CA2256555A1 - Alpha-olefin adhesive compositions - Google Patents

Abstract

An adhesive composition comprises a polymer or copolymer including one of 1) a plurality of C3 or larger alpha-olefin units wherein the polymer has an average number of branch points less than one per alpha-olefin unit; and 2) a plurality of C2 alpha-olefin units wherein the polymer has an average number of branch points greater than 0.01, said adhesive being selected from the group consisting of a pressure sensitive adhesive, a hot melt adhesive, and a polymerized glue. Optionally, the polymer can be crosslinked. Articles of the invention include the adhesive tapes, labels, and adherents comprising a coating of the polymerizable composition of the invention.

Description

ALPIIA-OLE~IN ADHE:SIVE COMPOSlIIONS

5 ~ield of the Invention This invention relates to adhesive compositions con.p~ g polyr,le.i~ d alpha-olefin l~dloca,l,on mol-n~ and methoAs for p~epa~alion and applic..1;on ofthe adhesive. Catalysts for the pol~",~i~alion include or~ -o,..c~llic complexes of Group VIII metals (C~S version of the Periodic Table), preferably Pd or Ni.
Rnrl.~ . vund of the Invention Polymeric adhesives cGnlp,;;,.ng one or more of a variety of polymers are known. Such adhesives are applied to adherends in various ways, the co...~.ol-feature being that the polymer wets the adherend surface. Thus, a polymeric 15 adhesive may be formul~ted to wet a surface at ~mbient t~."p~,.al-lre upon the ap~lir~tio~ of modest pressure, and be cl~ss:r~ed as a pressure sensitive adhesive.
Alternatively, a polymeric adhesive may be forrm~l~ted to wet a surface at elevated telllpc. alLlres~ so that the adhesive is applied as a hot, molten material or applied as a l~min~te film by the appl;c~tion of heat and/or pressure to the adhesive while it is 20 in contact with the adherend surface. In still another method of application, an adhesive c~i"p,;s;ng a .nono..~ r or low mole ;ul~r weight curable oligomer may be applied to an adherend and cured in place. A general description of adhesive materials may be found in Encyclopedia of Polvmer Science and F~ nee~in~e~ Vol.
1, "Adhesive CGmpG~;~;onc," pages 547-577, Wiley-Interscience Publishers (New 25 Yorlc, 1988). Also in this refelence is a general description of pressure sensitive adhesives (Erc~-,lopedia of Polymer Science and Png;nee~ing~ Vol. 13, "Pressure-Sensitive Adhesives," pages 345-368, Wiley-Interscience Publishers (New York, 1988)).
~ Adhesive polymers are chosen for a variety of propc. Iies, inC~ ~ polymer 30 glass l,d.~silion te~"pe~al~lre~ thermal stability, and ability to wet and adhere to specific surfaces. Other p,opc. lies, such as sensitivity to moisture, corrosivity or corrosion recist~nce, dielectric constant, presence of impurities, color, odor, to~icological propcll;es, pn)cPjs~ y, etc., may be impo.lau~l for specific applir~tion~ Adhesives comprising polymers of alpha-olefin mol-h,..~ . ~ are particularly desirable for r ~hPs!on to low e. er~y surfaces, and in arp1ir~ion~ where low sensitivity to moisture, low co,,.,s:~ily~ good corrosion ~~- cl~nce, low 5 dielectric corC~ low cost and low toxicity are desi.able or required.
The use of an oligomPr (up to 5000 molecl)lsr weight) of an alpha-olefin in thermoplastic hot melt adhesives has been ~icrlosed in U.S. Patent No. 5,512,625.
Copolymers of ethylene and linear alpha-olefins are des~,ibcd as adhesives in PCT
Patent ApplicationNo. WO 93/12151. I~ tion curable (croselinlr~ble) polyolefin10 pres~ule sensitive adhesives co-.~ g polymers which were p~pa.et under inert con~itinn~ using Ziegler-Natta catalysts are ~Aic~1osed in U.S. Patent No. 5,112,882.
Polyrnerizable adhesives Co~ Jlis;i1g alpha-olefin monomprs and Ziegler-Natta ormetallocene catalysts wl-e.ein polyl.,. ,i~alion occurs during use have not beendes~;lil.ed, because these poly~ a~ion catalysts are sens;li~_ to oxygen and 15 moisture and require special h~nAli~g Summary of the Invention Briefly, the present in~ ion des~lil,es adhesive cGlllpoa;lions comprising a polymer in~ ding one of 1) a plurality of C3 or larger alpha-olefin units wL~reill the 20 poly-mer has an average number of branch points less than one per alpha-olefin unit, and 2) a plurality of C2 alpha-olefin units wherein the polymer has an average number of branch points greater than 0.01, preferably greater than 0.05, most plef~ly greater than 0.10, per alpha-olefin unit. The invention de3vlil,es adhesive cGnlpos;lions co~lpl;ain~ the poly~ alion product of a polyllle, _ ~'e 25 cGlllpos;l;on compl;s;ng an alpha-olefin . ollo...cr and an effective amount of an ol~nn...Pt~llic polyllle.~alion catalyst com~ ing a Group VIII metal, preferablyPd or M, more pl ~fel~bly Pd. ~l.,fe~bly, the polymer Mw is greater than 5,000, more pl efe~ly greater than 90,000 and most pl tfe, ably greater than 100,000.
In another aspect, the invention provides a method CGIll~l;Sh.g the step of 30 applying the adhesive composition as stated above to at least one adherend surface.

More pa,li.;ul&l~, the i~l~'enLGI~ provides a method of r~heri~ m~teri~lc using an adhesive composition col..p-is;ilg the pol)"..e~alion product of a polyrnerizable C~ )os;liQIl cGIll~Jlisi.lg alpha-olefin .- ono~ r and an e~c.;~-~e amount of an or~ n,~,el~llic pol~...e.i~lion catalyst comprising a Group VIII
5 metal, pl~fe.~ly Pd or Ni, more preferably Pd. P~.,f~dbly, the pol~...er Mw isgreater than 5,000, more preferably greater than 90,000 and most preferably greater than 100,000.
In a further aspect, the invention des.;.il,es sdhesives co~ g a poly...e. ~'~ composition, the composition cG,nplis;llg at least one C5 or larger 10 alpha-olefin ...t~o~-cr and an effective amount of an org~lo...~Altir catalyst comprising a Group VIII metal, preferably Pd.
In yet another aspect, the invention describes a method of adhering materials with a poly...~ able compositio~ the composition CGIll~Jl;S;ng at least one alpha-olefin monomer having 5 or more carbon atoms (C~ or larger) and an effectiw 15 amount of an organomet~ c catalyst CG~ liS;llg a Group VIII metal, preferably Pd.
In some embo~irnentc, the present invention provides adhesives comprising crosslinked alpha-olefin polymers. In one embodin~nt a method employing high-energy irr~ tion of the polymer, pl - f~ .bly by elecll on beam irra~i~tion~ is used.
In another embodiment~ a method employing ultraviolet (UV) irrr li~tio n is used, 20 preferably further comprising the n~ition of W-activated clos~ ing agents. Inyet another embodiment~ a method involving thermal crosclinkin~ is used, pl efe~ably further comprising the ad~ition of thermally-activated cros~lir'-ingagents.
In other embo~lim~nt~ adhesives comprising mixtures of two or more 25 polymers s~lected from 1) alpha-olefin polymers colnyl;s;ng a plurality of C3 or larger alpha-olefin units wherein the C3 or larger units are incorporated so as to give a polyrner having an average number of branch points less than one per alpha-olefin unit, and 2) polymers col..r,ll~ g a plurality of C2 alpha-olefin units wLcreh~ the polymer has an average number of branch points greater than 0.01, pl~rel~bly 30 greater than 0.05, most preferably greater than 0.10 per alpha-olefin unit are within the scope of this invention. Preferably, for each polymer the polymer Mw is greater .

than 5,000, more preferably 90,000, and most p~felably greater than 100,000.
Adhe~ s CGI-lpli;~;ng, copolymers produced from two or more alpha-olefin ,-~onnr-~-~ or at least one alpha-olefin ~ Qn~e~ and one or more non-alpha-olefin .... .O~ are also within the scope ofthe present invention.
In this invention:
"alpha-olefin" and "alpha-olefin hJJIocarl~on'' are equivalent and mean a Lydloca.l~on cG..IA~ a double bond in the l-position, more particularly, ~Lyl~ eor a }-olefin con1A; ~;ng three or more carbon atoms which can be acyclic or cydic and pl~ bly i5 an acyclic alpha-olefin; the not~tion C,~ refers to an alpha-olefin which col~ X carbon atoms;
"alpha-olefin polymer" means a polymer formed from at least one alpha olefin mon(S~e~ which, not con~;dering end groups, co~ an average oftwo bonds col ~e~ g each monomPr unit to other monom~Pr units;
"branch point" means a C unit in the polymer backbone that is bonded to three other carbon atoms, e.g., C~ and f_c_~_c_ reples~ llt units with one and two branch points, res~e~ rely;
"steric bulk" means a size large enough and a location in the ligand s ~fficientto physically block access to non-polyllle.i~i.lg sites on the metal;
"alpha-olefin unit" means a group of carbon atoms in a polymer derived by polyll.f,,;,AtiOn from a single alpha-olefin molecule;
"high polymer" means a polymer having a weight average molecul~ weight (MW), greater than 90,000, and plere.ably greater than 100,000;
"poly" means two or more;
"org~nnmet~llic catalyst" means a catalyst colll~,li;,;ng a Group VIII metal, prerel~bly one of Pd and Ni, a bidçnt~te ligand having steric bulk suffi~iPnt topermit formation of polymers, and a metal to R bond, wherein R is H, a hydrocarbyl radical, or a hydrocarbyl radical substituted by at least one alkyl, haloallyl or aryl group, each group having up to 20 carbon atoms;

