Ul FOCCCCT CT CCCCT CCPC CUTE Eee tt accent iittala Thermoplastic Styrene Block Copolymers C..R, WILDER — Phillipe Petrofeum Compony. Barilesvitie, okluhorr I. INTRODUCTION illustrious history. However, #1 wasn't Synthetic cubker has ¢ long: rubbers became the "work hovses!" of the antil World War If thet syntheti industry that they are today. ith the shortage of natura eub céme ¢ necessity for the rubber industry to develop « substitute. combined effort thet reached across ecmpany boundaries, emu igod styxene-butedione rubber in today's form was evented. This which wos to be known as emulsion SBR, beeame the basic polymer for e industry ‘as well as many other segments of the rubber industry Butadiene and styrene have been combined in many ware to make rub- bery polymers. The emulsion SBR polymers hed a random distribution of the two monomers. end thls type of rubber accounted for a large portio the emulsion SBR production. Modification of emulsion SBR is mainly ove sible through changes in molecular weight and butediene/styzene ratios. Other changes In the polymer were possible through the use of different polynerization temperatures, initiator systems, end finishing techniques In more recent years, styrene-bused polymers have beer: produced in solu ‘lon polymerization systens that have permitted much wore control, partieu- ‘arly in such areas as microstructure (cis, trans, and vinyl matica), mole: cular configurstion, molecular weight distribution, and combination of co- monomers, These solution polymers are described by Hows (1974). ‘The discovery ond development of the row polymerization eystens has 1d to greater versetility in the preparation of claetomers, This knowles has been appliod to 9 number of menomora, ineluding styrene, butadiene and isoprene. Developments worthy of note are selectively structured vel Jeoprence (synthetic natural rubber and balate), polyoutediems (pelyrers of high cis, trans, and vinyl content), and random copolymers containing tyuore, Some of the most interesting polymers to come trom the techrloy of gelation pelymetitation are Hook polymers as described by Hans (1974) Buladione-styrene polymers with two blocks have been produced sino theid ie sa f Wilde used te blend with other earty 1900s. ‘Thess Bloele polymers have bees polymers to provide blends with improved prapersies: Sneluding combintions re rubbery polymers and piestics. They also find use a8 the sole pol mer in vulcanized rubber: compot ‘The applications of these types of polymers heve been deseribed by Kreus and Railébad asi). another group of block polymers of bigh intorsst are copolymers th multiple blocks of pelystyrene connected by segments (hit Oe essentially ubbery in nature, Polymars of this type exhibit High strength and elasto- ane charocteristios without the use of vulbanieation chenlc:'s, ‘Their ther nopastie nature can be expleined by a simplified exer) Sonsider the polymer oo having an $-%-8 structure, with the § Dang ‘locks of styrene Seperated fron ench other by a rubbery scgment designated as K. Tho X sriee aither polybutadiene, pdyisoprene, or palgethylenebulyiene. A troup of styrene-butadiene clastomerdo blosk pol’ mere with a more complex Errangement of the polymer segments is the primary Si ject of this chapter. There will be minor emphasis on etyrene-isoprene polyieers+ 2. HISTORY af homogeneous anionic polymeritetion eyetons in the 19508 provided new capebilides for controling the course ‘of polymerisation, which Broimn changed toe oynthotie outer Industry. Articles Py S140) Ip time 1380) and dhe Journal of the Amertcen Chemical Sopiety (SV igiscovery {lat the polymerization of styrene in wy sodium hiaphtbalene complex produced what he After the initial volume of styrene had been jon still remained, indicating The “living” polystyrene no! weight, but Developme! et al. 1981 teurahydcofueen in called a "living" polymer: consumed, the ved color of the polystyreny] that the reaction had not been ternineted. nly added additional styrene monomer to ineresse molecultt added other nionamers as well. Senare recognized the polsatidl for producing block Poly: nethod and svecceded In preparing block copolymers of styrene tn Osess@x ponene —-~ Onmsssstns © by this .d isoprene Lithium ails eleo initiate polymerization of styrene and dienes In sontenst to the sodiam raphthalens complex, which produece:® dlerionic species, lithium alkyls produce nonounions (Strevely 1956). Xovotkov and Podolski (1865) observed that when mistuscs of styrene and butadiene or isoprene were polymerized in an nen with the slower reaation reto poivinerized first. seston ena Tile (1958) dound thet duxing polymerization of butadiene ant styrene in benzene, the vajues of the meaotivity ratios WOE such that b poner with o styrene end tends to add tutagiene preferentially, The a toe of the resetivity retes inaleates that the addition of butadiene to © tetnaiene end is nore Wkely then the addition of styrene fo 6 Dut diene end. rate fyon 0 Philips Petroleim Company pefant (1888) descibing the poly- vetieation of tyonn, butadiene, and a 29/8 styrene: DUBAES” svistare in Nclohexene show now the angunt of bound styrene varies with conversion. ‘This is shown in Figure 1. z ‘ceils atyrene is added during the early stages of polymerization cvene butadiene mixture. 40 the butadiene 4s depleted, moss “°° rere pe polymer chain, and © section of the moleeale becomes tapered anionic system, the mono:Thermoplastic Styrome Block Copélymers 1 315 CONVERSION, % Fig. 1 Pereent bound styrene vs. conversion during polymerization of a 25/75 styrene-butediene mixture in oyslohexons, ‘Tho tapered section, which contains both butadiene and styrene, is short, ‘and polymere prepared in these aystems differ little from pure lock pol more polymerized by sequential polymerization of two polymers. ‘Tapered block polymers are alsa known as randot block polymers. ‘The first conmercial production of styrene-butadiene block polymers agen in 1963, when Philips Chemtes) Company (@ wholly: owned subsidiory of Phittips Petroteun Conpany) {ntroduced the solution aolymerized Solerene polymer line, Shell Chemical Company introduced their series of Kreton polymers in 1965. Shell's polymer tine initially bad the trademark Therm plastic. A peper preserited by Legge (1985) in a symposium on thermopl elastomers at the spring meeting of the ACS Rabber Division deoorib of the history of the developnent of Shell's thermoplastic elastomers 3, MANUPACTURE Block polymers are usvélly prodiited commercially in polymerization systems employing butyllithiam initiator in eyclohexane ag ¢ solvent, Sinea the re ation involves anionic specios, there are no termination reactions ftor: in teraction of polymer ehsins as there ane in free vedio] systems. Initiation $s very rapid, md singe the polymer cheins grow at the same rete. the mol- coular weight of the polymer 4s determined by the amount of initiator employed. ae = Helght_of monomer 2 Ih” noles of initiator If