ROHSTOFFE UND ANWENDUNGEN RAW MATERIALS AND APPLICATIONS

Recycling Á Rubber powder Á Chemical modification Á Grafting In material-sensitive recycling of crushed reclaimed rubber materials, which is achieved by admixing the recycled rubber with new rubber matrices, a drop is noted in the mechanical value level of elastomers. This drop is due to deficient grafting of the recycled rubber with the fresh rubber matrix. To improve grafting quality, the particle surfaces are modified chemically in different ways following a comprehensive morphological and chemical characterization of select types of rubber powder. Grafting with maleic anhydride and grafting of reactive silane-based coupling agents following epoxidation or hydroxylation have shown themselves to be the most promising methods. The criterion applied to evaluate the suitability and effects of the surface modification is the level of or the observable changes in the material's mechanical properties, such as, for example, fracture stress and dynamic modulus.

Interphase Grafting of Reclaimed Rubber Powder
A. Amash, U. Giese, R. H. Schuster, Hannover

Phasengrenzflachenhaftung È von zerkleinertem Altgummi
Recycling Á Gummimehl Á Chemische Modifizierung Á Anbindung Die stoffliche Wiederverwertung von zerkleinertem Altgummi durch Zumischen zu neuen Kautschukmatrices ist auf Grund mangelnder Anbindung ¹Altgummi ± frische Kautschukmatrixª mit einem Abfall des mechanischen Werteniveaus des Elastomeren verbunden. Zur Verbesserung der Anbindung werden verschiedene chemische Modifizierungen der PartikeloberflaÈ chen nach einer umfassenden morphologischen und chemischen Charakterisierung von ausgewahlten È Gummimehlen vorgenommen. Als aussichtsreiche Methoden haben sich sowohl die Pfropfung mit MaleinsauÈ reanhydrid als auch die Epoxidierung bzw. Hydroxylierung mit anschlieûender Anbindung von Kopplungsagenzien auf Basis reaktiver Silane herausgestellt. Als Kriterium zur Beurteilung der Tauglichkeit und Effekte der Oberflachenmodifizierung dient das È È Niveau bzw. die beobachteten Anderungen in den mechanischen Werkstoffeigenschaften, wie z. B. die Bruchspannung und der dynamische Modul.

As the production and use of rubber articles steadily increases, there is necessarily a concomitant rise in the incidence of discarded rubber. In the United States alone 170,000 metric tons of productionrelated rubber scrap is generated each year. This constitutes 5 % of overall production. In Germany approx. 550,000 metric tons of discarded tires accumulate each year, and the amount is likely to continue to rise. Only a small portion of the discarded tires is retreaded [1 ± 3]. It is a well-known fact that direct material recycling and reshaping is difficult because of the irreversible three-dimensional crosslinking of rubber. Countless attempts have nonetheless been proposed for material-sensitive recycling of rubber [1 ± 10]. Thanks to a favorable energy balance, the lion's share (approx. 60 %) of the discarded tires disposed of is recycled as energy in cement factories and power stations. This method does not, of course, represent the kind of materialsensitive recycling alternative one would want to strive for. It is ecologically questionable and has undesirable implications for the future in terms of the conservation of resources and a targeted reduction in the negative impact on the environment. There are a number of methods that can, in principle, be applied to meet these targets: pyrolysis, hydrogenation (combining or treating with hydrogen) and hightemperature atomization [3, 9]. Due to their low economic efficiency these methods enjoy only minor consideration as recycling concepts at the moment. One of the most proven raw-materialsensitive recycling methods for discarded rubber is what is referred to as regeneration or devulcanization. A number of different methods are possible here: chemical, mechanical, thermomechanical, cryogenic-mechanical, microwave and

ultrasonic [10 ± 16]. To be sure, these variants are disadvantageous in terms of product quality and efficiency. Most significantly, one of the results actually targeted ± a decrease in sulfur bridges ± has an undesirable side effect, that of a drop in the performance level of the reclaimed rubber due to significant depolymerization on the polymer chains. Today a small portion of the discarded rubber (< 10 %) is reduced to crumb or powder and used as a minor aggregate component in the production of new rubber compounds. A problem in this is that the rubber particles represent foreign bodies in vulcanized material. This is due to their having already been vulcanized and forming only a relatively minor particle surface component. As a result they interact only weakly with the ambient fresh rubber matrix and thus exhibit poor grafting quality, producing weaknesses in the material at certain points and detracting from the mechanical properties [2, 3, 17 ± 20]. This negative effect is slightly reduced by using rubber powder with a small particle size and structured surface quality, in which case the grafting quality is essentially influenced by physical forces. In general, grafting of two different polymer phases is achieved in a blend with adequate thermodynamic compatibility by interdiffusion of the molecular chain in the area of the phase boundary [21, 22]. This process rarely occurs in the case of rubber compounds containing recycled rubber. The reason for this is the prevailing crosslinking of the polymer matrix of the recycled rubber particles, even in the case of polymer systems that are, in principle, thermodynamically compatible. The basic precondition for high molecular chain mobility is not adequately provided. A very promising solution to this problem is that of grafting recycled rubber particle

