CA2034194C - Solid block and random elastomeric copolymers - Google Patents

Abstract

There is disclosed a linear block copolymer comprising at least one triblock I-B-I, wherein I is a block of a polymerized conjugated diene of at least 5 carbon atoms, such as isoprene, and B is a block of a polymer of a conjugated diene, different from that of formula (1), of at least 4 carbon atoms, such as 1,3-butadiene. The B block is selectively hydrogenated, while each of the I blocks retains a sufficient amount of its original unsaturation to vulcanize the copolymer. There is also disclosed an alternative linear block copolymer containing at least one triblock of the first polymer block made from an aryl-substituted olefin, such as styrene, and the conjugated diene used to polymerize the block I, the second middle polymer block of the diene used to polymerize the block B, and the third polymer block which is the same as the first polymer block. In this alternative copolymer, the middle block is also selectively hydrogenated, thereby leaving the terminal polymer blocks with a sufficient amount of double bonds to vulcanize the copolymer.
The polymers can be crosslinked or functionalized through the terminal blocks containing the vinyl unsaturation. There are also disclosed random and star-branched block and random copolymers made from the same monomers as the linear block copolymers.
Also disclosed are methods of producing and selectively hydrogenating the polymers.

Description

~ ~03~194 soT.m BLOCR AND Ru~nx~M ELA~ J~lC o~poLyME~s ~ h;c invention relates to ela~ ic block ccpolymers having ~ Lion only in the terminal blocks; and to ~ cP.
for the ~L~a~ion Ul~L~oL. More part;n~l~rly, the invPnt;~n relates to solid elastomeric block copolymers comprising triblock units wherein the ~ lP block of each triblock unit is .l;Ally sPlect;vely h~dkvy~ ~l~ (and Ul~L~Lvl~ c~tA;nc ~uL~l~r-l ;A11Y no lmcA~lrated groups) while each of the ~Prr;n blocks of each tribloGk unit contains a ~lff;~;Pnt amount of lmcA~lration for vl~lrAn;~Ation. The invention also relates to L~ll copolymers which, when cPlpct;vely h~k~y~ ~bd, contain elastameric molPOllp-c having SU~ ;Al1y saturated ba~hLul~
and L~ll~ ~J~ unsaturation. The invpnt;nn further relatPc to rh ~;cAlly ~;f;P~ derivative-c of the above blo~k and random capolymers.
CrQccl;nking of the polymers of the invPnt;~n produces vulcanizates having 1~ 1 and desirable ~.~L~ies; for example, high elorg~t;nn and ~y~pllpn~ aging characteristics.
Ela~ (or rukbers) of either natural or synthPt;~-origin usually require vlll~n;~tion (al_o ~ LL~ to as crosslinking) for ~L~ ~LvL~ ion into ;nc~ltlhlP, ~ eL~ ~hle high ~LL~IYU1 ela~,~Lic product_. BeLfore vulcan;7~t;n~, rubbers ~SP-~4 inferior ~k~LLies; for PX~mr1P, low ~LL~ ~ Ul, which limit their lutility.
There are a number of well known ~ 14 for achieving the vulcanization of unsaturated elas*Yx~cn~. Such l1.~1 include the u_e of sulfur and ~n~Pl~r~LuLs, peroxides, hPn7o~ one dioxime, certain phenolic resins and simlilar agents.
Any of the above or any other well kn3wn vlllrAn;7;n~ t~rhn;~lPc may be Itt;l;7~ to cros_link the ela~L~,~ of thi~c invention.

.

r 2 ~ 3 ~; ~ 9 4;

m e great majority of currently known 5~
ela~L~I~L~ are hased on polymers or copolymers of h ~A~;~n~ or m ese prior art ela~L~,t~, with either high or low levels of unsaturation, are characterized in that, having random unsaturation, they are ~ tly crnqsl;nked d~ring vtll~An;~A~;nn.
m e ~tl~cP-qc of v~ An;~Ation in i~ uL~Ling all mol~llAr chains into the final cr~cl;nked nP~rk with minimal "loose ends" is termed the degree of network ~LLe~L;nn An i~ LLe~L
network, wherein crosslinks occur r~ ~.ly and ~m~t;mes not ne ~
the end of a mnl~ r chain, ~L'~d~eS a vulcanized polymer having poor r -hAn;~Al and ela~ ic ~L~LLies c~llcp~ by chain ends which ~ e not a part of the tightly bound network. In order to in_ure the h;~h~ct degree of network perfection attainable, randomly unsaturated ela Lr~._~ must be cro~l;nked extensively. However, the l ~ ge number of cr~qcl;nks ~ P~ry (25 to 40 per 100,000 mol ~ ll~r w~;~h ~ At~-C that the ~V~L~ye dis*~mcs hP~~n crosslinks (Mc) must be relatively small in c~l4~lison with the dimLPn~;nnc of the whole mol ~ 1l~.
Elastomeric ~LL~e~Liec also ~PrPn~ greatly on Mc: the smaller the Mc the worse are the ela~L~,~ic ~l~t~Liec; for ~x~mrl~, the lower the elongation of the vulcanized polymer.
HiUleLLo, the ~ t h2s f~;lP~ to produ oe a polymer having a saturated backbone for oxidation stability which has unsaturated bonds only on the endc of the block polymer chain.
Such a block polymer could be vulcanized or ~PlFct;vely functiorAl;7~ at the terminal ends ul,~Or. The functionalization would expand the utility of the polymer.
As used herein, the symbols I and B refer to differing conjugated dienes. The symbols (I) and (B) refer to blocks of a copolymer, each such block comprising at least a minor am~unt of polymerised I and B, ~e~e~Lively. In addition, the block may comprise (a) further c~ (s); for example, (I) may comprise up to 70 molar ~k~ L of an aryl-substituted olefin which may be block or randcmly copolymerised therewith. Where this oocurs, (I) is ~m~;mY~c herein defined as (A) and (B) as (D), 2 0 ~ 4 1 9 4 ~ l;vely. In the ~ ols (I)x and (B)y, x and y ~f;nP the a~ge n~xr of (co)polymerised mo~r units in the block.
Where two such of these values may differ, as in a triblock ccpolymer or triblock s3~ L of a ccpolymer, they are differentiated as x and x . More generally, each such x is def~ as xi; for P~ lP, m a star-br~nrhF~ block ccpolymer xi Lq~e~l~ the value of the ith (I) branch while in a ~llt;hlsrk ccpol~ xi lq~l~ the value of the ith (I) block.
According to the present invention, in a broad a3pect, there is provided a solid, vulcanizable copolymer comprising at least two copolymerized mo~m~s which:
(i) when the copolymerized monomers are disposed as an at least tri-, or as a star-branched, block copolymer, has a middle block which is selectively and substantially completely hydrogenated to a block which contains no more than 10 percent polyethylene crystallinity while each terminal block, which may be the same or different, contains sufficient unsaturation for vulcanization; or (ii) when the copolymerized monomers are disposed as a random (including star-branched random) copolymer, has a backbone which is selectively and substantially completely hydrogenated while pendant groups contain sufficient unsaturation for vulcanization.
In one F~mhn~ t of the ~n~n~ , there is prcvided a high r~ r ~ ht, solid block copolymr-r cr~mprising at least three alternating blocks:
(I)x-(B)y-(I)x wherein I is a block of at least one polymerized conjugated diene having at least five (5) c~rhn~ atams and the following f~
Rl --C--C--C = C--R6 (1) whereLn Rl - R6 are each h~d~. or a hy~L~J~lbyl group, pr~vided that at least one of Rl-R6 is a hy~k~-~,Lyl grcup and further provided that the structure of the r~ ~lhle bond in the polymerized block I has the following fnnmll~
RII
RI _ C = C - RIII (2) h in RI RII RIII and RIV are each h~dL~Jy~l or a hyd~o~c~b~
grcup, provided that either both RI and * I are hy~l~JL~i~yl group6 or both RIII and RIV are h~d~c~b~l grcup6; B is a block of a polymer of at least one conjugated diene, ~ifferent from that used to polymerize the I block, having at least four (4) carbon atoms and the following formula R7 - C = C - C = C - R12 (3) R8 R9 R10 Rll ~ 3a _ 2~334~

wherein R7-R12 are each h~uy~l or a h~L-Y-rLyl group, provided that the structure of the r~ ~lhl~ bond in the polymerized conjugated diene of formula (3) (blo~k B) has the following formula Ra _ C = C _ Rc (4) Rd wherein Ra, Rb, Rc and Rd are each hy~Luy~, (H) or a h~Lu~b~l group, provided that one of Ra or Rb is h~L~ , one of Rc or Rd is h~Luy~l and at least one of Ra, Rb, Rc or Rd is a h~L-~-rb~l group; x is 1-100, ~l~LtLdbly 2-100, most ~L~r~I~bly 2-30, and y is 300-35,000, preferably 1,000-5,000, and most preferably 1,500-4,000.
It will be ~a~'Wl~ to those skilled in the art that in the rP~ ~lhl~ bond of formula (2) R', R " , R " ' and RIV may all ke hy~lu~cub~l groups.
The h~dlu~c~L~l group or groups in the formLlae (1) and (2) are the same or different and they are substituted or lm~lhctituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, ~ yl, alkaryl or aralkyl groups or any ;cnm~rc u,~Lt~r. Examples of suitable conju!gated dienes u_ed to polymerize the I block ~ e is~l~,e, 2,3-~;~~thyl hltAc~;P~e~ 2-methyl-1,3 ~y~ cl;p~e or myrcene. The h~c~Lu~b~l groups in fnr~ P (3) and (4) are the same as those described above in conjunction with the ~ l~C; on of fn~ll AP
(1) and (2). Suitable conjugated dienes ll~PA to polymerize the B
block are 1~3-hltA~;Pne or 1,3-~ ;PnP. AftPr the polymerization is cnmplPt~, the block polymer is h~c3Luy~ ~Led, so that the B block is cPlPct;vely h~c3Luy~ ~Led to such an extent that it contains s~L~L~lLially none of the original unsaturation, ~ ~Q3~

while each of the blocks I retains a ~lff;r;~t amcunt of its original unsaturation to cure (or vulcanize) the block copolymer. The block copolymer is ~r~;nAtP~ at both ends with a block I.
In an alL~Ll~Live e=~xxl~;cnt, there is provided a block copolymer comprising at least three alt~rnAt;n~ blocks:
(A)X-(D)y~(A)x wherein the A block is a random or block copolymer of at least one aryl-substituted ol~f;n, such as styrene, 2-phenyl alpha-ol ~f;nc, aIkylated styrene, vinyl ~ lP~e or aIkylat vinyl ~ .Al~ne, and at least one conjugated diene of formula ~ l~sP~ above, such as i~ e, 2,3-dimethyl ~ltA~;~P~
2-methyl-1,3-p~tA~;~ne or myrcene; and D is a block of a polymer of at least one conjugated diene of formula (3), ~; ~ l~ce~ above, which is different from the conjugated diene of form~la (1), e.g., 1,3-butadiene or 1,3 ~k~ n~. When the block A has r~l ~ llAr ~ ht of about 350 to about 7,500, it cc~p~;~&c about 50 to about 65%, ~L~re~bly about 50% by mole of the aryl-substituted olefin, and about 35~ to about 50%, ~L~L~Ldbly about 50% by mole of the conjugated diene of formula (1). When the block A has m~ llAr w~;~ht of about 7,500 to about 20,000, it compris~s about 1 to about 99%, ~l~L~Lably about 80 to about 98% by mole of the aryl-sub tituted ol~f;n, and about 99 to about 1%, prefer_bly about 2 to about 20~ by mole of the conjugated diene of form~la (1). When the block A has mol ~ llAr ~;ght of about 350 to about 7,500, x ~q~Le~*~lL~ the tokal nNmker of m~ ~L units in the block A, such that the block copolymer compris~s about 0.25 to about 10%, ~L~r~L~bly about 2 to about 10% wt. of the A blocX~s, and y Lq~L~*~lL~ the tokal numker of l~lK~L units in the block D, such that the block copolymer compris~s about 80 to about 99.5%, preferably about 80 to about 96% wt. of the D block~s. When the block A hac mo~ r weight of about 7,500 to about 20,000, the block copolymer compris~s 203~19~

about 0.25 to about 25%, ~ertL~bly about 10 to about 20% wt. of the A blocks and about 50 to abcut 99.5%, ~tr~L~bly about 60 to about 80% wt. of the D blo~ks.
After this block copolymer is polymerized, it is hydL~y~ ~Led, so that the block D is cPlFc~;vely h-y~r~ ~l~7 to such an ~yt~nt t~hat it cnnt~;ns suL~L~r~ lly none of the original ~ L~.~Lion, while each of the blocks A r~t~;nc a ~lff;~ t amount of the original ln~CA~lration of the conjl~7~te~
diene ~e~k~lL in each of the A blocks to c~re the block copolymer. m e block copolymer of th;~ embo~;r-nt is term;n~tç~
at both ends with a block A.
Yet another ~m~c~ t is ~;rec$ed to a block c~polymer camprising at least three alL~Ll~Ling blocks:
I-D-A
where the bloc;ks I, D and A are made fram the same ~ ;ve m~--K~ f;rF~ above, and the block A was mol~ r ~ ht of abaut 350 to about 7,500. m e block capolymer ca~pr;cPc ab~ut 0.1 to abaut 50%, preferably abaut 1 to abaut 5% by ~ ht (wt.) of the sum of blocks I and A, and about 50 to about 99.9%, ~bly abaut 95 to about 99% wt. of the block D.
The blocks A and I are r~reLl~d to hereinafter as the rr;nAl blockc"~ and the block-c B and D as the 'Imiddle bloc~c".
A~ U~tl em~xxL~ncnt of the inNP~t;~n is ~ Led to a random capolymer of at leact one conjl~3~te~ diene of formLla (1) and at leact one conjugated diene of formula (3), both ~ ]~ql above, pravided that the diene of form~la (3) is dirr~L~lL fram the diene of formula (1). Thi-c ,~ ~u copolymer conta m s abaut 0.1 to abaut 25, ~l~L~l~bly about 0.1 to abaut 5%, by mole of the polymerized conjugated diene of formula (1) and about 75 to abaut 99.9, preferably about 95 to about 99.9%, by mole of the conjugated diene of formula (3). This L~ll copolymer is also selectively h~d~y~ ~Led so that the polymerized diene of formula ~ ~ 203~

(3) QnntA;~S ~ 1ly none of the original l~.~ ~lration, while the polymerized diene of formula (1) retains a sllff;~ nt amount of the original unsaturation to ~lre the random copolymer.
~ U1~L e=ixxL~cnt of th;S invention is ~ ed to L~
copolymers of at least one aryl-substituted Ql~f;n, at least one ~ yaLsl diene of formula (1) and at least one ~ul~ diene of formula (3), both ~ ~sP~ akove, provided that the conjugated diene of formula (1) is different from the conjl~7~t~
diene of formula (3). This ~ 1 copolymer cnnt~;nC about 0.1 to about 15% by mole of the aryl-substituted ol~f;n, about 0.1 to about 25%, preferably about 0.1 to about 5%, by mole of the conjugated diene of formula (1), and the r~-;n~r of the conjugated diene of formula (3). This ~dl~ll copolymer is also l~ct;vely h~dl~y~laLed~ so that the polymerized diene of f,n ~ llA (3) containLs suL~L~,Lially none of the or;g;n~l n.,~.,dLion, while the polymerized diene of fn ~ llA (1) retains a -~lffi~ t .~ t of the original unsaturation to cure the ra~dom copolymer.
Yet d~ U1~L emb~;r-~t of the invention is diL~Led to ~L~L L~A~ block and random polymers. The ~L~ LLdl~le~ block polymers are made from any comh;n~;n~ of blocks I and B, A and D, or I, D and A providing that each free end (i.e., llr~y~rl~
end) of the star polymer is either an I or an A block, r~ J~I;vely. The ~L~ L~A~ blo~k polymers are ~elect;vely h~dLuy~ldLed to such an ~t~t that blocks B or D Gnn~A;n s~L~Ldu.Lially none of the original unsaturation, while each of the blocks I or A, L~ L;vely, retains a ~lff;~;~nt amount of the original unsaturation of the polymerized conju!gated dienes es*~lL therein to cure the ~L~ L~ ~lled block polymers.
The ~LAL ~Ld~K~led randam polymers are made from any combination of dien_s of f~n~llA~ (1) and (3), providing that the diene of formula (3) is different from the diene of f~ ~ llA (1), or from at least one aryl-substituted olefin, a diene of formula ~ ~ ~ 3 ~

(1) and a diene of formLla (3), providing that the diene of fnrrll~ (3) is ~;fferent from the diene of formula (1). m e ~Lal L~ ~7 random polymers are cPlFct;vely h~d~ W~e~l~ so that the polymerized diene of formLla (3) cnntA;nc suL~ ;Ally none of the original u~L~Lul~Lion, while the polymerized diene of formula (1) retains a ~lff;r~ t amount of the original ~Lion to cure the ~La~ LL~r~ 1 randam polymers.
The copolymers of all emlxxliYents are ~ under anionic polymerization conditions. After the Cplp~t;ve hy~L~y~ ~Lion re~r-t; n~, the h~L~ L; n~ catalyst is removed from the polymer.
In all embo~;m~t~ of this inNP~;nnl ~l~V~L a reference is made to the "r~;~lAl ~lhlP bond" of the block or L~ polymer (or copolymer), it is ~L~LOO~ to be the rP-c;~lAl ~lhlP bond prior to the ~Plp~t;ve h~JL~y~ ~Lion reA~t;n~. The structure of the rF~;~ ~l ~lhlP bond can be determined in any ~ullv~ Al m2nner, as is kncwn to those skilled in the art, e.g., by il~Ld~d (IR) analysis.
m e term "original l~CA~l~ation", as llCP~ in this A~pl;rAt;n~ means the sum total of the unsaturated ~LUU~O
e~lL in the copolymer prior to the ~elF~t;ve h~dLuy~ ~Lion rPArt;~. The unsaturation can be ~ ~nt;f;pA in any ~u~lv~lLional manner, e.g., by reference to the Tn~;nP Number of the polymer.
For P~AmrlP~ for a triblock ccpolymer of the first embodiment wherein the I blocks are polyis~L~le and the B block is polyh~A~;Pnp, the Iodine Number before cplpc~;ve hy~Luy~ ~Lion for each of the I blocks is 373 and for the B block it is 470.
After selective h~Luy~ ~Lion is ~n~rlPte~/ the TO~;nP Numker for each of the I blocks is about 37 to about 373, ~L~f~L~bly about 93 to about 373, more preferably abaut 186 to about 373, and most preferably ab~ut 373, and for the B block it is about O to about 50, and preferably about O to about 2.5.

