溶聚丁苯橡胶的最新技术进展2011

IwakazuHattori1,HiroshiTakino1andYoichiroHibiya1

ETICInc.1,NanakuboBldg.3F,1-11-11Toranomon,

Minato-ku,Tokyo,105-0001,JapanE-mail:i_hattori@elastec-intel.jp1.Introduction

TheKyotoProtocolwasadaptedatthethirdconferenceoftheUnitedNationsFrameworkConventiononClimateChangeinDecember1997.Itwasknownthatoneofthecausesfortheabnormalweatheristheincreaseofgreenhousegasemissionssuchascarbondioxideandmethane.Theprotocolrequiresindustrializednationstoreducethoseemissionsbycertainpercentfrom1990levelsduring2008to2012.Forexample,Japanisrequiredtoreducecarbondioxideby6%,andEUisrequiredtoreduceitby8%.

AlthoughtheeffectofglobalenvironmentalimprovementbasedonCO2

reductionoftheKyotoProtocolisdoubted,atpresent,amuchlargerCO2reductionplanthantheKyotoProtocolisbeingseriouslydiscussednotonlyintheUnitedNationsFrameworkConventiononClimateChange,butalsotheUnitedNationsSecurityCouncilandtheSummit,aswellasinternationalconferencesuchastheAsia-PacificEconomicCooperation.

Mattersrelatedtothis,suchasreductioninrollingresistanceoftires,useoflight-weightmaterials,improvementofrecyclability,biofuels,andtechnologytocorrespondtobiomaterialsaresomeoftheimportantthemesfortherubberindustry.In2010,inordertomakeiteasierfortheconsumerstounderstand,labelingregulationwhichisthetiremanufacturers’voluntarycontrolforlowrollingresistance(AAA,AA,A,B,C)andWetGrip(a,b,c,d)oftirescameintoeffect.ThevaluesofthetiressoldinJapanbasedonthetirelabelingregulation1areasshowninTable1.Althoughthedetailsofthetechnologyarenotmadepublic,thebasictechnologyforobtaininglowfuelconsumptiontiressuchasAAAandAAistheuseofterminalmodifiedS-SBR,highdispersionmethodofcarbonblackaswellasmasteringofsilicacompounds.

Inthisreport,authorswouldliketointroducethisbasictechnologyofchemicalmodifiedS-SBR,modifiedSEBSwhichisahydrogenatedpolymerofSBSproducedbysimilartechnologytochemicalmodifiedS-SBR,andhighcisBR.

Table1:TypeofTirebasedonTireLabelingRegulationinJapan1

TireMakerGoodyearDunlop

TypeofTireEfficientGripENASAVE97ENASAVERV503ENASAVEEC202

Bridgestone

ECOPIAEP100SECOPIAEP100ECOPIAEX10

Yokohama

BluEarthAE-01DNAEarth-1

Michelin

PrimacyLCENERGYSAVER

ToyoTire

SUPERECOWALKERECOWALKER

TireSize

185/65R1588H～205/60R1692H185/65R1588H～195/55R16175/65R1482H～225/45R19145/65R1369S～215/55R1794V185/65R1588H、195/65R1591H2Sizes

155/65R1373H～225/45R1891W155/65R1373S～245/45R1998W145/80R1375S～215/60R1695H155/65R1373S～245/35R2095W195/60R1588V～245/45R1998Y185/55R1480H～215/60R1699HXL195/65R1591HOneSize155/65R1373S～215/55R1794V

RollingResistance

WetSkidResistance

Filler,PolymerSilica,SpecialRubberSilica,Epoxy-NR?,ModifiedSBR?,MultimodifiedSBRC.B.,ModifiedSBR(NanoPro-Tec)C.B.,ModifiedSBRSilica,ModifiedSBRSilica,HighMwSBRSilica,ibidSBR+NRFullSilica,?FullSilica,?Silica,SuperActiveSBR

CB+Silica,ibidSBR

AAAAAAAAAA～AAA～AAAAAAAAA

bbccccbcb～ccccc～d

2.TrendofChemicalModifiedS-SBR

Inthispart,authorwouldliketointroduceindustrializationorchemicalmodifiedS-SBRtechnologywhichmayleadtobreakthroughforindustrialization.TrendsoftheseS-SBRsareshowninFigure1.