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KGK Kautschuk Gummi Kunststoffe 55. Jahrgang, Nr. 5/2002

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Soxhlet extraction is applied to separate soluble low-molar ingredients from the elastomer matrix of the rubber powder. 1). Experimental aspects The following steps describe the full approach taken in developing methods for chemically grafting recycled rubber onto a rubber matrix that is to be freshly vulcanized: ± physical and chemical characterization of recycled rubber powder ± chemical modification of the particle surfaces of reclaimed rubber powder ± manufacture of compounds containing rubber powder with particle grafting ± comparative characterization of vulcanizate and reference specimens A total of five rubber powder types available commercially are considered. D and E provides a particle surface of lesser roughness and of a lower anisometric factor than does warm grinding. Any existing double bonds in the recycled rubber powder matrix can be used as reactive centers for functionalization. 1 summarizes the data from the measurements of surface structure and specific surface. Chemical characterization The concentration of double bonds. 27] and dynamic difference calorimetry (DDC) [28 ± 30]. Plasticizers and other additives were determined by means of liquid chromatography (LC) and FT-IR spectroscopy [24. 25]. Nr. 1. The specific surface was calculated with the median of the particle size distribution (Gn).g. The relatively intensive follow-up cryogenic comminution of the rubber powder types C. rubber powder of type D exhibits a markedly lower particle size and a narrower distribution of particle size than the contrasting coarse-grained type A (Fig. When covulcanizing the recycled rubber and the fresh rubber matrix it should then be possible by means of coupling agents to completely graft the recycled rubber particles chemically onto the rubber matrix and achieve an improvement in the mechanical ± and in particular. the mechanical-dynamic ± performance level of the resulting elastomers. Tab. The anisometric factor F I is described by the maximum extension of the projection surface and of the diameter of a circular surface equivalent to the particle. As would be expected.and fine-grained rubber powder (types A and D) 220 KGK Kautschuk Gummi Kunststoffe 55. thickness < 120 lm) dispersed rubber powder was viewed microscopically under 32-fold enlargement. The mean grain size G was calculated as mean weight GW and mean number Gn. Particle size distribution of coarse.Interphase Grafting . Jahrgang. a factor that is extremely interesting in estimating chemical reactivity. e. The roughness of the surface-descriptive fractal dimension c for the circumference can be determined on the basis of the magnitude of the particle projection U and the particle surface. in the case of rubber powder type A (Tab. approximately 2000 ± 2500 particles from the embedded rubber particles were analyzed. D and E) from truck tire Results of the characterization of rubber powder types Morphology Fig. An overview of the quantitative composition of the rubber powder types was obtained with the help of thermogravimetric analysis (TGA) [27 ± 29]. The polymers were identified by means of pyrolytic FT-IR spectroscopy [26. 1). treads with a particle size < 160 lm (according to the manufacturer) were also considered. as a result of interdiffusion and a principal chemical valence bond by chemically modifying the surface of the rubber powder particles. 1 provides a representative display of the results for particle size distribution of a ªfine-grainedº rubber powder ± type D ± and of a ªcoarse-grainedº rubber powder ± type A. . Alongside two coarse-grained warm or warm and cryogenic reground rubber powder types (types A and B) with a particle size < 600 lm (according to the manufacturer). In a transparent EPDM matrix (film. assuming spherical symmetry and a density of a) b) Fig. 5/2002 . . with the distribution range V resulting from (GW/Gn )-1 [23]. was determined on the particle surface by means of titration with an aqueous potassium permanganate solution in alcohol. Chemical and physical characterization methods Characterization of the morphology The particle size distribution and the surface structure of the rubber powder were determined using an optical microscope [23]. To obtain statistically significant values. three fine-grained warm and then cryogenically reground rubber powder types (type C.

