SIGH TEMPERATURE BLOCK Cβf ^s 0t¥ME!$S AMI PROCESS FOR MλKJN€

he .

Ths& hivsuiion relates ϊo isovcl pol^mαn^uon processes to prepare alpha-methyl- stymie (aMS) / stvraiε ϋ ^' S) coμoiymws and blo-ek copolymer comprising the ssrne io which high eom-Tfskjm of &MS art.- achieved. The invention also relates i& &ϊ8&t&tnvήc block copolymers comprising aMS J ¹ S hi oeics having high ul;ss,s Sxamilion temperatures. The invention further r&lsu.s to compcursds which deffioαslmte excelk i high ^mperatare pcfioπϊϊMet;.

(a.K-IS) is a Leehnαiogically interesting monomer fbr bo moor trϊkndtioo temperature rig} of the pohrrjcrs ineoϊpor&tmg it. Inclusion of aMS US a cmusirLonier wjth monomers such as styrase a!i«.nvς uiilorϊng of the Tg of styrsajc blocks This is particularly sint&ble in ari ionic polynitrii'.aLions where both ^MS aixi styreae rs&dUy polymerb'e. Funher, such high glassy bluic ^' ks. can He expected k> iEo-cs&e the service c?f tliermopk&ϋc block inio which they are incorporated,

Om? well kiiown p^bkm su?weiated wύh aMS polymers is their low cdHog ^; en>peraiϋre ⁽ Tc). The cεslbg iempennute is tbe ξemperamre above whsch a polymer can spoMan£*jQsiy This presents a probletn during polymenzatioω wfei-rt n ^; u« bt- careftrih oishuamed bebw Te Further, m tsfeateci lernpersurro appjicLuitms sMS above Ts oneo decomposition is iβ to copolymerize aMS vviih high Tc Sue)? ϊS the case with copolymers of aKiS miά tyrene,

λ-s second problem, ^sMS pelyrnors, pM>f iύarly copalymu^ wϋk mimovmyl-mvm&xk; moωOϊωώrs, in which high eotsivmams of ϊSMS are ^ad

axp&sisive recycle openusorux Also. in black copolymer! zatkπi e.ffsekmt eatmimptkirs <A the aMS monome? can prevent eomammatiori of noo-ghssy bbel;$ -with, the high Tg ^KtS,

Block copolymers have previously been prepared comprising aMS^ ^' S esxib locks as lauglu m GB Fsfenl 1,264,741. The polymerization was coMueied to syntheske blocks having * andoml;y uisfcibut'ed cosTsoπomtTs, ?hs ^) assy sndhteeks of ihes« block copolymer comprised a majority of mMS aικi hetweeβ IO ami 40 md\% of sfyrene moiwrπer. vv^x conducted at eoki or cryogenic temparaiures from -K) IΏ -HIO ⁰ C

Tapered hlock copch^er$ eorstsmmg aMS liave be^ii Uωght m US PMSΏJ 4 _V 42TJ1> 1 The process taught thcreisi suffered from coriYtTβkms of kss thsn 10% of the aMS monoϊTisrr. T ^' ^us.. large ^cesees of aMS monomer vv«ϊ'§ reqaheu to iricorpyust^ modest imiouBls In the fkml pcsiymcr, Reeuvery of £he uBpdym^ri^ed aMS moτκ;n$cr presents a sigm flcasit practical problem,

F ^: ul!y hy<1rog®naϊed styreωe/aMS-Xlieae block eopolysners have bettsi taugh?. in IJS Parent Application 2005/006.1UV^, §m&ll rnioimis o.rp<. _* Iή.r co-soivent were wtili;?e<.1 hi order to liowever, ilύ& ■.sroeess also suffered from very low convert sons of the aMS monomer.

^' Thsre .yet. exists a nee<] to? a proex*? ^; ϊo eopolymcrke a.MS ■ ^■ ' ^' mor^winyl-aromaiic i^onorøers which can he corseted ;*t praeucul |K5!y3i"ssπ.?αtk>u ^mperatKres and which ?ιeine\es high coϋvsi^iou of ?h%? aJVfS s^oπomer Such ;'i pmcess will allow the coϊsstrucϋon of block copulyme^ h;mng high Tg glassy bkci<s and s^eh blosk copolymers will b& ^e ⁽ b ^ m makisjg high sendee? tempemnsre mhbcr e<.>mpoιm<b. The prs&ent :rϊvenϋθ5i is dire ted k> suc-b a process, high Tg bkκ\k copol>^ers aad rαbber cwrsjKJunda made from them.

In OTS e th^ ιτivετnioπ JS a process for the p5"φai;nh">ϊi of block copo!>iiiers, untά bloek copolymers made by ihe process, comprising adding slpka- copolymen/a?mn step, ihc sotidβ coutc«ι 6Όπ? 20 to 50 wl" _β such that ihe cosiCcrArador _* of H vim _?

polymeo-ki chain esids is from 50ft So 2500 ppm and wherem the amount of alpha - metbyksϊymnit is from 25 to 50 m»!% OB ihe basis of the fciUil amount of ^yrene and alpha-in^hyl-^tyts-se: adding $ p«!yniεrø.&tιø« modifier, ;κkkng an stύotύc mono ^s £τ continuously slid ccφ©!yni<?τix.ιn§ ssid styrcnc and uljsl^s^eth-yi-styeene to i&nxi a ijvsn^ glassy bkx-k at a teropsralure from ?*5 u> &) ^' "C wherehi sakl oiψoly.medgallon is conduct in such a -manner as to nmmtaks a high cønccαtrauon of a!ph&--meth>1- ^< ity?eoe pslauvs ^o scyneαe for the majority of tte copolymeπzarion ac-bievmg st bast 45% adding & conjugated dkmsϊ or a of eoajug^fed dis-nes, snd ρcd>it>eri?i^g said co^j αgat?;d dione or mixturt: <sf co?\|^ga?e<J diftues Io ϊbsiTs a living dsstomerk blo-ck wherein the ^0*-k hi a aooiber embodiment ths invention, is ao ela≤tome-iic comfx>sinon coϊupϊi^srϊg * block copolymer kiviag at Jea^t am- gb&sy bk>ck coαβj&tjrig of a mixture o! siyrem; and is (ix>m 23 to 50 mo!% on the basis of lho toϊol amotmt of in the yjaxsv hk>tk awl the peak molecular weight of ώe glass block is ,lϊx>«s 2,000 k> 30 _V 000 g/mc>l. asxi at k^f one tlasiomcrϊc block comprising s con _. iBg»r.sd ^iene or a mmαre of cα^iuga^l dienes wherein the ^lastomen^ block Kas a molecular w&igM iroiπ 2ik0lK.* so 300.0QD g.'mol and ihe amount &i ^' th& gi&ssy block ss from 10 to 40 \$\% md &n olefπ? p«!y5i"ssr or

ITS a further embodsmem the mv«^tκsn is ;s selectively hydrogemned elascomeric biock cop-ohm^ conipαsuig M least one gbs^y block asd a? leasi one efeton-scnc block wherein the ^las^y h\ ^: ,κk \s n copolymer of MI ylpha-alkyl-Yinyl-ammsπtr and morøvmyl- urwϊi&Uc oκ>oov?>e.fs and whttre ih«? mobr ratio of alpha- alky I -vinyl -arorυauc «\o«oo^er to αsonoviuyl^ϊromaiic nvaπomer is from 1$>1S to SO/SO, the d&stαmsrric biock i^ a bbck of at lcaxi one polymerized coηϊrsgs!t;d cik-Ti«- having a vinyl coistøα Ik* sn tetweeα 20 to 85Vs>, srώsequem to- hydxogsn&tton irut^ 0 u> aboαl 10% o£ tb-e ^e^e double bonds in the glassy block Imve been reduced UJKI at tesst Ot^i oi ^' tbt; conjugated double bonds have been ?£-dit«ed, each glassy block ba& ts peak weight from 2,OfX) to ^" HK(K)O g^tsoJ and e&ύh ^osght from 20,000 to 300,000 g--mok

copolymer mass _* and th*c glass transition temper&lure oftbes gi&ssy block ss from 120 to 14ø°C.