2 0 3 '~

In any polymers of any of the e=lxxl~Ynts of this inv~nt;o~, the mi~Lu~LL~cture of the polymerized conjugated diene of formula (3), e.g., blocks B or D in the block copolymers, must be such that the polymer is not ~P-cc;vely crystalline after the ~Pl~ct;ve hydL~uy~ ~Lion r~Ar~ , i.e., after the ~Pl~c~;ve h~dL'~y~ ~Lion r~Art;~ the polymer must retain its elastomeric ~ y~LLies~ e.g., the polymer Ch~ll~ contain no more than ab~ut 10% of polyethylene crys~All;n;ty. m is is accom~l;ch~ by introducing side branches into the polymerized conjl~p~e~ diene of formula (3), e.g., by controlling the mi~ LLucture of 1,3 h~ e if it is the predominant ,~ 'r in the diene of formula (3), by using a mixture of dienes of f~ A (3) containing l~CC than ~ inant amounts of 1,3-h ~;Pne, or by using a c;n71P diene of formula (3) other than 1,3-h ~A~;~nP.
More part;~llArly, if the conjugated diene(s) of formula (3) is predominantly (at least 50% by mole) 1~3-h ~A~;~nP~ the side branches are intro~l~e~ into the polymer by insuring that the polymerized diene of formula (3) cnntA;nC a ~lff;r;~t a ~ unt of the 1,2-units to ~L~v~lL the cPl~-t;vely h~k~J~ ~L~l polymer from being ~P~c;vely crystalline. m us, if the conjugated diene of fnr~llA (3) is ~L~l~ ;nAntly (at least 50% by m~ole, e.g., 100% by m~ole) 1,3-h~tA~;Pne, the polymerized diene of fnr~llA (3), prior to the s~l~ct;ve h~dLuy~ ~Lion r~A~-t; nn, must contain not more than about 75% wt., ~l~r~L~bly about 10 to about 70% wt., and most preferably about 35 to about 55% wt. of the 1,4-units (1,4-mi~Lo~LL~cture), and at least about 25% wt., preferably about 30 to about 90% wt., and most ~L~r~L~bly about 45 to abcut 65% wt. of the 1,2-mi~ LL~cture. If the polymerized diene(s) of formula (3) contains less than 50% by mole of 1,3-butadiene, e.g., 1,3-~k~lL~iene is used as the only diene of fn ~ llA (3), the mi~Lu~LL~cture of the polymerized diene of fnn~llA (3) prior to the ~elect;ve h~Luy~ ~Lion reaction is not critical since after h~Luy~ ~Lion the resulting polymer will contain suL~L~lLially no crystallinity.

~03~9~

In all en~xxlunents of the invP~t;on, mixtures of ~;Pn of formulae (1) or (3) may be llCP~ to ~Lt~CU~ block copolymers (I)x-(B)y~(I)x, (A)x-(D)y~(A)x or I-D-A, any of the random copolymers or ~Ld~ hLcu~led block and random polymers of th;~
invention. .~ rly, mixtures of aryl- ~lkRt;tuted ol~f;n~ may also be used to ~Lt~U~ blo~k, r~ ~1~ or ~ L~ P~ ccpolymers of this invention. Accordingly, ~l~V~I a L~Le~ e is made herein to a diene of f~r~ P (1) or (3) or to an aryl-substituted olefin, it may f~YX~ SS more than one diene of f~ P (1) or (3), ~ L;vely, and more than one aryl-substituted olefin.
nFr~TT~n u~uK~ u~ OF T~E INVENTION
The block copolymers of th;s invention csmprise three or more alLt!rl~Ling blocks, ident;f;r~ above. ~ ~vcr, block copolymers having more than three blocks are contemplated herein, although they do not CL~ea~ to e~hLibit better ~L~tLLies than the block copolymers containing only three blocks. In addition, ~L~ LL~ IPr1 block polymers containing any comh;n~t;~ and number of blocks I and B, A and D or I, D and A are also contemplated herein, providing that they are tPrm;nAted either by blocks I or A. ThLe middle block of each three block unit of the block copolymer is suL~L~ILially completely saturated, while the terminal blocks contain contL-olled levels of unsaturation, providing a h~d~ r~ ela~L~I~ with - unsaturation. ThLe length of the ~ P saturated block ~Pf;nPC the distance crosslinks (Mc) in the vulcanized el~stomers. RP~All~e of the pl~ nt of the unsaturation, very low levels of r~s;~lAl r~r~lhlP
bonds are re~uired to attain PX~PllP~k vulcanization- ThLe low level of unsaturation in the sPlPct;vely h~d~tl,cLLe~ tri-block polymer and its termunal positioning provide P~rPllP~t oxidative stability to the polymers of this invention.
Without wishing to he bound by any theory, it is believed that the - pl~PmPnt of unsaturation in the block polymers of ~ 203~:~9~

this Lnv~t;~n i~ wrL~ to the polymers ~Y~Pll~t elastomeric p~ LLies which were Ah~Pnt in prior art therh~ in~
ela~L~.~L~ which reguired a mul~;pl;~.;ty of relatively C1~CP1Y
c~~~ crnfisl; nks .
m e cnm~;nAt;~ of ~lA~ ic ~ Lies and ~Y;~At;ve stability ~Y~ rl by the polymers of this invPnt;~n makes them suitable for many end uses, such as dynamically v~ An;~
thermoplastic elastomer hl~n~c, belts and hoses, white tire c;~ ~ll~, roofing, l mers, impact mo~;f;~.rs, ~ ~cal goods, and ionic th~r~plA~tic elastcners.
Many variations in cnm~n~;tion, mol~llAr ~ ht, r~ llAr ~ ht distr;h77t;nn~ relative block lengths, mi~L W LL~ctLre, brAn~h;n~, crystallinity and Tg (glass transition L~.~ L~7re) attA;nAhlP with the use of the anionic techniques employed in the ~L~Y~Lion of oLr polymers will be obvious to those skilled in the art.
While not wishing to limit the molP~llAr w~;~ht range of solid ela~ L~ ac~ording to our invention, the r;n;~rm r~ 771Ar weight for these solid polymers is at least about 15,000, ~L~LeL~bly it is ab~ut 50,000 to about 2,000,000, more preferably about 80,000 to about 250,000 and most preferably about 100,000. The block c~polymers of this invention are v7llrAn;~Ahle. Without wishing to be bound by any theory of operability, it is believed that they can be crQccl;nked (or v7ll~An;~e~7.) in a controlled l~ ~L throu~h the unsaturated groups on the terminal blocks to provide a very ~LL~1~ and orderly matrix of crosslinkages havLng almost uniform distr;h7t;~n of molPollAr weig'hts hPt~7~n crosslinks, Mc. The random and ~L~l LL~ ~le~ copolymers of this i7~vention are also v~ An;~AhlP.
The designation Mc, as used herein for the block copolymers 7Y~ms t'he length of the r;~.7lP block. For L~ll ccpolymers, Mc is ~;71~ll~ted by dividing number average nx~lP~llAr weight, Mn, of the polymer by the average number of crosslinks per chain plus l.

203'~9~
-The inv~t;nn will be descri7~ed herei-~lLLtL in terms of the emtxxi~nents thereof s7~mmarized above. 7~ vcr, it will be ~yar~-L to those skilled in the art, that the invention is not limited to thesc p_rt;~7l1~7r en~XP;r~~tc~ but, rather, it covers all of the emlxxl~ments ~K~ ~CF~.7 by the ~uade~L scope of the descr;rt;n~ of the invention.
Block Copolymers Fr2m at Least TWO D;~c;r;lr7r Conjuqated Dienes In this ~çr7;r~~t of the invention, there is polymerized a block copolymer comprising at least three alternating blocks:
(I)X-(B)y~(I)x wherein:
I is a block of at least one polymerized conjl7~r,7tFn7 diene having at least five (5) ~r7~on atoms and the following fn ~ 71A
Rl _ C = C - C = C - R (1) wherein R1 - R6 are each h~dLuy~l or a h~dL.~ yl group, provided that at least one of Rl-R6 is a h~d~ L~l graup, and further provided that the structure of the r~-C;~lAl ~lhl~ bond in the polymerized block I has the following formula RII
RI _ C = C - RIII (2) RIV

h in R R I RIII and RIV are each hydLuy~ ar a h~
graup, provided that either both RI and RII are h~dL.~ yl groups or b~th R and R are h~d~uucL~yl grcups;
B is a block of at least one polymerized conjugated diene, different from that used to polymerize block I, having at least four (4) r~rbon atoms and the following formula R7 - C = C - C = C - R12 (3) R8 R9 RlO Rll 2 0 ~ 4 wherein R7-R12 are each h~Luy~l or a hy~L~dL~yl group, provided that the struct~re of the rP-C;~l~l A~lhlP bond in the polymerized block B has the following formula Ra _ C = C _ Rc (4) Rd wherein Ra, R , Rc and Rd are each h~dL~y~l (H) or a hy~L~dLbyl group, provided that one of Ra or Rb is hy~Luy~l, one of Rc or Rd is h~Luy~- and at least one of Ra, Rb, Rc or Rd is a h~L~ b~l group. In each of the I blocks, x is 1-100, preferably 2-100 and most preferably 2-30, i.e., each of the I blocks is polymerized from 1-100, preferably from 2-100, and most preferably from 2-30 mulK~.~L units. For some ~eC;Al Arpl;~Ations, each of the I
blocks is polymerized from 100-200 monomer units. The block polymers cont~;n;ng such large I blocks (i.e., cn~tA;n;n~ 100-200 monomer units) have i~ase~ vulcanization rate, as compared to those ~nn~A;n;ng cmAllPr I blocks, and ~ e co-v~llrAn;~AhlP with diene rubbers avA;lAhlP in the art, e.g., polyh ~AA;P~e and natural rubbers. m e block polymers cont~;n;n~ such large I
blocks can be hlPn~PA with diene rubkers by conventional , - ~
and ~lhc~lP~tly vulcanized to produce novel c~m~n~;tions of this invention. m e resulting materials are PxrPCtPA to have increased oxidation and ozone d~yL~Lion resistance as compared to known diene rubbers alone, and UltL~r~l~ ~ e ~PC~A to be VAlll~hlP materials for the prQ~l~t;nn of white c;A~ ~ of tires and ~;r;l~r ~ ticles.
In each of the B blocks, y is 300 to 35,000, ~L~r~L~bly 1,000 to 5,000, and most preferably 1,500 to 4,000, i.e., each of the B blocks is polymerized from 300 to 35,000, ~L~r~L~bly from 1,000 to 5,000, and most preferably from 1,500 to 4,000 ll~lKal~
units.

2Q3~i 9~

In the rr~ hl~ bond of formula (2), R , R , R
and RrV may all be h~dl~ ~rb~l graups. The structures of t,he r~;~lAl ~lhl~ bonds defin3d by fnrrll~ (2) and (4) are ~ y to produoe copolymers which can be ~Pl~ct;vely h~dLuy~ ~Le~ in the ,l~u~ descriked herein to produoe the sPlPct;vely h~luy~ ~ed block and randam copolymers of this mvP~t;nn. The block copolymer ccmprises abcut 0.1 to about 50%, preferably ab~ut 1 to abaut 5%, hy wt. of the I blocks, and about 50 to ab~ut 99.9%, ~LeL~Ldbly about 95 to about 99%, by wt. of the B blocks.
m e h~L~.d~b~l group or groups in the formulae (1) and (2) are the same or different and they ~ e substituted or unsubstituted aLkyl, aIkenyl, cycloaLkyl, cycloaLkenyl, aryl, aLkaryl or araLkyl graups or any isomers thereof. Suitable h~Lu~Lb~l groups are aLkyls of 1-20 c~rh~n atams, aLkenyls of 1-20 ~rbon atams, cycloalkyls of 5-20 ~rbon atams, cycloaIkenyls of 5-20 carbon atcms, aryls of 6-12 cArhnn atams, aLkaryls of 7-20 cArh~n atams or araLkyls of 7-20 cArhnn atams.
Fx~ s of suitable alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, methyl-decyl or hyldecyl. FX~mrlPC Of cll;t~hle aLkenyl groups are ethenyl, butenyl, k~.L~.~l or hexenyl. Examples of suitable cycloaLkyl gro~ps are cy~ h~yl or methylcyclnh~xyl. Examples of suitable cycloaLkenyl graups are 1-, 2-, or 3-cyr-lnh~xP~yl or 4-methyl-3-cycl~h~x~nyl. F~rlPc of suitable aryl graups are phenyl or diphenyl. FX~1PC of suitable aLkaryl graups ~ e 4-methyl-phenyl (p-tolyl) or p-ethyl-phenyl. Examples of suitable ~ aLkyl groups ~ e benzyl or phpnpthyl. Suitable oonjugated dienes of formula (1) used to polymerize the I block ~ e i~u~L~ e, 2,3-dimethyl-h~A~;Pn~, myroene, 2-methyl-1,3 ~-Lddiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-~ ~A~ e, 2-phenyl-1,3 y~.Ld~iene, 3-phenyl-1,3-~ iene, ~ ~ '' t ; f~

.. ~

2 ~ 3 4 1 9 4 2, 3~;~-~thyl--1, 3 ~ 7; PrlP~ 2--hexyl--1~ 3--hltAt7; Prle~
3-methyl-1,3-hP~r7;~e, 2-benzyl-1,3-h ~A~;~nP, 2-p-tolyl-1,3-hltA~;P~P or mixtures U~ f, ~ t~dbly i~u~4~le, myrcene or 2-methyl-1,3 ,~ .7;PnP, _nd most ~ t~dbly i~u~ e.
Ihe h~ uL~l grcup or groups m the f ~ (3) may or may nct be the same AS those in formula (4). Ihese h~Lu~a~b~l yu~u~S are the same A those descr;h~ above in ~ n with the ~;c~l~c;~n of the h~dL ~ yl groups of f~rm~lae (1) and (2).
Suitable - ,-k~ S for the B block are 1,3-h ~A~;~e, 1,3 ~Y~ ;PnP, 2,4-hPx~r7;~P, 1,3-hPY~7;~np, 1,3 ~lt~ ;~P, 2,4 l~ 7;PnP~ 1,3 o~l;pnp~ 2,4 o~7;PnP, 3,5 o~l~.7;PnP, 1,3 . K ,.~7;P~P, 2,4-norAr7;P~P~ 3,5 .~ -7;~e, 1,3 ~7P~I7;~ne~
2~4-r7PcAA;P~e~ 3,5-~PcAr7;~nP or mixtures Ul~L~f, preferably 1,3 h.l~7;p~e~ 1~3-~Y~ ;P~e or 1,3-hPY~ P, and most ~L~udbly it is 1,3-hltAr7;~nP. It is ~L~rt!L~l that each of the B blocks is polymLrized from a ~ m~ln~
~ he block copolym_r of this emko~;r~~ is terminated at both ends with a blo~k I.
~ he sccpe of this em}odiment and of any other en~xr7;~
of the invention wherein the block B is used also ~ H~
polymers wherein the central blo~k B may be comprised of copolymers of one or more conjugated diene of f~nrllA (3) and controlled ~m~l~t~ (about 0.1 to about 30 mole%) of an aryl-substituted olPf;n, e.g., styrene or okher suitable monomers (such as alkylated s~yrene, vinyl naphthalene or alkylated vinyl e), il~L~U~Led for control of glass transition tem~era~ ~e (Tg), density, Cnlllh;l;ty parameters and ~rL~iVe index. Suitable aryl-~lhct;tuted nl~f;~c are those describsd below in conjunction with the cPcnn~ embodiment of the invention.
S;m;lArly, the so~pe of this ~o~;ment also emo=mpasses polymers wherein the cen h dl block B may be comprised of copolymers of one or more conjugated diene of formula (3) and any other anionically A~

~ 2~3~19~

polymer; ~Ahl ~ r~hl ~ of polymerizing with the conjugated diene of formula (3).
It will be c~ar~lL to those skilled in the art that ~L~L choice of polymerization parameters can produce polymers with a great variety of ~r~ tional and structural diLL~
f~ll;ng within the sc~pe of our invention. ~.~.}~ in ~Yif~ition of the oe nLL-~l block B control the nature of the rubkery ~L~r~ies while ~ in the terminal blocks permit ~ e to different v~ An;~;ng ~Pnt~, e.g., sulfur-based ~ e systems and phenolic resin ~ e systems.
m e block copolymer is polymerized ky any ~llv~l~;n~Al block ccpolymerization ~L~e~S~ such as anionic polymerization, ~ sA~ in detail below. As will be ~k~L~IL to those skilled in the art, the copolymer of this e=lxxib~ent contains at least three al~L.~ing blocks, I-B-I, ~Lt~ to herein as the triblocks or triblock units, but it may cnnt~;n an unlimited number of blocks, so long as the entire block copolymer is t~rm;nAted at both ends by the I blocks. It is, h~vcr, ~ Led that the copolymer of this embodiment onn~A;n only one triblock I-B-I. Polymers having more than three bloc;ks (such as five) allow crosslinking to take pla oe at the ends and in the central portion, but maintain a controlled large d~sd;unce hP~I~~n crosslinks of the polymer. It is imE~LL~I~ to have the block copolymer terminated at each end with the I blocks to assure that there are un~saturated groups at each end of the bloc;k copolymer ~PrAhl;ng the block copolymer to be cross-linked or functio~l;7 at the terminal ends thereof. The term ~fim~t;~n~l;7e~ is used herein to describe rh~m;~Al r~;f;rAtions of the unsaturated groups to produce functional groups, the nature of which is described in detail below. The crosslinking of the fim~;nnAl;7e~ and nonfunctiorAl;7~ c~polymer oh~ins is conducted in a conventional l~ and is descrihP~ below.

