KR20000016706A - Alpha-olefin adhesive compositions - Google Patents

Abstract

PURPOSE: An adhesive composition including an alpha-olefin hydrocarbon monomer and preparation method thereof are provided which have lower corrosion, toxicity and electric constant. CONSTITUTION: 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, the 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 cross-linked. The articles include the adhesive tapes, labels, and adherents comprising a coating of the polymerizable composition.

Description

Alpha-olefin adhesive composition

Polymeric adhesives comprising at least one polymer are known. Such adhesives are applied to the adherend in a number of ways, the common feature being that the polymer wets the surface of the adherend. Thus, the polymeric adhesive may be formulated to wet the surface at ambient temperature when an appropriate pressure is applied, and such adhesive may be classified as a pressure sensitive adhesive. Alternatively, the polymeric adhesive may be formulated to wet the surface at high temperatures so that the adhesive may be applied as a hot melt or applied as a laminated film by applying heat and / or pressure to the adhesive while the adhesive is in contact with the surface of the adhesive. . In another application method, an adhesive comprising a monomer or a low molecular weight curable oligomer can be applied to the adherend and cured on the same system. A general description of adhesive materials is disclosed in Encyclopedia of Polymer Science and Engineering , Vol. 1, "Adhesive Compositions", p 547-577, Willy Intercity Publisher (New York, 1988). The references also collectively describe pressure-sensitive adhesives ( Encyclopedia of Polymer Science and Engineering , Vol. 13, "Pressure Sensitive Adhesives", p 345-368, Willy Science Publishers (New York, 1988).

Adhesive polymers are selected to suit a variety of properties, including polymer glass transition temperature, thermal stability, and the ability to wet and adhere to certain surfaces. Other properties such as moisture sensitivity, corrosive or corrosion resistance, dielectric constant, presence of impurities, color, odor, toxicological properties, processing aptitude, etc. may also be important for certain applications. Adhesives comprising alpha-olefin monomers are particularly preferred for adhesion applications on low energy surfaces and for applications where low sensitivity to moisture, low corrosiveness, good corrosion resistance, low dielectric constant, low cost and low toxicity are desirable or essential. .

The use of alpha-olefin oligomers (molecular weight 5000 or less) in thermoplastic hot melt adhesives is disclosed in US Pat. No. 5,512,625. Copolymers of ethylene and linear straight-chain alpha-olefins are disclosed as adhesives in PCT patent application WO 93/12151. A radiation curable (crosslinkable) polyolefin pressure sensitive adhesive containing a polymer made using a Ziegler-Natta catalyst under inert conditions is disclosed in US Pat. No. 5,112,882. Polymeric adhesives which contain alpha-olefin monomers and Ziegler-Natta or metallocene catalysts and which undergo polymerization reactions in use have not been disclosed, since such polymerization reaction catalysts are sensitive to oxygen and moisture and require special handling.

Summary of the Invention

In short, the present invention relates to a plurality of C ₃ or more alpha-olefin units, where the average number of branching points of the polymer is one or less per one alpha-olefin unit, and 2) a plurality of C ₂ alpha-olefin units, wherein The average number of branching points of the polymer relates to an adhesive composition consisting of a polymer comprising one of at least 0.01, preferably at least 0.05 and most preferably at least 0.10 per alpha-olefin unit). The present invention relates to an adhesive composition consisting of a polymerization reaction product of an alpha-olefin monomer and a polymerizable composition comprising an effective amount of an organometallic polymerization catalyst comprising a Group VIII metal, preferably Pd or Ni, more preferably Pd. It is about. M _w of the polymer is not less than 5,000 is preferable, and more preferably not less than 90,000, and most preferably at least 100,000.

The invention also relates to a method comprising the step of applying an adhesive composition as described above to at least one adherend surface.

More specifically, the present invention consists of a polymerization reaction product of a polymerizable composition consisting of an alpha-olefin monomer and an effective amount of an organometallic polymerization catalyst comprising a Group VIII metal, preferably Pd or Ni, more preferably Pd. Provided are methods for adhering materials using adhesive compositions. M _w of the polymer is not less than 5,000 is preferable, and more preferably not less than 90,000, and most preferably at least 100,000.

In addition, the present invention relates to an adhesive composed of a polymerizable composition consisting of at least one C ₅ or more alpha-olefin monomer and an effective amount of an organometallic catalyst comprising a Group VIII metal, preferably Pd.

The present invention also uses a polymerizable composition comprising an alpha-olefin monomer having at least 5 carbon atoms (C ₅ or more) and an effective amount of an organometallic catalyst comprising a Group VIII metal, preferably Pd. It relates to a method of bonding materials.

According to one feature of the invention, the invention provides an adhesive comprising a crosslinked alpha-olefin polymer. In one embodiment, a method of high energy irradiation treatment is preferably used by electron beam irradiation. In another embodiment, an ultraviolet (UV) irradiation method is used, and preferably a UV activated crosslinking agent is further added. In another embodiment, a method comprising a thermal crosslinking step is used, preferably further a thermally activated crosslinking agent is added.

According to another feature of the invention, 1) a number of C ₃ or more alpha-olefin units incorporated to provide a polymer having an average branch point number of 1 or less per alpha-olefin unit and 2) an average branch point number per alpha-olefin unit Also included within the scope of the invention are adhesives consisting of a mixture of two or more polymers selected from the group consisting of polymers comprising a plurality of C ₂ alpha-olefins of at least 0.01, preferably at least 0.05 and most preferably at least 0.10. For each polymer, the M _w of the polymer is preferably 5,000 or more, more preferably 90,000 or more, and most preferably 100,000 or more. Also included within the scope of this invention are adhesives comprising two or more alpha-olefin monomers, or a copolymer made from one or more alpha-olefin monomers and one or more non-alpha-olefin monomers.

The definitions of terms used in the present specification are as follows.

"Alpha-olefin" and "alpha-olefin hydrocarbon" are the same and are hydrocarbons containing a double bond in position 1, more specifically ethylene or carbon which may be an acyclic or cyclic, preferably acyclic alpha-olefin It means a 1-olefin having 3 or more atoms. The expression C _x refers to an alpha-olefin having x carbon atoms.

"Alpha-olefin polymer" means a polymer formed from one or more alpha-olefin monomers containing on average two bonds that connect each monomer unit to another monomer unit without taking into account end groups.

"Branch point" means a C unit in the polymer backbone bonded to three different carbon atoms. For example, Wow Denote units with one and two branch points, respectively.

"Steric bulk" means a sufficiently large size and a position in the ligand that is sufficient to physically block access to unpolymerized sites for the metal.

"Alpha-olefin unit" means a group consisting of carbon atoms in a polymer derived from a single alpha-olefin molecule by a polymerization reaction.

The term "high molecular weight polymer" means a polymer having a weight average molecular weight (M _w ) of at least 90,000, preferably at least 100,000.

"Poly" means two or more.

"Organic metal catalyst" means a Group VIII metal, preferably a metal of Pd and Ni, a bidentate coordination ligand with sufficient steric bulk to allow the formation of a polymer, and a metal-R bond, wherein R Means H, a hydrocarbyl radical or a hydrocarbyl radical substituted with at least one alkyl, haloalkyl or aryl group each having up to 20 carbon atoms.

The term "polymerizable composition" means a mixture comprising an alpha-olefin monomer with an effective amount of a Group VIII organometallic catalyst and optionally one or more of air and water.

"Polymerization product" means an alpha-olefin polymer prepared by polymerizing a polymerizable composition, optionally containing 0% to 3% by weight of metal residues in the form of metal elements or organometallic compounds.

"Group" means a species that may be substituted by conventional substituents that do not interfere with the desired product.

"Me" means methyl (CH _3- ).

"Et" means ethyl (CH ₃ CH _2- ).

"Bu" means butyl and "t-Bu" means t-butyl.

"i-Pr" means isopropyl.

"Gel fraction" means a fraction of polymer that cannot be dissolved in a suitable solvent, such as toluene after the crosslinking reaction.

Surprisingly, 1) an alpha-olefin polymer comprising a plurality of C ₃ or more alpha-olefin units, wherein the polymer has an average branch point number of 1 or less per alpha-olefin unit, and 2) an average number of branch points of the polymer is an alpha-olefin. Adhesive compositions consisting of a polymer comprising one of a plurality of C ₂ alpha-olefin units of at least 0.01, preferably at least 0.05 and most preferably at least 0.10 per unit are useful as adhesives, and other alpha having different branching forms. -Olefin polymers, for example alpha-olefin polymers comprising a plurality of C ₃ or more alpha-olefin units having an average number of branching points of the polymer per alpha-olefin unit, or an average number of branching points of the polymer being alpha - a different and superior properties when compared to adhesives made of olefin units - a plurality of C ₂ alpha-olefin units or less per one 0.01 Other produce. The adhesive of the invention consists of a polymer which is a polymerization reaction product of an alpha-olefin monomer with a mixture comprising an effective amount of a Group VIII organometallic catalyst, preferably Pd or Ni, more preferably Pd. Known alpha-olefin polymers, including commercially available alpha-olefin polymers, are usually prepared using known synthetic methods (eg, Ziegler-Natta or metallocene catalysis), and such polymers are prepared from the same alpha-olefin monomer. Even if they do, they have physical properties that can be distinguished from the polymers useful in the present invention, especially with regard to the branched form. It is also surprising that the polymerization reaction of the curable adhesive of the present invention proceeds at a useful rate even in the presence of air and / or water to produce the adhesive.

The present invention relates to adhesive compositions comprising polymerized alpha-olefin hydrocarbon monomers and methods of making and using such adhesive compositions. The catalyst used in the polymerization reaction comprises an organometallic complex of group VIII metal (CAS plate of the periodic table), preferably Pd or Ni.

The present invention relates to an alpha-olefin polymer comprising 1) a plurality of C ₃ or more alpha-olefin units, wherein the polymer has an average branch point number of 1 or less per alpha-olefin unit, and 2) the polymer has an average branch point number of alpha. -An adhesive composition consisting of a polymer comprising one of a plurality of C ₂ alpha-olefin units of at least 0.01, preferably at least 0.05 and most preferably at least 0.10 per olefin unit. The adhesive of the invention consists of a polymerization reaction product of a polymerizable composition comprising a C ₅ or higher alpha-olefin monomer and an effective amount of a Group VIII organometallic catalyst, preferably Pd or Ni. The M _w of the polymer is preferably 5,000 or more, more preferably 90,000 or more, and most preferably 100,000 or more. The invention also relates to an adhesive composed of a polymerizable composition comprising an effective amount of an organometallic catalyst consisting of at least one alpha-olefin monomer and a group VIII metal, preferably Pd.

Alpha-olefin hydrocarbon monomers useful in the present invention include substituted and unsubstituted alpha-olefin monomers including acyclic, branched and cyclic alpha-olefins, wherein the substituents on the olefins do not interfere with the polymerization reaction. . Preferred alpha-olefin monomers are from 2 to about 30 carbon atoms, specific examples are ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 Acyclic alpha-olefins such as -dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene and the like, and cyclic alpha-olefins such as cyclopentene and mixtures thereof. Most preferred alpha-olefin monomers include propene, 1-butene, 1-octene and other alpha-olefins having up to 20 carbon atoms. In embodiments such as adhesives comprising the polymerizable composition of the present invention, it is preferred to use liquid monomers, and monomers ranging from high boiling point alpha-olefins such as 1-pentene and cyclopentene to approximately 1-octadecene Particular preference is given to using.

One or more monomers are useful in the polymers and polymerizable compositions of the present invention, and copolymers of two or more different monomers are also included within the scope of the present invention. The copolymer may be a random copolymer or a block copolymer depending on the polymerization reaction rate and the processing procedure. Useful comonomers include other alpha-olefin hydrocarbons that may be present in any fraction. Other useful comonomers other than alpha-olefin hydrocarbons include alkyl acrylates and methacrylates, and acrylic acid and methacrylic acid and salts thereof. The non alpha-olefin comonomer is preferably present at up to 10 mol% of the total polymer composition, most preferably at most 5 mol% of the total polymer composition.

The organometallic catalyst is useful for preparing the polymer used in the adhesive composition of the present invention, and is useful for causing the polymerization reaction of monomers present in the polymerizable composition used in the method for bonding the materials. Organometallic catalysts useful for this purpose include Group VIII metals of the periodic table, ligands that provide sufficient steric bulk to enable the formation of polymers and metal-R bonds, where R is H, a hydrocarbyl radical, or at least one alkyl , A hydrocarbyl radical substituted with haloalkyl or an aryl group. Examples of the Group VIII metal of the periodic table include Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt, with Co, Ni, and Pd being preferred. Ni and Pd are particularly preferred, and Pd is most preferred. The ligand (L) may be selected to be of sufficient size to block steric access to certain coordination sites on the metal atom when coordinating to the metal atom. Examples of such ligands include ArN = C (R ¹ ) C (R ¹ ) = NAr, wherein Ar is 2,6-C ₆ H ₃ (R ³ ) ₂ , and R ¹ is each H or methyl, or two R ¹ groups may together form 1,8-naphthalenediyl, and R ³ is methyl, ethyl, isopropyl or t-butyl, respectively. While not intending to adhere to a particular theory, it is believed that blocking certain sites as described above may reduce or eliminate reactions that produce low molecular weight polymers by prematurely terminating the polymerization reactions due to metal substitution of the polymer chains. . Therefore, a high molecular weight polymer can be obtained by the steric bulk in the ligand.

Preferred catalysts include chelated ligands. Chelation means that a ligand molecule contains two or more atoms capable of forming a coordinating bond to a central metal atom. Preferred atoms or groups of atoms contain two electron donors, preferably nitrogen, more preferably imine groups It is an electron donor containing it. Most preferably, the chelated ligand comprises two imine groups. Imine groups containing a substituted or unsubstituted group on the nitrogen atom are preferred, and such groups are more preferably polysubstituted aryl, most preferably 2,6-disubstituted aryl. Substituents on the aryl ring include alkyl, haloalkyl and aryl, preferably alkyl, more preferably methyl or isopropyl, most preferably isopropyl. The catalyst also contains an atom or group R as described below, which is preferably H or methyl, most preferably methyl.

