US20070191545A1 - Microgel-containing composition - Google Patents

Microgel-containing composition Download PDF

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US20070191545A1
US20070191545A1 US10/947,874 US94787404A US2007191545A1 US 20070191545 A1 US20070191545 A1 US 20070191545A1 US 94787404 A US94787404 A US 94787404A US 2007191545 A1 US2007191545 A1 US 2007191545A1
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microgel
composition according
microgels
thermoplastic
tpe
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Ludger Heiliger
Thomas Fruh
Volker Muller
Heiko Tebbe
Werner Obrecht
Robert Schuster
Martin Muller
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DEUTSCHES INSTITUT fur KAUTSCHUKTECHNOLOGIE EV
Rhein Chemie Rheinau GmbH
Lanxess Deutschland GmbH
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DEUTSCHES INSTITUT fur KAUTSCHUKTECHNOLOGIE EV
Rhein Chemie Rheinau GmbH
Lanxess Deutschland GmbH
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Assigned to RHEIN CHEMIE RHEINAU GMBH, LANXESS DEUTSCHLAND GMBH, DEUTSCHES INSTITUT FUR KAUTSCHUKTECHNOLOGIE E.V. reassignment RHEIN CHEMIE RHEINAU GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MULLER, DR. MARTIN, OBRECHT, PROF WERNER, HEILIGER, DR. LUDGER, TEBBE, DR. HEIKO, MULLER, VOLKER, FRUH, DR. THOMAS
Publication of US20070191545A1 publication Critical patent/US20070191545A1/en
Priority to US12/004,941 priority Critical patent/US20080108755A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene

Definitions

  • the present invention relates to a composition containing thermoplastic materials and crosslinked microgels that have not been crosslinked by high-energy radiation, to a process for its preparation, to its use in the production of thermoplastically processable molded articles, and to molded articles produced from the composition.
  • EP-A-405216, DE-A-4220563 and GB-PS-1078400 disclose the use of CR, BR and NBR microgels in mixtures with double-bond-containing rubbers.
  • DE 19701489 describes the use of subsequently modified microgels in mixtures with double-bond-containing rubbers such as NR, SBR and BR.
  • DE 3920332 discloses rubber-reinforced resin compositions which comprise (i) a matrix resin having a glass transition temperature of at least 0° C. and (ii) from 1 to 60 wt. % of rubber particles dispersed in the matrix resin.
  • the dispersed particles are characterized in that they consist of hydrogenated block copolymers of a conjugated diene and a vinyl aromatic compound.
  • the particles inevitably have two glass transition microphase structure of separate microphase with segments and temperatures, one being at ⁇ 30° C. or less.
  • the particles exhibit a soft segments, in which the hard segments and the soft segments are alternately laminated with one another in the form of concentric multiple layers.
  • Polymeric materials can be divided into several groups according to their structure, their deformation-mechanical behavior and hence according to their properties and fields of use.
  • amorphous or semi-crystalline thermoplastics which consist of long, uncrosslinked polymer chains. Thermoplastics are brittle to viscoelastic at room temperature. These materials are plasticized by pressure and temperature and can then be molded.
  • elastomers or rubber materials there are the elastomers or rubber materials. Elastomers are a crosslinked rubber product. It may be natural or synthetic rubber. Rubbers can only be processed in the uncrosslinked state. They then exhibit viscoplastic behavior.
  • thermoplastic elastomers exhibit completely different behavior. These materials become plastic when heated and elastic again when cooled.
  • crosslinking in the case of elastomers is physical
  • the TPEs stand between the thermoplastics and the elastomers in terms of their structure and their behavior, and they combine the ready processability of the thermoplastics with the fundamental properties of rubber. Above Tg to the melting point or to the softening temperature, the TPEs behave like elastomers, but they are thermoplastically processable at higher temperatures.
  • a thermoreversible structure with elastic properties is formed on cooling.
  • TPE materials In contrast to the processing of rubber, the processing of TPE materials is based not on a cold/warm process but on a warm/cold process. If in the case of soft, highly elastic TPE materials in particular the pronounced intrinsically viscous melting or softening behavior is taken into account, then it is possible when processing TPEs to use the typical thermoplastic processes such as injection molding, extrusion, blow molding and deep drawing.
  • the product properties depend primarily on the structure and phase morphology; in elastomer alloys a large part is played, for example, by the particle size, the particle size distribution or the particle stretching of the disperse phase.
  • TPE materials over the conventional, chemically crosslinked elastomers can be seen in their fundamental suitability for recycling. As with all plastics, a fall in viscosity that increases with the number of processing steps is to be observed in the case of the TPE materials, but this does not lead to a significant impairment of the product properties.
  • TPEs Since the discovery of the TPEs, this class of materials has been distinguished by the fact that it is formed by a combination of a hard phase and a soft phase.
  • the TPEs known hitherto are divided into two main groups:
  • composition of the comonomers determines the ratio of hard phase to soft phase, determines which phase constitutes the matrix and determines the final properties.
  • a true morphology is recognizable at molecular level when, for example, the deficient component aggregates or crystallizes.
  • the temperature dependence of this physical morphology fixing is a problem with these materials, that is to say there is a limit temperature at which the morphology fixing is undone. This can cause problems during processing owing to changes in the properties associated therewith.
  • the block polymers include, for example, styrene block copolymers (TPE-S), such as butadiene (SBS), isoprene (SIS) and ethylene/butylene (SEBS) types, polyether-polyamide block copolymers (TPE-A), thermoplastic copolyesters, polyether esters (TPE-E) and thermoplastic polyurethanes (TPE-U), which are described in greater detail herein below in connection with the starting materials that can be used according to the present invention.
  • SBS styrene block copolymers
  • SIS isoprene
  • SEBS ethylene/butylene
  • TPE-A polyether-polyamide block copolymers
  • TPE-E polyether esters
  • TPE-U thermoplastic polyurethanes
  • the second main group of the material TPE are the elastomer alloys.
  • Elastomer alloys are polymer blends which contain both thermoplastic and elastomeric constituents. They are prepared by “blending” the raw materials, that is to say mixing them intensively in a mixing device (internal mixer, extruder or the like). Very different mixing ratios between the hard phase and the soft phase can occur.
  • the soft phase can be either uncrosslinked (TPE-0) or crosslinked (TPE-V).
  • TPE-0 uncrosslinked
  • TPE-V crosslinked
  • In the ideal TPE blend there are small elastomer particles which are uniformly distributed in finely dispersed form in the thermoplastic matrix. The finer the distribution and the higher the degree of crosslinking of the elastomer particles, the more pronounced the elastic properties of the resulting TPE.
  • TPE blends are prepared, for example, by so-called “dynamic vulcanization” or reactive extrusion, in which the rubber particles are crosslinked in situ during the mixing and dispersing process.
  • the property profile of these blends is accordingly substantially dependent on the proportion, degree of crosslinking and dispersion of the rubber particles.
  • Very different combinations can be produced by this blend technology.
  • the physico-mechanical properties and the chemical resistance and compatibility with contact media are substantially determined by the individual properties of the blend components.
  • By optimizing the “blend quality” and the degree of crosslinking it is possible to improve specific physical properties. Nevertheless, it is a characteristic of this class that the dispersed phase is present in irregular and coarsely dispersed form. The less compatible the polymers, the more coarse the resulting structure.
  • the non-compatible combinations such as, for example, a dispersed phase of NBR rubber in a PP matrix
  • a homogenizing agent can be added prior to the dynamic vulcanization. About 1% of the homogenizing agent is sufficient for many applications.
  • the homogenizing agents are generally based on block copolymers whose blocks are compatible with in each case one of the blend phases. Depending on the relative proportions, the two phases may constitute both the continuous and the discontinuous phase. Hitherto it has not been possible to adjust the morphology of this material in a reliable manner.
  • thermoplastic vulcanization products exhibit a maximum distribution of the diameter of the dispersed phase of from 2 ⁇ m to 4 ⁇ m with individual volume elements up to 30 ⁇ m.
  • elastomer alloys the most commonly used combinations are based on EPDM with PP.
  • EVA/PVDC blends Alcryn” blend of ethylene-vinyl acetate rubber (EVA) and polyvinylidene chloride (PVDC) as the thermoplastic phase
  • EVA/PVDC blends Alcryn” blend of ethylene-vinyl acetate rubber (EVA) and polyvinylidene chloride
  • a targeted adjustment of the morphology of the dispersed phase and hence a targeted adjustment of the desired properties of the TPEs in these polymer blend TPEs is virtually impossible, however, owing to the in situ formation of the dispersed phase and the many parameters involved therein.
  • the present inventors relates to novel compositions having thermoplastic elastomer properties which can easily be prepared from starting materials known per se and whose properties can be adjusted in a simple and foreseeable manner.
  • the novel compositions can be prepared on an industrial scale, and they should not give rise to problems relating to working safety. Furthermore, there should be no tearing effects in the compositions between the matrix and the dispersed phase on sudden stress so that the mechanical properties, the swelling behavior and the stress corrosion cracking, etc. are impaired.