~ 2Q3~
~ ~ ,=

After the block copolymer is polymerized, it is subjected to a CRlFc~;ve h~dL~y~ ~Lion rP~rt;nn during which the B blocks of the block copolymer are cPl~ct;vely h~ y~ ~Led to such an ~xtP~t that they contain suL~ lly none of the or;g;n~l unsaturation, while the I blocks retain a ~lff;r;~t amount of their original ~u~1LuL~Lion to cure the block copolymer.
Generally, for a block copolymer wherein the I and B blocks are polymerized from any of the ~ l~ce~ above, the Iodine Number for the I blocks after the selective hy~L~y~ ~Lion r~r~;nn is about 10 to about 100%, ~L~Le~bly abcut 25 to abcut 100%, more preferably abcut 50 to abcut 100%, and most ~L~L~bly about 100% of the Tn~;nP Number prior to the Cpl~ct;ve h~luy~ ~Lion reAr-t;nn, and for the B blocks it is about 0 to about 10%, ~L~L~bly ab~ut 0 to abaut 0.5%, of the TO~;nP Number prior to the ~elPct;ve h~Luy~ ~Lion rPA~t;nn. The Tc~;nP
Number, as is known to those skilled in the art, is ~Pf;nP~ as the UleuL~Lical numker of grams of iodine which will add to the unsaturation in 100 grams of olefin and is a qusntitative ,~a~uL~ment of unsaturation.
In this e=~xYL~ment of the invention, although the mi~Lu~LL~cture of the I blocks is not critical and may consist of any combination of 1,2-, 3,4and 1,4-units, ~ Lically ~q~Le5k~lLe~ below for the polyis~L~ e blocks, when a polar cf~qY~lnd is used during the polymerization of the I block, the I
blocks comprise primarily (at least about 80%) 3,4-units, the remainder being primarily (about 20%) 1,2-units; when the polar cr~Y~l~d is not u~F~ ~lring the polymerization of the I block, the I blocks cc~mprise primarily (about 80%) 1,4-units, the remainder being primarily 1,2-and 3,4-units.

2 0 3 ~

CH2 C - CH2 Cl - CH2 C = CH- CH2 -CH C = CH2 ~\ I

1,2 3,4- 1,4-As ~ l~cP~ above, when the ~l~d~.~nant monomer ll-CP~ to polymerize the B blocks is 1,3-~ ~A~ P, the mi.~ cture of the B blocks Ch~l~ be a mixture of 1,4- and 1,2- units Lically ~how.n below for the poly~ ~ ne blocks:

-CH2 I CH2~ oH CH CH2 C~
I\

1,2- 1,4-since the h~d~cy~ ~Lion of the predominantly 1,4-mi.L~LL~ctures produces a crystalline polyethylene segment. Ihe mi~u~L~ucture of the I and B blocks (as well as of the polymerized conjugated dienes of formNlae (1) or (3) in any polymers of this Lnvention) is controlled in a conventional 11~UL~ e.g., by controlling the amcunt and nature of the polar CY~lY~l~dS used during the polymerization rPA~t;~ and the rPAr~;~n t~.~L~re. In one ~, ~ f~3 , ~
~ ~ 3 4 1 9 4 part;~llArly ~r~LL~ erlxxl rncnt~ the poly~A~;~nP block Gnn~A;nc abcut 55% of the 1, 2 - and about 45% wt. of the 1,4-mi~w ~L~cture- If the B block is poly~ ~A~ P~ the h~ruy~ ~Lion of the B block cn~t~;n;~ about 50 to about 60% wt.
of the 1,2-mi L w LL~cture ~ prYy~l~pc an ela~~Yh3ric ~ L~I
block which is ~ .l ;Al ly an ethyl~ ~ 1~ 1 ccpolymer having ~ L~ILially no crys~All;n;ty. ~he rP~lrt;n~ of the 1,2~
mi~L~LLu~Lu~ in the poly~ ~A~;P~P block in a ~l~lLL~lled manner permits the i~lLL~I~;nn of controlled levels of c~ystAll;n;ty into the h~dLuy~ ~ polyh~A~; Pn~ block which provides a "green" (unvulcanized) ~LL~ ~ U1l~Y~ rY in certain ;c~tions. If the B block is polymerized frcm 1,3 ~ ;PnP, it is preferred that it have ~ ~.inantly (at least 50%) 1,4-mi~Lu~LLucture, which, after h~dl~y~ ~Lion, pr ~ lrF~ a suL~L~lLially non-crystalline elastomeric block.
~ he terms 1,2-, 1,4-, and 3,4-mi~Lu~LLucture or units as used in this A~pl;rAtion refer to the ~~ u~ of polymerization obtained, rP-c~ec~;vely, by the 1,2-, 1,4- and 3,4-, additions of units into the growing polymer chain.
We surprisingly dis~uv~L~l that the polymerized conjugated dienes of fnr~ll~ (3), e.g., the B blocks, of the poly~mers of th;~ invPn~;nn are cplpc~;vely hy~l~y~ ~Le~ in our h~LUy~Lion ~L~e~S much faster than the polymerized conjugated ~;~nF~ of formula (1), e.g., the I blocks. This is not evident from the teachings of Falk, JOURNAL OF POLYMER SCIENCE, Part A-1, Vol. 9, pp. 2617 - 2623 (1971), because Falk teaches that double bonds of the disubstituted 1,4-polybutadiene units are hydrogenated selectively in the presence of double bonds of the trisubstituted 1,4-polyisoprene units (which are not hydrogenated). We surprisingly discovered that the disubstituted double bonds of the 1,4-polybutadiene units are hydrogenated along with the monosubstituted double bonds of the 1, 2-polybutadiene units, while the disubstituted double bonds of the 3,4-polyisoprene units are hydrogenated at a much slower rate f~

2~J 3 ~ 3 4 than the aL~ li nnP~ h ~AA;~nP~. I hus~ in view of Falk's disclosure it is surprising that the disubstituted double bonds of the 1,4-polyh ~A~;P~P units are hy~ L~~7 ~PlPc~;vely in the ~L~C~l~ of the ~ ~Lituted ~lhl~ bonds of the 3,4-poly ~ L~ e UnltS. IhiS iS also surrrl~n~ m view of the ~eA~h;n~ of Hoxmeier, ~lhl;~h~ EhL~ Patent Arrl;r~;nn, ;rA~;n~ No. 0 315 280, who ~;~rlqfie~ that the ~;~ll~l;~ ~e~
hl~ bonds of the 1~4-polyh~A~;pnP units, nx~Yy~lhct;tuted l~ bonds of the 1,2-PO1Y~ ~A~ P units and ~;~lhct;tuted lP bonds of t~he 3,4-polyisu~L~le units are hydrogenated simull~ ly at s~Lsl~ ;A11Y the same rat~C. For example, for the block copolymers of ~h;~ inNP~ n, ~herein the I block is polyi~L~ ~ and the B block is polyh ~A~ e, Fourier Lr~ rc~m i~Ld~ed (~ K) analysis of ~Pl~ct;vely hy~l~y~ ~Led triblock l~ CD ~ ~t '~.e ~ J ~li.-n Oc ~ hle bosxlj 0 the 1~2-polyh ~A~;~nP units ~L~eaS ~cst rapidly, foll~r~ by the h~dL~y~ ~Lion of the ~1h1P bonds of the 1~4-poly*q~A~ e units. IS~L~L~ ahsorptions C~11CP~ by these ~LU~S ~ P~ r prior to ~ hlP hy~Luy~ ~Lion of the polyi~yLt~le units.
After the I-B-I blo~k copolymer is ~Lt~dLe~ it is subjected to a .Cplpct;ve hy~Luy~ ~Lion rPA~;n~ to h~Lur~ ~Le ily only the middle B unit of each of the triblocks. m e sPlPct;ve h~Luy~ ~Lion rPArt;c~n and the ca~lyst are descr;
in ~tA;l below. After the h~L~Iinn rpA~t;nn ic c~rlPt the CPlpc~;ve h~dLu~ n catalyrt irD removed from the block copolymer, and the polymer is ;C~ ue~ by c~lv~lLional ~L~X~h1neS~ e.g., Al~nhnl flo~x~llAtion, s-team stripping of solvent or non-A~Palc solvent e~vL~Lion. An ant;~Y;~A~t, e.g., "Irganox 1076"* (from Ciba-Geigy), is normally added to the polymer ~nll~;n~ prior to polymer isolation.

The ;C7lAtF~ polymer is vlllc~n;7~hlp thrcugh the tu~1LuL~Led end blocks I by a ~ l~r of well kncwn ~L~ P~
* Trademark -;~ 0 3 4 1 9 4 ~ ;l;~P~ currently for I l l~r ~ LI;n~ hy~L~ ~rt.~, Pl~ .~r.~.
Such ~ P~P~ are ~t~;lP~ in ~u~K~l~u~uLOGY, IHIRD
V~N N~3WND ~FrNRnTn a0MPANY, New York, 1987, Mauri oe Editor, ~ ~ ~ 2,9 and 10~
Triblo~k Cbpolymer of at l~ast One PolY-Diene Cb~ r Block and n~nal Blocks of Aryl-Sub6tituted Olefin/Diene Co~olymer In this alL~r.~l;Ye embcdimcnt of the imvP7~ , the block copolymer ccmprises at least one triblock of:
(A)X-(D)y~(A)x ~herein the block A is a ccpolymer of at least one aryl-substituted olefin and at least one conj7~gated diene of f~nm11;7 (1), defined above. ~he block A is either a L~ll or a block copolymer. When the block A has a molecular weight of about 350 to about 7,500, it cc~prises about 50 to a7~out 65%, ~-~r~L~bly about 50% by mole of the aryl-sub6tituted olefin, and about 35% to about 50%, ~L~LtL~bly about 50% by mole of the conj7~gated diene of formula (l). When the block A has a molecular u~;~ht of about 7,500 to about 20,000, it c~mprises about l to a7~out 99%, ~L~LeL~bly about 80 to about 98% by mole of the aryl-substituted ol~f;n, and about 99 to ab,out 1%, ~L~L~dbly about 2 to about 20~ by mole of the conjugated diene of fnnm71~
(1). When the block A has a molecular weight of about 350 to about 7,500, x rq~lt~*~lL~ the total ~Imker of l''--K~--'' 7~nits in the block A, such that the block copolymer ccmprises about 0.25 to abcut 10%, ~ltrt!,~bly about 2 to about 10% wt. of the A blocks, a7~l y ~q~le~lL~ the tokal Tumber of ~ r units in the block D, such that the block copolymer ccmprises about 80 to ab~ut 99.5%, preferably about 80 to about 96% wt. of the D blocks.
~hen the block A has a molecular weight of about 7,500 to about 20,000, the block copolymer comprises about 0.25 to abaut 25%, eL~bly about l0 to about 20% wt. of the A blocks a7~d about 50 to about 99.5%, preferably about 60 to about 80% wt. of the D

, , .

~ ~ 0 3 4 1 9 4 blocks. m e m~st ~LeLLed ~L~ y~Lel diene of formLla (1) is ~ e. In this block copolymer, D is a block of a polymer of at least one conjugated diene of formula (3), ~;C~l~e~ a~x~ve, which is diLL~r~.L frcm the canjl ~ ~e~ diene of formula (1). Ihe block copolymer of this emlxxL~snt may cn~t~;n several, e.g., 5-7, blocks of the afv~ L;nnp~ formula so long as it is t~rr;nAted at b~th ends with the blo~k A, b~t, ~er~Ldbly, it c~tA;~c only three blo~ks A-D-A. Suitable aryl-substituted olefins used to polymerize the A block have the formula Ar H
/C _ C \
R H
~here Ar is phenyl, aIkyl-substituted phenyl " ~~ yl or aIkyl-sukstituted ~ 1, Re is hy~Luy~l, methyl, ethyl, prcpyl, butyl or ~ yl. Examples of suitable ~ yl-suk6tituted olefins ~ e styrene, 2-phenyl alpha-ol~f;~c, such as al p a-methyl styrene, l~ h~nyl ethylene, aIkylated styrenes, vinyl ~ nP~ or any aIkylated vinyl ~y~ nP~. Suitable alkyl sukstituents in the alkylated styrenes or alkylated vinyl l~nPs ~ e methyl, ethyl, propyl, tert-butyl and sec-butyl.
Each of the alkylated styrenes or vinyl ~ nes may contain one or more aLkyl sub6tituents. E~reLLed aryl~ xstituted ol~f;nc are styrene, vinyln~phth~lene, alpha-methyl styrene, vinyltoluene and ~;~h~nylethylene. The mi~LuOLL~cture of the polymerized diene of formula (1) is not critical, but can be controlled in the ll~UL~ e~ above. In the most ~uef~ e~
~mho~;m-~t~ the A block of this tr;hl~r-~ copolymer is polymerized from i~L~ e and styrene in the molar ~Lu~uLLion of ab~ut 1:10.
m e block copolymer is polymerized by any ~ul~v~Lional block copolymerization ~Lu~S~ such as anionic polymerization, in ~tA;l below.
R~ ndless of the m~ r weight of the block A, the scope of this ~o~;m~t, and of any other emk~;r~~t of the 2 ~ 3 4 1 9 4 inv~nt;n~ wherein the block A ~c u_ed, also encompasses polymers wherein the blockc A are ~ d~ by, initially, polymerizing at least one aryl~lhc~;tuted olefin alone, and cllhs~lPntly rPArt;n~ the resulting poly-aryl ~IL~Lit~ted olPf;n with any ~n~r~ ~ c which, after chemi~l rPA~-t;nn with the poly-aryl-sub6tituted ol~;n~ will provide the r~c;~lAl ~lhlP
bonds to the A blo~k , as ~f;nr~ above in conjunction with the ~;c~l~c;nn of the conjl~tP~ diene of formLla (1). The resulting block A will U~L~ruLe have ~ r~ lly the same r~.Ci~lAl unsaturation (r~c;~l~l ~lhl~ bonds) on the tPrr;n~l blocks A as any other block A made in a~uL ~ ~e with this emb~;~P~t (or any other ~ç~;r~~ which llCPC the blo~k A), i.e., by copol~merizing the aryl-substituted ol~f;n with at least one c~ y~led diene of fnrnnll ;l (1) .
~ he block copolymer of th;c embn~ t is terminatecl at both ends with a blc~k A.
The sc~pe of this embodiment, and of any other embn~ ts of the invP~t;~n wherein the blo~k D is used, alco encompasses polymRrs wherein the central (middle) block D may be ccm~rised of c~polymRrs of one or more conjugated diene of fnnrll~ (3) and c~ntrollecl amounts (abcut 0.1 to ab~ut 30 mole%) of an aryl-substituted olefin, e.g., styrene or c~her suitable (such as aIkylated styrene, vinyl naphthalene or aIkylated vinyl ~ nP)~ Lel for ~Ull Lul of glasc transition L~ L~L~re (Tg), density, ~ lh;l;ty ~aL~ and refractive index.
M~st ~l~LeL~bly, in this e~n~ t of the invention, the block A of the capolymer has r~le~ r ~r;ght of ab~ut 7,500 to about 20,000, the A block is polymerized fram i~l~le and styrene, and the D block fram 1,3-h ~A~;~P, in such ~l~vLLions that the final capolymer ~l~rises about 1 to abaut 2~ wt. of the ~ r~le, about 25 to akout 36% wt. of the styrene, and ab3ut 62 to about 74% wt. of the butadiene units.

t- ~
-2 ~ 3 4 ~ ~ 4 After the polymerization is completed, the block copolymer is subjected to a ~ ct;ve h~ re~rt;nn.
After ~Plrct;ve h~ 3~L;n~, the polymer cn~t~;nC a ~lff~ nt amount of its or;~;n~l ~ULj1l -r~Lion in the t~:lL~nal blocks A to cure the block ccpolymer, U~ permitting chemical c~x~cl;nking or fim~t;~n~ t;nn in the m2nner ~; ~ l~cP~ below, while the r;~l~ block D cnn~;ns .~)~ lly none of the or;~;n~ ~n~ation. For PY~rlP~ for a blo~k ccpolymer wherein the A blocks are ccpolymers of styrene and iS~L~,e and the D block is poly~ ~A~;Pn~, the TQ~;nP Number before ~Pl~c~;ve hy~Luy~ ~Lion for each of the A blocks is 5-150 and for the D
block it is 250-470. After ~Pl~c~;ve hy~ 3~ ~Lion~ the Tn~;ne Numker for each of the A blocks is ab~ut 5 to about 150 and for the D block it is about 0 to about 10, ~,er~bly about 0 to abaut 2.5, and most preferably 0. Generally, for a block ccpolymer wherein the A and D blocks are polymerized from any of the monomers suitable for their polymer;7A~;nn, ~ lc~P~ above, the Tcd;nP Number for the A blocks after the CPl~;ve hy~y~ ~Lion is ~l~leted is about 10 to about 100%, preferably about 100~ of the Iodine Number prior to the ~lPct;ve h~L~y~ ~Lion r~t;n~, and for the D blocks it is about 0 to about lo~, pre~erably about 0 to a~out 0.5%, and most preferably 0~ of the Iodine Number prior to the cPl~ct;ve hy~uy~ ~Lion rPA~;nn. Thus, in this r~Q~;mPnt, the block D is also cPlPc~-vely hyd~uy~ Led in the same manner as A;~ e~ above for the central block B of the first embcdiment of the invention.
m e block copolymer of this embodiment is also a solid, and, after cPl~c~;ve h~Lcy~ ~Lion, the unsaturated groups in the tPrm;nAl A blocks of each of the triblocks provide a means of crnccl;nking the copolymer or filn~t;nnalizing the terminal blocks A, in the manner A;~l~CPA Pl~owhPre in this ~pl;~tion.
m e preferred polymers of this embcdiment, wherein the A
blocks have mnl~llAr ~;ghtc of ab~ut 7,500 to about 20,000, .
~r 2 ~ 3 ~ 1 9 4 whlle ~ P~s;n~ the s ~ ior ela~ ~ ic ~ tlLies of the thermoplastic elastomer triblocks in the uncured state, can be ~h ~;rAlly c~ l;nked to L~ ~L them ;ncnlllhl~ in most organic solvents and ~n~hl~ them to retain elastomeric ~4u~t~Lies at very high L~ dL~L'~. This elast4mer is ~;ct;nrt from RRU~X~ since X~n~N*has no ~ki~L~l~Led ~ c in the t~:~L~nal ~ e blocks and U~eLu~e cannot be ~h ~;~Ally crncc-linked t ~ these blocks.

