DE20080335U1 - Article such as tire laminate, is formed by contacting catalyst applied on first substrate and metathesizable material provided between surfaces of first and second substrates or as component of second substrate - Google Patents

Abstract

An article is obtained by contacting a catalyst applied on the first substrate surface with a metathesizable material provided between surfaces of first and second substrates or as a component of second substrate, so that the metathesizable material undergoes metathesis reaction and bonds surfaces of article substrates. An independent claim is also included for a tire laminate which comprises a tire carcass with an outer periphery surface, a tire tread with a bonding surface, and a metathesis polymer adhesive layer between the outer periphery surface of the tire carcass and the bonding surface of the tire tread.

Description

Article made of two substrates bonded together Background of the invention

The present invention relates to an article comprising two substrate surfaces bonded together by an adhesive layer.

Despite a long history of adhesive and coating development, there continues to be a need for adhesives and coatings that provide ever higher bond strengths under increasingly adverse conditions on a growing variety of substrate surfaces.

A particular need exists for environmentally friendly aqueous or water-based adhesive systems that avoid the use of volatile organic solvents. It has been relatively difficult to develop aqueous adhesives that perform at the same level as traditional solvent-based adhesives. A major problem associated with bonds formed from an aqueous adhesive is the relative vulnerability of the bonds to high temperature fluids and corrosive materials. Another need continues to exist for coatings or adhesives that provide superior bonding ability at low material cost. Furthermore, there is a need for coatings or adhesives that can be applied in relatively few steps and with minimal energy consumption. A few markets that have a particular need for superior adhesives or coatings are described below.

&phgr; * ϕ ϕ φ · ϕϕϕ ϕ &phgr; &phgr; φ φ φ φ φ &phgr; » ϕ ϕ ϕ ϕ •ϕ &phgr; t ϕ φ φ φ φ φ ϕ ϕ ϕ ϕ ϕ ϕ ϕ &phgr; • φ φ

The manufacture of articles, parts or structures that include an elastomeric substrate surface bonded to another substrate surface (either another elastomeric substrate or a non-elastomeric substrate) typically involves placing the non-elastomeric substrate in a mold, introducing a molten or liquid unvulcanized (i.e., uncured) elastomer into the mold, and then applying heat and pressure to simultaneously vulcanize the elastomer and bond it to the non-elastomeric substrate. However, there are problems with this vulcanization bond. The molds often require a complicated design and internal profile, the curing of the elastomer is slowed, pre-compressed elastomer parts cannot be incorporated into the structure, the structures are subject to thermal stress, the product leaving the mold often has additional flashes that must be removed, any subsequent addition of further mold parts can significantly compromise the previously formed adhesive bond, and there is only limited process flexibility.

It would be advantageous in certain circumstances to bond the elastomer substrate surface to the other substrate surface after the elastomer substrate has been fully cured or vulcanized. This post-vulcanization bonding is sometimes referred to in the art as cold bonding. However, post-vulcanization bonding is a notable area where adequate adhesive bonding is lacking, particularly when bonding to substrates composed of different materials, particularly metals or materials with low surface energy. For example, cured ethylene propylene diene terpolymer rubber ("EPDM") has a low surface energy that makes wetting difficult, and it contains only a relatively small amount of sites such as carbon-carbon double bonds that are suitable for subsequent bonding. Adhesive bonding to post-vulcanized or cured elastomers has had limited success. Cyanacrylate adhesives are used for post-vulcanization bonding, but they suffer from well-known problems in more demanding industrial applications involving harsh environmental conditions. For example,

Cyanoacrylates suffer from poor heat resistance, solvent resistance and flexibility (see Handbook of Adhesives, I. Skeist (ed.), pp. 473-476 (3rd ed. 1990)). Other post-vulcanization adhesives are solvent based and require high temperature and long cure times. Epoxy-5 or urethane adhesives typically require pretreatment of the elastomer surface, such as with oxidizing flames, oxidizing chemicals or electrical discharges/plasma discharges, to improve the bond. However, these pretreatment processes are expensive and time consuming.

The problems with current post-vulcanization adhesive bonding outlined above indicate that there is a long-felt need for an improved post-vulcanization adhesive bonding technology.

Another area of adhesive bonding where there is still a need is bonding with Santoprene®, a commonly used thermoplastic elastomer ("TPE") commercially available from Advanced Elastomer Systems. Pre-cured and cured Santoprene® TPE is particularly difficult to bond because it has a polyolefinic thermoplastic continuous matrix (similar to polyolefinic materials such as polyethylene and polypropylene) which has a particularly low surface energy of 28-30 dynes/cm according to U.S. Patent No. 5,609,962. Bonding to more polar substrates such as metal and glass is virtually impossible.

The tire retread bond is another area where there is a need for improvement. Tire tread replacement or retreading generally involves bonding a pre-cured or uncured retread material to a cured tire carcass. The retread material is placed around the perimeter of the tire carcass with an uncured adhesive (known in the art as an adhesive pad or cushion rubber layer) sandwiched between the retread material and the tire carcass. The resulting tire assembly is subjected to heat and pressure for a period of time to cure the adhesive pad layer. When the retread material is uncured, the process is sometimes referred to as

"hot vulcanization" because the heat and pressure applied must be sufficient to vulcanize the retread material. When the retread material is pre-cured, the process is sometimes referred to as "cold vulcanization." The application of heat and pressure to cure the adhesive is typically accomplished by placing the tire structure in a mold or autoclave, which may require a significant temperature (generally 80-250 ⁰ C depending on whether the retread material is pre-cured or uncured) for a significant period of time (up to 300 minutes). Reducing or completely eliminating this heat and pressure step would greatly contribute to reducing the cost of tire retreading.

It would also be advantageous to have a coating that can be applied without heat and extensive surface preparation, coats substrate materials that cannot currently be coated, has improved adhesion to the substrate surface, and provides a water-based coating for thermoplastic olefins that does not require heating.

Brief description of the invention

According to the present invention there is provided an article comprising a first substrate surface and a second substrate surface obtainable by:

(a) providing a catalyst on the first substrate surface;

(b) providing a metathetizable material between the first substrate surface and the second substrate surface or providing a metathetizable material as a component of the

second substrate; and

·

(c) contacting the catalyst on the first substrate surface with the metathetizable material such that the metathetizable material undergoes a metathesis reaction and bonds the first substrate surface to the second substrate surface.

The article according to the invention is produced by a method for bonding a material to a first substrate surface, which comprises providing a catalyst on the first substrate surface and contacting the catalyst on the surface with a material that undergoes a metathesis reaction so that the material is bonded to the first substrate surface. There are two embodiments of this method, a coating method and an adhesive method.

In the coating embodiment, the metathetizable material is applied to the catalyst on the substrate surface so that it undergoes metathesis polymerization to form the coating or a component of the coating. The resulting polymerized metathetizable material itself becomes the coating or a portion of the coating. As used herein, the term "coating" refers to any material that forms a film (continuous or discontinuous) on the substrate surface and serves a functional purpose and/or an aesthetic purpose.

0 This functional purpose could include environmental protection from corrosion, radiation, heat, solvents, etc., mechanical properties such as lubricity, electrical properties such as conductivity or resistance properties, and catalyst properties. A "coating" according to this invention also includes paints.

5 In the adhesive embodiment, the metathesis reaction is used to bond two different substrate surfaces together. In particular, a method for bonding a first substrate surface to a second substrate surface is provided, comprising: (a) providing a catalyst on the first substrate surface, (b) providing a metathesisable material between the first substrate surface and the

• J J··

- 6-

second substrate surface or providing a metathetizable material as a component of the second substrate and (c) contacting the catalyst on the first substrate surface with the metathetizable material so as to effect the metathesis reaction and bond the first substrate surface to the second substrate surface. According to a first adhesive embodiment, as shown in Figure 1, the metathetizable material is present as part of a composition located between the catalyst on the first substrate surface and the second substrate surface. In other words, the metathetizable material is similar to a conventional adhesive in that it is a composition that is different when applied to the two substrates. According to a second adhesive embodiment, as shown in Figure 2, the second substrate consists of or contains the metathetizable material and contacting this second substrate with the catalyst on the first substrate surface creates an adhesive interlayer between the first and second substrates. The adhesive interlayer comprises a thin layer of the metathetizable second substrate that has undergone metathesis.

Also provided is an article of manufacture comprising a surface of a first substrate, a surface of a second substrate, and an adhesive layer disposed between and bonding the surfaces of the first and second substrates together, wherein the first substrate surface comprises an elastomeric material and the adhesive layer comprises a metathesis polymer.

The invention offers the unique possibility of forming a strong adhesive bond on a variety of substrate surfaces (including difficult to bond post-vulcanized elastomeric materials and thermoplastic elastomers) under normal ambient conditions with a minimum number of steps and minimal surface preparation. The process 0 also avoids the use of volatile organic solvents since

it is essentially 100% reactive and/or can be carried out with aqueous carrier fluids.

The bonding process is particularly well suited to producing a tire laminate wherein the catalyst is applied to a tire tread or tire carcass, the metathetizable material is applied to the tire tread or tire carcass to which the catalyst has not been applied, and the tire tread or tire carcass with the applied catalyst and the tire tread or tire carcass with the applied metathetizable material are bonded together. This process allows tire retreading with no or minimal heat and pressure, does not require significant curing time, and should reduce equipment installation costs.

According to another embodiment, the method can also be used to produce multilayer structures for either coating or adhesive applications. In this embodiment, the catalyst and metathetizable material are first applied to the first substrate surface as described above. However, the catalyst site spreads within the coating layer where it remains as a stable active site for subsequent reaction with a metathetizable material.

0 In other words, active catalyst remains on the new surface created from the metathetizable material. Then a second metathetizable material is brought into contact with this "living" surface, and another new layer is created. This process can be repeated until the concentration of active catalyst remaining on the surface has dropped to 5 a level that is no longer practical. Note that the catalysts are not typically consumed or deactivated, and thus there may be no need for excess catalyst.

- 8 Short description of the drawings

Figure 1 shows a preferred embodiment of a first embodiment of a method for joining two substrates according to the invention;

Figure 2 shows a second embodiment of a method for joining two substrates;

Figure 3 shows a bonding process in which the catalyst is contained in a polymer matrix; and

Figure 4 shows a "living" coating process.

Detailed Description of the Preferred Embodiments

Unless otherwise specified, the description of components in chemical nomenclature refers to the components at the time of addition to any combination specified in the description, but does not necessarily preclude chemical interactions between the components of a mixture once mixed.

The following expressions, as used herein, have specific meanings:

"ADMET" means acyclic diene olefin metathesis;

"Catalyst" also includes initiators, cocatalysts and promoters;

"coating" includes a coating intended to be the final or outer coating on a substrate surface and a coating intended to be a primer for a subsequent coating;

"Fibrous substrate" means a woven or nonwoven fabric, a monofilament, a multifilament yarn or a fibrous cord;

"Filmogen" means the ability of a material to form a substantially continuous film on a surface;

"Metathesisable material" means a single or multi-component composition containing at least one component capable of undergoing a metathesis reaction;

"Non-fibrous substrate" means any type of substrate other than a fibrous substrate (non-fibrous substrate also includes a composite substrate containing fibers as a component, such as fiber-reinforced plastics);

"Normal ambient conditions" means temperatures normally found in workplaces with minimal atmospheric control (for example, about -20 ⁰ C to about 40 ⁰ C), a pressure of about 1 atmosphere, and an atmosphere of air containing a certain amount of moisture;

"ROMP" means ring-opening metathesis polymerization;

"Room temperature" means about 10 ⁰ C to about 40 ⁰ C, typically about 20 ⁰ C to about 25 ⁰ C;

"Substantially cured elastomer" and "post-vulcanized elastomer" are used interchangeably and mean thermally cured polymers above T ₉ for that polymer and thermoplastic polyolefins (Substantially cured or post-vulcanized elastomers are typically non-flowable); and

"Surface" means a region of a substrate formed by the outermost part of the substrate defined by a material/air interface and extending from about 1 atomic layer to many thousands of atomic layers into the substrate.

The bonding or coating adhesion that takes place according to the present invention occurs via a metathesis reaction. Various metathesis

reactions are described in K.J. Ivin and J.C. Mol, Olefin Metathesis and Metathesis Polymerization (Academic Press 1997). The metathesis reaction could be a cross metathesis reaction, an ADMET, a ring closing metathesis reaction, or preferably a ROMP. It should be understood that the surface metathesis polymerization which occurs in this invention is very different from bulk (including reaction injection molding), emulsion or solution metathesis polymerization in which a metathetizable monomer and a catalyst are mixed together in a single composition to effect the metathesis reaction. Bulk metathesis polymerization, particularly reaction injection molding, of a norbornene monomer to produce molded articles consisting of the resulting polynorbornene is known. For example, U.S. Patent No. 4,902,560 teaches a process for making a glass fiber reinforced polydicyclopentadiene article which involves saturating an uncoated glass fiber fabric with a polymerizable liquid containing dicyclopentadiene monomer and catalyst, subjecting the saturated fabric to reaction injection molding, and post-curing the resulting structure. In accordance with the present invention, the resulting metathesis polymer forms a filmogenic adhesive or coating rather than a molded article.