WO 97t48M7 5 PCT/US96/16837 ~polymerizable composition~ means a r.~ ., CO.llpliihlg an alpha-olefin monomer and an effective amount of a Group VIII Gl~ O~ ic, catalyst, and optionally at least one of air and water;
"polyl.lc.i~dtion product" means an alpha-olefin polymer produced by S allowing a poly...e.i~able compoc;lion to polyl"~ e, option~lly co~ 0 to 3percent by weight of metal re~ Jue~, either as elc, ..~ l metal or olg~nG...~ l;llic colllpo.lllds, "group" means a ~ hpmic~l species that allows for substitution or which may be subsfituted by conv., ~;on~l substit~)entc that do not hltelrele with the desired 10 product;
"Me" means methyl (CH3-);
"Et" means ethyl (CH3CH2-);
"Bu" means butyl; "t-Bu" means tertiary butyl;
"i-Pr" means isopro~l; and "gel fraction" means the fraction of polymer that is incoluble in an app,op.;ale solvent, e.g, tol~ne~ particularly after crosclinkin~
Su.~,li "n~ly, adhesive compositions cGn")ri~illg a polymer in~ tling one of 1) an alpha-olefin polymer u~ .;ng a plurality of C3 or larger alpha-olefin units wherein the polymer has an average number of branch points less than one per 20 alpha-olefin unit, and 2) a plurality of C2 alpha-olefin units wLc~c;h~ the polymer has an average number of branch points greater than 0 01, plefc-lubly greater than 0.05, most preferably greater than 0 10 per alpha-olefin unit are useful as adhesives, show difl~lc.~ and superior plo,uc.lies when co,llpa,cd to adhesives colll~.i ,ing other alpha-olefin polyrners with di~.h~l bl~nr~ g pallul,s, such as alpha-olefin 25 polymers colllplisillg a plurality of C3 or larger alpha-olefin units wl,c. ein the polymer has an average number of branch points of about one per alpha-olefin unit, or a plurality of C2 alpha-olefin units ~here;l. the polymer has an average number of branch points less than 0.01 per alpha-olefin unit. The adhesives of the i.,~,~,.,lion cG.ll~ise polymers that are the polymerization product of a mixture colll~uli;~;ng 30 alpha-olefin monomer and an effective amount of a Group VIII ol~nn~e~ c catalyst, p,efelably Pd or Ni, more preferably Pd. Known alpha-olefin polyrners, WO 97t48777 6 PCT/US96/16837 inclu(ling Co~ r . ~,lally available alpha-olefin polymers, typically are p~ d using known synthetic metho~s (such as the use of Ziegler-Natta or m~t~llocf~ne catalysis), have structural features, particularly with respect to b~ g that canbe .1;~ hed from poly ners useful in the present i,l~ tion, and have physical 5 plupc.lies, particularly with respect to crystallinity, that can be ~ . ched from polymers useful in the present i..~e.llion, even though they are p~ d from the same alpha-olefin mn~ . A further ~ .;se is that pol~ F-;~ ;nn ofthe curable adhesives of the invention proceeds in the p-. sence of air and/or water at useful rates to produce adhesives Detailed Description of Preferred Embodiments of the Invention The present invention desclil,es adhesive compositions COlllpli:~;l-g a polymer in~lu~ling one of 1) an alpha-olefin polymer col..~ g a plurality of C3 or larger alpha-olefin units wllc. dn the polymer has an a~ ge number of branch 15 points less than one per alpha-olefin unit, and 2) a plurality of C2 alpha-olefin units wherein the polymer has an average number of branch points greater than 0 01, preferably greater than 0 05, most plef~,.ubly greater than 0 10 per alpha-olefin unit The adhesives con~plise the polyl-.e~i~tion product of a polyrnerizable composition comprising a C5 or larger alpha-olefin . onG..Ier and an effective amount of a Group 20 VIII o~o ~ t~ c catalyst, preferably Pd or Ni Pr- ft;lably, the polymer Mw isgreater than 5,000, more preferably 90,000, and most p-e~..bly greater than 100,000 The invention also des~-il.es adhesives comprising a poly-.,c,;~able composition, the composition colll~J,;s;ng at least one alpha-olefin ...nn~...- r and sn effective amount of an or~nG~. ~t~ c catalyst comprising a Group VIII metal, 25 preferably Pd Alpha-olefin hydrocarbon ...OIlG .P ~ useful in the present invention indude Y~b.Qt;~ ed and unQubstituted, inClU~li~ acyclic, b-~cl,ed, and cyclic alpha-olefins, ~I.erein s ~ u .1~ on the olefin do not ;,lte.rele with the pol~".e.i~alion process.
~I~;re~l~d alpha-olefin monome~s can have ~om 2 to sbout 30 csrbon atoms, snd 30 indude acyclic alpha-olefins such as ethylene, plupene, l-butene, l-penhne, 1-hexene, l-hepte~ l-octene, I-decene, l-dodec~ne, l-tetradecene, l-h~Y~decene, l-octa'lecene, 1 f iCO;!Iel~f', and the like, and cyclic alpha-olefins such as cyclopentene, and co~ ;ons thereo~ Most pr~fe. c.bly, alpha-olefin ~..nl-h~
include ylop~ne~ 1-butene, l-hexene, l-octene, and other alpha-olefins up to about C20. In some embodiments~ such as adhesives con.prisillg poly.uc~ ~le 5 compQsition~, liquid .~o~o~. e~ are p--f~,.-ed, and higher boiling alpha-olefins, e.g., l-~r~.1e -e and ~jlOp~ f ne to about l-octr~ec~n~, are particularly p. ~ f~ ,d.
More than one l~ may be useful in pol),...e.~ and polymerizable conlrQ~itions ofthe invention, and copolyrners oftwo or more Ji~.~ ...o~o...~.~
are within the scope of this im~ention. Copolymers may be random or blocky (block 10 copolymers), dep~n~l:ng on poly.n~ ion kinetics and processes. Useful comonomers include other alpha-olefin hydrocarbons, which may be present in any y~opol Lion. Other useful comonomers which are not alpha-olefin hydrocarbons include alkyl acrylates and rneth~rylates, and acrylic and m~th~ ,rylic acids and salts thereof. Non-alpha-olefin co.~-ollo. ~ are p.ert;rably present at no more than 10 15 mole percent, most preferably at most 5 mole percent of the total polymer composition.
Org~nornet~llic catalysts are useful to prepare the polymers used in adhesive compositions of the invention, and to cause polymerization of the monom~rs present in the pol~,..c,i~ble compositions used in the method of adhering materials.
20 OrgPnr met~ c catalysts useful for these purposes colnp. ise metals of Periodic Group VIII, ligands providing steric bulk sl~ffici~nt to perrnit fo....ation of polymers, and a metal to R bond, wherein R is H, a hydrocarbyl radical, or a hydrocarbyl radical substi~uted by at least one of alkyl, haloalkyl or aryl groups.
Periodic Group VIII metals include Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt, and 25 ylcfellt;d metals are Co, Ni and Pd. Ni and Pd are especially pre~ d, and Pd is most pl~,fe-.. d. T ie~n~c ~L) can be sele~,led so that, when they are coordinated to the metal atom, they are of s~fficien~ size so as to block steric access to certain coordination sites on the metal atom. Fy~mrlec include ArN=C(R')C(RI)=NAr, ~hel~hl Ar is 2,6-C6H3(R3)2, where each Rl independently can be H or methyl or 30 the two R~ groups taken together can be 1~8-n~rhth~lene-diyl~ and each R3 independently can be methyl, ethyl, isopropyl, or tert-butyl. Without wishing to be bound by theory, it is bdk~e~ that ~'~r.L~ g certain sites may reduce or eliminate l~rocesses which result in disFl~r~empnt ofthe polymer chain from the metal, which prematurely t~ ates poly.,.~ alion and results in lower polymer ~clecul~r ~e;~ s. Thus, steric bulk in the ligand permits the fOllllalioll of high pol~."er.
Pn,f~.l. d catalysts CGIlllJliSe ligands that are Ghfl-l;ne ChPI~ e means that a ligand molec~le contains two or more atoms or groups of atoms that are able toform coo. dinale links to a central metal atom. Fl - f~ d atoms or groups of atoms are two ele~.un donors, preferably conl~ ;ng nitrogen, more preferably cG.~ts~
an imine ( ~=N--) group. Most pr~fi;,u~ly a ~ I.P~ g ligand co...p,ises two imine groups. Imine groups bearing a s~ u~d or 111- ~ sl;~uted group on the nll~o~en are pl.,f~ d, more preferably such groups are polysubstit~lted aryl, and most preferably they are 2,6-disubstituted aryl. Substit.~tents on the aryl ring include alkyl, haloalkyl, and 15 aryl, plerc. ~bly alkyl, more prefclably methyl or isopropyl, and most preferably iso~,lu~,yl. Catalysts also comprise an atom or group R, defined below, which ple~lably is H or methyl, most preferably methyl.
Org~nomet~ c catalysts useful for prepa~ing polymers for adhesive compositions and in pol~.l.. . L~.ble comrosition~ useful in the method of the 20 invention can be one-part or two-pa t. One-part catalysts are ore~nolnpt~llic salts of a Group VIII metal complexed with a polydentate ligand having steric bulk sl-ffirient to permit formation of polymer, and an anion selected from the groupcor~c;c~ e of B(C6F5)4-, PF6-, SbF6-, AsF6-, BF4-, B{3,5-C6H3(CF3h}i, (RfSO2)2C~, (RfSO2)3C, (RfSO2)2~, and RfSO3-, wLc~e;n Rf is as defined below, 25 which, when added to ~ nn..~r~ can imme~i~tely begin to cause polymer to form, such that no addition~l reagents or further reaction~ are necess?~ to gel elale an active polyll.~.;Lalion catalyst. Such catalysts are advantageous in certain synthetic procedures and methods, particularly when it is desired that a catalyst is to be added to the reaction rnixture i....~.e~ .ly before polymerization is to beBin. For eY~mrlc, 30 such catalysts can be useful in batch reactions used to prepare polyrner, or can be usefully added to .- ~-nc --Pr ;~ ed D~ely prior to &pplic~ )n of a poly...~,. b'e c~nlrosition to adherend ~urf~-~s One-part catslysts csn be i~s1~ted and are ~~s~e~ ly pure co.,.pou.lds. One-psrt cstslysts sre p,~fe~ly rC~io~'c complexes,snd further colll~l;se non-coG~ g coullte.ions.
S Fl~palalion of one-part Group VIII metal complexes has been d~s~,liL.ed in E~ropean Patent AppliCAtiQn No. 454,231, and by Johnson et al. (J. Am. Chem.
Soc., 1995, ~, 6414-6415 and sl F~ol~e ~1~. y materisl), .~h~ .L~ these cstslysts were ~;Crlos~d to be useful in inert atm~Sl~h~ es. The catalysts were chsrscterized as comp'ex~s having a c~ti~nic portion ofthe formula LM-R~
WLC.-e;ll M is a Group VIII metsl, L is a two elc~llon donor ligsnd or ligsnds, as defined sbove, st~bili7ing the Group VIII metsl, and R is H, a hydrocarbyl rsdical or a ~bstituted hydrocarbyl radical, ~herc;ll the substit.~ting groups can be alkyl (1 to 10 csrbon stoms), sryl (5 to 20 csrbon atoms), or halogen sul,~ ed slkyl. In Europesn Patent Appljc-~ion No. 454,231, M is eYemplified ss cobalt and a s~lbstituted t.,tl~.phenyll)orate snion is des~;lil.ed as the co~ te.ion. Tetra~yll,ol&le with (CF3) s~lbstihlents is said to be pl~,f~,lcd, and B{3,5-GH3(CF3)2}4 is PY~mplifie~l In the r~,ference, a pr~ l.,d c~tioniG portion has the formula (Ll)2M-R~
wherein the two L~ groups sre joined through ch~mir~l bonds and each Ll is a two-ele~ llon donor ligand as defined sbove, snd M and R are ss previously defined.
Johnson et al. (J. Am. Chem. Soc., 1995, ~, 6414-6415) describe catslysts c~r,l~l;s;ng nickel or p~ m cornp'~YPd with ligand groups chosen to provide steric bulk suffirient to permit formation of polymer. In psrticular, prt;fell~dPd(II)- snd Ni(II)-bssed catalysts for olefin pol~ le.~alions are cationic metalmethyl complexes of the general formula {(ArN=C(R')C(R')=NAr)M(CH3)(0Et2)}~B{3,5-C6H3(CF3)2}4~
wl,~ ~in M is Pd or Nl, Ar is 2,6-C6H3~R3)2 where R3 is ;SOPIO~ or methyl, snd each Rl indepen~Pntly is H or methyl, or the two R~ groups tsken together are 1,8-30 n~l~h~ ne diyl. A useful cstalyst is desclibed as:

{((2,6-C~ H3(i-pr)2)N=c(cH3)c(cH3)=N(2~6-c~l3(i-pr)2))pd(c~I3)~Et2o)}+{B(3~5 C~I3(CF3)2)4} .
Also useful in alpha-olefin poly,..e.i~dtions are co,~ v~ dc ofthe formula {(ArN=C(R')C~RI)=NAr)Pd(CH2 CH2CH2CO2R2)}~BAr';
~I,ere;n R2 can be -CH3, t-butyl, or -CH2(CF2)6CF3, as reported by Johnson et al.
(J. Am. Chem. Soc., 1996, 118~ 267-268 and s. l)pl ..,~ m~t~ri~l) to be useful in inert a1~ osphc ~s.
All~.,.ali~,c cou~ ,.ions can pro~ide improved catalysts. One p..,f~ ,d counterion is B(c6F~ which is safer to prepare than B(3,5-C~H3(CF3)2)i, is 10 co,l.~ .e~.,ially available from Boulder Sci~ntific Company (Mead, CO) and provides better control over polymer rno!ec..l~r weight The counterion B(C6F~); is particularly prefe.led in pol~,..e.i~..ble co~"?osilions used in the method of adhering materials of the invention. It is also p.~,fe~.~,d when one-part catalysts are used to prepare polymers useful in the adhesive compositions ofthe invention, pa.li~iul&ly 15 when the poly...c.i~lion leaclion is cond~cted in the l)rwence of an n1lleouc phase Other anions useful as the anionic portion of the catalysts of the present invention may be gene.~l1y cl~ccified as fluoli"&led (inrl~ldin~ highly fluo-;nAted and perfluorinated) alkyl- or arylsulfonyl-cont~ining compounds, as repl ~ senled byFormulae (Ia) through (Id):

(R~ SO2)2CH- (Rf SO2)3C- (Rf SO2)2N- RfSO3-~a) ~b) (Ic) ~d) whe[eh~ each Rf is ind~endently selected from the group con~:ct;~g of 25 highly fluGlh~ated or perfluolinalcd alkyl or fluGlilld~ed aryl radicals. Compounds ofFormulas Ia, Ib and Ic may also be cyclic, when a combina~ion of any two Rf groups are linked to form a bridge.
The Rf alkyl chains may contain from 1-20 carbon atoms, with 1-12 carbon atoms p.~fe...,d The Rf alkyl chains may be straight, b.~1cl-ed, or cyclic and 30 prefe-,~bly are straight. Hete.o~lol"s or radicals such as divalent non-peroxidic oxygen, trivalent nitrogen or hexavalent sulfur may interrupt the skeletal chain.

When Rf is or c~ a cyclic structure, such structure l~l~.ably has 5 or 6 ring ~-.c ~bf!~ ~, 1 or 2 of which can be hele, oato.,.s The alkyl radical Rf is also free of Cl}.yle~liC or other carbon-carbon lu~salu-alion: e.g, it is a ;,al-lldl~,d aliphatic, cycloo~ h~;c or h.,te~o~ clic radical. By "highly fluolinated" is meant that thedegree of fluorination on the chain is s~ffichnt to provide the chain with plOpC. lies similar to those of a perfluorinated chain. More particularly, a highly fluo~ ted alkyl group will have more than half the total number of hydrogen atoms on the chain replaced with fluorine atoms. ~lthollgh hydrogen atoms may remain on the chain, it is pref~ ,d that all hylllogen atoms be replaced with fluorine to form a perfluoroalkyl group, and that any hydrogen atoms beyond the at least half replaced with fluorine that are not replaced with fluorine be replaced with b~ol,lli~c and/or chlorine. It is more pl~felle,d that at least two out ofthree hydrogens on the alkyl group be re~ ced with fluorine, still more plefe.l~ d that at least three offour hydrogen atoms be replaced with fluorine and most pref. ,l~d that all hydrogen l 5 atoms be repl~-ed with fluorine to form a perfluorinated alkyl group.
The fluorinated aryl radicals of Formulas Ia through Id may contain from 6 to 22 ring carbon atoms, preferably 6 ring carbon atoms, where at least one, andprefelably at least two, ring carbon atoms of each aryl radical is substituted with a fluorine atom or a highly fluorinated or perfluorinated allyl radical as definedabove, e.g., CF3.
FY~mples of anions useful in the practice of the present invention include:
(C2F~S02)2N-, (C4FgS02)2N~, (C8Fl~S02)3C, (CF3S02)3C, (CF3S02)2N, (C4F9S02)3C, (CF3S02)2(C4FgS02)C, (CF3S02)(C4FgS02)N~, {(CF3)2NC2F4S02}2N, (CF3)2NC2F4S02C (S02CF3)2, (3,5-bis(CF3)C6H3)S0 S02CF3, C6F~S02C (S02CF3)2, C6F5S02N S02CF3, CF3S03, C,~F,7S03-, F~2C--S(~2 F2 Ics&
F2C\ N- F2C- &--S02CF3 F2C--SO2 , S02 WO 97/48777 12 PCTrUS96/16837 ~\ r~
O~N--C2F4SO2N-SO2CF3 O~N--C2F4SO2C-(SO2CF3)2 S

F2 lC~
F2C_so2 wl,e.~in F in the ring means the ring carbon atoms are pc.n.loli..ated, and the like.
More plefe"~d anions are those described by Formulas Ib and Ic ~l,elc;n Rf is a 5 perfluoroalkyl radical having 1-4 carbon atoms.
Anions ofthis type, and rep~senl~h~e syntheses are desc,ibed in, e.g., U.S.
PatentNos. 4,505,997,5,021,308,4,387,222,5,072,040,5,162,177, and 5,273,840, and in Turowsky and Seppelt, Inorg. Chem., 1988, 27, 2135-2137.
{C(S02CF3)33-, {N(SO2CF3)2}- and {N(SO2C2F5)2}- are p,.,f. .led, and {N(SO2CF3)2}- and {N(SO2C2F5)2}- are particularly p,er~.led. Such co.l.,le,;ons may be pfefe~,ed with certain metals and ligands, or in some processes. Other useful fluorinated non-coor.l;..Lt;l~g counterions include PF6-, SbF6-, AsF6-, and BF4 .
In the pl c?& aLion of one-part catalysts, diethyl ether can be useful but it isnot p-.,f.,.led because it can be dange.o~ls to store and handle due to its C,~tl ."c 15 I~ ty and tendency to form explosive peroxides. Alternative useful ethers are organic compounds cor.l~ g one ether-type oxygen atom and include tetrahydrofuran and methyl t-butyl ether. Methyl t-butyl ether is particularly preft" ed.
P~ fe.l~ d catalyst compositions useful in the practice of this invention can be20 of the formula {(ArN=C(R~)C(R~ NAr)Pd~Me)(ether)}+ Q~
whe:~;n Ar and R~ are as previously defined and ether can be t~ tl~ydror~ran, diethyl ether, or methyl t-butyl ether, and Q can be selected from B(C6F5)4, anions as sho~,vn in Formulas (Ia) through 25 (Id), PF6, SbF6, AsF6, and BF4. Particularly p,~ft;"~d are compounds ~herein ether is methyl t-butyl ether and Q is selected from B(C6F~)4 and anions as shown in Formulas Ia through Id.

CA 022~6~ 1998-11-30 Examples of l)re6~1~,d one-part catalysts include:
~((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)}+{B(C6Fs)4}, {((2~6-c6H3(i-pr)2)N=c(cH3)c(cH3)=N(2~6-c6H3(i-pr)2)) Pd(CH3)(Et20)}+{B(C6F~)4}', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3) (tetrahydrofilran)}+{B(C6F~)43', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)}+{N(S02CF3)2};
{((2~6-c6H3(i-pr)2)N=c(cH3)c(cH3)=N(2~6-c6H3(i-pr)2))pd(cH3) (Et2o)}+{N(so2cF3h}, {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-(tetrahydroru-~)} {N(S02CF3)2};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)}+{C (S02CF3)3};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-(Et2o)}+{c(so2cF3)3};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-(tetrahydrofuran)}+{C(S02CF3)3}', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)}+{N(S02C2Fs)2}', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-(Et20)}+{N(S02C2F5)2}, {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-(tetrahydrofi~ran)} {N(S02C2F5)2}', {((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(Me)2))Pd(CH3)(~e t-butyl ether)}+{B(C6Fs)4}, {((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(Me)2))Pd(CH3)-(Et20)}+{B(C6F~)4};

., .. , .. ~ . ,~.