１９８０１９９０２０００MichelinTirewithSilicaCompoundChemicalModifiedHV-BR,SBRForSilica&C.B.２０１０SBR+Smog+Photochemicalsmog+OilcrisisChemicalModified1975;CAFE,USA,HV-BR,SBRCorporateAutomotiveforC.B.FuelEfficiency1992ChemicalModifiedHV-BR,SBRForSilicaBRTi-BRCo-BRNi-BRNｄ-BRChemicalModifiedNd-BRSBSSEBSTiHydrogenationCatalystforSEBSPolymerEndModifiedSEBSSIBSFigure1:TechnicalTrendofPolydiene

2.1ChemicalModifiedS-SBR

Tireswhicharethelargestapplicationofrubber,arealsorelatedtothepreventionofglobalwarmingup,andbecauseoftheseverefuelconsumptionregulationsforvehiclesinJapan,Europe,andtheUnitedStates,studieswereadvancedonreinforcinganddispersingcarbonblackparticleswithevensmallerparticlesizesothatlowrollingresistanceandwetgriponwetroadsurfacewillcoexist,hasbeenthetrendsincetheoilshockinthelatterhalfofthe1970s.Againstsuchrequirements,inthe1980s,amongvarioustypesofsyntheticrubber,solutionSBR(S-SBR)whichallowsmodificationofthechainatbothendsbecamethecenterofresearch2.Startingfromaround1990,S-SBRremainedasthebasicrubber,butthecenterofresearchmovedtosilicacompoundsinspiteofproblemssuchascostandprocessability,becausetheyrealizedlowrollingresistanceandgoodwetgripincomparisonwithcarbonblack.Bothsilicaandcarbonblackrequiredstrongerreinforcement,andinearlypartofthe2000s,anexcellentS-SBRwasdeveloped.Morikawa3andothersstudiedseveraltypesofS-SBRthatintroducedfunctionalgrouphavinghighcompatibilitywithsilicaatinitialpointofpolymerization,chainend,andbothendsofSBR.Incaseprimaryaminogroupandalkoxysilylgroupareintroducedtotheterminatingend,itwasreportedthattherubberboundtosilicaandcarbonblackincreased,andtanδnearroomtemperaturewhichcorrespondstotherollingresistanceofthetires,andwearresistancewereimproved.Hayashi4andothersanalyzedthepolymerizationbehaviorof1,1-diphenylethylenederivatives,andbymerelychangingtheamountofmonomeradditionandthenumberoftimes,proposedamethodforintroducingfunctionalgroupstonotonlyoneendorbothends,butalsotoanarbitrarypositionintheS-SBRpolymerchain.

2-2.ChemicalModifiedHighcis-1,4BR

UnlikeS-SBR,itwasconsideredforalongtimethattransitionmetalcatalystsusedfortheproductionofhighcisBRhadnolivingpolymerizationproperty,andchainendmodificationcannotbedone.However,whenthepolymerizationbehaviorofNd-BRhavingpseudolivingpolymerizationpropertywasanalyzed,itwasmadeclearthatchainendmodification5waspossibleinthecaseofhighcisBRaswell,andindustrializationofBRwhichisbelievedtobeanapplicationofthistechnologyisreportedbyTadaki6.ThisBRhasimprovedprocessabilityandabrasionresistance.2.3ChemicalModifiedSEBS

SEBSexcelsinheatresistance,weatherability,andrecyclingproperties.Itcanmodifypolyolefins,anditisalreadyusedinautomotiveparts.

However,sinceSEBShasnomodifyingeffectonpolarpolymerssuchaspolyamideandpolyester,itwasmadeintoafunctionalgroupbyaddingmaleicanhydridetothesidechainsofSEBSbyradicalreaction.Inthiscase,compatibilitywithpolyamidewillbeimproved,butsincethenumberoffunctionalgroupsandmolecularcrosslinkingcausedbysidereactionscannotbecontrolled,therewastheproblemoftheflowbecomingextremelybadafterthemodification.Thus,afterproducingSBS,functionalgroupsthatwillbecome–COOH,-NHR,and–OHwereintroducedtotheendofthechains,thenhydrogenated.Asaresult,modifiedSEBSwasdeveloped.ModificationofpolylacticacidandPET,andnanocompositingofclayhavebeenreported.7Althoughdetailsareunknown,itissaidthatmodifiedSEBS8withexcellentperformanceascompatiblenessagentforPET/PPhasbeendeveloped.References

1.CarWatchH/P:http://car.watch.impress.co.jp/docs/special/20100709_379272.html2.GomuGizyutsuForumEd.:“GomuKougyouniokeruGizyutsuYosoku”,PostyCorp.,Tokyo(1990)

3.A.Morikawa,T.Sone,M.Shibata,andT.Tadaki:PreprintofIRC2005Yokohama,PaperNo.26-S1-I-01(2005)

4.M.Hayashi,K.Inagaki,A.Imai,andA.Hirao,：NipponGomuKyokaishi,78,91(2005)

5.I.Hattori,F.Tsutsumi,M.Sakakibara,andK.Makino:J.ElastomersPlastics,23,135(1991)

6.T.Tadaki:NipponGomuKyokaishi,76,441(2003)

7.K.Kato,M.Fujiwara,andY.Araki,:JETI,54(12),85(2006)8.I.Hattori:SettyakunoGizyutsu,25(2)12(2005)