The organometallic catalysts useful for preparing the polymers for use in the polymerizable compositions and adhesive compositions useful in the process of the present invention may be one- or two-part catalysts. One-component catalyst is a polydentate ligand complex with a Group VIII metal and B to form a (C ₆ F ₅₎ of sufficient steric bulk to allow the formation of polymer ^{_{4 -, PF 6 -, SbF}} 6 -, AsF 6 -, ^{_{BF 4 -, B {3,5-}} C 6 H 3 (CF 3) 3} 4 -, (R f SO 2) 2 CH -, (R f SO 2) 3 C -, (R f SO 2) 2 An organometallic salt consisting of an anion selected from the group consisting of N ⁻ , and R _f SO ₃ ⁻ , wherein R _f is as described below, which forms a polymer immediately when added to the monomer to form an active polymerization catalyst. It is a catalyst that does not require additional reagents or additional reactions. Such catalysts are advantageous in certain procedures and methods, especially where it is desirable to add the catalyst to the reaction mixture immediately before initiating the polymerization reaction. For example, such a catalyst is useful for the batch reaction used to prepare the prepolymer, or it is useful to add it to the monomer just prior to applying the polymerizable composition to the surface of the adherend. One-component catalysts are separable and are substantially pure compounds. It is preferable that a one-component catalyst is a cation complex, and it is preferable to further contain a non-coordinating counter ion.

Methods for preparing single component VIII metal complexes are described in European Patent Application No. 454,231 and in Johnson et al . , J. Am. Chem. Soc. , 1995, 117, 6414-6415 and supplementary materials, which disclose that the catalyst is usefully used under an inert atmosphere. The catalyst is characterized in that the complex having a cationic moiety represented by the formula:

LM-R ⁺

Wherein M is a Group VIII metal, L is a ligand (s) that donates two electrons to stabilize the Group VIII metal as described above, and R is a H, hydrocarbyl radical or substituted hydrocarbyl radical Wherein the substituent is alkyl (1-10 carbon atoms), aryl (5-20 carbon atoms), or halogen substituted alkyl. In European Patent Application No. 454,231, cobalt is illustrated as an example of M and substituted tetraphenylborate anions are disclosed as counter ions. Tetraarylborates with (CF ₃ ) substituents are shown as being preferred, for example B {3,5-C ₆ H ₃ (CF ₃ ) ₂ } ₄ ⁻ is illustrated. Preferred cation moieties in the above references are those represented by the formula:

(L ¹ ) ₂ MR ⁺

Wherein two L ¹ groups are linked together via a chemical bond, L ¹ is each a ligand that donates two electrons as described above, and M and R have the meanings as previously described.

Johnson et al . , J. Am. Chem. Soc. , 1995, 117, 6414-6415, disclose catalysts comprising nickel or palladium complexed with selected ligand groups to provide sufficient steric bulk to enable the formation of polymers. Specifically, preferred Pd (II) -based and Ni (II) -based catalysts for olefin polymerization are cationic metal methyl complexes represented by the formula:

^{{(ArN = C (R 1} ) C (R 1) = NAr) M (CH 3) (OEt 2)} + B {3,5-C 6 H 3 (CF 3) 2} 4 -

Wherein M is Pd or Ni, Ar is 2,6-C ₆ H ₃ (R ³ ) ₂ , wherein R ³ is isopropyl or methyl, R ¹ is each H or methyl, or two R ^One group together forms 1,8-naphthalenediyl. Useful catalysts include:

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {B (3,5-C ₆ H ₃ (CF ₃ ) ₂ ) ₄ } ^_ .

Also useful for alpha-olefin polymerizations are compounds represented by the formula:

^{{(ArN = C (R 1} ) C (R 1) = NAr) Pd (CH 2 CH 2 CH 2 CO 2 R 2)} + BAr '4 -

In the formula, R ² is —CH ₃ , t-butyl or —CH ₂ (CF ₂ ) ₆ CF ₃ . This compound is described in Johnson et al . , J. Am. Chem. Soc. , 1996, 118, 267-268 and supplementary materials, which are useful for use in inert atmospheres.

Other counter ions can also provide improved catalysts. One preferred counterion is _{B (C 6 F 5) 4} - a, which is _{B (3,5-C 6 H 3} (CF 3) 2) 4 - , and more secure than the fabricating, Boulder Scientific Company, It is commercially available from (Made, Connecticut), whereby the polymer molecular weight can be better controlled. Counter ions B (C ₆ F ₅ ) ₄ ⁻ are particularly preferred for the polymerizable compositions used to bond the materials according to the invention. In addition, when producing a polymer useful in the adhesive composition of the present invention using a one-component catalyst, it is particularly preferable when the polymerization reaction is carried out in the presence of an aqueous phase. Other anions useful as the anion portion of the catalyst of the present invention are generally fluorinated (including highly fluorinated and perfluorinated) alkyl-containing or arylsulfonyl, as represented by formulas (Ia)-(Id) Can be classified as a compound.

_{(R f SO 2) 2 CH} -

_{(R f SO 2) 3 C} -

_{(R f SO 2) 2 N} -

R _f SO ₃ ^-

Wherein R _f is each selected from the group consisting of highly fluorinated or perfluorinated alkyl or fluorinated aryl radicals. The compounds of formulas (Ia), (Ib) and (Ic) may be present as cyclic compounds when two arbitrary R _f groups combine to form a bridge.

The R _f alkyl chain may contain 1 to 20 carbon atoms, with the preferred number of carbon atoms being 1 to 12 carbon atoms. The R _f alkyl chain may be straight, branched or cyclic, preferably straight chain. Heteroatoms or radicals such as non-peroxide oxygen, trivalent nitrogen atoms or hexavalent sulfur atoms may be interposed in the skeletal chain. When R _f is a cyclic structure or contains a cyclic structure, such a structure preferably has 5 or 6 ring atoms, and one or two of the ring atoms may be a hetero atom. In addition, the alkyl radical R _f does not have an ethylenically unsaturated bond or other carbon-carbon unsaturated bonds. For example, the radical is a saturated aliphatic radical, a cycloaliphatic radical or a heterocyclic radical. The term "highly fluorinated" means that the degree of fluorination on the chain is sufficient to provide a chain having properties similar to the perfluorinated chain. More specifically, highly fluorinated alkyl groups will have at least half of the total number of hydrogen atoms in the chain replaced by fluorine atoms. While hydrogen atoms may remain in the chain, it is preferred to substitute all of the hydrogen atoms with fluorine to form perfluoroalkyl groups, with hydrogen atoms not substituted with fluorine except for at least half of the hydrogen atoms being substituted with fluorine. It is preferably substituted with chlorine. More preferably, at least two thirds of the hydrogen atoms on the alkyl group are replaced with fluorine, more preferably at least three quarters of the hydrogen atoms are replaced with fluorine, and all hydrogen atoms are replaced with fluorine to form a perfluorinated alkyl group. Most preferably it is formed.

The fluorinated aryl radicals of formulas Ia to Id may contain 6 to 22 ring carbon atoms, preferably 6 ring carbon atoms, and at least one of each aryl radical, preferably at least two ring carbons The atom is substituted with a fluorine atom or a highly fluorinated alkyl radical or a perfluorinated alkyl radical as described above, for example CF ₃ .

Examples of useful anions to practice the invention is _{(C 2 F 5 SO 2)} 2 N -, (C 4 F 9 SO 2) 2 N -, (C 8 F 17 SO 2) 3 C -, (CF 3 ^{_{SO 2) 3 C -, (}} CF 3 SO 2) 2 N -, (C 4 F 9 SO 2) 3 C -, (CF 3 SO 2) 2 (C 4 F 9 SO 2) C -, (CF 3 _{SO 2) 2 (C 4 F} 9 SO 2) N -, {(CF 3) 2 NC 2 F 4 SO 2} 2 N -, (CF 3) 2 NC 2 F 4 SO 2 C - (SO 2 CF 3 ) _2, (3,5-bis _{(CF 3) C 6 H 3} ) SO 2 N - SO 2 CF 3, C 6 F 5 SO 2 C - (SO 2 CF 3) 2, C 6 F 5 SO 2 N ^{_{- SO 2 CF 3, CF 3}} SO 3 -, C 8 F 17 SO 3 -, , , , , Etc., wherein F in the ring means that the ring carbon atom is perfluorinated. More preferred anions are the anions represented by the formulas (Ib) and (Ic) above wherein R _f is a perfluoroalkyl radical having 1 to 4 carbon atoms.

Anions of this type and representative methods of their synthesis are described, for example, in US Pat. Nos. 4,505,997, 5,021,308, 4,387,222, 5,072,040, 5,162,177 and 5,273,840, and Turovski and Sefeldt, Inorg. Chem. , 1988, 27, 2135-2137. _{{C (SO 2 CF 3)} 3} -, {N (SO 2 CF 3) 2} - and _{{N (SO 2 C 2 F} 5) 2} - are preferred, _{and, {N (SO 2 CF 3} ) 2 } ^- and _{{N (SO 2 C 2 F} 6) 2} - it is particularly preferred. Such counter ions are preferred for certain metals and ligands or for some processes. Examples of other useful fluorinated non-coordinating counter-ion, PF ₆ ^- may be mentioned ^{_{-, SbF 6 -, AsF 6}} -, and BF _4.

In preparing a one-component catalyst, it may be useful to use diethyl ether, but this is undesirable, since it is extremely flammable and tends to form explosive peroxides, which presents a risk of storage and handling. Because. Other useful ethers include organic compounds containing one ether type oxygen atom, examples of which include tetrahydrofuran and methyl t-butyl ether. Methyl t-butyl ether is particularly preferred.

Preferred catalyst compositions useful in practicing the present invention are represented by the formula:

^{{(ArN = C (R 1} ) C (R 1) = NAr) Pd (Me) ( ether)} ⁺ Q ^-

Wherein Ar and R ¹ have the same meanings as described previously, the ether may be tetrahydrofuran, diethyl ether or methyl t-butyl ether, Q is B (C ₆ F ₅ ) ₄ , Formula Ia To an and as shown in Id, PF ₆ , SbF ₆ , AsF ₆ and BF ₄ . Particular preference is given to compounds wherein the ether is methyl t-butyl ether, Q is B (C ₆ F ₅ ) ₄ and the anion is selected from formulas (Ia) to (Id) above.

The following is mentioned as an example of a preferable one-component catalyst.

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (tetrahydrofuran)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {N (SO ₂ CF ₃ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {N (SO ₂ CF ₃ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (tetrahydrofuran)} ⁺ {N (SO ₂ CF ₃ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {C (SO ₂ CF ₃ ) ₃ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {C (SO ₂ CF ₃ ) ₃ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (tetrahydrofuran)} ⁺ {C (SO ₂ CF ₃ ) ₃ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {N (SO ₂ C ₂ F ₅ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {N (SO ₂ C ₂ F ₅ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (tetrahydrofuran)} ⁺ {N (SO ₂ C ₂ F ₅ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (Me) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (Me) ₂ )) Pd (CH ₃ ) (Me t-butyl ether)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- ,

{((2,6-C ₆ H ₃ (Me) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (Me) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- ,

{((2,6-C ₆ H ₃ (Me) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (Me) ₂ )) Pd (CH ₃ ) (Tetrahydrofuran)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- ,

{((2,6-C ₆ H ₃ (Me) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (Me) ₂ )) Pd (CH ₃ ) (Me t-butyl ether)} ⁺ {N (SO ₂ CF ₃ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (Me) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (Me) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {N (SO ₂ CF ₃ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (Me) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (Me) ₂ )) Pd (CH ₃ ) (Tetrahydrofuran)} ⁺ {N (SO ₂ CF ₃ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {N (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ )} ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {N (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ )} ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (tetrahydrofuran)} ⁺ {N (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ )} ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {BF ₄ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {BF ₄ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {CH (SO ₂ CF ₃ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {CH (SO ₂ CF ₃ ) ₂ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {PF ₆ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {PF ₆ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {SbF ₆ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {SbF ₆ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {SO ₃ CF ₃ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {SO ₃ CF ₃ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {SO ₃ C ₄ F ₉ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {SO ₃ C ₄ F ₉ } ^- ,

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Me t -butyl ether)} ⁺ {NSO ₂ (CF ₂ ) ₂ SO ₂ } ⁻ , and

{((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ )) Pd (CH ₃ ) (Et ₂ O)} ⁺ {NSO ₂ (CF ₂ ) ₂ SO ₂ } ^- .

Two-component catalysts comprise two reaction reagents, ie neutral organometallic compounds and cocatalyst salts, which, upon mixing, optionally react in the presence of monomers to produce an active catalyst. Although the two-component catalyst is preferably partially mixed with the monomer and the organometallic compound (such as to obtain excellent solubility or suspension), it is also possible to start the polymerization reaction later, for example, when adding a second reaction reagent. It is particularly advantageous for synthesizing the polymers if desired. The process advantages resulting from the possibility of controlling the time to start the polymerization reaction are significant. The two-component catalyst also allows for the preparation of an inseparable active catalyst compound in situ, which is preferable even in situations where the additional time and cost required to separate the one-component catalyst is not guaranteed. Binary catalysts may be particularly useful in polymerizable adhesive compositions. Specifically, the polymerizable composition may consist of two separate parts, namely, part A containing the neutral organometallic compound and part B containing the promoter salt. The alpha-olefin monomer may be present in either or both of parts A and B. Upon mixing parts A and B, a polymerizable composition containing an active catalyst is produced, which can then be applied to the surface of the adherend. Alternatively, the portion A may be applied to one adherend surface and the portion B may be applied to the other surface, and the two adherends may be contacted to mix these portions. Various mixing sequences and means are well known to those skilled in the art. Such latent polymerizable compositions can be supplied as kits in two packages.

The bicomponent catalyst is a neutral organic comprising a ligand (s) as described previously, a partial R (H, hydrocarbyl radical or substituted hydrocarbyl radical and halogen atom (preferably chlorine)) and a promoter It is preferable to include a metal Pd or Ni compound. Preferred neutral compounds can be represented by the following formula.

{ArN = C (R ¹ ) C (R ¹ ) = NAr} M (R) X

Wherein Ar, R and R ¹ are as previously described and X represents a halogen atom, preferably chlorine or bromine, most preferably chlorine.