2. 1.53 1. rubber powder type D was shown to have the highest double bond concentration À 3.54 1. Results of the chemical analysis of fine-grain rubber powder of type D and of coarse-grain rubber powder of type A Ingredient Constituent Weight-% Fine powder Coarse-grained powder 38.06 0. The total share of these substances is much lower than in new materials (tire formulas).1 g/cm3.1 7.56 1.8 8. Previous extraction can prevent the low-molar ingredients ± especially the antioxidants ± from subsequently exerting any negative influence on chemical modification of the rubber powders. types C and E had 1.Interphase Grafting .1 < 5. FT-IR TGA TGA Extraction (methylene chloride) Extraction LC. On the basis of the results obtained as regards morphology.50 1. Carbon black is the sole filler added to these rubber powders (approx. The results hint at the same origin for both types of powder.5 ± 38. HC ± hydrocarbons PPD ± p-phenylenediamine TMQ ± 2.8*10À4 mol/g. Jahrgang.4 16. Morphological characterization and double bond concentration Rubber powder (RP) Median number Gn [lm] Median weight GW [lm] Distribution range V Anisometric factor F Fractal dimension of circumference c Specific surface [m2/g] Type A 284 487 0.71 1. powder from discarded rubber still possesses a primary prerequisite for chemical modification.9 3. 2.4:1. able prerequisites for chemical grafting.7*10À4 mol/g. DSC.5 1. pyrolysis. 8 %) and consist mainly of plasticizers. FT-IR Extraction LC. Chemical composition Depending on aging and comminution process.69 1. the originally unsaturated principal polymer chain exhibits an adequate double bonding concentration.06 0. . This points to a reduction in volatile constituents as a result of aging during use and perhaps also from the crushing and grinding process. the fine-grained rubber powder type D seemed particularly well suited for further study of the morphological aspects of grafting to a fresh rubber matrix.8*10À4 mol/g and 3. FT-IR Abbreviations used in Tab.5 < 2.06 0. Chemical analyses indicate that despite oxidative influences during use and in the crushing and grinding process. Modification of the particle surface of rubber powder Grafting with maleic anhydride Using maleic anhydride (MSA) to produce grafted polymers is.4-trimethyl-1.52 1. in principle.019 Type B 195 331 0. antioxidants and processing agents. The comparative values for coarse-grained rubber powder are 1.7 Method Polymer Fillers Minerals (calcined residue) Extractable parts Plasticizers (hydrocarbons) Antioxidant NR SBR carbon black metal oxide low-molar ingredients paraffinic/naphthenic HC aromatic HC PPD Remark: TMQ TGA . Applying the aforementioned method.4*10À4 mol/g and 1. relative narrow particle size distribution range (homogeneity) and more favorable value as regards particle structure.49 1. The chemical composition of the two rubber powder types A and D is extremely similar. 5/2002 221 . 2. a wellknown method for chemical modification [31 ± 33]. Conclusions drawn from the characterization of the rubber powders The morphological characterization of the rubber powders shows that type D fine rubber powder exhibits the more favor- KGK Kautschuk Gummi Kunststoffe 55.08 0.11 0. Because of its low particle size.4 7.5 1.5*10À4 mol/g respectively.6 7.2 30. 30 %). It is advisable to extract low-molar constituents such as antioxidants from the discarded rubber to prevent any negative impact on chemical modification. blended at a ratio of 2. Tab.2. The chemical composition of rubber powder type A and type D are summarized in Tab. FT-IR Extraction LC. Low-molar ingredients make up the extracted shares (approx.027 Type C 51 77 0.099 Type E 57 88 0. only the finegrained type D rubber powder is used for purposes of chemical modification and to make new compounds. The polymer base in each case is a blend of NR and SBR. namely reactive double bonds in the polymer chain.0 3.076 Type D 54 83 0.2 < 5. double bond content and chemical data. . accounting for a total share of roughly 58 % of the compound.8 29.2-dihydrochinoleine von 1.093 Tab. Nr.1 16.8 < 2.