Triblock Copolymer of at Least One Poly-Diene Center Block and at l~ast One lerminal Block of ArYl-Substituted Olefin/Diene Copolymer In this em~xxL~m~nt of the invention, the block ccpolymer compri~C at least one triblock of:

I-D-A
where the block I is a polymer of at least one polymerized diene of formula (1), ~Pf;nA~ abcve, the block D is a polymer of at least one c~njl ~ te~ diene of formula (3), defined above, which ic diLL~L~ fr~m the conjugated diene of f~r~ A (1), and the block A is a copolymer of at least one aryl- substituted olPf;n and at least one conjugated diene of formula (1), both defined above. qhe block A has a molecular weight of about 350 to about 7,500 and it camprices about 50 to about 65%, ~4tL~Ldbly about 50~ by mole of the aryl-sukctituted olefin, and about 35 to abcut 50, ~leL~Ldbly abcut 50~ by ~ le of the conjugated diene of f~rT~llA (1). This block copolymer comprises about 0.1 to about 50, preferably about 1 to about 5% wt. of the sum of bloc~ks I and A, and about 50 to about 99.9, ~L~r~Ldbly about 95 to about 99~
wt. of the block D. The block copolymer of this ~o~;m~nt may also cnntAin several, e.g. 5-7, blocks of the afc~e~ ncd f~rs~ P so long as it is terminated at both ends thereof with blocks I or A. The block copolymer is polymerized by any c~llv~lLional block oopolymerization ~ce~s, such as anionic polymerization, ~ l~cP~ in detail below.

* Trademark 2 0 3 ~ 1 9 4 ~ he ~ e of th;~ PmhQ~;ment of the i ~ ion also ~'~K~ Px polymers wherein the central block D may be ccmprised of copolymers of one or more cu~ y~Le~ diene of fnrr-llA (3) and LLolled ~ (abcut 0.1 to about 30 mole%) of an aryl -il~(;tuted olPf;n, e.g., ~L~ e or othQr ~ table monomers (such as alkylated styrene, vinyl naphthalene or alkylated vinyl ~ Alp~e)~ il~JJL~L~L~d for ccntrol of glass transition tem~3rature (Tg), density, ~s~lllh; l;ty parameters and refractive index. Suitable aryl-substituted olPf;n~ are those described above. S;r;lArly~ the scope of this er~xxL~Icnt also encompasses polymers wherein the central blo~k D may be comprised of copolymers of one or more conjugated diene of f~r~llA (3) and any other an;nn;~Ally polymerizable mu~ cArAhlp of polymerizing with the conjugated diene of fnr~llA (3). This Fmh~;r~nt also enCxD~;sei polymers wherein the blocks A are ~L~Y~d by, initially, polymerizing at least one aryl-substituted olPf;n alone and, ~lh~q~Pn~ly~ reacting the resulting poly-aryl-substituted olefin with any ccr~nlds which, after rh~m;rAl r~Art;nn with the poly-aryl-~lhc~;tuted nlPf;n, will provide the rPc;~lAl ~lhlP bonds to the A blocks, as ~f;n~d above in conjunction with the ~ ~c;nn of the conjugated diene of formula (1). The resulting block A will the]refore have ~L~ l;Ally the same rp-c;~l~l L~ LuL~Lion (rP-~;~lAl ~lhlP bonds) on the terminal blocks A as any other block A made in a~uldk~Kx with this embodiment.
r the polymeri~A~;n~ is cr~rlr~e~ the block copolymer is subjected to a cPl~ct;ve h~d~uy~ ~Lion rPAr-tin~. After selective h~dLuy~ ~Lion, the polymer contains a ~lff;riPnt amount of itc or;g;nAl unsaturation in the terminal blo~kc I and A to ~ e the block copolymer, thereby pcrmitting rh ~;rAl croccl;nking or fin~rt; n~Al; ~Ation in the ~ e~ below, while the m;~l e block D containLC sub~L~,Lially none of ~he original unsaturation.

.

~ 2 0 3 ~

G~K~ally, for a block ccpolymer wherein the I, D and A blocks are polymerized from any of the m~U~-~s .nl;t~hlP for their polymerization, as defined above, the Tcr7;7~P. Number for the I and A hlo~kc after the cel~ct;ve h~Lu~ ;~n is co~pl~t~ is a7~out 10 to ab~ut 100%, ~L~re~bly about 100~ of the T~r.7i7~P .~Imber prior to the ~le~t;ve hy~L~,~l;nn rGAr-t;nr7, and for the D
blo~ks it is about 0 to about 10%, preferably about 0 to abcut 0.5%, and most ~ rtLdbly 0~ of the Tcr7,;7~P .~lmber prior to the ~Plect;ve hy~uy~ ~Lion r~A~t1nn. Thus, in this e7~bcr7i7~ t, the block D is also ~cpl~ct;vely h~L~ ~Le~ in the same ~ r"~r as .7;~77ccPd a7~ove, while the terminal blocks I and A retain a suL~I~..l;Al amoL7nt of their original l7nCA~7ration.
The bloc;k c~polymer of this emlxxL~nent is also a solid, and, after ~PlPct;ve hy~uy~ ~Lion, the unsaturatl3d groups in the t~rminal I and A blocks of each of the triblocks provide a means of crosslinking the copolymer or functionalizing the terminal blocks I and A, in the manner P;~c77~cp~7 Pl~e~hP-re in this specification.
Rand~m Cbpolymers Random copolymers of this invention have ~ullLL~lled amounts of unsaturation i~ kuL~Led ~cu~ul~y in an otherwise saturated backkone. In cont7~ast to 3PDM, the level of lmcAtllration can be inp~pnc;vely and easily controlled, e.g., to p~x~uce polymers having an Iodine Number of about 5 to about 100, to provide a wide variation in ~ll~n;~7tion rate and ~u~-u~
cc~lmability with various highly tu~xlLuL~L~ r~ based on h7t~r7;~P~P or is~L~-In one ~mho~ir~~t, the 1cu~,l copolymers are poly~merizedfrom the same ll~lK~ used to polymerize the block copolymers (I)x-(B)y~(I)x~ i.e., fro~ at least one conjugated diene of f~ ~ llA (1) and at least one conjugated diene of fn ~ ll~ (3), both defined above, pr~viding that the diene of f~ (1) is different from the diene of formula (3)- miS L~ll copolymer ~;

~ 2Q341~q cnntA;n~ abaut 1.0 to about 25%, ~L~r~L~bly about 1.0 to abaut 10% by mole of the polymerized conjugat~d diene of formula (1) and abcut 75 to abaut 99%, ~L~L~bly about 90 to abaut 99% by mole of the polymerized conjugated diene of formLla (3).
Suitable ~u~ y~l~rl dienes of formLla (1) are exempl;f;P~ above.
m e most ~L~L~LL~d conjl ~ te~ diene of formula (1) for the copolymerization of these rand~m copolymers is isJ~L~ e.
Suit~ble conjl~Ate~ dienes of formula (3) are also exempl;f;~
ahove. 1,3-~ ~A~;P~e is the most preferred conjl ~ te~ diene of formula (3) for the polymerization of the rand~m copolymer of th;~ em~xxL~oent. m us, most preferably, in this ~c~;ment, the L~ll copolymer is polymerized from i~L~le and 1,3-~1tA~;~n~, and it contains about 1 to abaut 20% wt. of the i~L~ e units and about 80 to ahout 99% wt. of the h ~A~;~n~ units. m e is~L~Ie units have primarily (i.e., about 50 to abaut 90% wt.) the 3,4-mi~Lu~L~cture.
In another ~o~;ment, the randam copolymers are polymerized from the same 1I~1K~I~L~ used to polymerize the block copolymers (A)X-(D)y~(A)x, i.e., from at least one aryl-substituted ol~f;n, at least one conjugated diene of form~la (1), and at least one ~ulliuy~Le~ diene of formula (3), providing that the conjugated diene of form~la (1) is difr~L~IL from the conjugated diene of formula (3) used in the polymer;~t;~n. m e conjugated dienes of formulae (1) and (3) and the aryl-substitluted ol~f;n~ are defined albove. miS al~Ll~Live random copolymer contains ahout 0.3 to about 15% by mole of the aryl-substituted ol~f;n, ahout 1.0 to ab~ut 25%, ~LeL~L~bly about 1.0 to about 10%, by mole of the conjugated diene of f~r~ll~ (1), the remainder being the conjugated diene of formula (3).
me L~ll copolymers are then s~bjected to the ~Pl~r~;ve hyd~uy~ ~Lion reaction ~ l~cP~ abcve for the block copolymers, ~uring which polymerized conju~ated diene units of formula (3) are suL~L~,Lially ~pl~t~ly h~Luy~ ~Led, while the polymerized - ~ 2034~9~

conjugated diene units of formula (1) are h~d~ l~l to a ~ lly lesser extent, i.e., to such an ~x~t that they retain a ~lff;r;~t amount of their original n ~ r~Lion to v~ An;7e the copolymer, thereby pr~Yhlc;n~ solid elas*llDars having r~ ~ll unsaturation ~L~lLional to the ln~C~rration in the polymerized dienes of formula (1). For example, for a L~ ~IL
copolymer polymerized fr~m a diene of formula (1) and a d;C~
diene of formula (3), the Iodine Number before ~PlPct;ve h~L~y~ ~Lion for the polymer is about 450. After ~Pl~ct;ve h~ y~ ~Lion, the Iodine Number for the polymer is abaut 10 to about 100, mQst of the unsaturation being contr;hlt~ by the diene of formNla (1).
Generally, in such r~ copolymers, the Iodine Number for the polymerized dienes of fnnr~l~ (1) after the ~Pl~ct;ve hy~Lu~ ion r~ t;n~ is about 10 to about 100%, preferably about 25 to about 100%, more preferably ab~ut 50 to about 100%, and most ~L~L~l~bly about 100% of the To~;nP Number prior to the cpl~c~;ve hyd~y~ ~Lion rPArt;~n, and for the polymerized ~;P~PC
of fnn~l~ (3) it is about 0 to about 10%, ~.~L~L~bly about 0 to about 0.5% of the Iodine Number prior to the cplpc~;ve h~Loy~ ~Lion re~r~;n~. m e Tn~;nP Number for the polymerized dienes of formulae (1) and (3) before and after the hy~Luy~ ~Lian rP~rt;n~s in these r~ ~UIl~ copolymers can be estimated by any Lional techniques, e.g., by Fourier n ~ ~LuLm TI~L~Led (FrIR) analysis, as will be ~ L~lL to those skilled in the art.
S;~ rly, for a random copolymer of aryl-su~stituted olefins, a conjugated diene of form~la (1) and a conjugated diene of formula (3), diLL~ L fram the conjugated diene of fnnr~l~
(1), the Iodine Number before ~elPc~;ve h~L~y~ ~Lion for the polymer is about 300 to about 450. AftPr selective hy~Luy~ ~Lion, the Iodine Number for the polymer is about 5 to about 100, most of the unsaturation measNred by the Iodine Number being contributed by the polymerized diene of fn ~ ~l~ (1).
Generally, for the ~Ulll copolymer of this Pmho~ t the Iodine ~ ~ ~ 3 4 1 ~ 4 7~lmber after the CPl~c~;ve h~L~y~ ~Lion rPAr~;~7l for the polymerized diene of formula (1) is a7~out 10 to a7~out 100%, ~L~f~L~bly about 100~ of the Tor.7;7Y~ mber prior to the ~Pl~ct;ve h~dLv~ n reAr~;~7~ and for the polymerize~ die,ne of formula (3) it is about 0 to about 100%, ~L~L~L~bly a7~out 0% of the Tor7;nP , ~ r prior to the selPct;ve h~L~ n rPA~;nn.
~ he hy~Luy~ ~Led polymers may ~e v7l1r;7n;~F~.7. m e v771r;7n;~ec.7 L~U copolymers of this i7~VP7l~jn~ lave ela ~ ric ~LU~e~Lies ~ Ar to those of EP~M. ~he v7ll~n;~7t;~n rate of the polymers can ~e easily and ;7~pxppnsively increased by incrF~sing the Wl~ of the diene of formula (l), i.e., is~ ~ in the most ~l~r~LL~ n~;ment, in either F~o~;r~nt of the r~n~ copolymers to from about 5 to about 20% mole.
Star-BL~led Polymers m e invention is also directed to ~LdL L~ led block and L~ polymers.
The star-branched block polymer may typically be of the formula:
[P]iQ
in which:
P comprises blocks of the formula:
(I)x and (B)y wherein:
I is as defined previously herein, in page 3;
x represents a number from 1 to 100, the values for each block being the same or different;
B is a block of a polymer of at least one conjugated diene as defined previously herein in pages 3 - 4;
y represents a number from 300 to 35,000, the values for each block being the same or different;
each free end of P being an (I) block;
Q represents a coupling moiety; and i represents the number of star branches.
me ~L~L L~ le~ blo~k polymers are made frcm any cr~;nAtion of blocks I and B, A and D, or I, D and A, ~F~f;nr~
above, providing that each free end (i.e., the un~ ~1P~ end) of the ~a~ L~K11e~ polymer is either an I or an A blo~k in the ~ L~ ed block polymers made from blocks I and B, A and D or I, D and A. The ~a~ ~d,~led I-B block copolymers comprise about 0.1 to about 50%, ~l~L~Ldbly about 1 to abcut 5% by wt. of the I blocks and abcut 50 to about 99.9~ by wt. of the B blocks.
Ihe ~L~ LLd~K~led A-D block copolymers, simllarly to the A-D-A
block oopolymers, may have the A blocks of a low ~le2ll~r weight (about 350 to about 7,500) or of a high r~ r weight (about 7,500 to about 20,000). When the block A has a molecular weight of about 350 to abcut 7,500, it comprises about 50 to about 65%, preferably abcut 50% by mole of the aryl-substitut~d ol~f;n, and about 35% to about 50%, preferably abcut 50% by mole of the conjugated diene of fnnmll~ (1). When the block A has a molecular weight of about 7,500 to about 20,000, it oo~prises abcut 1 to - 30 a -~. .