The metathetizable material used in the invention is any material that can undergo metathesis when contacted with a suitable catalyst. The metathetizable material can be a monomer, oligomer, polymer, or mixtures thereof. Preferred metathetizable materials are those that contain at least one metathesis-reactive functional group, such as olefinic materials. The metathetizable material or component can have a functionality of the metathesis-reactive moiety in the range of from 1 to about 1000, preferably from about 1 to about 100, more preferably from 0 to about 1 to 10, moles of metathetizable moiety/mole molecules of the metathetizable component. In addition, materials that can undergo ROMP typically have an "inherent ring strain" as described in Ivin et al. on page 224, the elimination of which

et al. on page 224, where the removal of this ring strain is the driving force for polymerization. Materials that can undergo ADMET typically have terminal or nearly terminal unsaturation.

Exemplary metathetizable materials are those containing an unsaturated functional group, such as ethene, α-alkenes, acyclic alkenes (i.e., alkenes having unsaturation at the β-position or higher), acyclic dienes, acetylenes, cyclic alkenes, and cyclic polyenes. Cyclic alkenes and cyclic polyenes, particularly cycloolefins, are preferred. When cyclic alkenes or polyenes form the metathetizable material, the metathesis reaction is a ROMP.

A monomer or oligomer is particularly well suited when the metathetizable material itself is to form a coating on the substrate surface or when the metathetizable material itself is to act as an adhesive to bond one substrate surface to another substrate surface. Monomers are particularly well suited because they can diffuse into the substrate surface when applied. Particularly well suited as monomers on their own, as monomers for preparing oligomers, or for functionalizing other types of polymers are cycloolefins such as norbornene, cycloalkenes, cycloalkadienes, cycloalkatrienes, cycloalkatetraenes, aromatic-containing cycloolefins, and mixtures thereof. Exemplary cycloalkenes are cyclooctene, hexacycloheptadecene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclononene, cyclodecene, cyclododecene, paracyclophene, and ferrocenophene. Example cycloalkadienes are cyclooctadiene and cyclohexadiene. An example cycloalkatriene is cyclooctatriene. An example cycloalkatetraene is cyclooctatetraene.

Norbornene monomers are particularly suitable. The term "norbornene" as used herein means any compound containing a norbornene ring moiety, including norbornene itself, norbornadiene, substituted norbornenes, and polycyclic norbornenes. The term "norbornene" as used herein means any compound containing a norbornene ring moiety, including norbornene itself, norbornadiene, substituted norbornenes, and polycyclic norbornenes.

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"substituted norbornene" means a molecule having a norbornene ring moiety and at least one substituent group. As used herein, the term "polycyclic norbornene" means a molecule having a norbornene ring moiety and at least one additional fused ring. Exemplary norbornenes are those having structures represented by the following formulas:

or

or

or

• · · · ff

·

- 13 -

where X = CH ₂ , CHR ³ , C(R ³ ) ₂ , O, S, NR ³ , PR ³ , O=PR ³ , Si(R ³ ) ₂ , BR ³ or As-R ³ , R ¹ is each independently H, CH ₂ , alkyl, alkenyl (such as vinyl or allyl), cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, halogen, halogenated alkyl, halogenated alkenyl, alkoxy, oxyalkyl, carboxyl, carbonyl, amido, (meth)acrylate-containing group, anhydride-containing group, thioalkoxy, sulfoxide, nitro, hydroxy, keto, carbamato, sulfonyl, sulfinyl, carboxylate, silanyl, cyano or imido, R ² is a fused aromatic, aliphatic or heterocyclic or polycyclic ring and R ³ is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxy. The carbon-containing R groups can have up to about 20 carbon atoms.

Examples of substituted norbornene monomers are methylidene norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5- Octyl-2-norbornene, ethylidenenorbornene, 5-dodecyl-2-norbornene, 5-isobutyl-2-norbornene, 5-octadecyl-2-norbornene, 5-isopropyl-2-norbornene, 5-phenyl-2-norbornene, 5- p-Tolyl-2-norbornene, 5-a-naphthyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-isopropenylnorbornene, 5-vinylnorbornene, 5,5-dimethyl-2-norbornene, 5-norbornene-2-carbonitrile, 5-triethoxysilyl-2-norbornene, 5-norborn-2-yl acetate, 7-oxanorbornene, 5-norbornene-2,3-carboxylic acid, 5- Norbornene-2,2-dimethanol, 2-benzoyl-5-norbornene, 5-nor-0 bornene-2-methanol acrylate, 2,3-di(chloromethyl)-5-norbornene, 2,3-hydroxymethyl-5-norbornene diacetate and their stereoisomers and mixtures thereof.

Exemplary polycyclic norbornene monomers are tricyclic monomers such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclic monomers such as tricyclopentadiene, pentacyclic monomers such as tetracyclopentadiene and tetracyclododecene, hexacyclic monomers such as pentacyclopentadiene, heptacyclic monomers such as hexacycloheptadecene, and the corresponding substituted polycyclic norbornenes. Structures of exemplary cycloolefins are shown below.

• »·» ir· 3 &iacgr;' »

- 14 -

.0

C0

.0

_NCH3

_{C6H5 ​}

-C ₆ H ₅

( _CH2 ),

( _CH2 ) ₄

( _CH2 ) ₆

= _CHCH3

_COOCH3

_COOCH3

COOH

COOH

- 16-

_{COOCHoC6H5 ​}

COOCH ₂ C ₆ H ₅
0

COOCH ₂ CH ₃

COOCH ₂ CH ₃ COO(CH ₂ ) ₃ CH ₃

COO(CH ₂ ) ₃ CHb

CHO(CH ₂ ) ₅ CH ₃

_{CH2CO3 ​}

C O

COO(CH ₂ ) ₉ CHb

COO(CH ₂ )IiCH ₃

COO(CH ₂ )I ₁ CH ₃

_OCH3

_OCH3

A preferred metathetizable monomer is ethylidene norbornene, particularly 5-ethylidene-2-norbornene monomer (referred to herein as "ENB") and dicyclopentadiene (referred to herein as "DCPD"). Ethylidene norbornene surprisingly provides superior performance toward a variety of substrates.

When used as a coating or adhesive, the metathetizable monomer or oligomer can be used alone in a substantially pure form or as an engineered product. Of course, as described below, the metathetizable monomer or oligomer can also be used in a mixture with other components, or it can be significantly diluted with a solvent or carrier liquid. As used herein, the term "engineering grade" means a solution containing at least about 90% by weight of monomer or oligomer. The advantage of using an engineering grade is that the metathetizable composition is approximately 100% reactive and thus there are no workplace or environmental problems caused by volatile organic compounds or performance problems caused by unreactive additives and no need for purification.

Alternatively, the metathetizable monomer or oligomer may also be included in a multi-component composition such as an emulsion, dispersion, solution or mixture. In other words, the metathetizable material may be a multi-component composition containing at least one metathetizable component such as a metathetizable monomer or oligomer. Preferably, this composition containing a metathetizable component is in the form of a liquid, paste or meltable solid when applied. The metathetizable liquid composition may be prepared by mixing the components together by conventional means and may then be stored for an extended period of time (referred to herein as "shelf time") before use.

For example, the metathetizable monomer can be dissolved or dispersed in conventional organic solvents such as cyclohexane, methylene chloride, chloroform, toluene, tetrahydrofuran, N-methylpyrrolidone, methanol, ethanol or acetone or in water. A particularly suitable composition could contain the metathetizable monomer/oligomer dissolved in a polymer such as a polyester, polyurethane, polycarbonate, epoxy or acrylic resin. The metathetizable component can also be included in a multicomponent composition wherein the metathesis polymerization occurs in the presence of a preformed and/or co-forming material, resulting in the formation of an interpenetrating polymer network (IPN).

The metathetizable composition (either monomer alone or multicomponent) preferably has a solids content of about 100%. In other words, the composition contains essentially no amount of liquid that does not react to form a solid.

The amount of metathetizable material applied to a substrate surface should be sufficient to form a continuous film in the case of a coating or to provide sufficient bonding in the case of an adhesive. The amount will vary depending on a variety of

Factors including substrate type and desired properties, but it could be in the range of 0.01 to 1000, preferably 0.1 to 100, and most preferably 0.3 to 25 mg/cm ² substrate surface.

According to another embodiment shown in Figure 2, the second substrate contains a metathetizable component for connection to the first substrate. The metathetizable material may be present as a chemically or ionically bonded part of the substrate material, or it may simply be present in the form of a physical mixture (e.g. hydrogen bonding).

&iacgr;&ogr; Any catalyst capable of polymerizing the metathetizable material upon contact can be used. The catalyst should also have good stability after being applied to the substrate surface. In particular, for a compound under normal ambient conditions, the catalyst should be able to maintain its activity after being applied to the substrate material in the presence of oxygen and moisture for a sufficient time and until the metathetizable material is brought into contact with the catalyst. Experimental tests have indicated that certain catalysts can remain active for at least 30 days after being applied to the substrate surface.

0 There are numerous known metathesis catalysts that could be suitable for the invention. Transition metal carbene catalysts are well known - exemplary metathesis catalyst systems are rhenium compounds (such as Re ₂ O ₇ /AI ₂ O3, ReCI ₅ /AI ₂ O ₃ , Re ₂ O ₇ ZSn(CHs) ₄ and CH ₃ ReO ₃ /AI ₂ O ₃ -SiO ₂ ); Ruthenium compounds (such as RuCI ₃ , RuCI ₃ (hydrate), K ₂ [RuCI ₅ -H ₂ O], [Ru(H ₂ O) ₆ ](tos) ₃ ("tos" means tosylate), ruthenium/olefin systems (this means a solution or dispersion of a preformed complex between Ru and olefin (monomer), which also comprises a ß-oxygen atom, in the presence or absence of a soluble or dispersed polymer, where the polymer can be an oligomer or higher molecular weight polymer prepared by metathesis or another conventional polymerization synthesis) and ruthenium carbene-

- 20 -

Complexes (as described in detail below); Osmium compounds (such as OsCI ₃ , OsCI ₃ (hydrate) and osmium carbene complexes as described in detail below); Molybdenum compounds (such as molybdenum carbene complexes (such as t-butoxy and hexafluoro-t-butoxy systems), molybdenum pentachloride, molybdenum oxytrichloride, tridodecylammonium molybdate, methyltricaprylammonium molybdate, tri(tridecyl)ammonium molybdate and trioctylammonium molybdate); Tungsten compounds (such as tungsten-carbene complexes (such as t-butoxy and hexafluoro-t-butoxy systems), WCI ₆ (typically with a cocatalyst such as SnR ₄ (R means alkyl) or PbR ₄ ), tungsten oxytetrachloride, tungsten oxide, tridodecylammonium tungstate, methyltricaprylammonium tungstate, tri(tridecyl)ammonium tungstate, trioctylammonium tungstate, WCI ₆ /CH ₃ CH ₂ OH/

CH ₃ CH ₂ AICI ₂ , WO ₃ /SiO ₂ /AI ₂ O _3/ WCI ₆ /2,6-C ₆ H ₅ -C ₆ H ₅ OH/SnR _4/ WCI ₆ /2,6-Br-C ₆ H ₃ OH/ SnR ₄ , WOCl4/2,6-C ₆ H ₅ -C ₆ H ₅ OH/SnR ₄ , WÖCI ₄ /2,6-Br-C ₆ H ₃ OH/SnR ₄ ); TiCI ₄ /aluminium alkyl; NbO _x /SiO ₂ /isobutyl-AICI ₂ ; and MgCI ₂ . As already mentioned, some of these catalysts, in particular tungsten, require the presence of additional activator or initiator systems, such as aluminum, zinc, lead or tin alkyl. Preferred catalysts are ruthenium compounds, molybdenum compounds and osmium compounds.

