloaliphatic epoxy, Hexion)
  • Blanc fixe micro iller barium sulphate, Sachtleben
  • the grind value is determined according to DIN EN ISO 1524.
  • the A mixture is prepared and stored under nitrogen. It will be
  • Epikure Curing Agent 868 Adliphatic Anhydride, Fa.
  • Component A Composition according to A3
  • Component B Composition B7 Catalyst: 1, 2 g Epikote Amount ratio
  • A: B 1: 1
  • Cycloaliphatic epoxy resin wherein between 10% and 80% by weight of cycloaliphatic Epoxy resin, preferably between 40% by weight and 80% by weight of cycloaliphatic epoxy resin and very particularly preferably 45% by weight of cycloaliphatic epoxy resin are used,
  • Silicone oil in amounts between 0.1% and 5.9% by weight, a wetting and dispersing agent in amounts between 0.1% and 2.9% by weight,
  • Barium sulfate wherein between 1% and 50% by weight of barium sulfate, preferably between 20% and 45% by weight barium sulfate, and most preferably between 30% and 40% barium sulfate by weight, are used,
  • Anhydride preferably between 5% and 40% aliphatic anhydride by weight, and most preferably between 7% and 30% aliphatic anhydride, and an MSA modified polybutadiene, wherein between 99% and 50% by weight % MSA-modified polybutadiene, preferably between 90% and 65% by weight of MSA-modified polybutadiene and most preferably 70% by weight of MSA-modified polybutadiene are mixed in a ratio of 10 parts by weight of mixture B to 1 part by weight of mixture A to 1 part by weight of mixture B to 10 parts by weight of mixture A mixed with catalyst and mixed at 80 degrees Celsius to 120 degrees Celsius in a drum mixer with the rubber granules. It is also possible to adjust other mixing ratios and to dispense with the premixing of the coating components and at the same time add them to the submitted rubber granules.
  • the preferred mixing ratios are given in the table.
  • the B mixture can be prepared as follows:
  • Tego Dispers 650 wetting and dispersing agent, Evonik
  • Wingstay L antioxidant, Eliokem
  • the A mixture is prepared and stored under nitrogen. It will be
  • Epikure Curing Agent 868 Adliphatic Anhydride, Fa.
  • the coating can also be applied by all methods customary in coating technology, for example spraying, dipping, brush application, knife coating, rolling or the like.
  • the viscosity of the coating can be through
  • the coating system according to the invention bonds excellently with the rubber particles to be coated, and also the individual, completely or partially cured coating layers bond well with one another.
  • FIG. 1 shows a preferred embodiment of a device for irradiating granules.

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  • Wood Science & Technology (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

L'invention concerne un nouveau procédé de fabrication de particules enrobées constituées de granulés de caoutchouc, ainsi que l'enrobage, les particules enrobées avec cet enrobage et les utilisations de ces particules enrobées. L'enrobage est sans solvant.
PCT/EP2009/067978 2009-01-13 2009-12-29 Procédé de fabrication de particules de caoutchouc pourvues d'un enrobage multicouche et particules de caoutchouc pourvues d'un enrobage multicouche WO2010081632A1 (fr)

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DE102009000178A DE102009000178A1 (de) 2009-01-13 2009-01-13 Verfahren zur Herstellung von mehrschichtig beschichteten Gummipartikeln und mehrschichtig beschichtete Gummipartikel
DE102009000178.6 2009-01-13

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US20110305850A1 (en) * 2009-01-13 2011-12-15 Evonik Degussa Gmbh Method for the production of coated rubber particles, coated rubber particles, and solvent-free coating formulation
EP3216821A1 (fr) * 2016-03-11 2017-09-13 Polytex Sportbeläge Produktions-GmbH Remplissage de gazon artificiel
CN108221552A (zh) * 2018-02-02 2018-06-29 广州傲胜人造草股份有限公司 一种人造草坪复合填充颗粒及其制备方法
US10519301B2 (en) 2016-12-29 2019-12-31 Appia, Llc Method of recycling rubber
EP3604676A1 (fr) 2018-07-30 2020-02-05 Polytex Sportbeläge Produktions-GmbH Matériau de remplissage de gazon artificiel avec des granulés de coques dures de noix enrobés de pu
EP3604677A1 (fr) 2018-07-30 2020-02-05 Polytex Sportbeläge Produktions-GmbH Matériau de remplissage de gazon artificiel avec des granulés d'épi de maïs revêtus de polyuréthane
US11434353B2 (en) 2019-02-12 2022-09-06 Appia, Llc Method and product of modifying vulcanized rubber

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EP2530106A3 (fr) * 2011-05-31 2014-03-19 ART Asamer Rubber Technology GmbH Procédé de fabrication d'un composé élastomère-polymère
AT511516B1 (de) * 2011-05-31 2015-07-15 Art Asamer Rubber Technology Gmbh Verfahren zur herstellung eines elastomer-polymer-compounds
AT511515B1 (de) * 2011-05-31 2015-05-15 Art Asamer Rubber Technology Gmbh Verfahren zur herstellung eines elastomer-polymer-compounds
CN113957768B (zh) * 2021-11-01 2023-07-18 广东丰能环保科技股份有限公司 一种预制型运动面层及其成型工艺

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Publication number Priority date Publication date Assignee Title
US20110305850A1 (en) * 2009-01-13 2011-12-15 Evonik Degussa Gmbh Method for the production of coated rubber particles, coated rubber particles, and solvent-free coating formulation
EP3216821A1 (fr) * 2016-03-11 2017-09-13 Polytex Sportbeläge Produktions-GmbH Remplissage de gazon artificiel
WO2017153261A1 (fr) 2016-03-11 2017-09-14 Polytex Sportbeläge Produktions-Gmbh Remplissage de gazon artificiel et son procédé de fabrication
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US10519301B2 (en) 2016-12-29 2019-12-31 Appia, Llc Method of recycling rubber
CN108221552A (zh) * 2018-02-02 2018-06-29 广州傲胜人造草股份有限公司 一种人造草坪复合填充颗粒及其制备方法
CN108221552B (zh) * 2018-02-02 2024-03-22 广州傲胜人造草股份有限公司 一种人造草坪复合填充颗粒及其制备方法
EP3604676A1 (fr) 2018-07-30 2020-02-05 Polytex Sportbeläge Produktions-GmbH Matériau de remplissage de gazon artificiel avec des granulés de coques dures de noix enrobés de pu
EP3604677A1 (fr) 2018-07-30 2020-02-05 Polytex Sportbeläge Produktions-GmbH Matériau de remplissage de gazon artificiel avec des granulés d'épi de maïs revêtus de polyuréthane
US11434353B2 (en) 2019-02-12 2022-09-06 Appia, Llc Method and product of modifying vulcanized rubber

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