~ 2~3~94 about 99%, ~LeLe~dbly about 80 to about 98% by mole of the aryl-sukstituted olefin, and about 99 to akout 1%, ~1tr~Ldbly about 2 to abcut 20% by mole of the ~u~ y~L3~ diene of formula (1). When the blo~k A has a molecular weight of about 350 to about 7,500, the A-D ~L~ L~d~h~led blobk copolymer compr;cPc about 0.25 to about 10%, ~l~re~bly about 2 to about 10% wt. of the A
blocks, and about 80 to about 99.5%, ~r~Ldbly about 80 to about 96% wt. of the D blocks. When the block A has a molecular weight of about 7,500 to about 20,000, the A-D ~LCL ~L~1~e~ block copolymer comprises about 0.25 to about 25%, preferably ab~ut 10 to about 20% wt. of the A blocks and ab~ut 50 to ab~ut 99.5%, ~ f~Ldbly about 60 to abaut 80% wt. of the D blocks. In the ~Ld~ ed I-D-A block copolymers, the block A has a molecular e;~ht of about 350 to about 7,500. The ~l~r LLdl~led I-D-A
bloc~k copolymers comprise akout 0.1 to about 50%, ~ r~Ldbly about 1 to abaut 5% wt. of the sum of blocks I and A, and abo;ut 50 to about 99.9%, preferably abaut 95 to about 99% wt. of the blocks D.
m e ~L~ LL~led block polymers ~ e cPl~ct;vely h~L~ ~Led in the ~Pl~ct;ve h~Luy~ ~Lion p~ s to such an ~t~nt that bloc~s B or D cnntA;n suL~ lly none of the original unsaturation, while each of the blocks I and A, ~ ;vely, retains a ~lff;r;~nt am~unt of the original lm~b ~ation of the conjugated dienes ~L~s*~lL in these blocks to cure the star-branched block polymers. Thus, for the I-B st ~ -LL~ ~le~ block polymer, after the CplFc~;ve hy~L~y~ ~Lion reaction, the To~;nP N~m~r for the I
blocks is about 10 to abaut 100%, ~Lere~dbly abaut 25 to about 100%, more preferably about 50 to abaut 100%, and m~st preferably about 100% of their Iodine N~mber prior to the CplF~;ve h~druy~ ~Lion reaction, and for the B blocks it is ab~ut 0 to about 10%, preferably about 0 to about 0.5% of the Iodine Number prior to the ~Plect;ve h~dL~y~ ~Lion reaction. For the A-D
star-branched block polymer, after the selective h~d~uy~ ~Lion ~ ~ ~i 3 ~

r~A~-ti~n, the Iodine Numker for the A blocks is about 10 to about 100~, k~L~bly abaut 25 to abaut 100%, more preferably akout 50 to abaut 100~, and most preferably about 100% of the Tn~;~P
Number prior to the ~Pl~ct;ve h~dLuy~ ~Lion r~Ar~;n~ and for the D blocks it is about 0 to abaut 10~, ~L~LtLdbly about 0 to about 0.5~ of the TQ~;nP Number prior to the ~Pl~c~;ve h~d~uy~ ~Lion r~A~.t;~. Similarly, for the I-D-A star-brA~rh~ block polymer, the Tn~;nP Number for each of the I and A blocks after the cPl~c~;ve h~u~ ~Lion is completed is abaut lo to abaut 100%, ~leL~L~bly about 100% of the Tn~;r~P Number prior to the sPl~ct;ve h~Luy~ ~Lion rPArt;a~ and for the D blocks it is about 0 to about 10%, preferably about 0 to about 0.5%, and most preferably 0% of the Iodine Number prior to the selective h~d~oy~ ~Lion reaction. Thus, in this ~mk~;r~~t, the block D is also ~Pl~ct;vely hydLuy~ ~Le~ in the same ~ as ~ lqCP~ above for the central blocks B and D of the other embo~;~A~t~ of the invention.
m e ~L~r LL~rY~l~r~ l copolymers are made from any combination of at least one diene of form~la (1) and at least one diene of fnrrllA (3), or from any cnm~;nAtion of at least one aryl-substituted olefin, at least one diene of fnrrllA (1) and at least one diene of formula (3), all of which are the same as those ~ lqcP~ akove in conjunction with the block and L~ll copolymers. m e ~Ldl LL~K1le~ random copolymers of the dienes of formwlae (1) and (3), which must be difLe~lL from each other, camprise about 1 to abaut 25%, preferably ab~ut 1 to about 10% by mole of the polymerized conjugated diene of fnnrllA (1) and about 75 to about 99%, ~Lefe~bly about 90 to abaut 99% by mole of the polymerized conjugated diene of formula (3). me star-branched L~ll copolymers of the aryl-substituted olefin, at least one diene of formula (1) and at least one diene of form~la (3), d;fferent fr~m the diene of formula (1), comprise akout 0.3 to abaut 15% by mole of the aryl-substituted olefin, abaut 1 to -=

2~34~g abcut 25%, preferably about 1 to about 10% Ly mole of the conjugated diene of formula (1), and the remainder of the conjugated diene of formula (3). m e ~L~L LL~ F~ L~ll copolymers are also ~ ct;vely h~r~y~1Le~ in the cPl~ctive h~dLuy~wLiOn ~LOC~ to such an extent that the polymerized dienes of formula (3) contain ~L~lLially none of the or;~inAl ulL~lLuL~Lion, while the polymerized dienes of formula (1) retain a ~lff;~ t amount of the original unsaturation to cure the ~L~ LL~ IP~ LCU~II copolymers. m us, for the star~
L~ ~ll polymer of the conjugated diene of formLla (1) and a different diene of formula (3), both identified above, the Iodine Number for the polymerized diene of f~r~ (1), after the sPlPc~;ve h~d~oy~ ~Lion r~A~t;nn~ is ab~ut 10 to about 100%, preferably about 25 to about 100%, more ~LereLdbly about 50 to aboul 100%, and most ~L~L~Ldbly about 100% of the Iodine Number prior to the c~l~ct;ve h~dLuy~ wLion r~A~t;n~, and for the polymerized diene of form~la (3) it is about 0 to about 10%, preferably about 0 to about 0.5% of the To~;ne Number prio,r to the .CPlprt;ve h~d~uy~ ~Lion r~A~-t;nn. Similarly, for the ~L~r L~dlKlled L~ll polymers made fro~ at least one aryl-sub6tituted ~lPf;n, at least one diene of fn ~ llA (1) and at least one diene of formula (3), the To~;n~ Number for the polymerized diene of f~r~ (1), after the .sPl~ct;ve h~dLuy~ ~Lion reaction, is about 10 to about 100%, ~L~r~ldbly about 25 to about 100%, more ~L~Lt~bly about 50 to abo;ut 100%, and most preferably about 100% of the Iodine Num~er prior to the selective h~uy~ ~Lion rPA~;n~, and for the polymerized diene of fnn~llA (3) it is About O to ab~ut 10%, ~L~L~Idbly about o to about 0.5% of the Iodine Number prior to the selective h~d~oy~ ~Lion reaction.
Blends Of Inventive PolYmers With Other Materials The block or Ld~ll copolymers of this invention can, of course, be blended with any ru~bers, in which case the degree of ~
~ 0 3 4 1 9 4 mCA~lration of the copolymers of the invpntinn can be a~ Lel so that the v'llrAn;~At;~n rate of the two mater;~l~ is ~,l~l~ul;Ally the same. Suitable rubbers which can be hl~n~
with the copolymers of th;~ invP~;n~ are EPD~, butyl rubber and based on hl~A~;~P or ~ ~e.
The block and ~ l copolymers of this invP~t;~ can also be blended with plastics, e.g., isotactic polypropylene, polystyrene, polyethylene, nylon, poly~-t--~lP~, poly~L~L~ and St~L~ acrylonitrile resins. Ihermcplastic ela~L~-~L~ having ~Y~Pll~n~ ~Lu~t~Lies can be obtained by dynamically v~ An;~;n~ a blend of polypropylene and the elastomcrs of our invention, in which the ela~L~.~ are crosslinked to a very high deyL ~ . A
commercial material,~santoprene"(LL~ ---r~ of and pr~r~ by L~ ~hPm;~Al Co.) is based upon blends of poly~propylene and EPD~. netA;l~ of the ~lt~r~ion and ~L~LLies of such h1~r~ .
~ e ~L~ in T~ERM~PIASTIC EII~YYERS, A COMPREHENSIVE REVIEW, P~;ted by N. R. Legge et al., G~4~ 7, IL~c~ hl;~h~r~, Munich, Vienna and New York (1987) t Such dynamically v~llrAn;~
blends ~ ~a~ed with the polymers of the invention in a conventional manner, e.g., that of N.R. TFg~e et al., wherein the polymers of this invention are hlPr~F~ with polyprcpYlene, and most par~;rJllArly wherein the triblock polymers of this in~ention are hl~n~ with polypropylene, can prcvide I~P~ ~-lActic elast~ners with unique elastomeric ~L~LLies.
The block and L~ ~1l copolymers of this invP~t;~ can, of course, be c~ry m~r~ with ingre~ t~ kncwn to those skilled in the art, e.g., fillers, such as s;l;rA, rArhnn black, extender oils, A~t;~ A~ts, tackifying agents, vulcanizing a~ and ~;m; l Ar materials.
PolYmerization Reaction The block copolymers of this invention are polymerized by I . ~ f .
.

_ny kn2wn block polymer;~A~ u~ P~ Lt~dbly by an An;~ polymerization ~Loce~. An;nn;~ polymerization is w~ll kncwn in the art, and it is llt;1;7~d in the pr~ t;~n of a variety of commercial polymers. An PYrPll~t ccm~ L~ive review of thQ An;o~;r polymer;~At;nn ~U~P~cP4 ~ r~ in the text ADV~N~F~ IN POLYMER SCIENCE 56, ANIoNIC POLYME~T~A~Tn~, pp.
1-90, Spri.~e~ Verlag, Berlin, Heidelberg, New York, Tokyo 1984 in a m~ entitled ANIoNIC POLYMERIZAIION OF N0N-POL~R MSN~PERS
I~VU~Vl~G T.T~n~M~ by R.N. Young, R.P. Quirk and L.J. Fetters.
The anionic polymerization ~L~AX~S is ~on~l~tP~ in the ~LP-C~I~ of a suitable An;~nic catalyst (also known as an initiator), such as n-butyl-lithium, sec-butyl-lithium, t-butyl-lithium, scdium I~J~ P or cumyl potA~C;l~. m e amount of the catalyst and the amount of the ~ )Kn,~. in the polymerization rPA~-t;~n dictate the ~le~llAr weight of the polymLPr. The polymerization reaction is co ~ l~ç~
in ~ol~ n using an inert solvent as the polymerization m~
e.g., Al;~hAt;l h~ rl~ SU~tl as ~PYAl'lp~ cyrl~P~nP or hepkane, or a~ solvents, such as ~ ~le or toll~Pnp. In certain instanccs, inert polar solvents, such as tetrahy~oLu~l, can be used alone as a solvent, or in a mixture with a h~dL~ ~ solvent.
The block polymerization ~L~XSS will be P~rl;f;
bclow for the polymerization of the first emk~;m~t of the inv~n~;n~, and -~p~c;f;~lly for the ~L~L~LL~ emb~;m~t thereof, i.e., a triblock of polyisu~ ~ poly~ ~A~;~P-polyis~
However, it will be ~y~r~lL to those skilled in the art that the same ~L~cc prinrirl~ can be used for the polymer;~t;~ of all copolymers of the invention.
me ~LO~S~, when using a lithium-based catalyst, comprises forming a solution of the iSuyL~le ll~lK~Id~ in an inert h~r~j~r~ l solvent, such as cy~-lnh~-x~npl m~;fi~ by the ~Le~ therein of one or more polar cn~ ~ds 5Plecte~ from the 2~ ~ 4 ~ ~ 4 g ~ consisting of ethers, ~h;~ r~ and tertiary ~ , e.g., tetrahydrofuran. The polar cc~Founds are ~P~ry to c~llL~l the mir_Lu~LL,~cture of the h ~AA;~nP ~lL~I block, i.e., the ç~n~nt of the 1,2-structure Ul~r~f. The higher the c~ n~ of the polar ~ , the higher will be the ~ll~-l of the 1,2-structurc in these hl~r~c. Smce the ~L~ of the polar cc=pound is not ~ J l~ in the formation of the first polymer block with many ini~;~7t~r.C unless a high 3,4 ~LL~ re ~J..I~"l of the first block is desired, it is not l~re~ y to introduce the polar c~r~7n~ at this stage, since it may be illLL~7re~ just prior to or l~ r with the addition of the h7tAr7;P~P in the second polymer;~At;~n stage. FX~1PC of polar ç~77~dS which may be used are ~7;m~hyl ether, diethyl ether, ethyl methyl ether, ethyl propyl ether, dioxane, diphenyl ether, tripropyl amine, tributyl amine, trimethyl amine, triethyl amine, and N-,N-,N'-,N'-~LL~Ul~l ethylene diamine. ~;xhlres of the polar cf~ 7~c may also be used. Ihe am~unt of the polar ~n~777~d depends on the type of the polar ~ 7 and the polymeri~A~;~n conditions as will be ~ya~,L to thcse skilled in the art. The effect of the polar ~n~77~dS on the polyh7tA~i~7le mi~ L~cture is nP~A;lF~7 in A~1'K~W1AK et al, TEMPERAIURE AND aONCLNTRAIION
~ ON POL~R-M~Dl~lED ~ L TT~ ~ POLYME~T~A~T~S AMD
00~POLYMERIZAIIONS, J ~ L OF POLYMER SCIEN OE: Part A-1, Vol. 10, 1319-1334 (1972) . The polar cr~Y~l~ds also ~nrplF~rate the rate of polymerization. If ~ S other than butadiene, e.g., ~ ;F~, are used to polymerize the oe ntral blocks B or C, polar co~pclnds are not ~~c~ y to control the mi~L~L~cture hecAl~CP such monomers will inherently produoe polymers which do not crystallinity aftF~r h~luy~ ~Lion.
When the alkyl lithiumrbased initiator, a polar ccmpcond and an i5U~L~ 11~11~1~ are combined in an inert solvent, polymerization of the i~u~L~le ~Loceeds to produ oe the first ~' =~, 2 0 ~

tPrm;nAl block ~ho6e mO1P~11Ar ~ ht is detI~=clY3d by the ratio of the i~L~le to the initiator. m e "living" polyi~L~lyl anion formed in th;~ first step is 1*;1;7PA as the catalyst for LULU1~L polymer;7At;~n- At this ti~e, h ~A~;PnP monomer is intrQ~lfF~ into the system and block polymer;7At;~ of the CPcnr~
block ~~ e~s, the ~Le~h~ of the polar ccD~x~lld now ;nflllP~cing the desired degree of brA~rh;n~ (the 1,2-s~3xsture ...L~.IL.) in the polyh ~A~;PnP block. m e resulting product is a living ~;hl~rk polymer having a tPrr;nAl anion and a lithium counterion. m e living ~;hlork polymer serves as a catalyst for the growth of the final isLyL~Ie block, formed when i~yL~le mU~ ~L is again added to the rPArt;n~ vessel to produce the final polymer block, resulting in the formation of the I-B-I
triblock. Upon complPt;n~ of polymerization, the living anion, nKhT ~L~*~lL at the tPrm;~ of the triblock, is de~LLuyed by the addition of a ~LuLull donor, such as methyl Al~nhnl or ~Pt;c acid. m e polymerization rPAr-tion is usually co ~ l~te~ at a t~l~LdLure of hPt~T~n 0~C and about 100~C, although higher L~LdLures can be used. Control of a chosen rP~-t;nn temp~L~ is desirable since it can ;nf~ ce the effectiv~
of the polar cf~ lnd additive in controlling the polymer mi~L~LL~cture. m e rPA~t;nn L~.~dL~re can be, for ~Y~rl~, fram 50 to 80~C. m e rPAr~;nn pressure is not critical and varies from d~ iC to abaut 100 psig. If the pol ~
cr~Yl~ds ~ e ll~;l;7~ prior to the polymerization of the first I
se~ lL, I blocks with high 3,4-unit clull~.lL ~ e formed. If pol ~ cy~yy~nlds (some of which can be Lewis bases) ~ e added after the initial I se~ .L is ~Lt~U~ the first I se~ lL will ~}~c~P~c a high ~L~ILdy~ of 1,4-mi~lu~LL~cture (which is trisubctituted), and the second I se~ L will hav~ a high ~ o~.Ldy~ of 3,4-mi~Lu~LL~cture.
The production of triblock polymers having a high 1,4-unit content on both of the terminal I blocks is also 203 ~ 9~

pn~c;hl~ by the use of cY~?~ terhn;~l~c ill~LL~Led below for a polyis~L~ ~ polyh ~A~; P~e - polyiS~yL ~ ~ block copolymer:
Polar P~
lSC21~ 1, 4--pt)T.~ 1, 4--E~T-'~ I ~Y,~ --POLYB~DIENE
~ l;~nP

1, 4--pt )T .~r I ~ )I'K~E--POLY ~ DIl~NE--1, 4--pt~T ~ K~E <
(~)PLING AGE2~T

The sukstitution of myrcene for the iS~l~ ~ during the polymerization of the I block inSureC the i~n~jL~L~Lion of a high Lion of trisub~ctitut~ ~lhlP bonds, even in the of polar cx~xamds since m~rcene contains a ~ ulL
tri~lhctituted A~lhlP bond which is not involved in the polymer;~At;~ ~lo~e~. In a cayrl;~ u~ c;r;lAr to that described above, block polymers cn~tA;n;n~ polyisu~L~Ie end blocks (or any okher polymerized m~ ~L suit~ble for use in the I block) having a high 3,4-mi~L~LLucture content can be ~htA;nPA
by adding the polar cr~Y~m~ prior to the i~yl~ ~ (or ~ ~ U1~L
m~ln~l~L) polymerization.
Ihe use of the coly?l;ng terhn;~lP for the pr ~ lr~ of triblock polymers greatly reduces the reArt;~ time IK~o~~y for the c~?lPt;~n of polymerization, as C~ Le~ to a sequential addition of i~u~ e, foll~J~ by h ~AA;Pne, foll~l~ hy is~L~le. Such oyy?l;ng terhn;~lP-c are lwell known and l~;l;~p l;ng agents, such as esters, o~2, ;n~;n~, A;h~ln~lkanes~
c;R~nn tet~rachloride, divinyl bPnzene, aIkyl trichlorosilanes and diaIkyl A;~hlnrosilanes. Ihe use of tri- or tetra-functional ~ y?l;ng agents, such as alkyl trichlorosilanes or c;l;r~n tetrachloride, permits the formation of macromolP~ll~.c having 1-or 2- main chain branches, ~ L;vely. m e a~;tion of divinyl benzene as a c~rl;ng agent has been documented to pro~u oe .