oxygen, moisture, and other resptive materials ere rigorously ex @uded, the individual polyiner anions persist indefinitely. ‘Alter polymerization is complete, the reaction is shortstopped to prevent undesirable side reactions during the finishing stepa, Selvent is removed by steam stxipping or develatilizing in an extruder or other equipment. ‘The finished products are marketed as crumb, bale, pellets, ov powder.3.1 $B Diblock Polymers ‘The simple diblock polymers can bo produced BY ine routes, either by 52 ‘quential pslynerization or by ising monomers having ifferent esetion atest 4. Sequential polymerization: _-_ sgssasss© 1 998SSSSEBBEB Styrene + initistor ( sssssass© + bututione ——> ggssBSBBBBE 2, Differential rexction rates: § +B + initiator ——> 88 Sequential polynesizetion produces pure block polyTe sinee the seo na monomer is added only after the first hes "pean completely converted fo polymer, Tapered block pelymers result fran polymerization of ¢ mit- {© Belvrononers with differential reaction raice, Feo te produce tapered block polymers have been described by ‘oth Philips (1958) and Firestone (1966) patents 3.2 $-B-S Triblock Polymers oe tetrablock polymers of the 88S type wre progveed coamercialy by mn of by coupling of SB anions, Styrene + Buli ~~ BuSsss +B ——» BussssBBBE n© +» BuSSSSBBBESESS BussSS oii aussssaa09O 1s 42, cavity reactions: gaoegeoenene gO! + nil, > CoubBSeBEBE),Y * ais vmany reactive compounds nay be used te couple pO polymer anions. Dut some have undesirable side reactions and do 1% furnish high-quality poly~ "f the functionality of the coupling agent 16 2, the coupled polymers: TE the funotionality is greater than 2, edial polymers are p10 mers. are lines. uoed. 3.3 S-1-§ Teiblock Polymers tyzene (9-1-8) polymers #8 achieve’ ‘The manufacture of styrene-isoprene: by eoupling of 81 ty sequential polymerization of atyzone and Tseprene or polymer anions. 3:4 SEB-S Triblock Polymers (G-BB-8) palyners are produced hrofore they are recovered from styrene Saturated styzene-ethylenebutylen polymers by bydrogenating S-D-S or $+ solution i a 1 i} J 3) } i J a I 1 J 1m Thermoplastic Styrene Block Copolymers i, AVAILABILITY OF POLYMERS Block polymers are commercially available in diblock (9-B), triblock (S-B-S of S-I-5}, ssturated trlblock (S-BB-S), radial trichain, radial tetrachain, and radial nuldichain forms, Block polymers. are pocuced or marketed as (1) Bear (nonextended or neat), (2) oll-extended, ox (3) fully eom= pounded products, These products are based on polymers with saturated or unsaturated center blocks. Tables 1-3 give examples of thermoplastic polymers that have been or are being produced. ‘These tables also give an indication of the varintion in physical properties avellable from the types of thermoplastic block polymers, The examples in these tables ure only a partial listing. Petrofine 8.A. ourchased the interest of Phillips Petroleum Company in e jaintly owned sclution rubber plent in Belgium, Polymers from this Joetion were once marketed under the name Solprene but are now aveilable es Pinaprenes. Litereture references for a polymer with the ame numerioal designation and a Solprene or Finaprone prefix (iso, Sclprenp 403 and Fineprene 406) can bo considered ec oscentielly the some polymer. Polymers are also available from Celotrova $.A. (Spain) and ANIC (italy) in Europe, and from Japan Elastomers Company, Ltd. (JEC) in Ispan. The interest of Phillipe Petroloua Company in a jointly owned solution rubber plant in Spain was purchased by Calatrava, and polymers are rhenketed underthe Cslprane name, JEC markets polymers under the Asaprene and Solprene names, 5. PHYSICAL PROPERTIES Properties of block polymers result from the number, length, and type of block segnenis, When tro incompatible polymers are mixed, phase scpara ion can occur, with one polymer becoming the dispersed phése end the other the continuous phose. This presence of the two-phase structure in atyrone-diene polymers hos been verified by sloctron microscope sludios roported by Varizo (1986), Vowy smell areas, or domains, of polystyrene dispersed in rubbery matrix ean be seen. The domains are so sinall thet | they do not xefeaot light; hence the block copolymers axe trensparent, oven though a physical blond of the sane homopolymers would be translucent. i Gertsin of the biock polymers display high tensiie strength without } ‘vuleanization or filler neinforeement. Im these block polymers, one segment sueh & polystyrens, provides “domains” thet reit'foree end effectively act a8 erosslinks fo the rabbery segments. The structure of styrenic block polymers, without aesoelation into domains, is iustvated in Figure 2. Vig ‘ure 3 tllusteates these same polymers with the styrene blocks assoulated {into domeins, Block polymers of the S-B tepered-block type were desorived by Cro and Short (1961) ano by Rallsback ot al. (1994). Polymers uf this (ype ere illustrated in Figure 9 aud have been aveflable since the early 1800s, The polymers to be described in this paper resulted from the dovelop- nent and characterization of copolymers with polystyrene blocks on each end of the polybutadiene ot Isonrcno chaing, The development of this tex of polymer ean be followed by examining several patents fesued to Pillip Petroleum Company (1987, 1083, 108a,5), Sono of the poly styreno-blocks on both ends: aro dosextbed’ 48 tnoan en $18 o7 S and others as racial or (S-B),% structures, as illustrated in Figure 3,Etn---25-.1--1 avjnoojou remot Jo saowsjod ueyy royeq WBuETs oF sursjor !y3Buems opsusy so! ouexkys-ousypeyng oav su0yjo ‘eussKys uojsuayxe uo USN Inset SOATPPY WIS, nu uy “sear a WOSV, Aquo Bune 48 zo um ve 89 8 06 £6 ssoupam v 9404S coer ose oss osor oze 002 ose 002 % ‘uoREsuorE “ “ean acd ate ate s-or “0% pee onue 6-92 suBuens Sysuen 20 ae ae or a ee uy ty vaw ‘snrapow yoor (2% 8/0002) 6 ° > e e ° ¥ ° mou HEH z6"0 ¥6"0 26"0 z6'0 ¥6°0 $60 s6°0 Ayjavad opwods swourT seourl wou reper pew werent werpew aanjonais jo 24s, - - - - warn nor at sm “roW8 seize oe/oz astiss ov/o9 ovsoe ouascys/urjerora Storr Zour rrr sty ur vip 90 = wows jujg 0 ouesdyos Zz f@ dowueg pewwanesun WWM SuouAIOa PoPUNRxOUON | IIGVL ose era ee a eae ear SeThermoplastic Styrene ‘Block Copatymers #319 TACLE 2 Nonlextended Polymers with Saturated Center Blook® Solprene Kreton Keaton sae G 1850 6 1639 Olefin/styzene ratio 70/30 0/36 0/90 Specific gravity 0.91 os 0.81 i Molt flow (190°C /21.6 kg)” 0.9 0 2.5 f 300 modulus, MPa 50 a8 35 Tensile strength, Pa 29.6 35,5 23.5 Elongation, & 540 460 20 Shore A hardness a6 2 m “partial sisting only. : Pasty D 1233, 7 ‘The term "toloblack" is used to describe polymers with temuinal blooks of one of the monamers. ‘The radiat teleblocis polymers have three or mera polymer chains extending fom the ne central numb, with » polysts Ulocle atteched to the outer end of the polymer chain that extends from the conten hub. | As previously mentioned, a two-phase system Is formed at ambient tax persture, with the polystyrene segments associating into "domains" that are oonnested by flexible polybutadiene or polyisoprene chains. This 1e- salts in an elastomeric network being formed without the necessity of fore- | ing crossinks dy conventional sulfar-accelerator curing systems. Polymers of this type have high tensile steengti, resitfence, and onefficient of fric- | Vion. When heated, the polymers soften, the polystyrene domains disssoc~ ete, and the polymer will flow under pressure. In addition to high strength, elasticity, resilience, and thermoplecticity i | the polybutadiene-styrene telebtock polyners have other advantageous attri- i 1 Duies as listed below: They are elastonerte, Thelv serap can be recycied They brve high tensile strength et moderate tempersture. They cen be prepared or compounded to give a wide ange in hardness. They gossess a high coefficient of fe Vuleanization is not needed. They have good color. 