Particularly preferred are ruthenium, osmium or iridium carbene complexes 0 with a structure which is

^L &igr;

X _x | R

M=C / \ _D i

wherein M is Os, Ru or Ir, R ¹ is each the same or different and is H, alkenyl, alkynyl, alkyl, aryl, alkaryl, aralkyl, carboxylate, alkoxy, alkenylalkoxy, alkenylaryl, alkynylialkoxy, aryloxy, alkoxycarbonyl, alkylthio, alkyl-5sulfonyl or alkylsulfinyl, X is the same or different and is an anionic ligand group and L is the same or different and is a neutral electron donor group. The carbon-containing substituents can be up to about

- 21 -

20 carbon atoms. Preferably, X = Cl, Br, I, F, CN, SCN or N ₃ . Preferably, L = Q(R ² ) _a , where Q = P, As, Sb or N, R ² = H, cycloalkyl, alkyl, aryl, alkoxy, arylate or a heterocyclic ring and a = 1, 2 or 3. Preferably, M = Ru, R ¹ = H, phenyl ("Ph"), -CH=C(Ph) ₂ , -CH=C(CH ₃ ) ₂ 5 or -C(CH ₃ ) ₂ Ph, L is a trialkylphosphine such as PCy ₃ (Cy is cyclohexyl or cyclopentyl), P(isopropyl) ₃ or PPh ₃ ; and X = Cl. Particularly preferred catalysts include tricyclohexylphosphine ruthenium carbenes, particularly bisitricyclohexylphosphinibenzylidene ruthenium trichloride (referred to herein as RuCl ₂ (PCy ₃ ) ₂ =CHPh). Such ruthenium and osmium carbene catalysts are described, for example, in U.S. Patent Nos. 5,312,940 and 5,342,909, both of which are incorporated herein by reference, Schwab, P.; Grubbs, RH; Ziller, JW, Journal of the American Chemical Society, 1996, 118, 100; Schwab, P.; France, MB, Ziller, JW; Grubbs, RH, Angew. Chem. Int. Ed., 1995, 34, 2039; and Nguyen, ST; Grubbs, RH, Journal of the American Chemical Society, 1993, 115, 9858.

Another ruthenium carbene complex that may be suitable is a bimetallic catalyst with a structure defined by

_CH3 , _CH3CH

where M = Ru, Os or Rh. Such a catalyst is disclosed in Dias, E.L; Grubbs, R.H., Organometallics, 1998, 17, 2758.

Preferred molybdenum or tungsten catalysts are those represented by the formula

• *

- 22 -

^R1

- ^X M= ^CH3

R"

wherein M = Mo or W, X = O or S, R ¹ = alkyl, aryl, aralkyl, alkaryl, haloalkyl, haloaryl, haloaryl or a silicon-containing analogue thereof, R ² are each individually the same or different and are an alkyl, aryl, aralkyl, alkaryl, haloalkyl, haloaryl, haloaryl or together form a heterocyclic or cycloalkyl ring and R ³ = alkyl, aryl, aralkyl or alkaryl. Preferably M = Mo, X = O, R ¹ = phenyl or phenyl(R ⁵ ), wherein R ⁵ = phenyl, isopropyl or alkyl, R ² is:-C(CH ₃ ) ₃ ,-C(CH ₃ )(CF ₃ ) ₂ ,

or

or

(where R ⁴ = phenyl, naphthyl, binaphtholate or biphenolate) and R ³
-C(CH ₃ J ₂ C ₆ H ₅ .

- 23 -

Particularly preferred are 2,6-diisopropylphenylimidoneophylidene molybdenum(VI) bis(hexafluoro-t-butoxide) (referred to herein as "MoHFTB") and 2,6-diisopropylphenylimidoneophylidene molybdenum(VI) bis(t-butoxide) (referred to herein as "MoTB"). Such molybdenum catalysts are described in Bazan, G.C, Oskam, J.H., Cho, H.N., Park, L.Y., Schrock, R.R., Journal of the American Chemical Society, 1991, 113, 6899, and U.S. Patent No. 4,727,215.

The catalyst can be applied to the surface of the substrate by any method. Typically, the catalyst is applied to the substrate surface in a liquid composition. The catalyst in its substantially pure form can exist as a liquid or a solid under normal ambient conditions. If the catalyst is a liquid, it can be mixed with a carrier liquid to dilute the concentration of the catalyst. If the catalyst is a solid, it can be mixed with a carrier liquid so that it can be easily applied to the substrate surface. Of course, a solid catalyst can also be applied to the surface without the use of a liquid carrier fluid. The preferred RuCl ₂ (PCy ₃ ^=CHPh), homobimetallic ruthenium, MoHFTB and MoTB catalysts exist as solids under normal ambient conditions and are thus usually mixed with carrier fluids. The catalyst composition could also be considered a primer in the sense that it prepares the substrate surface for the subsequent application of a coating or adhesive.

Alternatively, the catalyst may be mixed in bulk with the substrate material. When the catalyst is mixed in bulk with the substrate material, it is preferably allowed to exude or "bleed" to the surface of the substrate. One method of making such a catalyst-containing substrate is to mix the catalyst in bulk with the substrate material and then form the substrate article from the resulting mixture by molding, extrusion, and the like. Of course, the catalyst must not be influenced by the composition of the substrate article.

- 24-

materials or by the process for manufacturing the substrate article.

The present invention preferably does not require prefunctionalization of the substrate surface prior to application of the catalyst. In other words, the substrate surface does not need to be reacted with an agent that prepares the surface to receive the catalyst. For example, the formation of a so-called monolayer or self-assembling layer made from a material other than the catalyst or metathetizable adhesive or coating (such as a thiol) is unnecessary. The catalyst can be applied so that it is in "direct contact" with the substrate surface. Of course, for metallic substrates, the substrate surface can be pretreated with conventional cleaning treatments or conversion treatments, and for elastomeric substrates, the surface can be wiped with a solvent.

The catalyst can be dispersed, suspended or dissolved in the carrier liquid. The carrier liquid can be water or any conventional organic solvent such as dichloroethane, toluene, methyl ethyl ketone, acetone, tetrahydrofuran, N-methylpyrrolidone, 3-methyl-2-oxazolidinone, 1,3-dimethylethyleneurea, 1,3-dimethylpropyleneurea and supercritical carbon dioxide. Ruthenium, osmium and iridium catalysts are particularly well suited in polar organic and aqueous carrier systems. The carrier liquid can be capable of evaporating from the substrate surface under normal ambient conditions or upon heating.

The amount of catalyst applied to the substrate should be sufficient to effect metathesis polymerization. The amount will vary depending on a variety of factors including substrate type and desired properties, but could range from 0.001 to 10, preferably 0.01 to 5, and most preferably 0.1 to 5 mg/cm ² of substrate surface area.

The adhesive or coating of the invention offers numerous advantages of ease of use. Metathesis polymerization occurs under normal ambient conditions in air regardless of the presence of moisture. An external energy source such as radiation, thermal or photochemical energy for curing to form the adhesive or coating is not required. The adhesive or coating thus adheres to thermally or solvent sensitive surfaces. In addition, there are only a minimal number of steps. It is not necessary to first react the substrate surface to form a particular type of functional group on the surface. There is no need for multiple, carefully controlled steps required to form so-called monolayers or self-assembling layers. The compound that is formed exhibits remarkable adhesive strength considering the ease of use of the process.

Another significant advantage is that the process is environmentally friendly. The catalyst can be applied to the substrate surface using an aqueous carrier liquid. A substantially pure or technical grade metathetizable monomer/oligomer can be used, and the monomer/oligomer is essentially 100% reactive. Consequently, essentially no volatile organic solvents are used.

Without wishing to be bound by any particular theory, we believe that the adhesive or coating formed achieves the remarkable bond due to several factors. The monomer and/or catalyst easily diffuses into the substrate surface, especially of elastomeric substrates. As a result of this diffusion, an interpenetrating network develops between the polymer chains formed from the metathetizable material and the molecular structure of the substrate material. Moreover, the metathesis polymerization reaction may well also favor the formation of strong covalent bonds formed between molecules of the metathetizable material and molecules of the substrate. A unique advantage of the coating is its excellent adhesion to the substrate surface.

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The adhesive or coating is an addition polymer formed via the metathesis reaction. The resulting polymer should be able to form a continuous film. Olefin metathesis typically yields polymers with an unsaturated linear backbone. The degree of unsaturation functionality of the repeat unit of the polymer backbone is the same as that of the monomer. With a norbornene reactant, the resulting polymer should have a structure characterized by

catalyst

where η can be from 1 to 20,000, preferably from 1 to 500, more preferably from 1 to 100, and most preferably from 10 to 100. The molar ratio of norbornene reactant to catalyst should be in the range of from 20,000:1 to 1:1, preferably from 500:1 to 1:1, and most preferably from 100:1 to 10:1.

The resulting polymer film can be brittle, but surprisingly superior bonding occurs even with flexible substrates. If there are cracks in the film, they do not appear to propagate into the substrate.

In a preferred embodiment, the liquid catalyst (either alone or as a component of a multi-component catalyst composition) is applied to the substrate surface. The catalyst may be applied using any conventional coating method such as spraying, dipping, brushing, wiping, roller coating or the like to provide continuous surface coverage or coverage only in predetermined selected areas. The metathetizable material may be contacted with the resulting catalyst-coated surface while it is still wet. However, the catalyst carrier liquid is preferably allowed to evaporate and then

-27-

the metathetizable material is applied to the dry catalyst-coated surface. Evaporation of the catalyst support liquid can occur over time under normal ambient conditions, or it can be accelerated by subjecting the catalyst-coated surface to heat or vacuum. A notable advantage of the invention is that the dry catalyst-coated surface remains stable and active for extended periods of time. Although we do not wish to be bound by specific limits, we believe that the dry catalyst-coated surface should retain its activity for at least five minutes, preferably at least 24 hours, more preferably at least 1 month, and most preferably at least 6 months. This stability contributes to manufacturing flexibility by providing a relatively long time during which the metathetizable material can be contacted with the catalyzed surface. For example, a series of substrates can be coated with the catalyst and then stored until needed for coating or bonding. In an alternative embodiment, the catalyst and the metathetizable material can be applied simultaneously to the substrate surface by spray coating.

Once the catalyst has been provided on the substrate surface, the metathetizable material (whether in the form of a second substrate, a coating, or an adhesive) will be contacted with the catalyst on the substrate surface. The metathetizable material typically begins to react upon contact with the catalyst. Film formation is caused by metathesis polymerization of the metathetizable material to form a substantially linear polymer. The rate of film formation could be increased by the addition of either Bronsted acids, Lewis acids, or CuCl to either the catalyst composition or the metathetizable composition. Methods for contacting the metathetizable material with the catalyst-coated surface depend on the intended use.

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If the metathetizable material itself is to form a coating, it may be applied to the catalyst-coated substrate surface in a liquid form under normal ambient conditions by any conventional coating method such as spraying, dipping, brushing, wiping, roller coating or the like. The metathetizable coating material could also be applied by extrusion if it is in the form of a molten material. The coating thickness may be varied depending on the intended use.

The metathetizable material, particularly in the form of a monomer, can be incorporated as a component in a multi-component exterior coating formulation, such as a paint or a sealant. In such a system, the catalyst should be incorporated into a primer formulation which is applied prior to the exterior coating.

When the metathetizable material is to form an adhesive to bond two substrates together, the metathetizable material can be applied directly to the catalyst-coated substrate surface in a liquid form under normal ambient conditions using any conventional coating/printing method such as spraying, dipping, brushing, wiping, roller coating or the like. Then, the other substrate surface is brought into contact with the metathetizable material before curing of the metathetizable material is complete. Preferably, however, the metathetizable material is applied to the substrate surface not coated with the catalyst and the substrate coated with the metathetizable adhesive and the catalyst-coated substrate can be brought into contact under normal ambient conditions to effect adhesive bonding. The metathetizable material can be applied directly to the non-catalyst-coated substrate surface in a liquid form under normal ambient conditions using any conventional coating/printing method such as spraying, dipping, brushing, wiping, roller coating or the like. The metathetizable material can be allowed to dry or it can remain wet before the two substrates

- 29 -

The metathetizable adhesive material could also be applied by extrusion in these two alternative processes if it is in the form of a molten material. If the metathetizable material is a solid at room temperature, it should be heated to at least partially melt or become semi-solid to facilitate bonding. Pressure could also be applied to a solid metathetizable material to achieve a microfluid surface layer.

The types of substrate surfaces that can be coated or bonded vary widely. The substrates, of course, are articles that are useful in their own right. Such substrates could include machined parts made of metal and elastomers, molded parts made of elastomers or engineering plastics, extruded articles such as fibers or parts made of thermoplastics or thermosets, metal sheet or roll products, fiberglass, wood, paper, ceramics, glass, and the like. The term "substrate" as used herein does not include conventional catalyst supports made from bulk materials such as alumina or silica. Conventional catalyst supports are useful only for supporting a catalyst to effect polymerization, but they would not be useful themselves without a catalyst.

0 Exemplary elastomer substrates are natural rubber or synthetic rubber such as polychloroprene, polybutadiene, polyisoprene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber ("NBR"), ethylene-propylene copolymer rubber ("EPM"), ethylene-propylene-diene terpolymer rubber ("EPDM"), butyl rubber, brominated butyl rubber, alkylated chlorosulfonated polyethylene rubber, hydrogenated nitrile rubber ("HNBR"), silicone rubber, fluorosilicone rubber, poly(n-butyl acrylate), thermoplastic elastomer, and the like, and mixtures thereof.

Exemplary engineering plastic substrates suitable for the invention are polyester, polyolefin, polyamide, polyimide, polynitrile, polycarbonate, acrylic , acetal, polyketone, polyarylate, polybenzimidazole, polyvinyl alcohol,

&tgr;»♦» · ■> · ¹ S * «

- 30-

Ionomer, polyphenylene oxide, polyphenylene sulfide, polyarylsulfone, styrene resins, polysulfone, polyurethane, polyvinyl chloride, epoxy resins and polyether ketones.