react with alkylenes Fig. MA is allowed to react with the polymatrix of the rubber powder at a high temperature (approx. 3. the grafting reaction can. Fig. Jahrgang. At moderate speed the rubber powder and MSA are mixed in the mixer in a weight ratio of 80:20. per-benzoic acid. likewise under the reaction of the respective MSA molecule with one or two adjacent polymer chains (Fig. in the case of isoprene or polyisoprene. 2. washed and dried. and the adsorption onto carbon atoms in the a position of the methylene groups. Grafting of maleic anhydride (MA) onto natural rubber Fig. 2a). FT-IR spectrum of hydroxylated rubber powder 222 KGK Kautschuk Gummi Kunststoffe 55. In the case of this variant. b) formation of ether bridges. such as. as. taking the example of NR.Interphase Grafting . It is then filtered and dried. hours-long heating is necessary at a temperature in excess of 100 8C.2-epoxyde is exploited for a concluding hydroxylation with formation of 1. c) formation of tetrahydrofuran groups Epoxidation and hydroxylation Organic per-acid. with the final variant being applied here.2 dihydric alcohol. be conducted in an emulsion or in a solid substance [34]. The literature contains countless published studies on the modification of NR to epoxidated NR (E-NR) [35 ± 37]. Fig. 4. If the oxirane ring is adjacent to a tertiary C atom. with the participation of one or more chains per MSA molecule (Fig. 2b). for example. With the help of FT-IR spectroscopy it was possible to provide proof of the successful grafting of MA at the particle surface on extracted material (vibration band of MA at 1780 cmÀ1). Successful hydroxylation of the rubber powder could be proven by means of FTIR spectroscopy. . Excessively high temperature and long reaction times ± above all in acidic media ± lead to an undesirable ring opening of the epoxies with secondary reactions in connection with the formation of glycols or their ethers (Fig. in principle. Chloroperbenzoic acid dissolved in dichloromethane is added to induce the epoxidation of the rubber powder suspension. Fig. 2 shows two different reaction possibilities that can be expected in grafting MA onto NR depending on the conditions ± e. temperature and radical initiator ± under which the reaction occurs. The degree of epoxidation is essentially a function of the temperature and duration of the reaction and the strength of the organic acid. If carried out in the presence of peroxide. and unsaturated polymers to form the corresponding epoxy compounds. water triggers hydrolytic splitting already at room temperature. The grafting of water onto 1. the solution is precipitated and the precipitate filtered. This reaction involves both intermolecular addition of the ethylene derivative to the polymer's double bonds. Epoxidated rubber powder is thus treated at room temperature with an excess of distilled water for a week under constant stirring. 5/2002 . 3). 200 8C) directly in the kneader for ten minutes. for example. Experimentally the epoxidation of reclaimed rubber powder was carried out in the following way: Extracted rubber powder is stirred in dichloromethane for approx. with little dicumylperoxide (DCP) being added. . 10 hours.g. The manufacture of the subsequent compound occurs immediately after this process. Side reactions of epoxidation. 4 shows the IR spectrum for the hydroxylated rubber powder. After a reaction time of 24 hours at room temperature. To obtain a complete reaction in the absence of catalysts. a) hydrolysis of epoxy to alcohol. Nr.

