CONTACT METATHESIS POLYMERIZATION

POLYMERISATION METATHESIQUE PAR CONTACT

English Abstract

A method for bonding a material to a first substrate surface that includes
providing a catalyst at the first substrate surface and then contacting that
surface with a
material that undergoes a metathesis reaction to bond the material to the
first substrate
surface. There are two embodiments of this method - a coating process and an
adhesive
process. In the coating embodiment, the metathesizable material is contacted
with the
catalyst on the substrate surface so that it undergoes metathesis
polymerization to form
the coating. The adhesive process includes (a) providing a catalyst at the
first substrate
surface, (b) providing a metathesizable material between the first substrate
surface and
the second substrate surface, and (c) contacting the catalyst on the first
substrate surface
with the metathesizable material so that the metathesizable material undergoes
a
metathesis reaction and bonds the first substrate surface to the second
substrate surface.

Claims

The embodiments of the invention, in which an exclusive property or privilege
is
claimed are defined as follows:
1. A method for bonding a first substrate surface to a second substrate
surface
comprising:
(a) providing a catalyst at the first substrate surface;
(b) providing a metathesizable material between the first substrate surface
and the
second substrate surface or providing a metathesizable material as a component
of
the second substrate; and
(c) contacting the catalyst on the first substrate surface with the
metathesizable
material so that the metathesizable material undergoes a metathesis reaction
and
bonds the first substrate surface to the second substrate surface.
2. A method according to claim 1 wherein at least one of the substrates
comprises
an elastomeric material.
3. A method according to claim 2 wherein the elastomeric material is a
thermoplastic elastomer.
4. A method according to claim 1 wherein one of the first or second substrates
comprises a metallic material and the other first or second substrate
comprises an
elastomeric material.
5. A method according to claim 4 wherein the metallic material comprises steel
and the elastomeric material is selected from natural rubber, polychloroprene,
polybutadiene, polyisoprene, styrene-butadiene copolymer rubber, acrylonitrile-
butadiene
copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-
diene
terpolymer rubber, butyl rubber, brominated butyl rubber, alkylated
chlorosulfonated
polyethylene rubber, hydrogenated nitrite rubber, silicone rubber,
fluorosilicone rubber,
poly(n-butyl acrylate), thermoplastic elastomer and mixtures thereof.
53

6. A method according to claim 1 wherein the first substrate comprises a tire
carcass and the second substrate comprises a tire tread.
7. A method according to claim 1 wherein step (b) comprises applying the
metathesizable material to the second substrate surface and step (c) comprises
contacting
the catalyst on the first substrate surface and the metathesizable material-
applied second
substrate surface.
8. A method according to claim 1 wherein at least one of the substrates is
substantially cured elastomeric material.
9. A method according to claim 4 wherein the elastomeric material is
substantially cured.
10. A method according to claim 1 wherein step (c) occurs at room temperature.
11. A method according to claim 1 wherein seeps (a)-(c) occur at room
temperature.
12. A method according to claim 6 wherein initial bonding in step (c) occurs
within one hour.
13. A method according to claim 1 wherein step (a) comprises applying a
catalyst
onto the first substrate surface.
14. A method according to claim 13 wherein the catalyst is dissolved or mixed
into a liquid carrier fluid.
15. A method according to claim 13 wherein the catalyst is included as a
component in a multi-component composition.
54

16. A method according to claim 1 wherein the catalyst is included as a
component of the first substrate.
17. A method according to claim 7 wherein the metathesizable material is in
the
form of a liquid, paste or meltable solid.
18. A method according to claim 7 wherein the metathesizable material is
included as a component in a multi-component composition.
19. A method according to claim 1 wherein the metathesizable material is
included as a component of the second substrate.
20. A method for bonding a metallic substrate surface to an elastomeric
substrate
surface comprising:
(a) applying a catalyst to the metallic substrate surface;
(b) applying a metathesizable material to the elastomeric substrate surface;
and
(c) bringing the metallic substrate surface and the elastomeric substrate
surface
together to contact the catalyst and the metathesizable material.
21. A method according to claim 20 wherein step (c) occurs at room
temperature.
22. A method according to claim 20 wherein the elastomeric substrate is a
substantially cured elastomeric material.
23. A method according to claim 1 wherein the catalyst is selected from at
least
one of a rhenium compound, ruthenium compound, osmium compound, molybdenum
compound, tungsten compound, titanium compound, niobium compound, iridium
compound and MgCl2.
24. A method according to claim 23 wherein the catalyst is selected from a
ruthenium compound, a molybdenum compound, iridium compound and an osmium
compound.
55

25. A method according to claim 24 wherein the catalyst has a structure
represented by
<IMG>
wherein M is Os, Ru or Ir; each R1 is the same or different and is H, alkenyl,
alkynyl,
alkyl, aryl, alkaryl, aralkyl, carboxylate, alkoxy, alkenylalkoxy,
alkenylaryl,
alkynylalkoxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl 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.
26. A method according to claim 25 wherein X is Cl, Br, I, F, CN, SCN, or N3;
L
is Q(R2)a wherein Q is P, As, Sb or N; R2 is H, cycloalkyl, alkyl, aryl,
alkoxy, arylate or a
heterocyclic ring; and a is 1, 2 or 3; M is Ru; and R1 is H, phenyl, -
CH=C(phenyl)2, -
CH=C(CH3)2 or -C(CH3)2(phenyl).
27. A method according to claim 26 wherein the catalyst is a phosphine-
substituted ruthenium carbene.
28. A method according to claim 27 wherein the catalyst is
bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride.
29. A method according to claim 1 wherein the catalyst is stable in the
presence
of moisture and oxygen and can initiate polymerization of the metathesizable
material
upon contact at room temperature.
30. A method according to claim 1 wherein the metathesizable material includes
at least one reactive unsaturated functional group.
56