Exemplary metal substrates are iron, steel (including stainless steel and electrogalvanized steel), lead, aluminum, copper, brass, bronze, monel metal alloy, nickel, zinc, tin, gold, silver, platinum, palladium, and the like. Prior to application of the catalyst, the metal surface may be cleaned by one or more methods known in the art, such as degreasing and blasting, and/or the metal surface may be converted (passivated) or coated by phosphating, electrodeposition, or autodeposition.

Example fiber substrates include glass fiber, polyester, polyamide (both nylon and aramid), polyethylene, polypropylene, carbon, rayon, and cotton.

Exemplary fiber reinforced or impregnated composite substrates are fiberglass reinforced prepreg ("FRP"), resin mat ("SMC"), and fiber reinforced elastomer composites. In the case of fiber reinforced elastomer composites, fiber substrates can be sandwiched between and bonded to the outer elastomer layers to form a multilayer composite structure, such as tires, automotive belts, hoses, air springs, and the like. The metathetizable adhesive of the invention could be used to bond fiber reinforced cord to tire materials.

The adhesive embodiment of the invention could also be used to make fiber reinforced or impregnated composites themselves. For example, the catalyst can be coated onto the fiber or cord and then either a separate metathetizable material is contacted with the catalyst treated fiber or cord to form an adhesive with the composite matrix material, or the composite matrix material is itself metathetizable.

- 31 -

The invention is particularly well suited to bonding two substrates together. The above types of substrate could all be bonded together. The substrates may each be made of the same material or of different materials. The invention is particularly well suited to bonding post-vulcanized or cured elastomer, especially to a substrate made of a different material, such as metal.

It has been found that superior bonding of cured elastomer substrates is obtained when the metathetizable material is applied to the cured elastomer substrate surface and then the elastomer substrate with the applied adhesive is contacted to the other catalyst coated substrate. This process is shown schematically in Figure 1. This preferred process is particularly applicable to the bonding of cured elastomer to metal and cured elastomer to cured elastomer. The catalyst is applied to the surface of the metal substrate and allowed to dry. The metathetizable adhesive is applied to the surface of the elastomer substrate. The catalyst coated metal substrate and the adhesive coated substrate are brought together under a minimum pressure sufficient to simply hold the substrates together and in place until the metathesis reaction initiated by contact with the catalyst has progressed to a sufficient point of cure to provide at least a "green strength" bond. Depending on the rate of diffusion of metathetizable material into the substrate and the rate of evaporation of the metathetizable material, up to 30 minutes may elapse before the two substrates are brought together, but preferably about 30 seconds to about 5 minutes. In the case of bonding cured EPDM to steel, green strength appears to develop within about five to ten minutes after the substrates are brought into contact with each other, and high bond strength appears to develop within about thirty minutes after the substrates are brought into contact with each other.

The bonding process is particularly well suited to bonding a substrate made of a thermoplastic elastomer such as Santoprene® to another thermoplastic elastomer substrate or to a substrate made of another material. Santoprene® is the trade name for a thermoplastic elastomer ("TPE") commercially available from Advanced Elastomer Systems that consists of elastomer particles dispersed in a continuous matrix of thermoplastic material. Such TPE blends are described in detail in U.S. Patent No. 5,609,962, which is incorporated herein by reference. TPE, as the term is used herein, also includes thermoplastic olefins ("TPO") such as those described in U.S. Patent No. 5,073,597, which is incorporated herein by reference.

The thermoplastic material used as the continuous TPE matrix is typically polyolefins. According to the '962 patent, they are desirably made from monoolefin monomers having 2 to 7 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 3-methyl-l-pentene, 4-methyl-l-pentene, 5-methyl-l-hexene, mixtures thereof, and copolymers thereof with (meth)acrylates and/or vinyl acetates. Preferred are monomers having 3 to 6 carbon atoms, with 0 propylene being preferred. The polypropylene may be highly crystalline isotactic or syndiotactic polypropylene.

A portion of the polyolefin component may be a functionalized polyolefin according to the '962 patent. In other words, nonfunctionalized polyolefins and functionalized polyolefins may be blended together to form the TPE. The polyolefins in the functionalized polyolefins may be homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, as well as copolymers of ethylene with one or more α-olefins. Preferred among the polyolefins are low density polyethylene, linear low density polyethylene, medium and high density polyethylene, 0 polypropylene, and random or block copolymers of propylene and ethylene.

The functionalized polyolefins contain one or more functional

- 33-

Groups that were incorporated during polymerization. However, they are preferably polymers onto which the functional groups have been grafted. Monomers that form functional groups are preferably carboxylic acids, dicarboxylic acids or their derivatives, such as their anhydrides.

The elastomer component of TPE consists of olefinic rubbers such as EPM, EPDM, butyl rubber, copolymer of a C^-isomonoolefin and a para-alkylstyrene, natural rubber, synthetic polyisoprene, polybutadiene, styrene-butadiene copolymer rubber, nitrile rubber, polychloroprene and mixtures thereof.

According to the '962 patent, the amount of polyolefin is generally from about 10 to about 87 weight percent, the amount of rubber is generally from about 10 to about 70 weight percent, and the amount of functionalized polyolefin is from about 3 to about 80 weight percent, provided that the total amount of polyolefin, rubber, and functionalized polyolefin is at least about 35 weight percent based on the total weight of polyolefin, rubber, functionalized polyolefin, and optional additives.

The olefin rubber component is generally present in the form of small particles, e.g. micro-sized, within a continuous polyolefin matrix. The rubber is partially crosslinked (cured) and preferably fully crosslinked or cured. Partial or full crosslinking can be achieved by adding a suitable rubber vulcanizing agent to the polyolefin-rubber mixture and vulcanizing the rubber to the desired degree under conventional vulcanization conditions. Preferably, the rubber is crosslinked by the dynamic vulcanization process, wherein the rubber is vulcanized under high shear conditions at a temperature above the melting point of the polyolefin component. Thus, the rubber is simultaneously crosslinked and dispersed in the form of small particles within the polyolefin matrix.

The bonding process is also particularly well suited to bonding an elastomeric or plastic tire tread to an elastomeric or plastic tire carcass. As described above, tire retreading generally involves bonding a precured or uncured retread material directly to a cured tire carcass. The metathetizable adhesive material of the invention can be used to replace the adhesive pad or pad rubber layer currently used in the retreading art.

The metathesis catalyst is applied to an adhesive surface of either the tire carcass or an adhesive surface of the tire tread, and the metathetizable material is applied to the other of the adhesive surface of the tire carcass and the tire tread. Preferably, the catalyst is applied to the tire carcass and the metathetizable material is applied to the tire tread. The carcass of the used tire can be roughened by known means to provide a surface that will accept the catalyst or metathetizable material. Preferably, the adhesive surface is slightly rough or only lightly sandblasted. The retread material coated with the catalyst or metathetizable material is placed circumferentially around the tire carcass coated with the catalyst or metathetizable material. The coated surfaces are then brought into contact with one another under a minimum pressure sufficient to simply hold the tread and carcass together. During curing of the metathesis material, the tread material and carcass may be held together by any conventional means in the retreading field, such as by stacking or placing a cover or film around the tire structure. Curing is initiated when the surfaces are brought into contact with each other, green strength begins to develop within about five to ten minutes, and high bond strength begins to develop within about 15 minutes to one hour.

The resulting tire laminate comprises a tire casing or cover, a new tire tread, and a metathesis polymer adhesive layer between the casing and the new tread. The tire laminate is suitable for various types of vehicle tires, such as passenger tires, light and medium truck tires, off-road tires, and the like. This bonding process is also applicable to the manufacture of new tires, wherein a tread is applied to a treadless tire casing or cover. The catalyst and metathesisable material are typically applied in liquid form.

Retread or tread material is well known in the art and may be any cured or uncured conventional synthetic or natural rubber such as rubbers made from conjugated dienes having 4 to 10 carbon atoms, rubbers made from conjugated diene monomers having 4 to 10 carbon atoms and vinyl substituted aromatic monomers having 8 to 12 carbon atoms, and mixtures thereof. Such rubbers generally contain various antioxidants, fillers such as carbon black, oils, sulfur, accelerators, stearic acid, and antiozonants and other additives. Retread or tread material may be in the form of a tape that is placed around the outer edge of the concentric circular tire carcass or tread. The cured carcass is similarly well known in the art and is made from conjugated dienes such as polyisoprene or natural rubber, rubbers made from conjugated diene monomers having 4 to 10 carbon atoms and vinyl substituted aromatic monomers having 8 to 12 carbon atoms, and mixtures thereof. Such rubbers generally contain various antioxidants, fillers such as carbon black, oils, sulfur, accelerators, stearic acid, as well as antiozonants and other additives.

The invention is described in more detail by means of the following non-limiting examples. Unless otherwise stated, the steel test strips used in the examples are made of blasted, fully hardened

·

tem, cold rolled 1010 steel, the strips of cured EPDM rubber are available from British Tire and Rubber under reference 96616 and all bonding and coating was carried out under normal ambient conditions.

The primary adhesion of the bonded specimens was tested according to ASTM-D 429, Method B. The bonded specimens are placed in an Instron machine and the elastomeric substrate is pulled away from the other substrate at an angle of 180° at 50.88 mm (2 inches) per minute. The average load at maximum load and the average energy to break

γ are measured. After being pulled apart, the samples are examined to determine the fracture behavior. The most desirable fracture behavior is rubber tearing, i.e. a portion of the elastomeric material of one of the substrates remains on the other substrate. Rubber tearing indicates that the adhesive is stronger than the elastomeric material.

Example 1 - Bonding EPDM to metal - Application of the catalyst by a drip or flood method

A catalyst solution was prepared by dissolving 0.021 g of RuCl ₂ (PCy 3 ) ₂ =CHPh in 1.5 mL of CH ₂ Cl _2. Three blasted steel sample strips were prepared by pipetting 0.5 mL of the catalyst solution onto each strip with a syringe so that its surface (34.9 mm × 25.4 mm) was just covered and the solvent was allowed to evaporate for three to four minutes in the open laboratory atmosphere. This yielded > 7 mg of RuCl ₂ (PCy ₃ ) ₂ =CHPh per strip. The metal strips were usually washed with acetone and dried prior to application of catalyst solution 5, but this was not necessary. In this example, the strips were unwashed. EPDM rubber strips were prepared by washing the bonding surface (34.9 mm x 25.4 mm) with acetone, drying for 3 to 4 minutes at room temperature, and then applying 0.03 ml of ENB to each strip with a syringe and spreading it evenly with the needle tip 0. The catalyst-coated metal strip was immediately

was placed on the ENB coated EPDM strip so that both treated surfaces were in contact with each other and a weight of approximately 100 g was placed on the contact area. The samples were left overnight under ambient conditions. None of the samples could be pulled apart by hand. They were evaluated using a 180° peel test with an Instron machine and showed only tearing of the EPDM rubber as failure behavior. A total of 12 samples were tested and the mean load at maximum load was 273.04 N and the mean energy to break was 37.87 J.

Example 2 - Bonding EPDM to metal

This test was conducted as a pre-screening test to evaluate different application methods for bonding EPDM to metal. The method described in Example 1 was used to apply the RuCl2( _PCy3 ) ₂ =CHPh catalyst solution or ENB to either a blasted steel strip or an EPDM rubber strip. The results are shown below in Table 1. Based on these results, the best bonding method appeared to be the one in which the catalyst was applied to the metal and the ENB was applied to the EPDM. In Table 1, the substrate type listed under the "catalyst" or "monomer" column is the substrate to which the catalyst or monomer, respectively, was applied.

Table 1. Comparison of the bond between application surfaces

catalyst Monomer Connection Remarks metal rubber good Could not pull by hand
be pulled apart. Metal ³ Metal ³ variable A sample could be pulled apart,
while the other two are not quite
could be pulled apart and
showed signs of rubber tearing. Metal ³ Metal ³ variable Fresh catalyst solution used. A
Sample could be pulled apart,
while the other two are not quite
could be pulled apart and
showed signs of rubber tearing. rubber metal bad Adhesion to rubber was good, on metal
bad. Rubber ⁰ Rubber ¹³ bad Adhesion to rubber was good, on metal
bad. Rubber" Rubber" bad Fresh catalyst solution used.
Adhesion to rubber was good, on metal
bad.

^a) Catalyst was applied to metal surface, then ENB was applied before assembly.

^b) Catalyst applied to EPDM surface, then ENB was applied before assembly.