Ethanol is released in the modification reaction.75 1. In the case of compound 7. While the anhydride molecules of the grafted coupling reagent MA and the rubber powder can be chemically linked to one another by esterification via the bifunc- tional alcohol ethylene glycol. The specified mixing temperature in the kneader is 75 8C. The hydroxyl groups formed can now be of good use in coupling reactions on fresh rubber using suitable agents.75 1. 3.Interphase Grafting . suitable cross-linking systems ± e.75 1. 5 shows the reaction of the reactive TESPT ethoxy groups with filler silanole groups.25 C7 70 ± ± ± 30 ± ± ± ± 4 4 2 1.25 C4 ± 70 ± 30 ± ± 4 4 5 ± 4 2 1. RP IR-g-MA Ethylene glycol MgO MA TESPT ZnO Stearic acid Sulfur CBS Ref. compatibility agents) were made in a lab test mixer (Haake E-380). resulting in the formation of an intermediate reactive product. hydroxylated g ªgraftº (chemically modified) MA maleic anhydride TESPT Bis-(3-triethoxysilylpropyl)-tetrasulfide Compared to extracted original powder.75 1.25 C3 70 ± ± 30 ± ± 4 4 5 ± 4 2 1. the polymer chains of the rubber matrix can subsequently be covulcanized with sulfur and accelerator. the rotor speed 50 rpm and the mixing time ten minutes. 3.25 C6 70 ± 30 ± ± ± ± ± ± 4 4 2 1. In the case of compounds 3 and 4 the compound in the mixer ± i. Pure MA serves as phase mediator. including comparative compounds.e.25 Ref. the hydroxylated rubber powder displays a much more pronounced and wider OH band in the 3000 ± 3700 cmÀ1 range and particularly intensive and broad absorption of the C-O bonds in the 1000 ± 1200 cmÀ1 range. Nr. In a second stage the crosslinking agents (sulfur and accelerator) are admixed on a lab mill at 50 8C with a homogenization time of five minutes. Silanization reaction of silicic acid with TESPT KGK Kautschuk Gummi Kunststoffe 55. This silane is normally used in the preparation of rubber compounds with silicatic (OH group bearing) fillers. .25 Abbreviations: Ref.g. Formulas for the rubber-powder compounds and reference compounds used (all data in phr) Constituent SBR-1500 SBR-g-MSA RP RP-g-MA hydr.75 1.25 C1 ± 70 ± ± ± ± ± ± ± ± 4 2 1. 2 70 ± 30 ± ± ± ± ± ± ± 4 2 1. The conspicuously stepped-up intensity of the deformation bands in the 1300 ± 1400 cmÀ1 range. the compound resulting from the process of modifying the rubber powder with MSA (see ªGrafting with MAº) ± is additionally mixed with 4 phr ethylene glycol 4 phr MgO and 5 phr pure MSA as phase mediator and the standard crosslinking system for six minutes in accordance with Tab.75 1.75 1. . point to broad (C-OH) underground absorption of an increased magnitude. Fig. reference compound C compound RP rubber powder hydr. A commercial bifunctional organosilane ± Bis-(3-triethoxysilylpropyl)-tetrasulfide (TESPT). to cite just one agent ± is available for this purpose [38. The composition of the compounds prepared. The tetrasulfide group of the filler/TESPT reaction product reacts in a coupling reaction. Tab. 39]. 1 100 ± ± ± ± ± ± ± ± ± 4 2 1. Fig.25 C8 70 ± ± ± 30 10 ± ± ± ± 4 2 1. Manufacture of compounds and vulcanizates Compounds E-SBR (Intol 1500) is used as fresh rubber matrix. 5/2002 223 .75 1. is based on the following formulas: The compounds of rubber and rubber powder as well as ZnO stearic acid and. Jahrgang.25 C5 100 ± ± ± ± ± ± ± 4 4 2 1.75 1. hydroxylated rubber powder is bound to the SBR matrix with the help of coupling agents. 5.g. moreover.75 1. Alcohols are reliably identifiable in all the absorption ranges referred to. other additives (e. in certain cases. among other things. on the basis of anhydrides and corresponding acids ± are used for gating modified rubber powders.25 C2 ± 70 30 ± ± ± ± ± ± ± 4 2 1. In accordance with the aforementioned relationships.