CA 022~6~ 1998-11-30 WO 97/48777 ~4 PCT/US96/16837 {~2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(Me)2))Pd(CH3)-(tetrah~dr~îu- ~n)}+{B(C6F~)4}', {((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(Me)2))Pd(CH3)(Me t-butyl ether)}+{N(S02CF3)2};
{((2,6-C6H3(Me)2)N=C(CH3)C(CH3)--N(2,6-C6H3(Me)2))Pd(CH3)-~Et20)}+{N(S02CF3)2}, {((2,6-C6H3(Me)2)N=C(CH3)C(CH3)=N(2,6-C6H3(~Me)2))Pd(CH3)(tetrahydrofuran)} {N(S02CF3)2}', {((2,6-C6H3(i-Prh)N=C(CH3)C(CH3)--N(2,6-C6H3(i-Pr)2))Pd(CH3)~Me t-butyl ether)}+{N(S02CF3)(S02C4Fg)~;
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-(Et20)}+{N(S02CF3)(S02C4Fs)};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-(tetrahydrofuran)}+ {N(S02CF3)(S02C4Fg)};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)}+{BF4};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(:Et20)}+{BF4};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)--N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)} ' {CH(S02CF3)2}', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)-(Et20)}+{CH(S02CF3)2};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)} {PF6};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Et20)} {PF6}, {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)} {SbF6}', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)-N(2,6-C6H3(i-Pr)2))Pd(CH3)(Et20)} {SbF6}', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)--N(2,6-C6H3(i-Pr)2))Pd(CH3)(Me t-butyl ether)}+ { S03CF3 }', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)--N(2,6-C6H3(i-Pr)2))Pd(CH3)-~t20)}+{SO3CF3}', {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH~)=N(2,6-C6H3(i-Pr)2))Pd(CH3)~Me t-butyl ether)}+{S03C4F9};
{((2~6-ccH3(i-pr)2)N=c(cH3)c(cH3)-N(2~6-c6H3(i-pr)2))pd(cH3) (Et20)}~{S03C4Ps};
{((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-CcH3(i-Pr)2))Pd(CH3)(Me t-butyl ether)}+{NS02(CF2)2S02}, and {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-GH3(i-Pr)2))Pd(CH3)(EtzO)} {NS02(CF2hS02}.
Two-part catalysts cG...p,;se two ~ c, a neutral org~nG~ t~ c 10 co",l)uund and a cocatalyst salt, that react upon mixing, optionally in the presellce of ~--o~ r~ to yield an active catalyst. Two-part catalysts are particularly advAnt~geo~s in polymer syntheses when partial mixing of mQnomPr and an o~;PnG~-etAllic compound is desired (such as to achieve good soh~bility or suspension) but when it is also desired to initiate poly...c.iLalion at a later time, for 15 i~ A~-ce, when the second reagent is added. Process advantages resulting from the ability to control the time at which pol~."e.i~alion begins are ~ignifir~nt Two-part catalysts may also allow for the in si~u gene~alion of active catalytic compounds which cannot be i~ol~tetl and may also be p~efe"~d for those sit~l~tion~ where the added time and e.~ nse of i~ol~tine a one-part catalyst are not w~ ted. Two-20 part catalysts can be particularly useful in a polymerizable adhesive composition~ Inparticular, the poly.l.criLable composition may co""~,;se two separate portions, a portion A which col~lAi~c neutral org~nometAllic compound and a portion B which conlAi~c cocatalyst salt. Alpha-olefin monomer may be present in one or both of portions A and B. Upon mixing of portions A and B, a pol~,.,e. i,able cor"i~os;~ion 25 co.,l~in: ~g active catalyst is gelle,~ted, which may then be applied to adherend s. ~Ç~ces. In another variation, portion A may be applied to one adherend surface and portion B to another, and mixing is ~ccomp!i~hed by b.ingil,~, the two adherends into contact. Variation of the order and means of mixing are appa~ t to those skilled in the art. Such latently polyn,e.i~ablc compositions can be supplied as 30 two-package kits.

wo 97t487M 16 PCT/US96116837 Two-part catalysts preferably coinp,i3e a neutral Gr~Pno. . tallic Pd or Ni co,l.you"d which incl~des a ligand or ligands as previously d~fin~ a moiety R
which is H, hydrocarbyl radical, or s~b~ ed hydrocarbyl radical, and a ~~lo{~f~natom (prefer..bly chlorine), and a cocatalyst. F~ ~fe., ~d neutral cGmpounds can be of 5 the general ~1ll~ &
~ ArN=C~R')C(Rl)=NAr}M(R)X
where Ar, R and R' are as defined above, and X ~ep,~~e.~l~ a halogen atom, p~efe,ably chlorine or ~ron~ine, most preferably chlorine.
Examples of p~ ~,f~ d neutral co -.l o! l d~ inrl~de 10 (2,6-dimethylphenyl)N=C(Me)C(Me)=N(2,6-d;.nelhylphenyl)Pd(Me)CI, (2,6-di;sopropylyhenyl)N=C(Me)C(Me)=N(2,6-diisopropylphenyl)Pd(Me)CI, (2,6-dimethylphenyl)N=C(H)C(H)=N(2,6-d;",ell-yl~,henyl)Pd(Me)CI, (2,6-diisopl opyll)h~,.,yl)N=C(H)C(E~)=N(2,6-diisopropyli)h~ n~l)Pd(Me)CI, (2,6-dimethylphenyl)N=( 1 ,2-acçnqrhthylene-diyl)=N(2,6-dimethylphenyl)Pd(Me)CI, wherein 1,2-~ren~phthylene-diyl is repres~.lted by the structure ~' (2,6-d;;sopr~pylphe.,~l)N=(1,2 ac~nsrbthylene-diyl)=N(2,6-d;;sop,opylllhenyl)Pd(Me)Cl, 20 (2,6-dimethylphenyl)N=C~Me)C(Me)-N(2,6-dimethylphenyl)Ni(Me)CI, (2,6-diisopropylphenyl)N=C(Me)C(Me)--N(2,6-d.isopl ~pylphenyl)Ni(Me)CI, (2,6-dimethylphenyl)N=C(H)C(H)=N(2,6-di".elhylphenyl)Ni(Me)CI, (2,6-diisopropylphenyl)N=C(H)C(H)=N(2,6-diisopropylphenyl)Ni(Me)CI, (2,6-dimethylphenyl)N=(1,2-acenarhthylene-diyl)=N(2,6-dimethylphenyl)Ni(Me)CI, and (2,6-diisopropylphenyl)N=( 1 ,2-acP~ hylene-diyl)--N(2,6-diisopropylphenyl)Ni(Me)Cl.
F~reri~lly plefe..~d neutral compounds include (2,6-.l;,...,l}.~ ,he~.~l)N=C(Me)C(Me)=N(2,6-dimethylphenyl)Pd(Me)CI and WO 97/48777 17 PCT/US96t16837 (2,6-diisop~up~ylphcnyl)N=C(Me)C(Me)=N(2~6-diisopr~ylphenyl)Pd(Me)CI.
Useful cocatalyst salts are of the general formula A+Q-~h~.. ;n A is scle~cd from silver, th~llium, and metals of Periodic Group IA, and Q
S is selected from B(3,5-C6H3(CF3)2)4, B(C6F~)4, anions as shown in Formulas Ia through Id, PF6, SbF6, AsF6, and BF4, and solvates and h"d. ~les thereof. For some ~plic~l;on~ silver salts are pl~fe.l~d and can have the formulae Ag{B(C6F5)4}(arene)p and Ag{B(C6H3(CF3)2)4}(arene)p ~L~reill arene can be an aromatic hydrocarbon group having 6 to 18 carbon atoms that can be substit~ted by up to 6 alkyl or aryl groups each having up to 12 carbon atoms, preferably arenecan be bel~h~e, tolllPne~ ortho-, meta-, or para-xylene, and mesitylene, and p can be an integer 1, 2, or 3. However, in some applic&lions the less ~ ,e~.s;.~e alkali metal salts (Periodic Group lA) are plefe,.~.d. Particular counterions may be prefe..ed under specific reaction con~lition~ For example, in two-part systems collll,.is;ng a second aqueous phase, B(C6F5)4 is pref~"ed.
FY~Inp'e- of pl ef~ d cocatalyst salts include:
Ag+{B(C6F5)4}'(toluene)3, Ag+{B(C6F5)4}~(xylene)3, Ag {B(3,5-C6H3(CF3)2)4}
(toluene), Li+{B(C6F5)4}', Na+{B(3,S-C6H3(CF3)2)4}; Li {N(S02CF3)2};
Li+{B(C6F5)4}'(Et20)2, Li+{N(SO2CF3)(SO2C4F9)}', Li +{N(S02C2Fs)2}; Li +{N(S02C2F5)2}'(hydrate), Li+{N(S02C4Fg)2)', Li { NS02(CF2)2S02}', Ag+{C(S02CF3)3}', Li+{C(S02CF3)3}', Ag+{CH(S02CF3)2}; Li {CH(S02CF3)2};
Ag+{BF4}', Na+{BF4}', Na+{PF6}', Ag+{PF6}', Na+{SbF6}; Ag {SbF6};
Na+{AsF6}', Ag+{AsF6}', Ag+{S03CF3}', Na+{S03CF3}', Na+{S03C4Fg}; and Ag+{S03C4Fg}'.
Still other co.~.bind~ ;ons of catalyst and cocatalyst can be used to prepare polymers useful in adhesive compositions of the invention.
FYSI PI e s of one-part Ni catalysts include {(2,6-d;;soplo~ rlphenyl)N=C(Me)C(Me)=N(2,6-diisoplopyllJhe.l,~l)Ni(Me)(Et20)}
{B(C6F5)4};
{(2~6-dhllelh~lphenyl)N-c(H)c(H)=N(2~6-dimethylphenyl)Ni(Me)(Et2o)}
{B(C6Fs)4}, , . . . .. ..

{(2,6-diisoi~r~;ll,ke..~l)N=(1,2-a~cn~~ .ne diyl)=N(2,6 diisopiopyll,h_..yl)Ni(Me)(Et20)}+ {B(C6F5h}, ~Lc.~ in n~e ~~ph~ rlene-diyl is as above, {(2,6-di;sop~ ylph~,..yl)NzC(Me)C~Me)=N(2,6-diisoplo~lphe..~l)Ni(Me)(Et20)}
{B(3,5-C6H3(CF3h)4}, {(2,6-d;lll~lLylp}~ yl)N=c(H)c(H)-N(2~6-dill~ ylphc~ l)Nl(Me)(Et2o)}+
{B(3,5-C6H3(CF3)2)4} and {(2,6-di;sopi~ lphe..yl)N-(1,2-acenaphthylene-diyl)=N(2,6-diiso~,f~lph~.lyl)Ni(Me)(Et20)} {B(3,5-C6H3(CF3)2)4}.
10 Ni catalysts which are generated in si~u may also be useful Pl~ f~ d are Ni compounds used in co hi~ iQn with ~ minnm activators cG ~ g alkyl groups.
F---mr'es of Ni compounds are (2,6-~l;isop~opyll,h~..yl)N=C(Me)C(Me)=N(2,6-diisop~o~ ylphenyl)NiBr2, (2,6-dimethylphenyl)N=C(H)C(H)=N(2,6-dimethylphenyl)NiBr2 and (2,6-d;.soplc.pylphenyl)N=(1,2 a~r!nAphlhylene-diyl)=N(2~6-diisopl oyylphe~ l)NiBr2.
Useful ~11....;... -.. activators include methyl~h....;~o~ c (MA0) and Et2AICI.
Pd and Ni catalysts may be useful for the prepa,a~;on of polymers comprising one of 1) a plurality of C3 or larger alpha-olefin units ..hc.e;n the20 polymer has an average number of branch points less than one per alpha-olefin unit, and 2) a plurality of C2 alpha-olefin units vvLc~e;n the polymer has an ~e-uge number of branch points greater than 0.01, preferably greater than 0.05, most ple~lably greater than 0.10, per alpha-olefin unit. These polymers may be plepaled under a variety of condition~ inr.l~ ing inert conditions, prior to their incolyolalion 25 into adhesive compositions Pd catalysts may be prerelled for polymer synthesis because they tolerate a wider variety of pol~-~-e- ;,A~;Qn process CQn~lition~
Pd one-part and two-part c&~l~ts are pl-,f, .l~d in adhesives co.npl;,;ng polymerizable compositions, particularly if the poly~ C~.llpGS lion is to be applied in Al~hiG .I ~9tmoSph~re (COI~I~ Q;~g oxygen and variable ~mo~mts of 30 moisture).

.. . ... ~

Polyolefins p,e~par.,d using Pd or Ni catalysts, as syr~thesi~ed or after ~d~itir~nsl procc,~ g steps, may be in various forms such as puw~le.~, n~icros,lhe~s, pellets, blocks or so' Ition~, which can be useful forms for h~ndling the polymers in the pr~pai~lion of adhesive comrositiot~
S One- and two-part catalysts can be present in polyrner pl~pz.alions and poly",c.iLable compositions in the range of 0.0001 to about 20 weight percent, preferably 0.001 to 5 weight percent, most preferably 0.01 to 2 weight percent of the total cG",~os;lion. Poly",e.iL~Iion products may contain metal-c~ i..g residues, either as ele~ 1 metal or as inorganic or or~~n~..el~tlic compounds, in the arnount 0 to 3 percent by weight of metal. Additional process;ng may be employed to remove metal residues from late metal polyolefin in the poly",~liLalion products. Adjuvants optionally useful in the practice of the invention include solvents such as methylene chloride, and the like.
Additives, adjuvants and fillers as are known in the art can be added to the pol~",e. ~e co",pos;lion ofthe i,.~ ion, providing they do not interfiere with the int~n~ed po~",e.iL~lion process or adversely affect the chemir~l and physical pl'OpC~ lies of the resultant adhesive. Additives, adjuvants and fillers can incl~de, but are not limited to, glass or ceramic microspheres or microbubble~ pi~,m~ c, dyes, or other polymers. Adjuvants may be present in the composition in the range of 0.1 to 90 weight percent. These same adjuvants may be present in adhesive compositions of the invention. It may be advantageous to add adjuvants to monomers prior to polyn,cli~alion. A wider range of adjuvants, inrl~ltii~ ones which may adversely affect pol~"~e,izdlion, can also be incorporated into adhesive compositions of the invention by mixing into already-formed polymers.
Particularly useful additives inclutling tackifying resins, pl~ctiri~ers~ waxes,cryst~11i7~tiQn accelerators, and oil may be used to modify adhesive llropG, lies such as a~hesiQn to various surfaces, p~h~;on under various co~ ;on~, useful te~"?~al~lre range, fleYibility~ open time, morphology and the like. FY~r'es of such additives include tackifiers such as EscorezTM resins ~Exxon Ch~mic~l Co., ~oucton TX), Wingtack~ resins such as Wingtack ExtraTM from Goodyear (Goodyear Tire and Rubber Co., Alcron, OH), Piccolyte S25~, Foral AX~, , Piccor~ll A135TM, Piccolyte S 15~5 and Regalrez 11261M from IIe.cwles (Hercules,Inc., Wil~ Gn~ DE), and Arkon Pl 15~ and Arkon P140~ from Arakawa (Arakawa ~hpmicpl (USA) Inc., Chicago, IL, for Arakawa Chemical Tt.~ ni~ S
Ltd., Japan), oil such as Sh~llflPY 371~ (Shell Chemir~l Co., ~ollston~ 1~, and 5 waAes such as polyethylene and polypropylene waxes, specifically Vesto-.aAIM
(Hi~ls America, Inc., Piscala~lvay~ NJ), EpolenelM (F~tm~n Chemical, Kin~;~y TN), and Fscomçr~ ocon C: hem:~sl Co., Houston, TX) materials. A large number of resins, waxes, and oils are co.-~ cially available from these and other sul)?lie.~, and ~hese examples are not ;..l~ ~ded to be limiti~
Relatively acidic organic compounds such as, e.g., phenols and C&IbOA~rI;C
acids, can be present in the poly.,.c.izable compositions ofthe invention v deleterious effect on the subsequçnt poly...e.iLalion reactiûn. Thus, poly--.e. ' compositions of alpha-olefin mom)m~r further comprising a hindered phenol-type antioxidant (such as Irganox 1010TM, commprcially available from Ciba-Geig,v Corp., Hawthorne, NJ) are useful in the method of the invention. Hindered phenol-type antioxidants useful in the practice of the invention are well known to those skilled in the art, and are described in Jesse Fdenba~m Plastics Additives and Modifiers Handbook. Van Nostrand ~einhold, New York (1992) pp. 193-207. It is adv~nt~eous to add hindered phenol-type antioxidants to polymers to improve poly-mer pe,~---lance and aging. It is particularly advantageous to add the ~ntioxirl~nt to liquid .,,onh~ . Mixing is easier in morlt-m~r than in viscous polymer. It is particularly advantageous to add ~ntioxid~nt to poly~ ble compositions useful in the method of the invention, because it would be .lifficult or impossible to add ~ntioxi~l~nt at a later time in the process.
Other antio~id~nt~ CGn~ g phosphorus, for example, as phosphine or phosphite, are also known as additives in polymers. These secontl~ ntioyi~n~
halt poly--lc.i~lioll, and are not usefully added to ~ons)l~ r prior to poly,.l.,.i~ion (as in polymerizable compositions) but may be usefully added to adhesive composition wL~ ein the polymer is already formed. Sulfur co~ co-.ll)ounds such as thiols also halt polyrnerization, as do strong oxidants such as bleach (sodium hypochlorite).