31. A method according to claim 30 wherein the metathesizable material
comprises an olefin.
32. A method according to claim 31 wherein the metathesizable material is
selected from ethene, .alpha.-alkene, acyclic alkene, acyclic diene,
acetylene, cyclic alkene,
cyclic polyene and mixtures thereof.
33. A method according to claim 32 wherein the metathesizable material
comprises a cycloolefin.
34. A method according to claim 33 wherein the metathesizable material is a
monomer or oligomer selected from norbornene, cycloalkene, cycloalkadiene,
cycloalkatriene, cycloalkatetraene, aromatic-containing cycloolefin and
mixtures thereof.
35. A method according to claim 34 wherein the metathesizable material is a
norbornene monomer or oligomer.
36. A method according to claim 35 wherein the norbornene has a structure
represented by
<IMGS>
57

or
<IMGS>
wherein X is CH2, CHR3, C(R3)2, O, S, N-R3, P-R3, O=P-R3, Si(R3)2, B-R3 or As-
R3; each
R1 is independently H, CH2, alkyl, alkenyl, 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; R2 is a fused aromatic, aliphatic or heterocyclic or polycyclic
ring; and R3 is
alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxy..
37. A method according to claim 36 wherein the metathesizable material
comprises ethylidenenorbornene monomer or oligomer.
38. A method according to claim 1 wherein the metathesizable material
comprises
liquid ethylidenenorbornene monomer.
58

39. A method according to claim 1 wherein the catalyst is applied in an
aqueous
solution or mixture and the metathesizable material is applied in the form of
a liquid that
is substantially 100 percent reactive.
40. A method according to claim 1 wherein the method is substantially free of
the
use of volatile organic solvents.
41. A method according to claim 20 wherein the metathesizable material
comprises norbornene monomer or oligomer having a structure represented by
<IMGS>
59

or
<IMG>
wherein X is CH2, CHR3, C(R3)2, O, S, N-R3, P-R3; O=P-R3, Si(R3)2, B-R3 or As-
R3; each
R1 is independently H, CH2, alkyl, alkenyl, 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; R2 is a fused aromatic, aliphatic or heterocyclic or polycyclic
ring; and R3 is
alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxy;
and the catalyst is
selected from a ruthenium compound, a molybdenum compound and an osmium
compound.
42. A method according to claim 41 wherein step (c) occurs at room
temperature.
43. A method according to claim 1 wherein step (a) comprises applying a
ruthenium catalyst in a liquid carrier to the first substrate surface, step
(b) comprises
applying a metathesizable liquid norbornene monomer to the second substrate
surface and
step (c) comprises contacting the catalyst-applied first substrate surface and
the monomer-
applied second substrate surface.
44. A method for bonding a tire tread to a tire carcass comprising:
(a) applying a catalyst to the tire tread or tire carcass;
(b) applying a metathesizable material to the tire tread or tire carcass; and
60

(c) contacting the catalyst-applied tire tread or tire carcass and the
metathesizable
material-applied tire tread or tire carcass together so that the
metathesizable material
undergoes a metathesis reaction and bonds the tire tread to the tire carcass.
45. A method according to claim 44 wherein step (c) occurs at room
temperature.
46. A method according to claim 44 wherein the tire tread comprises precured
retread stock.
47. A method according to claim 44 wherein the metathesizable material
comprises norbornene monomer or oligomer having a structure represented by
<IMGS>
61

<IMG>
wherein X is CH2, CHR3, C(R3)2, O, S, N-R3, P-R3, O=P-R3, Si(R3)2, B-R3 or As-
R3; each
R1 is independently H, CH2, alkyl, alkenyl, 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; R2 is a fused aromatic, aliphatic or heterocyclic or polycyclic
ring; and R3 is
alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxy;
and the catalyst is
selected from a ruthenium compound, a molybdenum compound and an osmium
compound.
48. A method according to claim 44 wherein the catalyst is applied to the tire
carcass and the metathesizable material is applied to the tire tread.
49. A method according to claim 13 wherein the catalyst is applied so that it
is in
direct contact with the first substrate surface.
50. A method for adhering a material to a first non-fibrous substrate surface
comprising:
(a) providing a catalyst at the first non-fibrous substrate surface; and
(b) contacting the catalyst on the non-fibrous substrate surface with a
material that
undergoes a metathesis reaction upon contact with the catalyst to adhere the
material to the first non-fibrous substrate surface.
51. A method according to claim 50 wherein the catalyst is applied so that it
is in
direct contact with the first non-fibrous substrate surface.
62

52. A method according to claim 50 wherein the metathesizable material forms a
coating directly on the first non-fibrous substrate surface.
53. A method for providing a coating on a substrate surface comprising:
(a) providing a catalyst at the substrate surface; and
(b) contacting the catalyst on the substrate surface with a material that
undergoes
a metathesis reaction to form a coating on the substrate surface.
54. A method according to claim 53 wherein the coating is formed directly on
the
substrate surface.
55. A method according to claim 53 wherein the coating has a thickness that is
less than the thickness of the substrate.
56. A method according to claim 53 wherein the substrate comprises a
substantially cured elastomeric material.
57. A method according to claim 56 wherein the elastomeric material is a
thermoplastic elastomer.
58. A method according to claim 53 wherein step (b) occurs at room
temperature.
59. A method according to claim 53 wherein steps (a)-(b) occur at room
temperature.
60. A method according to claim 53 wherein step (a) comprises applying a
catalyst onto the substrate surface.
61. A method according to claim 60 wherein the catalyst is dissolved or mixed
into a liquid carrier fluid.
63