The following is mentioned as an example of a preferable neutral compound.

(2,6-dimethylphenyl) N = C (Me) C (Me) = N (2,6-dimethylphenyl) Pd (Me) Cl,

(2,6-diisopropylphenyl) N = C (Me) C (Me) = N (2,6-diisopropylphenyl) Pd (Me) Cl,

(2,6-dimethylphenyl) N = C (H) C (H) = N (2,6-dimethylphenyl) Pd (Me) Cl,

(2,6-diisopropylphenyl) N = C (H) C (H) = N (2,6-diisopropylphenyl) Pd (Me) Cl,

(2,6-dimethylphenyl) N = (1,2-acenaphthylenediyl) = N (2,6-dimethylphenyl) Pd (Me) Cl {where 1,2-acenaphthylenediyl is a structural formula Marked}},

(2,6-diisopropylphenyl) N = (1,2-acenaphthylenediyl) = N (2,6-diisopropylphenyl) Pd (Me) Cl,

(2,6-dimethylphenyl) N = C (Me) C (Me) = N (2,6-dimethylphenyl) Ni (Me) Cl,

(2,6-diisopropylphenyl) N = C (Me) C (Me) = N (2,6-diisopropylphenyl) Ni (Me) Cl,

(2,6-dimethylphenyl) N = C (H) C (H) = N (2,6-dimethylphenyl) Ni (Me) Cl,

(2,6-diisopropylphenyl) N = C (H) C (H) = N (2,6-diisopropylphenyl) Ni (Me) Cl,

(2,6-dimethylphenyl) N = (1,2-acenaphthylenediyl) = N (2,6-dimethylphenyl) Ni (Me) Cl, and

(2,6-diisopropylphenyl) N = (1,2-acenaphthylenediyl) = N (2,6-diisopropylphenyl) Ni (Me) Cl.

Particularly preferred neutral compounds are as follows.

(2,6-dimethylphenyl) N = C (Me) C (Me) = N (2,6-dimethylphenyl) Pd (Me) Cl, and

(2,6-diisopropylphenyl) N = C (Me) C (Me) = N (2,6-diisopropylphenyl) Pd (Me) Cl.

Useful promoter salts are salts represented by the formula: and solvates and hydrates thereof.

Q ⁺ A ^-

Wherein A is selected from the group consisting of silver, thallium and periodic table group IA metal, Q is B (3,5-C ₆ H ₃ (CF ₃ ) ₂ ) ₄ , B (C ₆ F ₅ ) ₄ , It is selected from anions, PF ₆ , SbF ₆ , AsF ₆ and BF ₄ , such as those represented by formulas Ia to Id above. In some cases, silver salts are preferred, and these silver salts have the formulas Ag {B (C ₆ F ₅ ) ₄ } (arene) _p and Ag {B (C ₆ H ₃ (CF ₃ ) ₂ ) ₄ } (arene is represented by _p ) where arene may be an aromatic hydrocarbon having 6 to 18 carbon atoms, each of which may be substituted with an alkyl or aryl group having up to 12 carbon atoms or up to 6 aryl groups, and arene, benzene, toluene, orthoxylene , Metaxylene, paraxylene and mesitylene, and p is an integer of 1, 2 or 3. However, in some cases, inexpensive alkali metal salts (group IA of the periodic table) are preferred. Under certain reaction conditions certain counter ions may be preferred. For example, in the case of a two-component system comprising a second aqueous phase, B (C ₆ F ₅ ) ₄ is preferred.

Examples of preferred cocatalyst salts include the following.

Ag ⁺ {B (C ₆ F ₅ ) ₄ } ^- (toluene) ₃ , Ag ⁺ {B (C ₆ F ₅ ) ₄ } ^_ (xylene) ₃ , Ag ⁺ {B (3,5-C ₆ H ₃ ( CF ₃ ) ₂ ) ₄ } ^- (toluene), Li ⁺ (B (C ₆ F ₅ ) ₄ } ^- , Na ⁺ {B (3,5-C ₆ H ₃ (CF ₃ ) ₂ ) ₄ } ^- , Li ⁺ {N (SO ₂ CF ₃ ) ₂ } ^- , Li ⁺ (B (C ₆ F ₅ ) ₄ } ^- (Et ₂ O) ₂ , Li ⁺ {N (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ )} ^- , Li ⁺ (NSO ₂ C ₂ F ₅ ) ₂ } ^- , Li ⁺ {N (SO ₂ C ₂ F ₅ ) ₂ } ^- (hydrate), Li ⁺ {N (SO ₂ C ₄ F ₉ ) ₂ } ^- , Li ⁺ {NSO ₂ (CF ₂ ) ₂ SO ₂ } ^- , Ag ⁺ {C (SO ₂ CF ₃ ) ₃ } ^- , Li ⁺ {C (SO ₂ CF ₃ ) ₃ } ^- , Ag ⁺ {CH (SO ₂ CF ₃ ) ₂ } ^- , LI ⁺ {CH (SO ₂ CF ₃ ) ₂ } ^- , Ag ⁺ {BF ₄ } ^- , Na ⁺ {BF ₄ } ^- , Na ⁺ {PF ₆ } ^- , Ag ⁺ {PF ₆ } ^- , Na ⁺ {SbF ₆ } ^- , Ag ⁺ {SbF ₆ } ^- , Na ⁺ {AsF ₆ } ^- , Ag ⁺ {AsF ₆ } ^- , Ag ⁺ {SO ₃ CF ₃ } ^- , Na ^{+ _{{SO 3 CF 3} -,}} Na + {SO 3 C 4 F 9} - , and _{^{Ag + {SO 3 C 4 F}} 9} -.

In addition, other catalysts and cocatalysts can be combined to produce polymers useful for preparing the adhesive compositions of the present invention.

Examples of the one-component Ni catalyst include the following.

{(2,6-diisopropylphenyl) N = C (Me) C (Me) = N (2,6-diisopropylphenyl) Ni (Me) (Et ₂ O)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- ,

{(2,6-dimethylphenyl) N = C (H) C (H) = N (2,6-dimethylphenyl) Ni (Me) (Et ₂ O)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- ,

{(2,6-diisopropylphenyl) N = (1,2-acenaphthylenediyl) = N (2,6-diisopropylphenyl) Ni (Me) (Et ₂ O)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- [where acenaphthylenediyl is as defined above],

{(2,6-diisopropylphenyl) N = C (Me) C (Me) = N (2,6-diisopropylphenyl) Ni (Me) (Et ₂ O)} ⁺ {B (3,5 -C ₆ H ₃ (CF ₃ ) ₂ ) ₄ } ^- ,

{(2,6-dimethylphenyl) N = C (H) C (H) = N (2,6-dimethylphenyl) Ni (Me) (Et ₂ O)} ⁺ {B (3,5-C ₆ H ₃ (CF ₃ ) ₂ ) ₄ } ^- , and

{(2,6-diisopropylphenyl) N = (1,2-acenaphthylenediyl) = N (2,6-diisopropylphenyl) Ni (Me) (Et ₂ O)} ⁺ {B (3 , 5-C ₆ H ₃ (CF ₃ ) ₂ ) ₄ } ^- .

Ni catalysts prepared in situ may also be useful. Ni compounds used in combination with aluminum activators containing alkyl groups are preferred. Examples of the Ni compound include the following.

(2,6-diisopropylphenyl) N = C (Me) C (Me) = N (2,6-diisopropylphenyl) NiBr ₂ ,

(2,6-dimethylphenyl) N = C (H) C (H) = N (2,6-dimethylphenyl) NiBr ₂ , and

(2,6-diisopropylphenyl) N = (1,2-acenaphthylenediyl) = N (2,6-diisopropylphenyl) NiBr ₂ .

Useful aluminum activators include methylaluminoxane (MAO) and Et ₂ AlCl.

Pd and Ni catalysts are characterized by: 1) a number of C ₃ or more alpha-olefin units having an average number of branching points of one or less per alpha-olefin unit, and 2) an average number of branching points of a polymer of 0.01 or more per alpha-olefin unit. It may be useful to prepare a polymer comprising one of a plurality of C ₂ alpha-olefin units, preferably at least 0.05, most preferably at least 0.10. Such polymers may be prepared under a variety of conditions including inert conditions and then incorporated into the adhesive composition. Pd catalysts are preferred for synthesizing polymers because they are resistant to a wide range of polymerization reaction conditions.

Pd monocomponent catalysts and bicomponent catalysts are preferred for adhesives comprising polymerizable compositions, particularly when the polymerizable composition is to be applied in an ambient atmosphere (containing oxygen and varying amounts of water).

Polyolefins prepared using Pd or Ni catalysts can exist in various forms, such as powders, microspheres, pellets, blocks, or solutions, either in the synthesized state or after a post-treatment step, which forms during the preparation of the adhesive composition. It may be in a form useful for handling the polymer.

The one-component and two-component catalysts are present in the polymer formulation and the polymerizable composition in an amount of 0.0001% to about 20%, preferably 0.001% to 5%, most preferably 0.01% to 2% by weight of the total composition. May exist. The polymerization reaction product may contain metal containing residues in the form of metal elements or in the form of inorganic or organometallic compounds, the amount of which is from 0% to 3% by weight of the metal. Post-treatment can be used to remove metal residues from the metal polyolefins formed at the end of the polymerization reaction product. In some cases, as an auxiliary agent useful in carrying out the present invention, a solvent such as methylene chloride may be mentioned.

As is known in the art, additives, auxiliaries and fillers may be added to the polymerizable compositions of the present invention under conditions that do not adversely affect the chemical and physical properties of the adhesives formed or interfere with certain polymerization reactions. . Additives, auxiliaries and fillers include, but are not limited to, glass or ceramic microspheres or microbubbles, pigments, dyes or other polymers. Adjuvants may be present in the composition in amounts of 0.1% to 90% by weight. The same adjuvant may be present in the adhesive composition of the present invention. Adjuvants are advantageously added to the monomer prior to the polymerization reaction. A wide range of auxiliaries can be incorporated into the adhesive compositions of the present invention by incorporating a wide range of auxiliaries into preformed polymers, including those that may adversely affect the polymerization reaction.

Particularly useful additives, including tackifying resins, plasticizers, waxes, crystallization promoters and oils, can be used to provide adhesive properties such as adhesion to various surfaces, adhesion under various conditions, useful temperature ranges, flexibility, opening times, morphological characteristics Etc. can be modified. Examples of such additives include tackifiers such as Escorez ^™ resin (Exxon Chemical Company, Houston, Texas), Wingtack ^™ resin (e.g., Wingtack Extra ^™ ) from Goodyear (Akron, Ohio). Goodyear Tire and Rubber Company), Piccolyte S25 ^TM , Foral AX ^TM , Piccofyn A135 ^TM , Piccolyte S15 ^TM and Regalrez 1126 ^TM (Hercules Incorporated, Wilmington, Delaware) Arkon P115 ^TM and Arkon P140 ^TM (Arakawa Chemicals, Inc., Inc., Chicago, Illinois, on behalf of Arakawa Chemical Industries Limited, Japan) sold by Arakawa, oils such as Shellflex 371 ^TM ( TX shell Chemical Company, of Houston, product) and waxes, such as polyethylene and polypropylene waxes, specifically Vestowax ^TM (New Jersey Piece Kata hyulseu America, Inc. Products of the way material), Epolene ^TM (can be a Kingsport, Tennessee, Eastman Chemical Products of the material) and Escomer ^TM (Texas, Exxon Chemical Company, of Houston-based products) material. Various resins, waxes and oils are commercially available from these and other sources, and the additives used in the present invention are not limited to the examples listed above.

Relatively acidic organic compounds such as phenol and carboxylic acid may be present in the polymerizable composition of the present invention without adversely affecting subsequent polymerization reactions. Accordingly, a polymerizable composition of alpha-olefin monomers further comprising a steric independence phenolic antioxidant (e.g. Irganox 1010 ^™ available from Ciba-Geigy Corporation, Hodoon, NJ) is useful in the method of the present invention. . Three-dimensional non-free phenolic antioxidants useful in practicing the present invention are well known in the art and are described in Jess Edenbaum, Plastics Additives and Modifiers Handbook , Van North Rhine-Rhold, New York (1992) pp. 193-207. It is advantageous to add sterically rich phenolic antioxidants to the polymer to modify polymer performance and maturation. It is particularly advantageous to add antioxidants to the liquid monomers. In the case of monomers, the mixing is easier than in the case of viscous polymers. It is particularly advantageous to add antioxidants to the polymerizable compositions useful in the process of the invention, since it is difficult or impossible to add antioxidants later in the process.

Other phosphorus containing antioxidants such as phosphine or phosphite are also known as additives used in polymers. Such incidental antioxidants stop the polymerization and are not useful for adding to the monomer prior to the polymerization (as in the case of the polymerizable composition), but it may be useful for the polymer to be added to the previously prepared adhesive composition. have. Sulfur containing compounds such as thiols, like strong oxidants such as bleach (sodium hypochlorite), also stop the polymerization reaction.

The polymerization reaction for preparing the polymers useful in the adhesive composition of the present invention can be carried out at various temperatures. The reaction temperature is preferably -78 ° C to + 35 ° C, more preferably -40 ° C to + 25 ° C, and most preferably -10 ° C to + 20 ° C. For reactions performed in an aqueous liquid medium, a minimum reaction temperature of about −5 ° C. is preferred. Temperatures above about 40 [deg.] C. may deactivate the catalyst, and the polymerization reaction of the alpha-olefin monomer is exothermic, so it is desirable to control the heat well. It is particularly advantageous to attempt to control the reaction temperature using a second aqueous phase as a heat sink.

The polymerization reaction to provide a polymer useful as the adhesive composition of the present invention can be carried out at atmospheric pressure, and especially at a pressure above atmospheric pressure when one of the monomers is a gas. However, liquid monomers are preferred in order to reduce the costs associated with pressurized reaction vessels. Liquid monomers are preferred for methods of adhering materials using polymerizable compositions. Particular preference is given to monomers having a boiling point of at least about 100 ° C., for example 1-octene and higher alpha-olefin monomers.