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Properties of compounds containing rubber Characterization methods Strain-stress measurements were conducted at room temperature on a universal testing machine (Zwick) with optical length-change sensor in accordance with DIN. be crosslinked with the rubber via sulfur bridges. The conclusion to be drawn is that modification in a solid substance provides a suitable method for grafting reclaimed rubber powder. On the basis of the mechanical data it is also possible to conclude that the incorporation of strictly hydroxylated rubber powder free of silane additives gives rise to a particularly marked increase in elongation at rupture and a reduction in rupture stress. as shown in the case of compound 8. 7. forming crosslinking points with doublebond-bearing types of rubber (NR. 3. TESPT. Influence of post-hydroxylation grafting As mentioned above. While esterification by means of ring opening occurs on the one hand. in a fluid state). 6. G = rubber powder. i = TESPT. In general it is evident that the material's elongation at break decreases with the admixture of MA to the rubber during the mixing process. A further possibility for coupling the hydroxylated rubber powder onto the rubber mix is to use MSA-g-IR (maleic anhydride grafted polyisoprene.). SBR etc. Dynamic-mechanical analyses (DMA) were characterized on select compounds by means of temperature-dependent measurements taken at a frequency of 1 Hz in torsion with ªrheometric dynamic analyzerº (RDA II). Good crosslinking of the whole matrix can serve as an explanation for this. . 6 shows Fig. was used to graft the hydroxylated rubber powder to the new rubber matrix. which is determined on the basis of vulcametric measurements (Monsanto rheometer) plus two minutes. Results of tensile testing carried out on MA grafted rubber powder (S = SBR. The successful chemical reaction between the powder's OH groups and the silane's ethoxy groups could be demonstrated by the ethanol released (headspace-GC-MS). Jahrgang. a bifunctional polysulfidic organosilane. this is accompanied by a marked improvement in rupture stress. on the other hand. The uniaxial deformation was effected at a deformation speed of 20 mm/min. These conditions include. The performance level and the chemical pretreatment were evaluated in all cases on the basis of the tensile strength (rmax) and elongation values (eb) at break. To be sure. This can be explained mainly by an increase in crosslinking points in the rubber matrix. h = hydrose. The highest stress value is delivered by the specimen containing both modified rubber as fresh matrix and grafted rubber powder. 2-mm slabs were vulcanized in a press at T ˆ 160 8C and a press pressure of 180 bar. with the strength level serving as the criterion for evaluation of the interphase grafting. Fig. preferably in combination with vulcanization accelerators (with and without sulfur). Nr. The mechanical properties of vulcanizates based on SBR and hydroxylated rubber powder was first characterized by means of tensile testing (Fig. leading to a certain incompatibility with the rubber matrix. the vulcanizates were subjected to comparative mechanical characterization on the basis of the formulas in Tab. 7). m = maleic anhydride) Results for vulcanizates with modified rubber powders Influence of grafting with maleic grafting In order to determine the influence of certain components. While it is generally evident that silane brings about a drastic reduction in elongation at break. m = maleic anhydride) KGK Kautschuk Gummi Kunststoffe 55. it increases tensile strength just slightly. the readings obtained in tensile testing. the coupling agent's polymer chain can. Unfavorable mixing conditions play a major role in the case of compounds containing rubber. 5/2002 225 . for example. G = rubber powder. a temperature that is not optimum for the reaction between polymer and silane. Fig.Interphase Grafting . The crosslinking time results from the t90-value. . This effect can be attributed to the increase in the powder particles' chemical polarity as a result of hydroxylation. Results of tensile testing carried out on hydroxylated rubber powder (S = SBR.