62. A method according to claim 60 wherein the catalyst is included as a
component in a multi-component composition.
63. A method according to claim 53 wherein the catalyst is included as a
component of the substrate.
64. A method according to claim 56 wherein the elastomeric material is
selected
from natural rubber, polychloroprene, polybutadiene, polyisoprene, styrene-
butadiene
copolymer rubber, acrylonitrile-butadiene copolymer rubber, ethylene-propylene
copolymer rubber, ethylene-propylene-diene terpolymer rubber, butyl rubber,
brominated
butyl rubber, alkylated chlorosulfonated polyethylene rubber, hydrogenated
nitrile rubber,
silicone rubber, fluorosilicone rubber, poly(n-butyl acrylate), thermoplastic
elastomer and
mixtures thereof.
65. A method according to claim 53 wherein the catalyst is selected from at
least
one of a rhenium compound, ruthenium compound, osmium compound, molybdenum
compound, tungsten compound, titanium compound, niobium compound, iridium
compound and MgCl2.
66. A method according to claim 65 wherein the catalyst is selected from a
ruthenium compound, a molybdenum compound, an iridium compound and an osmium
compound.
67. A method according to claim 66 wherein the catalyst has a structure
represented by
<IMG>
64

wherein M is Os, Ru or Ir; each R1 is the same or different and is H, alkenyl,
alkynyl,
alkyl, aryl, alkaryl, aralkyl, carboxylate, alkoxy, alkenylalkoxy,
alkenylaryl,
alkynylalkoxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl 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.
68. A method according to claim 67 wherein X is Cl, Br, I, F, CN, SCN, or N3;
L
is Q(R2)a wherein Q is P, As, Sb or N; R2 is H, cycloalkyl, alkyl, aryl,
alkoxy, arylate or a
heterocyclic ring; and a is 1, 2 or 3; M is Ru; and R1 is H, phenyl, -
CH=C(phenyl)2, -
CH=C(CH3)2 or -C(CH3)2(phenyl).
69. A method according to claim 68 wherein the catalyst is a phosphine-
substituted ruthenium carbene.
70. A method according to claim 69 wherein the catalyst is
bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride.
71. A method according to claim 53 wherein the catalyst is stable in the
presence
of moisture and oxygen and can initiate polymerization of the metathesizable
material
upon contact at room temperature.
72. A method according to claim 55 wherein the metathesizable material
includes
at least one reactive unsaturated functional group.
73. A method according to claim 72 wherein the metathesizable material
comprises an olefin.
74. A method according to claim 72 wherein the metathesizable material is
selected from ethene, .alpha.-alkene, acyclic alkene, acyclic diene,
acetylene, cyclic alkene and
cyclic polyene and mixtures thereof.
65

75. A method according to claim 53 wherein the metathesizable material
comprises a cycloolefin.
76. A method according to claim 75 wherein the metathesizable material is a
monomer or oligomer selected from norbornene, cycloalkene, cycloalkadiene,
cycloalkatriene, cycloalkatetraene, aromatic-containing cycloolefin and
mixtures thereof.
77. A method according to claim 76 wherein the metathesizable material
comprises a norbornene having a structure represented by
<IMGS>
66

<IMG>
wherein X is CH2, CHR3, C(R3)2, O, S, N-R3, P-R3, O=P-R3, Si(R3)2, B-R3 or As-
R3; each R1 is independently H, CH2, alkyl, alkenyl, 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; R2 is a fused aromatic, aliphatic or heterocyclic or
polycyclic
ring; and R3 is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl,
aralkyl or alkoxy.
78. A method according to claim 77 wherein the metathesizable material
comprises ethylidenenorbornene monomer or oligomer.
79. A method according to claim 53 wherein the metathesizable material is in
the
form of a liquid.
80. A method according to claim 53 wherein the metathesizable material is a
component of a multi-component composition.
81. A method according to claim 53 wherein the catalyst is applied in the form
of
an aqueous solution or mixture and the metathesizable material is applied in
the form of a
liquid that is substantially 100 percent reactive.
82. A method according to claim 53 wherein the method is substantially free of
the use of volatile organic solvents.
83. A method according to claim 53 wherein step (a) comprises applying a
ruthenium catalyst in a liquid carrier to the substrate surface and step (b)
comprises
67

applying a metathesizable liquid norbornene monomer to the catalyst-applied
substrate
surface.
84. A manufactured article produced by the method of claim 1.
85. A manufactured article that includes a first substrate surface, a second
substrate surface and an adhesive layer interposed therebetween, wherein the
first
substrate surface comprises an elastomeric material and the adhesive layer
comprises a
metathesis polymer.
86. A manufactured article according to claim 85 wherein the second substrate
surface comprises a metallic material.
87. A manufactured article according to claim 85 wherein the metathesis
polymer
is produced from a norbornene monomer having a structure represented by
<IMG>
68

<IMG>
wherein X is CH2, CHR3, C(R3)2, O, S, N-R3, P-R3, O=P-R3, Si(R3)2, B-R3 or As-
R3; each
R1 is independently H, CH2, alkyl, alkenyl, 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; R2 is a fused aromatic, aliphatic or heterocyclic or polycyclic
ring; and R3 is
alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxy.
88. A manufactured article according to claim 87 wherein the norbornene
monomer comprises ethylidenenorbornene.
89. A manufactured article according to claim 85 wherein the elastomeric
material comprises a thermoplastic elastomer.
90. A tire laminate comprising a tire carcass have an outer periphery surface,
a
tire tread having 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.
91. A tire laminate according to claim 90 wherein the metathesis polymer is
produced from a norbornene monomer having a structure represented by
69

<IMGS>
wherein X is CH2, CHR3, C(R3)2, O, S, N-R3, P-R3, O=P-R3, Si(R3)2, B-R3 or As-
R3; each
R1 is independently H, CH2, alkyl, alkenyl, 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; R2 is a fused aromatic, aliphatic or heterocyclic or polycyclic
ring; and R3 is
alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxy.
92. A manufactured article according to claim 91 wherein the norbornene
monomer comprises ethylidenenorbornene.
93. A method according to claim 53 wherein step (b) comprises contacting the
substrate surface multiple times with the metathesizable material so as to
form multiple
coating layers.
94. A method according to claim 93 wherein an active amount of catalyst
remains
on the substrate surface after each successive coating sufficient to
polymerize the
subsequent application of the metathesizable material.
95. A method according to claim 24 wherein the catalyst comprises a bimetallic
catalyst having a structure represented by
<IMG>
wherein L is p-cymene or 1,3-di-t-butylcyclopentadiene and M is Ru, Os or Rh.
96. A method according to claim 66 wherein the catalyst comprises a bimetallic
catalyst having a structure represented by
<IMG>
wherein L is p-cytnene or 1,3-di-t-butylcyclopentadiene and M is Ru, Os or Rh.
71