Example 3 - delayed bonding of catalyst coated substrates

A catalyst solution was applied to blasted metal strips according to the procedure described in Example 1, but the catalyst-coated strips were allowed to dry and stored in the laboratory under ambient conditions (apart from a dust cover) for 3, 10, 20 and 33 days, respectively.

before being bonded to the EPDM with ENB. All samples showed tearing of the EPDM rubber when subjected to a 180° peel test. The 3-day samples had a mean load at maximum load of 291.49 N and a mean energy to break of 39.29 J; the 10-day samples had a mean load at maximum load of 298.32 N and a mean energy to break of 40.18 J; the 20-day samples had a mean load at maximum load of 262.79 N and a mean energy to break of 35.76 J; and the 33-day samples had a mean load at maximum load of 313.26 N and a mean energy to break of 48.48 J.

Example 4 - Application of catalyst to substrate by brushing method

A catalyst solution was prepared by dissolving 0.021 g of RuCl ₂ (PCy ₃ ) 2 = CHPh in 1.5 mL of CH ₂ Cl ₂ in a screw-capped vial under N ₂ . This solution was applied with a brush to three blasted steel strips over the area to be bonded (34.9 mm × 25.4 mm), and the solvent was allowed to evaporate in the open laboratory atmosphere during the brushing process, leaving the catalyst powder evenly distributed over the surface of the metal strip. After drying, all prepared samples were weighed to determine the amount of catalyst on the surface, which was 5.8 ± 1.8 mg per strip. When the first prepared solution was used up, another batch of fresh catalyst solution was prepared as described above. A total of 12 samples were prepared in this manner. EPDM rubber strips were prepared by washing the bonding surface (34.9 mm x 25.4 mm) with acetone, drying for 3 to 4 minutes at room temperature, and then applying 0.03 ml of ENB to each strip using a syringe and spreading it evenly with the needle tip. The catalyst-coated metal strip was immediately placed on the ENB-coated EPDM strip so that both treated surfaces were in contact with each other, and a weight of approximately 100 g was placed on the contact area. The samples were left overnight under ambient conditions. No tearing was observed the next morning when attempting to

to pull the samples apart by hand. They were evaluated using a 180° peel test with an Instron machine and showed a uniformly distributed tear of the rubber on the EPDM at failure. A total of 12 samples were tested and showed a mean load at maximum load of 283.87 N and a mean energy to failure of 41.72 J.

Example 5 - Application of catalyst in water to substrate

A catalyst solution was prepared by dissolving 0.015 g

and 0.006 g of dodecyltrimethylammonium bromide ("DTAB") as surfactant (0.488 wt. %) in 1.21 g of water. The aqueous catalyst solution was painted onto two blasted metal strips using the procedure described in Example 4, except that the strips were heated on a 40 ^° C hot plate to assist in the removal of water. The strips were cooled to room temperature and bonded to EPDM with 0.04 ml of ENB as described in Example 4. The next morning, the samples could be pulled apart by hand.

In another example, a catalyst solution was prepared from 0.0272 g RuCl ₂ (PCy ₃ ) ₂ =CHPh and 0.0024 g DTAB (0.068 wt%) in 3.5 g water. The aqueous catalyst solution was painted onto three blasted metal strips as described above, cooled to room temperature, and bonded to EPDM with 0.04 ml ENB as described in Example 4. They were evaluated using a 180° peel test with an Instron machine and showed cracking of the rubber on the EPDM at failure. A total of three samples were tested and showed a mean load at maximum load of 215.07 N and a mean energy to failure of 23.09 J.

Example 6 - Residence time of ENB monomer on EPDM substrate

-41 -

Bonding of EPDM to blasted steel strips was performed as in Example 1 except that 0.04 ml of ENB was allowed to stand on the EPDM surface to be bonded for 0, 2, and 4 minutes, respectively, before bonding to the metal. For the 4-minute test, an additional 0.03 ml of ENB was applied to two of the EPDM strips as the liquid was absorbed into the EPDM. All samples showed tearing of the EPDM rubber when subjected to the 180° peel test. The 0-minute samples had a mean load at maximum load of 256.41 N and a mean energy to tear of 29.45 J; the 2-minute samples had a mean load at maximum load of 273.12 N and a mean energy to tear of 35.34 J; and the 4-minute specimens had a mean load at maximum load of 247.28 N and a mean energy to break of 22.82 J.

Example 7 - Bonding EPDM to metal using different steel substrates

Phosphated and unprocessed 1010 steel were bonded to EPDM rubber according to the procedure described in Example 1. The bond strength was reduced compared to blasted steel, but all samples still showed some tearing of the EPDM rubber when subjected to the 180° peel strength test. The phosphatized steel samples had a mean 0 load at maximum load of 158.69 N and a mean energy to tear of 13.49 J; and the unprocessed 1010 steel samples had a mean load at maximum load of 209.07 N and a mean energy to tear of 19.88 J.

Example 8 - Application of catalyst to substrate by spraying

5 A catalyst solution was prepared by dissolving 0.5 g RuCl2(PCy ₃ ) ₂ =CHPh in 20 ml CH ₂ CI _2. The catalyst solution was sprayed onto 12 blasted steel strips in a sweep pattern until a uniform coverage of the bonding area (34.9 mm x 25.4 mm) was obtained. The solvent was allowed to dry for 1.5 hours in the open laboratory

atmosphere. After drying, all prepared samples were weighed to determine the amount of catalyst on the surface; it was 9.0 ± 0.95 mg per strip. EPDM rubber strips were prepared by washing the bonding surface (34.9 mm × 25.4 mm) with acetone, drying for 3 to 4 minutes at room temperature, and then applying 0.06 mL of ENB to each strip using a syringe and spreading it evenly with the needle tip. The catalyst-coated metal strip was immediately placed on the ENB-coated EPDM strip so that both treated surfaces were in contact with each other, and a weight of approximately 100 g was placed on the contact area. The samples were left overnight under ambient conditions. The next morning, none of the samples could be pulled apart by hand, and they showed only tearing of the EPDM rubber after analysis on an Instron machine. A total of 12 samples were tested and showed an average load at maximum load of 352.47 N and an average energy to break of 61.23 J.

Example 9 - Bonding EPDM to metal using other metals

A catalyst solution was prepared by dissolving 0.030 g RuCl ₂ (PCy3) ₂ =CHPh in 2.5 mL CH ₂ Cl _2. The catalyst solution was coated on metal strips of steel Q-sheet, aluminum, and chromated aluminum, and the 0 metal strips were bonded to EPDM rubber strips with 0.04 mL ENB monomer per strip as described in Example 4. Three separate but identical batches of catalyst solution were used to prepare the metal strips, resulting in 7.3 ± 1.2 mg catalyst per strip after weighing. The samples were analyzed using an Instron machine with a 180° peel test. All three metals showed very little rubber tearing with an adhesive fracture pattern as the primary fracture behavior since most of the ENB polymer film adhered to the rubber at failure. Higher bond strengths were observed on the chromated aluminum surfaces.

&iacgr; 2·J · ♦«·« ·

-43 -

Table 2. 180° peel test data for samples with EPDM on steel, on aluminum, and on chromated aluminum

Sample type Load at maximum
Load (N) Energy to
Tear (J) Steel Q-Sheet 81.08 3.91 Steel Q-Sheet 87.08 3.78 Steel Q-Sheet 79,95 3.04 Average 82.71 3.58 Al 84.45 3.59 Al 82.03 4.37 Al 114.25 6.33 Average 93.58 4.76 chrom. Al 173.28 13,00 chrom. Al 113.86 6.88 chrom. Al 144.55 8.54 Average 143.89 9.47

Example 10 - Examples of bonding Santoprene® to metal

A catalyst solution was prepared by dissolving 0.030 g of RuCl ₂ (PCy ₃ ) ₂ =CHPh in 3.0 mL of CH ₂ Cl _2. The catalyst solution was applied to blasted steel strips and the steel strips were bonded to three samples of four grades of Santoprene® (101-64, 201-64, 201-87 and 8201-90) with 0.08 mL of ENB monomer per strip as described in Example 4. When weighed, it was found to contain an average of 9.4 ± 1.2 mg of catalyst per strip. The rubber surface was grit blasted prior to application of monomer of each type. The bonded samples were analyzed using the Instron machine with the 180° peel test and the results are shown in Table 3 below. All three samples of the two softer rubbers, 101-64 and 201-64, showed excellent rubber tearing, while the stiffer rubbers, 201-87 and 8201-90, showed no rubber tearing

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and for most of the ENB polymer films that adhered to the rubber, an adhesive failure pattern predominated after pulling apart these samples. Good bond strength data were obtained for all samples.

Table 3. 180° peel test data for sandblasted Santoprene® specimens with rubber-to-metal bond

Sample type Load at maximum
Load (N) Energy to
Tear (J) 101-64 106.60 2.49 101-64 98.75 5.60 101-64 105.32 2.25 Average 103.56 3.45 201-87 72.76 3.69 201-87 87.64 3.27 201-87 103.56 3.96 Average 87.99 3.64 201-64 72.45 4.09 201-64 114.54 3.30 201-64 90.27 5.41 Average 92.42 4.27 8201-90 165.54 4.35 8201-90 165.24 6.02 8201-90 230.06 8.54 Average 186.94 6.30

Example 11 - Bonding natural rubber to blasted steel

RuCI ₂ (PCy ₃ ) ₂ =CHPh was coated onto blasted steel strips and bonded with 0.10 ml of ENB monomer per strip using the procedure described in Example 4. Four natural rubber samples were prepared. Two samples were sandblasted and two samples were not sandblasted.

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blasted. The bonded samples were allowed to rest for a period of two days. On the third day, the two samples made from the sandblasted natural rubber were pulled apart by hand. A thin ENB polymer film remained on the natural rubber strip and some rubber tearing was observed. The two samples made from non-sandblasted natural rubber could not be pulled apart by hand and were analyzed using the Instron machine with the 180° peel test. The bonded samples had a mean load at maximum load of 183.14 N and a mean energy to break of 12.20 J. Rubber tearing was observed in the sample with the higher values.

Example 12 - Bonding EPDM to blasted steel with MoTB catalyst

A catalyst solution was prepared by dissolving 0.021 g of 2,6-diisopropylphenylimidoneophylidene molybdenum(VI)bis(t-butoxide) (MoTB) in 2 mL _{of CH2Cl2} . The catalyst solution was coated onto blasted steel strips, and then the steel strips were bonded to EPDM rubber strips using 0.08-0.09 mL of ENB monomer per strip as described in Example 4. Because of the sensitivity of the catalyst to air and moisture, all handling of rubber and metal strips and catalyst solutions was performed in a glove box under an argon atmosphere. Once bonded, the samples were kept in the glove box until mechanical testing was performed. The original blasted metal and rubber strips had been kept in the glove box for several months to ensure complete removal of any water or oxygen contamination. It was later found that this was unnecessary, as bonding was observed even in samples that had only a few hours of glovebox time. It was noted that the strips could not be turned over within 5-10 seconds of the two surfaces being joined together, suggesting that polymerization had occurred. All samples were analyzed on an Instron machine using the 180° peel test. Results are averages for two

separate data sets: the original two bonded samples (long residence time in the glovebox) - mean load at maximum load of 46.57 N and mean energy to break of 1.54 J; and three new samples (surfaces were thoroughly washed with acetone before being placed in the glovebox and subsequently washed in the box with CH ₂ CI ₂ before adding the monomer) - mean load at maximum load of 139.26 N and mean energy to break of 11.12 J. Some degree of rubber breakage was observed in all samples except one.

Example 13 - Bonding of EPDM to blasted steel using a homobimetallic ruthenium catalyst

A catalyst solution was prepared by dissolving 0.030 g of RuCl ₂ (p-cymene)RuCl ₂ (PCy ₃ ) ₂ =CHPh in 3.1 mL of CH ₂ Cl _2. The catalyst solution was applied to blasted steel strips and then the steel strips were bonded to EPDM rubber strips with 0.08 mL of ENB monomer per strip as described in Example 4. The bonded samples were analyzed on the Instron machine using a 180° peel test. The bonded samples had a mean load at maximum load of 226.60 N and a mean energy to break of 26.78 J. 0 Rubber breakage was observed in all samples.

Example 14 - Bonding EPDM to blasted steel using DCPD as monomer

A catalyst solution was prepared by dissolving 0.031 g of RuCl ₂ (PCy ₃ ) ₂ =CHPh in 3.2 ml of CH ₂ CI _2. The catalyst solution was applied to blasted steel strips and then the steel strips were bonded to EPDM rubber strips with DCPD monomer as described in Example 4. The procedure for applying the DCPD varied slightly from that for ENB. The EPDM surface was washed with acetone before applying the DCPD monomer, which allowed gentle melting of the distilled dicyclopentadiene with a

heat gun, pipetting the liquid onto the EPDM surface and spreading the liquid with a pipette. Upon cooling, the DCPD solidified. Once the monomer was applied, the DCPD coated surface was gently heated with a heat gun to melt the solid; the metal and rubber parts were immediately bonded together and weighted with approximately 100 g. The bonded samples were analyzed with the Instron machine using a 180° peel test. The bonded samples had a mean load at maximum load of 290.78 N and a mean energy to break of 44.44 J. Rubber rupture was observed in all samples.