4 They axe therneplesti Pe They have good low-temperature properties. ‘hele die swell is low though the polymers have all the advanteges listed ebove, there ere Hons. Tensile strength and hardnass decrease as temperature in- creases. with strength and hardness boveming low ae the softening point of the polymers is approached. The unssturated nature of the polybutadiene Bnitsaw ‘enmpod $008 gE G/D0007) MOT MPM Ayana: op DETS s ‘erqnroneaa nme 30 oSALee = eo vcvyursote cret-cuatn (TETRA-CHATN A Bb Fig. 2 Linear and radial heenched butadlene-styrene copolymers — roLveuTAgiene sa ea nd PoLrstraine 12) { | Fig. 3 Structure of butadions-atyrene block polymers alter assoclation of | the styrene blecks. uDaaa | wileer susceptible 10 © ance £6 O80 techniques .4 by hydreeen a segment stakes 1 we desorbed end i ynparison attack ean be improve Denes of ene ‘(asesi. one ores of paper by Senge tes exnirted by the SB ff tensile proper! two palywers, the SEES antate bazner mecUes the Higher assosiation OCTET and the apsenee stantial interface V2 wpe in the S-EB-S POWNT The alengation > oiyimer i2 100" Sean te SES TOE as #0 jn tempers Tor the SBS PASE th yelationeny allows the ft would not be possible er ssinetler conto ture is such 1 < pp-S polymer mem 5 for THe rynis aitference in *he Temporoture tensile Steen SLER-S polymer 10 be Use “replications wnere | to utilize the S-B-8 19 polymers: ne block porymers would pele cont tensiie proneTEle® fof SB poner $ give eostinetiy gt Tensile Strength resgerctin’ of the marDTOICey of styre G) the aeddedly £0 areed v0 S-B-8 and (2) 9 the redial & ugner tensile cree 1 ‘the other to *YDES: me aloned ag ouster of ‘yoiecates formed DY agooriat ermente: with payenbadle span extending Tor #7 Sean, atthoueh the PONT rains axe neld rigse! 1h polvetyrone ends ths eadiene crams are THIN NOE eeraceive sorees end SSF ininon of oneis eneamelenes rors have wre fenele ef ast be corer tw ero she associated an contrast te the ongth itt rubbery prouul ors of elven the Tineer © sadiot type oenibit I contigs in the ‘uncured state thet ere typical of what 15 expected frou ruleanized 7ubOe?. ‘phe unusually HED green sireneth ‘of these palymeTs Tocultg, fron the Extenls © networ created a5 THE poiyatyreno HlOCRS form reehy conaine- 1% addition pe domaine provicing Se that oer? 3S pertain acaount of enh eampiement of te SUDDRTE fictive ovens HKS: portion of the mele ‘ogous aoe ite et whion the UE TE merits is in dtsell 6h effective er some 60! to understand fon of the palststyZEn? etyren® ely polymers veuall the §-B-S pout jensile PrOP™ cece tno veri POAYSETT TS nea, the S-B-S pore ‘og fs one important rasstinks- ernioal are not easily orally roveTsle TAGLE » stress Strait propertics Percent styren® 30 Moteculer weight 180,000 spenatle strengits MRE aot 90% modulus. MPa 28 wlongations 0 112211222 prowextie® quality roversibl®. Tooting aennene?wnnded 9929991121 11721112ET a ee eT Se OS SST ee eee Cee eee Thermoplastic Styrene Block Copolymers f 323 TENSILE STRENGTH, MOLECULAR MPa 20 20 a 60 TEST TEMPERATURE, “C Fig. ¢ Tho influmae of molecular welght of an S+B-S polymer on service temporsture. the $-2-S polymers to 4 temperature above the soflening point of the poly: siyrene allews them to be processed as thermoplastics, As the polymer cools, the network 1s again established, and the orlginel propertiss ore restored The tonsile strengin of $-B-S polymers increases with atl increase in poreant styrene or an increase ti inlecular welgli, Aa exauple of thete responses is shown in Table 4. An ineresse in moleealan weight will result in an inevesse in the service tenpeseture of the 8.D-S polymers, The change iu service tempersture for w change in noleoular weight of 60/40 5-B-8 polymers is showa in Figure 4. Moston et al, (1968) reported thet the stress-strain properties of 8-1 polymers that contain 20-49 wt & polystyrene and have molecular weights in the range of 60,000--160,000 chow Tittle effect of molecular weight vinen canpered at constant composition. Zolinelt and Cididens (1805) found that . fat higher molcoulae weights, increasing molecular weight causes an ineroese in tonsils strength, Polymers having the best balance of rupoer properties veuslly contein 20-40 wt € polystyrene. Below this range the tensile strength ie reduced. Above this range. polymers have yield points and exhibit cold draw properties. 5.2 Hardness Hardness of an S-B-8 styrene polymer is siromgly dependent on polystyzene content. The Store hardness increese with an increase in polystyrene oon tent is shown in Table 5, a 5.3 Melt Flow | Nell flow of 6-B ond $:B-S po'ywons has boon studled by Kraus und Gruver (1361), ‘They reported the melt vizeoaities of block pelymers to Le higher then those of either the homopolymers or the corresponding random eepoly mers. The higher viscosities are attributed to the poreietence of thr3m) wilder TABLE 5 Effect of Styrene Content on Harsies wes Moteculor ‘Styrene Weight 20 160, 000 a 0 140,000 6 Cy 120,000 atwont in eho mett, ‘Van der Big ond Vig (1900) reported Uy af femporatire on melt viscosity is anich more pronounce at low ener rtee,” Processing under low-shiear conditiont should te dove the upper gna of the tempersture renge. igh-skesr processing such os injestion molding, ean be done over & wider tempersfire "INES 5.8 Stress Softening opetted extension of conventionally crosslinked of cared clactomers Jeads server atresses at the came exteneion, This stress soffotnG also 0b te nea with $-B-8 polywers, Zoinsld snd Childers (1068) ond Childers #2 Finmus (1$67) reported that B-B-S polymers with styzon® °° ext above 306 voit vied golais and atrege saflening, With Ineeensing SI" ostent. e yield point ceeurs Inferconnections betsteen demulrs increase, sed eee eryenk je broken. In polymers that do. rot shit el points ies rpiening:ocoune when polystyrene J3 puled out of 18 CCR sey oflening of 8-8-8 potyners ts reversible: If the seni rdexed aera ae at elevated temporctanes, the original stese-et7tn propertioe are recovered. 