Figure I h a GPC chrυrnatogr&m of inventive polymer 5 from Example U.

IMsliiiiJltiiiiiitlMMAfJiiitiilM

The process of the _* present uweatkssi is a unique polymen&atiεm process asd moBovisyi- srom&tie copolymers ano: h!sχ;k copolymers euruairsmg tb-m. Th« general features, σf anionic pofysrseri^uUOB _^ for e,κamp!s solvents, issiosiors, sxiά cosspling &gsnts _x m&y be ώvo^vc α>mαnørm ^> f ϊϊddjisoα schema solids cosilai^ msge, preferred copolymerizsrbn Icmpcrsiures and polar αs-solvems among other ieafures described herein,

M ψ&rtitiύ&r, the inventive process is αtϊhzed to synthesize therøiopkstic block copoϊyTners having high glass tr&usitioa teβperatαre fTg) glassy blocks. As used teτi.α ^iv themx>ptetk; bfock copoly^ner" Is defined as a block copolymer having &t Wyst θϊ>fe elass-y bk>ck geiieisHy ρolyme?ized katn alpBϋ-a!i^1-viay|~aroorødc and monovioyK aroin&dc nujnoBiers waύ ui least from one or more clienes. The prsssm invsnno« incbjdcs a thermoplastic block copolymer eomposif ioα,, which may be a deblock, ϊridlαck copolymer, or rrsulti-bbck cαrrφo&iiioo. ϊΆ ih& case of the diblock eopfjlyrωήr α>mps.sssdor!, one block is tbe glassy copolymer block ami the second po!yϊ-aer block is d&sto.rnerix atπi is s«bstsnbaUy eomøosed of eønjjugated di«>s, IB the ease of tbe tribiock coϊtipOsuicju, it comprise glassy erjdbloc-ks as'ϊd άsi elusiomerie rnnlbloek. Where & inblotk eopolyjner composition is pfeparetl ihθ conjugated diene block can b« designated as "B and the ajphu-&ikyl-vmyl-;u ^" om&tk •• ^•' monovirsy}-&rom^Hc blocks designated as 'VV" χχιύ "V\ The A-BC tnhlock eomposifiorsβ can be made by ^β ciiueniuU polyosen^ation, λ-B-λ frsbiøek Gonipositioss^ cars b^ ni^.le by eαiφiing livin λ-B hi addksors tύ ϊbo hnesr mbioek eonfigurabons, she blocks e&5i be. srructoed jo form a radish (br^nchodl oolymer. I ₁ A-BkX, or bt>tli iype^ of sir5ictuτ«s c^ be eomhmod In a raixturs Som^ A-B diblock polys

As defined herein, a high Tf value means having a glass transition tesmpeϊiMure greater than 100 ^C C. Typically, Myn-nie polymer*, inc. lisdrng :«yτeme bJoek copolymers hsiVβ s gfossy block Tg value approaching !Cs(I ¹ C. Che ob|ett td ^' thc present mveniion is io construct bUxk ecsp-tdyraers having gl&ssy blo-cks comprising ;dphsκsil;yl"viriyl" aromatk . ^■ ' vhwl arornaiie ecφolYrøtsf blocks, having a giuss tr&srssuoft temperature g.rs;der ih&& thϋt s ^" ^«o!Uπ« m a. JϊKϊSIO vinyl- sfornstk homopolyr^er block. For hisijmce, ^esar !00 ^' "C, monomer such as alpha- meλh>i^tyτene oar _: k';ad to i«e?e&st.-s ss l^rge as 4(> ^ύ C In the present mvcntiosu tkz copolymer block compri^πg siphf^alkyi-vinyi-aromatic j-αisd ^aonox'i^y^aromsdc monomers h«s & value irom 120 to !40 ⁰ C, Prefeited axe copftiyτrs$r blocks having Tg v&ϊues ih>m 130 to 140"'G

The mosomtxs liδcd in tfe pølvτn«π?.uikm process of lhe present invention include a!pha»alky!-- v myi-arcvmattc monome-rs dieoes. The alpha- aikyl-vinyl-amm&tsc monomer can be selected from alρha4nethyI-s^yτene {aMS), a!ρh&-ethy1 s^yrene aftd s^bsiiϊute-:! slphs-^lkyi ^lyrenes such as (aMS? is ihe most, preferred The mono vinyl- aromatic raosomer caa he s«?iect€<i Ikxm styrϋπe,. an<i para-iferl-bistyl styτ-eπe or nnxkϊres tKareof. Of the^e, slyrene is xr^ost prcfciϊctl axjd s& commercially av^ϊkble, and s-elatsvely inexpe«six->s, from a The conjugated dieses for use herein are O4>ut;κtsene ami sufeUkUsti butadienes such a.<; sϊoprene, piperyleac, 2,3« diϊTιeϊhyi-L3-b«iadiene _x a5-κl l-phsn>l ^» l ,3-bLuadiene _; or mixtures ϊherrjof. Of these, i J- bαuidsofie satd s&opreπs are most preferred. A-S used herdn, and ihe el;iim§, 't>uiadiene ^{^} refers specs Ilea ily io ' ^* ! ^butadiene", lite doc-≤ sun reuse r the living ;m ionic -cbaui eod ϋf fe foπning polyiner, is ea&sly hsϊKU^i in ^ζ mmnt ^j ckil poly^ierszadon units, tod offers Uis appropriate s-okhdiiy chaTacknsucs lor ihe pmdiset poly ^p λtr. For exaπψkx tϊoπ-polar aliphatic whicti are used ∑ϋ-≤: cyehe &ikaBδά, such s:s eyebhexanc cvelohepiane, and

eycJooetaoe.. all of which ;ire rehniveϋy no^-pofe Other suitable solvents will be knows to OωC skilled in ihe an and can be sdoet&d to perform ϋffoetjvdy m & given set of process conditions, with temperature being one of the major factors taken isto consideration.

Anionic polymerisation initiators in tbe pre^nt invent JOB include, for exssτspk% alkyi lithium compounds arxi other organofkrshini compounds such as s4ustylHthknn, si~ binyfiiiMnm, t-h-utyllithn-ms, ^■ iϊnyUϊthium ami fee like, iactudiag <^ .in.it i stars such as fee di-^ee-hutyi Hlhunn adtfees: of «>dnsoρropeϊϊyl beniHtαis, Other such di-irsiti&tors i«~e di?slv>sed m U. S Pat Nd. 6,4^2,469. Of ihe varknss polynierhϊauor; kiitlatorβ, s~ bi5i>lϊuhium is ωiixime (hicludiϊig πioaomers aud solvon?) ia an amount calculated *>n the b^sis of one inidaior molecule pi-r tkvsis^d pol>m^r chήn. The lithium iuύiator process i« welj kiκv*r _; and is deacϊibsd u?» fo? gKampie, U.S. Paisms 4,059,5^3 and Ie. 27, 145, which descriptions mv hicoτpi5π.ued bcrais by refeeξica.