CA 02256555 l998-ll-30 Pol~ l;on~ to prepare pO~ h~ useful in adhesive compositions oftbe in~e.l~ion can be con~ucted at various tcn~?~,.dt-lres. Preferably, the re~ ~innth~ ule is -78~ to +35~ C, more p.~fe.~bly -40~ to +25~ C, and most preferably-10~ to +20~ C. ~or reactiQnQ conducted in aqueous liquid media, a .. ;n .. ~ ..S reaction tC.~lpC. al-lre of about -5~ C is 1~ ~ f~ d. Tempc. al~res above about 40~ C
may deactivate the catalyst, and good thermal control may be plef..-~,d since the pol~.l.~,.iz~t;onofalpha-olefin. ~l-or~ is~,~.otll~,....lc. Itmaybeparticularly adv~nt~eou~ to employ a second aqueous phase as a heat sink to aid in the control of reaction te~llpc.alllre.
Poly--.e.i~lions to provide polymers useful as adhesive cGll~po~ ol~C ofthe invention can be conducted at atmospheric pressure and at pressures greater thanatmosphçric, particularly in cases where one or more of the monom~rs is a gas.
However, to avoid the ~AI,ense of pr~ssu.i~ed reaction vessels, liquid ..~ "~
may be pref~..cd. Liquid ~ ono~nc s are plef~-led in the method of adl.c~;ng 15 materials with a polyln~ able composition. Particularly p~fe.-~,d are ~onomf~rs with boiling points greater than about 100~C, such as 1-octene and higher alpha-olefin mo~ ",~" j The method of adhering materials with a pol~ e.i~dblc col..i)os;Lion can be conducted at over a te.llpc. ~ re range of -40 to 3 5~C, preferably -20 to 25~C
20 Poly.-~.,.i~a~ion exotherms may cause some heating during pol),--lcli~A~ion in the practice of the method, but adherend materials will absorb some of this heat andtransport it away. Pol~..l~,.i~lion rates and te.npc. ~ res may be controlled byvarying the amount of catalyst, with lower catalyst Amn!lntS providing slower c,~olh~......... .s and lower overall tl .llp.,.alu~cs.
Water can be present in the polymerizable co.. ,pos;lions of the method of the invention and during pol~ ion ~ tion~ conducted to make polymers useful in the adhesive compositions of the invention in the range of 0.001 up to 99 weight percent of the total co ~po~ :~ ;on Water may be present in minor ~m~n~nts when care is not taken to dry the ~ onon~f r or optional organic solvents. Preferably 30 it is present in naturally-occurring ~m~llnts~ in mono~ers as supplied and handled in air. For e~ lf, water is soluble in l-hexene to the extent of appro,~ f,ly 480 WO 97/48777 22 PCTtUS96/16837 parts per million at room te.l.pe..~t~lre, and such co~c~ alion is within the scope of the present invention. Mol~r..Y~ are o~en ;,.I~plied with varying ~ ~-v~ of water, from 0.001 weight percent up to the .- ~;-.. sD~ ity of water in the .. ~ n.. rr, ~epe~ut;i~g on tel~?~,~lule, specific ~ m ~o~ ,l, ambient humidity, storage con~lition~
S and the like. Optional solvents similarly contain varying ~mol~ntC of water. Oxygen can be present in an amount of 0.001 to about 2 weight percent or more ofthe total co--.; os;l;on I~ol~o---~-~ and solvents may contain varying fi""~ S of oxygen from the ~nosphe-e dc~ g on temperature, specific ~ no.~ or solvent, storage con~;~;ol-s, and the like. Oxygen can also be present in ~-.osl.k~-;c a ~ O~ in em~i,o~ surrounding the polymerizable mixture. It is adv~nt~P,ous to avoid the ~ ,nse and process steps of drying and deoxygenalillg ~--onn~ 1 and solvent.Polymers useful as adhesive cGIllpGs;lions of the present invention include alpha-olefin polymers coln~,l;sii)g a plurality of C3 or larger alpha-olefin units wherein the polymer has an average number of branch points less than one per alpha-olefin unit. Without wishing to be bound by theory and rec~,~ g that state-of-the-art analytical techniques are ~ - eq~l~te to determine all structural features, particularly minor ones, it is believed that polymers ob~ah.ed using catalysts of the invention consist esspnt~ y of two types of lel)eali.lg units:
{-CHz-CHR4-},~ and {~(CH2)n~}y W~ C,;n n is the number of carbon atoms in the alpha-olefin monompr used to make the polymer and R4 is {CH3(CH2)(" 3)- } . The number of bl ~ched units {-CH2-CHR4-} is less than the total number of mnnompr units in the polymer, that is, x has a value from 0.01 to 0.99, pr~fe.ably 0.20 to 0.95, more preferably 0.40 to 0.90, and (x + y) has a value of 0.90 to 1.00. Thepolymer structure will vary as the monomP~r or ~--ono--~c, ~ used in the polylllel- b'e composition vary. For ey~mple~ a polymer made from 1-octene, that is, n = 8, has a structure concistine essenti~lly of {-CH2-CH(n-hexyl)-},~ and {-(CH2)8-}y, wherein x is in the range 0.45 to 0.70, and (x + y) is in the range 0.90 to 0.98. In another e~ plG, a polymer made from l-hexene, that is, n = 6, has a structure co~ C'; ~B çssç ~ lly of {-CH2-CH(n-butyl)-},~ and {-(CH2)6-}y, ~h~,.~n x is in the range 0.50 to 0.75, and (x + y) is in the range 0.90 to 0.98. Polymers made from ethylene contain eQ~nti~lly two types of lepe~ units: {-CH2-CHR5-}p and WO 97/48777 23 PCr/US96/16837 {-(CH2h-}q ~.he~e,,.l R5 is a linear or b,anched alkyl group of at least one carbon atom, up to at least 4 carbon atoms, p is at least O.Ol, pl~f~,.ably 0.05, most preferably 0.l0, and p+q is in the range of 0.90 to 0.98. Current NMR
s~ e~ lr~,sco~ c methods are inQIlflir;f nt to determine the m~ value for the 5 number of carbon atoms in R5 which preferably is less than lO0. Those skilled in the art will r.,CG~e that variations in polymerizable cGlllpGs;~ion, such as the kind and amount of optional solvent or nqueQll~ phase or the catalyst selected and pol~,..,e.i~dlion method can affect the polymer structure Polymer structure can affect polyrner pr~pe.lies, such as crystaUinity or m~dl~ s~
Polyolefins p.~pared with G.~P~-o.. e~;tllic Pd or Ni catalysts have physical propc~ lies, particularly with respect to crystallinity, that can be ~lictin~ hed from polymers prcpared with Ziegler-Natta or metallocene catalysts. Crystallinity can be deteeted as a melt l~i.ç~;(;o,- in dil~e..lial sc~ ~nit~p calo.i.ncl~y (DSC) analyses of polyolefins Crystallinity in a given sample depends on sample history, particularly 15 thermal history, and qu~ e measu.~...e.lls ofthe amount of crystallinity are sor,.e. hal dep~ndent on ..,eas~lle.~.e.-t technique Even so, polyolefins p.. pa.cd with org~no~ e ~ c Pd or Ni catalysts are readily di~tin~liched For example, polyoctene s~mp'~s ple.parC~Cl using or~,~no~ 1;G Pd catalysts show broad melt tran~itiQ~ls with heats of fusion in the range of about 30 to 60 J/g. Polyoctene20 prepal cd with Ziegler-Natta catalyst shows little or no detect~ble melt trancitiQn Similar colllpa,isons can be made for other polyolefins prepa~cd with other 1 o~ . Melt trp~citionc have also been detected for polyolefins made with o~ ns~f t~;c Pd and Ni catalysts and alpha-olefin monomers in~ butene, 1-pel.lfne, l-hexene, l-decene, l-dodecçn~ oc~decen~" and l eico3~ne 25 Without wishing to be bound by theory, it is believed that the crystallinity obs~ d in polyolefins made with org~rlompt~llic Pd and Ni catalysts is due to the pr~,sence of repeat units {-(CH2)n-} in the polymer backbone (as desclil,ed above).
For many applic~tion~, a high polymer (Mw over 90,000, preferably over 100,000, up to about lO,000,000, pr~fe.ably up to about 2,000,000) is highly 30 desirable, res~lting in improved product pe~l,..ance. High polymers can be obtained by, for ;..~t~ce, an approp-iale choice of catalyst-to-~nonomer ratio. In .. ....... . ..

~d-lition high polymers can be obtained by contin~ing the poly.,~.,,i~ion reaction ess~ ly to completion, that is, cQh I ~~lltion of s~bs~ lly all available ~QnG~ n However, in other applic~l;on~ polymers of lower slecl~lsr weight, that is M~ of 5,000 to 90,000 are prcf~ l~d. Such mrleclll~r ~.e~6hls can be 5 achieved by, for il.Qt~-c~, an app~ ;ale choice of catalyst-to-mon- mP,r ratio, generally higher than that used to achieve high mnlcc-l~r weight polymer (that is, use of more catalyst results in lower ~le c~ weight). In r l~itjnn, lower molec~ weight can be obla;"ed in reactions in which ...~ n~ ,l is i~co...l l~lely converted to polymer, optionally by the ad~litiQn of ~age"ls which slow or 10 deactivate the catalyst.
Adhesive compositions ofthe present invention comp,i3e at least one of 1) an alpha-olefin polymer cGIlllJlis;ng a plurality of C3 or larger alpha-olefin units wheleh~ the polymer has an average number of branch points less than one per alpha-olefin unit, and 2) a plurality of C2 alpha-olefin units u/Le~ ein the polymer has an average number of branch points greater than 0.01, pre~, ~bly greater than 0.05, most preferably greater than 0.10, per alpha-olefin unit. They may further co".~,i3e additives, and, in particular, additives include tzcl irying resins, pl~Qt;~ ;~e-~, waxes, cryst~lli7~tion accelerators, and oil may be used to modify adhesive prope. Iies such as a~he~ion to various surfaces, ~rlh~ n under various cQrlrl;l;o~ useful 20 te,llp~ ure range, fleYibility~ open time, morphology and the like. Ex~ l e s of such additives have been noted above.
When the adhesive composition can be applied to adherend surfaces at about -40 to 30~C, with modest yl~aul~; (for example, by hand), it is a p,~s~
sens;li~ adhesive, and is useful in constructions such as tapes and labels. When the 25 adhesive co",pGs;lion is not sticky at about 30~C, but will wet adherend surface at higher te~"~e~at~res~ it is a hot melt adhesive, that is, an adhesive that is useful when applied to adherend surfaces at tcl"?~ ures above 30~C, generally from about 30 to 400~C, more preferably 40 to 300~C.
The t~ pc.alule ranges used here to dif~l.,nliale presau~e sensitive 30 adhesives from hot melt adhesives are not int~nded to be limitin~ and, in some cases, these te."pe.alu,~ ranges may overlap. Hot melt adhesives are adhesives that are solid in the temperalu.e range required by a given use (usually, but not ~-ecçsC~- ily, room t~mpe.~lure), but which are applied to the s~itlales to be joined in the form of a melt (liquid offlowable viscosity), solidifying on cooling after the ;~ul/sllales have been ~ led P~ sensitive adhesives do not change their 5 physical state from the initial stage of adhesion, i.e., application, to the final breaking ofthe adhesive bond; they remain pc~ AnP~ y deformable, and may alter under even slight appli~ption of pl~..;,ule. By definition, they are adhesives that are p~ n.,l~lly tacky as used, typically at room te".pc,~t.lre, and that firmly adhere to surfaces upon mere cont~ct Hot melt adhesives are usefully applied as molten m~terWs, for exarnple, as a bead of molten material delivered through a hot nozzle or "gun" to sheets, films or articles made of wood, metal, or polymer. Hot melt adhesive compositions may also be fabricated into films and applied with heat and/or pressure to adherend surfaces such as in a l~ .ng process.
The adhesive COmrosition can also be applied as a polymerizable composition to adherend surfaces. Wetting of the adherend surface occurs at the t~llpe~al~lre of appl;c~;nn~ pl~fe~ably about ~0 to 30DC, and in particular small surface fed~ul~s may be wetted by the polyl"el b'e co,l,posilion, which generally is of lower viscosity than pressure sensitive adhesive or hot melt adhesive 20 compositions. Polymerizable adhesive compositions are of viscosity of 0.2 to 300,000 ce,~ ,oise, preferably 0.2 to lO0,000 centipoise, dependil g on ~..o,,-~1s and types of additives present (inclu~ing polymers such as alpha-olefin polymers).
Adhesive compositions that are applied as poly,,lc;,;Lable co"lpGs;lions are typically descl;l.ed as glues or curable adhesives. The invention desc,;bes a method 25 of adhering materials with a pol,vmerizable composition, the composition comprising at least one alpha-olefin m- norntor and an effective amount of an or~ o,~et~llic catalyst cor"pl;s;l~ a Group VIII metal, pl~ldbly Pd. The method CGnl~l;SeS applying the pOI)/ll..,.- b!e cou",o~;lion to at least one adherend surface, and allowing poly"le.i~Lion to occur. The adhesive composition can also be 30 applied to two or more adherend s~lrf-ces which are the sarne or di~.c;lll.

. ~, . ~ .. ..