~ 2~41~4 having up to 20 or more ~ Lely joined ~J ~
m e use of some of the C~y?l;~g agents provides a conv~n;~t means of prq~l~-;n~ ~L~ L~ 7 blo~k and random polymers. The ~L~L L~K~le~ blo~k polymers are made from any comh;n~t;nn of blocks I and B, A and D or I, D and A, ~; ~ l~CP~
above, providing that each free end (i.e., ln~y~rl~ end) of the ~Lal L~ ~l polymer is either an I or an A block, r~ L;vely.
m e ~L1L L~ polymers are made from any comb m ation of at least one diene of formula (1) and at least one diene of formNla (3), diLL~ L from the diene of fnrrll~ (1), or from at least one aryl-substituted qlf~f;n~ at least one diene of fqr (1) and at least one diene of form~la (3), d;fferent frolm the diene of fnr~llA (1). m e molf~llAr ~;r~ht of the ~L . L~ led block and r~ ~l; copolymers will f7Pr~nf7 on the number of L~K~le~
in each such copolymer, as will be ~4~a~lL to those skilled in the art. Suitable o~yrl;nf3 agents and rf~Af~;n~s are ~7;~clf~r7 in the following references: U.S. Patents 3,949,020; 3,594,452;
3,598,887; 3,465,065; 3,078,254; 3,766,301; 3,632,682; 3,668,279;
and Great Britain Patents 1,014,999; 1,074,276; 1,121,978.

me L~l- copolymers of the invf~t;f~ are polymerized and/or o~rlf~f7 in a similar fA~h;n~ but ~11 mUlK~I~L~ e.g., ~ L~le and h ~f7;f~e, are muxed in a ~lU~ ratio prior to the reaction with the polar f~r~ 7;f;-f~f7 alkyl-lithium. In the ~ 1 polymer ~ L~Lion, of o~nn~ only one stage is ~ ~ ry.
Selective H~dlu4~ ~Lion Ihe cPl~ct;ve h~u7L~y~ ~Lion rf~Af~;n~ will also be df-c-r;h~ below using a triblock of polyisu~ c poly~lt~f7;f~e-polyis~ e as an f~Y~rlf. ~f,~Jcvcr, it will be ~~~IL to those skilled in the art that any polymers of this invention can be ~Plf~c~;vely h~Luy~ ~Led in the same 11~ .

~ ~ 3 4 1 9 4 The block copolymer is cPlP~t;vely h~L~y~L~l to saturate the m;~A1P (polyh7tAr7;P7~) block of each of the triblocks. The r~lhnP. of cplp~t;vely hy~L~y~ ~Li7Yg the poly~7~A~;PnP block is ~;m;1,7r to that of Falk, "Cocrr7;7~7~;~n Catalysts For The SPlP~t;ve ,~L~I,;nn of Polymeric Ih~j~L~L~Lion", JOURN~L OF POLYMER SCIEN OE : PARr A-l, Vol7~me 9, 2617-2623 (1971), but it is Co~7~tfP with the novel hy~luy~ ~Lion catalyst a7~d ~ 7used herein. ~y okher kncwn ct;ve h~Luy~ ~Lion m~Ulo~s may also be 7used, as will be ~k~a~IL to those skilled in the art, but it is ~L~LL~ to use the ,~llfr7 d~crribed herein. In summary, the ~PlPC~;ve h~oy~ ~Lion l~lnr.7 ~L~r~Ldbly used herein comprises oontA~;n~
the previously-~L~ya~d block copolymer with hy~Luy~l in the ~L~ e of the novel catalyst cn~rnc;tion.
The novel hydrogenation catalyst composition and hydrogenation process are described in detail in ~n~ n Application Serial Number 2,034,221 of T.S. Coolbaugh et al, pllhl;.~h~ July 17, 1991.
The hydrogenation catalyst composition is synthesized from at least one transition metal compound and an organometallic reducing agent.

Suit~ble transition met~l clolxYunls are cr~y~7n~s of of Group IVb, Vb, VIb, or VIII, preferably IVb or VIII of the Periodic Table of the Elements, 7~lhl;~l~Pr7 in I~iGE's H~ND300K
OF CHEMISTRY (13th F~7;tion, 1985, ~oGraw-.~ill 30~k C~mpany, New York, John A. Dean, Editor). Non-limiting ex~mples of such cYr~Y~mr7~ are metal hAl;~, e.g., titanium tet~ hl~ride, vdnadium tetrachloride; vdnadium oxytric~loride, tit~n;lnn and vdnadium alk~ c, wherein t7ne alkoxide moiety has a ~cl~.ed or ~u~dlKlled aIkyl rA~7.;~Al of 1 to about 20 Ca~bU1l at~ms, preferably 1 to abo~t 6 c~rbon ats~ns. F~L~Ll~ transition metal cf~Y~ds are metal cArhn~ylat~ or aIk~ P~ of Group IVb or VIII of the Periodic l~dble of the Elements, such as nickel (II) ~ ~ : ~
.

f~ 3 2-ethylheY~noate, titanium is~4~ , cobalt (II) ~oaLe, nickel (II) ~hP~nY;~P and ferric acetylA~
The u~ ;c re~ agent is any one or a ccmh;nA~ of any of the materials commonly empl~yed to activate ~;-pgl~r-Natta olefin polymerization catalyst co~
con~A;nin~ at least one ccrpound of the elements of Grcups Ia, IIa, IIb, IIIa, or IVa of the Perin~;c Table of the Elements.
EXamples of such reducing agents are met~l alkyls, metal hydrides, aIkyl metal hydrides, alkyl metal hAl;~s, and alkyl metal alk~-Y;~, such as aIkyllithium c~ ~c, diaIkylzinc c~ylnds~ triaIkylboron c~ mr7c, trialkylAll~;~rm c~
alkylAll~;num hAl;~7~.~ and hycrides, and tetraalkyl-p. -~um c~mroll~ds. M~xtures of the r~c;n~ agents may also be emplc~ed.
,~pec;f;~ Amrl~-~ of useful reducing agents include n-butyllithium, diethylzinc, di-n-propylzinc, triethyIboron, diethylAll~;nnnP~hn~ , triethylAll~;~um, trimethyl~l~;num~, tr;;~nhr~ylaluminum, tri-n-hexylaluminum, ethylAl-~;num ~;~hlnride, dibromide, and dihydride, ;c~ ~yl All~;m ~ ~;chlnride~
dibromide, and dihydride, diethylAl-~;m ~ chlQride, bromide, and hydride, di-n-propylAll~;~um chloride, brc~ide, and hydride, ~;;~nh ~ylAl-~;num chloride, bromide and hycride, t~LL~,~U~ ium, and tetraethylgermanium. CL~r~l~ll;c re~-c;n~ agents which are ~L~rt~L~d are Group IIIa metal aIkyls and dialkyl metal hAl;~C having 1 to about 20 c~Lul- atoms per aIkyl rA~;~Al. More preferably, the r~ ;n~ agent is a trialkylAl~;num c~r~lnd having 1 to about 6 ~d~bUll at~ms per al~yl rA~;cAl. Other reducing agents which can be used herein are d;~cl sse~ in Stevens et al, U.S. Patent No. 3,787,384, oolumn 4, line 45 to column 5, line 12 and in Strobel et al, U.S. Patent No. 4,148,754, colurn 4, line 56 to c-olumn 5, line 59, Part;~llArly preferred reducing agents are metal aIkyl or hydride ' ~ ' 203~

derivatives of a metal selected from Groups Ia, IIa and IIIa of the Periodic Table of the Elements, such as n-butyl lithium, sec-butyl lithium, n-hexyl lithium, phenyl-lithium, triethylAl~ um, tri-isobutylaluminum, trimethylaluminum, diethylaluminum hydride and dibutylmagnesium.
The molar ratio of the metal derived from the r ~ l~-;n~
agent to the metal derived from the transition metal ccnçx~md will vary for the selected combinations of the r ~ l~;n~ agent and the transition metal c~oçxlmd, but in general it is about 1:1 to about 12:1, preferably about 1.5:1 to about 8:1, more preferably about 2:1 to about 7:1 and most preferably about 2.5:1 to about 6:1. It will be ~ r~.L to those skilled in the art that the optimal ratios will vary depending upon the transition metal and the organome~All;c agent used, e.g., for the trialkylAltr-;ln~/nickel(II) systems the ~L~Le~L~ aluminum: nickel molar ratio is about 2.5:1 to about 4:1, for the triaIkylAllnn;~um/cobalt(II) systems the ~L~LtLle~ aluminum:
cobalt molar ratio is about 3:1 to about 4:1 and for the triaIkylAll~;num/titanium(IV) alkn~;~F~ systems, the preferred A~ titanium molar ratio is about 3:1 to about 6:1.
The mode of addition and the ratio of the reducing agent to the transition metal cr~$Y~l~d are impuLL~lL in the pro~lct;
of the ncvel h~L~y~ ~Lion catalyst having superior CPl~Ct;Vity~
~ffi~ cy and stability, as compared to prior art catalytic systems. During the syn~h~ of the h~d~y~ ~Lion catalysts it is preferred to maintain the molar ratio of the rPAr~A~c used to syn~h~-c;~e the catalyst ~I~L~-Lially ~.~L~.L. This can be done either by the addition of the reducing agent as rapidly as ~Yy~c;hle to a Coll~;nn of the transition metal cfryY~lnd, or by a ~ ~L~ILially simultanF~ous addition of the st~al~Le ~LLe~.~ of the reducing agent and the transition metal cr~qx~l~d to a catalyst syn~hFc;~ vessel in such a .l~u~ that the selected ~ 2~31~9~

molar ratios of the metal of the rP~7~ agent to the metal of the transition metal cY~Y~n~ are maintained ~ ;Ally wl~L~lL th~x~h~rt c~ rll;Ally the entire time of addition of the tw~ c~ . The time required for the addition must be such that P~Pcc;ve pressure and heat build-up are avoided, i.e., the L~ L~L~re Ch~ll~ not P~Fe~ about 80~C and the prpc~nre Ch~ll~ not exceed the safe ~ ule limit of the catalyst synthP-c;c vessel.
In a preferred cm~xxl~ment, the reducing agent and the tran_ition metal cnm~olm~ are added ~~ lly simulL~ ~u~ly to the catalyst syn~h~-c;c ves_el in such a II~U~ that the selected molar ratio of the reducing agent to the transition metal cn~oll~d is maintained ~l~L~lLially wl~L~IL during suL~L~ILially the entire time of the a~;tion of the tw~
cxn~xY mds. This preferred emlxXl~nent permits the control of the exoth~rm;~- reaction so that the heat build-up is not ~P-qc;ve, and the rate of gas prahl~ during the catalyst 5~ P~;C is also not ~P-qcive-accordingly the gas build-up is relatively slow. In this em}xxl~cnt, c ~ ried out with or with~ut solvent nt, the rate of addition of the catalyst c~ ulK~ILj is adjusted to maintain the synth~-c;c r~A~;nn t~.4~L~re at or below about 80~C, which ~L~I~Les the formation of the c~lpct;ve h~Luy~ ~Lion catalyst. Furth~rr~re, the selected molar ratios of the metal of the reducing agent to the metal of the transition metal cr~Y~lnd are maintained s~L~ L;Ally wl~L~lL thr~h~lt the entire duration of the catalyst ~L~a~Lion when the sim~ltaneous mixing technique of this embcciment is employed.
In ~I~L~L ~mho~ nt, the catalyst is formed by the addition of the reducing agent to the transition metal ccD~x~ind.
In this ~mho~;m~nt, the timing and the order of addition of the two reactants is ~,~LL~L to obtain the h~Luy~ ~Lion catalyst h ving superior selectivity, efficiency and stability. Thus, in ~ 2 0 ~

th;c emb~;r~~t, it is impuLL~lL to add the reducing agent to the transition metal cn~ d in that order in as short a time period as prArt;~Ally EXY~c;hl~. In thi_ erlxxlment, the time allokted for the ~dd;tion of the r~lr-;n~ agent to the transition metal cc}~x~md is critical for the pro~lr-t;nn of the catalyst. Ihe term "as short a time period as prAr-~;cAlly pn~c;hle~l means that the time of addition is as rapid as pncc;hl~, such that the r~Act;~n L_.r~L~re is not higher than ahaut 80~C and the r~Art;nn pr~CCIlre d~PC not ~e~ the safe pre~Cllre limit of the catalyst synthesis vessel. As will he ~ L to those skilled in the art, that time will vary for each synth~-c;~ and will depend on such f~r-tnrc as the types of the reducing ~ntc, the transition metal cnmroll~ds and the solvents used in the synth~c;c, as well as the relative amounts thereof, and the type of the catalyst synth~c;~ vessel used. For p~L~oses of illustration, a colllt;n~ of about 15 ml of triethylalumuumm in hexane ch~ll~ he added to a ~olttt;n~ of nickel(II) ~L~Le in mineral spirits in about 10-30 se~ . Generally, the addition of the reducing agent to the transition metal cYx~x~m~ should be c ~ ried out in about 5 sec~l~s (sec) to about 5 minutes, depending on the quantities of the ~ea~lL~ used. If the time period during which the reducing agent is added to the transition metal cnm~oll~d is prolonged, e.g., more than 15 minutes, the synth~-c;~ catalyst is l~CC cPlpct;ve~ less stable and may be L~LC~S.
In the embodiment wherein the reducing agent is added as rapidly as po~c;hl~ to the transition metal çY~qY~l~d, it is also ~ uLL~IL to add the reducing agent to the transition metal cn~7~ d in the aforementioned sequence to obtain the novel catalyst. The reversal of the a~;tion sequence, i.e., the addition of the transition metal cnry~ d to the reducing agent, or the r~e~Live solutions ~,t~r, is detrimental to the stability, selectivity, activity and h~ leity of the catalyst and is therefore undesirable.

i ~

~ 9 In all ~o~ nt~ of the hy~k~ ~1 inn catalyst 5~ , it is preferred to ucP c~ll~;r~c of the reducing agent and the transition metal cn~r~m~ in suitable solvents, such as h~L~ ~r~-ll solvents, e.g., cy~l~hP-X~n~, hPY~P, ~k~ltcUle, e~L~ e, hpn~ne~ tolune or mineral oils. The solvents used to ~tya~ the ~ll~;nnc of the r~lrin~ agent and of the transition m2tal c~Ylnd may he the same or dirL~L~lL, h~t if they are different, they m~st he c~r~t;hl,P with each other so that the ~ol~ n~ of the rA~lc;n~ agent and the transition metal ~n~m~
are fully colllhlP in each other.
m e h~Luy~ ~ion ~l~C~S~ ccmpri ~ s ~nntArt;ng the unsaturated polymer to he h~dLuy~ ~Lel with an am~unt of the catalyst ~oltlt;n~ containing akout 0.1 to ahout 0.5, ~L~rtL~bly about 0.2 to about 0.3 mole ~L~ L of the transition metal based on moles of the polymer unsaturation. m e h~d~oy~l partial pr~C~Ire is about 5 psi to ahout several hundred psi, hut preferably it is about 10 to abcut 100 psi. The temperature of the h~d~uy~ ~Lion reaction mixture is ahout 25 to ahout 80~C, since higher t~.~ Lures may lead to catalyst ~PArt;vation. The length of the hy~koytl~Lion reArt;~n may he as short as 30 minutes and, as will he ~a~lL to those skilled in the art, d~ to a great extent on the ~ 1 r~Ar~ conditions employed. The h~dlùytl~Lion ~u~e~ may he monitored by any conventional means, e.g., infra-red ~e~L~ h~dLuy~l flow rate, total hy~kuy~l consumption, or any combination thereof.
Af er the hy~kuytî~Lian r~t;~ is c~pl~t~ the hy~k~y~ ~Lion catalyst must be rem~ved frcm the polymer ky any ~ullv~lLional means, for PXA~rl~ in the r~cP of a nickel-k~sed catalyst by contacting the polymer with a co~plexing agent, such as a high ~l~llAr weight diamine (e.g.,''J~ffAm;neUD-2000 fro~m Texaco), and then with an acid, e.g., sulfuric, ph~ ic or hydrochloric acid, in the ~e~e of an ~Y;~;7;ng agent, e.g., * Trademark .