Another effect of ifw mo-difier in pi-cssrnt invention is iy co trol the block. Hm is particularly imp-ottani whesi Ihs; el^iomenc blocks will bo hvdrogeBsied. 'The \sxm tm the polymer cluiirh When refeπing to *hc use of butadiais as tte c-ooiugsϊed di«n«, a k preferred that about 20 to about H5 sued p^rceni of the c^; devised butadiene mύx& in the copolymer block have K2 vinyl conliguratsβn as deicmnπcti by prtncm NMR analysis. Far selecHvely hyerogemued block preferably aixjuf. 30 to shout 7b m<λ percent αf the conjugated dkse us- ^; its. should have vinyl

1Ώ ihc -process of the it is ess<?ntial to mxutttain u hsgh corico5tnvι!o« of th-e «lρhs-alkyi-vmyl-aromatsc monomer relativ-e to th^ rnαπo^^srvl" aronisitic ?τir>nojnes- during the hi the case of copolymers nation of alvlS with styrene, ths j-tyrene moBomer tes ihe higher raie of poiymcriz^tion. If both monomers were added in a bench fashion as έbe hegitming of ι\\z e.op(Ayτr-,tϊiz&noϊi rheo siyjene vvfsuld prefcrcntiaily poiymcπzc. a noo-umfwtu. or laperedv dsstributior.: of iomooomars would b«* ohi&med aufl a low co:ivfrsk-«? of aMS

would be achieved, ft has fee?;?! discovered that use oi a ;s©m$ ^» b&teh ϋs-Mmon of crøioτio?nm ^■ w/hs-jre all <■£ the &MS aod ooty a fraction of the styrrøs: ss added at ths beguiling of Ihe copolymers^ ; on h orst way to ^ebieve unsform ciistfibolkms and high iiMS conversions. The remskmg fbseten of styreae monomer required for completion oLuoug the oompofyiϊteπ.£&tκ>ϊs, IR ari alteϊ ^' nadvs ρroceάs> both monomers can fee added continiiousiy with tfec aϊpha-alkyl-vinyl-arosϋatic monomer bemg added at a much higher nue, In a preferred alternate embodiment, ajj βf The &MS is 3<k1e<.1 at the bftgύ^ϊBg of copolymers ;-^.α1os> sx-.d tύl of the styrene ^ added daπng copolymers ?;sstioϋ over a period .Crom niorc thaa 15 ivJαutes up to ! 80 miAose? or logger. Bxceedlsgly k>ftg addition times c&n lead to high incsdiersces of ^χ vhκ:h ss αjxiesn-ahle. Ta ili<? most pκπ>ττed enibodini««t$ the

In !fe fully copolyπrø" blcck, iKs alρha-a)ky1-vsαyl-ait>mauc mori'vrnsr makes up from 25 to 50 m<J% of ih^ total arøtmtic monmtisrs, Eφuv&femly expressed, the molar mtio of s!ρha--a1k>1 -vinyl ^sromsrse monotner to monavinyl-^romatie 3)K>rκ>menβ IVom 25/7$ to 50/5Cl Ths? most preferrϊH! rstio of ?Jphf.!-»lky1~vinyi-aroa'satic motR-jirsor to moriomer is from 40/60 to 50. ^'' SO. As the ssmcαml of is jϊκ ^; reas&dv the res»hhig Tg vαiut; of the cqxϊtyrrse? mcrc&gcs. Below 25 ϊπO!^« aiphs-alkyl-viByi-aromaϊϊO mosiomsr, lbs Tg vak;e ineteusc i^ 8ϊns.>L [& the nuige o£ 25 Io SO »1%, the c-opolymer will l:&ve a Tg vϋhie of Hi least 120 ^' HT aad as MgJh s& 140 ^" -(T In th« present invenhosi, the mt»?e preferred compo&ήbiis. lead to Tg Yαhjes from 130 to I4O' ^X 'CT

Ths glass imnsύkm temperatm'e of a p&lymsr ϊs often vvitU ihe Senφerature of onset of sorlαimg. At Tg the polyn-sK-r undergoes s b^fw^en gla^y solid and xiscens hqmά states. For she polymers of the preset «rvemh"?n the Tg rah.ie can be tncsisurtNj by f.sny o.ne the of the comt^o^ o$ethθih _> employing for «χm«p!e tnos-'Kϋriicai, them^aJ, or electrical sneans, conducted at tcrapo-rstwres 30 vtnd ^s >0" ^'' (T hi the present hxveniior*, it is έmporuiru to conduct the ternp<s?stu.re tn ike raogo of 3S - 60 ^v ( ^' λ hi ihi-i range afvtS

is efficiently eopolyraeti^ed while termhiatioji: k mmhnked Preferably, ikv £sψύyιrs.ύήz'λUCiiι k conducted at a ternrλ^yre from 35 to 50 ⁰ C,

It js impoitaϊU to raamtaύs a hign cfmcfcriiraHon <ή living eals rø _< sitemap Iy a high UtIi iiun couceMrsuon, This ss done by o.>nOireu.m; the eopoiymenz&tioB at high so Ms eυrus^ts, In the presem wernion- ^{^} solkfe eontem ^"' r^esns fe iaiiύ 5ViSSS of monomers to be polymerized or eoρø1ymcri?ώd expanses as & percctitsge of the tuUU lϊn^ss of mon.θ!mτs, solvents snd modiϋers. The preferred soikfe cosnent i& from 20 to 50 ^V λ ϊ%. The mαrt ^! prcfen-^l s«hds content ss y<i κι 45 wrt-b &nd ϊBost preferred is frøm .>5 κ> 45 \vt%. Under these conditions the ccsLC&atfation of Isvuig polym r-lsthsum ehaiπ end is trorn 500 to 250(5 ppm (0 QOB - 0A)4 rϊuτκ>l/g). The snost preferred eoncentr&tion of living pol>tneτ-lithium chain ends is from 1000 to 25(K) ppm (Oisits - 0.04 rømol/g)

The Islhuim coucc^tratior^ xs aha effected by Lh<? molecular weight of ξhe polymers, λU other conditions bεirsg equal lower molec lar weight polyξBers ryquire hi ihe pϊcs«3U uivendtni, _S U: upper molecular weight limit is resiϊy.ed for the copolymer block lot imy given sol of solid? corntMits, eopoIymena-atioR modifier, ajxi temptυ;iUs.re order so acbiove high monomer con version. The prelVmd peak møJ ^ή oukr copoϊym^r block is fesn 2,000 to 30,000 g ^ή racsk aad most psti ^' srred as from 5,000 to 2(: _: 000 g.-moJ,