Sar,Jwich constructions where the adhesive comrocition is used to bond two adherends togethe~ are also within the scope of the ;..~ lion.
The invention provides methn~Q of adhering Illal, ;als with an adhesive composition co...~.isin~, a polymer i~c~ one of 1) a plurality of C3 or larger 5 alpha-olefin units ~.Lereil1 the polymer has an average ..u.,lbc- of branch points less than one per alpha-olefin unit, and 2) a plurality of C2 alpha-olefin units wherein the polymer has an average IlUlll~e~ of branch points greater than 0.01, pl ef~ ablygreater than 0.05, most yl~fe.ably greater than 0.10, per alpha-olefin unit, CGIllpli;~irlg the step of applying the adhesive composition to at least one adherend 10 surface. In one ~ ;al,on, I,le~.,.e sensitive adhesive col.~posi~;snc are applied to at least one adhe.end surface at about -40 to 100~C, p.. f~.~bly -40 to 40~C, optionally with pressure, by hand, with the use of an application device, or by m~ hin.o In some appl;c~tionc~ pressure sensitive adhesives (PSAs) are form~ tedso that they can also be removed, preferably cleanly, from adherend in a later step.
15 In another variation, hot melt adhesive compositions are applied to at least one adherend surface at about 30 to 400 C, preferably 40 to 300 C, optionally with pressure, in forms such as molten beads, drops, powders, or films, with the use of means such as tools or devices with hot zones or nozzles (such as "guns") or by extrusion through a die, or by heating an adhesive plus adherend construction.
20 Other means of delivering hot adhesive materials to adherent s.~,r~ces are appalent to those skilled in the art In another variation, a film cor..~li;,h-g a hot melt adhesive comrosition is placed in contact with at least one adherend surface at an elevated tc.-l?c.~ re, typically 40 to 400 C, optionally with the applic~tion ofp- ~s;,.l. G.
Particularly useful is the method of applying a pol~n.c, ~ble composition to at least one adherent surface, and allowing poly."e,i~lion to occur while in contact with the surface(s). By this means, particularly good contact bet~ en the pol~...c,i~able adhesive composition and the adherend is achieved. Poly..le. ~ble adhesive compocitionc~ preferably of a low viscosity in the range of 0.2 to 100,000 30 centipoise (cP), can be applied as a liquid, preferably at amhient tenl?c.aL~Ire, both to wet the adherend surface and to flow into the crevices and aspc.ilics universally found in solid surfaces. A low ~cos.ly provides for better wetting ofthe substrate to be bondc l this in turn pruvide~ for better ar~hp~ e; n The ...r~.~.hAI) ~ ,. of adhesive action known as mechanical interlocking occurs when the substrate surface, upon which the adhesive is spread, col-~A~ pores into which the adhesive may flow or 5 projec~ C around which the adhesive so~ fies The adhesive then acts as a o~ anchor. Physical bonding may result from the ~cne~,alion of adhesive mQleclJlPs into the s.-~sl,ale by ~iffi-Qicn A liquid adhesive may dissolve and diffi~se into the ~.lbs~lale material. The extent of diffi-~ion depends upon the affinity ofthe di~re.ll types of rolec~les for one another.
The pol~,.,e.i~able adhesive compositions ofthe invention co",p,i3e ~Jbst~ ~~ ;DllY non-polar liquid hydrocarbon ...ono,. ~r - ~ (or ~ lu. ..s thereof, optionally with additives that do not hlle.~,e with the pol~,l"e~i~lion), which better allows them to wet low surface energy sub;,l, ~les and thereby gain the above-det~iled benefits of better wetting and cG~pa~ ity, without l-~ccss~-ily requiring a 15 pr~t.~l...e~.~ ofthe surfaces, although pre~ s may be employed if desired.
The pol~lllc.i~illg adhesive compositions ofthe invention can be used on porous or smooth surfaces.
The present invention provides adhesives conlp,;si"g crosslinked alpha-olefin polymers. In some applic~;Qns, a crosclinl~Pd adhesive comro~ition provides 20 better product pe~rollllallce. Crosslinking may be n~ca..~pli~hP,d during thepol~ll,c.i~a~ion reaction by copol~.-lel~alion with a polyfunctional mono~mer~ or may be effected by Ghemi~l reactions brought about by thermal means or actinic radiation, inc~ ing high energy sources such as electron beams, ga--m-ma raAi~tion or ultraviolet irradiation, oc.;u--;ng after polyn,e.i~alion. Adhesive compositions 25 w",~,;s;"g crosslinked polymers are within the scope ofthis invention.
In one embo~impnt~ a method employing high ene.~ irradiation ofth adhesive composition, pref~,.ably by ele~ on beam irra~iatio~ is used. Adhesive compositions of the invention can be croso~in1~d via irradi~tion with electron beams at dosag~Ps preferably in the range of 20 MRad or less, more preferably 1030 MRad or less. Advantageously, ~irosc~ ed adhesive compositions can be free ofadded ~ ":c~l crosslinl~ing agents that might otherwise impair the ch~mic~l or .. . , .. ~.. .... . ..

ph~;.;cdl propc~lies ofthe adhesive or be disadv ~ ~eo~s in s.:bse~ use, for example, due to color or leaching. Further, ~le~,lron-beam crosslinking can be carried out after fal),icalion or other procc ~ ng of the adhesive composition by, e.g., e.,l,~li.;on, solvent casting, co~ting 1no! ling~ and the like, to give crosslinked S consl. .Iclions such as films. Other useful high ener~ sources are known, and are vithin the scope of the present invention.
In ~lolhcr e--lbod;~ 1 a method employing ultraviolet (UV) irrP~i~tion is used, plefe.ably further cGI~lpli~;ng the a~ition of at least one W-activated crosslinking agent. In yet another f~mbo~limf~nt a method involving thermal 10 crocclinking is used, preferably further cGIn~ g the ~t~ition of at least onethermally-activated crostlinL ing agent. Preferably, and willloul wishing to be bound by theory, additives that absorb ultraviolet light and subsequently react to give radicals by homolytic cleavage and/or hydrogen abstraction are mixed with the polyrner prior to irr~listion Typical additives include trih~ln~ hjl substitlltf d s-15 lli~h~es (such as 2-(4-methoxyphenyl)-4,6-bis(trichlorul,lelLyl)-1,3,5-triazine), aryl alkyl ketorles (such as acetophenonP, bf ~~ni~l ethers, and ketals of benzil), and diaryl ketonee (such as benzophenonr and anthraquinone). Similarly, additives which thermally generate radicals, such as peroxides, are useful for thermal cros~ ;ng Other useful additives will be appa~ t to those sL illed in the art and 20 are within the scope of this invention. Closclil~Ling by ultraviolet irr~ ti~n or therrnal activation is p~cfe.l~d in certain processes and product constructions,wLcrein it is nrcçcc~. y to process an uncro~et~ red polymer, 8S in a soll-tiorl or an e ~ sion process, to yield forms such as films or fibers, prior to cn,s~ .L ;,~gAdhesive compositions of the invention may be applied and used in various 25 constnlctione~ such as supported or free ,n nding films, as coatin~s or layers on one or more flexible or rigid ba~L ing~ as molded or shaped articles, in disposable or recyclable CG..~ or delivery systems or kits such as in tubes or b~,h..,~,n release liners, as powde. ~ or in co.. .hin~;one thereo~ Methods of applying the adhesive composition to ;~.lppGI ls or bacl~ing~e include solvent coating~ extrusion, spraying 30 and variations and comhinstiQne ofthese metho~$ Constructions comprising adhesive co",?os;lions of the invention are within the scope of the invention.

, WO 97/48777 29 rCT/US96/16837 Useful adherends hclude metals, fabrics, polymers, e,yecia!l)r polyolefins such as high density pol~cthjlel~, linear low density polyethylene, low density polyethylene, pol~ro~lene, and other low-surface enc~r polymers such as poly(tetrafluor~elll~rlene), and cÇ~ lor;cs such as wood, paper and other wood-5 derived products such as cardboard.
Objects and advantages of this invention are further illustrated by the following examples, but the pal liclll&r materials and slmO~ tQ thereof recited in these ~ ~leY as well as other cQntlitinnQ and details, should not be construed to unduly limit this invention.
EXAMPLES
All pret)alalions and l~;.r..ples were condllcted in air unless otherwise noted, and reagents were used as surp' ~ d and were h~n~4d in air, with no attempt to reduce or remove oxygen or water in r~ age.lls, solvents or glassware. Solvents 15 used were typical reagent grade, not al~lyd,ous grade. "Ambient t~,pe.~ re" is appJ o~ y 23~ C. Throughout these examples, the shGI llland notation Cz is used to refer to an alpha-olefin con~ g z carbons. Thus, C2 is ethylene, C3 is propylene, C6 is l-hexene, C8 is 1-octene, and so on. All r.hem~ carl be obtained from Aldrich ~h~m;c~l Col~,pan~ (Milwaukee, Wicconsin) unless otherwise noted.
Molec~ r weights were dete. Illhled by gel-pe., - f ~l ~o~ ch~olllatography, ref~re.lced to pol~;,tyl~nt st~d~ds.

Preparation of Catalysts Throughout these examples, the material l. f, .l~ d to as Pd-A was {(2,6-diisoproyrlphenyl)N=C(Me)-C(Me)-N(2,6-diisoplop~lphenyl)}PdMeCI, pn pa.~d according to known procedures:
A. Synthesis of ligand (2,6-C6H3(i-Pr)2)N=C(C}I3)C(CH3)=N(2,6-C6H3(i-Pr)2).
The ligand was pl~pared a~o d;llg to the procedure des~,lil,ed in H. t.
Dieck M. Svoboda, T. Greiser Z. ~uh~r~ c~. 36b, 823-B32. A mixture of 625 mL meth~nol, 41.7 g 2,3-b~lt~nedione, 171.75 g 2,6-diisoplop~laniline and 6.75 g formic acid was l~r~a~,d in air, then stirred under nlhugen ~ -o~pk, ~, at ambient t~ p.,.al~lre for applu~ fly 18 hr. A yellow prec.;~ e fc nn~l and was collected by filtration. The p,~c;r~ e was re.ily~ ed from hot ethanol to yield 152.6 gm of {2,6-C6H3(iPr)2}N=C(CH3)C(CH3)--N{2,6-C6H3(i-Pr)2}. This ligand 5 was hqn~lled and stored in air.

B. Synthesisof(1,5-cyclooctadiene)Pd(Me)Cl The col.lpound was ~I~,pared according to the }~rocedllle des~,lil,ed in R.
Rullce, J. M. Ernsting, A. L. Spek, C. . Elsevier, P. W. N. M. van Meeuwen, K.
Vrieze Inorg Chem., 1993, 32, 5769-5778. All procedures were co~ cted in a dry nillogen atmosphçre. The bright yellow solid (1,5-cydooctac'iene)PdCl2, 49.97 g, was placed in 1 L of dry, deoxygenated CH2Cl2. While stirring, 37.46 g Me4Sn was added, and the reaction was stirred at ambient t~llpc~al~lre for a total of about 4 days. Black solids (pr~.,.. ~bly Pd metal) formed, and were removed 15 ocç~c;ollqlly during this time by filtration through a pad of Fuller's Earth (filter aid).
When the reaction solution was a pale yellow, it was filtered once more, and solvent was removed. There was ob~ ed 63.94 g white (l~5-cyclooctq~ ene)pd(Me)cl.
This compound was pr~fe.~bly hsndled in an inert atmosphere.

C. Synthesis of {{2,6-C6EI3(i-Pr)2}N=C(CH3)C(CH3)=N{2,6-C6~3(i-Pr)2}~Pd(CH3)Cl, Pd-A.
This neutral olg~nG..~cl~llic co~pol~n~ was plepaltd accor~lLlg to the procedure desc,ibcd in L. K.Johnson, C. M. Killian, M. Brookhart J. Am. Chem.
Soc., 1995, 117. 6414-6415 and supplc -~ / material. In an inert q-tmosph~re (nlLIugen), 31.64 g (1,5-cyclocct~ nç)pd(Me)cl (synthesis B, above) was placed in 375 mL of dry deoxy~nqted diethyl ether. The (l,S-cyclooct-qdi~ne)Pd(Me)CI
was not con~ tçly dissolved. To this mixture was added 48.31 g {2,6-C6H3(i-Pr)2}N=C(CH3)C(CH3)=N{2,6-C6H3(i-Pr)2} (synthesis A, above). An orange c ~ e soon formed. The reaction mixture was stirred for about 18 hr, after which 44.11 g { {2,6-C6H3(i-Pr)2}N=C(CH3)C(CH3)=N{2,6-C6H3(i-WO 97/48777 3 1 rCT/US96/16837 Pr)2}}Pd(CH3)CI was c~l'ected by filtration. This corrpo~n~ was handled and stored in air.

D. Synthesis and isolation Or One-Psrt Catalyst Des~,.;bed here is the prep~alion of {(2,6-diisoplu~"~lph.,.lyl)N-C(Me)-C(Me)=N(2,6-d;isopl~.~,yl~ he..yl)PdMe(methyl t-butyl ether)} {N(S02CF3)2}'.
A sclution of 12.44 g LiN(SO2CF3)2 (HQ1151M, co~ c;ally available from 3M, St. Paul, MN) and 7.36 g AgNO3 in 350 mL d~ioni7ed water was stirred with a SCI ltiOt~ of 22.13 g Pd-A in 350 mL methyl t-butyl ether. A color change10 was evident within minute~ The ether layer was sep~aled from the water and solids that formed, and washed with a second portion of water, then taken to dryness in vacuo to produce 30.79 g {(2,6-diisopropylphenyl)N=C(Me)-C(Me)=N(2,6-di;sopropylphenyl)PdMe(methyl t-butyl ether)} {N(S02CF3)2};
86 % ofthcoi~ l;.,al yield. NMR jpe~llu~cGy~/ conrll".ed the identity ofthis 15 compound.
Sirnilarly, Pd ca~ s cont~ g the following counterions were plepar~:
{C(SO2CF3)3}', {B(C6Hs)4}'~ ~B{3,5-C6H3(CF3~2}4}', (SO3C4Fs), {N(SO2C2Fs)2~;
and {NSO2(CF2)2SO2}'. In other pl ~?a, ations~ diethyl ether was used in placed of methyl t-butyl ether, and the resulting one-part catalysts then cor"l)rised diethyl 20 ether.

r&tion of Polymers E. Preparation of Polymer Using Two-P~rt Catalyst A rnixture of 1351 g water, 900 g 1-octene, and a solution of 1.44 g Pd-A
25 in 67 gm CH2Cl2 was placed into a large jar. The mixture was cooled to about 0~C, 3.23 g Li{B(C6H5)4} ~Example 1) W8S added, and the mixture was r.~ .ed at 0~ to 4~ C with ch~l~i~ After about 18 hr, a solid plug of polyrner filled the cO~ ,r, and the weight yield of polymer after drying in a vacuum oven at 50~C
for two days was deterrnined to be 65%.
Polymer Analysis: Mw 3.99 x 105, M" 2.24 x 105.

.... . . . .....

F. P~ &tionofPolymers In these p-c?~alions, catalyst was mixed with .nonn.-..,~ and optional solvent as indicpted in Table 1. Pol~ ..~alion was con~ucted at the t~,~,.pc.al-lre and for the time indicated. All proc~ules were cc!nd~lcted in air and with no 5 attempt to remove water from .~ nh~ or solvent.
In these pr~paralions, one-part catalysts had the formula {{(2,6-C6H3(isoprol ~I)z)N=C(Me)C(Me)=N(2,6-C~I3(isopropyl)2)}Pd(Me)(ether)}+Q, ~IIC~ ether and Q are as speç;r~ed in Table 1, below.
In Table 1, in the column "Rxn Cond," reactions cond;l;on~ are ~ ;c~ed as 10 follows: A general procedure (i~ t a~cd by A through D)/reaction te.l,pe.alLIre in degrees Centigrade/l~aGtior~ time in hours. Specifics ofthe procedures are as in~icated below.
(A): cor t~ined one-part catalyst, and varying anlollnls of liquid monomer and CH2CI2 solvent. In specific procedures, the ~moun~s by weight of ,..oncs."e~ to CH2CI2 are: A-l, 1 to 1; A-2, 3 to 1; A-4, 7.7 to 1; A-5, 1 to 2; A-6, 3.8 to 1;A-7, 5 portions of each cGI~oncin~ t to 1 portion of CH2CI2; and A-8, 5 to 1.
Re~ction mixture was homog~neous initially, and polymer pre~ .led in some cases depending on ...ono. ,er, tempc.alLlre and extent of reaction. In A-3, one-part catalyst was dissolved in CH2CI2 in a pre;,;,~l,G vessel and gaseous ~.,ono",e. was 20 added, but the exact amount of monomer charged was not recorded. For the s~"ples where reaction times are shown as UliLIowll, reaction progress was not carefully monitored and reaction times were greater than 100 hours, but not known with CG~ l-lY-(B): cont~in~d one-part catalyst, 4 portions by weight of ethyl acetate, and 25 1 portion by weight of Illonolller. ~eactiorl mixture was initially homogeneous, but polymer soon began to p, ec ~ e from solution.
(C): ccsn~ ed two phase (monom~r and water) ~ lure with two-part catalyst, as de~,v,ibed in Pl~p&alion E.
~ ) con~;..cd one-part catalyst and ~oncs...~, with no solvent. R~actiQ~
30 mixture formed a solution and polymer yrccip;~ ed from the solution as it formed.
Re~ction progress was not carefully monitored and reaction times were greater than 100 hours, but not known with c~i.lainly. D~ cQ..t~;~.ed one-part catalyst and 1portion by weight of each of two cornonG.. ~
In the column '~Mono/Pd" is in-lic~ted the amount of mnn~ in grams, divided by the amount of Pd in moles.
S For the last two c~mples in Table 1, copoly.l.c~i alions were cond~tcted by mixing the two or more comono~ers listed with one-part catalyst in the An.n..nl~
in~lir~te~