  • the preparation of the microgels for the composition should be simple and allow the particle size distributions of the microgel particles to be adjusted in a targeted manner to very small average particle sizes.
  • thermoplastic elastomer compositions are obtained by the incorporation of microgels into the thermoplastic materials, it is possible to separate the adjustment of the morphology of the dispersed phase from the production of the TPE material in terms of both space and time.
  • the morphology production can be reliably reproduced because the dispersed phase is a microgel whose morphology can be controlled in a manner known per se during preparation and which substantially does not change further on incorporation into the thermoplastic material.
  • the polymer microstructure of both the dispersed phase and the continuous phase can be varied within wide limits, so that customized TPEs can be produced from any desired thermoplastic materials, which was not possible according to the known processes for the production of conventional TPEs.
  • the desired properties of the resulting TPEs can be controlled further.
  • the glass transition temperature of the dispersed microgel phase can also be adjusted in a targeted manner within the range of from ⁇ 100° C. to less than 50° C., as a result of which the properties of the resulting TPEs can in turn be adjusted in a targeted manner.
  • the difference in glass transition temperature between the dispersed phase and the continuous phase can also be adjusted in a targeted manner and can be, for example, from 0° C. to 250° C.
  • the novel class of TPEs provided by the present invention it is additionally possible to combine thermodynamically compatible and thermodynamically incompatible polymers to form new TPEs which were not obtainable by conventional processes.
  • the dispersed phase and the continuous phase may each constitute the hard phase and the soft phase.
  • the dispersed phase can be present in the matrix in the form of aggregated clusters or in uniformly distributed form and in all intermediate forms.
  • thermoplastic plastics permits the production of thermopastic elastomers
  • incorporation of microgels into, for example, thermoplastic elastomers produced by conventional processes allows a targeted improvement in their properties, such as, for example, dimensional stability and transparency.
  • compositions according to the present invention can be prepared on an industrial scale by a simple process, without using microgels crosslinked by high-energy radiation.
  • the microgels used according to the present invention permit a less immediate change in modulus between the matrix phase and the dispersed phase, which leads to an improvement in the mechanical properties of the composition.
  • thermoplastic elastomers as component (A).
  • the present invention provides a composition which contains at least one thermoplastic material (A) and at least one microgel (B) based on homopolymers or random copolymers that has not been crosslinked by high-energy radiation.
  • FIG. 1 illustrates an image of the composition according to Example 4.
  • FIG. 2 illustrates an image of the composition according to Example 1.
  • FIG. 3 illustrates an AFM image of a dynamically vulcanized TPV from Example 5.
  • FIG. 4 illustrates hot air storage of the test specimens at different temperature.
  • the microgel (B) used in the composition according to the present invention is a crosslinked microgel based on homopolymers or random copolymers. Accordingly, the microgels used according to the present invention are crosslinked homopolymers or crosslinked random copolymers.
  • the terms homopolymers and random copolymers are known to the person skilled in the art and are explained, for example, in Vollmert, Polymer Chemistry, Springer 1973.
  • the crosslinked microgel (B) used in the composition according to the present invention is a microgel that has not been crosslinked by high-energy radiation.
  • High-energy radiation here preferably means electromagnetic radiation having a wavelength of less than 0.1 ⁇ m.
  • microgels completely homogeneously crosslinked by high-energy radiation are disadvantageous because it is virtually impossible to implement on an industrial scale and causes problems associated with working safety. Furthermore, in compositions prepared using microgels completely homogeneously crosslinked by high-energy radiation, tearing effects between the matrix and the dispersed phase occur on sudden stress, with the result that the mechanical properties, the swelling behavior and the stress corrosion cracking, etc. are impaired.
  • the primary particles of the microgel (B) present in the composition according to the present invention preferably exhibit approximately spherical geometry.
  • primary particles are the microgel particles dispersed in the coherent phase which can be individually recognized by means of suitable physical processes (electron microscope) (see e.g. Römpp Lexikon, Lacke und Druckmaschine, Georg Thieme Verlag, 1998).
  • An “approximately spherical” geometry means that the dispersed primary particles of the microgels recognizably form substantially a circular surface when a thin section is viewed using an electron microscope (see e.g. FIG. 1 ).
  • the compositions according to the present invention differ substantially from the dispersed phases produced by the in situ processes, which are generally larger and have an irregular shape (see e.g. FIG. 3 ).
  • the substantially uniform spherical shape, resulting from the separate preparation process for the microgels, of the microgel particles dispersed according to the invention is retained substantially unchanged on dispersion in the thermoplastic material
  • TPEs conventionally produced TPEs
  • the dispersed phase does not have uniform morphology, and for that reason individual primary particles cannot be located therein.
  • compositions according to the present invention there may be used, for example, all known TPEs, especially TPE-Us or TPE-As, as the continuous phase.
  • the microgels (B) into the known TPEs, preferably TPE-Us or TPE-As, the dimensional stability under heat of the TPEs, preferably TPE-Us or TPE-As, can surprisingly be improved.
  • the transparency of the microgel-containing compositions according to the invention based on TPE-U or TPE-A is also improved.
  • the known TPE-Us are not transparent, while the microgel-containing compositions according to the present invention based on TPE-U are transparent.
  • the variation in the diameters of an individual primary particle is preferably less than 250%, more preferably less than 200%, most preferably less than 100%.
  • At least 80%, more preferably at least 90%, yet more preferably at least 95%, of the primary particles of the microgel exhibit a variation in the diameters, defined as [(d1 ⁇ d2)/d1] ⁇ 100, wherein d1 and d2 are any two diameters of any desired section of the primary particle and d1>d2, of less than 250%, preferably less than 200%, more preferably less than 100%.
  • the above-mentioned variation in the diameters of the individual particles is determined by the following process.
  • a TEM image of a thin section of the composition according to the present invention is first prepared as described in the Examples. An image is then recorded by transmission electron microscopy at a magnification of, for example, from 10,000 times to 85,000 times. In an area of 833.7 ⁇ 828.8 nm, the largest and smallest diameters d1 and d2 are determined on 10 microgel primary particles. If the variation is less than 250%, more preferably less than 200%, yet more preferably less than 100%, in all 10 microgel primary particles, then the microgel primary particles exhibit the above-defined feature of variation.
  • the concentration of the microgels in the composition is so high that pronounced overlapping of the visible microgel primary particles occurs, the evaluatability can be improved by previously diluting the measuring sample in a suitable manner.
  • the primary particles of the microgel (B) preferably have an average particle diameter of from 5 to 500 nm, more preferably from 20 to 400 nm, most preferably from 50 to 300 nm (diameter data according to DIN 53206).
  • the average particle diameter of the dispersed primary particles corresponds substantially to the average particle diameter of the microgel used.
  • the microgels (B) that are used advantageously contain at least about 70 wt. %, more preferably at least about 80 wt. %, most preferably at least about 90 wt. %, portions that are insoluble in toluene at 23° C. (gel content).
  • the portion that is insoluble in toluene is determined in toluene at 23° C.
  • 250 mg of the microgel are swelled in 25 ml of toluene at 23° C. for 24 hours, with shaking. After centrifugation at 20,000 rpm, the insoluble portion is separated off and dried. The gel content is obtained from the difference between the weighed portion and the dried residue and is given in percent.
  • the microgels (B) that are used advantageously exhibit a swelling index in toluene at 23° C. of less than about 80, more preferably of less than 60, yet more preferably of less than 40.
  • the swelling indices of the microgels (Qi) can preferably be between 1-15 and 1-10.
  • 250 mg of the microgel are allowed to swell in 25 ml of toluene for 24 hours, with shaking.
  • the gel is removed by centrifugation and weighed and then dried at 70° C. until a constant weight is reached and then weighed again.
  • the microgels (B) that are used preferably have glass transition temperatures Tg of from ⁇ 100° C. to +50° C., more preferably from ⁇ 80° C. to +20° C.
  • the microgels (B) that are used advantageously have a breadth of glass transition of greater than 5° C., preferably greater than 10° C., more preferably greater than 20° C.
  • Microgels that have such a breadth of glass transition are generally not completely homogeneously crosslinked—in contrast to completely homogeneously radiation-crosslinked microgels. This has the result that the change in modulus from the matrix phase to the dispersed phase does not lead to tearing effects between the matrix and the dispersed phase, with the result that the mechanical properties, the swelling behavior and the stress corrosion cracking, etc. are advantageously affected.
  • the glass transition temperature (Tg) and the breadth of the glass transition ( ⁇ Tg) of the microgels are determined by differential scanning calorimetry (DSC). For determining Tg and ⁇ Tg, two cooling/heating cycles are carried out. Tg and ⁇ Tg are determined in the second heating cycle. For the determinations, 10 to 12 mg of the chosen microgel are placed in a DSC sample container (standard aluminum ladle) from Perkin-Elmer. The first DSC cycle is carried out by first cooling the sample to ⁇ 100° C. with liquid nitrogen and then heating it to +150° C. at a rate of 20 K/min. The second DSC cycle is begun by immediately cooling the sample as soon as a sample temperature of +150° C. has been reached.
  • DSC differential scanning calorimetry
  • Cooling is carried out at a rate of about 320 K/min.