As used heresn, Lhe ierm ^iv m<-5lscutaf wdghm ^"1 refers tα ihe true mαkc^kr weight tn g'Vuol of Ow pclymcr or block of ihe copolymer. The molecular weights refoτec.1 to in tbis sptjϊsikaUosi a?:fl eU':im<; e _* m be measured Wstb ge! p«rm*-siifm cbmreato^rapbv i€ ^j PC) using polystyrene calibration standards, sach a^ ^ eone sccordmg to ASTM 3536. CiPl ^" is a svα11--k;χwn are sqwat&d according to moleeαkr ^f 'i«, the lar ^g est mo!ec«W dutta^ first The chroiiKHoer-iph i^ CiiHbraied issma £.osm«ereiiiiH' available polystyrene molecular wouglu weight of pelyme ^yβ nrøfecular weighs T he styrcUt, eiiuiviJein molecuku- foe eors versed to trus ■uolccular weight

wte! the xtyr\?n^ e<mu>nt of the poijtner ami the vmyi eorstenf of the diene segments are known. The detecso? tssed is preferably a combination ults-aviolet s?κ1 rcfmerive mitex άetec&st. The mokxniax weighs sxpressed herein ^re measured at ihe peak of ^ he QFC ϊ?ace, convert to trtse molecular weights, ssxi are commonly referred iø as " ^" "p^&k mok* ^* ui;u ^' wεs glu^ ^' ,

Tl k 5rarx>rtfmi to ^nilke a 8αpøl>τn£rkaH<m modifier. TIm moάύiϋϊ ^< im\m to improve the <?fβo icnc> of nicorpor;.uion of the rϋτπf*nonters dumif copolymer! gabion. Tvpicsi ct>ρo1ym?.-r5/adort modi6er; mdyde, for example,, pokr modille^ s^ch as dimethyl ether, diethyl ether, etbyj hεlatirsg |>o1ar mcdificts ^ch as <keth.o>xy propone (DEFK !,I- dioxy-ethaae fdioxok miά (ODM 8 > &nά the hie. 'I he itnouBt of BKxiiSer HX|iύrgd deρ<sn<ix upon dis tyjve of NoiB- chelating, polar ^■ BodlHers ^uch a;> diethyl etber (DEE) ar^ typically mαsL efYeciivc ai relatively high levels. The preferred raαge of norv-ehdam-sg, polar ϊrhJUHi€Tδ is from 2 Ea 20 wt% basis lhe iϊϊihre poUsr modifier is 4 to K wt%. WheB the modsfter is ® ebelstiag, p-okr modiδer sisch ss distho^y-propane (D E? | or oτtbo-dlmeihoxy benss&ne K)DMBl llisji lower anu.Huus arc gewuj, is from SO U> !C^: ^)r) ψpm. basis the aid re mass of solvent plus modifier, Whsrs Sk chelating mo-ditle? k; DHP then the preferred :sn ^" >oun^ oϊ m&άtiitr ιt> imm 400 to 1000 ppm and the m^t prefeπ-tVi. amount ss fri>m 500 to 700 ρpr?>. When the chelating modifier is ODMB Tho^ Oie preferred amtsuπt of m*κi: lkr ?s from 50 to 5f)0 ppxn and the.- most prefcrmi i? from 100 u> 300 ppu^ tJhlizhig the condniosis specified tein very ygh conversi n of the alpha-alkyhvinyharomatic. eomoπomer can he ρτgferre<l conduiαas eo.si\-e.r^h?ns of at least 45% are achieved. Umfcr more prδf«rr&d coudit:ons nf at k&st ??0% are achieved άn<f nrϊu&τ most _| jϊ-«fcrred cdπdϋioos e:>rrversbns ef ut ie^t 00 ⁰ ^.; are achkvtd. The^ hsgh coBvorsjons. re^uir in s^ effick^t iϊicorpisπitmrs αf the monomer into the copolymer <mά ohvϊ&re the rseed tbx grf>ss ynd recxjvery of lhe ϊr _: os)r>mer.

Copolymer blocks of aVph>?i&:y!-vi&!yi~&romaik and monovisyl^rofaatk m»nom*:rs can k- used us construct block copolymers according to we U known synthetic strategies. In geusrπϊt the bving, anionic ]Xs!ymerk. _< Ukm isstxϋ to conduci. ihe cupolynstfrmttisrt c&π. be continued with lhe synthesis of othsr blocks of amomeaUy poiymerizable monomers, Fm ύrc purposes* of ins present rnvenbon, eonlmiϊ&tion of polyrrsgπλsiboπ. to ibrm elastomerk blocks e«mρπsmg etmjugatsd ulenes Ls preferred. The conjugated diene hkxics m&y consist of a shigk eoαjugήted diene, mixtures of co r\j is gated dk-nes or mixtures v^'ith other .«.αn-<Jieπe monon^erx. The ρτefe«xxi moiscolar weight of the dastomeπi. blocks is; from ^o _^ OOύ to 300..O00 g/mtJ mά ih<& røosi preferred mohicukr wdgh! is Ham 30.000 to KiO ₁ OOO of ϊite ^.ϊhse<|uent eoι\iαga.ιed diene block at least a S ^! 0% ci.m'-'crskxu of ^iosi^msr Is rt;o;usfeoL Tbe TOGSt prcfcrrad conveftjions are at ieκ$t ^S ⁴ :'-*, hi block copQlyjϊrøMUOB same f^acUon of the «!pha-alky!-vmy|-aro?i^tk / nionoxiByUatomatic block ro&y not cross-over to corijϋgatccl diene po1yιiκπ?.8tioft. This iϊusy !^pe« dικt to inidvesic^t tttrminarion of the block at thu imroάutvon of ccπ}ng»u;ύ cherso moϊ^omcr or may happen by intentional sddijϊftn of a teTOiiaatisig sgcsit. hi ύm casi ¹ , some aipha-alkyUvbyt^som&Hc / nionrsvi«yj-arojsalk block will be present hi the final block copolymer Th^ block a^ay pivsest ihe adv;u^sge of « highly compatible, bsgb Ig ?e$?n for the high Tg blocks kiv>og low volablky aM blooming ch^actcris:!κ&. IB the ps-escπt uwemϋo^ up to 50% of the >' monovmvbammaOc blocks may ht so terminated Wben the presence of a ϊjon-voktϊk lUsw pr<->ϊϊioter iϊ dcsirtxl ilien the hjglier amounts m ihs rrøge of 25 to SO ure dε^ύ^.1 When lsigh strength b'Ock: cαpoiyτn<:rs are desired rø«s ti^e mnotmi i>i ^' than A preferably less ihsπ B ⁾ % and most preferably Ie^ than 5*-*.