Table 1 ~onomerCatalyst Rsn cond Mono/Pd Polymer Molecular Weight '' I or2 ether Q M~v Mn Mw/Mn C4 one-part Me t-Bu O N(S02CF3)2 A-3/0- (unknown)1.04 x 1055.55 X 104 1.88 Cs one-part Et20 B(C6Fs)4 A-1/0/68 2.55 x 1052.40 x 1058.11 x 104 2.95 C6 one-part Et20 B(C6Fs)4 A-1/0/68 2.63 x 1055.20 x 1052.67 x 105 1.94 D
C6 one-part Me t-Bu O N(SO2CF3)2 A-1/0/18 4.01 x 1051.35 x 1054.44 x 104 3.04 ~, C6 one-part Me t-Bu O N(SO2CF3)2 B/04/68 4.16 x 1053.49 x 1058.23 x 104 4.23 ..
Cg one-part Et20 B(C6Fs)4 A-1/0/66 2.62 x 1056.64 x 1053.05 x 105 2.17 C8 one-part Me t-Bu O N(SO2CF3)2 B/0-4/90 6.07 x 1056.78 x 1051.30 x 105 5.21 ", C8 one-part Me t-Bu O N(SO2CF3)2 A-1/10/23 1.57 x 1053.55 x 1051.21 x 105 2.94 r C8 two-part (none) B(C6Fs)4 C/04/18 3.51 x 1053.99 x 1052.24 x 105 1.78 C8 one-part Et2O SbF6 A-1/0/68 8.97 x 1041.16 x 1058.66 x 104 1.34 C8 one-part Et20 N(SO2C4F9)2 A-2/0/68 2.86 x 1051.06 x 1051.67 x 105 6.32 C8 one-part Et2O C(SO2CF3)3 A-1/0/68 1.01 x 1051.47 x 1051.00 x 105 1.47 C10 one-part Et2O B(C6Fs)4 A-1/0/68 2.70 x 1056.76 x 1051.92 x 105 3.53 C10 one-part Me t-Bu O N(SO2CF3)2 B/04/68 4.16 x 1055.48 x 1051.63 x 105 3.36 ,~
Cl2 one-part Et2O B(C6Fs)4 A-1/0/70 2.62 x 1056.89 x 1052.43 x 105 2.82 ~w Table 1 Monomer Catalyst R~n cond MonolPd Polymer Molecular Weight 1 or 2 ether Q Mw Mn Mw/Mn C~2 one-part Me t-Bu 0 N(S02CF3)2 A-1/0/68 4.01 x 1054.84 x 1051.93 x 105 2.51 Cl8 one-part Et20 B(C6F5)4 A-1/23t 1.76 x 1053.36 x 1051.30 x 105 2.58 (unknown) C20 one-part Et20 B(C6Fs)4 A4/231 4.40 x 1051.00 X 1063.91 x 105 2.57 D
(unknown) o cyclopenteneone-part Et20 B(C6Fs)4 D/0 to 23/ 8.84 x 1052.02 x 1051.08 x 105 1.87 Ul~luwll cyclopenhnc one-part Et20 B(C6Fs)4 A-5123/24 9.17 x 1041.01 x 1054.50 x 104 2.48 C7 one-part Et20 B(C6F5)4 A-81231 2.78 x 1059.06 x 1045.98 x 104 1.52 unh~own C9 one-part Et20 B(C6F5)4 A-61231 2.56x 1051.12x 105 6.99x 104 1.60 unknown C" one-part Et20 B(C6Fs)4 A-61231 2.56 x 1054.01 x 1051.68 x 105 2.39 ~luv~l Cl3 one-part Et20 B(C6F5)4 A-61231 2.56 x 1051.17 x 1057.87 x 104 1.48 unknown Cl4 one-part Et20 B(C6F5)4 A-61231 2.56 x 1052.23 x 1051.30 x 105 1.71 owl~ ~
Cl5 one-part Et20 B(C6F5)4 A-61231 2.56 x 1059.86 x 1045.64 x 104 1.75 unknown Cl6 one-part Et20 B(C6Fs)4 A-61231 2.56 x 1052.67 x 1051.36 x 104 1.96 unknown ~~' Table 1 ,, Monomer Catalyst R~n cond Mono/Pd Polymer Molecular Weight 1 or 2 ether Q Mw Mn Mw/Mn Cl7 one-part Et20 B(C6Fs)4 A-6/231 2.56 x 1051.46 x 1058.60 x 104 1.89 unknown Cls one-part Et20 B(C6Fs)4 A-61231 2.S6 x 1057.96 x 1052.81 x 105 2.84 C6~ one-part Et20 B(C6Fs)4 D*;23; 8.53 x 1051.05 x 1055.79 x 104 1.81 D
cyclopentene unknown ~
C6, C8, CIO,one-part Et2O B(C6Fs)4 A-7123148 2.18 x 1054.00 x 1051.36 x 105 2.93 C12 ~"

Polymers picp~cd in this manner, optionally with the removal of solvent, could be used in the p.~p&.alion of adhesive comrositiQnc S G. Preparation of polymers as microspheres in the presence of an aqueous medium.
In these preparations, polymers were p.~pa.cd in mic.~,s~)h~ rc form. Polymer micfo3ph~ s were p,e~a.. d by mixing dçioni~cd water, alpha-olefin .. onGf~ , Pd-cont~ catalyst {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)--N(2,6-C6H3(i-Pr)2))Pd(Me)(Et20)}~{B(C6F~)43~ (~ ~alion D) dissolved in a small amount of CH2CI2 and surf~ctqnt at the tc...p~,lalules in~ic~q~ted~ and allowing the ~ es to remain at that tc...~. .alure for the i~ ed times Polymer .. icroi.~,heres were obtained. The ~ no~ s of n~ Gr.c, water, surfactant and any other additives are 15 indic~ted in Table 2. The order of mixing was variable; the only sig1-ificpnt effect of such variation on laboratory scale prepa.~lions which was observed was that nd~litiQn of solid catalyst to water/monomer l. i"lulCS resulted in incor-plele delivery of catalyst to the monomer phase, with some catalyst re ~ g as a third, solid phase. Initialmixing was 2ccon-rli~hed by m~othotlc such as sti~ing with a msgn~tic stir bar (B) or 20 by shaking (S) Some ~qmpîes were agitated during polymerization as well:
intermittently (I) or stirred continuol~sly (C), or not at all (N). Generally, for otherwise similar s~nples, higher shear rates or incl~ased stirring resulted in smaller microspheres The .. iclos~,heres (MS) were 1 .~n.il~ed under a mic.oscope to determine their size, which is indicated as a range of di~meters observed under the microscope at 92 times rt~gnificstion.

In Table 2:
DDSNa is dode~ c llfPte~ sodium salt.
(not det) means the in~ic~ted values were not Illcas.l~ ed for those pa. ~ lar r r l e r ~, Wingtack PluslM is a resin avsilable from Goodyear Tire and Rubber Co., Akron Ohio. It was dissolved in alpha-olefin m-~nnm~r snd this so!lltir~n was added ~o other materials in the sample.
ALS is ~ . lauryl sulfate, snd the weight inf~icQted is the weight used of 5 a gel of ALS in water, 29% solids, a.lpplied _s Stepanol AM-VIM by Stepan Co.,Northfield, IL.
Colloidal silica is N_lco 11301M, 30% in water ( Nalco Ch~m;rgl CO., Naperville, IL) (ag) indicQtes that in the sample ~ ed by mi~,roscope, the largest spheres 10 appearcd be agglornerated with smaller spheres.
In Sample G-10, a two p rt catslyst was used: 36 mg of ((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(Me)CI (pl~alalion C) in 2.210 g CH2CI2 was added to 8.032 g 1-octene, and this was added to a mixture of 112 mg Li B(C6F5)4 in 12.131 g water. This reaction exothermed in about 6 I~;nul~> and at the 15 elevated telllpe~aLul~e the catalyst was deactivated, halting ~ignifir.~nt filrther poly",e, i~ alion.

Table 2.
Monomer WaterSurf~t~-~t, Cat/CEl2CI2 - Other, Temp/timeMSsize Sample ~ g ~ mg/~ ~ deg C/hrA~itation micron~
G-1 C6, 20 117.5DDSNa, 0.8 200/20 (none) 0/17 S,N 10 - 130 G-2 C6, 20 60 DDSNa, 0.4 229/1.6 (none) 0/17 S,C 10- 80 G-3 C6, 20 60 DDSNa, 0.4 115/1.3 (none) 0/41 S,C 15 - 180 D
G~ C6, 5.023 15.003DDSNa, 0.102 57/0.687 (none) 0118 S,C 10- 140 G-5 C8, 5.025 14.998DDSNa, 0.103 58/0.795 (none) 0/18 S,C 10 - 70 ,~
G-6 C6, 5.076 15.056DDSNa, 0.101 63/0.562 ~mgtackPlus, 0/18 S,C 10-50 0.753 ~o ~
G-7 C,~, 5.016 14.998DDSNa, 0.103 61/0.978 WmgtackPlus, 0/18 S,C 10- ~"
0.756 150(ag) G-8 C8, 25.00 75 ALS, 1.73 100/1.51 WmgtackPlus, 10/66 B,C 5 - 120 2.51 (ag) G-9 C6, 4.976 20.043Tergitol 7, 27/0.800Colloidal Si, 0.226 0/90 S,N <5 - 60 0.059 G-10 C8,8.032 12.131LiB(C6F~)4 (xs) 36/2.210 (none) 23/0.2 S,I 10- 140 x CA 02256555 1998-ll-30 The microspheres in Sample G-2 were dried and the polymer m~le~ r weight was dete.l.lllled to be M~, 341,000, ~, 186,000. The mic.us~heles in Sample G-3 weredried and the polymer mole ~ r weight was dcle..~ ed to be Mw 240,000, ~, 5 132,000.
Polyrners prepsr~d in this manner, optionally dried, could be used in the p-~p&hlion of adhesive co...l~os~ ns .fir~lion of polymer microspheres in the presence of an organic 10 liquid medium.
Pûlymer mic~s~,heres were pr~cd by mixing organic liquid .~ç.li-~.. alpha-olefin r..onû~er~ and Pd-conlA:n;ng catalyst {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2~Pd(Me)(Met-Buether)} {N(S02CF3)2}
alalion D) at the te-l,p~hl-lres in~l;coterl and allowing the mixtures to remain at 15 that te.llp~,.alu~e for the in~iic~ted times. Polymer lll.clusphe.es formed. The ~mo of materials and con~t;l ;ons are inrlic~ted in Table 3 . Initial mixing was ~s c~lllplished by methods such as stirring with a magretic stir bar (B), shaking (S), or ~,,ç~ n;~lly driven paddle (P). Some sa.,.ples were ~git~ted during polymerization as well:
inte,~ lly (I) or stirred continl~ollsly (C), or not at all (N). The l.licrospher~s 20 were e ~ ed under a microscope to determine their size, and for srlected ssmp' es the mole~ r weight ofthe polymer in the miclos~,beres was also dett;l..l--led.
Generally, the lower size mi~;rospberes (~;...~nc:on t~i~meter) were present in small amounts, having mostly agglomerated to larger irregular shapes of the appl c,x;~ e larger size (d;~ n~ on m~ mum length) in~ sted For some s~mrlec, pGIlions ofthe 2~ mi~.ospheres were collected by filtration, and dried to give powders.

Table 3 '' Monomer Solvent Cat Other, R~nCond MSsize Sample ~ g mg g deg C/hr Agitation micron H-l C8, 200ethyl acetate, 800 596 10/18 B,C 5 - 350 H-2 C" 160ethyl acetate, 602 670 0/90 B,C 10-250 H-3 C8, 155ethylacetate, 604 670WmgtackPlus, 0/90 B,C 5 - 300 D
7.607 O
H~ C8, 1 MEK*, 5.009 12 0/18 S,N 5 -300 ,.1 H-5 C8, I Met-Bu ether, 10 0/18 S,N I -5 1-5.004 ~ x H-6 C~2, 1000CH2CI2, 1011 2230 0/72 S,N 10- 250 1-H-7 C,2, 5ethyl acetate, 20 30 0/18 S,N 10-200 H-8 C,0, 5ethyl acetate, 20 30 0/18 S,N 10-300 H-9 Cl8, 5ethyl acetate, 20 30 0/18 S,N 10-140 H-10 C6, 5ethyl acetate, 20 30 01/18 S,N 10-nd**

* methyl ethyl ketone ~O
~* agglometation was particularly pronounced so the ~ size was not deterrnined (nd) In these samples, dete ..~ ;nn ofthe largest di.~ on ofthe agglnme~ated microspher s was subject;ve and should be conr;dered quslit~tive.
The a~lomerates were small enough to allow for easy h~ndling and pro.es,:ng and the microsphere ~ spe~.~ onC forrned in organic liquid were hsn(lled as fluids, by 5 means such as pou~;ng.
Polymer ple~.&~.d in this manner, with solvent oplionally re.l.o.~, can be used in the pfep&,dlion of adhesive com~G~ I;

E~ample 1. Pre~surc Sensitive Adhai~a.
Polyoctene used in this example was piepa.ed from 100 g l-octene in 100 g CH2CI2 using 0.5 g of catalyst {((2,6-COH3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-Cf~3(i-Pr)2))Pd(Me)(Et20)}+{B(C6F,)4}- at 0~C for about 2 days, to give polymer of Mw 3.27 x 105, Mn 1.76 x 105. Polyhexene was prepfil~ d similarly, to give polyrner of Mw 2.37x 105, M~ 1.50 x 105. Wingtack ExtralM is a t~cl~ifi~r available from 15 Goodyear (Goodyear Tire and Rubber Co., Akron, Ohio).
Each polymer was dissolved in toluene to give a solntion that was 25% by weight polymer. To samples of polymer solution were added materials as in~icatedin Table 4. Additives were present in the dried coatingc at the weight perCf'~ltS
indicated, and the If .~A;~ weight is polymer. In Sample l-C, for ~ ..ple there 20 is 20% by weight of added Wingtack ExtralM, and 80% by weight of polyoclf ne. These solntiQn~ were then coated onto 0.025 mm (1 mil) poly(ethylene te.el)h~ te) (PET) film, air dried, then oven dried at 93~C for several minl~tesCoating weights were as indic?ted in the Table. ~lhe~;on of these films to steelwas measured at 180~ at 30.5 cm/min, according to ASTM D 3330-81 (Method A).
25 ~olding power was measured on steel for a 1.27 by 1.27 cm area with a 1 kg weight, accor.l,ng to ASTM D3654-87 (Procedure C).

WO 97/~8777 43 PCT/US96116837 T~ble 4 Adhesion Holding Coating Weight Additive(s) g/cm l'ower m~cm2 S~mplcPolymer wt % (oz/in) Removal min (~r~ins/24sq in) I-A octenenone 32.9 (3.4) clean 103 3.97 (9.5) 1-B hexenenone 15.6 (1.4) clean 4.2 3.97 (9.5) l-C octene 20Wingtack 1200(108)split 240 4.51(10.8) Extra 1-D hexene 20Wingtack 585(52.5)Iightfog 0.4 4.60(11) Extra This ~~ "le c~çmo~ ated that polymers inClu~ine one or more of a plurality of C3 or larger alpha-olefin units wl,~,. e;n the polymer had an average S number of branch points less that one per ...ono... ~l unit were useful as press.l~
sensitive adhesives, and that adhesive pc~roln.ance was modified, when desired, by the addiflon of other materials, such as tackifiers, to the polyrner.

E~Ample 2. Pressure Sensitive Adhesives This ~ ~'e deillorlstlatet form~ tion of pressure sensitive adhesives com~lia;ng a polymer inCl~l~ing one or more of a plurality of C3 or larger alpha-olefin units v~l,crein the polymer has an average number of branch points less that one per monomer unit. In this ~,.a...~le, polymers of l-octene were used. Polymer molec~ r weight varied, and M~v for each polymer was as in(lie~ted in Table 5. In S~mrles 2-A through 2-C, polyrner ~ was 1.76 x 105. In Samples 2-D through 2-M, polymer Ma was 2.89 x 105. ~?mrleS were prepared and tested as in Fy~mrle 1. Additives are co. ~ Pl cially available as follows: WingtackT~ Extra from Goodyear (Goodyear Tire and Rubber Co., Akron OH), PiccolyteTM S25, Foral~M AX Piccofyn~ A135, PiccolyteTM S15 and RegalrezlM 1126 from Hercules 20 (Hercules, Inc., Wilmington~ DE), oil (Sh~l1fl~Y~M 371) from Shell (Shell Chemical Co., Houston, TX) and ArkonrM P115 from Arakawa (Arakawa Chemical (USA) Inc., Ch:c~go lL, for Arakawa Chemical Industries Ltd., Japan). Por the holding power tests, s---rp'e~ were left in place for up to 10,000 min, and an entry of WO 97/48777 44 PCT/USg6/16837 "10,000 +" i~ c~les that the sarnple had not failed in that time and was not tested for a longer period of time.