The method of adhering the material using the polymerizable composition can be carried out at a temperature in the range of -40 ° C to 35 ° C, preferably -20 ° C to 25 ° C. The exotherm of the polymerization reaction may cause some heating during the polymerization reaction in carrying out the process of the invention, but the adherend material will adsorb and remove some of this heat. The rate and temperature of the polymerization can be controlled by varying the amount of catalyst, the lower the amount of catalyst the slower the exotherm and the lower the overall temperature.

In the polymerizable composition of the method of the present invention, and during the polymerization reaction carried out to prepare a polymer useful in the adhesive composition of the present invention, water may be present in an amount of 0.001% to 99% by weight of the total composition. Smaller amounts of water may be present if care is required to dry the monomer or any organic solvent. Water is preferably present in the monomer as it is supplied in naturally occurring amounts and handled in air. For example, water can be dissolved in 1-hexene up to about 480 ppm at room temperature, such concentrations being within the scope of the present invention. The monomers are often supplied in a state containing varying amounts of water ranging from 0.001% by weight to the maximum solubility of the water in the monomers, depending on the temperature, the particular monomer used, ambient humidity, storage conditions and the like. Any solvent similarly contains varying amounts of water. Oxygen may be present in an amount from 0.001% to about 2% by weight of the total composition. The monomers and solvents may contain various amounts of oxygen from the atmosphere depending on the temperature, the specific monomers or solvents, the storage conditions, and the like. It may also be present in the atmospheric content in the environment around the polymerizable mixture. It is advantageous to exclude the cost and processing steps required to dry and deoxygenate monomers and solvents.

Polymers useful as the adhesive composition of the present invention include many C₃Alpha-olefin polymers containing the above alpha-olefin units and having an average number of branching points per one alpha-olefin unit of the polymer are included. While not intending to adhere to a particular theory and not admitting that analytical techniques are inadequate for determining all structural features, particularly collateral features, at the skill level of the art, polymers obtained using the catalysts of the present invention Two types of repeat units, i.e. {-CH₂-CHR⁴-}_x And {-(CH₂)_n-}_yIt is considered to have as a main component. Where n is the number of carbon atoms in the alpha-olefin monomer used to prepare the polymer, and R⁴Is {CH₃(CH₂)_(n-3)-}to be. Branched unit {-CH₂-CHR⁴The number of-} is less than the total number of monomer units in the polymer. That is, x is 0.01 to 0.99, preferably 0.20 to 0.95, more preferably 0.40 to 0.90, and (x + y) is 0.90 to 1.00. The polymer structure will vary as the monomer (s) used in the polymerizable composition vary. For example, polymers made from 1-octene (ie n = 8) may be {-CH₂-CH (n-hexyl)-}_xAnd {-(CH₂)₈-}_yIt has a structure containing as a main component. Where x is in the range of 0.45 to 0.70 and (x + y) is in the range of 0.90 to 0.98. As another example, a polymer made from 1-hexene (ie n = 6) may be selected from {-CH₂-CH (n-butyl)-}_xAnd {-(CH₂)₆-}_yIt has a structure containing as a main component. Where x is in the range of 0.50 to 0.75 and (x + y) is in the range of 0.90 to 0.98. Polymers made from ethylene have two types of repeat units, namely {-CH₂-CHR⁵-}_pAnd {-(CH₂)₂-}_qWith R as the main component, where R⁵Is a straight or branched chain alkyl group having 1 to 2 carbon atoms, p is at least 0.01, preferably at least 0.05, most preferably at least 0.10, and p + q is in the range from 0.890 to 0.98. The commonly used NMR spectroscopic method is R⁵Although it is insufficient to measure the maximum value with respect to the number of carbon atoms in the inside, the value is preferably 100 or less. Those skilled in the art will appreciate that modifications to the polymerizable composition may affect the polymer structure, for example, by any solvent or aqueous phase or by the type and amount of catalyst selected and the method of polymerization. The polymer structure can affect polymer properties such as crystallinity or modulus.

Polyolefins to be prepared using organometallic Pd or Ni catalysts have physical properties that can be distinguished from polymers prepared using Ziegler-Natta or metallocene catalysts, especially in terms of crystallinity. Crystallinity can be detected as a melt transition in differential scanning calorimetry (DSC) of polyolefins. The crystallinity of a given sample depends on the history of the sample, in particular the thermal history, and the quantitative measure of the amount of crystallinity depends somewhat on the measurement technique. Even so, polyolefins prepared using organometallic Pd or Ni catalysts are readily distinguishable. For example, polyoctene samples prepared using organometallic Pd catalysts exhibit a wide range of melt transitions when using heat of fusion in the range of about 30 J / g to 60 J / g. Polyoctenes made using Ziegler-Natta catalysts have little or no melt transition detection. Similar comparisons can be made to other polyolefins made using other monomers. In addition, polyolefins prepared using organometallic Pd and Ni catalysts and alpha-olefin monomers including 1-butene, 1-pentene, 1-hexene, 1-decene, 1-dodecene, 1-octadecene and 1-icocene Melt transition has also been detected for. While not intending to adhere to a particular theory, the crystallinity observed in polyolefins prepared using organometallic Pd and Ni catalysts is due to the presence of repeating units {-(CH ₂ ) _n- } in the polymer backbone (described above) It is thought to be.

For many applications, high molecular weight polymers are highly desirable (M _w 90,000, preferably at least up to about 10,000,000, preferably from 100,000 up to about 2,000,000), and improve the performance of the product. High molecular weight polymers can be obtained, for example, by appropriate choice of catalyst to monomer ratio. In addition, the high molecular weight polymer can be obtained by continuing until the polymerization reaction is completed, that is, until almost all of the effective monomers are consumed. However, for other uses, low molecular weight polymers having M _w of 5,000 to 90,000 are preferred. Such low molecular weight monomers can be obtained, for example, by using a higher catalyst-to-monomer ratio as appropriate, generally higher than that used to obtain high molecular weight polymers (ie the more catalyst used, the lower the molecular weight). . In addition, low molecular weight polymers can be obtained in reactions that incompletely convert monomers into polymers, optionally by adding reagents that relax or inactivate the catalyst.

The adhesive composition of the present invention comprises 1) an alpha-olefin polymer comprising a plurality of C ₃ or more alpha-olefin units, wherein the average number of branching points of the polymers is 1 or less per alpha-olefin unit) and 2) a plurality of One of the C ₂ alpha-olefin units, wherein the average number of branching points of the polymer is at least 0.01, preferably at least 0.05 and most preferably at least 0.10 per alpha-olefin unit. The adhesive composition of the present invention may further include an additive, and examples of the additive may include tackifying resins, plasticizers, waxes, crystallization accelerators, and oils, and the adhesive composition may be used for adhesion to various surfaces, adhesion under various conditions, Adhesive properties such as useful temperature ranges, flexibility, opening times, morphological characteristics and the like can be modified. Examples of such additives are described above.

When the adhesive composition is applied to the surface of the adherend under moderate pressure (eg hand pressure) at about −40 ° C. to 30 ° C., it is useful as a pressure sensitive adhesive for structures such as tapes and labels. If the adhesive composition is not tacky at about 30 ° C., but at high temperatures wets the surface of the adherend well, it is a hot melt adhesive, which is a temperature of at least 30 ° C., generally from about 30 ° C. to 400 ° C., more preferably 40 ° C. It is an adhesive useful for applying to the surface of the adherend at a temperature of from 300 ° C.

The temperature range used to distinguish between the pressure sensitive adhesive and the hot melt adhesive is not limited, and in some cases, the temperature range may overlap. Hot melt adhesives are applied to a substrate to be bonded in the form of a melt (liquid having a flowable viscosity), but solid in the temperature range required for a given application (usually room temperature, but not necessarily room temperature), and is bonded to the substrate. It is an adhesive that solidifies immediately after cooling. The pressure sensitive adhesive does not change its physical state from the initial adhesion step, i.e., from the application step to the final failure of the adhesive bond, remains permanently deformable and can be deformed with only a little pressure. Pressure sensitive adhesives are generally defined as adhesives that are permanently tacky at room temperature and that adhere firmly to the surface with simple contact.

Hot melt adhesives are useful to apply as a melt, for example in the form of a bead, wood, metal or polymer film or article of melt that is transferred to a sheet from a hot nozzle or "gun". The hot melt adhesive composition may be prepared in the form of a film to apply heat and / or pressure to the surface of the adherend as in the case of the lamination process.

The adhesive composition of the present invention can also be applied to the surface of the adherend in the form of a polymerizable composition. Wetting of the surface of the adherend occurs at an operating temperature, preferably from about -40 ° C to 30 ° C, and specifically, small surface shapes can be wetted by polymerizable compositions having a lower viscosity than the pressure sensitive adhesive or hot melt adhesive composition. . The viscosity of the polymerizable adhesive composition is from 0.2 centipoise to 300,000 centipoise, preferably from 0.2 centipoise to 100,000 centipoise, depending on the type and amount of additives (including polymers such as alpha-olefin polymers) present.

Adhesive compositions applied as polymerizable compositions are commonly referred to as glues or curable adhesives. The present invention provides a method of adhering a material using a polymerizable composition, ie a composition consisting of an effective amount of an organometallic catalyst comprising at least one alpha-olefin monomer and a Group VIII metal, preferably Pd. The method includes applying a polymerizable composition to at least one adherend surface and causing a polymerization reaction. The adhesive composition may be applied to the same or different two or more adherend surfaces. Sandwich structures in which two adherends are bonded using an adhesive composition are also included within the scope of the present invention.

The present invention relates to 1) a plurality of C ₃ or more alpha-olefin units, wherein the average number of branching points of the polymer is one or less per one alpha-olefin unit, and 2) a plurality of C ₂ alpha-olefin units, wherein the polymer Provides a method of adhering materials using an adhesive composition consisting of a polymer comprising at least 0.01, preferably at least 0.05 and most preferably at least 0.10 per alpha-olefin unit of The method includes applying the adhesive composition to one or more adherend surfaces. In one variant, the pressure sensitive adhesive composition is optionally pressurized by hand, at a temperature of about -40 ° C to 100 ° C, preferably -40 ° C to 40 ° C, by using an applicator or by means of a machine Applied to the surface. In some cases, the pressure sensitive adhesive (PSA) is formulated so that it can later be preferably removed cleanly from the adherend. In another variant, the hot melt adhesive composition is optionally pressurized at a temperature of about 30 ° C. to 400 ° C., preferably 40 ° C. to 300 ° C., to provide a tool or device or nozzle (e.g. Or by extruding through a die, or by heating a structure consisting of adhesive and adherend, to one or more adherend surfaces in the form of molten beads, droplets, powders or films. Other means of transferring the hot material to the surface of the adherend are well known to those skilled in the art. In another variation, the film comprising the hot melt adhesive composition is placed in contact with the adherend surface of the lower bag or more by optionally applying pressure at high temperature, typically 40 ° C. to 400 ° C.

Particularly useful are methods of applying the polymerizable composition to one or more adherend surfaces and causing the polymerization reaction while in contact with the surface (s). By this means, particularly good contact between the polymerizable adhesive composition and the adherend is achieved. The polymerizable adhesive composition, preferably having a low viscosity in the range of 0.2 centipoise (cP) to 100,000 centipoise, is preferably applied as a liquid at ambient temperature to wet the surface of the adherend and commonly found gaps in the solid surface. And flow into the unevenness. Lower viscosities allow for better wetting of the substrate to be bonded, thereby providing better adhesion. The mechanism of action of the adhesive, known as mechanical interlocking, occurs when the surface of the substrate on which the adhesive is electrodeposited contains pores into which the adhesive enters or protrusions around which the adhesive solidifies. In this case, the adhesive acts as a mechanical fixing means. Physical bonding can occur as adhesive molecules penetrate into the substrate by diffusion. The liquid adhesive can dissolve and diffuse into the substrate. The degree of diffusion depends on the affinity that different types of molecules have for each other.

Since the polymerizable adhesive composition of the present invention contains liquid hydrocarbon monomers (or mixtures thereof, optionally including additives which do not interfere with the polymerization reaction) which are almost non-polar, it is possible to wet the substrate having a low surface energy well in some cases. Although pretreatment may be used, it is possible to obtain the advantages as described above due to excellent wetting and compatibility without the need for pretreatment of the surface. The polymerizable adhesive composition of the present invention can be used on a porous surface or on a smooth surface.

The present invention provides an adhesive comprising a crosslinked alpha-olefin polymer. In some cases, the crosslinked adhesive composition provides better adhesive performance. The crosslinking can be carried out by copolymerization with a polyfunctional monomer during the polymerization reaction or by a chemical reaction occurring after the polymerization reaction, caused by heating means or by a high energy source such as actinic radiation, including electron beams, gamma rays or ultraviolet rays. Can be. Adhesive compositions comprising crosslinked polymers are also included within the scope of the present invention.

In one embodiment, a method using high energy radiation, preferably electron beam irradiation, of the adhesive composition is used. The adhesive composition of the present invention may be crosslinked via electron beam irradiation, preferably at a capacity in the range of 20 MRad or less, more preferably 10 MRad or less. It is advantageous for the crosslinked adhesive compositions to be free of added chemical crosslinking agents, where such chemical crosslinking agents, if present, may impair the chemical or physical properties of the adhesive, or may be disadvantageous for subsequent use, for example due to coloring or dissolution. The electron beam crosslinking method may also be carried out after fabricating or otherwise processing the adhesive composition, for example after processing by extrusion, solvent casting, coating, molding, etc., thereby providing a crosslinked structure such as a film. Other useful high energy sources are known and their use is also within the scope of the present invention.

In another embodiment, ultraviolet (UV) irradiation is used, preferably further comprising adding at least one UV activated crosslinker. In another embodiment, a method comprising thermal crosslinking is used, which preferably further comprises adding at least one thermally activated crosslinking agent. While not intending to adhere to the theory, it is preferred to mix with the polymer prior to investigating additives that absorb ultraviolet light and subsequently react to provide radicals by homolytic desorption and / or hydrogen removal. Typical additives include trihalomethyl substituted s-triazines (eg 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) , Aryl alkyl ketones (eg, acetophenone, benzoin ether and benzyl ketals), and diaryl ketones (eg benzophenone and anthraquinone). Similarly, additives such as peroxides that generate radicals by heat are useful for thermal crosslinking reactions. Other useful additives are well known to those skilled in the art, and these are also included within the scope of the present invention. The method of crosslinking by ultraviolet or thermal activation is preferred for the resulting structures and the specific processes required to treat the uncrosslinked polymer to provide a film or fiber-like form prior to crosslinking, such as solution or extrusion processes.