The dteπBopiastJc block wpolymers of the pres&ns invention can be ϊ^pres^tsd by, Inn sucv, the COπϊHIUS& A Ii _. A - B - C ₁ and (A - B)nX. rviany o ^t ht-r srjangcmsats of A, Ii ^J rf V bKκk& cars he euvisioned in a thermoph^siie block copelytncs- of Ihe prescoi u;veniks?t In Ihe general fbminbc A and C" ^re gia^y copolymer blocks of sipha-ulkyhvu-syh aromatic itmJ πjαnovmyNsron-saik monomers. B is a is θkstomsrk block cαrrjpnsϊng cosm.ψ;iieα dixies, X k me ?e$idιse of a coupling a^ent

and n refrce^enes the average norssber of e«s.ιpk;l A - B arms. The ari>:>!.rm of ihe glassy block in the. thermoplastic block copolymer is from K ⁾ to <& ^' ) wt% basis, the total block copolymer mass, in this range the block copolymer exhibits thermoplastic elastomer

hi ihe general formula for a coupled polymer, CA - B)n.%, si is from 2 to abom 3ft, preferably iτom about 2 κ> about I S and most preferably from 2 π> 6 WIKII n k 2 the block eespiilymer has a linear configuration When n is greater than 2 the block s;opc<iymcr may be referred to &s radial, branched or *?&?\ Ths coupling reaction may be conduct*;! Io link & traction of ife Uvksg arms, te genersi, the ϋrøoiαit of lh-hϊ§ s,rι« which ss lira k ^I hi the coupling reaction is rtpostsd &s fee "coupling κ!Tsc^ncy ^' \ Ih^? coupling eiϊkicBcy i& i ^' fe mas<; of biυck s^ linked basis the total n>ass of block copolymer, Inπ example, s black copolymer bavi»g a coupling efficiency of 90*4 would have $0*4 of ihe polymer in a coupled conilgurafiors and Ii A - B livmg amis were being coupled ihas this vvoidd leave \ Q% A - B dibioek, Irrsporiϋrαly, die coupling s? gensraily a sististica! prosu^s $r _c ά n h m\ average mimber of coupled arms as iaughi in US Pateot Appllcadons 2003A ^' )2252(.b> aticl 2004'0 5409O. For example, m a coupled block copolymer having sp^cie^ wkh 2, 3,, 4 ;iαd 5 srms iliε average a rsay be 3» ^' flieri' will he ^n ^rm ^ursiber distribution vvUich w;ll be ;m|ϊcsrtii.«ι ni eor^usrksg the phy?k;5l properties o£ the pαlyπ^c For example, coupled polymers with an average si ^κ; o bm ki^in^ a reJutsveiy kϊge 5-actιorj of si - S will have a higher viscosity and iowsr m£-U flow than Sbe comparable coupled pαlymsr having &o average n ^:: - 3 but a srosll ixactioo of n ^: - 5. ϊn the presem hivemion tbe coupling efficiency ca.» be brosdiy varied depejsolmg npnn tbe de&ιr«d polymer properties. For example, low ct>up!iπy effkkncses {<5< ^' V;- ₅ >} can lead to bicbly proces^able polytiiers bavuig iosv viscosities- ^%b coiipiiug eBkienci&s ?>50^^} tan kad to polysners b&vi«g higts strength and eksi^ity,

A sanely c!iba^> alka^es j-slicoo hukdes., sibxanes, nmltisbiicdtsnul epoxides, polyalkenyi compounds, including and the like, silica compounds, including a&'oxy«χdsm.'S, alkyl-Silanes,

I i

carboxylic aesεh, including diroethyt &dipate and the like, and er>6?ddk£d oUs*.. Preferred are ktta-aikoxysskffi^ such as t&ita-stho^yssh^e (I EOS l ask! tetra-mefexysdane, aikyi- ixuitkoxydhnes -such ss methyhiximsthoxy sparse (MTMS), alipbsaic diostsrs saoh as ekmslhyl a<jφκte «nd diethyl &dipate, ami digiycklyϊ aromatic erx»;y compounds such as digfyeκlyi ethers ckrivifsg from the reacuαn of his-p-lwol A and epichiorohydrin. When subsequent hydrogensfion or selective hj'd.rogeuafioB ix ύesir^l the coupling ag^tt should be cbαsoR such thm ; _; my residual ^nreacted toxψisng fsgt^fs, coupling :igeut reskkses incorporated hito tlie polpncr diam or by-products of ϋlis coupling reaction do not isterfcrc witl^ thi* hydrogeπatioω.

Iu Ae ombodimoni of &c pj-εscat whsr« coupled block copolymers arc snsde the coupling &gmt is added Us ihe living poh-iϊisr in D molar r«ύo to produce The coupled pidymei with the d^Mfsd arm ^imϊbcr dismbution. The coupling stg&sit can h<:- &likά as ;s ρ-ars compoπnά or can be diimed tn aa ioeαi sol VCTU for oaso of metering the addition ρrott>co! can have an effect «u ihe arm ?Mmher distribution Afler coupluϊgs ϊemiin;nion is noπnslly noϊ requited

In the embodiment ol ^' ikfc preset invention where m>s<oup!od l> ^' kx-k copolyn^cTs are produced, the polymerisation is stoppyci by addilKsr _* of a tsmunating agent. Anionic the lithium from lhc poWsnei ehsso cad a& lithium hydroxide CLiOH) or by sdriitioa of an alcohol (KOM) io remove Uic hifύum as a liύimm alkoxide (LsORK The ^rmir^siag agesns; aro added ϊ\ι » PλUϊM excess Io the living chain ends. When subso _: .]uent or selective hydro^euaUon is desired the termmati^g ugent lype. and ? or amount should be chosen such ih&i maiάiuύ mminsmw zρ?tu r»r termination by-r>rs^ds.rets do stoi nitocfere with HyiirogeRfUion.

Hydro^enaύ5n eaiϊ ho carts sd otst via any Qϊ the several hydnjgenauoa or ^!erJs%'e hydrogen&Lioπ processes kmiwo in the prior art For c^^i^ple, sueh hydre>gu:aa ^< *ft hfϊ& beesi ac4.'£jr?ψhs ^; hed ^siag ir.eihads such as those taught in, for srx^roplc, U ^, S Patent 3395,942 ^; 3,634,549; 3,6?0 _S 054; and Re. 27,145, five disclosure ol which :ire incorporatod ^] teres Ώ hy retereisee. Tb see atethods. operas ^ hydrogenate ^t h&sed upon fjperaUoo -of a

ssmafek preferably comprises a Groϊip VIIl racial such as suckel or cobalt which ss combined with a suύκb!t reducing agenl such as ;$fs alurmmsπi slkyl or hydride of a metal selected ironi Groups I-A, H-A asid U)-B of the Pc ^ή odif ^' Fable of the Oemrøts, pankufaϊjy fuhsnn ^' K magnesium or aluminum. This can t.κ? accoajplkhed m s suitable solvent or dtluem at & tempeπuure from about 2CfC to sfoii&i StT ⁵ O, Other catalysts tha? axe useful ksduds titanium bsa^d causlys? systerυs

Hydro^enaiion can be earned out snckf s.^cb comlUioαβ tnaf at least Jϊboui 90 percent of tbe. eoβj ^' ugaUh! iliene double bctsids have been reduced _^ s^d between ^e^o and 10 percent of the δxo-πiatic do>uhk bonds hav« beea reduced. F^s-fsrrsd rsmges ^re at feast about ^s ^5 percent of the ccsjugaied. die^e double hoticfe yeduesd, &nά more prcfembly ahoy* ⁸ >8 psrcc^t of the i-αnjugϋted dk«e double bonds arc reduced. Aiterπstively, h is pos^ϊbk to h>i1?ogemue the polymer such Ou* aromaύc missiursfbn is slso rtHlutre-d beyoϊui tbe 1 C ⁾ percent level n'Jt-nUOBed shove. Such exhaustne hydrog&nation is usαaiϊy achieved at higher temperatures, hi ik&i ea;-,e, the double bonds oi ^' botl^ the conjugated <kene ^nd aronsatjc u^iks may be reduced by 90 p&reeni or more