97. A method according to claim 24 wherein the catalyst has a structure
represented by
<IMG>
wherein M is Mo or W; X is O or S; R1 is an alkyl, aryl, aralkyl, alkaryl,
haloalkyl,
haloaryl, haloaralkyl, or a silicon-containing analog thereof; R2 are each
individually the
same or different and are an alkyl, aryl, aralkyl, alkaryl, haloalkyl,
haloaryl, haloaralkyl, or
together form a heterocyclic or cycloalkyl ring; and R3 is alkyl, aryl,
aralkyl or alkaryl.
98. A method according to claim 66 wherein the catalyst has a structure
represented by
<IMG>
wherein M is Mo or W; X is O or S; R1 is an alkyl, aryl, aralkyl, alkaryl,
haloalkyl,
haloaryl, haloaralkyl, or a silicon-containing analog thereof; R2 are each
individually the
same or different and are an alkyl, aryl, aralkyl, alkaryl, haloalkyl,
haloaryl, haloaralkyl, or
together form a heterocyclic or cycloalkyl ring; and R3 is alkyl, aryl,
aralkyl or alkaryl.
72

Description

CA 02318711 2000-09-13
Attorney Docket No. IK-2~88(ET)
CONTACT METATHESIS POLYMER1ZATION
Background of the Invention
The present invention relates to a method of bonding or coating a material to
a
substrate surface and to bonding together two substrate surfaces.
Despite a long history of adhesive and coating development, a need continues
to
exist for adhesives and coatings that provide increasingly higher bonding
strengths under
increasingly adverse conditions on an increasing variety of substrate
surfaces.
A particular need exists for environmentally friendly aqueous or waterborne
adhesive systems that avoid the use of volatile organic solvents. It has thus
far been
relatively difficult to develop aqueous adhesives that perform at a level
equal to
traditional solvent-based adhesives. One major problem associated with bonds
formed
from an aqueous adhesive is the relative susceptibility of the bonds to high
temperature
fluids and corrosive materials. Another need continues to exist for coatings
or adhesives
that deliver superior bonding capability at an inexpensive material cost. A
further need
exists for coatings or adhesives that can be applied with relatively few steps
and minimal
energy use. A few markets that are especially in need of a superior adhesive
or coating
are described below.
The manufacturing of articles, parts or assemblies that include an elastomer
substrate surface bonded to another substrate surface (either another
elastomer substrate
or a non-elastomer substrate) typically involves placing the non-elastomer
substrate in a
mold, introducing a molten or liquid non-vulcanized (i.e., uncured) elastomer
info the
mold and then applying heat and pressure to simultaneously vulcanize the
elastomer and
bond it to the non-elastomer substrate. There are problems, however, with such
vulcanization bonding. The molds often require a complicated design and
interior profile,
curing of the elastomer is slowed, there can be no incorporation of pre-
compressed
elastomer parts info the assembly, the assemblies undergo thermal stress, the
produce
exiting the mold often has extra flashing shat must be removed, any subsequent
addition
of more molded parts can significantly deteriorate the previously formed
adhesive bored
and there is limited process flexibility.
1

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
It would be advantageous under 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 one noticeable area in
which
adequate adhesive bonding is lacking, particularly when bonding to substrates
made from
different materials, especially metal or low surface energy materials. For
example, cured
ethylene-propylene-dime terpolymer rubber ("EPDM") has a low surface energy
that
makes wetting difficult and it includes a relatively low amount of sites such
as carbon-
carbon double bonds that are useful in subsequent bonding. Adhesive bonding to
post-
vulcanized or cured elastomers has met with limited success. Cyanoacrylate
adhesives are
used for post-vulcanization bonding but these suffer from well known problems
in more
demanding industrial applications that are subjected to harsh environmental
conditions.
For example, cyanoacrylates suffer from poor heat resistance, solvent
resistance and
flexibility (see Handbook of Adhesives, edited by Skeist, L, pp. 473-476 (3d
ed. 1990)).
Other post-vulcanization adhesives are solvent-based and require high
temperature and
long curing times. Epoxy or urethane adhesives typically require elastomer
surface
pretreatment such as with oxidizing flames, oxidizing chemicals or
electrical/plasma
discharges in order to improve bonding. These pretreatment methods, however,
are costly
and time consuming.
The problems outlined above with current post-vulcanization adhesive bonding
indicate that there is a long-felt need for an improved post-vulcanization
adhesive
bonding technique.
Another adhesive bonding area in which there continues to be a need is bonding
to SANTOPRENE~, a commonly-used thermoplastic elastomer ("TPE") commercially
available from Advanced Elastomer Systems. Pre-cured and cured SANTOPRENEOO
TPE is particularly difficult to adhesively bond because it has a polyolefinic
thermoplastic
continuous matrix (similar to polyolefinic materials like polyethylene and
polypropylene)
that has an especially 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
practically
impossible.
Tire retread bonding is another field in which there is a need for
improvement.
Tire tread replacement or retreading generally involves adhering a pre-cured
or uncured
2