  • the sample is again heated to +150° C., as in the first cycle.
  • the rate of heating in the second cycle is again 20 K/min.
  • Tg and ⁇ Tg are determined graphically on the DSC curve of the second heating operation. To that end, three straight lines are plotted on the DSC curve. The first straight line is plotted on the part of the DSC curve below Tg, the second straight line is plotted on the branch of the curve passing through Tg with the point of inflection, and the third straight line is plotted on the branch of the DSC curve above Tg. Three straight lines with two points of intersection are thus obtained. The two points of intersection are each characterized by a characteristic temperature.
  • the glass transition temperature Tg is obtained as the mean of these two temperatures, and the breadth of the glass transition ⁇ Tg is obtained from the difference between the two temperatures.
  • microgels (B) based on homopolymers or random copolymers present in the composition according to the present invention, which microgels have not been crosslinked by high-energy radiation, can be prepared in a manner known per se (see, for example, EP-A-405 216, EP-A-854171, DE-A 4220563, GB-PS 1078400, DE 197 01 489.5, DE 197 01 488.7, DE 198 34 804.5, DE 198 34 803.7, DE 198 34 802.9, DE 199 29 347.3, DE 199 39 865.8, DE 199 42 620.1, DE 199 42 614.7, DE 100 21 070.8, DE 100 38 488.9, DE 100 39 749.2, DE 100 52 287.4, DE 100 56 311.2 and DE 100 61 174.5).
  • microgels (B) used in the composition according to the present invention are preferably those which are obtainable by emulsion polymerization and crosslinking.
  • the following free-radically polymerizable monomers are used in the preparation of the microgels used according to the invention by emulsion polymerization: butadiene, styrene, acrylonitrile, isoprene, esters of acrylic and methacrylic acid, tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, 2-chlorobutadiene, 2,3-dichlorobutadiene, and also double-bond-containing carboxylic acids, such as, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc., double-bond-containing hydroxy compounds, such as, for example, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxybutyl methacrylate, amine-functionalized (meth)acrylates, acrolein, N-vinyl-2-pyrrolidone, N-allyl-urea and N-allyl-thiour
  • Crosslinking of the rubber gel can be achieved directly during the emulsion polymerization, such as by copolymerization with multifunctional compounds having crosslinking action, or by subsequent crosslinking as described herein below.
  • Preferred multifunctional comonomers are compounds having at least two, preferably from 2 to 4, copolymerizable C ⁇ C double bonds, such as diisopropenylbenzene, divinylbenzene, divinyl ethers, divinylsulfone, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, 1,2-polybutadiene, N,N′-m-phenylenemaleimide, 2,4-toluylenebis(maleimide) and/or triallyl trimellitate.
  • acrylates and methacrylates of polyhydric, preferably di- to tetra-hydric, C2 to C10 alcohols such as ethylene glycol, 1,2-propanediol, butanediol, hexanediol, polyethylene glycol having from 2 to 20, preferably from 2 to 8, oxyethylene units, neopentyl glycol, bisphenol A, glycerol, trimethylolpropane, pentaerythritol, sorbitol, with unsaturated polyesters of aliphatic diols and polyols, as well as maleic acid, fumaric acid and/or itaconic acid.
  • polyhydric preferably di- to tetra-hydric, C2 to C10 alcohols
  • C2 to C10 alcohols such as ethylene glycol, 1,2-propanediol, butanediol, hexanediol, polyethylene glycol having from 2 to 20, preferably from
  • Crosslinking to form rubber microgels during the emulsion polymerization can also be effected by continuing the polymerization to high conversions or by the monomer feed process by polymerization with high internal conversions. Another possibility consists in carrying out the emulsion polymerization in the absence of regulators.
  • Suitable chemicals having crosslinking action are, for example, organic peroxides, such as dicumyl peroxide, tert.-butylcumyl peroxide, bis-(tert.-butyl-peroxy-isopropyl)benzene, di-tert.-butyl peroxide, 2,5-dimethylhexane 2,5-dihydroperoxide, 2,5-dimethylhexane 3,2,5-dihydroperoxide, dibenzoyl peroxide, bis-(2,4-dichlorobenzoyl) peroxide, tert.-butyl perbenzoate, and also organic azo compounds, such as azo-bis-isobutyronitrile and azo-bis-cyclohexanenitrile, and also di- and poly-mercapto compounds, such as dimercaptoethane, 1,6-dimercaptohexane, 1,3,5-trimercaptotriazine and mercapto-
  • the optimum temperature for carrying out the post-crosslinking is naturally dependent on the reactivity of the crosslinker and can be carried out at temperatures from room temperature to about 180° C., optionally under elevated pressure (see in this connection Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Volume 14/2, page 848).
  • Preferred crosslinkers are peroxides.
  • crosslinking of rubbers containing C ⁇ C double bonds to form microgels can also be carried out in dispersion or emulsion with the simultaneous partial, or complete, hydrogenation of the C ⁇ C double bond by means of hydrazine, as described in U.S. Pat. Nos. 5,302,696 and 5,442,009, or optionally other hydrogenating agents, for example organometal hydride complexes.
  • Enlargement of the particles by agglomeration can optionally be carried out before, during or after the post-crosslinking.
  • the preparation process used according to the present invention always yields incompletely homogeneously crosslinked microgels which can exhibit the above-described advantages.
  • microgels for the preparation of the composition according to the invention there may be used both non-modified microgels, which contain substantially no reactive groups especially at the surface, and microgels modified by functional groups, especially microgels modified at the surface.
  • the latter can be prepared by chemical reaction of the already crosslinked microgels with chemicals that are reactive towards C ⁇ C double bonds.
  • reactive chemicals are especially those compounds by means of which polar groups, such as, for example, aldehyde, hydroxyl, carboxyl, nitrile, etc., and also sulfur-containing groups, such as, for example, mercapto, dithiocarbamate, polysulfide, xanthogenate, thiobenzthiazole and/or dithiophosphoric acid groups and/or unsaturated dicarboxylic acid groups, can be chemically bonded to the microgels.
  • polar groups such as, for example, aldehyde, hydroxyl, carboxyl, nitrile, etc.
  • sulfur-containing groups such as, for example, mercapto, dithiocarbamate, polysulfide, xanthogenate, thiobenzthiazole and/or dithiophosphoric acid groups and/or unsaturated dicarboxylic acid groups
  • Preferred methods of modification are the grafting of the microgels with functional monomers and reaction with low molecular weight agents.
  • aqueous microgel dispersion which is reacted under the conditions of a free-radical emulsion polymerization with polar monomers such as acrylic acid, methacrylic acid, itaconic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, acrylamide, methacrylamide, acrylonitrile, acrolein, N-vinyl-2-pyrrolidone, N-allyl-urea and N-allyl-thiourea, and also secondary amino-(meth)acrylic acid esters such as 2-tert.-butylaminoethyl methacrylate and 2-tert.-butylaminoethylmethacrylamide.
  • microgels having a core/shell morphology, wherein the shell should be highly compatible with the matrix. It is desirable for the monomer used in the modification step to be grafted onto the unmodified microgel as quantitatively as possible.
  • the functional monomers are preferably metered in before crosslinking of the microgels is complete.
  • Suitable reagents for the surface modification of the microgels with low molecular weight agents are especially the following: elemental sulfur, hydrogen sulfide and/or alkylpolymercaptans, such as 1,2-dimercaptoethane or 1,6-dimercaptohexane, also dialkyl and dialkylaryl dithiocarbamate, such as the alkali salts of dimethyl dithiocarbamate and/or dibenzyl dithiocarbamate, also alkyl and aryl xanthogenates, such as potassium ethylxanthogenate and sodium isopropylxanthogenate, as well as reaction with the alkali or alkaline earth salts of dibutyldithiophosphoric acid and dioctyldithiophosphoric acid as well as dodecyldithiophosphoric acid.
  • alkylpolymercaptans such as 1,2-dimercaptoethane or 1,6-dimercapto
  • the mentioned reactions can also be carried out in the presence of sulfur, the sulfur being incorporated with the formation of polysulfide bonds.
  • free-radical initiators such as organic and inorganic peroxides and/or azo initiators can be added.
  • modified microgels such as, for example, by ozonolysis as well as by halogenation with chlorine, bromine and iodine.
  • a further reaction of modified microgels such as, for example, the preparation of hydroxyl-group-modified microgels from epoxidized microgels, is also understood as being the chemical modification of microgels.
  • the microgels are modified by hydroxyl groups, especially also at the surface thereof.
  • the hydroxyl group content of the microgels is determined as the hydroxyl number with the dimension mg of KOH/g of polymer by reaction with acetic anhydride and titration of the acetic acid liberated thereby with KOH according to DIN 53240.
  • the hydroxyl number of the microgels is preferably from 0.1 to 100, more preferably from 0.5 to 50, mg of KOH/g of polymer.
  • the amount of modifying agent used is governed by its effectiveness and the demands made in each individual case and is in the range from 0.05 to 30 wt. %, based on the total amount of rubber microgel used, particular preference being given to from 0.5 to 10 wt. %, based on the total amount of rubber gel.