5,5 Glass Transition Temperature styrene-butediene random copolymers exbibt single Bl) tronaition tenper- atures intermediate botween those of polystyrene ‘and polybatediene. | Blodk Gopelynens of butadiene ard styrene with sufficiently Ig blocks exhibit two guise transition pointe or fenperatures close 19 the ilase tronsition temperatures of the individual homopely mers 5.6 Environmental Resistance Weather resistance of styrene block copolymers that have ungeturated mid renee antler to that of excision op solution SDR. indore’ phenols in combination with aithiodiprepionate asters are weeftl o sidants. zine dibutyl dltlocarbanaie improves high-temperature properties, Ozone re Metanee of styrene biosk copetymers can be mprovel by s6c0le of 20-90 SL EPDM or BVA. The satureted styrame block enpelyieess 2% much Teslstant to aging than the ansaruratel types: -Appuestion of these teah- hologies will be éisivased in Section 6 5.7 Abrasion Resistance ‘The ebrecion resistence of the solution blook: polymers *§ sufficient any B fe gt a suitable us would be in stor soles TREThermeplastic Styrene Block Copofymers /. 325 TABLE 6 Teleblock Polymers ut Byual Foriulation Viscosity (10/30 Buttadiene-Btyrene Copolymers) Shear Resistance, chain Molecular Formulation Hours to Fail Structure Weight Visoosity, Pars at 90°C binver 84,000 1.82 ie Trichoin 136,000 1.68 a4 Tetrachain 193,000 18 as yesistence can be improved by the incarporation of such compounding in- gredients as siliee, clay, or carbon bleck 5.8 Coefficiant of Friction ‘The euefficient of friction characteristies of the 8-B-S thermoplastic poly- ‘ners are in Uie Same range ws rubbers such as natural rubber aud euulsioa SBR. This property is distinctly advantageous compared to the velues ex- uibleed by many flexible plastics 5.9 Crack Growth { | the solvtion §--8 themeplnstic duster growth that ie good und ox Ge sign! 5.10 Shear Rasistance in Adhesives. Mononex etic, moléenlan weight, and tiranchiny influence the resistance to failure under shecr of the butadiene-styrene polymens used 1n adinesives Higher molecular weight, styrene content, and inereased branching ali in- creas the shear resistance. Increases in moleculat weight and styrene content incresse viscosity: nowever, a Menegse 1a branching recuves viscosity. At sintlar formulation viscosity, there Is an Inerease in shear resistance as the golyner chein structure changes from Unear te trichain to tetrachain. ‘This change wes shown by Marrs et al. (1973). This infor: pation fs shown In Table # 5.11 Peal Streneth in Adhesive Formulations Peel atrengtis follow the same general trends 93 aheor strengths. Best peel strengths are obtained with relatively high styrene eontente (oxg-. 408). Iligher ncleoulor weights give beller peel strengths. ‘The increase in molecular weight or styrene content may be Hnited by the desired took and viscosity, 6 COMPOUNDING Various materials miy be added to S-B-S oF S-I-S block thermoplastic cor polymers to, modify properties or lozer the enst af the compound for ¢326 | Wilder pamicular use, ‘these meterlats include filers, plasticizers, wesins. anll- Gogeadants, and other polrners. Thermoplestie polymers of the 5-B-S ‘type com also de used to modify properties of othor polymers such 8 poly olefins and polystyrene, The block polymere when used es modifiers can often be used without other ingrediants. Tho thermoplastic block polymers find use as modiflers for asphaltic material. 1 Fillers: Reinfording finers do uot improve the tonsile strength but do increase modulus, tear strength, hardness, flex life, and abrasion resistence. Gooper et al, (1978) reported en the influer-> of a range of carbon blacks varying in surface area, structure, and surfece chemistry in S-B-8 thermo: plastic polymers (plastomers). In simple compounds with plestomers, 2H” toa blacks imperted improved resistance to ultraviolet light, improved room” temperature and fol teor resistonge, and Inpraved fot tensile etrengt> Fillers ouch ao titanium éioxide and sine oxide may aloo be used to give improved resistance lo ultraviolet radiation. Whiting incresoos harénoes to a loesar daytee than clay but coonessas toneile strength and sbrasion resistance, Melt flow is reduced by mineral fillers. £.2 Qils anc Plasticizers Addition oF process oils 10 thermoplastic blosk $-B-S polymers: generelhs inareases melt flow and Nex life. Conversely, tensile strength, hananoss, and abrasion resisiance are veckced, Naphthenio oile eve a less harmful Influence on tensile strengity and hardness than aromatic oils oF ester plas tisizers. The ester plasticizers and aromatic oll hava-a tendency ta soften tiie polystyrene Wock of the S-B-S pelymers. Only low levels of paraffinic iis Should be used, as these alls are besically incompatible wlth tthe block copolymers and tend to bleed from the polymer or conpcund, Materiele other tha oils way be uscd ao plasticizers, especiaily where the compounds fe at Kigher teeperatures. Sone plasticizers may reduce the stability of ‘compounds 5 degradation by uliraviolet light. In sun cases It may b° necessary lo add pigmenio or other ultraviolet stabilizers, 6.3 Resins Resins are useful in edjusting hardness and In Increasing melt How und adhesion. A combination of resing is often used to achieve @ desired bal aneo of pvopertion. Many of the resins tend to reduce the rubbery fecl of the thomnoplasite polymers. Resins exe commonly used in combination with other ingredients (fillers and oils), Resins sre used in adhesives 0 1" prove adhesion, tock, peel strength, and sheer slrength. In molded yonds and in extvuded goods, plesties and xésins can be odded to the compounds to adjast nardness, improve distortion resistanos, and reduee viscosity at plevated temperatures lo inprove elevated temperature processing, |The influence of « number of different resins in a variety of applications was Gescribed by Baws and Wright (1976) 6,4 Stabilization When, blended with block elestomere, unsaturated polymers such as BP and with tow on (2-g++ FPDM) ere usefit in Inproving the re rere ae ae ee ee er ee er a ee ee eeta - FGIIFTTEIIETE Thermoplastic Styrene Block Copolymers / 327 TABLE 7 Summary of Rffects of Compounding Ingredients ———— Malt Abrasion Flex Flow Tensile Toar Hardness Resistance Life ford chy, sites ff { ie oe (Se a [panes Polystyrene Sere eat { t as polyindene vests PT = 1 Naphthente ofl t 4 Leet | 1 stability of the thermoplastic block polymers. Improved stability may also be obtained by use of suitable antioxidants and antiozonants. 6.5 Summary of Compounding Compounding of the thermoplastic polymers for many applications is siniler The influence of many compounding ingredients in footWear wus deseribed in bulletin $01-A, "Footwear and Shoe Products," published by Phillipe Chemice) Company. ‘Table 7 summarizes those data for shoe soles. Siutlur trends would be expected for many other applications, The changes to be pected for increasing lovels of ingredionts are indicated by the arrows #s follows: , increase; |, decrease; horlzontal arrow with turned head indi- cates slight incvesse or decrease; and angled arrow indicates that property goes through « maximum. 