CA 02318711 2000-09-13
Attorney Docket No. lrt-2588(~T)
retread stock to a cured tire carcass. The retread stock is placed
circumferentially around
the tire carcass with an uncured adhesive (known in the art as an adhesive
cushion or
cushion gum layer) disposed between the retread stock and the tire carcass.
The resulting
tire assembly is subjected to heat and pressure for a period of time to cure
the adhesive
cushion layer. If the retread stock is uncured, the process is occasionally
referred to as
"hot vulcanization" because the applied heat and pressure must be sufficiently
great to
vulcanize the retread stock. If the retread stock is pre-cured, the process is
occasionally
referred to as "cold vulcanization". Application of the heat and pressure for
the adhesive
cure is typically accomplished by placing the tire assembly in a mold or
autoclave which
can require a significant amount of heat (generally from 80°-
250°C depending on whether
the retread stock is pre-cured or uncured) for a significant time period (up
to 300
minutes). Reduction or complete removal of this heat and pressure step would
greatly
contribute to a cost reduction for tire retreading.
It also would be advantageous to have a coating that can be applied without
heat
or extensive surface pretreatment, coat substrate materials that cannot
currently be coated,
has improved adhesion to the substrate surface and provide a waterborne
coating for
thermoplastic olefins that does not require heating.
Summary of the Invention
According to the present invention there is provided a method for bonding a
material to a first substrate surface that includes providing a catalyst at
the first substrate
surface and contacting the catalyst on the surface with a material that
undergoes a
metathesis reaction to bond the material to the first substrate surface. There
are two
embodiments of this method - a coating process and an adhesive process.
In the coating embodiment, the metathesizable 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 metathesizable
material itself
becomes the coating or part of the coating. As used herein, "coating" denotes
any
material that forms a film (continuous or discontinuous) on the substrate
surface and
serves a functional purpose and/or aesthetic purpose. Such functional purpose
could
include environmental protection from corrosion, radiation, heat, solvent,
etc., mechanical
3

CA 02318711 2000-09-13
Attorney Docket No. iu-2588(ET)
properties such as lubricity, electric properties such as conductive or
resistive and
catalystic properties. Paints are included in a "coating" according to this
invention.
In the adhesive embodiment, the metathesis reaction is utilized to adhere
together
two distinct substrate surfaces. In particular, there is provided a method for
bonding a
first substrate surface to a second substrate surface comprising (a) providing
a catalyst at
the first substrate surface, (b) providing a metathesizable material between
the first
substrate surface and the second substrate surface or providing a
metathesizable material
as a component of the second substrate, and (c) contacting the catalyst on the
first
substrate surface with the metathesizable material 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 I, the metathesizable material is
present as part
of a composition interposed between the catalyst on the first substrate
surface and the
second substrate surface. In other words, thepnetathesizable material is
similar to a
conventional adhesive in that it is a composition that is distinct from the
two substrates
when applied. According to a second adhesive embodiment as shown in Figure 2,
the
second substrate is made from or includes the metathesizable 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 metathesizable second substrate that has undergone
metathesis.
There is also provided a manufactured article that includes a first substrate
surface,
a second substrate surface and an adhesive layer interposed between and
bonding the first
and second substrate surfaces, wherein the first substrate surface comprises
an elastomeric
material and the adhesive layer comprises a metathesis polymer.
The invention offers the unique ability to form a strong adhesive bond on a
variety
of substrate surfaces (including difficult-to-bond post-vulcanized elastomeric
materials
and thermoplastic elastomers) at normal ambient conditions with a minimal
number of
steps and surface preparation. The method also avoids the use of volatile
organic solvents
since it is substantially 100 percent reactive andlor can be done with aqueous
carrier
fluids.
The adhesive method of the invention is especially useful to make a tire
laminate
wherein the catalyst is applied to a tire tread or tire carcass, the
metathesizable material is
applied to the tire tread or tire carcass to which the catalyst has not been
applied, and the
4

CA 02318711 2000-09-13
Attorney Docket No. lii-2688(ET)
catalyst-applied tire tread or tire carcass and the metathesizable material-
applied tire tread
or tire carcass are bonded together. This method allows for tire retreading
with no or
minimal heat and pressure, does not require significant curing time and should
reduce the
cost of equipment installation.
According to further embodiment of the invention, the method can be used to
make multilayer structures for either coating or adhesive applications. In
this
embodiment, the catalyst and the metathesizable material are initially applied
to the first
substrate surface as described above. The catalyst site, however, propagates
within the
coating layer where it remains as a stable active site for a subsequent
reaction with a
metathesizable material. In other words, active catalyst remains on the new
surface that
has been created from the metathesizable material. A second metathesizable
material then
is contacted 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
diminished to a level that is no longer practically useful. It should be noted
that the
catalysts typically are not.consumed or deactivated and thus there may be no
need for
excess catalyst.
Brief Description of the Drawings
Figure 1 depicts a preferred embodiment of a first embodiment of a process for
bonding two substrates according to the invention;
Figure 2 depicts a second embodiment of a process for bonding two substrates
according to tire invention;
Figure 3 depicts a bonding process according to the invention wherein the
catalyst is included in a polymer matrix; and
Figure 4 depicts a "living" coating process according to the invention.
Detailed Description of the Preferred Embodiments
Unless otherwise indicated, description of components in chemical nomenclature
refers to the components at the time of addition to any combination specified
in the
5

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
description, but does not necessarily preclude chemical interactions among the
components of a mixture once mixed.
As used herein, the following terms have certain meanings:
"ADMET" means acyclic dime olefin metathesis;
"catalyst" also includes initiators, co-catalysts and promoters;
"coating" includes a coating that is intended to be the final or outer coating
on a
substrate surface and a coating that is intended to be a primer for a
subsequent coating;
"fibrous substrate" means a woven or non-woven fabric, a monofilament, a
multifilament yarn or a fiber cord;
"filmogenic" means the ability of a material to form a substantially
continuous
film on a surface;
"metathesizable material" means a single or mufti-component composition that
includes at least one component that is capable of undergoing a metathesis
reaction;
"non-fibrous substrate" means any substrate type other than a fiber (non-
fibrous
substrate includes a composite substrate that includes fibers as one component
such as
fiber-reinforced plastics);
"normal ambient conditions" means temperatures typically found in minimal
atmosphere control workplaces (for example, about -20°C to about-
40°C), pressure ef
approximately 1 atmosphere and an air atmosphere that contains a certain
amount of
moisture;
"ROMP" means ring-opening methathesis polymerization;
"room temperature" means about 10°C to about 40°C, typically
about 20°C to
about 25°C;
"substantially cured elastotner" and "post-vulcanized elastomer" are used
interchangeably and means thermoset polymers above Tg for that polymer and
thermoplastic polyolefins (substantially cured or post-vulcanized elastomers
typically are
not capable of flow); and
"surface" means a region of a substrate represented by the outermost portion
of the
substrate defined by material/air interface and extending into the substrate
from about 1
atomic layer to many thousands of atomic layers.
The bonding or coating adhering that takes place according to the present
invention occurs via a metathesis reaction. Various metathesis reactions are
described in
6