The adhesive compositions of the present invention are disposable or recyclable, such as in a tube or between release liners, as a coating or layer on one or more flexible or rigid supports, on a variety of structures, such as supported or free standing films. It may be applied and used as a molded product in a container or delivery system or kit, as a powder, or as a mixture thereof. As a method of apply | coating an adhesive composition to a support body or a backing, solvent coating, extrusion, spraying, and the modification and combination of these methods are mentioned. Structures comprising the adhesive composition of the present invention are also included within the scope of the present invention. Useful adherends include metals, textiles, polymers, in particular polyolefins (e.g., high density polyethylene, linear low density polyethylene, low density polyethylene, polypropylene, and other polymers with low surface energy, such as poly (tetrafluoroethylene) and celluloses, Examples include wood, paper and other wood-derived products (eg cardboard).

Hereinafter, the purpose and advantages of the present invention will be further described. However, the specific materials and amounts used in the examples described below and other conditions and details do not limit the scope of protection of the present invention.

Unless otherwise noted, all preparations and examples were carried out in air, the reaction reagents were used as supplied and handled in air, attempting to reduce or remove oxygen or water in the reaction reagents, solvents or glass vessels. Did not. The solvent used is of conventional reagent grade and not of anhydrous grade. "Ambient temperature" is about 23 ° C. Throughout the examples the abbreviation C _z is used to refer to alpha-olefins having z carbon atoms. Thus, C ₂ means ethylene, C ₃ means propylene, C ₆ means 1-hexene, C ₈ means 1-octene and the like. All chemicals were purchased from Aldrich Chemical Company (Milwaukee, WI) unless otherwise noted.

Molecular weight was measured by gel permeation chromatography using polystyrene as a reference material.

Preparation of the catalyst

Throughout the examples, the material referred to as Pd-A was prepared according to known procedures, {(2,6-diisopropylphenyl) N = C (Me) -C (Me) = N (2,6- It refers to diisopropylphenyl) PdMeCl.

A. Ligands (2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ Manufacturing

Such ligands are described in H. t. Dieck, M. Svoboda, T. Gracer, Z. Naturforsch . 36b, 823-832. A mixture consisting of 625 ml of methanol, 41.7 g of 2,3-butanedione, 171.75 g of 2,6-diisopropylaniline and 6.75 g of formic acid was prepared in air and then stirred at ambient temperature for about 18 hours under a nitrogen atmosphere. A yellow precipitate formed, which was collected by filtration. Precipitation was recrystallized from hot ethanol such that {2,6-C ₆ H ₃ (i-Pr) ₂ } N = C (CH ₃ ) C (CH ₃ ) = N {2,6-C ₆ H ₃ (i -Pr) ₂ } 152.6 g were obtained. This ligand was handled and stored in air.

B. Synthesis of (1,5-cyclooctadiene) Pd (Me) Cl

Such compounds are described in R. Rulk, JM Ernst, AL Spec., C. Elsevier, PWNM Van Miuben, K. Vrieze Inorg. Chem. , 1993, 32, 5769-5778. All procedures were performed in a dry nitrogen atmosphere. 49.97 g of (1,5-cyclooctadiene) PdCl ₂ , a pale yellow solid, was placed in 1 l of deoxygenated anhydrous CH ₂ Cl ₂ . While stirring, 37.46 g of Me ₄ Sn was added and the reaction mixture was stirred at ambient temperature for a total of 4 days. A black solid (presumably Pd metal) was formed, which was optionally removed by filtration through a fuller's Earth (filter aid) pad during this period. If the reaction solution was light yellow, it was filtered once more and the solvent was removed. 63.94 g of white (1,5-cyclooctadiene) Pd (Me) Cl were obtained. It is preferable to handle this compound in an inert atmosphere.

C. {{2,6-C ₆ H ₃ (i-Pr) ₂ } N = C (CH ₃ ) C (CH ₃ ) = N {2,6-C ₆ H ₃ (i-Pr) ₂ }} Pd (CH ₃ ) Cl, i.e., preparation of Pd-A

The neutral organometallic compounds are described in LK Johnson, CM Killian, M. Brookhart, J. Am. Chem. Soc. , 1995, 117, 6414-6415 and supplementary materials. In an inert atmosphere (nitrogen), 31.64 g of (1,5-cyclooctadiene) Pd (Me) Cl (Synthesis B) was placed in 375 ml of deoxygenated anhydrous diethyl ether. (1,5-cyclooctadiene) Pd (Me) Cl was not completely dissolved. This mixture contains {2,6-C ₆ H ₃ (i-Pr) ₂ } N = C (CH ₃ ) C (CH ₃ ) = N {2,6-C ₆ H ₃ (i-Pr) ₂ } ( 48.31 g of Synthesis A) was added. An orange precipitate formed immediately. After stirring the reaction mixture for about 18 hours, {{2,6-C ₆ H ₃ (i-Pr) ₂ } N = C (CH ₃ ) C (CH ₃ ) = N {2,6-C ₆ H 44.11 g of ₃ (i-Pr) ₂ }} Pd (CH ₃ ) Cl were collected by filtration. This compound was handled and stored in air.

D. Synthesis and Separation of One-Component Catalysts

This synthesis example is {(2,6-diisopropylphenyl) N = C (Me) -C (Me) = N (2,6-diisopropylphenyl) PdMe (methyl t-butyl ether)} ⁺ {N It is described how to prepare (SO ₂ CF ₃ ) ₂ } ⁻ .

A solution of 12.44 g of LiN (SO ₂ CF ₃ ) ₂ (HQ 115 ^TM , sold by 3M, St. Paul, Minn.) And 7.36 g of AgNO _{3 in} 350 ml of deionized water was dissolved in 350 ml of methyl t-butyl ether. Stir with 22.13 g of Pd-A solution. Discoloration appeared within minutes. The ether layer was separated from the solid formed with water, washed with two portions of water and then dried in vacuo to find {(2,6-diisopropylphenyl) N = C (Me) -C (Me) = N (2 , 6-diisopropylphenyl) PdMe (methyl t- butyl _{^{ether)} + {N (SO 2}} CF 3) 2} - 30.79 g was obtained with a theoretical yield of 86%. NMR spectroscopy confirmed the identity of the compound.

Similarly, a Pd catalyst was prepared containing the following counter ions: {C (SO ₂ CF ₃ ) ₃ } ^- , {B (C ₆ H ₅ ) ₄ } ^- , {B {3,5-C _{6 H 3 (CF 3) 2}} 4} -, (SO 3 C 4 F 9) -, {N (SO 2 C 2 F 5) 2} - and _{{NSO 2 (CF 2) 2} SO 2} -. In another preparation, diethyl ether was used instead of methyl t-butyl ether, and the one-component catalyst obtained at this time included diethyl ether.

Preparation of Polymer

E. Preparation of Polymers Using Two-Component Catalysts

A mixture consisting of 1351 g of water, 900 g of 1-octene and 1.44 g of Pd-A in 67 g of CH ₂ Cl ₂ was placed in a large vessel. The mixture was cooled to approximately 0 ° C. and 3.23 g of Li {B (C ₆ H ₅ ) ₄ } (Example 1) were added and the mixture was kept at 0 ° C. to 4 ° C. with shaking. After about 18 hours, the solid mass of polymer was filled into the container and the yield based on the weight of the polymer was determined to be 65% after 2 days drying at 50 ° C. in a vacuum oven.

Polymer analysis: M _w 3.99 × 10 ⁵ , M _n 2.24 × 10 ⁵ .

F. Preparation of Polymer

In this preparation, the catalyst was mixed with monomers and optional solvents as shown in Tables 1A and 1B below. The polymerization reaction was carried out at the specified temperature for the designated time. All procedures were performed in air and no attempt was made to remove water from monomers or solvents.

In this preparation example, the one-component catalyst is represented by the formula {{(2,6-C ₆ H ₃ (isopropyl) ₂ ) N = C (Me) C (Me) = N (2,6-C ₆ H ₃ (iso) Propyl) ₂ )} Pd (Me) (ether)} ⁺ Q ⁻ , where ether and Q are as shown in Tables 1a and 1b below.

In Tables 1a and 1b, in the “Reaction Conditions” column, the reaction conditions are described as follows: General Procedure (A-D Procedures) / Temperature / Reaction Time (hr) in ° C. Specific procedures are described below.

(A): contained a one-component catalyst and various amounts of liquid monomers and a CH ₂ Cl ₂ solvent. In a specific procedure, the weight ratio of monomer to CH ₂ Cl ₂ is as follows: A-1, 1: 1; A-2, 3: 1; A-4, 7.7: 1; A-5, 1: 2; A-6, 3.8: 1; A-7, 5 parts by weight of each comonomer: 1 part by weight of CH ₂ Cl ₂ ; And A-8, 5: 1. The reaction mixture was initially homogeneous and in some cases the polymer precipitated, depending on the monomer, temperature and degree of reaction. In A-3, the one-component catalyst was dissolved in CH ₂ Cl ₂ in a pressure vessel and gaseous monomer was added, but the exact amount of monomer fed was not recorded. For samples where the reaction time was known as unknown time, the progress of the reaction was not carefully monitored and the reaction time was more than 100 hours, but not exactly known.

(B): 1-component catalyst, 4 weight part of ethyl acetate, and 1 weight part of monomers were contained. The reaction mixture was initially homogeneous but immediately began to precipitate out of solution.

(C): A two phase (monomer and water) mixture containing a two component catalyst as described in Preparation Example E was contained.

(D): contained a one-component catalyst and a monomer without a solvent. The reaction mixture formed a solution and the polymer precipitated out of solution upon formation. The progress of the reaction was not carefully monitored and the reaction time was over 100 hours, but not exactly known. D ^* contained a one-component catalyst and 1 weight part of two types of comonomers, respectively.

In the corresponding column of the table "mono / Pd" indicates the amount of monomer in g divided by the amount of Pd in moles.

In the last two samples of Table 1a, the copolymerization reaction was carried out by mixing the two or more comonomers shown together with the one-component catalyst in the specified amounts.

Monomer catalyst Reaction conditions Mono / Pd Polymer molecular weight 1 or 2 components ether Q M _w M _n M _w / M _n C ₄ 1 ingredient Me t-Bu O N (SO ₂ CF ₃ ) ₂ A-3 / 0-25 / 22 Unknown 1.04 × 10 ⁵ 5.55 × 10 ⁴ 1.88 C ₅ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-1 / 0/68 2.55 × 10 ⁵ 2.40 × 10 ⁵ 8.11 × 10 ⁴ 2.95 1 or 2 components ether Q M _w M _n M _w / M _n C ₆ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-1 / 0/68 2.63 × 10 ⁵ 5.20 × 10 ⁵ 2.67 × 10 ⁵ 1.94 C ₆ 1 ingredient Me t-Bu O N (SO ₂ CF ₃ ) ₂ A-1 / 0/18 4.01 × 10 ⁵ 1.35 × 10 ⁵ 4.44 × 10 ⁴ 3.04 C ₆ 1 ingredient Me t-Bu O N (SO ₂ CF ₃ ) ₂ B / 0-4 / 68 4.16 × 10 ⁵ 3.49 × 10 ⁵ 8.23 × 10 ⁴ 4.23 C ₈ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-1 / 0/66 2.62 × 10 ⁵ 6.64 × 10 ⁵ 3.05 × 10 ⁵ 2.17 C ₈ 1 ingredient Me t-Bu O N (SO ₂ CF ₃ ) ₂ B / 0-4 / 90 6.07 × 10 ⁵ 6.78 × 10 ⁵ 1.30 × 10 ⁵ 5.21 C ₈ 1 ingredient Me t-Bu O N (SO ₂ CF ₃ ) ₂ A-1 / 10/23 1.57 × 10 ⁵ 3.55 × 10 ⁵ 1.21 × 10 ⁵ 2.94 C ₈ 2-component none B (C ₆ F ₅ ) ₄ C / 0-4 / 18 3.51 × 10 ⁵ 3.99 × 10 ⁵ 2.24 × 10 ⁵ 1.78 C ₈ 1 ingredient Et ₂ O SbF ₆ A-1 / 0/68 8.97 × 10 ⁴ 1.16 × 10 ⁵ 8.66 × 10 ⁴ 1.34 C ₈ 1 ingredient Et ₂ O N (SO ₂ C ₄ F ₉ ) ₂ A-2 / 0/68 2.86 × 10 ⁵ 1.06 × 10 ⁵ 1.67 × 10 ⁵ 6.32 C ₈ 1 ingredient Et ₂ O C (SO ₂ CF ₃ ) ₃ A-1 / 0/68 1.01 × 10 ⁵ 1.47 × 10 ⁵ 1.00 × 10 ⁵ 1.47 C ₁₀ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-1 / 0/68 2.70 × 10 ⁵ 6.76 × 10 ⁵ 1.92 × 10 ⁵ 3.53 C ₁₀ 1 ingredient Me t-Bu O N (SO ₂ CF ₃ ) ₂ B / 0-4 / 68 4.16 × 10 ⁵ 5.48 × 10 ⁵ 1.63 × 10 ⁵ 3.36 C ₁₀ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-1 / 0/70 2.62 × 10 ⁵ 6.89 × 10 ⁵ 2.43 × 10 ⁵ 2.82 C ₁₂ 1 ingredient Me t-Bu O N (SO ₂ CF ₃ ) ₂ A-1 / 0/68 4.01 × 10 ⁵ 4.84 × 10 ⁵ 1.93 × 10 ⁵ 2.51 C ₁₈ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-1 / 23 / (unknown) 1.76 × 10 ⁵ 3.36 × 10 ⁵ 1.30 × 10 ⁵ 2.58 C ₂₀ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-4 / 23 (unknown) 4.40 × 10 ⁵ 1.00 × 10 ⁶ 3.91 × 10 ⁵ 2.57 Cyclopentene 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ D / 0 to 23 / (unknown) 8.84 × 10 ⁵ 2.02 × 10 ⁵ 1.08 × 10 ⁵ 1.87 Cyclopentene 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-5 / 23/24 9.17 × 10 ⁴ 1.01 × 10 ⁵ 4.50 × 10 ⁴ 2.48 C ₇ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-8 / 23 / unknown 2.78 × 10 ⁵ 9.06 × 10 ⁴ 5.98 × 10 ⁴ 1.52 C ₉ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-6 / 23 / unknown 2.56 × 10 ⁵ 1.12 × 10 ⁵ 6.99 × 10 ⁴ 1.60