7. MIXING AND PROCESSING Internal mixers, open roll mills, or dry-blending methods may be used to trix the thermoplastic block polymers with the various compounding ingved- ients. 7.1 Open Mill Mixing Mixing on an open roll will xequives mill rolls to be maintained in the range of 80-105°C. Smooth banding fs not obtalned if roll temperatures are too cool, while sticking occurs if rolls are too warm, 7.2 Banbury Mixing Internal mixers such as Banburys permit fast and efficient processing. The tnermopiastic polymere will build up heat as ey sre mastiented. Use of a prehccted mixer chamber may further sid incorporation if » larg ameunt of filler or ofl will be added. Incremental addition of oll is xequired if large amounts of ofl are to be added, Addition of the firet portion of oil early in the mixing cyclo may be beneficiel to flux tho ingrodionts. If # high-melting resin such as polystyrene ov polyothylene is to be added,328 | Wilder the melt temperature should be reached before any oll is added, | 7 obtain ood fluxing and proper mixing and blending, temporsture contro! £3 impor ver with tie thermoplastic polymers. Tt ia rooommended that the pps Iimits of mixer discharge tenpereture not exceed 150-160°C. ‘k suggested Banbury mixing eyele $= shown below for # high filler/ high of! compound ela. eee ee Prohest mixer to 65-95°C, 0 min Add all ingredionts except oll.* 23 min Sorape and add one-fourth the ofl. When power load jnereases, add another inerement of oil; end continue ty odd ofl in this manner until ell ofl Is added. 148-160°C Discherge. sheet off on a roll mill wth roll emperotures of 85~ 108°C. ‘For very high ofl and filer levels, a smell amount of oil may bbe added at 4 min to wet the fillers. 7.3. Dey Blending Dry blending is defined as the mechanical mixing of the comport of « compound to give an even dispersion thraughout the mixtthh without causing the mixing temperature to rise above tho melting temperature of the polymers ov ingredients, With this mixing procedure, D4 results are saedeaty it the materials to bo blended are neerly the sane particle size. Tt is particulasly cesinabie to have all polymenie materiel nearly the same particle site, Absorbed ol tends to cover the surface of ‘tho polymer par~ Files ana enould ind the costing of filers, stebilizers, and powdered reeins- rhe advantages of dry blending in coaporison to other mixing tech- niques are that it: 1. Hiiminates internal mixers 2. Eliminates pelletizing by feeding typical plastic fabrication equip- ment with the dry blend 3, Reduces mixing tine 4, Reduces mixing cost the éry-mixing technique requires that the plastoners be ueee 1 & tree-fowing powder. The thermoplastic polymers em be purchase! in free-flowing Dom petyaer cam be ground on sito in commereialy availabe equipment. A typical dxy-blend nix oyele for a Welox sit mixer with @ water-cooled jacket is tho following: Sig i wees es eee en 0 min ‘Aad ail ingredients orcopt any resins aelting bolow 1100+ Mix for 40 soe with mixer specd of 99 KE (1500 rom)» 0.5 min Begin gradual addition of ofl. Reduce speed ‘0 29 HE (1200 wn) during ofl addition, An addition tine of 45-60 eee is suggested for 40-50 phr of of!‘ TA Thermoplastic Styrene Block Copolymers / 329 Mix at 90 kilz (1500 xpm) until the compound appears te be free-flowing. ff powdered resins are being added, add after the mixture is free flowing and mix en ad tional 80 see at 39.3-41.7 He (2000-2500 rpm) 1.5 min Discharge the batch. The temperature of the compound should be at or below 65°C to prevent softening and ‘agglomeration of the ingredients, Be i ce 4-6 min 1.4 Peleting and Chopping rounded stock that is to be utilized in an injection-molding machine will feed to the molder, Dry-blended compounds in which they are discharged from the dry Bender, Compounded stock mixed in an internal mixor is normally milled. stripped, pelletized, ot chopped for ease of feeding to the injection-mold- ing machine, One method of pelletizing is io strip-food into an extruder ind oxtrade through a multistrand die, Strands are thoroughly cooled end fre dried if they have been cooled in a water bath. Strands are fo to & pelleizer, where they are cut into pellets. Pelletizer blades must be sharp and adjusted to very low clearance. Comp must be in a form that are satisfactory in the form 8, APPLICATIONS The unique combination of the thermoplastic and eustoneric natures of the §-B, $-B-S, SIS, and radial, triblock, or multiblock $-B-8 cqpolymere offers many advantages to industrial users. Major fields of applications are footwear, molded or extruded goods, adhesives, and 3s modifiers for asphalt and thermoplastic resins. 8.1 Footwear Footwear represents the single largest use of styrene block copolymers, Benefits of styrenic thermoplastic olestomers include the following: 1, Sttiefactory abrasion resistance end flexiniity 2. Intense eolorability 3. Good traction 4, Firmness 5. Low cost 8, Elimination of vulcanization with attendant savings in curatlves, processing, snd curing cost 7. Reusebility of corap ond trimmings 8, High tensile strength . 8, Ability to be made translucent 10. Capability of being compounded or manufactured to a wide varie tion in harness 1. Good moldabitity In addition to the above properties, en injection-molding compound must be capable of being used in low-pressure motling machines for molsing soles directly to shoe uppers. Good flow is also « requirement for the molding cof unit-type soles, which are cemented to shoe uppers.330 / Wilder TABLE @ Effects of Silica and Whiting in Soling Formula Solprene 475 150 150 350 150 Precipitated, hydrated silica 20 40 20 35 Precipitated whiting 80 #0 80 80 Naphthenie oit 60 100 100 130 Polystyrene 80 80 100 100 Stearic acid a nied 3 Dileuryl thiodipropionate 0.50 0,50 0.50 0.50 Hindered phenol 0.30 0.30 0.30 0.20 Properties Specific gravity 112 1a 1.10 113 Melt flow (2.16 kg, 190°C), 28 2 44 4 g/10 min 3008 modulus, MPa 1.82 2.34 1.62 2.48 Tensile strength, MPa 45 4.40 4.00 5.48 Elongation, § 500 510 410 420 Crescent tear, KN/m 26.25 4.50 21.0 21.0 Shore A hardness # aT 3 a Ross flex, em growth at 0.18 0.15 0.29 0.15 100,000 flexures Solprenes 475 and 481 (see Table 3) possess many of the basic physical properties necessary for this application, including inherently high green tensile strength and good low-temperature properties, and aro considered to be self-reinforcing. The addition of mineral fillers and certaln resins Imodifies such properties as tear resistance, hardness, abrasion resistance, anf flex life. Abrasion resistance, modulus, and melt flow are influenced by polystyrene resins and naphthenie oils. ‘The eost snd physical prop- erties of the shoe sole compotinds are controlled by proper selection of the types and ratios of these ingredients. Typical mineral fillers are silions and whitings. Fillers of these types have