Example 15 - Bonding EPDM to blasted steel using methylidene norbornene as monomer

A catalyst solution was prepared by dissolving 0.031 g of RuCl ₂ (PCy ₃ ) 2 = CHPh in 3.2 ml of CH ₂ Cl ₂ , applied to three blasted steel strips, and then the steel strips were bonded to EPDM with 0.10 ml of methylidene norbornene monomer per strip as described in Example 4. The bonded samples were analyzed on the Instron machine using a 180° peel test. The bonded samples had a mean load at maximum load of 40.55 N and a mean energy to break of 1.48 J.

Example 16 - Bonding EPDM to EPDM

A catalyst solution was prepared by dissolving 0.030 g of RuCl ₂ (PCy ₃ J ₂ =CHPh) in 2 mL of CH ₂ Cl _2. The catalyst solution was applied to two EPDM strips. Each catalyst-coated EPDM strip was bonded to another EPDM strip using 0.02 mL of ENB monomer per strip as described in Example 1. The EPDM rubber strips were washed with acetone and allowed to dry before applying either catalyst solution or ENB monomer. Two strips were bonded together on a surface (34.9 mm × 25.4 mm) in a lap-shear configuration; one

Examination of the samples the next day showed that they could not be pulled apart by hand. They were then analyzed using a lap shear tensile test on an Instron machine after being kept in ambient conditions for three months and showed a mean load at break of 419.42 N.

A catalyst solution was prepared by dissolving 0.027 g of RuCl ₂ (PCy ₃ ) 2 = CHPh in 2.5 mL of CH ₂ Cl _2. The catalyst solution was applied to three EPDM strips. Each catalyst coated EPDM strip was bonded to an EPDM strip using 0.07-0.10 mL of ENB monomer per strip as described in Example 4. The EPDM rubber strips were washed with acetone and allowed to dry before applying either catalyst solution or ENB monomer. Six samples were bonded in the 180° peel test mode. Three were sandblasted prior to bonding. All samples were stuck and could not be pulled apart by hand and were analyzed with an Instron machine using a 180° peel test. The sandblasted specimens had a mean load at maximum load of 166.51 N and a mean energy to break of 25.56 J, and the non-sandblasted specimens had a mean load at maximum load of 176.16 N and a mean energy to break of 26.97 J. Fracture pattern analysis showed that the sandblasted specimens showed rupture of the rubber, but that the non-sandblasted specimens showed deeper rupture of the rubber with pieces torn away.

Example 17 - Bonding EPDM to EPDM with MoTB catalyst

Two separate catalyst solutions were prepared to self-bond non-sandblasted and sandblasted EPDM samples, respectively. The first solution was prepared by dissolving 0.0216 g of 2,6-diisopropylphenylimidoneophylidene molybdenum(VI)bis(t-butoxide) (MoTB) in 2 mL of CH ₂ CI _2. The catalyst solution was applied to two non-sandblasted EPDM rubber strips, which were then bonded to EPDM rubber strips using 0.08 mL of ENB monomer per strip, as described in Example 12. The second

Solution was prepared by dissolving 0.0211 g of 2,6-diisopropylphenylimidoneophylidene molybdenum(VI)bis(t-butoxide) (MoTB) in 0.7 mL of CH ₂ Cl _2. The catalyst solution was applied to sandblasted EPDM rubber strips, which were then bonded to EPDM rubber strips with 0.13 mL of ENB monomer per strip as described in Example 12. All samples were analyzed on an Instron machine using the 180° peel test. Results are averages for two separate sets of data: the original two non-sandblasted bonded samples (long residence time in the glovebox) - mean load at maximum load of 9.41 N and mean energy to break of 0.27 J; and two new samples (surfaces were sandblasted before being placed in the glove box and then washed in the box with CH ₂ CI ₂ before adding the monomer) average load at maximum load of 12.97 N and average energy to failure of 0.76 J. No rubber failure was observed in any sample.

Example 18 - Bonding of EPDM to EPDM using homobimetallic ruthenium catalyst and ENB

A catalyst solution was prepared by dissolving 0.031 g of RuCl ₂ (p-cymene)RuCl ₂ (PCy ₃ ) ₂ =CHPh in 3.1 mL of CH ₂ Cl _2. The catalyst solution 0 was coated onto three EPDM rubber strips, which were then bonded to EPDM rubber strips with 0.16 mL of ENB monomer per strip as described in Example 4. The bonded samples were analyzed on the Instron machine using a 180° peel test. The bonded samples had a mean load at maximum load of 126.28 N and a mean energy to break of 11.38 J. Rubber breakage was observed in all samples.

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Example 19 - Bonding EPDM to EPDM using DCPD as monomer

A catalyst solution was prepared by dissolving 0.031 g RuCI ₂ (PCy ₃ ) ₂ =CHPh in

3.1 ml of CH ₂ CI _2. The catalyst solution was coated onto three EPDM strips, which were then bonded to EPDM strips using DCPD monomer as described in Examples 4 and 14. The bonded samples were analyzed with the Instron machine using a 180° peel test. The bonded samples had a mean load at maximum load of 181.75 N and a mean energy to break of 26.46 J. Rubber rupture was observed in all samples.

Example 20 - Bonding rubber to rubber using differently hardened rubbers

A catalyst solution was prepared by dissolving 0.031 g RuCI ₂ (PCy ₃ ) ₂ =CHPh in

3.2 ml of CH ₂ CI ₂ . This solution was applied to three rubber strips which were then bonded to themselves with ENB monomer (see Tables 4 and 5 for the amount of ENB applied to each sample) as described in Example 4. Once this catalyst solution was used up, another identical batch was prepared and used to bond three more samples. Both EPDM and natural rubber A225P-0 strips were molded and cured to different degrees of cure as shown in Tables 4 and 5. The degree of cure is shown as a percentage determined using a Monsanto Oscillating Disk Rheometer (for example: T ₉₀ = time at 90% maximum torque). Surface treatment of both surface types included washing with acetone. The 5 A225P was sandblasted while the EPDM was not sandblasted. The EPDM was cured to 100, 70 and 40% and the A225P was cured to 100, 90, 70 and 40%. The Instron results from the 180° peel test are shown in Tables 4 (EPDM) and 5 (A225P).

Table 4. 180° peel test data for degree of cure study for EPDM-on-EPDM samples

Sample type Amount of
Monomers (ml) Load at max.
Load (N) Energy to
Tear (J) 100% 0.16 178.58 24.87 100% 0.16 162.50 23.44 100% 0.16 173.38 24,99 Average 171.48 24.43 70% 0.16 251,00 65.69 70% 0.16 226.94 52.32 70% 0.16 236.04 57.10 Average 238.07 58.37 40% 0.10 203.10 50.35 40% 0.13 216.24 52.99 40% 0.15 238.01 63.51 Average 219.11 55.62

All samples showed excellent rubber tearing. However, no deep rubber tearing was observed. The 40% EPDM samples showed better rubber tearing than the 70% and 100% samples.

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Table 5. 180° peel test data for degree of cure study for A225P on A225P samples

Sample type Amount of
Monomers (ml) Load at max.
Load (N) Energy to
Tear (J) 100% 0.10 375.01 40.07 100% 0.10 304.20 29.16 100% 0.10 396.97 46.42 Average 358.73 38.55 90% 0.16 334.60 54.27 90% 0.16 261.64 40.10 90% 0.16 285.37 42.51 Average 293.87 45.63 70% 0.16 297.73 48.58 70% 0.18 264.58 42.11 70% 0.18 310.87 51.10 Average 291.06 47.26 40% 0.10 328.91 59.14 40% 0.14 356.18 63.42 40% 0.16 420.21 76.88 Average 368.44 66.48

The 100% A225P samples showed good rubber tearing, and the 90%, 70%, and 40% A225P samples showed deep rubber tearing. Note that the 100% A225P strips were approximately twice as thick as those for the other three types of cured rubber.

Example 21 - Bonding Santoprene® to Santoprene®

A catalyst solution was prepared by dissolving 0.030 g of RuCI ₂ (PCy ₃ ) ₂ =CHPh in 2.5 ml of CH ₂ CI _2. This solution was applied to three strips of four types of Santoprene® (101-64, 201-64, 201-87 and 8201-90), which were then

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bonded to themselves with ENB monomer as described in Example 4. The amount of ENB applied depended on the Santoprene® surface treatment: 0.06 ml for non-sandblasted and 0.16 ml for sandblasted samples. Once this catalyst solution was used up, another identical batch was prepared and used to bond three more samples. The bonded samples were analyzed using an Instron machine with the 180° peel test and the results are shown in Tables 6 and 7. All non-sandblasted samples showed no rubber tearing and showed an adhesive failure pattern as a polymer film was observed on a large portion of the rubber surface. All three grit-blasted 101-64 samples showed excellent rubber tear, two 201-64 samples showed excellent rubber tear, and both of the stiffer rubbers, 201-87 and 8201-90, showed no rubber tear.

Table 6. 180° peel test data for rubber-to-rubber specimens using non-grit blasted Santoprene® specimens

Santoprene® type Load at max.
Load (N) Energy to
Tear (J) 201-64 9.55 0.46 201-64 6.58 0.38 201-64 5.58 0.30 Average 7.24 0.38 201-87 9.14 0.43 201-87 5.45 0.27 201-87 3.39 0.19 Average 5.99 0.30 101-64 4.39 0.29 101-64 7.98 0.43 101-64 7.79 0.30 Average 6.72 0.34

8201-90 7.16 0.14 8201-90 3.68 0.17 8201-90 3.00 0.15 Average 4.62 0.15

Table 7. 180° peel test data for rubber-to-rubber specimens using sandblasted Santoprene® specimens

Santoprene® type Load at max.
Load (N) Energy to
Tear (J) 101-64 85.49 3.38 101-64 93.01 3.11 101-64 58.47 3.59 Average 78.99 3.36 201-64 48.52 2.61 201-64 107.29 4.29 201-64 60.50 3.40 Average 72.10 3.43 201-87 67,95 4.00 201-87 63.76 4.03 201-87 73.98 4.36 Average 68.56 4.13 8201-90 29.85 1.69 8201-90 31.91 1.81 8201-90 21.82 1.28 Average 27.86 1.60

Example 22 - Tire retreading applications

A catalyst solution was prepared by dissolving 0.031 g of RuCI ₂ (PCy ₃ ) ₂ =CHPh in 3.1 ml of CH ₂ CI _2. Three types of compounds were performed: (1)

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tread to tread; (2) carcass to carcass; and (3) carcass to tread. For the carcass-to-tread samples, the catalyst was applied to the carcass and the ENB monomer was applied to the tread. The bonding procedure was as described in Example 4. Once the catalyst solution was used up, another identical batch was prepared. The amount of ENB applied depended on the sample and is shown in Tables 8 and 9. Mechanical properties were obtained from both non-sandblasted and sandblasted combinations of carcass and tread material. The bonded samples were analyzed using an Instron machine with a 180° peel test. Table 8 shows data for the non-sandblasted samples. All non-sandblasted samples showed rubber cracking. The tread-to-tread samples showed some superficial rubber cracking. The carcass-on-carcass and carcass-on-tread samples showed deep rubber tearing.

Table 8. 180° peel test data for rubber to rubber bonding using non-grit blasted carcass and tread materials.

Sample type Amount of
Monomers (ml) Load at max.
Load (N) Energy to
Tear (J) Tread/Tread 0.06 72.84 6.08 Tread/Tread 0.06 60.79 4.90 Tread/Tread 0.08 71.18 7.73 Average 68.45 6.24 Carcass/Carcass 0.10 261.83 36.81 Carcass/Carcass 0.14 205.64 20.79 Carcass/Carcass 0.16 349.31 48.82 Average 272.27 35.47 Carcass/tread 0.06 186.91 29.43 Carcass/tread 0.08 134.94 17,99 Carcass/tread 0.10 140.14 16.36 Average 154,00 21.26

·

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Table 9 shows data for grit blasted samples. These all also showed rubber tearing. However, the rubber tearing was deeper compared to the non-grit blasted samples. The tread-on-tread samples showed the least amount of tearing, but still more than the non-grit blasted version. The carcass-on-carcass samples showed excellent deep rubber tearing. Finally, the carcass-on-tread samples also showed excellent rubber tearing, but not as good as the carcass-on-carcass samples.

Table 9. 180° peel test data for rubber to rubber bonding using grit blasted carcass and tread materials.

Sample type Amount of
Monomers (ml) Load at max.
Load (N) Energy to
Tear (J) Tread/Tread 0.12 146.41 29.31 Tread/Tread 0.12 146.12 29.34 Tread/Tread 0.12 118.27 21.51 Average 136.93 26.72 Carcass/Carcass 0.16 362.55 50.16 Carcass/Carcass 0.16 421.78 53.61 Carcass/Carcass 0.16 296.06 45.30 Average 360.13 49.69 Carcass/tread 0.14 287.73 58.74 Carcass/tread 0.14 300.87 56.43 Carcass/tread 0.15 218,00 43.35 Average 268.86 52.84

Example 23 - Bonding metal to metal

A catalyst solution was prepared by dissolving 0.021 g RuCl2(PCy3)2=CHPh in 1.5 ml CH ₂ CI _2. The catalyst solution was applied to three blasted steel strips, which were then coated with 0.02-0.03 ml ENB monomer per strip.