  • the modification reactions can be carried out at temperatures of from 0 to 180° C., preferably from 20 to 95° C., optionally under a pressure of from 1 to 30 bar.
  • the modifications can be carried out on rubber microgels without a solvent or in the form of their dispersion, it being possible in the latter case to use inert organic solvents or alternatively water as the reaction medium.
  • the modification is preferably carried out in an aqueous dispersion of the crosslinked rubber.
  • non-polar thermoplastic materials such as, for example, polypropylene, polyethylene and block copolymers based on styrene, butadiene, isoprene (SBR, SIR) and hydrogenated isoprene-styrene block copolymers (SEBS), and conventional TPE-Os and TPE-Vs, etc.
  • modified microgels is especially preferred in the case of polar thermoplastic materials (A), such as, for example, PA, TPE-A, PU, TPE-U, PC, PET, PBT, POM, PMMA, PVC, ABS, PTFE, PVDF, etc.
  • A polar thermoplastic materials
  • the mean diameter of the prepared microgels can be adjusted with high accuracy, for example, to 0.1 micrometer (100 nm) ⁇ 0.01 micrometer (10 nm), so that, for example, a particle size distribution is achieved in which at least 75% of all the microgel particles are from 0.095 micrometer to 0.105 micrometer in size.
  • Other mean diameters of the microgels especially in the range from 5 to 500 nm, can be produced with the same accuracy (at least 75 wt. % of all the particles are located around the maximum of the integrated particle size distribution curve (determined by light scattering) in a range of ⁇ 10% above and below the maximum) and used.
  • the morphology of the microgels dispersed in the composition according to the present invention can be adjusted virtually “point accurately” and hence the properties of the composition according to the present invention and of the plastics, for example, produced there from can be adjusted.
  • Adjustment of the morphology of the dispersed phase of the TPEs produced according to the prior art by in situ reactive processing or dynamic vulcanization is not possible with such precision.
  • microgels so prepared can be worked up, for example, by concentration by evaporation, coagulation, by co-coagulation with a further latex polymer, by freeze coagulation (see U.S. Pat. No. 2,187,146) or by spray-drying.
  • flow auxiliaries such as, for example, CaCO 3 or silica, can also be added.
  • thermoplastic materials (A) used in the composition according to the invention preferably have a Vicat softening temperature of at least 50° C., more preferably of at least 80° C., yet more preferably of at least 100° C.
  • the Vicat softening temperature is determined according to DIN EN ISO 306:1996.
  • thermoplastic material (A) is advantageously chosen from thermolastic polymers (A1) and thermoplastic elastomers (A2).
  • thermoplastic polymers (A1) are used as starting material for the composition according to the invention, then compositions having thermoplastic elastomer properties are first formed by the incorporation of the microgels used according to the present invention.
  • thermoplastic elastomers (A2) are used as starting material for the composition according to the present invention, then thermoplastic elastomer properties are retained, and the properties of the thermoplastic elastomers (A2) can be modified in a targeted manner, as shown herein below, by the addition of the microgels (B) of suitable composition and suitable morphology.
  • the properties of the known TPEs such as TPE-U and TPE-A, such as especially the dimensional stability under heat and the transparency of the TPE-Us or the oil resistance of the TPE-As, can be improved by the incorporation of the microgels (B).
  • the difference in glass transition temperature between the thermoplastic material (A) and the microgel (B) is advantageously from 0 to 250° C.
  • the weight ratio thermoplastic material (A)/microgel (B) is from 1:99 to 99:1, preferably from 10:90 to 90:10, more preferably from 20:80 to 80:20.
  • thermoplastic polymers (A1) are used as the thermoplastic materials (A)
  • the weight ratio (A1)/(B) is preferably from 95:5 to 30:70.
  • thermoplastic elastomers (A2) are used as the thermoplastic materials (A), then the weight ratio (A2)/(B) is preferably from 98:2 to 20:80, more preferably from 95:5 to 20:80.
  • thermoplastic polymers (A1) which can be used in the composition according to the present invention include, for example, standard thermoplastics, so-called techno-thermoplastics and so-called high-performance thermoplastics (see H. G. Elias Makromoleküle Volume 2, 5th Edition, Huthig & Wepf Verlag, 1992, page 443 ff).
  • thermoplastic polymers (A1) which can be used in the composition according to the present invention include, for example, non-polar thermoplastic materials, such as, for example, polypropylene, polyethylene, such as HDPE, LDPE, LLDPE, polystyrene, etc., and polar thermoplastic materials, such as PU, PC, EVM, PVA, PVAC, polyvinylbutyral, PET, PBT, POM, PMMA, PVC, ABS, AES, SAN, PTFE, CTFE, PVF, PVDF, polyimide, PA, such as especially PA-6 (nylon), more preferably PA4, PA-66 (Perlon), PA-69, PA-610, PA-11, PA-12, PA 612, PA-MXD6, etc.
  • non-polar thermoplastic materials such as, for example, polypropylene, polyethylene, such as HDPE, LDPE, LLDPE, polystyrene, etc.
  • polar thermoplastic materials such as PU, PC, EVM, PVA, PVAC
  • thermoplastic polymers (A1) include: PP, PE, PS, PU, PC, SAN, PVC and PA.
  • thermoplastic elastomers (A2) which can be used in the composition according to the present invention include, for example, the above-mentioned thermoplastic elastomers known from the prior art, such as the block copolymers, such as styrene block copolymers (TPE-S: SBS, SIS, as well as hydrogenated isoprene-styrene block copolymers (SEBS), thermoplastic polyamides (TPE-A), thermoplastic copolyesters (TPE-E), thermoplastic polyurethanes (TPE-U), the mentioned blends of thermoplastics and elastomers, such as thermoplastic polyolefins (TPE-O) and thermoplastic vulcanization products (TPE-V), NR/PP blends (thermoplastic natural rubber), NBR/PP blends, IIR (XIIR)/PP blends, EVA/PVDC blends, NBR/PVC blends, etc.
  • TPE-S styrene block copo
  • thermoplastic elastomer (A2) examples include the following:
  • TPE-S Styrene Block Copolymers
  • the three-block structure of two thermoplastic polystyrene end blocks and an elastomeric middle block characterizes this group.
  • the polystyrene hard segments form domains, that is to say small volume elements having uniform characteristics, which act technically as spatial, physical crosslinking sites for the flexible soft segments.
  • the middle block a distinction is made between the following styrene block copolymers: butadiene (SBS), isoprene (SIS) and ethylene/butylene (SEBS) types.
  • SBS butadiene
  • SIS isoprene
  • SEBS ethylene/butylene
  • Branched types of block copolymer can be produced by linking via polyfunctional centers.
  • TPE-A Polyether-polyamide Block Copolymers
  • the block copolymers based on polyether (ester)-polyamide are formed by insertion of flexible polyether (ester) groups into polyamide molecule chains.
  • the polyether (ester) blocks form the soft and elastic segments, while the hard polyamide blocks assume the function of the thermoplastic hard phase.
  • the hard segments acquire their high strength as a result of a high density of aromatic groups and/or amide groups, which are responsible for the physical crosslinking of the two phases by hydrogen bridge formation.
  • Thermoplastic copolyesters are composed of alternate hard polyester segments and soft polyether components.
  • the polyester blocks formed from diols (e.g. 1,4-butanediol) and dicarboxylic acids (e.g. terephthalic acid), are esterifies in a condensation reaction by long-chain polyethers carrying hydroxyl terminal groups. Very different hard regions can be established according to the length of the hard and soft segments.
  • TPE-U Thermoplastic Polyurethanes
  • the block copolymers of polyurethane are synthesized by polyaddition of diols and diisocyanates.
  • the soft segments formed in the reaction between diisocyanate and a polyol act as elastic components under mechanical stress.
  • the hard segments (urethane groups) serving as crosslinking sites are obtained by reaction of the diisocyanate with a low molecular weiaht diol for chain extension.
  • the finely divided hard segments form domains which effect quasi-crosslinking via hydrogen bridges or generally via order states in which two or more domains enter into relationship with one another. Crystallization of the hard segments may occur thereby.
  • polyester, polyether and chemically combined polyester/polyether types according to the diol used as starting monomer.
  • thermoplastic TPEs A2
  • elastomer alloys which can be used according to the invention include, for example, the following:
  • EPDM terpolymers are generally used for the rubber phase, polypropylene is mostly used as the polyolefin.
  • the soft phase can be either uncrosslinked (TPE-0) or crosslinked (TPE-V). Where the PP component is dominant, the thermoplastic constitutes the continuous phase. If the elastomer content is very high, the structure can also be reversed, so that EPDM blends of high PP content result.
  • This class of elastomer alloys therefore covers a wide range of hardnesses. All representatives are distinguished by high resistance to UV radiation and ozone as well as to many organic and inorganic media. On the other hand, resistance to aliphatic and aromatic solvents is poor to moderate.
  • NR can also be compounded with PP and also with PP/PE mixtures to form a thermoplastically processable natural rubber (TPNR).