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
Ivin, K.J. and Mol, J.C., 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
recognized that the
surface metathesis polymerization that occurs in this invention is very
different than bulk
(including reaction injection molding), emulsion or solution metathesis
polymerization in
which a metathesizable monomer and a catalyst are mixed together into a single
composition to effect the metathesis reaction. Bulk metathesis polymerization,
particularly reaction injection molding, of norbornene monomer for producing
molded
articles made of the resulting polynorbornene is known. For example, U.S.
Patent No.
4,902,560 teaches a method for making a glass fiber-reinforced
polydicyclopentadiene
article that involves saturating an uncoated woven glass fabric with a
polymerizable liquid
that includes dicyclopentadiene monomer and catalyst, subjecting the saturated
fabric to
reaction injection molding and post-curing the resultant structure. According
to the
present invention, the resulting metathesis polymer forms a filmogenic
adhesive or
coating rather than a molded article.
The metathesizable material used in the invention is any material that is
capable of
undergoing tnetathesis when contacted with a proper catalyst. The
metathesizable
material may be a monomer, oligomer, polymer or mixtures thereof. Preferred
metathesizable materials are those that include at least one tnetathesis
reactive functional
group such as olefinic materials. The metathesizable material or component can
have a
metathesis reactive moiety functionality ranging from 1 to about 1000,
preferably from
about 1 to about 100, more preferably from about 1 to 10, mvl metathesizable
moiety/mol
molecule of metathesizable component. In addition, materials capable of
undergoing
ROMP typically have "inherent ring strain" as described in Ivin et al. at page
224, with
relief of this ring strain being the driving force for the polymerization.
Materials capable
of undergoing ADMET typically have terminal or near-terminal unsaturation.
Illustrative metathesizable materials are those that include an unsaturated
functional group such as ethene, a-alkenes, acyclic alkenes (i.e., alkenes
with unsaturation
at (3-position or higher), acyclic dienes, acetylenes, cyclic alkenes and
cyclic polyenes.
Cyclic alkenes and cyclic polyenes, especially cycloolefins, are preferred.
When cyclic
alkenes or polyenes are the metathesizable material, the metathesis reaction
is a ROMP.
7

CA 02318711 2000-09-13
Attorney Docket No. 1R-2588(E'I')
A monomer or oligomer is particularly useful when the metathesizable material
itself is intended to form a coating on the substrate surface or when the
metathesizable
material itself is intended to act as an adhesive for bonding one substrate
surface to
another substrate surface. Monomers are especially useful because they can
diffuse into
the substrate surface when they are applied. Particularly useful as monomers
by
themselves, as monomers for making oligomers, or for functionalizing other
types of
polymers, are cycloolefins such as norbornene, cycloalkenes, cycloalkadienes,
cycloalkatrienes, cycloalkatetraenes, aromatic-containing cycloolefins and
mixtures
thereof. lllustrative cycloalkenes include cyclooctene, hexacycloheptadecene,
cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene,
cyclononene,
cyclodecene, cyclododecene, paracyclophene, and ferrocenophene. Illustrative
cycloalkadienes include cyclooctadiene and cyclohexadiene. Illustrative
cycloalkatrienes
include cyclooctatriene. Illustrative cycloalkatetraenes include
cyclooctatetraene.
Norbornene monomers are especially suitable. As used herein, "norbornene"
means any compound that includes a norbornene ring moiety, including
norbornene per
se, norbornadiene, substituted norbornenes; and polycyclic norbornenes. As
used herein,
"substituted norbornene" means a molecule with a norbornene ring moiety and at
least
one substituent group. As used herein, "polycyclic norbornene" mean a molecule
with a
norbornene ring moiety and at least one additional fused ring. Illustrative
norbornenes
include those having structures represented by the following formulae:
RtRt
Rt
Rt
Rt Rt It
R
or
Rt
Rt X Rt
Rt Rt Rt
8

CA 02318711 2000-09-13
Attorney Docket No. 1R-2588(ET)
or
R
R
R'
or
g Rt
t
R
wherein X is CH2, CHR3, C(R3)2, O, S, N-R3, P-R3, O=P-R3, Si(R3)2, B-R3 or As-
R3; each
R' is independently H, CH2, 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, vitro, hydroxy, keto, carbamato,
sulfonyl,
sulfinyl, carboxylate, silanyl, cyano or imido; R2 is a fused aromatic,
aliphatic or hetero
cyclic or polycyclic ring; and R3 is alkyl, alkenyl, cycloalkyl, cycloalkenyl,
aryl, alkaryl,
aralkyl or alkoxy. The carbon-containing R groups may have up to about 20
carbon
atoms.
Exemplary substituted norbornene monomers include methylidenenorbornene, 5-
methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-
2-
norbornene, 5-hexyl-2-norbornene, S-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-toluyl-2-norbornene, 5-oc-naphthyl-2-
norbornene,
5-cyclohexyl-2-norbornene, 5-isopropenyl-norbornene, 5-vinyl-norbornene, 5,5-
dimethyl-
2-norbornene, 5-norbon~ene-2-carbonitrile, 5-triethoxysilyl-2-norbornene, 5-
norborn-2-yl
9