In one embodiment of ihe presenl inveots^n a block poiyruer conipϊisjϊϊg at least αne gla&sy and mouovhjiyl-ammaUc mos-Knnεr^ ;snd st least one efeslororαc block is compounded with okππ polymers Oleliv, eιhykn«/abha»okππ copolymers, Loptslymers, high impact |>ol>prof _t y!ens, butylene bomopoJymers, ba^yiene/sipha ofctln copolymers., snd iπhsr alpha oiefm copoiyrω&rs or irsferpolvmcrs. Tho&e polynier? ea^ range from the low flow to high and very high flow polyolefms otkτι referred &$■ Hv«e&. polyokflns include, for example but are not limited Lu, inear ethylene polymers, br*mched Ihjear «tb>tene polyrrsers, heteroge^eoMsly brancbedi lhiear ethylene fsoiymers, including iinear low dsnsky p-olyeLhykn« (LtDFE), ultra os vsry kssv deusύy polyethylene C MLDPE or VLDPK), πiedsun\ deoβity polyε^hykne (MDPE k high density p«lysj!bylene CIIDPE^ aod h^h ps^ymers me.h;ded bc;.reiuκler are acid i EεM copolymers, acid <i;:M AA ) ioiiouiei^.

ednieof/vmyl &eeu*te f EV Au copolymers, «hγkτιf.vvby! alcohol ( EV OH) copolymers, eϊhylene'cyclic okfits copolymers, homoρolyrnerϊ> arul copolymers, propyleno ^' sfyrsrsis copoly^c^x, £Chy!en£."pϊ"opy|erκ; copolymers, polybetyiesis, Klbvletse Carbon monoxide mkTpohiϊKrs ( for example, ethylene- (ECO) copolymer, eϊhykneλ*α-yhe ueκl/cadxm monoxide tsrpolymer and fee like. Still c*ther pcsb'røe^: included hereunder are styreme type of polymers Oc copolymers iske the FS λBS, aaκ>imts of oh&x pol>TOcr υβefol .for she isvcritivc eksiostseric compositio are from 5 Io St)O parts per 100 parts of bbfJv copαl^et The pre ferred amount of ύiefin p&lymςr v$ from IO to 50 parts per I OD pans of block" copolymer.

The claslomeαc block copdymssre of 4 he present also be coi^pounded with low m*3leciϊl*ϊ? wsigbt tackifyisig rt-sins. Low laσk&ular weight ^ekifyiag resits Pelade alpba-alkyl vinyl sromasjc / sκ»o vinyl ammsnc block ccnr:p?:Ubk: re^«& &nά elastαmeric block compatible reβins. 7 he aikyl vmyi aromaltc >•' EϊϊOπO vinyl aromatic block coBipadble re-sin may be: settled from fcbe ^roup of eouinarøBc-indene resin, pohiudesic re&fe, poly(me?b.V! in*lene) resύu polysLyrsiie resiis, vr _; >yhohiene-; ^: dρbame-ihyls ^; l:yτ^-;e r^^n, alphanictbylstyr&rie resin and polypheaylena ^ther, hi. rϊJβlns a^ e y. sold wde/ the tr&dsmaits ^{^} HBKCURBS". "εNDEX", "KHISTALEX ^" ; ^■V NEV ⁽ ;; ^{| |} EM~- a^d "FICCOTBX ^1' '. Low molceubr w-ei _. ^hi tacks fyh;g resits compatible uh the ek&kssrufrie bk-ek may b« fto?u the group coBSisring of compatible C^ r€skκ» kydrogersskxf C 5 kydrcearbϋn resioa, sτ>τβna?cd C 5 resϊm;, C5/C9 resmSs siyrerjated ^rpsue resins fully hydrogenaiϋd or partially .hycirogermted C<i h>ik ^" ocaτbon resins, rosins esters, røsms derivnUves aod o^xϊures ibereof. The^e resins ^ ^■ e e ^, g. sold und<^ rha tradsmarks "REGALiTE ^N \ "REGALREZ'; ^ESCORBZ'; ^' t ⁾ PPER A ^" and ^{^} ARXON In the prssert invcriύou C5 or C^ basket tackifymg res-ins are prdemxl Tf the ekiintnTserso block is hydregenatixl u is preferred k> i^e tsydro^ensϊed raoksfyirsg resins. The aπxnuH of iow mαtecukϊ Lacks f> ing resiϊi enφloyed sb&ut 5 to abcnU 300 paxis by weigln per hundred parts by vvf%b* Hock copolymer, prsterably abc^ut 10 to about SO pans by weight.

The ekstomenc block copolymers oi the cars also be compounded with low inotecuiar weight processing oils. Especially pr^f&rrsd aϊe the types ol oih tlust are compatible with the etsisiomenc block. If the slasionutric block is hyckogerøteo ¹ , it $$ prdene-d Io use hydrogeoMed oils. Petrokimi^ased xvhus oils having low wMstifUy aod less than ICB'o aκ>matk contain sre preferred. Typical parajFuise processing white. oHs with less thMt 2V _a aroma! if: can be tssed to soften sπd ώxtcjκ1 ιx>!ymerβ of the prexem. itivenuoit. The oils should additionally have low volatility,. prctbffihk having a Clash pomt above 200 ⁰ C, At the saaκí o;!^ sho^sld have a relatively low vjjcosJty Io alk-vo i ^' kcilo com|>θiuκJs;^g, The smouut of oil eroployed v am-s sbsts aboia 5 to sbotn 300 parts by weiglsf p^r buπdrsd parts by weigh* rubber, or block copolymer, preft:rsbly ;s.hαut 10 to about 100 parts by weight. Coropmmu^ng or melt proce&sing cat? bit aceomphsbed αsiftg any of ihe co^ϊtnonly applied puJyr^&r coϊvψoijndmg equipment or teehi^sq^es. Of paπicuW irnpor^nts ars tfxlru&røn or sojectiois raαldlng techniques nsing ekh^r single 6CTftw or twit's screws λ Particularly iαteresimg application is m os'er-molding ^vherfc u cotnposition cotitaimsig the high Tg value bbck coρol>τner an<l opuo aliy uth&T ihzxmophstsz polymers and p?ocs«s ai< ^] es ϊλrvα- inj?:ctbn snokJεό! orno a sisbsirate of a more rksd polyuier to impart a sorter fse[ or different nictjona! ohάπic teπstjcs,

In oris lbrlher aspect ol the p?ese?u invontiαn. &n siticle contprisl«g s.he hsgh Tg bioek copolymer caa be roude 5π ihe IOπB of a £ύm. sheet midii-layer laminate. eo;^irs*, baud, ϊoznu tape, fabric, tlxraad, fdsirøe«ι ₅ libbon. fibs*, plur&btv oi fibers, nosvvs^ven mats or u ⁽ ϊhrous web, Anoiher particularly iMerestuig application ^j & trie5τno| ^} iastϊc filin ^g which re-toia the proceasabslity of styreok block copolyrotrs but oxlnbu a hsLiiet "elastic po^ of ^imsbr to spandex polyur^ thanes. An even further iαtorosύϊig ;-ippl.$carioo is polyolefin modi tie a Li on sphere from 20 to SOVAI block Ciφol>TO&r ^s ewiipomKied wnli a polyolefin or oicfm topolynier.