  • TPNR thermoplastically processable natural rubber
  • the dynamic crosslinking of NR generally takes place in the presence of peroxides above 170° C.
  • TPNR blends have markedly higher resistance to weathering and ozone.
  • pre-crosslinked or partially crosslinked acrylonitrile-butadiene rubber is dispersed as the elastomeric phase in the PP hard phase.
  • Characteristic features of these blends are high resistance to fuels, oils, acids and alkalis as well as to ozone and the effects of weathering.
  • Butyl or halobutyl rubbers constitute the elastomeric phase constituents in this class.
  • a diene rubber of non-polar nature common NR/IR
  • the excellent permeation properties of butyl rubber towards many gases are used for the property profile of the TPE blends obtainable in a blend with PP.
  • thermoplastic phase ethylene-vinyl acetate rubber (EVA) and polyvinylidene chloride (PVDC) as the thermoplastic phase.
  • EVA ethylene-vinyl acetate rubber
  • PVDC polyvinylidene chloride
  • the property profile in the middle hardness range of from 60 to 80 ShA is marked by good oil resistance and outstanding resistance to weathering.
  • NBR acrylonitrile-butadiene rubber
  • PVC polyvinyl chloride
  • thermoplastic elastomers (A2) include: TPE-U, TPE-A and TPE-V.
  • compositions according to the present invention contain the following combinations of components (A) and (B): Thermoplastic material (A) Microgel (B) based on TPE-U SBR (OH-modified), peroxidically crosslinked PP SBR (OH-modified), EGDMA- crosslinked PP SBR (unmodified), DVB-crosslinked TPE-A SBR (OH-modified), EGDMA- crosslinked PP NBR, peroxidically crosslinked PA NBR, peroxidically crosslinked
  • compositions according to the present invention generally behave like thermoplastic elastomers, that is to say they combine the advantages of thermoplastic processability with the properties of the elastomers, as described in the introduction in connection with the TPEs from the prior art.
  • compositions according to the present invention can additionally comprise at least one conventional plastics additive, such as inorganic and/or organic fillers, plasticizers, inorganic and/or organic pigments, flameproofing agents, agents against pests, such as, for example, termites, agents against marten bite, etc., and other conventional plastics additives.
  • plastics additives such as inorganic and/or organic fillers, plasticizers, inorganic and/or organic pigments, flameproofing agents, agents against pests, such as, for example, termites, agents against marten bite, etc.
  • plasticizers such as a plasticizers, inorganic and/or organic pigments, flameproofing agents, agents against pests, such as, for example, termites, agents against marten bite, etc.
  • flameproofing agents agents against pests
  • agents against pests such as, for example, termites, agents against marten bite, etc.
  • other conventional plastics additives such as, for example, termites, agents against marten bite, etc.
  • compositions according to the present invention are obtainable by mixing at least one thermoplastic material (A) and at least one crosslinked microgel (B) that has not been crosslinked using high-energy radiation.
  • the present invention relates also to the use of crosslinked microgels (B) that have not been crosslinked using high-energy radiation, in thermoplastic materials (A).
  • crosslinked microgels (B) that have not been crosslinked using high-energy radiation, in thermoplastic materials (A).
  • the present invention also relates also to a process for the preparation of the compositions according to the invention by mixing at least one thermoplastic material (A) and at least one microgel (B).
  • the preparation of the compositions according to the invention is generally carried out in such a manner that the microgel (B) is prepared separately before being mixed with the thermoplastic material (A).
  • compositions according to the present invention containing (optionally) modified microgel (B) and the thermoplastic material (A) can be prepared by various methods: on the one hand, it is of course possible to mix the individual components.
  • Apparatuses suitable therefore are, for example, mills, multi-roll mills, dissolvers, internal mixers or mixing extruders.
  • Suitable as mixing apparatuses are also the mixing apparatuses known from rubber and plastics technology (Saechtling Kunststoff Taschenbuch, 24th Edition, p. 61 and p. 148 ff; DIN 24450; Mixing of plastics and rubber products, VDI-Kunststofftechnik, p. 241 ff), such as, for example, co-kneaders, single-screw extruders (with special mixing elements), twin-screw extruders, cascade extruders, degassing extruders, multi-screw extruders, pin extruders, screw kneaders and planetary extruders, as well as multi-shaft reactors. Preference is given to the use of twin-screw extruders rotating in the same direction, with degassing (planetary extruders with degassing).
  • compositions according to the present invention containing (optionally) modified microgel (B) and the thermoplastic materials (A) with additional fillers and optionally conventional auxiliary substances, as mentioned above, can be carried out in conventional mixing apparatuses, such as mills, internal mixers, multi-roll mills, dissolvers or mixing extruders.
  • Preferred mixing temperatures are from room temperature (23° C.) to 280° C., preferably approximately from 60° C. to 200° C.
  • the present invention relates also to the use of the compositions according to the present invention in the production of thermoplastically processable molded articles, and to the molded articles obtainable from the compositions according to the present invention.
  • molded articles include: plug-type connectors, damping elements, especially vibration dampers and shock absorbers, acoustic insulating elements, profiles, films, especially insulating films, foot mats, clothing, especially insoles for shoes, shoes, especially ski shoes, shoe soles, electronic components, housings for electronic components, tools, decorative molded bodies, composite materials, moldings for motor vehicles, etc.
  • the molded articles according to the present invention can be produced from the compositions according to the invention by conventional processing methods for thermoplastic elastomers, for example by melt extrusion, calendering, IM, CM and RIM.
  • the preparation of the NBR microgel OBR 1102 C was carried out as described in DE 19701487.
  • An NBR latex was used as starting material.
  • the NBR latex had the following features: content of incorporated acrylonitrile: 43 wt. %, solids concentration: 16 wt. %, pH value: 10.8, diameter of the latex particles (d 2 ): 140 nm, particle density: 0.9984 g/cm 3 , the gel content of the latex is 2.6 wt. %, the swelling index of the gel portion in toluene was 18.5 and the glass transition temperature (Tg) is ⁇ 15° C.
  • DCP dicumyl peroxide
  • the preparation of the microgel was carried out by crosslinking an SBR latex containing 40 wt. % of incorporated styrene (Krylene 1721 from Bayer France) in latex form with 1.5 phr of dicumyl peroxide (DCP) and subsequently grafting with 5 phr of hydroxyethyl methacrylate (HEMA).
  • SBR latex containing 40 wt. % of incorporated styrene (Krylene 1721 from Bayer France) in latex form with 1.5 phr of dicumyl peroxide (DCP) and subsequently grafting with 5 phr of hydroxyethyl methacrylate (HEMA).
  • DCP dicumyl peroxide
  • HEMA hydroxyethyl methacrylate
  • the crosslinking of Krylene 1721 with dicumyl peroxide was carried out as described in Examples 1) to 4) of U.S. Pat. No. 6,127,488, 1.5 phr of dicumyl peroxide being used for the crosslinking.
  • the underlying latex Krylene 1721 has the following features:
  • the hydroxyl modification of the 1.5 phr-crosslinked SBR latex was carried out by grafting with 5 phr of hydroxyethyl methacrylate.
  • the reaction with HEMA, stabilization and working up of the hydroxyl-modified latex were carried out as described in U.S. Pat. No. 6,399,706, Example 2.
  • microgel Before the microgel is used in TPU, it is dried to constant weight at 100 mbar in a vacuum drying cabinet from Haraeus Instruments, type Vacutherm VT 6130.
  • This microgel was carried out by copolymerization of 23% styrene, 76% butadiene and 1% divinylbenzene in emulsion.
  • Microgel based on hydroxyl-modified BR prepared by direct emulsion polymerization using the crosslinking comonomer ethylene glycol dimethacrylate (OBR 1118).
  • aqueous solution consisting of 170 g of water, 1.69 g of ethylenediaminetetraacetic acid (Merck-Schuchardt), 1.35 g of iron(II) sulfate*7H 2 O, 3.47 g of Rongalit C (Merck-Schuchradt) and 5.24 g of trisodium phosphate*12H 2 O is then metered in.
  • the reaction was started by addition of an aqueous solution of 2.8 g of p-menthane hydroperoxide (Trigonox NT 50 from Akzo-Degussa) and 10.53 g of Mersolat K 30/95, dissolved in 250 g of water.
  • EGDMA ethylene glycol dimethacrylate
  • the diameter d z was defined according to DIN 53 206 as the median or central value, above and below which in each case half of all the particle sizes lie.
  • the particle diameter of the latex particles was determined by means of ultracentrifugation (W. Scholtan, H. Lange, “Beées der GeneralchengröBenvertechnik von Latices mit der Ultrazentrifuge” [Determination of the particle size distribution of latices by ultracentrifuge], Kolloid-Zeitschrift und Zeitschrift für Polymere (1972) Volume 250, Issue 8).
  • the diameter data in the latex and for the primary particles in the compositions according to the present invention are almost identical, because the particle size of the microgel particles remains practically unchanged during the preparation of the composition according to the invention.
  • Tg and ⁇ Tg For the determination of Tg and ⁇ Tg, a DSC-2 device from Perkin-Elmer is used.
