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  MATERIALE PLASTICE ♦   50 ♦ No. 2 ♦ 2013http://www.revmaterialeplastice.ro 137 Maleinized Linear Styrene-butadiene Block-copolymers LORENA IANCU*, PAUL GHIOCA, BOGDAN SPURCACIU, RAMONA MARINA GRIGORESCU, CRISTIAN-ANDI NICOLAE,RALUCA AUGUSTA GABOR  National Institute for Research & Development in Chemistry and Petrochemistry - ICECHIM, 202 Splaiul Independentei, 060021,Bucharest, Romania This paper presents the maleinization study of linear styrene-butadiene block-copolymers carried out in solution by radical mechanism.   The vinyl microstructure effect of the polybutadiene block on the kinetics reaction was established and the physical and mechanical properties were correlated with the maleinization degree of the elastomers. Keywords: styrene-butadiene block-copolymers, maleic anhydride, functionalized block-copolymers The styrene-butadiene block copolymers (SBS) withpredominantly content of diene, show vulcanized rubberproperties, at ambient temperature. This behaviour is theresult of thermodynamic incompatibility betweencomponent blocks, achieving a segregation of dispersedpolystyrene blocks, in the form as domains in continuouspolybutadiene phase, thus ensuring physical crosslinkingof the elastomer at ambient temperature. The styrenebutadiene block copolymers show thermoplasticsproperties at temperature higher than the glass transitionof polystyrene phase, so they can be processed in similarconditions to plastics [1-3]. These properties have allowedthe use of elastomers in different plastics modification,especially for their poor impact strength improvement [4,-6].In order to enhance theperformance of blockcopolymers in polar plastics modification we consider theincreasing of their compatibility degree, by introducing of polar groups in polydienic block, which is the continuousphase in direct contact with plastomers.For increasing of SBS polarity post-polymerizationmodification is used, especially through polymer-analogousreactions like: grafting [7], epoxidation [8], sulphonation[9], halogenation [10], both in solution and by mechanical-chemical grafting directly into the extruder during themodification process [11, 12].The maleinization is one of the frequently used processesin the modification of elastomers like: natural rubber [13],polyisoprene, polybutadiene, styrene-butadiene blockcopolymers [14], styrene-isoprene block copolymers [15-17] and in some plastomers functionalization (polystyrene,polyethylene, polypropylene [18, 19]).The grafting of styrene-butadiene block copolymers withmaleic anhydride occurs by radical mechanism [14, 20].In literature are presented both the grafting mechanismand the influence of reaction conditions: concentration,structure, and position of the grafted anhydride, dependingon the used method (solution, melt state and solid state), * email: lorena.iancu@icechim.ro; Tel.: 021 3163096  and the temperature, pressure, concentration, solvent,additive, etc. [21].The maleinized styrene-butadiene block copolymersused in the polyolefin composites improve the impactstrength by compatibilizing effect. Experimental part The   linear styrene-butadiene block copolymersweresynthesized by anionic sequential polymerization of themonomers in solution.In order to obtain materials withimproved properties SBS was chemical modified by introducing polar functional groups, through radical additionreactions which occur preponderantly at the vinyl doublebonds [22].Two types of linear block copolymers SBS with different vinyl microstructure were used in the maleinization study, whose properties are shown in table 1.The functionalization reaction of the styrene-butadieneblock copolymers with maleic anhydride (MAH) wascarried out in butyl acetate solution using 2, 2 ' -azo-bis-isobutyronitrile (AIBN) as initiator. The plant consisted in areactor with three necks, equipped with thermometer andstirrer, immersed in an ultrasonic bath for keeping thetemperature constant.The maleinization process in solution was preferable tomechanical-chemical modification because the secondary reactions that could disturb the proper correlationsbetween the maleinization degree and the properties of modified block copolymers can be avoided.The following parameters: reaction time, anhydride andinitiator concentration  were studied in the chemicalmodification of block copolymers with maleic anhydride.The block-copolymers were dissolved in butyl acetate,at room temperature, then maleic anhydride was addedunder