Monomer catalyst Reaction conditions Mono / Pd Polymer molecular weight 1 or 2 components ether Q M _w M _n M _w / M _n C ₁₁ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-6 / 23 / unknown 2.56 × 10 ⁵ 4.01 × 10 ⁵ 1.68 × 10 ⁵ 2.39 C ₁₃ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-6 / 23 / unknown 2.56 × 10 ⁵ 1.17 × 10 ⁵ 7.87 × 10 ⁴ 1.48 C ₁₄ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-6 / 23 / unknown 2.56 × 10 ⁵ 2.23 × 10 ⁵ 1.30 × 10 ⁵ 1.71 C ₁₅ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-6 / 23 / unknown 2.56 × 10 ⁵ 9.86 × 10 ⁴ 5.64 × 10 ⁴ 1.75 C ₁₆ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-6 / 23 / unknown 2.56 × 10 ⁵ 2.67 × 10 ⁵ 1.36 × 10 ⁴ 1.96 C ₁₇ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-6 / 23 / unknown 2.56 × 10 ⁵ 1.46 × 10 ⁵ 8.60 × 10 ⁴ 1.89 C ₁₉ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-6 / 23 / unknown 2.56 × 10 ⁵ 7.96 × 10 ⁵ 2.81 × 10 ⁵ 2.84 C ₆ , cyclopentene 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ D ^* / 23 / unknown 8.53 × 10 ⁵ 1.05 × 10 ⁵ 5.79 × 10 ⁴ 1.81 C ₆ , C ₈ , C ₁₀ , C ₁₂ 1 ingredient Et ₂ O B (C ₆ F ₅ ) ₄ A-7 / 23/48 2.18 × 10 ⁵ 4.00 × 10 ⁵ 1.36 × 10 ⁵ 2.93

In this way, polymers prepared by removing solvents can optionally be used to prepare adhesive compositions.

G. Preparation of Polymer in Microsphere Form in the Presence of Aqueous Media

In this production example, a microsphere-shaped polymer was prepared. Pd-containing catalyst dissolved in deionized water, alpha-olefin monomer, small amount of CH ₂ Cl ₂ {((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i-Pr) ₂ ))} Pd (Me) (Et ₂ O)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- (Preparation D) and interface Polymer microspheres were prepared by mixing the actives at the specified temperature and maintaining the mixture at the temperature for the specified time. Polymer microspheres were obtained. The amounts of monomers, water, surfactants and other optional additives are shown in Tables 2a and 2b below. The mixing order was variable, and the effect observed to change the mixing order on the laboratory scale production process was that only a solid catalyst was added to the water / monomer mixture to incompletely deliver the catalyst onto the monomers, and some catalysts It could be left in three solid phases. Initial mixing was performed by a stirring method using a magnetic stirring bar (B) or a method by shaking (S). Some samples were likewise stirred intermittently (I) or continuously (C) or none at all (N) during the polymerization reaction. In general, for similar samples, higher shear rates and increased agitation resulted in smaller microspheres. Microspheres (MS) were irradiated with a microscope and the size thereof was measured, which was expressed as a diameter range observed under the microscope under a 92x magnification.

In Tables 2A and 2B below, DDSNa is the dodelyl sulfate sodium salt.

(nd) means that the value specified for the sample was not measured.

Wingtack Plus ^™ is a resin available from Goodyear Tire & Rubber Company, Akron, Ohio. This resin was dissolved in the alpha-olefin monomer and the solution was added to other materials in the sample.

ALS is ammonium lauryl sulfate and the weight described is the use weight of an ALS gel with 29% solids in water, which is available from Stepanol AM-V ^™ from Stefan Company, Northfield, Illinois.

Colloidal silica is 30% Nalco 1130 ^™ in water (Nalco Chemical Company, Naperville, Ill.).

(ag) describes that in the sample examined under the microscope, the largest spheres appear to aggregate with smaller spheres.

In sample G-10, a two-component catalyst was used. ((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (soluble in 2.210 g of CH ₂ Cl ₂ ) 36 mg of i-Pr) ₂ )) Pd (Me) Cl (Preparation C) was added to 8.032 g of 1-octene, which was added to a mixture of 112 mg of LiB (C ₆ F ₅ ) ₄ in 12.131 g of water. The reaction exothermed after about 6 minutes and at high temperatures the catalyst was deactivated to stop further effective polymerization.

Sample Monomer g Water g Surfactant g Cat / CH ₂ Cl ₂ mg / g G Temperature / hour ℃ / hr Stirring Microsphere size micron G-1 C ₆ , 20 117.5 DDSNa, 0.8 200/20 (none) 0/17 S, N 10-130 G-2 C ₆ , 20 60 DDSNa, 0.4 229 / 1.6 (none) 0/17 S, C 10-80 G-3 C ₆ , 20 60 DDSNa, 0.4 115 / 1.3 (none) 0/41 S, C 15-180 G-4 C ₆ , 5.023 15.003 DDSNa, 0.102 57 / 0.687 (none) 0/18 S, C 10-140 G-5 C ₈ , 5.025 14.998 DDSNa, 0.103 58 / 0.795 (none) 0/18 S, C 10-70 G-6 C ₆ , 5.076 15.056 DDSNa, 0.101 63 / 0.562 Wingtack Plus, 0.753 0/18 S, C 10-50

Sample Monomer g Water g Surfactant g Cat / CH ₂ Cl ₂ mg / g G Temperature / hour ℃ / hr Stirring Microsphere size micron G-7 C ₈ , 5.016 14.998 DDSNa, 0.103 61 / 0.978 Wingtack Plus, 0.756 0/18 S, C 10-150 (ag) G-8 C ₈ , 25.00 75 ALS, 1.73 100 / 1.51 Wingtack Plus, 2.51 10/66 B, C 5-120 (ag) G-9 C ₆ , 4.976 20.043 Tergitol 7, 0.059 27 / 0.800 Colloidal Si, 0.226 0/90 S, N <5-60 G-10 C ₈ , 8.032 12.131 LiB (C ₆ F ₅ ) ₄ (xs) 36 / 2.210 (none) 23 / 0.2 S, I 10-140

In sample G-2, the microspheres were dried and the polymer molecular weight was determined to be M _w 341,000, M _n 186,000. In sample G-3, the microspheres were dried and the polymer molecular weight was determined to be M _w 240,000, M _n 132,000.

Polymers prepared in this manner and optionally dried may be used to prepare the adhesive composition.

H. Preparation of Polymer Microspheres in the Presence of Organic Liquid Media

Organic liquid medium, alpha-olefin monomer and Pd containing catalyst {((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6- C ₆ H ₃ (i-Pr) ₂ )) Pd (Me) (Me t-Bu ether)} ⁺ {N (SO ₂ CF ₃ ) ₂ } ^- (Preparation D) were mixed at the specified temperature and the mixture was Polymer microspheres were prepared by maintaining at this temperature for a specified time. Polymer microspheres were obtained. The amount and presence of the material is shown in Table 3 below. Initial mixing was performed by a stirring method using a magnetic stirring bar (B), a method by shaking (S), or a method by a paddle (P) mechanically driven. Some samples were likewise stirred intermittently (I) or continuously (C) or none at all (N) during the polymerization reaction. The microspheres were examined under a microscope to measure their size, and for the selected samples, the molecular weight of the polymer in the microspheres was also measured. In general, small microspheres (dimensions: diameter) were present in small amounts, most of which agglomerated into approximately larger (dimensions: maximum length) irregular shapes. For the same sample, a fraction of the microspheres was collected by filtration which was dried to give a powder.

Sample Monomer g Solvent g Catmg G Reaction condition ℃ / hr Stirring Microsphere size micron H-1 C ₈ , 200 Ethyl acetate, 800 596 10/18 B, C 5-350 H-2 C ₈ , 160 Ethyl acetate, 602 670 0/90 B, C 10-250 H-3 C ₈ , 155 Ethyl acetate, 604 670 Wingtack Plus, 7.607 0/90 B, C 5-300 H-4 C ₈ , 1 MEK ^* , 5.009 12 0/18 S, N 5-300 H-5 C ₈ , 1 Me t-Bu ether, 5.004 10 0/18 S, N 1-5 H-6 C ₁₂ , 1000 CH ₂ Cl ₂ , 1011 2230 0/72 S, N 10-250 H-7 C ₁₂ , 5 Ethyl acetate, 20 30 0/18 S, N 10-200 H-8 C ₁₀ , 5 Ethyl acetate, 20 30 0/18 S, N 10-300 H-9 C ₁₈ , 5 Ethyl acetate, 20 30 0/18 S, N 10-140 H-10 C ₆ , 5 Ethyl acetate, 20 30 1/18 S, N 10-nd ^{** *} Methyl ethyl ketone ^** Particularly high aggregation, unable to determine maximum size (nd)

In the sample, the maximum size of aggregated microspheres should be regarded as subjective and qualitative values. Agglomerates are small enough to be easily handled and processed, and the microsphere suspension formed in the organic liquid phase is treated as a fluid by means such as injection.

Polymers prepared in this manner and optionally freed of solvent can be used to prepare the adhesive composition.

Example 1 Pressure Sensitive Adhesive

The polyoctene used in this example is a catalyst of {((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) from 100 g of 1-octene in 100 g of CH ₂ Cl ₂ . _{C (CH 3) = N (} 2,6-C 6 H 3 (i-Pr) 2))} Pd (Me) (Et 2 O)} + {B (C 6 F 5) 4} - 0.5 g of By reacting at 0 ° C. for about 2 days to prepare a polymer having M _w 3.27 × 10 ⁵ , M _n 1.76 × 10 ⁵ . Polyhexene was prepared in a similar manner to obtain a polymer having M _w 2.37 × 10 ⁵ , M _n 1.50 × 10 ⁵ . Wingtack Extra ^™ is Goodyear's commercial tackifier (Goodyear Tire and Rubber Company, Akron, Ohio).

Each polymer was dissolved in toluene to give a solution containing 25% by weight of polymer. To the sample of polymer solution was added the material as shown in Table 4 below. The additive was present in the weight percents given in the dried coating, with the remaining weight being polymer. For example, in Sample 1-C, 20% by weight of Wingtack Extra ^™ was added and the polyoctene was 80% by weight. This solution was then coated on a 0.025 mm (1 mil) poly (ethylene terephthalate) (PET) film, air dried and oven dried at 93 ° C. for several minutes. The weight of the coating is shown in the table below. The adhesion of this film to steel was measured at a rate of 30.5 cm / min at 180 ° according to ASTM D 3330-81 (Method A). Fixing force was measured for an area of 1.27 × 1.27 cm using 1 kg weight on steel according to ASTM D3654-87 (Procedure C).

Sample polymer Additive (s) Weight% Adhesive force g / cm (oz / in) remove Holding force (min) Coating weight mg / cm ² (grain / 24 inch ² ) 1-A Octene none 32.9 (3.4) Clean 103 3.97 (9.5) 1-B Hexene none 15.6 (1.4) Clean 4.2 3.97 (9.5) 1-C Octene 20 WingtackExtra 1200 (108) split 240 4.51 (10.8) 1-D Hexene 20 WingtackExtra 585 (52.5) Thin afterglow 0.4 4.60 (11)

This example is useful as a pressure sensitive adhesive, wherein a polymer comprising at least one of a plurality of C ₃ or more alpha-olefin units and having an average number of branching points of one or more polymers per monomer unit is useful as a pressure sensitive adhesive, and the performance of the adhesive is a tackifier as needed. It can be seen that it can be modified by adding other materials such as to the polymer.

Example 2 Pressure Sensitive Adhesive

This example describes the preparation of a pressure sensitive adhesive consisting of a polymer comprising at least one plurality of C ₃ or more alpha-olefin units, wherein the polymer has one or more average branch points per monomer unit. In this example, a polymer of 1-octene was used. Polymer molecular weights were variable and the M _w for each polymer is listed in Tables 5A and 5B below. In Samples 2-A to 2-C, the polymer M _n was 1.76 × 10 ⁵ . In Samples 2-D to 2-M, the polymer M _n was 2.89 × 10 ⁵ . Samples were prepared and tested in the same manner as in Example 1. The additive was commercially available as follows: Wingtack ^TM Extra (Goodyear Tire and Rubber Company, Akron, Ohio) and Hercules (Hercules Incorporated, Wilmington, Delaware). commercially available Piccolyte ^TM S25, Foral ^TM AX, Piccofyn ^TM A135, Piccolyte ^tm S15 and Regalrez ^TM 1126, shell (TX shell Chemical Company, of Houston,) of the oil (Shellflex ^TM 371) and Arakawa (Japan material, available from Arakawa that Arkon ^TM P115 available from Arakawa Chemical (USA), Chicago, Illinois, on behalf of Chemical Industries Limited. For the fixation test, the sample was left in place for up to 10,000 minutes, and writing "10,000+" means that the sample did not break within that time and no longer tested after that time.