2 ~ 3 ~ ~ ~ 4 air or hy~L~y~. peroxide. qhe polymer c~ll~;n~ iS then ~L~L ~ P~ and the polymer ;~nlAtP~ by ~llv~ ;nnAl ~ Y
e.g., steam or ~lnnhnl floxx~llAt;nn or solvent ~vo~u~aLion.
Crosslinkin~ And Functionalization Of The Terminal Blocks In A~;t;nn to acting as sites for ~lln~n;~Ation~ the P~r;nAl hlnr~c of the block polymers of ~;c invPnt;n~ can be chemically m~;f;P~ to provide benefits nh~A;r~
with s;r;lAr rr~;f;rA~;ons of existing c~.u.~uial materials, such as butyl rubber or EPDM. In some il~L~ s, the benefits obtained by a rhPm;~l rr~;f;r~tion of butyl rubber or EPDM may be r~gn;f;~ using the ela~ s of our inv~nt;n~ as a matrix i.~Lead of the butyl rubber or EPDM h~cAIl~e of their intr;n~;~Ally superior ela~ ic ~ ies.
An ~x~rl~ of such a chemical r-~;f;r~tion of the polymers of this inv~n~;n~ is sulfonation of the olPf;ni~
n~lration of the I blocks or polymerized dienes of fnr~r~l~ (1) of any polymers of this inv~n~i~n containing the I blocks or polymerized ~;~ng~ of formula (1), foll~od by ~ i7~t;~n of the thus-formed polymeric sulfonic acid with metal ions or amines. When such a ~;f;~tion is ~~,Lulmed on a cx~ rcial ethylenc ~u~lene-diene ~ K~ (EPaM) rubber, a It.~ tic ela~ which behaves like a vulcanized rubber at room temperature but can be sh~rF~ at hiqher t~,4~ rres is pr~lrF~
A description of an ~x~mrle of a ~L~ces~ for and pro~uct description of such a ~h~m;~lly m~;f;~ EpnM can be found in IONS IN POLYMERS, A~v~ in Chemistry Series 187, American rh~micpl .So~;~ty, Was~Lr~rbon, D.C. 1980, pp. 3-53, Following the procedures used for EPDM described in the aforementioned publication with the triblock of our invention, thermoplastic elastomers with greatly improved elongation properties were prepared.
It is known that the h~lo~nation of the unsaturation in butyl rubber (based upon isu~r~K' l~lK~L~) prior to the ~ '_ 2 0 ~

n;~Ation treatment, prod-Sces dramatic ~Sa~ in n;~Ation rate and provides ~L~L~r ~ ~Lility in the ~hn;t~
of ~llrAn;~ agents. Since the rps;~lAl unsaturated gra~ps in the first ~l;r~-lt of our invpnt;nn~ sJLes~s.L in the I blo~k, in the most preferred emb~i~t, may also be based on is~ S,e JSI~ the hAl~PnAt;on of the polymer of this e~rb~li~t provides the same ~nPf;ts, but with the ~ -L~- ,l ;nn of the yL~aL~
Plnn~t;ml c'naracteristics inherent in the invention polysner.
'me same benefits will ke obtained with any other dienes which cAn be used to 5~J~ ~s~ the blo~k I of this eml~i~t of the invention, and Ul~Lefure any polys~s of this invention containing any s~-sch dienes c_n be hA14~.u Le~ in the same ",cu as the butyl rul~er. Any other polymers of th;s invention containing the polymerized dienes of formula (1) or blo~ks I can also be hAl~nated in the same manner.
It is also knawn that the r~A~-t;nr~ of EPDq with maleic anhydride at elevated temperatures (e.g., about 150~C to about 250~C) produces maleic mr~;f;~ EPDM which is used commercially as an impact mr~;f;~r, part;~11Arly for Nylon. S;~ r mo~;f;~Ation of the polymers of any ~ ;r~~ts of our invention oocurs readily, since the r~ uyL~Ie unsaturation, primarily of the ill~LL~Le~ 3,4-type, is known to be more reactive with ~ ;c anhydride than are the internal bonds found in EpnM. 'me resultant ;my~t r~;f;~r, ~PCA11~P of its greater elongation, provides superior ~Lu~L~ies when blended with Nylon.
EPDM polymers which have been m~;f;~ with polar functionality are llt;l;~P~ as di~t~culL type viscosity index improvers in multigrade lubricants. A great number of patents ~ e ~vuLed to such mr~;f;rAtions. Any of the ~r~;f;cAtions ~e~LvLll~d on EP~M for this purpose can be ~e~L~Lmed with the polymers of this invention. Typical modifications which can be used with the polymers of this invention are described in: U.S.
Patents 3,099,644; 3,257,349; 3,448,174; 3,997,487; 3,870,841;
3,642,728; 3,847,854; 3,437,556; 4,557,849; 4,032,700; 3,899,434;

4,557,847; 4,161,452; 4,170,562; 4,517,104; 4,320,017; 4,502,972;
~4,098,710; 4,007,121; 4,011,380; 4,033,888; 4,145,298; 4,402,844;
and 4,146,489, and in British Patent 1,072,796.

m e above examples ;ll~ Le only same of the L~ILially v~ hl~ chemical mo~;f;~tions of the polymers of this invention. m e high mol~ r ~ ht block polymer,s of this inv~t;~, providing a means for a wide variety of chemical ~ ;f;~t;nnc only at the ends of the ~l~lle (i.e., at the I
blocks only), ~Le~*~lL the u~uLL~nity to ~lq ~r~ materials previously in~;~;hl~ h~llc~ of the lack of av~ h; l;ty of such polymers. Some examples of well kncwn chemical r~rt;~nC which can be ~LLu~ d on polymers of this invention are found in E.M.
~ , CHEMICAL R~AfTT~NS OF POLYMERS, High Polymers, Vol. 19, John Wiley, New York, 1964~
Until the instant invP~t;~n~ it has not been ErY~c;hl~ to produce h~d~u~r~ elastcmers having very large dis~moe hPt~cn crosslinks (high Mc) after v~ ni~At;~. Our invention provides block h~d~ r~ . polymer-c c~rAhle of being v~ n;~ to a e~L netwcrk with a dif~rooe h~ crnccl;~ks ~L~L~ILially equivalent to the dimensio-ns of the u~n~ An;7A~ elastomeric mol ~ ll~. In addition to the ~ Yl i~ lL~ in ela~L~I~ic Lies, the saturated main chain of the polymers of our inv~nt;nn provides a high degree of oxidative and th~rr-l ctAh;l;ty. Unique mat~rials can also be ohtained by ~h~m;~l mo~;f;cAtions of the block polymers of this invention, since such m~;f;~t;~nc can be carried out cPlect;vely only at the unsaturated terminal ends of the mol~
The c~xY;cl;nking of the ~Plrct;vely h~dLuy~ ~Led block polymers of th;s invPnt;~n is conducted in a ~llv~l~ional ~
by contacting the block copolymer with a suitable crosslinking agent or a combination of such agents. m e crosslinking ~LO~e~S
pr ~ lc~c a c~polymer having umiform distance h~t~l~cn cross-links.

203~1~4 m e block copolymers can also be fin~t;nn~ F~ by r~r~ the t~r~;nAl blocks containing unsaturated groups with uarious ~e~ nl-c to produce functional groups, such as hydroxyl, epoxy, sulfonic acid, l~L~LJ, acrylate or c~rhnYyl grcups.
mrt;~nalization ~ hnll~ are well known in the art.
The random copolymers may also be cross-linked or fimrt;~rA~ in the same manner as the block copolymers.
The block and L~ll copolymers, ;~r-l~;ng the sLa~ LL~.ed polymers, of this invention can be used in a variety of applications, e.g., to produce electrical insulation, pressure sensitive ~h~-~;ves, sealants, rubkerized ~rh~lts, in automotive applications, e.g., hoses, tubing, weatherstripping, in c~llsLL~ction in~ustry, e.g., to produ oe gaskets, rubber 5h~e~;ng for roofing, pond and ditch liners, and in many other ~pl;~tions.
The following Fx~ further ill~LL~Le additional feahlres of the invention. ~evcr, it will be a~ya~lL to those skilled in the art that the .~er-;f;~- reactants and r~A~-t;~n conditions Il~P~ in the Examples do not limit the scope of the invention.
In all of the following examples, the exper;rA~tAl work was ~eLrurll~d with dried reactors and ~l;pr~nt and under strictly anaerobic conditions. Extreme care must be used to P~ air, moisture and other impurities cAp~hl~ of interfering with the ~FIl;~Ate rhF~;cAl balan oe involved in the synthF-C;~ of the polymers of this invention, as will be ~y~L~lL to those s'killed in the art.
EXP~MPIE 1 (IS~YL~ ~ Butadiene-Isu~L~Ie Triblock Polymer) Two hundred r;ll;l;ters (ml) of purified dried cycl~hPY~ne (99.5~ avA;lAhle from Ph;ll;~ Petroleum Co.) were intro~lfF~ under niLLuy~l al~ Fre into a two quart glass bowled stirred pressure reactor. The reactor was F~l;~P~ with ~ ~ 3 4 ~ 9 4 an air driven stirrer, a pressure gau~e, a thermometer well, a heat e~ uly~ coil, a tcp surface inlet valve, a dip tube ~ee~
with valve, a syringe inj~rt;nn port ~n~t~;n;~ a ~Viton~* rubber y~k~ and a blow-out disk ( 200 psi). Three m;llil;ters (ml) of a 0.01 M ~ll~;on of dipy-ridyl ;n~ tnr in cy~lnhpx~ne and 6.5 ml (70 millimoles-mm) of fr~chly distilled ~Ldhly~LOLuL~l were mjected into the reactor, whose c~ t~~ were then 1~PWI~1 to 54~C. The snll~;n~ was ti~L~Lel ky slow addition of 0.1 molar butyl lithium (~lT,;) until a red color was o~b~v~l indicating the ~tp~;vation of all impurities. Next, 3.0 ml (2g., 30 mm) of purified i~ e and 20 ml of 0.1 m ~lT,; ~nll~;~n were injected into the reactor. oR ~ rization of the iS~ ~ to form the initial block was ~nm~l~te~ in approximately one hour. Tb the ~ ~;n~ of living polyis~L~l~l anions was added an addit;~nAl one liter of pre-titrated cy~lnh~Ane. Tb form the ~Fr~ block 100 grams of purified h'tA~;~e were slowly pressurized into the reactor at a rate to m~;ntA;n tem~d~uLe below 60~C. After an hour, the reactor pressure had ~L~ye~ to the initial value and the formation of the i~L~htt~ nP blo~k copolymer was c~mrl~te. The ~;hlork living anion was c~ ~1F~ to a triblock havLng twice the mole~llAr ~ ht of the ~;hlnrk by the intro~t~;~n of 11 ml of a 0.1 M phenyl I - 1l7.0~e ~slttt;nn (in cy~lnhPY~nP). The muxture, which c~nt~;ned a 10% s~o;~h;~m~ric ~P~C of the c~ ~l;ng agent, was kept with stirrIng at 50~C for an a~;tional thirty minutes and then pressurized fro~ the reactor. A portion of the unh~L~J~I~le~l triblock polymer w~as isolated by fls~ tion in is~L~ ol cnntA;ning an ant;~Y;~nt "Irganox 1076"** to prevent the crosslinking of the highly unLcat~rated triblock. m e solid polymer ~rlF~ was filtered and dried in a vacuum oven for 18 hcurs. ~ ~la~d (rllK) analysis s-,howed the ~ ~;Fne mi.l~LL~cture to have 50% 1,2- and 50% of 1,4-~nmrn~;tion. Gel ~r~Lion chromatography of the sample, using differential refractive index and D~WN~aser * Trademark ** Trademark ~ Trademark ~ 20 ~ 4 1 9 4 light-s~LL~ing dual ~l~L~L~ L~ -;nFA the number ~v~ye mol~llAr we;~ht (Mn) and ~ ht av~y~ m~l~ollAr weight (Mw) of the polymer to be 135,900 and 139,400, ~ Lively, for a ~icrPr~;ty (Nw~Mn) of 1.08.
EX~MPLE 2 (H~dl~4~ ~Lion of Central Pol ~ ~A~;~e Block of Is~
Butadiene~ y.~ e Triblock) This ~x~rl~ illu~LL~L~ the ~elPc~;ve h~Lu~ ;~n Of the cenLL~l polyh ~A~i~e blo~k of an ibJ~l~ ~ ~A~;~ne-is~L~,e triblock polymer.
One hundred ri 11 i 1 iter (ml) of cycl~hPx~ne containing 8 grams of ~ olved triblock polymer as ~Lt~C~ in Fx~m~lP 1 WAS
intro~l~ into a PA ~ sh_ker hy~Luy~ldLion a~LdL~s. This amount of polymer ~L'~llLi 0.142 moles of poly~ ~A~;ene unsaturation. The h~d~,4~ aLion catalyst wAs ~L~a~l by adding 10.8 ml of a nickel octoate ~ n (6% by weight nickel) to a ~oll~;~n of 45.2 millimoles of triethyl aluminum in 102.2 ml of hexane. The nickel o~Q~le was added slowly (over abaut 1 hcur) using a syringe pump to give a final catalyst coll~;n~ which w_s 0.1 molar in nickel and had an Al/Ni molar ratio of 3.6/1Ø Ihe shaker apparatus was purged 4 times with hyd~. gas, ~PA~
heated and pressured to 50 psig with hy~luy~~ dL~re was maint~;n~ at 50~C and t,he rp~-t;n~ v ~CPl was shaken for four hours. Analysis of an ~l;~l~t of the pro~uct by ~ K
LL~Led ~r~-letP loss of absorption related to the 1,2-h ~A~i~n~ (910 and 994 cm 1) and trans 1,4-h ~A~;~ne (967 cm 1), but retention of a~sorption related to 3,4-i~u~Ltlle (vinylidene) structure (888 cm ). m e r~A~t;~n r; ~ ~e was ~A~CP~ an~ treated with 3-4 drops o~'J~ff~m;në D-2000 (a polyether diamune) and 1 ml of HCl (6N). After stirrin,g for a short time, the dark catalyst color had ~ y~d and the solution was added to 200 ml of is~ *~l containing an ant;~x;~t (0.5 g of'~rganox 1076~'. The precipitat~d polymer * Trademark (each instance).

, ~ ' 1 ~ 2 0 3 ~ 1 9 4 was ;Cnl~ter.7 and dried in a vacuum cven. Analysis of the polymer ;7~.7;c~e~ ~CP~ntiAlly no rP.C;~71Al nickel (less than 1 E~xn).
EX~MPLE 3 (I~uyl~ ~/Styrene ~ 3utadiene - IsvyL~le/styrene ~riblock PolYmer) This example ;11~7~l~a~es the ~L~ a~ion of a triblock polymer wherein the terminal blocks consist of i~L~ ~styrene copolymers. ~L~v~a~ion of low levels of styrene into the end block is hP7lpf;~;Al with certain m~Ulo~ of ~llrAn;~;n~ the final cPl~;vely h~dL~y~ ~Led triblock.
520 y-rams of cycl~hpxAn~ 7.4 ml of tetrahydrofuran, 5 grams of i~u~l~le and 5 grams of ~Ly~le w~re ~ y~l into a clear, dry one ~llnn A~ c-lAve kept under a 5 psig N2 press~re.
The contents were stirred (1500 rpm) and ~rr-~ to 55~C.
Polymerization was initiated by the addition of 3.6 ml of a 1.6N
Coll~;~n of n-butyl lithium. The r~A~t;~n was All~7~ to ~ 7 for two hours (over 10 half times) at which time 1536 g of cycl~h~Ane (pre-titrate~ with ~lT,; to a dipyridyl end point) were added to the reactor. ~ ~A~;~n~ (400 ml) was pumped as a 1;~;~ into the reactor. C~R ~ water was employed as l~yy~ ry to m~;~tA;n 55~C. Polymerization of the h~A~;Pne was Cnm~lPt~
in one hour. m e formed ~;hl~rx was then ~ ~plF~ by the addition of 2.75 m;ll;m~lp~ of phenyl ~ Le as a 0.1 molar solution in cy~lohP~A~e. After 0.5 hour r~Act;~n time the final polymer was pr~c~lred from the reactor. Tctal cnl;~c meas~ L co~f;rr-~100% ~ n~ cull~e~ion. A small sample was isolated for analysis by precipitation in i~L.~Iol. The vinyl (1,2-) content of the hl~A~ e center block was shown to be 52% by . A GPC analysis using the Dawn .~ ch~r~:

= 93,470 = 96,210 = 1.03 Mn * Trademark ~ 2Q~41 9 4 l~e magnit~e of the ~lP~llAr ~ ht and narm~,cc of the rnl~llAr ~;~3ht dist:r;h~t;nr~ c~nf;rr~ the Cll~"C of the rPA~; nr~ .
EX~ 4 c~Lion of Ex~nPle 3 Tr~bloc~k Pol~) exa~qple d~_.Jl I~LL~Le~ the hy~- ~ l i nn of the ~riblo~k polymer ~JL~ r~L;Al ly in ~ e ma~ er of Ex ~ ple 3~ llt;l;~ a cat21yst ~L~C~a~ in a diLL~L~-L manner than that decrribPd in F~ 2.
A 400 ml ~L'~S5~La bottle ccntA;n;~ a ~ -y ~~ stir h~r was CA~P~ with a rubker liner and two-holed b~ttle cap. To the bottle was added 160 ml of cyçlnhPx~nP and 21.6 ml of nickel o~LoaLe ~ n (6% nickel) to give 22.5 ~;ll;mol~C of nickel as a 0.124 molar ~oll~;~. One hole of the b~ttle cap was pierced with a 50 ml syringe, with syringe lock, cnntA;n;ng 46.4 ml of 1.73 molar triethyl aluminum (80.27 m;l~ lp-c). The other hole was pierced with a flP~;hl~ needle cannula whose other end was c~ qi in mineral oil. While the content-c of the bottle were stirred, the triethyl~ll~;~um solt~;~n W25 added as rapidly as ~ C;hle without allowing the ~llL~l~ of the bottle to boil.
Ihe resultant homogeneous dark solution was 0.1 molar in nickel and Q.36 molar in aluminum. This order of a~;tion is the I~V~Se of that Lq~L~e~ by Falk and, in addition to being l~CC
time consuming, ~eaL5 to give a catalyst with superior ;l;ty and lifetime.
Into a one gallon Alr~Y-lAve was charged 155 gramLC of the tr ihlock polymer ~L~kar~d su~L~lLially in the ~ILu~ of Fx~m~lP
3 as a 7.5 wt. percent ~lllt;on in cy~ h~YAne. ThiC amount of polymer contained 2.75 moles of ~Lu~Lion from the poly~A~;~e se~ . Ethoxy A~t;~ acid (3.1 ml of 0.1 M) was added and stirred at 1500 rpm for 0.5 hours to c~rl~tp the P~ _ -1~ 20341~4 cn~ Y with the Li cation. To this ~nl~;n~ wzs added 70 ml of the catalyst snll~;n~ ~t~ua~ above. Ihe reactar was ~a~uy~
several times with h~Luy~l and then pressured to 70 ~Y~nn~c with h~L~y~, and warmed to 55~C. Several other catalyst additions, tot~ 60 more ml, fo~ . After 4 hours, only the viny~ P (3,4-mi~L w LL~cture) ~ Lion was o~bl~able by lK. After h~dLuy~ ~Lion, the polymer sol~;n~ was ~ ~ ~
and the polymer was isolated as d~crr;bP~ in FY~m~l~ 2. The polymer contained less than 1 ppm of r~-c;~lAl nickel; its Mn was 118,500, the ~ was 129,000 and the ~ = 1.09.
m e Mn of the starting polymer was 110,000, its ~ was 112,900, with ~ = 1.03.
~ h~ r~imetric analysis (T~A) of a ~mrl~ of this h~Lcy~ ~Led polymer in niLLuy~l showed that only 10% of the polymer w~;qh~ was lost at 435~C and that T~A in oxygen resulted in a 10% weight 1QSS at 360~C (10 degree t~.~k~L~re rise per ~;n~). The Tg of the ela~ was -60~C.
m ese results illu~LL~Le the ~Y~P~ thermal and n~;~t;ve stability of the polymers of this invention.
EX~MPLE 5 (ComParison of EY~nnple 4 Polymer With C~.ul~ial EP~M Rubkers) mis ~Y~mr~- e~u~ u~LLies of the triblock polymer of FX~m!rl~ 4 and two ccmmercial EPDM rubbers with and withcut r~ m~ L~l~Le filler ("Mult~lex"*M M).
m e curatives (vlllc~n;~ agents) used are known to those skilled in the art and are ;~ if;r~ in the previcusly -cited r~L~L~. me ingredients listed below were muxed in a ErZ~k~L extruder at 50 rpm allowing the temperature to rise to about 100~C. m e ~r'~ were cured in a Carver pr~CC for one hour at 160~C under 6000 psi pr~C~l~e and ~110hT~ to stand at least 24 hours at room tem~erature prior to testing. ~he r~lts ~eku,Led below are, in each case, the average obtained from two separate but iden~ical mixes.