CA 022~6~ 1998-11-30 Table 5 h~ri~?n Coating Weight Polymer &/cm2 ~o~ gPower m~cm2 Sample Mw Additive(s) wt% (ozrm) min (~rainst24 sq in) 2-A 3.27 x5 Wingtack Extra 328 t29.4) 1620 4.36 (10.42) 2-B 3.27 x5 Piccolyte S25 232 (20.8) 431 4.30 (10.29) 10~
2-C 3.27 x 5 oil 66.9 (6) 115 4.34 (10.39) 2-D 7.02 x20 Arkon P115 399 (35.8) 10,000 + 3.88 (9.28) 10' 2-E 7.02 x 20 Foral AX 18.9 (1 7) 3170 3.76 (8.99) 2-F 7.02x20Picco~mA13S 365 (32.8) 10,000+ 4.17(9.97) 2-G 7.02 x20 Piccolyte S115 381 (34.2) 10,000 + 3.78 (9.04) 10~
2-H 7.02 x20 Regalrez 1126 260 (23.3) 10,000 + 3.73 (8.92) 10~
2-I 7.02 x20 Wingtack Extra 349 (31.3) 10,000 + 3.74 (8.95) 10' 2-J 7.02 xS Wingtack Extra 325 (29.2) 10,000 + 3.53 (8.44) 10' 2-K 7.02 x5 Piccolyte S25 13.4 (1.2) 10,000 + 3.64 (8.71) lo5 2-L 7.02 x 5 oil 0 to 1.1 7100 3.75 (8.97) 1O~ (0 to 0.1) 2-M 7.02 x(no additives) 2.22 (0.2) 10,000 + 3.25 (7.77) 2-N 7 x 105(no additives) 81.3 to 160 0.1 0.648 (1.55) (7 3 to (comp) 1i.4) This ~ r 'e showed that adhesive pl up~. lies could be varied by r~ es in forml~lstion Removal of sdhesive from the steel was clean, except in Samples 2-D, 2-E, 2-H and 2-J, where a fog was visible on the steel a~er removal. In Samples 2-5 F and 2-X peel was shocky. For p.~",oses of colnpa,;son, a pressure sensitive adhesive CG~ ..;C: ~ a polyrner COlll~liS;.~g alpha-olefin units ~hereill the polymer had an average number of branch points of about one per ...Ol-O...I~- unit (Sample 2-N) was also I ~A-..;.Ud; the polyoctcne in Sample 2-~ had been plepared using Ziegler-Natta catalyst (as des libed in U. S. Patent No. 5,298,708, "Polyrners A"), 10 had an Mw of ~bout 700,000, and was coated from a s~lntion of about 7% solids.
Note that Colll~aLi~e polymer 2-N showed much poorer shear p~,lf~,llllance (as measured by holding power) than a similar forn ~ tion Sample 2-M, comprising a polymer inclu~line alpha-olefin units v rL~ the polymer had an average number ofbranch points less than one per mo~ clr unit. Sample 2-N was a so~ adhesive that15 left a residue upon removal (an undesirable feature), and was the only one of the s~...rles to fail by splitting in the holding power test.

Ex~mple 3. Crosslinked Pressure Sensiti~e Adhesives Polyoctene and polyh~ nc were pl ~pal . d as in Example 1. sc' ~tion~ were 20 prepaled Co~ 8 70 parts by weight of polymer, 30 parts by weight of Arkon P 1 15 resin (as in Example 2), 0. 5 parts by weight of Irganox~M 1010 anti oxidant (Ciba-Geigy, Hawthorne NJ), in 210 parts toluene and 30 parts xylene. S~mrles 3-C and 3-D also co,~ pd 0.1 part by weight 2-(4-methoxyphenyl)~,6-bis(trichlolvm~lllyl)-1,3,5-triazine (the pr~pardtion of which is described in German Patent 1,200,314). Solutions were coated onto PET as in Example 1, at the coating ~,.eighls ;--~ic~ed ~s~mp~es were then subjected to e-bearn or ultraviolet irradiation, at the dose as ;~ c~l~d in Table 6. The e-beam source was 175 kilovolt, and Samples 3-A and 3-B were exposed at 762 cm/min. (25 feettmin). W
(high pressure mercury lamp) exposure for Samples 3-C and 3-D was under a nllrogcn atmosphere. Adhesive plupc~lies were tested using the mP.tho~s dcs_.;bed in FY~mple 1. For holding power tests, a "+" in~ic~tes that the sample had not .

failed in the time ~ c~le~ and was not tested for longer times. "Failure mode"
des_.il,es the type of det~hm~nt ofthe adhesive from the test substrate during the test. "A" ~ icPtes adhesive failure, that is, the adhesive s~ paialed from the steel test panel. "B" il~liedtes full or partial (as a pe,c~ age) separation ofthe adhesive 5 from the PET backing. "C" intljc~tes cohesive failure, that is, the adhesive material split and was found on both backing (PET) and test substrate (steel) after detachment. The amount of crosslin' çd polymer was ..,eas.ln d as "% Gel," that is, the amount by weight of polymer which was in~Ql~lbte in toh~n~ Results are t~b.~l~ted in Table 6.

Table C.
Holding L. 'lifi~ S'~ - Failure Po~er FailureCoating Weight %
Sample ~ol~ -dose ozlin g/cmMode min. Mode~rains/24 5q. in m~/cm2 Gd e-be~un, Mrad 3-A C~ 0 74 821 A 940 A 12~ 5.02 0 S 50 555 A 10,000+ A 12.15.06 41 S00 A 10,000+ A 12.25.10 71 o 3-B C~ 0 155 1721 C O.S C 11.64.85 0 S 52 577 B 1.8 C 11.64.85 0.3 '~
48 533B(80%) 650 B 11.74.89 38 W, mJ/Crll2 ~~ 1-3-C C~ 0 70 777 A 1880 A 12.45.18 0 302 58 644 A 10,000+ A 12 5.02 11 596 58 644 A 10,000+ A 12 S.02 34 3-D C~ 0 151 1676 C 0.6 C 11.74.89 0 302 67 744B(50%) 2.2 C 11.44.77 2.5 596 56 622 B 4.2 C 11.44.77 2.9 x ;

This ~ ..ple dc ,.o..ctlated that p~OOU~ sensitive adhes;~,es were cJos~ e~ by e-beam or W irr~ tion Certain adhesive pl~p.,. Iies, such as holding power, were improved by crosslinking.
S
E~ample 4. Adhesive Film applied with ~eat.
This example d~ r~ ahd adhesive films col"p,ishlg a polymer including one or more of a plurality of C3 or larger alpha-olefin units wh~ ;n the polymer had an average "u",ber of branch points less than one per monom~r unit, and a method of10 applying such films by the use of heat.
Sqmp1~s were prepawd from pol~ ..O inclu~i~ alpha-olefin units ~.h~.~;n the polyrner had an average number of branch points less than one per ~ Ql~ unit, and wL. .~h~ the alpha-olefin (..~ol-~,- cr, ind;epted by number of carbons, that is, Cl2 is dodecen~, and so on) unit and polymer Ino~e~ r weights were as indicated in Table 6.
15 Sr ~p!es of each pol,vmer (formed as a microsphere pre~ ;pi~ ~le from solvent during synthesis and thus in p~wder forrn) were pressed between two hot (200 ~C) plates with spacers present, to give films ofthickness about 0.5 mm ("thicl~ness before" in Table 7). Portions ofthese films were cut into 2.54 x 2.54 cm (l-inch x l-inch) squares.
The polyrner films were then placed at one end of a 2.54 cm wide piece of test 20 substrate, and a second piece of test substrate was placed on top of that, so that 2.54 cm ofthe second substrate overlapped the film (and first O~bollale llndern~th)~ and the rem~in~ler ofthe second piece eYter~ded in the opposite direction ofthe first piece. The construction of substrate pieces and polymer film was then placed in a 120~C oven for 10 min, with pleSSul~ applied by placing a 1 kg weight on the top piece of substrate, 25 above the polymer film. Samples were cooled at r~ t t~,-,lpe,~ e, with no weight applied.
With this cor.st~ ion, a square having area 6.45 cm2 of polymer was in contact with each piece of substrate, and the substrates coutd be gripped at opposite ends and pulled apart at a 180~ angle. The overlap shear force l-~cess- y to break the 30 bond was measured with an Instron Model 1122 (Canton, MA). A SkN load cell was used. The pieces of substrate were held with 2.54 cm grips on the top and bottom ~.ll,s~lates. Samples were pulled apart at 1.27 or 0.127 cm/min, as i~ ed in Table 7. The stress at break to pull the samples apart was ~.,eas.-l. d in Ib and since the area ,.,e~.l.ed was 1 in2, this was also the stress at break in psi, as shown in Table 7.
Also shown is the conversion to MPa. "Thickness aP~er" in Table 7 was the thickness S of the d.obon~1ed adhesive after testing.
Test substrates were as follo~.~; Stainless steel panels for adhesive testing were 18 gauge, matte finish, debu..~d, and masked on one side, and ,..easu.ed 5.1 x 12.7 cm with the grain in the long direction. Polymer panels for testing were obt~ ed from M;l~"eSOlA Plastics (Eden Prairie, MN) and n.eas. l.,d 0.95 x 2.54 x 12.7 cm. The 10 following abbreviations are used: SS ~ WP~s steel; HDPE - stress-reli~ d highdensity polyethylene; LDPE - low density polyethylene; PP - natural stress-relieved pol~yloy~lene; PC - I~A~chest~ polycdll,Gndle, general purpose (General Electric GE
9034); AC - clear poly(...~ Ll~y' ' - ,rylate); ABS - natural acrylonitrile-but~ ne-styrene polyrner; TEF - virgin Teflon. Both sides of the PC and AC panels and one 15 side of the SS panels were moQI~ed These masks were removed prior to testing, and bonding was done using the previously masked sides. No surface ple~a~ were employed. ~ rnimlm plates (5054 z~ minl~m, mill finish) were 0.1 cm thick, 10.2 cm long and 2.54 cm wide. Cold rolled steel plates were 0.122 cm thick, 12.7 cm long and 5.1 cm wide. The wood substrate, fir, was 0.813 cm thick 2.54 cm wide and 20 10.2 cm long.

Table 7 Adhesion Test Thickness, mm rate stresstobreak Monomer ~ M~ Substratebefore and after cm/min psi MPa Cl2 193000 484000 HDPE 0.53, 0.53 0.127 145.6 1.00 193000 484000 LDPE 0.50, 0.50-0.53 0.127 122 0.84 Cl2 193000 484000 PP 0.49, 0.45-0.59 0.127 20.5 0.14 C,2 193000 484000 ABS 0.49, 0.49-0.64 0.127 12.3 0.08 C,2 193000 484000 AC 0.41, 0.45-0.55 0.127 15.8 0.11 Cl2 193000 484000 TEF 0.45, 0.46-0.49 0.127 59.3 0.41 C,2 193000 484000 fir 0.49, 0.46-0.54 0.127 110.6 0.76 C,2 193000 484000 fir 0.5, 0.62 0.127 108.9 0.75 Cl2 193000 484000 HDPE 0.52, 0.52 1.27 197.9 1.36 C,2 193000 484000 LDPE 0.54, 0.49-0.66 1.27 136.4 0.94 C,2 193000 484000 PP 0.54, 0.49 1.27 132.9 0.92 C,2 193000 484000 ABS 0.58, 0.59-0.63 1.27 18.3 0.13 C,2 193000 484000 AC 0.58, 0.54 1.27 5.2 0.04 Cl2 193000 484000 TEF 0.6, 0.67 1.27 63.1 0.44 C~2 193000 484000 Alllmimlnn 0.58, 0.6 1.27 66.3 0.46 Adhesion Test '~
Thickness, mm rate stresstobreak x Monomer M~ M~ Substratebefore and a~er cm/min psi MPa C,2 193000 484000 Steel 0.55, 0.6 1.27 167.1 1.15 C,2 193000 484000 fir 0.54, 0.4~0.48 1.27 163.8 1.13 C10 163000 548000 ABS 0.62, 0.54 0.127 57.6 0.40 C,o 163000 548000 Steel 0.62, 0.54 0.127 142.7 0.98 C~O 163000 548000 fir 0.68, 0.63-0.8 0.127 175.6 1.24 0 C,0 163000 548000 fir 0.64, 0.81 0.127 83.9 0.58 Ct 175000 383000 fir 0.45, 0.43-0.62 0.127 125 0.86 '~
C6 82300 349000 fir 0.59, 0.54 1.27 54.5 0.38 Cs 175000 383000 fir 0.46, 0.49~.52 1.27 132.5 0.91 ~
C~o 163000 548000 fir 0.58, 0.59-0.62 1.27 159.5 1.10 o Cl4 43400 200000 fir 0.72, 0.8-1.1 1.27 132.8 0.92 Cl6 98100 156000 fir 0.29, 0.13-0.35 1.27 191.3 1.32 E 1060- 14200 44200 fir 0.5 0.127 16.3 0.11 (comp) E 1060 ' 14200 44200 HDPE 0.5 0.127 20.9 0.14 (comp) &
~E 1060 is Eastoflex 1060~ ~om F~ctm~n Chemical (King~oll, IN). It is a lower molecular weight polyolef~n ~.~ pa,~d using a Ziegler-Natta catalyst, and showed much poorer adhesive pelroll,~ ce than polyoctenes of the in~,elllion.

For all ofthc pol~ .ic and metal sulJs~ntes tested, the mode offailure was adhesive, that }s, the adhesive film dcl,o~ied from one substrate rather than tearing.
With an acrylic ~.tldle (AC), the film adhered rather poorly, and crept down thesub~tlales rather than suddenly debQ~ g at a high loading. For the wood samples,5 the polymer film showed variable lh;~ c after d~ondin, as the polymer took on the shape or contours ofthe wood surface. Polymer films e~ ed aRer ~elon~ g from wood 5g . 1~ showed wood fibers still stirl~in8 to the polymer, in(~ie~i~ that part ofthe failure mode inclllded removal of wood fibers from the wood substrate.
This example de~ n~aled that these materials and metho~c were particularly 10 useful for low surface energy sul~ les, such as HDPE, LDPE, PP, and Teflon, and were also useful for metals and wood.

Esample S. Adhesi~es applied as molten materials.
This .~ ,~le illustl~led that an adhesive can be made from a pol~."er jnr~ g 15 one or moK of a plurality of C3 or larger alpha-olefin units wherein the polymer has an average number of branch points less that one per .~ ~o~o--- , unit. Good ~h~os;ol~ cun be obt~;nPd by applying the polymer while it is in a molten state, that is, at un elevated tc...pe.~tute where it flows more readily than at ambient te~llpc~alLlre.
Polyoctene of Mn 175~000~ Mw 383~000 (as rnicrospheres in powder form, 20 syntheci7pd as described in ~l~palalion H) was added in several portions to a mold ; ed at about 160 ~C, und it melted to give a molded c~linder of ~ -et.,~ 1.4 cmand length about 14 cm. This "stick" was loaded into a Polygun TC~M, 150 watt, 120 VAC, 60 CPS (3M Adhesives Coatings and Sealers Division, St. Paul MN), which heated the sample and delivered it to through a nozzle (at about 182~ to 199~ C) as a 25 hot, molten bead to the test substrates. Substrate materials and shapes were as des. . ;I,ed in Example 4. A hot bead of sn appro~ e "S" shape was applied to the bottom ~ sllale~ und a second piece of s-Jt,~ e wss i~ e~ ely applied to the bead and pressed by hand into place. The app~ e uea of overlap of the substrate pieces was 6.45 cm2, and the two pieces ~Ytended in opposite d;rec,liolls, in a 30 configllration similar to that in Exumple 4. The amount und shape ofthe adhesive bead were difficult to control, but the weight was l..eas~lr. d, and the ll~ cl ~f'5.5 a~er . .. . .

debonding was also measured. The polymer density (determined from a pressed filmof the same polymer) was about 0.94 gm/cm3, and these three values (weight, density and thic1~n~ss) were used to e~lc~ te the irregularly shaped area cont~ct Samples were tested in an Instron 1122 at 1.27 cm/min, as in FY~mrle 4. The force n~.ce~C~y to pull the s~ s apart and the c~lc~ t~d area of contact were used to c~ te the force in psi. The data is shown in Table 8, below. The conversion to MPa is shown.