stirring and when reaction mixture was heated at75 o C, the initiator (AIBN) was added under stirring and thetemperature was kept constant for maximum 8 h. Table 1 PHYSICO-MECHANICAL PROPERTIES OFSTYRENE-BUTADIENE BLOCKCOPOLYMERS  MATERIALE PLASTICE ♦   50 ♦ No. 2 ♦ 2013http://www.revmaterialeplastice.ro 138 The unreacted maleic anhydride was removed by precipitation in isopropanol and dissolving in butyl acetate.The procedure was repeated three times for a moreadvanced removal. At the end of reaction was dosed amount of 1% (withrespect to elastomer) of 2,6-di-tert-butyl-4-methylphenol(TOPANOL OC), in order to stabilize against thermal-oxidative degradation and finally the polymers were Fig. 1. The reaction scheme of SBS maleinizationFig. 2. FT-IR spectra of styrene-butadiene block copolymer with 10% vinyl (SBS 10)Fig. 3. FT-IR spectra of maleinized styrene-butadiene blockcopolymer (SBS 10 MAH) precipitated in isopropyl alcohol and dried in an oven underreduced pressure, at a temperature not exceeding 60 o C.Figure 1 shows the scheme of the SBS maleinizationreaction [23].The initial and maleinized SBS molecular weight wasdetermined by gel permeation chromatography (GPC). Thephysico-mechanical properties were determined onpolymer films obtained by centrifugal casting from toluenesolution using a FPZ 100 Dynamometer, with an elongationrate of 500 mm/min, according to the specificcharacterization requirements of styrene-diene blockcopolymers.The maleinization degree of SBS block-copolymers wasinvestigated by Fourier Transform Infrared Spectroscopy (FT-IR) on a Perkin Elmer Spectrum GX device, equipped with ATR, in normal conditions [21].The DMA characterization was carried out on a TA Instruments DMA-Q 800 apparatus, according to ASTM D4065 standard, at 1 Hz frequency, a temperature range of -120-180 o C with a heating rate of 3 o C/min, in air. Results and discussions The maleinization of SBS block copolymers was carriedout at 75 ° C, the reaction time being varied between 1 to8 h, using the following formulation:100 g SBS was dissolvedin 1 L butyl acetate then 2,5-5 g maleic anhydride wasintroduced next 2-7,5 g AIBN.Figures 2-5 show the FT-IR spectra of SBS andmaleinized SBS.The FT-IR spectra of maleinized block copolymers SBShave revealed the elastomers absorption bands (figs. 3 and5):- 690 cm -1 for polystyrene;- 730 cm -1 for cis-1,4 bonds of polybutadiene;- 910 cm -1 for vinyl bonds (type 1,2);- 965 cm -1 for trans-1,4 bonds of polybutadiene.There were also visible the polar groups specific bands,especially noticing the appearance of the characteristicabsorptions of carboxyl and carbonyl groups, as can beseen in figures 3 and 5.Introducing of maleic groups in styrene-butadiene blockcopolymers leads to an increase in glass transitiontemperature for polybutadiene phase by macromolecularchain stiffening, as can be seen from table 2.The glass transition temperature decreases forpolystyrene phase indicates a less advanced separation of these domains from the polybutadiene matrix. Thismorphological change is a consequence of increasing thetwo phases compatibility due to maleic groups presencein the elastomeric block. Fig. 4. FT-IR spectra of styrene-butadiene block copolymer with 35% vinyl (SBS 35)  MATERIALE PLASTICE ♦   50 ♦ No. 2 ♦ 2013http://www.revmaterialeplastice.ro 139 The research aimed the obtaining of some blockcopolymers with maximum 1% maleic groups, beingavoided accentuated modifications in mechanicalproperties of SBS elastomers, changes which could limittheir field of application. As expected, the increasing of maleinization degree withreaction time and initiator concentration was confirmedby the reaction kinetics study of styrene-butadiene blockcopolymers modified with maleic anhydride (fig. 6).The preferential enchainingin 1, 2 butadieneposition(SBS 35) facilitates the maleinization reaction, inaccordance with the mechanism presented in figure 1, Fig. 5. FT-IR spectra of maleinized styrene-butadiene block copolymer (SBS 35 MAH) Table 2 GLASS TRANSITION TEMPERATURES OFBLOCK COPOLYMERS, FROM THE DMA DETERMINATIONSFig. 6. Variation of maleinized degree depending on reaction timeand AIBN concentrationFig. 7. Variation of molecular weight of maleinized block-copolymers with 10% vinyl depending on reaction time and AIBN concentrationFig. 8. Variation of molecular weight of maleinized block-copolymers with 35% vinyl depending on reaction time and AIBN concentrationFig. 9. Variation of tensile strength of maleinized block-copolymersdepending on reaction time and AIBN concentrationFig. 