Sample Polymer M _w Additive (s) Increase% Adhesive force g / cm (oz / in) Holding force (min) Coating weight mg / cm ² (grain / 24 inch ² ) 2-A 3.27 × 10 ⁵ 5 Wingtack Extra 328 (29.4) 1620 4.36 (10.42) 2-B 3.27 × 10 ⁵ 5 Piccolyte S25 232 (20.8) 431 4.30 (10.29) 2-C 3.27 × 10 ⁵ 5 oil 66.9 (6) 115 4.34 (10.39)

Sample Polymer M _w Additive (s) Increase% Adhesive force g / cm (oz / in) Holding force (min) Coating weight mg / cm ² (grain / 24 inch ² ) 2-D 7.02 × 10 ⁵ 20 Arkon P115 399 (35.8) 10,000+ 3.88 (9.28) 2-E 7.02 × 10 ⁵ 20 Foral AX 18.9 (1.7) 3170 3.76 (8.99) 2-F 7.02 × 10 ⁵ 20 Piccofyn A135 365 (32.8) 10,000+ 4.17 (9.97) 2-G 7.02 × 10 ⁵ 20 Piccolyte S115 381 (34.2) 10,000+ 3.78 (9.04) 2-H 7.02 × 10 ⁵ 20 Regalrez 1126 260 (23.3) 10,000+ 3.73 (8.92) 2-I 7.02 × 10 ⁵ 20 Wingtack Extra 349 (31.3) 10,000+ 3.74 (8.95) 2-J 7.02 × 10 ⁵ 5 Wingtack Extra 325 (29.2) 10,000+ 3.53 (8.44) 2-K 7.02 × 10 ⁵ 5 Piccolyte S25 13.4 (1.2) 10,000+ 3.64 (8.71) 2-L 7.02 × 10 ⁵ 5 oil 0-11 (0 -0.1) 7100 3.75 (8.97) 2-M 7.02 × 10 ⁵ No additives 2.22 (0.2) 10,000+ 3.25 (7.77) 2-N (comparative example) 7 × 10 ⁵ No additives 81.3-160 (7.3-14.4) 0.1 0.648 (1.55)

This example shows that the adhesive properties can be changed by changing the composition. With the exception of samples 2-D, 2-E, 2-H and 2-J, the adhesive was cleanly removed from the steel, and in these samples 2-D, 2-E, 2-H and 2-J the steel was removed after removal Afterimage could be seen in the image. The samples 2-F and 2-H peeled off abruptly. For comparison purposes, a pressure sensitive adhesive (Sample 2-N) consisting of a polymer comprising alpha-olefin units and having an average number of branching points of polymer per monomer unit of about 1 was also tested, in which the polyoctene in Sample 2-N was a Ziegler-Natta catalyst. ("Polymer A" described in US Pat. No. 5,298,708), M _w is about 700,000 and the polymer is coated from a solution of about 7% solids. Polymer 2-N of the comparative example was found to be much inferior in shear performance (measured as fixation force) compared to similar formulation sample 2-M containing alpha-olefin units and having an average number of branching points of polymer per monomer unit of about 1 or less. Sample 2-N was a soft adhesive that left a residue upon removal (an undesirable feature) and was the only sample that was broken by cleavage in the fixation test.

Example 3. Crosslinked Pressure Sensitive Adhesive

Polyoctene and polyhexene were prepared as described in Example 1. A solution containing 70 parts by weight of a polymer, 30 parts by weight of Arkon P115 resin (Example 2), and 0.5 parts by weight of Irganox ^™ 1010 antioxidant (Shiba-Geigi, Hodoon, NJ) in 210 parts of toluene and 30 parts of xylene Prepared. Samples 3-C and 3-D were prepared as disclosed in 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (German Patent No. 1,200,314). ) 0.1 parts by weight more. The solution was coated on PET as in Example 1 with the coating weight described. The samples were then processed under the doses listed in Table 6 using either electron beam or ultraviolet radiation. The electron beam source was 175 kilovolts and samples 3-A and 3-B were exposed at a rate of 762 cm / min (25 feet / min). UV (high pressure mercury lamp) exposure to Samples 3-C and 3-D was performed under nitrogen atmosphere. Adhesion was tested using the method described in Example 1. For fixation testing, "+" means that the sample did not break within the specified time and no longer tested. "Break mode" refers to the type of adhesive that detaches from the test substrate during the test. "A" means adhesive failure, ie the adhesive is separated from the steel test plate. "B" means that the adhesive is separated completely or in part (expressed as a percentage) from the PET support. "C" means cohesive failure, ie, the adhesive material is found on both the support (PET) and the test plate (steel) after the cleavage and detachment. The amount of crosslinked polymer was measured as "% gel", which is the weight of the polymer insoluble in toluene. The results are shown in Table 6 below.

Sample polymer Irradiation capacity Adhesion Breaking way Holding force Breaking way Coating weight % Gel Electron beam oz / in g / cm Grain / 24 in ² mg / cm ² 3-A C ₈ 0 74 821 A 940 A 12 5.02 0 5 50 555 A 10,000+ A 12.1 5.06 41 10 45 500 A 10,000+ A 12.2 5.10 71 3-B C ₆ 0 155 1721 C 0.5 C 11.6 4.85 0 5 52 577 B 1.8 C 11.6 4.85 0.3 10 48 533 B (80%) 650 B 11.7 4.89 38 UV, mJ / cm ² 3-C C ₈ 0 70 777 A 1880 A 12.4 5.18 0 302 58 644 A 10,000+ A 12 5.02 11 596 58 644 A 10,000+ A 12 5.02 34 3-D C ₆ 0 151 1676 C 0.6 C 11.7 4.89 0 302 67 744 B (50%) 2.2 C 11.4 4.77 2.5 596 56 622 B 4.2 C 11.4 4.77 2.9

This example shows that the pressure sensitive adhesive can be crosslinked by electron beam or UV irradiation. Certain adhesive properties, for example anchoring forces, have been improved by crosslinking.

Example 4. Adhesive Film Coated by Heating

This example illustrates an adhesive film comprising a polymer comprising at least one plurality of C ₃ or more alpha-olefin units and a polymer having an average number of branching points of one polymer per monomer unit or less, and a method of applying the film using heat. It is.

Samples were prepared from polymers comprising alpha-olefin units having an average number of branching points of polymers of 1 or less per monomer unit, where the alpha-olefin (monomer, C _{12 in} terms of carbon atoms, dodecene, etc.) units and the polymer molecular weight are shown in Table 6 As shown in. A sample of each polymer (formed in powder form as formed as a microsphere precipitate from the solvent during synthesis) was pressed between two high temperature (200 ° C.) plates in the presence of a spacer to produce a film thickness of about 0.5 mm (Table 7a and Table below). "Thickness before treatment" in 7b). The film was cut into squares measuring 1 inch x 1 inch (2.54 x 2.54 cm). This polymer film is then placed at one end of a 2.54 cm wide piece of test substrate, a second piece of test substrate is placed thereon so that 2.54 cm of the second substrate overlaps the film (and the first substrate at the bottom), and the second The remainder of the fragment was allowed to extend in the opposite direction of the first fragment. The structure consisting of the substrate fragment and the polymer film was then left in a 120 ° C. oven for 10 minutes and loaded with 1 kg weight on the upper fragment on the polymer film of the test substrate under pressure. The sample was heated at ambient temperature without weight loading.

Using this structure, a square of 6.45 cm ² in polymer was contacted with each piece of substrate and the substrate was grasped at the opposite end and pulled out at 180 ° angle to separate. The overlap shear force required to break the bond was measured using Instron Model 1122 (Canton, Mass.). A 5 kN weight was used. Substrate fragments were fixed with 2.54 cm grips on the top and bottom substrates. Samples were separated by tension at 1.27 cm / min or 0.127 cm / min as described in Tables 7a and 7b. The stress at break for tensile separation of the sample was recorded in pounds, because the measured area is 1 in ² and this stress is also reported as stress at break in psi as shown in Tables 7a and 7b. . Values in terms of MPa are also presented. In Tables 7a and 7b, the "thickness after treatment" is the thickness of the adhesive detached after testing.

The test substrate is as follows: The stainless steel sheet for adhesion test was subjected to an 18 gauge sintered finish, and had unevenness, which was shielded with a mask on one side and measured along the grain in the longitudinal direction at 5.1 × 12.7 cm. Test polymer plates were purchased from Minnesota Plastics, Eden Prairie, Minn., And measured dimensions of 0.95 × 2.54 × 12.7 cm. The following abbreviations were used: SS-Stainless Steel Plate, HDPE- Stress Relaxed High Density Polyethylene, LDPE- Low Density Polyethylene, PP- Untreated Stress Relaxed Polypropylene, PC- Manchester Polycarbonate, General Purpose (General Electric GE 9034), AC-clear poly (methylmethacrylate), ABS-untreated acrylonitrile-butadiene-styrene polymer, TEF-untreated Teflon. Both sides of the PC and AC plates and one side of the SS plate were shielded. The mask was removed before testing and the bonding was done in terms of previously shielded. No surface pretreatment was used. The aluminum plate (5054 aluminum, mill finish) was 0.1 cm thick, 10.2 cm long and 2.54 cm wide. The cold rolled steel sheet was 0.122 cm thick, 12.7 cm long and 5.1 cm wide. Fir, a wood substrate, was 0.813 cm thick, 2.54 cm wide, and 10.2 cm long.

Monomer M _n M _w materials Thickness, mm before and after Speed cm / min Stress at break of adhesion test psi MPa C ₁₂ 193000 484000 HDPE 0.53, 0.53 0.127 145.6 1.00 C ₁₂ 193000 484000 LDPE 0.50, 0.50-0.53 0.127 122 0.84 C ₁₂ 193000 484000 PP 0.49, 0.45-0.59 0.127 20.5 0.14 C ₁₂ 193000 484000 ABS 0.49, 0.49-0.64 0.127 12.3 0.08 C ₁₂ 193000 484000 AC 0.47, 0.45-0.55 0.127 15.8 0.11 C ₁₂ 193000 484000 TEF 0.45, 0.46-0.49 0.127 59.3 0.41 C ₁₂ 193000 484000 fir 0.49, 0.46-0.54 0.127 110.6 0.76 C ₁₂ 193000 484000 fir 0.5, 0.62 0.127 108.9 0.75 C ₁₂ 193000 484000 HDPE 0.52, 0.52 1.27 197.9 1.36 C ₁₂ 193000 484000 LDPE 0.54, 0.49-0.66 1.27 136.4 0.94 C ₁₂ 193000 484000 PP 0.54, 0.49 1.27 132.9 0.92 C ₁₂ 193000 484000 ABS 0.58, 0.59-0.63 1.27 18.3 0.13 C ₁₂ 193000 484000 AC 0.58, 0.54 1.27 5.2 0.04 C ₁₂ 193000 484000 TEF 0.6, 0.67 1.27 63.1 0.44 C ₁₂ 193000 484000 aluminum 0.58, 0.6 1.27 66.3 0.46 C ₁₂ 193000 484000 steal 0.55, 0.6 1.27 167.1 1.15 C ₁₂ 193000 484000 fir 0.54, 0.46-0.48 1.27 163.8 1.13 C ₁₀ 163000 548000 ABS 0.62, 0.54 0.127 57.6 0.40 C ₁₀ 163000 548000 steal 0.62, 0.54 0.127 142.7 0.98 C ₁₀ 163000 548000 fir 0.68, 0.63-0.8 0.127 175.6 1.24 C ₁₀ 163000 548000 fir 0.64, 0.81 0.127 83.9 0.58

Monomer M _n M _w materials Thickness, mm before and after Speed cm / min Stress at break of adhesion test psi MPa C ₈ 175000 383000 fir 0.45, 0.43-0.62 0.127 125 0.86 C ₆ 82300 349000 fir 0.59, 0.54 1.27 54.5 0.38 C ₈ 175000 383000 fir 0.46, 0.49-0.52 1.27 132.5 0.91 C ₁₀ 163000 548000 fir 0.58, 0.59-0.62 1.27 159.5 1.10 C ₁₄ 43400 200000 fir 0.72, 0.8-1.1 1.27 132.8 0.92 C ₁₆ 98100 156000 fir 0.29, 0.13-0.35 1.27 191.3 1.32 E1060 ^a (comparative) 14200 44200 fir 0.5 0.127 16.3 0.11 E1060 ^a (comparative) 14200 44200 HDPE 0.5 0.127 20.9 0.14 ^a E 1060 is Eastoflex 1060 ^™ available from Eastman Chemical (Kingsport, Tennessee). This is a low molecular weight polyolefin made using a Ziegler-Natta catalyst, which exhibits inferior adhesive performance than the polyoctene of the present invention.

For all polymer and metal substrates tested, the mode of failure means the manner in which the adhesive is broken, that is, the manner in which the adhesive film is separated from one substrate rather than tearing. When using an acrylic substrate (AC), the films adhered relatively inferiorly and slowly bent from the substrate rather than suddenly separating under high load. For wood samples, the polymer film showed variable thickness after separation when the polymer took the shape or contour of the wood surface. The polymer film investigated after separation from the wood sample showed wood fibers still adhered to the polymer, suggesting that the wood fibers were removed from the wood substrate as part of the fracture mode.

This example demonstrates that the materials and methods described above are particularly useful for low energy surfaces such as HDPE, LDPE, PP and Teflon, as well as for metals and wood.

Example 5 Adhesive Coated as Melt

This example illustrates that an adhesive can be prepared from a polymer comprising at least one plurality of C ₃ or more alpha-olefin units and having an average number of branching points of the polymer per monomer unit of 1 or less. Good adhesion can be obtained while the polymer is in the molten state, ie by applying it at a high temperature where the fluidity of the polymer is greater than at ambient temperature.