been shown to reduce cost, im part hardness, stiffness, and abrasion resistance, ond improve flex iif. An example of the influence of these compounding ingredients ts shown in Table 8. A low-melting-point crystal polystyrene is an excellent additive for use in §-B-S multiple block radial polymer soling compound, Poly-0- nethylotyrene 1s another usoful resin in the block polymers. Beth are clear thermoplastic rasins with low specific gravitles. Polystyrene acts #s a reinforeing agent in soling compounds. “Poly-c-methylstyrene is less reinforeing than polystyrene but increases melt flow and lowers the costThermoplastic Styrene Block Copolymers { 337 4, in normal pellet form, polystyrene requires grinding of soling compoun to permit it to be adequately dispersed if dxy-mbs pro- into a finer form cedures are used. ‘Oils are used as softeners and processing dids in radjal-teleblock-based polymer ($-B-8) soling compounds. Used in combination with mineral fillers iid the resins, oils can reduce hardness and cost and inpre*® melt flow. Rephthenie oils heve been found to be the Dest lls for Hee in butadiene iyrene block copolymers. Aromatic oils are compatthle with the S-B-S black polymers but produce poor color and poor color stability. Paraffinic vite are generauy nanginel in compatiblity and tend to bleot from many fompounds. Ircompatible ails are detrimental to adhesion with shoe sole Sompounds and other perte of the shoe, Tuble 9 tlusteates formulations Grd the influence of resins and napht\nic oll. TABLE § Effect of Polystyrene and Oil in $-B-S Multichain Soling Compound® Formula Solprene 475 180 150 150 130 Polystyrene - 40 - a) 80 90 180 180 Precipitated silica 1 | Titanium dioxide 20 0 1 Naphthenic oi 0 x0 30 0 = Polyindons resin wo 30 30 30 | Stearic acid 3 3 3 3 ' Dilaury! thiodipropionate 05 0.8 0.5 0.5 ' Hindered phenol 0.3 0.3 03 03 ' Properties ' Specific gravity 1.19 118 1,35 1.31 ' Melt flow (2.16 ke, 190°C), 2 6 49 % g/30 min | 300% modulus, MPa ag 2.98 4.02 2.89 ' Tensile strength, MPa 9.28 1.58 5.98 6.20 ' Elongation, 1900 10 1050 00 | Crescent tear, kN/ 3568.0 280 38.5 | Shore A hardness 80 8 8 50 oss flex, em growth at or 0 0 0.18 t 100,000 flexures | ®regt values determined on compression-molied semples-t 332 J Wilder ‘As monufactured, the S-B-S radial multiple block polymers contain in the range of 0.5~1.0% stabilizer. In addition to the usual aging chavacter- isties expected for shoe soling and shoe products, other conditions of manu- facture and stability during use must be considered. ‘These added condi- tions include (1) stability during high-temperature molding (up to 280°C) and (2) color stebility in ultraviolet light. For general protection it is recommended that 0.5 phr of dilsuryl thiodipropionate and 0.3 phr of @ hindered phencl-type antioxidant be incorporated into tle stock during compounding. In translucent soling, up to 0.5 phr of an ultraviolet light absorber should be added for additional ultraviolet igh: protection. In white soling compounds, the use of titanium dioxide or zine oxide to pro- ‘vide the white color elso provides screening of the ultraviolet light rays. ‘The combination of white mineral fillers with ultraviolet ight absorbers provides the maximum protection. Conditions for injection molding will depend on the type of formulation used and the type of injection-molding machine to be used. Some suggested conditions to be used, as ¢ starting point, are given below for two types of equipment: 1. For multistation or single-station’injection-molding machines designed for molding soles to uppers, the compound should have high melt flow (20-60 g/10 min at 2.16 kz end 190°C). Barvel temperature Injection pressure (30-2070 kPa Infection time 1.5-3 sec Cycle time 20 see to 2 min, depending on the type of injection and cooling methods Mold temperature 052 °C 2. For higher presstire reciprocating screw injection machines, melt flow of the soling compound should be similar to that used for the mmultistation machines. Other conditions for this type of machine are: Cylinder temperature 130~170°C Injection pressure 8.89-3.4.45 MPa Mold temperature 0-379 8.2 Molded and Extruded Goods . The properties of the $-B-S redial block polymers provide many advantages in molded and extruded applications or so-called mechanical rubber goods (WRG). ‘These polymers eliminate the costly curing operations, and eorap is reussble, ‘Compounds for outdoor applications usually employ 8-EB-S thermoplastic polymers because of thelr improved aging resistance. Important uses are -wv VIFFTFFECCIFTFCFEFECCCCC ©crcrucss plastic Styrene Block Copolymers / 333 Thermo BLE 19 Formulation and Properties of ¢ TA uttiblock $-B-S Polymer in a CoverB Compound gS ee Formulation eine sotprene 406 100 Soft. clay 400 Naphthente il 6 ‘Aliphatic hydrocarbon resin 10 stearic cid 5 Properties Extrusion, Garvey die, at 160°C. m/min 29 g/min 165 ‘Appearance (0-12, 12 best) we ‘Tensile strength at 27°C, MPs 6.2 Flongation et 21°C, & 80 Crescent tear at 27°C, KN/m 28 80 sions, wire and Compounds for these nthenic oil. and je compounds saften 5, Lumper and fender exte yasas, and gaskets. automobile body filler panel hnose and tubings. cove 0 ‘calcium carbonate fillers, nap! cables, applications typicelly eontein other thermoplastic resins. usually contain polypropylene for ing at elevated temperatures. though in many eases the S-B-6 multiblock polple are not used slong (sole polymer) jn molded and extruded goods, ‘hese polymers have @ tide application as processing aids for many other ‘yypes of elastomers. At Tevels up to 208, the multibleck polymers improve ‘mold flow, extrusion rate, se wtemperature properties and reduce die swol Other advantages to the §-2-S polymers in blends include incressed hardness and good flex life ‘A typical cove base compound formulation ant ‘the properties obtained with it are shown in Table 10. This type of eompound is typically low in fost, and the added savings eveilable from the liminstion of the curing step by the use of the S-B-S polymer becomes significant factor. igh seeeg of clay and oll reduce tho total cst of the ‘compounding ingredients. tthe outstanding ozone resistance obtrined by the combination of a S-B-S block polymer with ¢ low-saturation polymer 1s flustrated in Table 11, This table ghowe typical formulation «nd properties ‘of an extrusion or molding goods conpound. Although this compound ‘contains wax to impart improved rote resietance, it ig considered that ost of the Smprovement results from sng used to provide ozone ‘Automotive and wire and cable added stiffness and resistance to s the use of the BPDM polymer, The test specine mrciatence date for this table were tested 5 bent loops and strips elongated 10-208.534 | Wilder TABLE 11 Extrusion or Nolding Compound vith Outstanding Ozone Resistance Formulation Solprene 475 150 EPDM (Epsyn 5508) 20 Hard clay 80 Naphthenfc ofl 50 Polystyrene 49 Wax: 6 Stearic acid 3 N660 carbon black 5 Properties Melt flow (180°C, 