The iollowiBg exaπspk^ am provided as iHuj>tτa!iotsa of the present iπve^non. They are not meurst u ^; fi ^g limiting, hoi πnher as enahling HU^trations of Hie fee _& i mode of She invention. 1 he weights &nά mφíciλ&r were

I S

dcterm.med using gd permeation ehrornattsgϊ&phy tGP€) The composήiion of ihe copolymers wss measured issin^ ^'' U NMR. The Tg values were measured using dilteremisd scanning eabrimetry ( DSC), SOJϊK? of fc tern*? ?a\mά m shs examples are defined hi I ^' sbk- A.

lahie A.

In the following ex angles <tϊid data Uibies the poiymers of the mvendou are «U£ft£fic&!$y $rsoh ^' e.sie<I The comparative pαhym«τ$ axe ideotifkd with a "C ¹ prefix.

Exsmpk I

Copolymer glassy blocks ofaKIS ami styreoe wets synthesized in th.?c absence of a polymsn&it k>B mod; lkr m a 11. ^amless steel smtoeUwe. €yclohmsns; mtd the &MS were 8<lde<1 to she reaciok In this example no poiymerkaikxn modified %va≤ &£«?! lύ the Cβtse of ϊ«iv^bsteh sty?eue vopol ym α^stion (polynκτs C i . C"2 ami €3} ih@ hϋJch portM^rs of the snresie nKmoaier v.^^ al^o added. See-lπnyl lithium JiS tbe?? sάύzά io iniimt^ φi ^ή ytv& ^ή z&ύon. The remaining sϊwsrm; munoaiKT was sdd«d ;n a cou&tant rάic over a sp&cifssd ρrograi« lϊme, ussn^ a hi^h pressure syringe Dump. The examples of the mvcntion were r&sgbg ft-oos SO so ?0°C. bv additios ^' j of isoprυpanol The exTcjn of polymenzatiors of both juonomers wax t^iinvuεd ba^ed on :,lis cθ:κentraιsons of the mrsnomen pfescm at the end of fi>? poiytjteriaatiost, u& estimated by ⁵ H NMR af the r^achou oiixtuie. l.hibss <JI!ISΆVIS$ not«<J _s essesuisily all of the styrene roo«εsn~scr %vas eo5isuτ5is<i: s! vrene conversion was 1*X)% Tbe polymer was

T? ^, hk> ! sii^ws the result? of aMS ■ ^■ siyrene eopolymerfeatioris conductsd ^t 5ts*-« solk ^' is Suitably high &MS conversioαs cfrom 67 to ?li%) were obϊanied hi polyrners L 2 aiϊd 3 * ^" hich ^ ^' ere eo duetesl usώo^? a batch charge of «t>τenc tno^ot^er at the onseε of Wheo a sαπύ-hstcli proioeol w^s «sed and stytene moriomer was present at dir <H5set «{ ^' rcaeoen and bw aolkis car^ent^ ^vsre expcri^e^l, aMS COB versions of i^s than 3O' ^v H ^; .

Example Il

Oφohπjsr gks^y hlocks othiMS mύ styreuε* were sw^hexk<ed according to the proee^ of O£E a _λ a polymeru-'aocn-.s..o^odUler. Ah oi ^' thx: siyrene monomer wax λ<ides;i i« u co«ύnuou^ ikφio _ϋ ,

No fraction of tf;s rfyrsnε monomer was prcstait In the rcaetbn m.Lκmro at the onset of coρo!ynuϊriaatk.»n. Table 2 shows the result of RMS ' styrem? copolymers >ta dons conducted ai high solids contents {%<>%} mά with 0 % diethyl ether as |>dymcnjatioϊ$ modifier. TKs- poivroers had aλ>lS conversions tbosft 48 to §7% aτκ< reselling Ig values fϊom 128 to !40°C. Narrow mπiec alar weight distnbuiiems of the- poh/mers were obtained TIu- niokeukr weight dLsirώuison, as measured by GFC, s-s shewn in F;gtM ^" e 1 fm pfifymer 5,

ExampJe Hi

Copolymer glassy blocks of aMS and s?yrene were synthesized act-ordiαg io tht process of Example II sit v&πous yoli^s contents. Di&tln-I ^ther at *.s \vβ-« was u&c<f &s a poK-TϊK.'nzmion modifier. 1 he sty ft ^. numoaier w^g Mdαl continuously ovaj a 6 ^' ύ tn-soiste period Tbe coρ6Kτne!-5/.<iiion« wersr conduced at 50 ^;V C ^' fable 3 showώ the results of the &.MS / &tyτ$ne cαpoly^enzu^oos. Cojxϊhϊtϊsήzaikss ai solids, conrenis from 20 io 5*3 w!% snd molecular weights less ύrnn 20,CK>0 g'mo) gave iahium concentrations liorvi 9<H> us 300 rapm. A? 0u\se conditions high aMS eonvenio^s wersr achieved. For the polders tn^de at 30 to 50% solid? she aJMS corsversioa was 85% or greater. The ronultiαg T^ value of the eopolysners %va? from 120 to L^V ^" -f;,

Exars"ip!e IV

Copolymer glassy blocks of aMS and slyxcne xvere syntlisdzed accordmg ?o ihe pme&ss of Ii x amp k- Il at various po!yiυ€iizsk>a modifier levels. The eøixih/rneriEMkm ie;nperattir& was 50 ^" C< Table 4 K dse results of afvfS f styrene copoiymcdϊjaUoϊis eoϊidi.iCL*d u&ing vangus kve ^' b of «ue1hy! ether DteAyi efter levels of 20 w\% or less gave Ngri eonve^iOiϊ of aMS con^onomer and Ig values Jtom LM to 14ϋ*C

Copolymer glassy blocks of of rather ϊhan DEE. Table 5 ?>hovvs the ₄ 'ssuϊ ortho-

i t t

dsmetbtsxy bewens? (ODMB ⁾ , The chelating modelers gave copolymers having high &y S conversion &nά low molecular weight p-ohxfepes'sjty.

Example Vl

Copolymer gla&sy bbelg (vfaMS ami slyrene were according to She protest of Example ^; Ii at vsnotss toptslyrnesiz&Uon ismρeπ.uwes aud styrene monϋtner additrøn me^. Table ft shows the results of aMS ^; styrene eopolymeiisr&Uons conduced at k:mpt;raiures ranging from 30 to 5O'X\ The invemK'e poi>niarή h;ki aMS eonvenioiis ltom 55 to S-/!- .x

E^an^ple VII

DiHock coj:x>!)^ers having a gl&s&y block of &M ^' S ;uκi ^tyreBe a»d &n sl&shmi&ic block of U - bufadsene were syulbe-siied aecordmg to the me&oii of Esarepls II with ϊha foVi.f.nvi.ng exeepdons. All of lhe ex;ιraplss were perιbrtτ<e<! us-iπg continuous iκk!UHiτ; of &i>ταie mo^os^er. ftere was no styrene aύύ^ά to the reaerk>α mixture- prior to smlktkrt As: lhe completion ofths glassy block eopofymem&Uon, butsdk^e >vas a _< MesJ ia a smgie batch charge, T^b^c 7 shows ihe s:esuifs tor th« (aMS / s,tyre?whbu&dieoe diblock copolymers. Comparative polymers C 7 ;s.rul CR were xtyrene4χ^udi&ne at block eoisld be joeorpor*ts?d miu the copolymer when styreus vv;^ added over at less! a 30 mm^e persod, at iemperínwe& oi ^' ai basϊ 40°C\ and m the presence of 6% DEE. When fee coρo!ymsri?.atk>^ v>.-as condiicttid at (polymer 27} & high eonvcrssor* of aMS was achssved φQ%) nnύ these was good cro^s-over io the butadiene block (UVA ^~ 2 !? ^• ;>}. Copolymem&uwi peH ^' bn.ned at 30 ⁰ C ^ith a 30 rasrmt^ s^vrene addittoa (C9| recited hi relatively ksw sMS conversion (22^*) dunng Step ] eopolvTi-isπzation msd & ^Iu lively high fraction of cfcims XhM did noi. ώeotporate a