Polyoctene (microspheres in powder form, synthesized as described in Preparation H) with M _n of 175,000 and M _w of 383,000 was added several times to a mold maintained at about 160 ° C. and melted to obtain a diameter of 1.4 A molded cylinder of about 14 cm in length and cm was obtained. This “stick” was placed in a Polygun TC ^™ , 150 watt, 120 VAC, 60 CPS (3M Advanced Coatings and Sealers Division, St. Paul, Minn.) To heat the sample, followed by a nozzle (about 182 ° C. to 199 ° C.) was delivered to the test substrate in the form of hot molten beads. The description and the form are as described in Example 4. Hot beads having an approximately "S " shape were applied to the substrate and the second piece of substrate was immediately attached to the beads and pressed by hand in place. The overlapping area of the substrate fragments was approximately 6.45 cm ² , with the two fragments extending along the opposite direction in a shape similar to that described in Example 4. The amount and shape of the adhesive beads was difficult to control, but their weight was measured and the thickness after separation was also measured. The polymer density (measured through the pressed film of the same polymer) was about 0.94 g / cm ³ , and these three values (weight, density and thickness) were used to calculate the irregularly shaped contact area. Samples were tested at an Instron 1122 as in Example 4 at a rate of 1.27 cm / min. The force was calculated in psi using the force required to tension-tear the sample and the calculated contact area. The results are shown in Table 8 below. The value converted in MPa unit was also described.

materials Polymer Bead Thickness (mm) Weight (g) Newtons (lb) Calculated contact area cm ² (in ² ) Stress at Break psi Mpa ² HDPE 0.68 0.17 285 (64.1) 2.81 (0.435) 147 1.01 LDPE 0.57 0.13 254 (57.1) 2.56 (0.397) 144 0.99 PP 0.4 0.12 421 (94.6) 3.37 (0.522) 181 1.25 ABS 0.48 0.17 280 (63) 3.97 (0.616) 102 0.70 AC 0.48 0.14 355 (79.7) 3.27 (0.507) 157 1.08 TEF 0.43 0.14 181 (40.8) 3.65 (0.566) 72 0.50 fir 0.5 0.31 525 (118) 6.97 (1.08) 110 0.76 aluminum 0.58 0.07 111 (24.9) 1.35 (0.21) 119 0.82

The data in Table 8 above show that the calculation of the force required to separate the polymer from the substrate is in the same range as the force observed in Example 4 for the same polymer and similar substrate (wood), which melts the polymer. Application to the substrate in a state suggests that the surface of the substrate can be excellently wetted and excellent adhesion can be obtained.

Example 6 Preparation and Testing of Curable Adhesives

In this example, the catalyst {((2,6-C ₆ H ₃ (i-Pr) ₂ ) N = C (CH ₃ ) C (CH ₃ ) = N (2,6-C ₆ H ₃ (i -Pr) ₂ ))} Pd (Me) (Et ₂ O)} ⁺ {B (C ₆ F ₅ ) ₄ } ^- (Preparation D) after dissolving in 0.1 g of CH ₂ Cl ₂ (promoting dissolution) 1.0 g of designated 1-alkanes as described in Table 8. The mixture was vigorously stirred to give an orange solution. The solution was then applied to the test plate at an application rate of 6 drops (about 0.3 ml) per 6.45 cm ² of overlap. The top plate was placed on the plate to form an overlap junction of the designated area, which was held in place with a force of about 122 g (two SS test plates) regardless of the overlap area. Samples were cured at room temperature (about 23 ° C.) for 2.5 hours. In other tests, longer times (4 hours) were used, but had no effective effect on the results.

The test plate is as described in Example 4. The substrates used in the test were two identical plates, as shown in Table 9, arranged to form an overlap of 2.54 × 5.1 cm for SS, 1.27 × 2.54 cm for LDPE, and 2.54 × 2.54 cm for all other substrates. . Single overlap shear tests were performed on Instron Model 1122 using a constant crosshead speed of 0.127 cm / min for substrates specified according to ASTM D1002-94 (unless otherwise noted).

The alpha-olefin monomers used in the curable adhesives of this example are indicated by C _x in the table below, where x is the number of carbon atoms in the monomer. The thickness of the adhesive polymer film formed between the test plates is 0.05 mm to 0.175 mm, usually 0.075 mm to 0.10 mm. Adhesive bonds were generally broken between the polymer and the top plate, the mode of failure being usually broken by the adhesive with little cohesive failure.

For the matters shown in Table 10, the tests were conducted in a similar manner except that two different substrates were used. The plates were placed so that the overlap area was 2.54 × 2.54 cm.

Stress at Break (MPa) in Shear of Single Overlap SS HDPE LDPE PP ABS PC AC TEF C ₈ 0.30 1.17 0.51 0.82 1.66 0.57 0.43 0.39 C ₁₀ 0.92 1.29 0.68 0.99 1.08 0.63 0.45 0.40 C ₁₂ 0.81 1.48 0.82 0.57 1.59 0.41 0.11 0.54 C ₁₄ 1.35 1.31 0.68 0.37 1.59 0.60 0.32 0.48

Stress at Break (MPa) in Shear of Single Overlap SS-HDPE ABS-SS ABS-HDPE C ₁₂ 1.66 2.06 1.28

The binding capacity of the above system was prepared, as described above, by preparing a solution of the Pd catalyst and C ₈ , using one drop of this solution, and using two drops of Engage 8150 ^TM (ethylene-octene copolymer, Chippe, Wisconsin, Pa.). Film supplied by Consolidated Thermoplastics Company; further demonstrated by bonding together strips of Dow Chemical Corporation, Midland, Michigan (thickness 0.063 mm, width 2.54 cm) together. Curing conditions were as described above and the area applied by the cured adhesive was about 1.56 cm ² . In this sample, the film was stretched and no adhesive bond breakage occurred. When further tensioned by hand, the film broke and did not bond.

Example 7 Formulated Hot Melt Adhesives

As described in Preparation H, polyoctene and polydodecene were prepared in ethyl acetate using the following amounts and conditions. For polyoctene, 100 g of 1-octene, 400 g of ethyl acetate, and 5.483 g of Pd catalyst were constantly stirred for 3 hours while maintaining at 0 ° C., and left at 0 ° C. for a period of about 15 hours or more (no stirring) ). 200 ml of isopropanol and 0.2 g of triphenylphosphite were added to terminate the polymerization reaction. In the case of polydodecene, 100 g of 1-dodecene, 400 g of ethyl acetate and 5.4856 g of catalyst were treated in a similar manner. The weight yield of the polymer suggests that 100% of the monomer was converted to the polymer.

Samples of each polymer and Arkon P140 ^™ (Arakawa Chemical) were subjected to Brabender Plasti-Corder Type EPL-V3302 (Braven Instruments Instruments, Haken, NJ) according to the weight fractions shown in Table 11 below. Mixed and Irganox ^™ 1010 was added in an amount corresponding to 0.4% by weight of the total composition. In the formulation column, the fractions are shown as Arkon P140 parts: parts of polymer, and polyoctene and polydodecene are shown as (C ₈ ) or (C ₁₂ ), respectively. Thus, 1: 2 (C ₈ ) means a formulation consisting of 1 part by weight of Arkon P140: 2 parts by weight of polyoctene.

The formulation was then molded as a cylinder or stick in a mold and delivered to the test substrate in the form of a hot bead as described in Example 5. The amount of adhesive and the force required to tension separate the sample were measured at a rate of 0.127 cm / min as described in Example 5. The breaking method is as described in Example 3 (when there is nothing described in the table, it means that the breaking method is not observed by visual inspection).

Sample Formulation materials Polymer Bead Weight Thickness (g) (mm) Lb newton Density g / ml Calculated contact area in ² cm ² Breaking way Calculated Stress at Break psi MPa 7-A 1: 2 (C ₈ ) wood 0.297 0.65 153 681 0.807 0.88 5.66 C 174 1.20 7-B 1: 2 (C ₈ ) steal 0.555 1.04 146 649 0.807 1.03 6.61 A 142 0.98 7-C 1: 2 (C ₈ ) HDPE 0.247 est0.79 148 658 0.807 0.60 3.87 C 247 1.70 7-D 1: 2 (C ₈ ) acryl 0.402 est0.79 176 783 0.807 0.98 6.31 C 180 1.24 7-E 1: 2 (C ₈ ) ABS 0.48 est0.79 176 783 0.807 1.17 7.53 C 151 1.04 7-F 1: 1 (C ₈ ) wood 0.497 est0.79 216 961 0.807 1.21 7.80 C 179 1.23 7-G 1: 1 (C ₈ ) steal 0.704 0.97 207 921 0.927 1.21 7.83 A 171 1.18 7-H 1: 1 (C ₈ ) HDPE 0.267 0.77 168 747 0.927 0.58 3.74 290 2.00 7-I 1: 1 (C ₈ ) acryl 0.407 est0.79 259 1152 0.927 0.86 5.56 C 301 2.08 7-J 1: 1 (C ₈ ) ABS 0.268 est0.79 187 832 0.927 0.57 3.66 C 329 2.27 7-K 1: 1 (C ₈ ) Teflon 0.349 0.69 96 427 0.927 0.85 5.46 A 114 0.79 7-L 1: 1 (C ₈ ) PP 0.44 est0.79 209 930 0.927 0.93 6.01 224 1.54 7-M 1: 2 (C ₁₂ ) wood 0.251 est0.79 280 1245 0.88 0.56 3.61 C 500 3.45 7-N 1: 2 (C ₁₂ ) steal 0.472 0.94 24 107 0.88 0.88 5.71 A 28 0.19 7-O 1: 2 (C ₁₂ ) HDPE 0.312 0.63 220 979 0.88 0.87 5.63 C 253 1.74 7-P 1: 2 (C ₁₂ ) acryl 0.415 0.73 202 898 0.88 1.00 6.46 C 202 1.39 7-Q 1: 2 (C ₁₂ ) ABS 0.36 0.69 67 297 0.88 0.92 5.93 A 73 0.503 7-R 2: 1 (C ₁₂ ) wood 0.382 est0.79 489 2180 est0.87 0.86 5.56 C 567 3.91 7-S 2: 1 (C ₁₂ ) steal 0.378 est0.79 12 53.4 est0.87 0.85 5.50 A 14 0.097 7-T 2: 1 (C ₁₂ ) HDPE 0.32 0.9 55 245 est0.87 0.63 4.09 A 87 0.600 7-U 2: 1 (C ₁₂ ) acryl 0.453 0.81 135 600 est0.87 1.00 6.43 A 135 0.93 7-V 2: 1 (C ₁₂ ) ABS 0.368 0.73 41 182 est0.87 0.90 5.79 C 45 0.310

For some samples, it was difficult to accurately measure the thickness of the adhesive after tensile separation, especially in case of cohesive failure. To obtain an estimate of the thickness, the average of the thicknesses measured for the other samples was used. However, these figures (described as "est 0.79" in the thickness column) are only estimated values and may have an error of up to 0.18 mm (about 25%). Therefore, the values calculated using these numbers (contact area and calculated force per area) are only estimates. For Samples 7-R through 7-V, the formulation density was not measured but was estimated (error about 10%), and the calculated value is also an estimated value.

The polyoctene and polydodecene formulations were also pressed into a film as described in Example 4 except that Sample 7-G was evaluated at a rate of 5.1 cm / min. Samples were prepared and evaluated at 0.127 cm / min as described in Example 4. All samples showed cohesive failure. The results are shown in Table 12 below.

Sample Thickness mm Stress at Break psi MPa 7-AA 2: 1 (C ₈ ) wood 0.75 160 1.10 7-BB 2: 1 (C ₈ ) steal 0.77 193 1.33 7-CC 2: 1 (C ₈ ) acryl 0.67 108 0.74 7-DD 2: 1 (C ₈ ) ABS 0.73 162 1.12 7-EE 1: 1 (C ₁₂ ) wood 0.52 295 2.03 7-FF 1: 1 (C ₁₂ ) HDPE 0.52 205 1.41 7-GG 1: 1 (C ₁₂ ) acryl 0.5 235 1.62 7-HH 1: 1 (C ₁₂ ) ABS 0.52 234 1.61

Those skilled in the art will recognize various modifications and changes without departing from the spirit and scope of the present invention, and the protection scope of the present invention is not limited to the specific embodiments described above.

Claims (14)

1) a number of C ₃ or more alpha-olefin units, where the average number of branching points of the polymer is one or less per alpha-olefin unit, and 2) a number of C ₂ alpha-olefin units, where the average branching point of the polymer Wherein the number is at least 0.01 per alpha-olefin unit), wherein the adhesive is selected from the group consisting of pressure sensitive adhesives, hot melt adhesives, and polymerized glues, the adhesive composition optionally The adhesive composition further comprises at least one additive selected from the group consisting of tackifiers, oils, polymers, antioxidants, ultraviolet activated crosslinkers or thermally activated crosslinkers, wherein the adhesive composition is optionally crosslinked by high energy irradiation. The adhesive composition of claim 1, which is optionally crosslinked by ultraviolet, heat or electron beam irradiation. The polymerizable composition according to claim 1 or 2, comprising an effective amount of an organometallic polymerization catalyst consisting of a group VIII metal complexed with a ligand having sufficient steric bulk to form an alpha-olefin monomer and a polymer. Adhesive composition, wherein the adhesive composition optionally has a weight average molecular weight of at least 5,000. The process according to claim 1 or 3, wherein the alpha-olefin polymer is ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, The adhesive composition derived from an alpha-olefin selected from the group consisting of 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene and cyclopentene. The adhesive composition according to any one of claims 1 to 4, which is selected from the group consisting of freestanding films, supported films, coatings and powders. The adhesive composition according to any one of claims 1 to 5, wherein the Group VIII metal of the catalyst is Pd or Ni. An article comprising a substrate having the adhesive composition of claim 1 on at least one surface. 8. The article of claim 7, wherein the article is an adhesive tape or label. A method comprising applying the adhesive composition of any one of claims 1 to 6 to at least one surface of an adherend, wherein the surface of the adherend is selected from the group consisting of polymers, cellulosic surfaces, metals and fabrics. Which method is chosen. A polymerizable adhesive composition comprising an effective amount of an organometallic catalyst consisting of a polydentate ligand having sufficient steric bulk and a Group VIII metal to form at least one C ₅ or more alpha-olefin monomer and a polymer, wherein the viscosity of the composition is And from 0.2 centipoise to 300,000 centipoise, wherein the polymerizable adhesive composition optionally further comprises an additive selected from the group consisting of tackifiers, oils, antioxidants, and polymers. The polymerizable adhesive composition of claim 10 which is a glue. The polymerizable adhesive composition according to claim 10 or 11, wherein the catalyst is a one-component catalyst comprising an organometallic salt or a two-component catalyst comprising a neutral organometallic compound and a promoter. A kit for preparing a potentially polymerizable adhesive composition according to any one of claims 10 to 12, wherein the composition has components that can be mixed when the composition is desired to be applied, and the kit A combination of a first package containing an amount of an organometallic compound of a two-component catalyst and a second package containing a promoter of the two-component catalyst, the kit comprising one or two packages of the kit And further comprising at least one alpha-olefin monomer present. 1) applying the polymerizable composition according to any one of claims 10 to 13 to the surface of at least one adherend, and 2) causing a polymerization reaction.