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
acetate, 7-oxanorbornene, 5-norbornene-2,3-carboxylic acid, 5-norbornene-2,2-
dimethanol, 2-benzoyl-5-norbornene, 5-norbornene-2-methanol acrylate, 2,3-
di(chloromethyl)-5-norbornene, 2,3-hydroxymethyl-5-norbornene di-acetate and
their
stereoisomers and mixtures thereof.
Exemplary polycyclic norbornene monomers include 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
polycyctic
norbornenes. Structures of exemplary cycloolefins are shown below.
O ~O O ~O O
C C
C
C ~ NH NCH3
II C~ C
O ll I
O O
O O O O
C~ C~
%1 C6H5 ~-C6H5 I I
C C/
O II
O
i i yi ~
to

CA 02318711 2000-09-13
Attorney Docket No. 1R-2588(ET)
(CH2)2 ~ (CHZ)4
(CH2)6
O
I I
C~O~CH2
CH CI-I3
o \ /
O O
COOCH3 COOH
COOCH3 COON
11

CA 02318711 2000-09-13
Attorney Docket No. IR.-2588(ET)
O
COOCH2C6H5 COOCH2CH3
)CH2C6H5 COOCH2CH3
O
COO(CII2)3CH3
COO(CH2)3CH3
O O
COO(CH2)SCH3 COO(CH2)9CH3
COO(CH2)CH3 COO(CHZ)9CH3
O O
CH2-O-C-R COO(CH2)11CH3 .
CH2-O-i -R
O COO(CH2)11CH3
'7 n
O
CF3
CF3
O O
CH3
CF3
CN
CF3
OCI-I3
12

CA 02318711 2000-09-13
Attorney Docket No. Ift-2588(ET)
Si(CI-I3)3 CH2NHCH3
CH2NHCH3
P(C~s)2 CH20(CH2)sOCH3
P(C6Hs)2
A preferred metathesizable monomer is ethylidenenorbornene, particularly 5-
ethylidene-2-norbornene monomer (referred to herein as "ENB"), and
dicyclopentadiene
(referred to herein as "DCPD"). Ethylidenenorbornene surprisingly provides
superior
performance over a wide variety of substrates.
When used as a coating or an adhesive the metathesizable monomer or oligomer
may be used by itself in a substantially pure form or technical grade. Of
course, as
described below the metathesizable monomer or oligomer can be included in a
mixture
with other components or it can be substantially diluted with a solvent or
carrier fluid. As
used herein, "technical grade" means a solution that includes at least about
90 weight %
monomer or oligomer. The advantage of using a technical grade is that the
metathesizable composition is approximately 100% reactive and thus there are
no
workplace or environmental problems caused by volatile organic compounds or
performance problems caused by non-reactive additives and there is no need for
purification.
Alternatively, the metathesizable monomer or oligomer can be included in a
multi-
component composition such as an emulsion, dispersion, solution or mixture. In
other
words, the metathesizable material can be a mufti-component composition that
includes at
least one metathesizable component such as a metathesizable monomer or
oligomer.
13

CA 02318711 2000-09-13
Attorney Docket No. 1R-2588(ET)
Preferably, such metathesizable component-containing composition is in the
form of a
liquid, paste or meltab)e solid when it is applied. The metathesizable liquid
composition
can be prepared by mixing together the components according to conventional
means and
then can be stored for an extended time period prior to use (referred to
herein as "shelf
life").
For example, the metathesizable 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.
One particularly useful composition could include the metathesizable
monomer/oligomer
dissolved in a polymer such as a polyester, polyurethane, polycarbonate, epoxy
or acrylic.
The metathesizable component can also be included in a multi-component
composition
wherein the metathesis polymerization occurs in the presence of a pre-formed
andlor
simultaneously forming material resulting in the formation of an
interpenetrating polymer
network (1PN).
The metathesizable composition (either monomer alone or multi-component)
preferably is substantially about 100% solids. In other words, the composition
does not
include substantially any liquid amount that does not react to form a solid.
The amount of metathesizable material applied to a substrate surface should be
sufficient to form a continuous film in the case of a coating or provide
adequate bonding
in the case of an adhesive. The amount varies depending upon a variety of
factors
including substrate type and desired properties but it could range from 0.01
to 1,000,
preferably, 0.1 to 100 and more preferably 0.3 l0 25 mg/cm2 substrate surface
area.
According to another embodiment shown rrl Figure 2, the second substrate for
bonding to the first substrate includes a metathesizable component. The
metathesizable
material can be present as a chemically- or ionically-bonded portion of the
substrate
material or it can be present simply in the form of a physical mixture (e.g.,
hydrogen
bonding).
Any catalyst that is capable of polymerizing the metathesizable material upon
contact can be used. The catalyst should also have good stability after it is
applied to the
substrate surface. In particular for normal ambient conditions bonding, the
catalyst should
be capable of maintaining its activity in the presence of oxygen and moisture
for a
reasonable period of time after application to the substrate material and
until the
14

CA 02318711 2000-09-13
Attorney Docket No. IFi-2688(ET)
metathesizable material is brought into contact with the catalyst.
Experimental tests have
indicated that certain catalysts can remain active for at least 30 days after
coating on the
substrate surface.
There are numerous known metathesis catalysts that might be useful in the
invention. Transition metal carbene catalysts are well known. Illustrative
metathesis
catalyst systems include rhenium compounds (such as Rez07/A1203, ReC151A1203,
Re207/Sn(CH3)4, and CH3Re03/A1203-Si02); ruthenium compounds (such as RuCl3,
RuCl3(hydrate), K2[RuCls-H20], [Ru(H2O)6](tos)3 ("tos" signifies tosylate),
ruthenium/olefin systems (meaning a solution or dispersion of preformed
complex
between Ru and olefin (monomer) that also includes a (i-oxygen 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 other conventional
polymerization synthesis), and ruthenium carbene complexes as described in
detail
below); osmium compounds (such as OsCl3, OsCl3(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)ammoniutn molybdate, and
trioctylammonium molybdate); tungsten compounds (such as tungsten carbene
complexes
(such as t-butvxy and hexafluoro-t-butoxy systems), WC16 (typically with a co-
catalyst
such as SnR4 (R signifies alkyl) or PbR4), tungsten oxytetrachloride, tungsten
oxide
tridodecylamtnonium tungstate, methyltricaprylammonium tungstate, '
tri(tridecyl)ammonium tungstate, trioctylammonium tungstate,
WCI6/CH3CH20HICH3CH2A1C12, W03/SiOz/A1203, WCl6/2,6-C6H5-C6HSOH/SnR4,
WCl6/2,6-Br-C6H30HISnR4, WOCl4/2,6-C6H5-C6HSOH/SnR4, WOCIq/2,6-Br-
C6H30H/SnR4); TiCla/aluminum alkyl; NbOx/Si02/iso-butyl AlCl2; and MgCl2. As
indicated above, some of these catalysts, particularly 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
having a structure represented by