5 kg), @/10 min 9 Extrusion at 128°C (window channel die) 5 m/min 50.8 efmin 13 Tensile strength, MPa 4.96 Elongation, % 300 Shore A handna 50 Ozone resistance (Ozone Chamber, No cracking 26 days, 50 pphm ozone) 8.3. Asphalt Modification Due to the relatively low cost of asphalt, it is widely used in paving and Toofing, as e water barrier in construction, as a joint sealer in road con- struction and maintenance, in mastics, in eutomobile undercoating, and tn waterproofing materials. The chief disadvantages to asphalt in many of ‘these applications are (1) brittleness at low temperatures, (2) excessive flow at high temperatures, and (3) low elasticity. Incorporation of thermo- plastic block copolymers into esphelt grestly extends the serviceability of the asphalt, although these polymers are effective in paving asphalts, alleviating low-temperature brittleness and imparting resistance to flow st higher temperatures, their relatively high cost in relstion to the cost of the asphalt hes to some extent inhibited extensive use in road surfacing. This is not the ease in the other applications mentioned previously, since price is not as serious a deterrent in the smaller volume applications, The use of S-B-8 thermoplastic polymers appears to be particularly sttractive in high- quality membranes. In this application the carrier base may be nonwoven fabric, end the asphalt may contain 10-148 of a linear or multiblock $-B-S polymer. Asphalts are very complex mixtures of many different materials ranging from oils to high-moleeular-weight compounds. For simplicity, they aro usually considered to bo of two principal fractions, maltenas and asphwwe wwvwvwwwe ww www#weeaeuvwveesuevs®e Sere Thermoplastic Styrene Black Copolymers, / 335 ave the lower-moleculer-weight components, serve us qhe solvent for the asphaltenes of Tigher-motacular-woight cateriels. Kraus int, Rollmann (1980) reported that ‘§°B-S-modified asphalt exhibits two prose structure at T00m Temperature. The polymer, swollen 0¥ the maltene Fraction of the esphelt, forms & Network extending throughout the system. fre other phase is the asphaltene, fontaining Bttle or no rubber. At qrainary temperatures, the polybutadiene microphase conteins most of the ‘the rubber network remains tne modified ase ‘pne maitenes, fraitene diluent. At ordinary temperatures, Titect and provides the elastomeric characteristics displayed by t fephatt. At service temperatures, §-B-S thermoplastic polymers incr: fhe viscosity of the asphalt, and How greatly reduced. However, at processing @n mmporatures, the viscosity at the elevated tem peratures is sharply decrens® ities of the polymer-asphalt xd, and the viseo Frends axe only slightly higher than that of the esphelt alone. xeorporate ‘The block polymers are inc if into the asphalt by stirring the 4 form into the molt aiymer in powdered oF Broun fen asphalt at « temperature Pr ya)-205°C. High-shear mixers af ‘useful but ere not essential. Times fo incorporate the polymer into the asphalt ere 20 min to 1 hr. 8 hr at the elevated temperatures, mrelts ore fairly steble. However, after tion is evident by large increases In aie degradation cceurs. The degrade wt visoosity. If storage of the hot ixture cannot be avoided, it is recom metided that the temperature be redueed’ © ‘blanket of inert gas be employed, wd the use of high-shear mixers be avoided re modification of saphalt by block polyaen (u9se), Kelly and Bresson (1982) geseribed the wse of th the riodifiction of asphalts for use Jn paving applications 15 was described by Kraus ye $-B-S polymers 8.4 Plastic Modification jon of other plas~ styrene loc copolymers are widely used 5p odificatio ily processed in conventional piss Se resins, The S-B-S polymers are res tie equipment. The polyners blend wel ‘xith most plastics, including poly Styrene, polyethylene, and polyPropyien- es the block poly styerea‘es a modifier can be mixed with th ye blend during fabriestion 1 in the use of $-B-8 polymers for tho modification ‘The inherent adventage of plastics are discussed below for nigh-density potyettglene and polystyrene: In many cas .e basie resin in a sim High-Density Polyethylene tal adattlon of $-B-S block polymers wil density polyethylene coffer the following Increment rable changes to high Jd impact strength ness (elongation a fe of molded parts it the application 1, Improves 2. Improved tough wnd tear strength) 3, Reduced warpagt iL, Varieble flexibility to em Polystyrene tal addition of yrene will result in Increment g-B+8 polymers to general-purpose ont {impact net telowing desirable property changes" grade poly 1, Improved impact strength 3 Improved toughness (elongation and tear strength) Improved floxibflty336 / Wilder ia In selecting the most effective modifier, the following generalizations can be used: 1. Higher butadiene levels offer greater impact {improvement and flexibility l 2, Higher-moleeular-weight polymers are more efficient modifiers 3. Lower-molecular-weight polymers are more easily dispersed To obtain the optimum improvement of resin properties, it is necessary to achieve a homogeneous blend. Extruder screws thet sro designed to function as melt pumps generelly give unsatisfactory results. If improved mixing is needed in e plant operation, a mixing section or mixing pins can be added to @ screw already in use. Extensive mixing of certain elastomer-plastic resin blends ean provide less than the optimum improvement in properties, For example, blends of radial $-B-S polymers with crystal polystyrene prepared ine Banbury mixer have lower impact strength than the seme blends that have been prepared by extrusion mixing, This indicates it is possible to disperse the elastomer Into particles thet are so small thet they lose some of their effectiveness. An example of the impact strength of polystyrene being significantly improved by blending an S-B-S multiblock polymer with the polystyrene is shown in Table 12, 8.5. Adhesives Styrenic thermoplastic elastomers have found application in many different types of adhesives, vecause they ean be formulated to provide a wide range of properties. They ave soluble in conmon solvents and can be applied as coments or mastios. Ther thermoplastic nature also allows them to be form- ulated and applied as hot melts. Sone of the advantages of the $-B-S block polymers are Polymers are directly soluble—no milting necessary Solution times are shorter—greater output Solutions are more uniform—better control a Solution viscosity is lower—higher solids level, lower colvent cost Solutions are stable—longer shelf life TABLE 12 Modification of the Impact Strength of Polystyrene by Incorporation of a Thermoplastic $-B-S Multiblock Polymer General-Purpose Generel-Purpose Polystyrene Blended Property Polystyrene with 198 Solprene 417 Nelt index 35 4.0 ‘Tensile strength, MPa 63.2 38.2 Elongation, & 9. 