  • the swelling index QI was determined as follows:
  • the swelling index 250 mg of the microgel are allowed to swell for 24 hours in 25 ml of toluene, with shaking.
  • the (wet) gel swelled with toluene is weighed, after centrifugation at 20,000 rpm, and then dried to constant weight at 70° C. and weighed again.
  • the OH number (hydroxyl number) was determined according to DIN 53240 and corresponds to the amount of KOH, in mg, that is equivalent to the amount of acetic acid liberated in the acetylation of 1 g of substance using acetic anhydride.
  • the acid number is determined as already mentioned above according to DIN 53402 and corresponds to the amount of KOH, in mg, that was required to neutralize 1 g of the polymer.
  • the gel content corresponds to the portion that was insoluble in toluene at 23° C. It was determined as described above.
  • the glass transition temperatures were determined as mentioned above.
  • the breadth of the glass transition was determined as described above.
  • compositions according to the invention were carried out by means of a laboratory internal mixer (Rheocord 90, Rheomix 600 E mixing chamber, Haake) with tangent rotors, compressed-air cooling and a chamber volume of 350 cm 3 . Mixing was carried out at a speed of 100 rpm, an initial chamber temperature of 160° C. and a degree of filling of 70%. Mixtures comprising a rubber microgel (B)/thermoplastic material (A) in the indicated ratios of, for example, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90 are prepared. To that end, the thermoplastic was first placed in the mixer and melted in the course of 4 minutes.
  • microgel is metered in, the die was closed and mixing was carried out for 8 minutes. A rise in temperature occurs thereby. The torque passes through a maximum with a final plateau. After mixing, visually homogeneous samples are removed, which exhibit approximately the coloring of the microgel.
  • the morphology was determined by means of transmission electron microscope images (TEM) and by means of atomic force microscopy (AFM).
  • AFM Topometrix Model TMX 2010.
  • microgel was too highly concentrated, i.e. if the primary particles overlap, dilution can be carried out beforehand.
  • the microgel OBR 1118 from Preparation Example 4 was mixed with PP Atofina PPH 3060 (produced by ATOFINA) as indicated below.
  • Mixtures having a MG/PP weight ratio of 5/95%, 10/90%, 15/85%, 20/80%, 25/75%, 30/70%, 35/65% are prepared.
  • the PP and MG are first metered into the extruder continuously by means of gravimetric metering scales. In the extruder, a rise in temperature to 180 to 195° C. takes place. After processing, visually homogeneous samples are removed, which have approximately the coloring of the microgel.
  • TPE-V Syntoprene Rubber 201-87
  • M1 Advanced Elastomer Systems
  • the microgel from Example 2 (OBR 1046 C) was mixed with a PP Atofina PPH 3060 (produced by Atofina) as indicated below.
  • Mixing was carried out at a speed of from 100 to 220 rpm, an intake-zone temperature of 165° C. and a throughput of 5 kg/h.
  • Mixtures having a MG/PP weight ratio of, for example, 5/95%, 10/90%, 15/85%, 20/80%, 25/75%, 30/70%, 35/65% are prepared.
  • the PP and MG were first metered into the extruder continuously by means of gravimetric metering scales. In the extruder, a rise in temperature to 190 to 210C. took place. After processing, visually homogeneous samples were removed, which have approximately the coloring of the microgel.
  • TPE-V Syntoprene Rubber 201-87
  • M1 Advanced Elastomer Systems
  • Microgels (OBR 1126 E) from Example 3 were mixed with a PP Moplen Q 30 P (produced by Montel Polyolefins) as indicated below.
  • Mixtures having a MG/PP weight ratio of, for example, 5/95%, 10/90%, 1 5/85%, 20/80%, 25/75%, 30/70%, 35/65% are prepared.
  • the PP and MG are first metered into the extruder continuously by means of gravimetric metering scales. In the extruder, a rise in temperature to 175 to 190° C. takes place. After processing, visually homogeneous samples were removed, which have approximately the coloring of the microgel.
  • TPE-V Syntoprene Rubber 201-87
  • M1 Advanced Elastomer Systems
  • the microgel from Preparation Example 2 (OBR 1046C) was used as the microgel.
  • the PP and MG are first metered into the extruder continuously by means of gravimetric metering scales.
  • a rise in temperature to 195° C. takes place.
  • visually and physically homogeneous samples were removed, which have approximately the coloring of the microgel and were transparent.
  • a conventionally prepared TPU (Desmopan 385) (M1) was used as a reference for the microgel-based TPE-Us.
  • Standard tensile test specimens were injection-molded from the resulting granules of the MG-based TPE-Us and of the pure Desmopan 385. This was carried out using an injection-molding machine (type 320S from Arburg) at a machine temperature of 205-215° C., a ram pressure of 10 bar and a tool temperature of 60° C. The residence time of the sample in the machine and in the tool was 50 seconds. The shot was 29.5 g.
  • FIG. 1 shows an electron microscope image of the material obtained in Example 4. The dispersed, approximately spherical microgels are clearly visible.
  • 50% F3 standard test rods were prepared from all the samples. This was carried out for all materials by injection-molding of test sheets. The test specimens were prepared from the test sheets. All the standard rods have a width of 14 mm in the head region and a web width of 7 mm. The thickness of the standard rods was 2 mm.
  • the tensile test of the samples was carried out on 50% F3 standard test rods (see above) according to DIN 53455.
  • the testing was carried out using a universal testing machine (type 1445, Frank) with optical length pick-ups.
  • the measuring range of the force pick-up was 0 to 1000 N.
  • the results of the measurements were summarized in Table 5. The following machine parameters were specified: preliminary force 0.1 N speed to preliminary force 1 mm/min load 1000 N Vtest 400 mm/min
  • test specimens were additionally stored at +80° C. and at ⁇ 2° C. in each case for 64 hours and conditioned for 1 hour at RT before the measurement. Within the scope of measuring accuracy, the samples with microgel exhibit no significant changes in Shore A hardness. The calculated values were summarized in Table 6.
  • the color of the test sheets was determined according to DIN standards DIN 5033 and DIN 6174 using a Match Rite CFS57 colour-measuring device from X-Rite GmbH. The calculated color values were summarized in Table 6. Although the microgel-containing test sheets have an inherent color, they remained transparent even with a content of 30% MG.
  • test specimens according to the invention are more dimensionally stable with the addition of the microgel than without, the dimensional stability increasing as the microgel content increases.
  • the preparation of the TPE-As was carried out by means of a laboratory internal mixer (Rheocord 90, Rheomix 600 E mixing chamber, Haake) with tangent rotors, compressed-air cooling and a chamber volume of 350 cm 3 . Mixing was carried out at a speed of 100 rpm, an initial chamber temperature of 190° C. and a degree of filling of 70%. Mixtures having a rubber microgel/thermoplastic ratio of 70/30 were prepared (samples 1 and 2). To that end the thermoplastic (Grilamid L 112 G) was first placed in the mixer and melted in the course of 4 minutes. Then the microgel was metered in, the die was closed and mixing was carried out for 8 minutes.
  • Grilamid L 112 G thermoplastic
  • a conventional TPE-A (sample 5) having the same rubber/thermoplastic ratio was prepared as a reference for the microgel-based TPE-As according to the present invention.
  • the PA used had the name (Grilamid L 1120 G) from EMS-GRIVORY and the nitrile rubber used has the name (Perbunan NT 3465) from BAYER AG.
  • the crosslinker used is a dicumyl peroxide. It has the name Poly-Dispersion E(DIC)D-40 from Rhein Chemie Corporation. It is a 40% blend of DCP in an EPM binder. 5 phr of the chemical were metered in.
  • phase mediator Trans-Polyoctenamer (Vestenamer 8012 from Degussa AG) were metered into the internal mixer after the addition of the NBR rnbber (Perbunan NT 3465), before the crosslinker was added.
  • microgel-based TPE-As As a further reference for the microgel-based TPE-As according to the present invention, pure PA (Grilamid L 1120 G (sample 3)) and pure NBR vulcanization product (Perbunan NT 3465 crosslinked with 5 phr of Poly-Dispersion E(DIC)D-40 (sample 4)) were used.
  • Rods were injection-molded from the granules of the TPE-As and the pure thermoplastics. This was carried out using a laboratory injection-molding machine (Injektometer, Göttfert) at a machine temperature of 230-240° C., a pressure of 10 bar and a tool temperature of 120° C. The residence time of the sample was about one minute in the machine and in the tool.
  • a laboratory injection-molding machine Injektometer, Göttfert
  • the residence time of the sample was about one minute in the machine and in the tool.
  • S2 standard rods were prepared from all the samples. This was carried out by cutting in the case of the pure thermplastic materials (sample 3). The standard rods of all the other samples were stamped out. All the prepared standard rods had a width of only 10 mm in the head region because the injection-molded blanks had a diameter of only 10 mm. The thickness of the standard rods is 4 mm.
  • the tensile test of the samples was carried out on S2 standard rods (see above) according to DIN 53504.
  • the testing was carried out using a universal testing machine (type 1445, Frank) with optical length pick-ups.
  • the measuring range of the force pick-up is 0 to 2000 N.