M. Rubber Chem. 5. p. Cammenga. H. Berlin: Umweltbundesamt.V. È Dr. San Diego: Academic Press. p. N. Vol. Vol. and I. Bruck. Vol. 416. the grafting of maleic anhydride and epoxidation or hydroxylation followed by coupling reactions ± are to be deemed the most promising and suitable processes. II. und J. 1998. Vol. 1960. R. Kluppel.. [23] A. Vol. Affolter. Vol 6. p. p. Isayev. Levin. [26] D. Gelling. Dissertation. 1979. 51. 53. Kautsch. H. 1996. Technol. Vol. p. E. 2001. Kim and A. Abschluûbericht: Interphasenanbindung von Altgummimehlenº. Spittel. p. 173. 1994. Spittel. [31] Y. 1991. Fuhrmann. Vol. p. 1973. 395. admixture of coupling reagents etc. Peterseim and R. Berlin.V. Gummi Kunstst. (eds. (eds.). [25] S. Hemminger and H. 855. 45. 5. [35] A. È 1986. Kautsch. 8 shows the corresponding results. Schmidt. [37] Y. 304. [10] H. [12] R. Kohler. 9. [20] M. p. H. Technol.Interphase Grafting . ªMengen. Pett and D. Kautsch. 12. S. L. 39. 1998. Vol. in Bostrom. [9] W. 5/2002 . Vol.) have a crucial influence on the physical and chemical property profile of the elastomers containing rubber powder. Jackson. p. 437. Olabisi. Kautsch. Schuster. I. È 1998. Gummi Kunstst. in Mark. It is conceivable that a reduction in both the degree of hydroxylation and in the amount of the coupling agent added is necessary to achieve better results. Brazier. [38] U. 1974. Gummi Kunstst. Gummi Kunstst. S. Karger-Kocsis. Kautschuk-Handbuch. p. [4] W. È (DIK)º in Hannover Corresponding author Deutsches Institut fur Kautschuktechnologie e. 18. [28] D. J. Gummi Kunstst. p. 52. Gunther. Hasegawa. Gummi Kunstst. [2] U. 1970. 8. they do apparently allow for grafting the treated powder particles onto the new rubber phase. 2001. p. Schuster. Lugginsland. and S. 1998. 1995. 2. et al.. Kurusu. The specimen with hydroxylated rubber powder exhibits a slightly higher module than the compound with the untreated powder. Vol.). p. Verwertung und Entsorgung von Altreifen in der Bundesrepublik Deutschlandº. V. (ed. 1 ± 2. [24] U. 474. 12. Giese is head of the elastomer chemistry department. 11. Ide. 1165.. [30] W. 5. I. U. Brothers. . NL). D. 513. Kautsch. Hartung. Gummi Kunstst. Vol. Vol.. T. [22] O. Kautsch. 1992. p. M. Fig. [32] F. [6] F. 1. 1969. p. Schuster is director of the ªDeutsches Institut fur Kautschuktechnologie e. Ceresa in Mark. Gummi Fasern Kunstst. [21] R. Gorl. K. 985. Polym. Vol. Kautsch. Gummi Kunstst.. and M. 373. 1989. Ruccan.. p. Weinheim. H. What's more. Vol. Kautsch. 202/203. Vol. [3] H. Gummi Fasern Kunststoffe. Gummi Asbest Kunstst. Massie and R. Rubber World. H. 1997. et al. (ed. Kautsch. Dr. 1999. Vol. 33. Giese. Koch. Vol. È 1988. Cunneen. The authors Dr. 12. a slight upward shift in the rubber matrix's glass transition temperature is also evident. A. Porter. Nicholas. 41. Vohwinkel. H. Halasa. R. p. [18] F.. 909. Uder. Rubber Chem. p. Roûler and H. 1989. 10. M. [27] D. Kautschuktechnologie. Vol. Berlin: Umweltbundesamt. p. 963. Schuster. Vol 13. Chemie. Gummi Kunstst. Vol. The testing and [13] P. p. 50. Leca. New York: Wiley Interscience. 1993. 1997. p. and R. No. Vol. Vol. 1993. Fig. 7. in Morton. Minoura. Schuster. 