Table 8 Polymer Bead Calculated Thickness wt (g) Force contact ares Stress at Break Substrate (mm) Newton (Ib) cm2 (in2) psi Mpa2 HDPE 0.68 0.17285 (64.1)2.81 (0.435) 147 1.01 LDPE 0.57 0.13254 (57.1)2.56 (0.397) 144 0.99 PP 0.4 0.12421 (g4.6)3.37 (0.522) 181 1.25 ABS 0.48 0.17280 (63) 3.g7 (0.616) 102 0.70 AC 0.48 0.14355 (79.7)3.27 (0.507) 157 1.08 TEF 0.43 0.14181 (40.8)3.65 (0.566) 72 0.50 Fir 0.5 0.31525 (118) 6.97 (1.08) 110 0.76 rnimlm 0.58 0.07111 (24.9) 1.35 (0.21) 119 0.82 The data in Table 8 show that the c~lcul~ted force to debond the polymer from the substrate was in the same range as the forces observed in Example 4, for the same polymer and a similar ~ hale (wood), ;~ c"~ that there was good wetting of the substrate surface and good ~hPQ;on when the polymer was applied in a molten state to the substrate.
E~ample 6. Preparation and Testing of a Curable Adhesive.
In these trials, 20 mg of catalyst {((2,6-C6H3(i-Pr)2)N=C(CH3)C(CH3)=N(2,6-C6H3(i-Pr)2))Pd(Me)(Et20)}+{B(C6F5)4}~ epalalion D) was dissolved in 0.1 g CH2Cl2 (to accelerate ~ ollltion) and then 1.0 g of the inllicated l-alkene was added, 20 as shown in Table 8. The mixture was vigorously ~git~ted to give an orange sol~.tio~
The solution was applied to the bottom test panel at the coverage rate of 6 drops _ . . ... , , ................................ _ (about 0.3 mL) per 6.45 cm2 of overlap. The top test panel was placed over the bottom one to form the overlap joint of the specified area, and was held in place by app.uulnately 122 g (two SS test panels) regardless ofthe size ofthe overlap area.
The samples were allowed to cure for 2.5 hours at room temperature (about 23 ~C)prior to testing. In other trials, longer cure times (4 hours) did not app~,iably change the results.
Test panels were as desc,il,ed in FYr ~le~ 4. Substrates used in trials shown inTable 9 were two id~nti~ ~l panels, placed to give 2. S4 x 5.1 cm overlap for SS, 1.27 x 2.54 cm overlap for LDPE, ~.54 x 2.54 cm overlap for all other s~stl ales. Single overlap shear testing was p~îulllled accordil~g to ASTM D 1002 - 94 (except as otherwise .",ecirled) on the inAic~sted substrates on an Instron Model 1122 with a cor.~ ;.os~ l~P~d speed of 0.127 cm/min.
The alpha-olefin .... no~ used in curable adhesives in this example are intliczted in the Table by C", where x is the number of carbons in the ~nr r~om~r The ll.i ~ Pc~e of the adhesive polymer films formed between the test panels was 0.05 - 0.175 mm, usually 0.075 - 0.10 mm. The adhesive bond generally failed bcl~.een the polymer and the top panel, and the failure mode was mostly adhesive with little cohesive failure.
Trials were pelrull,-cd similarly for the entries in Table 10, except that two di~. ~nl substrate materials were used. The panels were placed to give an overlap area of 2.54 x 2.54 cm.

Table 9. Stress at Break for Single Lap Shear, MPa SS HDPE LDPE PP ABS PC AC TEF
C8 0.30 1.17 0.51 0.82 1.66 0.57 0.43 0.39 C10 0.92 1.29 0.68 0.99 1.08 0.63 0.45 0.40 C12 0.81 1.48 0.82 0.57 1.59 0.41 0.11 0.54 C14 1.35 1.31 0.68 0.37 1.59 0.60 0.32 0.48 .. , . . . . . ~ ..

Table 10. Stress at Break for Single Lap Shear, MP~I ¦
SS - IIDPE ABS - SS ABS - HDPE
Cl2 1.66 2.06 1.28 The joining ability of this system was further shown by p~ , a sol~tion of Pd catalyst and C8 as des~i,il,cd above and using 1 drop ofthe sc~ ltion to glue togeth~r two 0.063 mm thick 2.S4 cm wide strips of Engage 81501M (ethylene-octene S copolymer, Dow Chemical Corp, Mi~lon.~ plied as a film by Consolid~ted Thcl",oplastics CO.~ Ch;ype~.a Falls, WI). Curing co~ itions were as des~,l;bed above, and the area covered by the cured adhesive was applo~ ely 1.56 cm2. In this sample the film elonp~l~d and no adhesive bond failure occurred. Upon further manual pulling, the film broke, not the bond.
E~ample 7. Fonnulated ~ot Melt Adhesives Polyoctene and pol~dodecenc were p,~,pa.~d in ethyl acetate as desc,il,ed in Pl~ aliOn ~ using the following Pn~o~ ts and con~lition~ For polyoctene, 100 g 1-octene, 400 g ethyl acetate, and 5.483 g Pd catalyst were kept at 0~C with consl~l stirring for 3 hr and st~n~ g (no ~git~tiorl) at 0~C for about 15 hr more. 200 rnL
isopropanol and 0.2 g triphenylphosphite were added to halt poly",c~lion. For polydodecen~, 100 g 1-dodec~ne~ 400 g ethyl acetate, and 5.4856 g catalyst were treated similarly. Weight yield of poly ner in-~ic~ted that about 100% of l"onon.~ . had been converted to polymer.
S~mple ~ of each l~ol~",er and Arkon P 140TM (Arakawa ~hemir~l) were mixed at 100~C in a Brabender Plasti-Corder Type EPL-V3302 (Br ~ Llul"~ , Inc., S. H~f~ ~-.C-~-'L NJ) in the weight pl'O~)GI Lions in~ic~ted in Table 11, with Irganox~
1010 added in the arnount of 0.4 weight percent ofthe total co",pos;lion. In theForml.lPtion colllmn the propo,Lions are in-lic~ted as parts Arkon P140 to parts25 polymer, with polyoctene or polydo~ecene inflic~ted as (C8) or (Cl2), repeclively.
Thus, 1:2 (C8) in~ tes a form..l~tioll of one part by weight Arkon P140 to 2 parts by weight polyoctene.

These form~ tion~ were then formed into molded ~iylind~ or sticks, and deli~,.cd as a hot bead to test ;,.~t.ates as desclilJed in F~;.n.ple 5. The amount of adhesive and force to pull samples apart was l.,eas.~d as in Example 5 at 0.127 cm/min. Failure modes are as desclilJed in Example 3 (if there is no entr~r, the mode of 5 failure was not dete.l~ ed by visual examination).

Table 11 Polymer Bead Calc contact Calculated Stress '' Wt~h:- L"~ " Forcedensity area Failure at Break Sample Fo~Tnulation Substrate (g) (mm) lb Newton g/ml in2 crn2 Mode psi MPa 7-A 1:2 (Cs) Wood 0.2970.65 153 681 0.807 0.88 5.66 C 174 1.20 7-B 1:2 (Cs) Steel 0.5551.04 146 649 0.807 1.03 6.61 A 142 0.98 7-C 1:2 (Cs) HDPE 0.247est 0.79 148 658 0.807 0.60 3.87 C 247 1.70 7-D 1:2 (Cs)Acrylic 0.402est 0.79 176 783 0.807 0.98 6.31 C 180 1.24 D
7-E 1:2 (Cs) ABS 0.48est 0.79 176 783 0.807 1.17 7.53 C 151 1.04 7-F 1:1 (Cs) Wood 0.497estO.79 216 961 0.807 1.21 7.80 C 179 1.23 7-G 1:1 (Cs) Steel 0.7040.97 207 921 0.927 1.21 7.83 A 171 1.18 7-H 1:1 (Cs) HDPE 0.2670.77 168 747 0.927 0.58 3.74 290 2.00 oo 7-I 1:1 (Cs)Ac~ylic 0.407estO.79 259 1152 0.927 0.86 5.56 C 301 2.08 7-J 1:1 (Cg) ABS 0.268est 0.79 187 832 0.927 0.57 3.66 C 329 2.27 7-K 1:1 (C8)TEFLON 0.3490.69 96 427 0.927 0.85 5.46 A 114 0.79 7-L 1:1 (Cs) PP 0.44estO.79 209 930 0.927 0.93 6.01 224 1.54 7-M 1:2 (C,2)Wood 0.251est 0.79 280 1245 0.88 0.56 3.61 C 500 3.45 ~
7-N 1:2 (C12)Steel 0.4720.94 24 107 0.88 0.88 S.71 A 28 0.19 2 7-0 1:2 (C~2)HDPE 0.3120.63 220 979 0.88 0.87 5.63 C 253 1.74 2 Polymer Bead Calc contact Calcvl~t~d Stress wt Ih:- Lf~cc Force density area Failure at Break Sample Form~ tioll Substrate (~) (mm) Ib Newton g/ml in2 cm2 Mode psi MPa ~' 7-P 1:2 (C~2) Acrylic 0.4150.73 202 898 0.88 1.00 6.46 C 2021.39 7-Q 1:2 (C~2) ABS 0.36 0.69 67 297 0.88 0.92 5.93 A 73 0.503 7-R 2:1 (C~2) Wood 0.382estO.79 489 2180 est 0.86 S.56 C 5673.91 0.87 7-S 2:1 (C~2) Steel 0.378est 0.79 12 53.4 est 0.85 5.SO A 14 0.097 D
0.87 0 7-T 2:1 (C,2) HDPE 0.32 0.9 55 245 est 0.63 4.09 A 87 0.600 0.87 7-U 2:1 (Cl2) Acrylic 0.4530.81 135 600 est 1.00 6.43 A 1350.93 0.87 7-V 2:1 (Cu) ABS 0.3680.73 41 182 est 0.90 5.79 C 45 0.310 ,,, 0.87 '~

WO 97/48777 60 PCTlUSg6/16837 For some s~nplAc~ accurate measurement of the thickness of the adhesive a~er pulling apart, eSpeci~lly in the case of cohesive failure, was diffic~lt To obtain an ectim~te of thiel~nf~c~ an average of the ~ c~ .cc llleas~lied for other samples was used.
However, this number, in~licnted as "est 0.79" in the thi~n~oss c~ mn was only an 5 estim~te~ and may have been up to 0.18 rnm (about 25%) in error. Thus cslc~ ted values (contact areas and c?lcul~ted force per area) using this value were also only e~ ts For Samples 7-R II"o.l~,h 7-V, the form~ tiQn density was not measured, but e,~ ed (with error of about 10%), so again c~lcul~ted values were e~ les Polyoctene and polydodecene fol- ~YI~;onc were also pressed into films as 10 described in F~ e 4, except that Sample 7-GG was evaluated at 5.1 cm/min.
S~mplAs were pr-,palcd and evaluated at 0.127 cmlmin, as in r~ ple 4. All s---showed cohesive failure. Results are t~b~ ted in Table 12, below.

Table 12 ThicL ~ess Stress at Break Sample mm psi MPa 7-AA 2:1 (C~) Wood 0.75 160 1.10 7-BB 2:1 (C8) Steel 0.77 193 1.33 7-CC 2:1 (C8)Acrylic 0.67 108 0.74 7-DD 2:1 (Cs) ABS 0.73 162 1.12 7-EE 1:1 (C,2)Wood 0.52 295 2.03 7-F~ 1:1 (Cl2)HDPE 0.52 205 1.41 7-GG 1:1 (Cl2)Aclylic 0.5 235 1.62 7-HH 1:1 (Cl2) ABS 0.52 234 ~.61 Various mo~lific~tionc and alterations of this invention will become appalenl tothose skilled in the art without depa, Ih~B ~om the scope and spirit of this invention, and it should be understood that this invention is not to be unduly limited to the illustrative e~"bo.l;~..f ~s set forth herein.

Claims (14)

We claim:

1. An adhesive composition comprising a polyrner including one of 1) a plurality of C3 or larger alpha-olefin units wherein the polymer has an average number of branch points less than one per C3 or larger alpha-olefin unit, and 2) a plurality of C2 alpha-olefin units wherein the polymer has an average number of branch points greater than 0.01 per C2 alpha-olefin ~, said adhesive being selected from the group consisting of pressure sensitive adhesives, hot melt adhesives, and polymerized glues, said adhesive composition optionally further comprising one or more additives selected from the group consisting of tackifiers, oils, polymers, antioxidants, and W- or thermally-activated crosslinking agents, said adhesive composition optionally being crosslinked by high energy irradiation.

2. The adhesive composition accofding to claim 1 which is crosslinked, optionally by any of W, thermal, or election beam irradiation.
said polymer being polymenzation product of a polymerizable composition comprising an alpha-olefin monomer and an effective amount of an organometallic polymerization catalyst comprising a Group VIII metal which is complexed with a ~ ligand having steric bulk sufficient to permit formation of a polymer

3. The adhesive composition according to claims 1 or 2 having a weight aversge molecular weight greater than 5,000.

4. The adhesive composition according to any of claims 1 or 3 wherein said alpha-olefin polymer is derived from slpha-olefins selected from the group consisting of ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, andcyclopentene.

5. The adhesive composition according to any one of claims 1 to 4 which is selected from the group consisting of a free-standing film, a supported film, a coating, and a powder.

6. The adhesive composition according any one of to claims 1 to 5 wherein said Group VIII metal of said catalyst is Pd or Ni.

7. An article comprising a substrate having on at least one surface thereof the adhesive composition according to any one of claims 1 to 6.

8. The article according to claim 7 which is an adhesive tape or label.

9. A method corresponding the step of applying the adhesive composition according to any one of claims 1 to 6 at least one adherend surface, said adherend surface optionally being selected from the group consisting of polymers, cellulosics, metals, and fabrics.

10. A polymerizable adhesive composition comprising one or more of C5 or larger alpha-olefin monomers, an effective amount of an organometallic catalyst comprising a Group VIII metal and a polydentate ligand having steric bulk sufficient to permit formation of polymer, said composition having a viscosity in the range of 0.2 to 300,000 centipoise, said polymerizable adhesive composition optionally further comprising an additive selected from the group consisting of tackifiers, oils, antioxidants, and polymers.

11. The polymerizable adhesive composition according to claim 10 which is a glue.

12. The polymerizable adhesive composition according to claims 10 or 11 wherein said catalyst is a one-part catalyst comprising an organometallic salt or a two-part catalyst comprising a neutral organometallic compound and a cocatalyst.

13. A kit for preparing a latently polymerizable adhesive composition according to any one of claims 10 to 12, said composition having component partscapable of being mixed when the composition is to be applied, said kit comprising a combination of a first package containing an amount of an organometallic compound of a two-part catalyst, and a second package comprising a cocatalyst salt of said two-part catalyst, said kit further comprising one or more of alpha-olefin monomers which are present in one or both packages of said kit.

14. A method comprising the steps of 1) applying the polymerizable composition according to any one of claims 10 to 13 to at least one adherend, and 2) allowing polymerization to occur.