  • the results of the measurements are summarized in Table 1.
  • the breaking elongation and stress at break values of the microgel/PA-based TPE-As were between the values of the pure constituent elastomer and thermoplastic phase.
  • the level of properties of a conventionally prepared TPE-A having the same polymers can be reached.
  • the microgel OBR1102C (Preparation Example 1) having the high ACN content was used, the stronger TPE-A was achieved.
  • the swelling of the samples was carried out on S2 standard rods (see above) according to DIN 53521 at a temperature of 125° C. and for a duration of 4 days in the reference test liquid IRM 903 ( I ndustry R eference M aterial, highly hydro-treated heavy naphthene distillate).
  • IRM 903 I ndustry R eference M aterial, highly hydro-treated heavy naphthene distillate.
  • the microgel domains that is to say the domains of the elastomer phase
  • the microgel domains are smaller and more uniform by orders of magnitude than the elastomer domains, formed by dynamic vulcanization, of conventional dynamically vulcanized TPVs, both with (>5 to 30 ⁇ m) and without phase mediator (>10 to 35 ⁇ m, FIG. 3 ).

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100252254A1 (en) * 2007-06-21 2010-10-07 Swelltec Limited Apparatus and Method with Hydrocarbon Swellable and Water Swellable Body
US20100314134A1 (en) * 2007-06-21 2010-12-16 Swelltec Limited Swellable Apparatus and Method of Forming
US20110224357A1 (en) * 2008-05-23 2011-09-15 Lanxess Deutschland Gmbh Carbon nanotubes and organic media containing microgels
EP2796503A1 (de) * 2013-04-26 2014-10-29 LANXESS Deutschland GmbH Zusammensetzungen, enthaltend Thermoplasten auf Basis von Polyvinylchlorid sowie mit Hydroxylgruppen modifizierte, vernetzte NBR-Mikrogele
US10589452B2 (en) 2015-07-02 2020-03-17 Entex Rust & Mitschke Gmbh Method for processing products in an extruder

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10345043A1 (de) * 2003-09-27 2005-04-21 Rhein Chemie Rheinau Gmbh Mikrogel-enthaltende Zusammensetzung
DE10344976A1 (de) * 2003-09-27 2005-04-21 Rhein Chemie Rheinau Gmbh Mikrogele in vernetzbaren, organischen Medien
DE10344975A1 (de) * 2003-09-27 2005-04-21 Rhein Chemie Rheinau Gmbh Mikrogele in nicht-vernetzbaren organischen Medien
CN1989782B (zh) * 2004-09-15 2011-12-07 上岛一夫 音响机器用垫
DE102004062551A1 (de) * 2004-12-24 2006-07-06 Rhein Chemie Rheinau Gmbh Mikrogel-enthaltende duroplastische Zusammensetzung
DE102005014272A1 (de) 2005-03-24 2006-09-28 Rhein Chemie Rheinau Gmbh Mikrogele und Verdickungsmittel enthaltende Zusammensetzungen
DE102005014270A1 (de) 2005-03-24 2006-10-05 Rhein Chemie Rheinau Gmbh Verwendung von vernetzten Mikrogelen zur Modifikation des temperaturabhängigen Verhaltens von nicht-vernetzbaren organischen Medien
US7947782B2 (en) 2005-05-16 2011-05-24 Rhein Chemie Rheinau Gmbh Microgel-containing vulcanisable composition
DE102005023213A1 (de) * 2005-05-16 2006-11-23 Rhein Chemie Rheinau Gmbh Mikrogel-enthaltende vulkanisierbare Zusammensetzung
EP1844917A3 (de) 2006-03-24 2008-12-03 Entex Rust & Mitschke GmbH Verfahren zur Verarbeitung von zu entgasenden Produkten
FR2910877B1 (fr) 2006-12-28 2009-09-25 Eurocopter France Amelioration aux rotors de giravions equipes d'amortisseurs interpales
DE102007011427A1 (de) 2007-03-08 2008-09-11 Rhein Chemie Rheinau Gmbh Verwendung von protonenliefernden und/oder protonenakzeptierenden Polymerteilchen
EP2289687A1 (de) 2007-05-16 2011-03-02 Entex Rust & Mitschke GmbH Verfahren zur Verarbeitung von zu entgasenden Produkten
JP5620276B2 (ja) * 2008-02-08 2014-11-05 エーエムエス−パテント アクチェンゲゼルシャフト 加水分解耐性ポリアミド−エラストマー混合物、それから製造される成形品及びそれらの使用
DE102008008098A1 (de) 2008-02-08 2009-08-13 Ems-Patent Ag Hydrolysebeständige Polyamid-Elastomer-Mischungen, hieraus hergestellte Formteile sowie deren Verwendung
DE102008042368A1 (de) 2008-09-25 2010-04-01 Ems-Patent Ag Hydrolysebeständige Polyamid-Elastomer-Mischungen, hieraus hergestellte Formteile sowie deren Verwendung
DE102008052116A1 (de) * 2008-10-20 2010-04-22 Lanxess Deutschland Gmbh Kautschukmischungen mit funktionalisierten Dienkautschuken und Mikrogelen, ein Verfahren zur Herstellung und deren Verwendung
TWI477540B (zh) 2009-03-16 2015-03-21 Toray Industries 纖維強化樹脂組成物、成形材料及纖維強化樹脂組成物之製造方法
US8028800B2 (en) * 2009-04-10 2011-10-04 Saint-Gobain Performance Plastics Rencol Limited Acoustic damping compositions
WO2010118359A2 (en) * 2009-04-10 2010-10-14 Saint-Gobain Performance Plastics Corporation Acoustic damping composition having elastomeric particulate
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DE102017006638A1 (de) 2017-07-13 2019-01-17 Entex Rust & Mitschke Gmbh Füllteilmodul in Planetwalzenextruderbauweise
JP6929768B2 (ja) * 2017-12-27 2021-09-01 株式会社クラレ 熱可塑性ポリオレフィン制振材
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4694042A (en) * 1984-02-02 1987-09-15 Basf Aktiengesellschaft Elastomeric thermoplastic molding materials and their preparation
US5075380A (en) * 1987-12-22 1991-12-24 Bayer Aktiengesellschaft Soft, thermo-plastically processible polymer alloys containing polyamide
US5237001A (en) * 1990-06-21 1993-08-17 Bayer Aktiengesellschaft Thermoplastic compositions of polyurethanes and partly crosslinked alkyl acrylate copolymers
US5591798A (en) * 1988-04-11 1997-01-07 Advanced Elastomer Systems, L.P. High temperature stable, low solvent swelling thermoplastic elastomer compositions

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2187146A (en) 1936-10-24 1940-01-16 Du Pont Process of coagulation
GB1078400A (en) 1963-08-13 1967-08-09 Rubber Res Inst Of Malaya Boar Processing improvements to synthetic rubbers
US4173556A (en) * 1976-03-03 1979-11-06 Monsanto Company Elastoplastic compositions of rubber and polyamide
DE3312542A1 (de) 1983-04-07 1984-10-11 Bayer Ag, 5090 Leverkusen Weiche polymerlegierungen
CA1332992C (en) * 1986-08-27 1994-11-08 Susan Marie Liwak Impact-strength modifiers for thermoplastic polymers
JPS6381158A (ja) 1986-09-24 1988-04-12 Japan Synthetic Rubber Co Ltd 熱可塑性エラストマ−組成物
US4879328A (en) * 1987-05-18 1989-11-07 Toray Industries Aromatic polyester composition and process for producing the same
US5013793A (en) * 1990-07-26 1991-05-07 Exxon Chemical Patents Inc. Dynamically cured thermoplastic olefin polymers and process for producing the same
JP2717229B2 (ja) 1988-06-21 1998-02-18 旭化成工業株式会社 樹脂補強用ゴム粒子及び補強樹脂組成物
JPH0253803A (ja) * 1988-08-19 1990-02-22 Hitachi Chem Co Ltd スチレン系ミクロゲルの製造方法、塗膜性能向上剤．レオロジーコントロール剤及び熱可塑性樹脂の改質剤
US5075280A (en) 1988-11-01 1991-12-24 Ampex Corporation Thin film magnetic head with improved flux concentration for high density recording/playback utilizing superconductors
US5302696A (en) 1989-05-16 1994-04-12 Olin Corporation Process for minimizing residual free hydrazine in polymer latices
DE3920745A1 (de) 1989-06-24 1991-01-03 Bayer Ag Kautschukmischungen enthaltend schwefel-modifizierte polychloroprengel
DE3922103A1 (de) * 1989-07-05 1991-01-17 Bayer Ag Mischungen thermoplastischer polymerisate in pulverform
US5112910A (en) 1989-07-05 1992-05-12 Bayer Ag Mixtures of thermoplastic polymers in powder form