1980. Acknowledgements The authors greatly acknowledge the financial support provided by the Umweltbundesamt (Berlin) and by Vredestein Rubber Resources (Maastricht.. Klingensmith und K. Bruck. Heidelberg: Springer Verlag. p. 6. J. 3. [29] U. duration of reaction. 1499. Schuster. 836. p. 2000. 41. Sinn. 1982. p. Vol. This can be attributed to the inherent properties of the highly viscous polymer fluid added. Rubber Chem. [17] H. Kaminsky. [39] H. R. U. p. Jahrgang. A. 1998. Despite the fact that the modification variants studied still do not provide a clearly satisfying performance level for compounds containing recycled rubber powder. Gummi Kunstst. p. U. New York: Van Nostrand Reinhold.. Giese Eupener Str. Amash is manager of the processing department and Prof. and J. Reinke. Kuhrcke and R. Kautsch. 1996. New York: Academic Press. 875. 23. Robeson and M. Literature [1] A. È 1996. H. [5] ªBeitrag zum Thema Recyclingº. 356. Adv. Vol. R. 898. Kohjiya. p.e. H. Vol. 747. .1997. Gummi Kunstst. 55. 67. 1993. April 5/6. 106 ff. Shaw. [8] K.. F. 32. Rothemeyer. Giese. Vol. Journal of Applied Polymer Science. (GAK). [36] I. and A. Science and Technology of Rubber. Rubber World. Amash. Vol. p. 48. È 1991. und D. 44. 58. This can be confirmed by the complete results of the physical and chemical characterization. [16] M. 1992. A. Sommer... J. Hashim. Vol. [7] A. p. Rubber World. [15] A. As part of the continuing work on surface modification of discarded rubber aimed at achieving an optimum grafting on a fresh rubber matrix. reaction conditions selected in the pretreatment (temperature. which produces here simultaneously both an interphase grafting and a plasticizers effect. Polymer-Polymer Miscibility. F. it is particularly important to optimize the reaction parameters and conditions of MA grafting and of epoxidation and hydroxylation. Gummi Kunstst. Makromol. Kautsch. Gummi Asbest Kunstst. This points to an improvement in the compatibility of the components and thus in the mechanical-dynamic properties. 669. Summary The tested methods for chemical modification of rubber powder ± i. W. ªKautschukregeneratº. [11] J. [34] J. 51.. 208. Technol. p. Universitat Hannover. 729. Gummi Kunstst. Giese. Journal of Applied Polymer Science. S. Stuttgart: Berliner Union Verlag. P. No. Baranwal. O'Neill. 1994. Angew. Technol. Nr. F. P. Vol.). Kautsch. and A. H. Dr. pp.. [14] V. Vol. È Kautsch. Vol. Encyclopedia of Polymer Science and Technology. 47. D-30519 Hannover 226 KGK Kautschuk Gummi Kunststoffe 55. Kautsch. [33] A. E. Methoden der thermischen Analyse. Gummi Kunstst.). 1625. ªKautschukregeneratº. lecture presented at VDI-Seminar Schadensanalyse. (GAK). 159. È È S. È 46. Theodore. 1995. Mechanicaldynamic results for compounds with hydroxylated rubber powder Adding MA-graft-IR instead of silane greatly increases the vulcanizate's elongation at rupture and reduces its rupture stress even further. The silane vulcanizates manufactured are subjected to dynamic-mechanical analysis. 846.. [19] I. p. Yu. 9C. 896. ªSchadensaufklarung mittels ThermoÈ analyseº. 1986.

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