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were bonded to other blasted steel strips as described in Example 1, except that the monomer was applied to the catalyst coated metal strip. The other steel strip was immediately bonded to the treated surface and weighted down with a 100 g weight. After three days of resting at ambient conditions, none of the three samples could be pulled apart by hand. The samples were analyzed on an Instron machine using a lap shear tensile test and showed a mean load at break of 375.99 N.

Example 24 - Bonding glass to glass

A catalyst solution was prepared by dissolving 0.040 g of RuCl ₂ (PCy ₃ ) ₂ =CHPh in 3.0 mL of CH ₂ Cl _2. The catalyst solution was coated on three glass slides, which were then adhered to other glass slides with 0.15-0.20 mL of ENB monomer per slide as described in Example 1, except that not all of the catalyst solution was used, but only just enough to cover the defined area. The solvent was allowed to evaporate for 3 to 4 minutes before the ENB was pipetted onto the catalyst-containing surface. Immediately, one slide was placed on top of the other slide and held in place with a 100 g weight. After 1.5 hours, the two glass slides were examined and found to be held together as the substrates could be picked up without falling apart.

Example 25 - Gluing paper to paper

A catalyst solution prepared by mixing 0.040 g RuCI ₂ (PCy ₃ ) ₂ =CHPh in 3 ml CH ₂ CI ₂ was applied to a single piece of laboratory filter paper as described in Example 1. The solvent was allowed to evaporate for approximately 2 minutes. ENB monomer was applied to another piece of filter paper. Immediately, the two paper surfaces were placed together and held in place with a 100 g weight. After 1.5 hours, the

Both pieces of paper were examined and it was found that they were held together and could not be pulled apart.

Example 26 - Spraying of RuCI ₂ (PCy ₃ ) ₂ =CHPh and coating formation using ENB on various substrates

A catalyst solution was prepared by dissolving 0.75 g of RuCl ₂ (PCy3) ₂ =CHPh in 25 mL of CH ₂ Cl _2. This solution was then applied by spraying onto a 7.62 cm x 15.24 cm substrate surface, which had previously been wiped with acetone to remove any surface contamination, in a sweep pattern until uniform appearing coverage was obtained. The solvent was allowed to evaporate in the open laboratory atmosphere for 30 minutes, leaving the catalyst coated surface. Black Santoprene®, Manila Santoprene®, acrylonitrile butadiene styrene (ABS), polypropylene, polymethyl methacrylate (PMMA), aluminum, chromated aluminum, stainless steel, polycarbonate film, Delrin acetal resin film, uncoated Mannington Classic polyvinyl chloride (PVC) embossed flooring (referred to as "MC"), and Tarkett/Domco polyvinyl chloride flooring (referred to as "T") were sprayed with ENB monomer and allowed to dry. Both static and kinetic coefficients of friction were measured for all coated samples by measuring mechanical resistance with an Instron instrument (see PR Guevin, "Slip Resistance," in the "Paint and Coating Testing Manual, Fourteenth Edition of the Gardner-Sward Handbook, JV Koleske (ed.), ASTM Manual Series: MNL 17, ASTM, Philadelphia, 1995, Chapter 50). The results are shown in Tables 10 and 11 below. For all but a few samples, the static and kinetic coefficients of friction after spray coating with ENB were lower than the control (shown in the table as Aluminum-C, for example) of that sample. Lower static and kinetic coefficients of friction indicate improved surface slipperiness.

Table 10. Static and kinetic friction coefficient results for ENB spray coated metal substrates

Sample ID static
Friction coefficient,
Average static
Friction coefficient,
Standard deviation kinetic
Friction coefficient,
Average kinetic
Friction coefficient,
Standard deviation Aluminium-1 0.440 0.086 0.107 0.011 Aluminium-2 0.307 0.078 0.155 0.017 Aluminium-3 0.277 0.041 0.143 0.013 Aluminium-4 0.244 0.047 0.154 0.042 Aluminium-C 0.746 0.150 0.242 0.118 chromated
Aluminium-1 0.263 0.093 0.112 0.025 chromated
Aluminium-2 0.287 0.039 0.162 0.018 chromated
Aluminium-3 0.341 0.076 0.095 0.018 chromated
Aluminium-4 0.256 0.042 0.152 0.014 chromated
Aluminium-C 0.755 0.430 0.233 0.138 Stainless steel-1 0.397 0.062 0.119 0.013 Stainless steel-2 0.297 0.049 0.119 0.005 Stainless steel-3 0.259 0.031 0.131 0.015 Stainless steel-4 0.256 0.063 0.121 0.005 Stainless steel-C 0.244 0.008 0.184 0.006

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Table 11. Static and kinetic friction coefficient results for ENB spray coated plastic substrates

Sample ID static
Friction coefficient,
Average static
Friction coefficient,
Standard deviation kinetic
Friction coefficient,
Average kinetic
Friction coefficient,
Standard deviation ABS-I 0.216 0.068 0.073 0.011 ABS-2 0.436 0.224 0.075 0.048 ABS-3 0.343 0.108 0.077 0.032 ABS-4 0.172 0.023 0.086 0.015 ABS-C 0.291 0.021 0.163 0.011 Delrin-1 0.550 0.067 0.215 0.039 Delrin-2 0.475 0.080 0.188 0.012 Delrin-C 0.599 0.023 0.521 0.031 EPDM-I 0.535 0.088 0.265 0.040 EPDM-2 0.630 0.078 0.305 0.034 EPDM-3 0.749 0.069 0.174 0.015 EPDM-4 0.296 0.031 0.183 0.012 EPDM-C 2,547 0.036 1,997 0.896 MC-I 0.514 0.063 0.419 0.084 MC-2 0.631 0.187 0.334 0.022 MC-3 0.654 0.097 0.465 0.025 MC-4 0.589 0.061 0.399 0.042 MC-C 1,810 0.198 1,031 0.243 Polycarbonates-1 1,364 0.142 0.083 0.000 Polycarbonate-2 0.989 0.048 0.164 0.048 Polycarbonate-3 0.674 0.162 0.178 0.028 Polycarbonate-4 0.211 0.034 0.187 0.000 Polycarbonate-C 0.963 0.263 0.301 0.011 PMMA-I 0.392 0.156 0.083 0.031 PMMA-2 0.322 0.187 0.086 0.027 PMMA-3 0.433 0.108 0.150 0.054 PMMA-4 0.402 0.176 0.083 0.000 PMMA-C 0.517 0.062 0.386 0.018 Polypropylene-1 0.174 0.029 0.040 0.057 Polypropylene-2 0.145 0.016 0.110 0.026 Polypropylene-3 0.187 0.044 0.122 0.010 Polypropylene-4 0.161 0.041 0.077 0.019

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Polypropylene-C 0.394 0.056 0.225 0.057 Black Santoprene-1 0.369 0.064 0.143 0.009 Black Santoprene-2 0.332 0.026 0.145 0.064 Black Santoprene-3 0.290 0.022 0.100 0.027 Black Santoprene-4 0.253 0.008 0.099 0.021 Black Santoprene-C 2,581 0.033 2,204 0.115 Manila Santoprene-1 0.282 0.021 0.080 0.011 Manila Santoprene-2 0.364 0.026 0.107 0.072 Manila Santoprene-3 0.272 0.023 0.112 0.021 Manila Santoprene-4 0.287 0.037 0.080 0.010 Manila Santoprene-C 1,050 0.063 1,065 0.562 T-I 1,379 0.162 0.579 0.022 T-2 1,317 0.129 0.530 0.058 T-C . 4,328 0.300 -0.016 0.023

Adhesion measurements were determined by lightly scratching a grid pattern into the coating surface with a razor blade. Five lines spaced approximately 3.2 mm apart and five additional lines spaced approximately 3.2 mm apart in a grid pattern. A 50.8-63.5 mm long strip of 25.4 mm wide Scotch masking tape (2500-3705) was applied over the grid area and pressed flat with a finger. After a second or two, the tape was quickly peeled away from the surface. An adhesion rating scale was established with 1 being the best rating and 5 being the worst (see Table 12).

Table 12. Cross-cut test definitions

Value Description 1 absolutely excellent - nothing on the tape 2 excellent - only grid pattern 3 good - grid pattern and spots on the edges 4 satisfactory - grid and between lines 5 bad - everything deducted

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Adhesion ratings of poly(ENB) coatings on rubbery substrates such as Santoprene® and EPDM are shown in Table 13. They show that both Santoprene® samples gave excellent adhesion with only a grid pattern visible on the tape. EPDM adhesion was only a 4 with a single poor coating and a 1 with a second uniform coating. As long as a good uniform coating of poly(ENB) was applied, good adhesion to rubbery substrates was observed.

Table 13. Cross-cut test results for poly(ENB) coatings on various substrates

Sample ID Liability assessment Type of substrate Manila Santoprene 4 2 rubbery Black Santoprene-1 2 rubbery EPDM-I 4 rubbery EPDM-4 1 rubbery Aluminium-4 2 metal chromated aluminum-4 2 metal Stainless steel-4 1 metal Polypropylene-4 2 plastic ABS-4 1 plastic Propylene carbonate-4 1 plastic PMMA-I 2 plastic MC-4 5 Flooring T-2 5 Flooring Delrin-2 5 Flooring Silicon wafer 2 inorganic Teflon 1-2 plastic

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Example 27 - Application of RuCI ₂ (PCy3) ₂ =CHPh by spraying and formation of layered coatings

A catalyst solution was prepared by dissolving 0.75 g of RuCl ₂ (PCy ₃ ) ₂ =CHPh in 25 mL of CH ₂ Cl _2. This solution was then applied by spraying onto the surface of four 7.62 cm x 15.24 cm EPDM pieces, which had previously been wiped with acetone to remove any surface contamination, in a sweep pattern until uniform appearing coverage was obtained. The solvent was allowed to evaporate in the open laboratory atmosphere for 30 minutes, leaving the catalyst coated surface. The samples were then sprayed with ENB monomer and allowed to stand in the open laboratory atmosphere until no longer tacky. Additional ENB was applied to EPDM-4 and the sample was allowed to dry overnight. The amounts of catalyst and resulting polymer are given in Table 14. Increasing the coating weight after the second spraying of ENB on EPDM-4 demonstrated that layers of poly(ENB) can be built up on an existing EPDM surface and that the catalyst remained active.

Table 14. Catalyst and monomer amounts for catalyst/ENB coated EPDM samples

Sample ID Substrate weight
(G) Catalyst weight
(G) Weight of the 1st
Polymers (g) Weight of the 2nd
Polymers (g) EPDM-I 43.1487 0.0258 0.0555 EPDM-2 43.4636 0.0260 0.0393 EPDM-3 42.6556 0.0236 0.0365 EPDM-4 43.9878 0.0264 0.0440 0.2332

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Example 28 - Application of RuCI ₂ (PCy ₃ ^=CHPh by spraying and formation of coatings with other monomers

A catalyst solution was prepared by dissolving 0.75 g of RuCl ₂ (PCy ₃ ) ₂ =CHPh in 25 mL of CH ₂ Cl _2. This solution was then applied by spraying onto the surface of an ABS sample (10.16 cm × 15.24 cm), which had previously been wiped with isopropanol to remove any surface contamination, in a sweep pattern until a uniform appearing coverage was obtained. The solvent was allowed to evaporate under a fume hood in the open laboratory atmosphere for 30 minutes, leaving the catalyst coated surface. The samples were then sprayed with the monomers DCPD, methylidene norbornene (MNB) and cyclooctene (CO) and allowed to stand in the open laboratory atmosphere for 2.5 hours before being weighed. The amounts of catalyst and resulting polymer are given in Table 15. Friction coefficient data and cross-cut test data are given in Tables 15 and 16, respectively. No polymer formation was observed for the cyclooctene sample; the cyclooctene appeared to volatilize from the surface.

Table 15. Friction coefficient data for various monomers sprayed onto ABS.

Monomer catalyst
weight (g) polymer
weight (g) static
Friction,
Average static
Friction,
Standard deviation kinetic
Friction coefficient,
Average kinetic
Friction coefficient,
Standard deviation DCPD 0.167 0.948 0.25 0.03 0.11 0.01 MNB 0.125 0.142 0.27 0.08 0.10 0.01 CO 0.248 - 0.27 0.08 0.10 0.01

· mm

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Table 16. Cross-cut test data ^a for various monomers sprayed onto ABS.

Monomer Liability assessment DCPD 1 MNB 3

^a) 1 = excellent - nothing on the tape; 2 = excellent - only grid pattern; 3 = good - grid pattern and spots on the edges; 4 = satisfactory - grid and between lines; 5 = poor - everything stripped.