DE4220563A1 (de) 1992-06-24 1994-01-13 Bayer Ag Kautschukmischungen enthaltend Polybutadien-Gel
EP0656388B1 (de) * 1993-11-26 2001-04-11 Atofina An Thermoplasten haftende Thermoplast-Kautschukpolymerlegierungen
US5424356A (en) 1994-03-21 1995-06-13 The Goodyear Tire & Rubber Company Process for the preparation of hydrogenated rubber
US5536613A (en) * 1995-02-23 1996-07-16 Xerox Corporation Processes for preparing toner
JPH09302007A (ja) * 1996-05-09 1997-11-25 Japan Synthetic Rubber Co Ltd ゴム状重合体ラテックス、ゴム強化ビニル系重合体、および熱可塑性重合体組成物
DE19701489A1 (de) 1997-01-17 1998-07-23 Bayer Ag Modifizierte Kautschukgele enthaltende Kautschukmischungen
DE19701488A1 (de) 1997-01-17 1998-07-23 Bayer Ag SBR-Kautschukgele enthaltende Kautschukmischungen
DE19701487A1 (de) 1997-01-17 1998-07-23 Bayer Ag NBR-Kautschuke enthaltende Kautschukmischungen
DE19826343A1 (de) 1998-06-12 1999-12-16 Contitech Holding Gmbh Verfahren zur Herstellung eines thermoplastischen Elastomers
DE19834804A1 (de) 1998-08-01 2000-02-03 Continental Ag Kautschukmischung
DE19834803A1 (de) 1998-08-01 2000-02-03 Continental Ag Kautschukmischung
DE19834802A1 (de) 1998-08-01 2000-02-03 Continental Ag Kautschukmischung
DE19845740A1 (de) * 1998-10-05 2000-04-13 Basf Coatings Ag Beschichtungsmittel, Verfahren zu seiner Herstellung und seine Verwendung als Effekt-Klarlack, insbesondere zur Beschichtung von Kunststoffen
DE19921415A1 (de) 1999-05-08 2000-11-16 Inst Verbundwerkstoffe Gmbh Verfahren zur Herstellung von Polymermischungen, insbesondere thermoplastischen Elastomerzusammensetzungen, unter Verwendung von Glycidyl-funktionalisierten Nitrilkautschuken
EP1063259A1 (de) 1999-06-26 2000-12-27 Bayer Ag Mikrogelhaltige Kautschukcompounds mit schwefelhaltigen Organosiliciumverbindungen
DE19942614A1 (de) 1999-09-07 2001-03-08 Bayer Ag Verfahren zur Herstellung von Telechelen und ihre Verwendung
DE19939865A1 (de) 1999-08-23 2001-03-01 Bayer Ag Agglomerierte Kautschukgele enthaltende Kautschukmischungen und Vulkanisate
DE19942620A1 (de) 1999-09-07 2001-03-08 Bayer Ag Mikrogelhaltige Kautschukmischungen mit verkappten bifunktionellen Mercaptanen und hieraus hergestellte Vulkanisate
EP1083186B1 (de) * 1999-09-07 2009-01-28 Bayer MaterialScience AG Oligomere und polymere Telechelen
ES2280244T3 (es) 1999-12-03 2007-09-16 China Petro-Chemical Corporation Caucho en polvo totalmente vulcanizado con diametro de particula controlable, procedimiento de preparacion y uso del mismo.
DE10021070A1 (de) 2000-04-28 2001-10-31 Bayer Ag Gelhaltige Kautschukmischungen für dynamisch belastete Reifenbauteile
DE10035493A1 (de) * 2000-07-21 2002-01-31 Bayer Ag Verfahren zur Herstellung vernetzter Kautschukpartikel
DE10038488A1 (de) 2000-08-08 2002-02-21 Bayer Ag Isocyanatosilan- und mikrogelhaltige Kautschukmischungen
DE10039749A1 (de) 2000-08-16 2002-02-28 Bayer Ag Kautschukmischungen auf Basis von unvernetzten Kautschuken und vernetzten Kautschukpartikeln sowie multifunktionellen Isocyanaten auf Polyuretbasis
DE10052287A1 (de) 2000-10-20 2002-04-25 Bayer Ag Kautschukgele und Phenolharzedukte enthaltende Kautschukmischungen
DE10054533A1 (de) 2000-11-03 2002-05-08 Bayer Ag Mikrogelhaltige Kautschukmischungen mit Phoshorylpolysulfiden und hieraus hergestellte Vulkanisate bzw. Formkörper
DE10056311A1 (de) 2000-11-14 2002-05-16 Bayer Ag Gelhaltige Kautschukmischungen mit anorganischen Peroxiden
DE10061174A1 (de) 2000-12-07 2002-06-20 Bayer Ag NBR-Gele in Butylkautschukcompounds
CN1177895C (zh) 2001-10-12 2004-12-01 中国石油化工股份有限公司 一种增韧热固性树脂及其制备方法
JP2003129991A (ja) * 2001-10-24 2003-05-08 Boc Edwards Technologies Ltd 分子ポンプ
DE10345043A1 (de) * 2003-09-27 2005-04-21 Rhein Chemie Rheinau Gmbh Mikrogel-enthaltende Zusammensetzung
DE10344976A1 (de) * 2003-09-27 2005-04-21 Rhein Chemie Rheinau Gmbh Mikrogele in vernetzbaren, organischen Medien
DE10344975A1 (de) 2003-09-27 2005-04-21 Rhein Chemie Rheinau Gmbh Mikrogele in nicht-vernetzbaren organischen Medien
DE102004062551A1 (de) 2004-12-24 2006-07-06 Rhein Chemie Rheinau Gmbh Mikrogel-enthaltende duroplastische Zusammensetzung
DE102005014272A1 (de) 2005-03-24 2006-09-28 Rhein Chemie Rheinau Gmbh Mikrogele und Verdickungsmittel enthaltende Zusammensetzungen
DE102005014270A1 (de) 2005-03-24 2006-10-05 Rhein Chemie Rheinau Gmbh Verwendung von vernetzten Mikrogelen zur Modifikation des temperaturabhängigen Verhaltens von nicht-vernetzbaren organischen Medien
DE102005014271A1 (de) 2005-03-24 2006-09-28 Rhein Chemie Rheinau Gmbh Mikrogele in Kombination mit funktionalen Additiven
US7947782B2 (en) 2005-05-16 2011-05-24 Rhein Chemie Rheinau Gmbh Microgel-containing vulcanisable composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4694042A (en) * 1984-02-02 1987-09-15 Basf Aktiengesellschaft Elastomeric thermoplastic molding materials and their preparation
US5075380A (en) * 1987-12-22 1991-12-24 Bayer Aktiengesellschaft Soft, thermo-plastically processible polymer alloys containing polyamide
US5591798A (en) * 1988-04-11 1997-01-07 Advanced Elastomer Systems, L.P. High temperature stable, low solvent swelling thermoplastic elastomer compositions
US5237001A (en) * 1990-06-21 1993-08-17 Bayer Aktiengesellschaft Thermoplastic compositions of polyurethanes and partly crosslinked alkyl acrylate copolymers

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100252254A1 (en) * 2007-06-21 2010-10-07 Swelltec Limited Apparatus and Method with Hydrocarbon Swellable and Water Swellable Body
US20100314134A1 (en) * 2007-06-21 2010-12-16 Swelltec Limited Swellable Apparatus and Method of Forming
US8540032B2 (en) * 2007-06-21 2013-09-24 Swelltec Limited Apparatus and method with hydrocarbon swellable and water swellable body
US20110224357A1 (en) * 2008-05-23 2011-09-15 Lanxess Deutschland Gmbh Carbon nanotubes and organic media containing microgels
US8592512B2 (en) 2008-05-23 2013-11-26 Lanxess Deutschland Gmbh Carbon nanotubes and organic media containing microgels
EP2796503A1 (de) * 2013-04-26 2014-10-29 LANXESS Deutschland GmbH Zusammensetzungen, enthaltend Thermoplasten auf Basis von Polyvinylchlorid sowie mit Hydroxylgruppen modifizierte, vernetzte NBR-Mikrogele
WO2014174068A1 (de) * 2013-04-26 2014-10-30 Lanxess Deutschland Gmbh Zusammensetzungen, enthaltend thermoplasten auf basis von polyvinylchlorid sowie mit hydroxylgruppen modifizierte, vernetzte nbr-mikrogele
JP2016520685A (ja) * 2013-04-26 2016-07-14 ランクセス・ドイチュランド・ゲーエムベーハー ポリ塩化ビニルをベースとする熱可塑性プラスチックを含み、かつヒドロキシ基で変性された、架橋されたｎｂｒミクロゲルを含む組成物
US10287425B2 (en) 2013-04-26 2019-05-14 Arlanxeo Deutschland Gmbh Compositions, containing thermoplastics based on polyvinyl chloride and containing cross-linked NBR microgels modified with hydroxyl groups
US10589452B2 (en) 2015-07-02 2020-03-17 Entex Rust & Mitschke Gmbh Method for processing products in an extruder

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CA2540077A1 (en) 2005-04-14
US20080108755A1 (en) 2008-05-08
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US8188187B2 (en) 2012-05-29
EP1670851B1 (de) 2012-12-12
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BRPI0414600A (pt) 2006-11-07
ES2398655T3 (es) 2013-03-20
CN1860158B (zh) 2012-06-27

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