Example VlIl

Xi

Trihløek copolymers having a gkise> block of &MS and stymie mύ m thmonmήc block of ! .3 - bufedlaie ^vore 3ynth&s.&s?od ^ccordmg to the method of E >: ample H with the folknvirsg eκf.epuom. The iπblocks were in & tvvc- rcactor μroccss. The &.MS ■ ^>' stymie glassy Mocfe copotymerksri 5? high solids in a ilr&έ reactor Ai completion of this Step 1 pulyrnerkstiori (he trvπsg t:h;ur< ss'ms were transferred to ϋ &txoϊκ! The :second reactor contained punfϊcti biuudϊene rnonou ^' ier, eydohcocsne sohent and diethyl sϋser modifier. Only approxtmsteiy 10% of the biaadituu' rcqtnred fo? elaθtoraar hlαck ρo!ymefizst^>n was initiaUy prexern AOer transfer αf the Hving chasD CJKIS 10 the ses:on*i reactor she remíymkr of the butadsoK moπosωsr was ^dds^i coniiαumtsly over 55 50 - SO minute i&tcrvai As. the eoωpleoosi of this s*:corid biock polymers s,veιt; cαiφkd with methyl- triroeshoxy sϋane (MTMS). TbD molar rai^q of MlMS to Li was about 0.45. The coupled product WSB substaiitially & eoxspiεd Mn^&s- tribbck. Tahte S shows ihe rcsulLs of (l.aMS ^ $iyτ«me)"bm&e!ie«e};; blutk coρ«I>-ϊrier?, Hhgh conversiotis of aMS (4? ■- 9S%). good ks tfje butsd :«? ^" :e bϊock (U Vλ <25%) and good coupling sfHekncy (.12 - 80%) w&s achieved.

Polymers 32 a.od 3? * ^• £« sek^ively hydrogc^at&d Io a residual dieite a^u^ & Vx ^y M axuύy≤t up to iihout 7TC, The cat&fysL was oxκiϊ;??ct snd sxtr&ctssi by the cement v?ith gas bkud. The fcment w&s then washed with dϊsliOed waivr {while sp-urghig with N-yO _; ) until the cement was nϋuirsi ima tested using ^N λ CI pB p&p&r). ^" The poiyraers wore then recovered by hot w^ter coagidsnion,

block copolymer vv^s msute with ks^v ntok-cular wdyht processit^ od ami hnmopolyoropyleoe TU& ptopcru ^' es of the mvems vt- cf>ϊ5ψoιu5d were ioe^ured arid ^p olynier ClO is a t-osiverniorsai δtyrti^-etUykue/biHyk'nL-ss^Tene block copolymer

having a -siyr^nG ersdhloek eositem of 2ts.6 wrU, a $tyrer _* £ end block paak: molecular weigh* of ^ 0,000 and 3. vmyl content before hulrogen ;nk.ni of 50%. C buip&r&UYs- polymer Cl 1 is a coovcαtioπδl styr£r:& ~etb>1sπe- ^; b<Uyku£'§i.ymi£ block copolymer having a sryrene emiblock contest of S ^' O a sty* ens sralhlock peak mokeuksr wesgh?: of 10,000 g-'Vfio! nnύ a \"inyϊ coBtens before hydrogciϊadon of 40%.

The cαmp*mn<is 1 ⁽ #ϊ puns by weigh ϊ of Mock copolymer, SQ parts of Primo! 352 _; a oil, -mά 3S pans of Moplen F30S ho.mopo.Kφropylcne. Tbe compoϋπris were prep&røl by rt"*ixiδg tiic coin^x>n&nts lor 10 ffiinuses m a brsibendcr mixer hea^tx at 190 ^" 'C &nd the- melt kifspersuur? was fecor<le^ at ?.|ia end of thai mixiag poried The collated cimip<5unds s.hcu ρrssso _* J isxto (kx&n lhkk plat&sat ISO ¹⁰ C with 150 iws foτ lτat«utc, then eool^i itnanx ps^ss-ure till roorrϊ iemperatiire. s^t (CS) ^- ss nιcasme<J accoahng to ASl ^' KI T>395, The mdϊ Oo^ rate fMFR.it was measured accordjog to ASTM Dl 23 S ushig 200 ^'" °C and 5 Kg,

Tfibic 9 sho-ws ihα ctvmpϋimά ihrnmlMαyns, snd \ht res is king physical propetikϊs. The faults &how exce-lleof higii tcnipitnjlure properties of ^e ϊnveafivc: compoiuni rdsrh'e to compounds cαnέairsitig converitiojϊ&l SHBS i>kκk copolymers. While recovery ^ sigratic&mly hsgber £>r tb& compound fcnmϊl&tjon aucoκkr5g to the at TO ⁰ C Ai aqϊiivnleni h&κirissss ibe iαve?>ovc polyi^eϊ has ss βigmOcamly improved (i.e , lower vaiuss) compression set at ?0^ ^' €/24h^. Dsspuc a iowtr tπbiock cαnteot ths hivtsmjve cofstpouad based 00 polynssr 32 expert srjces a set of only 85% i« ibϊx condύκ>ϊ? firtemperattjre and ϊbϊe while the cennoiwativύ coτr:pssϋnd based on CK) s comjiϊessroB set o£ 94% «si<i dis comξϊarative compound b;ξs.e<i on Cl I h&ά n ct _> mprs$ssoo sei of 100%

:k' S .

prog hrne unDu sMS 8tø .s' ^; sxsjvmsr Modifier FFM Md EMiJ.

DEP 600 50 1 9% 44%

15 OOMδ 150 30 1138) 9.4% vv .'CJ 35 DEP 50 30 10.4% 41? 36 OEP 30 44 J 10.6% 580 ¹ SV eo% 16 DEP 70 107,100 11.?% 302 39% 56%

' Coπcsπtraϋ of af^S, which is calc has polymerized.

Tsblc 6. tc|t $ys tgUMS theα preg MpK uops t ^MS &M§ nUB sopdy iwi;&i i£ CGfiV

&o% S^ % 50% 50 60 14.910 2, s% 89% 00% so% 53% 50% SCs 3ø 15,560 3. 1 % SS% i>0%

1 ? ^>\.' ,'v 4() 30 VK 13ø 6, 6% ??% 46%

⁵ Coric«in?rats©o of 3i|>ha~m-e?hy1 siyreπe in St/a^S €αpolymβf (%wt) based OR the convers?ofi of aMS _% whsch *s cslςulated Dy assuming ^hsf sny aMS ijifsww ^^ ss wA delected as residual h%$ _> polym&n;

Tabic 9.

> ^■ ?