Example 29 - Coating formation using MoTB catalyst and ENB

A catalyst solution was prepared by dissolving 0.1692 g of 2,6-diisopropylphenylimidoneophylidene molybdenum(VI)bis(t-butoxide) (MoTB) in 5 mL of CH ₂ Cl ₂ . The catalyst solution was coated onto a 10.16 cm x 15.24 cm ABS substrate in the glove box as described in Example 12. The catalyst thickened and the surface became rough with thick brush marks as the solvent dissolved the ABS surface. Using a pipette, ENB monomer was applied in front of a 1 mil pull bar and the bar was pulled over the catalyst coated area. Attempting to pull the bar over a second time scratched the newly formed coating as the monomer polymerized so quickly. This resulted in a wrinkled, dark brown coating in the catalyst coated area and a chalky yellow border where the area was not contacted by the ENB monomer.

To overcome this surface dissolution problem, another MoTB catalyst solution (0.1192 g MoTB in 3 mL CH ₂ CI ₂ ) was again coated on a surface, but this time on a 10.16 cm × 15.24 cm 5 substrate of chromated aluminum (AC). A more uniform coating of poly(ENB) formed on the surface. The coated sample of

·*♦

Chromated aluminum (AC) showed a static friction coefficient of 0.44 ± 0.03 and a kinetic friction coefficient of 0.14 ± 0.05. These data were obtained only for the AC sample because the ABS surface was too rough, as described above. Cross-cut test data for both samples are given in Table 17.

Table 17. Cross-cut test data ^a for various monomers/substrates

Monomer Substrat Liability assessment ENB SECTION 4 ENB AC 3

^a) 1 = excellent - nothing on the tape; 2 = excellent - only grid pattern; 3 = good - grid pattern and spots on the edges; 4 = satisfactory - grid and between lines; 5 = poor - everything stripped.

Example 30 - Coatings by applying catalyst or monomer in a polymer matrix

A matrix solution was prepared (2 g PMMA, 0.1 g RuCl ₂ (PCy ₃ ^=CHPh and 50 mL CH ₂ CI ₂ ) and coated onto a PMMA substrate by spraying. The coating was not uniform and therefore three to four drops of the above matrix solution were coated onto the PMMA substrate and spread using a glass rod. Upon drying, a clear uniform coating was formed which was sprayed with ENB.

Changes in the surface tension of the coatings were evaluated using a set of Accu-Dyne solutions. These solutions are used to match their surface tensions to that of the surface in question. A surface tension match is determined when the applied solution wets the surface being tested. The surface tension of the solution is then correlated to the surface tension of the surface.

No change in surface tension was observed before and after spraying ENB onto the PMMA/Rua ₂ (PCy 3 ) 2 =CHPh matrix described above (γ = 38 dynes/cm). Additional RuCl ₂ (PCy ₃ ) ₂ =CHPh was added to the PMMA/RuCl ₂ (PCy 3 ) ₂ =CHPh matrix so that the total amount of catalyst in the PMMA matrix was 0.35 g. This new solution was coated onto a new 5.08 cm x 5.08 cm PMMA substrate, dried, and then sprayed with ENB. The surface tension remained at 38 dynes/cm. Again, further addition of catalyst brought the total amount to 0.55 g of RuCl ₂ (PCy ₃ ) ₂ =CHPh in the PMMA matrix. This surface, processed as described above, exhibited a surface tension of 34 dynes/cm. This result demonstrated that the catalyst remained active when incorporated into a polymer matrix and that coatings can be applied over this active surface.

A solution containing 0.25 g RuCl ₂ (PCy ₃ ) ₂ =CHPh in 15 mL CH ₂ Cl ₂ was sprayed onto a 10.16 cm × 15.24 cm PMMA substrate surface, yielding 0.0384 g catalyst on the surface after drying. The PMMA/ENB matrix (2 mL ENB, 1 g PMMA, in 10 mL CH ₂ Cl ₂ ) serving as the topcoat was applied to the catalyst-coated surface with a glass rod, and the resulting surface tension was 46 dynes/cm. This compares to a surface tension of 36 dynes/cm for an uncoated control PMMA substrate.

Example 31 - Coating of paper by spray application of
RuCI ₂ (PCy ₃ ) ₂ =CHPh and various monomers

Samples of commercial filter paper (Whatman No. 41) were cut into fifteen bone-shaped samples (11 cm total length, 40 x 7.2 mm drawing area) and coated by spraying with a solution of RuCl ₂ (PCy ₃ ) ₂ =CHPh as described in Example 8. After drying in laboratory air for 30 minutes, the samples were weighed, and then five samples were coated by spraying with DCPD (5 ml), five samples were coated by spraying with ethylidene norbornene (8 ml), and five samples were coated on one side

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of the paper with cyclooctene (5 ml). After drying under a fume hood for 16 hours, the samples were weighed to determine the amount of monomer reacted and their tensile properties were determined using an Instron device (Table 18). Paper bones coated with PoIy(ENB) and PoIy(DCPD) showed increased values of maximum strain, while polycyclooctene did not. Statistical analysis (t-test) showed an increased displacement at maximum strain for DCPD at a confidence level of 95%. Little polycyclooctene was formed, probably due to its high volatility compared to the ROMP rate.

Table 18. Tensile strength data for paper bone specimens ^a .

ID Monomer catalyst
quantity (g) Coating
quantity (g) Shift in
maximum load
(mm)
[Mean/St.Dev.] 0.187 Load at
maximum load
(kgf)
[Mean/St.Dev.] 0.190 A ENB 0.0072 0.0941 0.624 0.083 2,636 0.661 B DCPD 0.0066 0.0949 0.644 0.047 3,401 1,064 C Cycloocten 0.0060 0.0018 0.574 0.051 0.894 0.189 D - - - 0.514 1,024

^a) Whatman No. 41 filter paper, 5 samples each.

Example 32 - Fiber coating by application of RuCI ₂ (PCy3) ₂ =CI-IPh and monomer

Kevlar®, Nomex® and nylon threads (size 69, 0.2032 mm) were cut into 30.48 cm lengths, soaked for one minute in a solution containing approximately 0.04 g RuCI ₂ (PCy ₃ ) ₂ =CHPh in 5 mL CH ₂ CI ₂ and allowed to dry in a stretched position. After 20 minutes the threads were sprayed with 8 mL ENB. After two hours the threads appeared stretched and stiff. Using an Instron machine the tensile properties of these samples were compared to those of uncoated threads (Table 19). No real comparisons were made.

·

• *

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differences in the tensile data were observed. However, each thread was thicker, proving that the threads were indeed coated.

Table 19. Tensile properties of ENB coated and uncoated threads

thread Load at maximum
Load (kg) Max. percent
strain Thickness (mm) ^a Kevlar 3.947 ± 1.089 9,310 + 2,354 0.27 Kevlar - coated 4.330 + 0.008 10,659 + 1,056 0.31 nylon 2.633 ± 0.477 59.069 ± 17.614 0.26 Nylon - coated 2.601 ±0.651 31.154 ±8.324 0.30 Nomex 1.893 ±0.129 31.289 ± 3.006 0.27 Nomex - coated 2.018 ± 0.260 30.452 ± 6.182 0.28

^a) These measurements were made with gauges and then confirmed with a thickness gauge.

Example 33 - Textile coating by application of RuCl2(PCy ₃ ) ₂ =CHPh and monomer

Strips of cotton, fiberglass, polyester and era mid fabric were cut into pieces with a geometry of 2.54 cm x 15.24 cm, immersed in a solution containing 1.0 g RuCl ₂ (PCy ₃ ) 2 = CHPh in 100 mL CH ₂ CI ₂ for one minute and allowed to dry. It was observed that excess catalyst rose to the surfaces of the fabrics by capillary action during the drying process. The excess catalyst was shaken off each fabric. All fabrics had a reddish-violet color, indicating that catalyst had been adsorbed on the surface.

Approximately 30 ml of ENB was sprayed on both sides of the fabric strips.

All fabric samples became stiff as polymerization occurred. Tensile properties were determined using an Instron machine for six coated and six uncoated samples (Table 20). The fabrics were stiff but could be easily bent like uncoated fabric.

• ··· ♦♦ · . &igr;

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Coating the polyester fabric with Poly(ENB) almost doubled the load at peak, but the differences in displacement or percent elongation were only slight. This suggests that the strength of the tightly woven polyester fabric is strictly increased by the addition of Poly(ENB). Aramid and Ba um wo 11 fabrics showed a halving of the displacement and percent elongation at peak and a slight increase in the load at peak, or no change, respectively. Thus, these fabrics lose some of their elongation with the addition of Poly(ENB) but do not lose any of their strength. For glass fiber, the load at peak and energy to break increase significantly, while the displacement and percent elongation at peak show no change.

Table 20. Tensile properties of ENB coated and uncoated fabrics ³ .

ID Type of
Materials Postponement on
Maximum (mm)
[Average/
St.dev.] 0.481 percent stretch
at the maximum
(%) [Average/
St.dev.] 1,892 Load on
Maximum (klM)
[Average/
St.dev.] 0.045 Energy to
Tear (J)
[Average/
St.dev.] 0.577 control polyester 10,882 0.181 42,841 0.712 0.889 0.076 7,036 0.866 8165-27 A polyester 11,575 0.746 45,571 2,937 1,511 0.008 7,723 0.072 control Aramid 15,500 1,616 61,417 6,364 0.168 0.019 1,397 0.289 8165-27 B Aramid 8,282 0.404 32,605 1,590 0.237 0.022 1,758 0.218 control Cotton 6,972 0.470 27,448 1,850 0.702 0.106 2,102 0.227 8165-27 C Cotton 3,380 0.034 13,307 1,197 0.805 0.085 1,951 0.858 control glass fiber 2,925 0.166 11,516 0.653 0.641 0.203 1,841 3,042 8165-27 D glass fiber 3,050 12,008 1,917 8,669

^a) determined using six 1" x 6" strips of each fabric.

Claims (9)

1. Article comprising a first substrate surface and a second substrate surface obtainable by: a) providing a catalyst on the first substrate surface; b) providing a metathetizable material between the first substrate surface and the second substrate surface or providing a metathetizable material as a component of the second substrate; and c) contacting the catalyst on the first substrate surface with the metathetizable material such that the metathetizable material undergoes a metathesis reaction and bonds the first substrate surface to the second substrate surface. 2. An article comprising a first substrate surface, a second substrate surface, and an adhesive layer disposed therebetween, wherein the first substrate surface comprises an elastomeric material and the adhesive layer comprises a metathesis polymer. 3. The article of claim 2, wherein the second substrate surface comprises a metallic material. 4. An article according to claim 2, wherein the metathesis polymer is obtainable from a norbornene monomer having one of the following structures:


or


or


or


where X = CH ₂ , CHR ³ , C(R ³ ) ₂ , O, S, NR ³ , PR ³ , O=PR ³ , Si(R ³ ) ₂ , BR ³ or As-R ³ , R ¹ is each independently H, CH ₂ , alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, halogen, halogenated alkyl, halogenated alkenyl, alkoxy, oxyalkyl, carboxy, carbonyl, amido, (meth)acrylate-containing group, anhydride-containing group, thioalkoxy, sulfoxide, nitro, hydroxy, keto, carbamato, sulfonyl, sulfinyl, carboxylate, silanyl, cyano or imido, R ² is a condensed aromatic, aliphatic or heterocyclic or polycyclic ring and R ³ is alkyl, alkenyl, cycloalkyl, cycloalkenyl, Aryl, alkaryl, aralkyl or alkoxy. 5. The article of claim 4, wherein the norbornene monomer comprises ethylidene norbornene. 6. The article of claim 2, wherein the elastomeric material comprises a thermoplastic elastomer. 7. A tire laminate comprising a tire carcass having an outer peripheral surface, a tire tread having an adhesive surface, and a metathesis polymer adhesive layer between the outer peripheral surface of the tire carcass and the adhesive surface of the tire tread. 8. A tire laminate according to claim 7, wherein the metathesis polymer is obtainable from a norbornene monomer having one of the following structures:


or


or


or


where X = CH ₂ , CHR ³ , C(R ³ ) ₂ , O, S, NR ³ , PR ³ , O=PR ³ , Si(R ³ ) ₂ , BR ³ or As-R ³ , R ¹ is each independently H, CH ₂ , alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, halogen, halogenated alkyl, halogenated alkenyl, alkoxy, oxyalkyl, carboxy, carbonyl, amido, (meth)acrylate-containing group, anhydride-containing group, thioalkoxy, sulfoxide, nitro, hydroxy, keto, carbamato, sulfonyl, sulfinyl, carboxylate, silanyl, cyano or imido, R ² is a condensed aromatic, aliphatic or heterocyclic or polycyclic ring and R ³ is alkyl, alkenyl, cycloalkyl, cycloalkenyl, Aryl, alkaryl, aralkyl or alkoxy. 9. The article of claim 8, wherein the norbornene monomer comprises ethylidene norbornene.