38 Notched izod impact, J/em om 0.95 =TITIFTIFTTIGUUIIII III] Thermoplastic Styrene Block Copolymers | 337 Sensitive Adhesives TABLE 13° Hot-Melt Pres: 8-1-8 Polymer, 15 polystyrene Og tackifying resin, soft. point 100°C 100100100100 C5 teckifying resin, soft. point 10°c - - 0 Naphthenie oil 20 40 Se Brookfield viscosity, Pa-s at 177°C 76.5 425 Od 32 Rolling ball tack, em 250 18 lo 2.0 Polyken tack, ¢ 10 = sto t020 90 180° peel, KN /m 09)" 06 ta oe Pressure-Sensitive Adhesives Pressure-sensitive adhesives based on §-B-S and 8-1-8 thermoplastic block copolymers have outstanding resistance to creep, since the polymer can undergo viscous flow only by detachment of polystyrene blocks from do- mains with subsequent reattachment of the blocks to other domains. Com- pounding of pressure-sensitive (permanently tacky) adhesives is essentially a compromise, ‘The mass coat must be soft enough to wet the substrate yet have sufficient strength to withstand moderate stresses. Certain types of resins designated as tackifying resins are commonly used to increa tack of the clastom lyivers. Resins that teckify styrene block eo- polymers apparently conbine with the rubbery midblock portion of the bloc Polymer. Kraus et al. (1977), using electron micrographs of a blend of a Tosin ester tackifying resin with a radial block copolymer, found there was 4 volume inerease in the rubbery phase, with the overall morphology re- naining unchanged. The type of rubbery midblock will determine which tackifying resin are used, A variety of resin types are effective tackifiers for the poly isoprene midblocks. Rosin esters, pinene resins, and synthetic dipentene type resins are suitable for the polyisoprene midblocks. utadiono mig blocks are more difficult to tackify, and the choice of resins is limited: Rosin esters, some mixed olefin resins, and low-melting synthetic terpene resins can be used with the §-B-S thermoplastic polymers. Tho saturated midblocks are the most difficult to tackify, and it is often necessary to dd oi! or other plasticizers in adaition to the tackifying resins, Hot-Meit Adhesives Styrenie thermoplastic elastomers have mado possible the development of tubber-based hot-melt adhesives. This development has bean partiownrly important to formulators feed with increased solvent cost and government restrictions on the types and amounts of solvents that ean be réloased to he atmosphere, Table 19 illustrates the versatllity of styrene block oo nere in hot-melt pressure-sensitive adhesives. id plasticizers, such naphthenic oils wiecular-weight resins, ond polylscbutylenes, may be used to lower the melt visoosity. Plasticizexs weuelly enhance tack but my have a hermful effect on peel and shéar strengths. The high temperatures necessary for mixing hot-melt adhesives require that the e protected tr +A blanket of eaxbon dtoxd pol4 il i q 33a f Wider TABLE 14 Solvent Cements PO eh ae cee 8-B-S polymer, 30% styrene 100 100 Hydrogenated rosin ester 8 40 Coumarone-indene resin 0 0 Acetone 200 200 Hexane 230 250 Toluene 100 100 pet strength on cotton duck, KN/m 10.7 30.7 fabric fabric foilure failure ox nitrogen, in combination with antioxidant, fg useful in preventing do- gradation. mnors are preferred over S-B-S polymers for hot-melt ‘a higher level of tack and eihesives, because the 8-I-S polymers provide satos Tkely to form gel ducing process Partial replacement of S-I-S polymer with S-B polymer in hot met sahesive formulations provides Lower eet compounds. ‘Tho polymer blends tnin good adhgstve properties end adequate stability. Mosties and Cements tensile strength and ready solubility race advantages in solvent comonts and ‘mostics. The existence of two separate and essentially incompatible ogments in tho sone molecule shoud enatfen into eceount when the S-B-S Dlock polymers are compounded 2 ve Tent cements. Aromatic solvents dissolve ppoth polybutadiene and poly fiyrene and are good solvents for these polymers. Aliphatic solvente 5+ sire anty the polybutadiene blocks and news ‘will diseolve only thoee block uiymers whose styrene content i® 1o¥ ‘Biends of eiphatic and aromatic or Polar solvents em be used. The necoss ey fanount of polar solvent is de pifmined by the molecular weight and polystyrene ‘content of the polymer. The high of S-B-8 polymers are impor TABLE 18 Construction Adhesive ‘Typical Forimulation is $--8 polymer, 308 styrene 100 Hydrocarbon resin, softening Pent s00¢ 100 sydzocasvon resin, softening pint 14g 100 Hard clay 200 Polymerized 4,2-cihydro-2,2,4-trimethylquineline 2 pi-Senaphthvl-p-phenylenediamine 05 ‘Toluene u Textile spirits 350 12.5 et i be \Ber 8 BhCUSIP IEUV LEI LIGITIIIUGA Thermoplastic Styrene Block Copolymers | 339 ‘Typical high-strength cements are shown in Table 14. The best per- formance is often obtained by using a resin that preferentially associates with the midblock (midblock-associating) and styrene-associating resins. ‘Tackifying resins improve adhesion but usually lower the temperature re- sistanee. Conversely, a high-melting styrene-associating resin improves the temperature resistance but usually decreases the open time. At elevated temperatures, bond strength increases with increasing molecular weight and polystyrene content of the copolymer. Construction Adhesives ‘There is a growing use of mastics in construction projects for adhering wall panels and. plywood subflooring. The S-B-8 block polymers are particularly well suited for this application because of their high uncured strength. These mastics contain « rather nigh proportion of resin and clay. Hydro~ carbon resins with low residual unsaturation are suggested for better aging properties. Solvents are mostly naphtha with enough toluene added to dis- solve the polymer. A typical adhesive formulation is shown in Table 15 Clear Sealants Saturated $-EB-S thermoplastic polymere are used in clear sealant compo- sitions. The high tensile strength and good aging characteristics of those polymers provide high performance and long service life ‘The unique properties obtained without conventions) vulecnization makes the thermoplastic block polymers, with polystyrene bl-cks and rubbery midblocks of butadiene, isoprene, or saturated polymen. well suited for many applications. The association of the polystyrene into domeins accounts for the thermoplastic and elastomeric properties of these polymers, which in turn account for their use in many rubbery products. Their solubility characteristics combined with thelr inherent strengtn make the thermopias~ tle block polymers attractive for use in adhesives and for other solvent related applications. ACKNOWLEDGMENT ‘The contributions of Dr. B. D. Simpson, Phillips Chemieal Company, to this manuseript are gratefully acknowledged. REFERENCES Childers, C. W., and Kraus, G. (1967), Rubber Chem. Technol. 40:1189. Cooper, W. T., Railsbeck, H. B., and Wilder. C. R. (1978), J. Elastomers Plast. 10:173. Crouch, W. W., and Short, J. N. (1961), Rubber Plast. age 42: Firestone Rubber Company (1966), Neth. Pat. 67,1933, Gergen, W. P. (1985), 124th Mocting of the Rubber Division, ACS, Houston, Oot. 25-28, paper No. 57