10. Variation of elongation at break of maleinized block-copolymers depending on reaction time and AIBN concentration  MATERIALE PLASTICE ♦   50 ♦ No. 2 ♦ 2013http://www.revmaterialeplastice.ro 140 leading to higher increase of reaction rate and thereforesignificantly increase of maleinization degree.From the kinetic study was found that AIBN scissionrate is not dependent of its concentration in the systemand after 6 h, the reaction rate is limited due to initiatorconsumption.In the used synthesis conditions, the number of macromolecular chain scission reaction is low, but acorrelation between the decrease of molecular weight andthe initiator concentration can be observed, as shown infigures 7 and 8.The polar groups presence in polybutadiene chaindisturb the block copolymers morphology, by modifyingthe phases separation degree (evidenced by higher glasstransition temperatures) and by decreasing theentanglement, which leads to tensile strength andelongation at break diminution for maleinized elastomers(figs. 9 and 10).Introducing of polar groups in polybutadiene chain leadsto its stiffening, the phenomenon being evidenced by hardness increase of the modified block copolymers incorrelation with the maleinization degree, as can be seenin figure 11. Conclusions The modification study of the styrene-butadiene blockcopolymers by radical grafting in solution, emphasized thefavourable effect of increasing the vinyl microstructureproportion in polybutadiene block, manifested by a higherreaction rate and maleinization degree. This observationis an additional argument that sustains the reactionmechanism, which indicates the preferentially free radicalsattack to the 1, 2 double bond of polybutadiene.The influence of the maleinization degree on physicaland mechanical properties of modified styrene-butadiene Fig. 11. Variation of hardness of maleinized block-copolymersdepending on reaction time and AIBN concentration block copolymers in correlation with their vinylmicrostructure was established.Finally, we can conclude that dramatic variations of physical-mechanical properties are not produced to amaleinization degree up to maximum 1 %. Therefore thecurrent field of application of block copolymers is notaffected, moreover this can be extended by a more efficientmodification of polar polymers. References 1.HSIEH, H.L., QUIRK, R., Anionic Polymerization, Marcel DAEKKER,New York, 2008;2.HOLDEN, G., LEGGE, N.G., SCHRODER, E., ThermoplasticElastomers, Hauser Publishers, Viena, 2006;3.CRAVER, C.D., CARRAHER, C.E., Applied Polymer Science, New York, 20004. GHIOCA, P., IANCU, L., SPURCACIU, B., COSEREA, R.M., CINCU, C.,GARDU, R., Mat. Plast., 50 , no. 1, 2013, p. 325. GHIOCA, P., BUZDUGAN, E., CINCU, C., SPURCACIU, B., IANCU, L.,ZAHARIA, C., Mat. Plast., 44 , no. 3, p. 1276. GHIOCA, P., BUZDUGAN, E., CINCU, C., IANCU, L., ZAHARIA, C.,ZECHERU, T., Mat. Plast., 44 , no. 3, 2007, p. 1757. BHATTACHARYA A., MISRA B.N., Prog. Polym. Sci. 29 , 2004, p.767;8.KHATIWADA S. P., YADAV A. P., LEBEK W., SAITER J. M., ADHIKARI R.,Bibechana 9 , 2013, p.50;9.HWANGA H. Y., KOHA H. C., RHIM J. W., NAMA S. Y., Desalination, 233 , 2008, p. 173;10.BUZDUGAN E., GHIOCA P., STRIBECK N., BADEA E.G., SERBAN S.,IOVU M. C., Eur Polym J, 34 ,10, 1998, p.1531;11. MAURANO C. H. F., PORTAL L., NETO R. B., MAULER R. S., PolymerBulletin 46 , 2001, p. 491;12.LASALLE V.L., FAILLA M.D.,VALLES E.M., CEPEDA-JIMENEZ C.M.,TORREGROSA-MACIA R., MARTINEZ J.M.M., MARTINEZ, J. AdhesionSci. Technol., 17 , 12, 2003, p. 1713;13.   SAELAO J., PHINYOCHEEP P., J Appl Polym Sci, 95 , 2005, p.2814.AIMIN Z., CHAO L., Eur. Polym. J., 39 , 2003, p.129115.MITOV Z., VELICHKOVA R., Eur. Polym. J., 29 , 1993, p. 597;16. MITOV Z., VELICHKOVA R., Eur. Polym. J., 29 , 1993, p. 603;17.MITOV Z., VELICHKOVA R., ZLATKOV T., Eur. Polym. J., 29 , 8, 1993,p. 1129;18.KARIAN H. G., Handbook of Polypropylene and PolypropyleneComposites, 2nd ed.Marcel Dekker: New York, 2003;19. RZAYEV ZAKIR M. O., Int. Rev. Chem. Eng., 3 , 2011, p. 153;20.CHAO L., XU C., QIJIA H., AIMIN Z., Acta Polym Sin, 1 , 6, 2002,p.791;21.ROOVER B., SCLAVONS M., CARLIER V., DEVAUX J., LEGRAS R.,MOMTAZ A., J. Polym. Sci, Polym. Chem., 33 , 1995, p. 829;22.CIARDELLI, F., AGLIETTO M., PASSAGLIA E., PICCHIONI F., Polym Advan Technol, 11 , 2000, p.371;23.PUCCI A., BARSOCCHIA C., RAUSA R., D’ELIA L., CIARDELLI F.,Polymer, 46 , 2005, p. 1497Manuscript received: 19.03.2013
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