* Trademark ; '; f~

~LE 1 RUN A B C D E
~ients ELhSDOMER OF EXaMP~E 4 (parts) 100 - - 100 ROYALENE 501 (parts) - 100 - - 100 NORDEL 1470 (parts) - - 100 MULTIFLEX MM~ (parts/100 parts of ruk~ ~) - - - 100 100 IMTDi (phr) 2 2 2 2 2 DTDMii (phr) 1.5 1.5 1.5 1.5 l.S
~DBDciii (phr) 1.5 1.5 1.5 1.5 1.5 znMDciv (phr) 1.5 1.5 1.5 1.5 1.5 SULFUR (phr) 0.4 0.4 0.4 0.4 0.4 Zno (phr) 2.5 2.5 2.5 2.5 2.5 STE~RIC ACID (phr) 1.5 1.5 1.5 1.5 l.S

X From Uniroyal Chemical Co. ("Royalene" is a trademark).
Y From E.I. DuPont ~ de Nemours and Co. ("Nordel" is trademark).
Z Untreated Calcium Carbonate (From Pfizer) ("Multiflex" is a trademark).
i = I~TRaeET9YL TffIURAM DISULFIDE
ii = Dll~lO~ K~ULINE
iii = ZINC DIBUTYL DrTRT~rARB~M~rE
iv = ZINC DIMETHYL Dl mlOC2RBAM~IE

203~94 PHYSICAL ~kU~KUl~

RUN A B C D E

% Gel 89.3 88.6 88.4 - -~CENsrr.~
S~E:X~nH (PSI) 264 284 346 1210 782 ELoNGa~ION (~) 738 410 435 1797 671 W ~n~hlpt Extr~r-t;n~ By Boiling Hexane; 24 hrs; 1 gram sample m e superior elongation of the elast1~ers of our invention is clearly evident in the f;ll~ and unf;ll~ muxes.
The high ~lnn~tion is not the result of undervulcanization, as shown by the low level of extractibles in the gel determination.
EX~MPLE 6 fSequential PolYmerization of Triblock Copolymer) miS example illu~LLaLes the ~L~L~Lion of triblock polymer essentially identical to that described in Fx~rl~c 3 and 4, but syn~h~-c;7.~ via sequential polymerization.
The a~a~L~s 1~;1;7~ was the same as that described in FX~mrl~ 1. In this Fx~m~l~, which does not require a çol~?l;~g step as earlier described, the three blocks of the polymer chain are polymerized sequentially to produoe a polymer of 100,000 Mn directly. While catalyst usage is de~l~a~ed in this , Ihorl~ the time ~s~,y for .l~l~letion of the polymerization rG~r~;~n is greatly increa~ed. It is not, ul~Lef~e~ the ~lere~Le~ technique for the pro~lct;n~ of s~ .~.Lical triblocks but does have the ad~du,L~y~ of permitting the ~Le~*~e of two dissimilar end blocks, if desired.

-' 'j 1 ~

2 ~ 3 4 ~ 9 4 T~ form the initial block, the ~u~u~ures of Fx~
were fo~ , except that one gram of i~ ~ e and one gram of styrene were polymerized using 1.0 n~llir~ of BuLi. After addition of the solvent as in EXample 1, 96 qrams of h~ n~
were added to the reactor and All~ to polymerize for one h~ur-One gram each of i~u~L~e and styrene were added and the polymer;~Ati~ was All~T~d to ~l~eed for 15 hours. ~h;~
lengthy reaction time is necessary and reflects the low ~ ~nl,~Lion of cataly~t and m~lK~I~L ~ ;tated by the conditions in this block seguential polymerization.
Work up and h~d~u~ ion of the polymer as in Fx~
1-4 pro~e~ a ~elect;vely h~ruy~ ~ed triblock having Mn-104,200 and M~T=112, 540.
EX~MPLE 7 (Hiqh Styrene Content Triblock CbpolYmer) This Px~mrlp describes the ~ aLion of a polymer ~;m;lAr to that of FXA~1P 3, but having ~n~ prably h;~hPr styrene content.
To the d~ aLus descrihp~ in Example 1 was ~ ~ry~ 1100 ml of cycl~hPY~ne, 3 ml of 0.01 m dipyridyl, 6.5 ml of tetrahydrofuran (THF), 33 ml (30g) of styrene and 3 ml (2g) of isu~l~e.
The ~ll~;nn was ~rr~~ to 55~C and titrated with BuLi, and after the end point, 20 ml of 0.1 mol ~ ~lT-; were added.
After 2 hours, 70.3 grams of purified h ~A~iPne were added. The hJtA~;Pne was All~l~ to polymerize for an hour and 11 n~ of a 0.1 M phenyl ~ ~oaLe solution were added to c~ the ~;hl~ck.
The polymer work up and h~dkoy~ ~Lion was as previcusly described. The polymeric product ~;~rlAyed unsaturation hy FTIR
w~ r e~u~ ng to vinylidene (3,4- i~o~L~ e) ~lhl e bonds only.
The resultant material ~i~plAyed l~ ~lA~tic ela~L~
u~LLies ~;m;lAr to polymers made without the low level of e used in this example. m e polymer of the ~XA~rle can, .

-~ 4 ~

however, be ~hp~;cAlly v~ n;~P~ hy any normal method. Thus, the polymer of this Px~m~l~ is both a thermoplastic ela~L~,~r when uncured and a ~h~ ela~L~.~ if cured. m is invPnt;nn provides the n~Pr with a choice not av~ hlP in ~eL~Lu~uLe existing w ~ ial h~dLo~ , ela~Lull~Ls and also provides an elastomer whose P~PllP~t physical ~lu~LLies provided by the styrene end blocks of current ~hP-r~plA~tiC ela~L~I~ can be rPtA;n~ at greatly elevated temperatures (100-150~C).
EX~MPLE 8 fThPrmnplastic Ionic Ela~Lull~) In this PX~mple~ the ~ a~Lion of a ~hPrm~plA~tic ionic ela~L~I~ ut;l;~;~g a ~PlP~t;vely h~dL~y~naLed triblock polymer as a su~LL~Le is described.
Fifty grams of triblock polymer (Mn-111,820) similar to those described in Fx~m~lP~c 1 and 2 were ~;~c~lved in 1 liter of cyclnhPx~e. Acetyl sulfate was ~Lt~a~ed by mixing 2.7 ml of e~;c anhydride (28.6 mm) with 1 m,~ (18 mm) of culK~.LL~Led sulfuric acid at 0~C. The formed acetyl sulfate was added dropwise with stirring to the rubber ~olllt;nn After stirring at ro~m t~,~ re for 1/2 hour, the resultant product was divided into two equal portions.
To one portion (A) was added 1.85 grams of ~c~;tnn acetate ac a so~t~;~n in methanol and water. Next, there was added 0.25 grams of "Irganox" 1076 antioxidant and 12.0 grams of zinc stearate as an inolyzer. After brief stirring, the mixture was added to one liter of i~v~Lo~x~lol to precipitate the polymer. m e flo~x~-lAted polymer was isolated and dried in a vacuum oven to ~L~ weight.
m e second portion (B) was LLe~Le~ similarly except that 4.9 grams of zinc acetate were sub~ctituted for the ~c~it~m acetate.
Both portions, (A) and (B), were indiv;~Ally h~m~Pnized ~e ~ ~ 203419~

by mixing them in a Brabender mixer. m e samplec were then se~ in a mold at 160~C for 30 r;~ ~PC at 6000 poundc ~les~uLe to give molded squarec approximately of 70 mil-c thicknes-c. m e str~cc =ctrain ~ ~LLies of ~ ~Pllc cut from the molded sguarec were then measured.
SAm~lPc A B
Cationc Na + Zn 2 zn+2 lencile, pcig 1459 3055 Elongation, % 1359 1736 m e cAm~l~c, with their widely ~A~P~ ionic domains, P~ smoothly and eacily. m e measured elongations are far above those reported for EPDM LL~aLe~ in a c;m;lAr manner to our polymer of the portion B where a t~nc;l~ ~LL~ ~L~l of 3040 psig and an elongation of only 460% were O~S~LV~ (e.g., IONS IN
POLYMERS, Adi Eis*~ Ly, Editor, Pdh~r~es in Chemistry Series, 187 American ~hP~;~Al ~or-;~ty, WAch;n~tan~ D.C. 1980, p. 42).

Claims (34)

1. A solid, vulcanizable copolymer comprising at least two copolymerized monomers which:
(i) when the copolymerized monomers are disposed as an at least tri-, or as a star-branched, block copolymer, has a middle block which is selectively and substantially completely hydrogenated to a block which contains no more than 10 percent polyethylene crystallinity while each terminal block, which may be the same or different, contains sufficient unsaturation for vulcanization; or (ii) when the copolymerized monomers are disposed as a random (including star-branched random) copolymer, has a backbone which is selectively and substantially completely hydrogenated while pendant groups contain sufficient unsaturation for vulcanization.

2. A solid block copolymer according to claim 1 which comprises at least three alternating blocks of the formula:
(I)x-(B)y-(I)x' wherein (I) represents a block comprising at least one polymerized conjugated diene I having at least five (5) carbon atoms and the formula:
in which:
R1 to R6, which may be the same or different, each represents a hydrogen atom or a hydrocarbyl group, provided that:
(a) at least one of R1 to R6 represents a hydrocarbyl group; and (b) the structure of the residual double bond in the polymerized block has the formula:

in which:
RI, RII, RIII and RIV, which may be the same or different, each represents a hydrogen atom or a hydrocarbyl group, provided that both RI and RII
represent hydrocarbyl groups and/or both RIII and RIV
represent hydrocarbyl groups;
(B) represents a block comprising at least one conjugated diene B, different from the diene I, having at least four (4) carbon atoms and the formula:
in which:
R7 to R12, which may be the same or different, each represents a hydrogen atom or a hydrocarbyl group, provided that the structure of the residual double bond in the polymerized block has the formula:

in which:

Ra, Rb, Rc and Rd, which may be the same or different, each represents a hydrogen atom or a hydrocarbyl group, provided that:
(c) one of Ra or Rb represents a hydrogen atom;
(d) one of Rc or Rd represents a hydrogen atom; and (e) at least one of Ra, Rb, Rc or Rd represents a hydrocarbyl group;
x and x', which may be the same or different, each represents a number from 1 to 100, and y represents a number from 300 to 35000.

3. A solid star-branched block polymer according to claim 1 of the formula:
[P]iQ
in which:
P comprises blocks of the formula:
(I)x and (B)y wherein:
I is as defined in claim 2;

x is as defined in claim 2, the values for each block being the same or different;
B is as defined in claim 2;
y is as defined in claim 2, the values for each block being the same or different, each free end of P being an (I) block;
Q represents a coupling moiety; and i represents the number of star branches.

4. A solid random copolymer according to claim 1 which comprises at least one polymerized conjugated diene I and at least one polymerized conjugated diene B wherein:
I is as defined in claim 2; and B is as defined in claim 2.

5. A solid star-branched random copolymer according to claim 1 which comprises at least one polymerized conjugated diene I and at least one polymerized conjugated diene B, wherein:
I is as defined in claim 2; and B is as defined in claim 2.

6. A solid copolymer according to claim 1, 2, 3, 4 or 5 which comprises at least one polymerised aryl-substituted olefin and which, in a block copolymer, may be contained, randomly or block copolymerized, in an (I) block.

7. A solid copolymer according to claim 6 wherein the aryl-substituted olefin has the formula:

wherein Ar represents a phenyl, alkyl-substituted phenyl, naphthyl, or alkyl-substituted naphthyl group; and Re represents a hydrogen atom or a methyl, ethyl, propyl, butyl or aryl group.

8. A solid block copolymer according to claim 6, wherein at least one of the (I) blocks, which may be the same or different, comprises at least 50 molar percent of the aryl-substituted olefin.

9. A solid block copolymer according to claim 6, wherein the (B) block(s) comprise from 99.5 to 50 weight percent of the copolymer.

10. A solid random copolymer according to claim 6, which comprises from 0.3 to 15 molar percent of the aryl-substituted olefin.

11. A solid random copolymer according to claim 10 which comprises from 1 to 25 molar percent of I wherein I is as defined in claim 2.

12. A solid random copolymer according to claim 11 which comprises from 1.0 to 10 molar percent of the conjugated diene I, and, correspondingly from 90 to 99 molar percent of the conjugated diene B.

13. A solid block copolymer according to claim 2 or claim 3 wherein x represents 2 to 100 and y represents 1000 to 5000.

14. A solid copolymer according to claim 2, 3, 4 or 5 wherein the diene I comprises isoprene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, or a mixture thereof.

15. A solid copolymer according to claim 14 wherein the diene I comprises isoprene.

16. A solid copolymer according to claim 2, 3, 4 or 5 wherein the diene B comprises 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, 3,5-decadiene, or a mixture thereof.

17. A solid copolymer according to claim 16 wherein the diene B comprises 1,3-butadiene.

18. A solid copolymer according to claim 2, 3, 4 or 5 wherein the or each of the (B) blocks, or the polymerised conjugated diene B, prior to the selective hydrogenation reaction, is a mixture of 1,4- and 1,2-units.

19. A solid copolymer according to claim 18 wherein the or each of the (B) blocks, or the polymerized conjugated diene B, prior to the selective hydrogenation reaction, has at least 25 weight percent of the 1,2-units.

20. A solid polymer according to claim 2 which has been selectively hydrogenated so that the or each of the blocks (B), has been substantially completely hydrogenated while each of the blocks (I), retains sufficient unsaturation for vulcanization.

21. A solid polymer according to claim 3 which has been selectively hydrogenated so that the or each of the blocks (B) has been substantially completely hydrogenated while each of the blocks (I) retains sufficient unsaturation for vulcanization.

22. A solid polymer according to claim 4 which has been selectively hydrogenated so that the polymerized conjugated diene B, has been substantially completely hydrogenated while the polymerized conjugated diene I, retains sufficient unsaturation for vulcanization.

23. A solid polymer according to claim 5 which has been selectively hydrogenated so that the polymerized conjugated diene B, has been substantially completely hydrogenated while the polymerized conjugated diene I, retains sufficient unsaturation for vulcanization.

24. A solid polymer according to claim 20, 21, 22 or 23 which comprises at least one polymerized aryl-substituted olefin.

25. A solid copolymer according to claim 20, 21, 22 or 23 wherein, after the hydrogenation reaction, the Iodine Number for the blocks (I), or the polymerized conjugated diene I, is from 10 to 100% of the Iodine Number prior to the hydrogenation reaction.

26. A solid copolymer according to claim 20, 21, 22 or 23 wherein, after the hydrogenation reaction, the Iodine Number for the blocks (B), or the polymerized conjugated diene B, is 0 to 10% of the Iodine Number prior to the hydrogenation reaction.

27. A halogetated derivative of the copolymer according to any one of claims 2, 3, 4, 5, 20, 21, 22 and 23.

28. A maleated derivative of the copolymer according to any one of claims 2, 3, 4, 5, 20, 21, 22 and 23.

29. A sulfonated derivative of the copolymer according to any one of claims 2, 3, 4, 5, 20, 21, 22 and 23.

30. A blend of a copolymer according to any one of claims 2, 3, 4, 5, 20, 21, 22 and 23 with at least one of isotactic polypropylene, polystyrene, polyethylene, nylon, polycarbonate, polyester or a styrene-acrylonitrile resin.

31. A process for the production of a solid block copolymer according to claim 2 or claim 3, which process comprises:
polymerizing the conjugated diene I, under anionic polymerization conditions, to form (I);

adding the conjugated diene B to the reaction mixture and polymerizing it to block (B);
repeating the sequential addition of monomer feed to provide the solid block copolymer;
selectively hydrogenating the solid polymer so produced so that each of the blocks (B), or the polymerized conjugated diene B, has been substantially completely hydrogenated while each of the blocks (I), or the polymerized conjugated diene I, retains sufficient unsaturation for vulcanization; and wherein I and B are as defined in claim 2.

32. A process for the production of a solid random copolymer according to claim 4 or 5, which process comprises:
polymerizing the conjugated diene I with the conjugated diene B under anionic polymerization conditions to provide the solid random copolymer, and selectively hydrogenating the solid polymer so produced so that each of the blocks (B), or the polymerized conjugated diene B, has been substantially completely hydrogenated while each of the blocks (I), or the polymerized conjugated diene I, retains sufficient unsaturation for vulcanization.

33. A process according to claim 32 wherein the polymerized conjugated diene B comprises from 75 to 90 molar percent of the solid random copolymer.

34. A process according to claim 31 wherein at least one monomer feed comprises an aryl-substituted olefin having the formula:

wherein:

Ar represents a phenyl, alkyl-substituted phenyl, naphthyl, or alkyl-substituted naphthyl group; and Re represents a hydrogen atom or a methyl, ethyl, propyl, butyl or aryl group.