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
L
X~ ( /R
M=C
X/ ~ \Rt
L
wherein M is Os, Ru or Ir; each Rt is the same or different and is H, alkenyl,
alkynyl,
alkyl, aryl, alkaryl, aralkyl, carboxylate, alkoxy, alkenylalkoxy,
alkenylaryl,
alkynylalkoxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl 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 may have up
to about 20
carbon atoms. Preferably, X is Cl, Br, I, F, CN, SCN, or N3. Preferably, L is
Q(R2)s
wherein Q is P, As, Sb, N or imidazolin-2-ylidene; R2 is H, cycloalkyl, alkyl,
aryl, alkoxy,
arylate or a heterocyclic ring; and a is I, 2 or 3 . Preferably, M is Ru; Rt
is H, phenyl
("Ph"), -CH=C(Ph)2, -CH=C(CH3)2 or -C(CH3)2Ph; L is a trialkyl- or triaryl-
phosphine or
mixed alkylaryl tertiary phosphine such as PCy3 (Cy is cyclohexyl or
cyclopentyl),
P(isopropyl)3 or PPh3; and X is Cl. Particularly preferred catalysts include
tricyclohexyl
phosphine ruthenium carbenes, especially
bis(tricyclohexylphosphine)benzylidene
ruthenium(IV) dichloride (designated herein by RuCl2(PCy3)2=CHPh). Such
ruthenium
and osmium carbene catalysts are described, for example, in U.S. Patents No.
5,312,940
and 5,342,909, both incorporated herein by reference; Schwab, P.; Grubbs,
R.H.; Ziller,
J.W., Journal of the Arrcerican Chemical Society, 1996, 118, 100; Schwab, P.;
France,
M.B., Ziller, J.W.; Grubbs, R.H., Angew. Chem. Int. Ed. , 1995, 34, 2039; and
Nguyen,
S.T.; Grubbs, R.H., Journal of the American Chemical Society, 1993, 1 I5,
9858.
Another ruthenium carbene complex that may be useful is a bimetallic catalyst
having a structure represented by
L-
Cl ~ Ru=C~
PCy3 H
Cl
M.,.,,,,' C1 C1 \ /
16

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
wherein L is p-cymene or 1,3-di-t-butylcyclopentadiene and M is Ru, Os or Rh.
Such a
catalyst is disclosed in Dias, E.L.; Grubbs, R.H., Organorrcetallics, 1998,
17, 2758.
Preferred molybdenum or tungsten catalysts are those represented by the
formula:
Ri
N
2/ X ~~,.~ - C
R
~X
R
wherein M is Mo or W; X is O or S; R' is an alkyl; aryl, aralkyl, alkaryl,
haloalkyl,
haloaryl, haloaralkyl, or a silicon-containing analog thereof; R2 are each
individually the
same or different and are an alkyl, aryl, aralkyl, alkaryl, haloalkyl,
haloaryl, haloaralkyl, or
together form a heterocyclic or cycloalkyl ring; and R3 is alkyl, aryl,
aralkyl or alkaryl.
Preferably, M is Mo; X is O; R~ is phenyl or phenyl(RS) wherein RS is phenyl,
isopropyl
or alkyl; RZ is -C(CH3)3, -C(CH3)(CF3)2,
\ R4 Ra
Ni CH3
or
Ph Ph CH3 \~ or
Ph Ph Ra
Ra
or
(wherein R4 15 phenyl, naphthyl, binaphtholate or biphenolate); and R3 is -
C(CH3)ZC6H5.
Particularly preferred are 2,6-diisopropylphenylimidoneophylidene molydenum
(VI)
17

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
bis(hexafluoro-t-butoxide) (designated herein as "MoHFTB") and 2,6-
diisopropylphenylimidoneophylidene molydenum (VI) bis(t-butoxide) (designated
herein
as "MoTB"). Such molybdenum catalysts are described in Bazan, G.C., Oskam,
J.H.,
Cho, H.N., Park, L.Y., Schrock, R.R., Joccrnal of the American Chemical
Society, 1991,
I 13, 6899 and U.S. Patent No. 4,727,215.
The catalyst can be delivered at the surface of the substrate by any method.
Typically the catalyst is applied in a liquid composition to the substrate
surface. The
catalyst in its substantially pure form may exist as a liquid or solid at
normal ambient
conditions. If the catalyst exists as a liquid, it may be mixed with a carrier
fluid in order to
dilute the concentration of the catalyst. If the catalyst exists as a solid,
it may be mixed
with a carrier fluid so that it can be easily delivered to the substrate
surface. Of course, a
solid catalyst may be applied to the surface without the use of a liquid
carrier fluid. The
preferred RuCl2(PCy3)2=CHPh, homobimetallic ruthenium, MoHFT B and MoTB
catalysts exist as solids at normal ambient conditions and thus are usually
mixed with
carrier fluids. The catalyst composition could also be considered a primer in
the sense
that it primes the substrate surface for subsequent application of a coating
or an adhesive.
Alternatively, the catalyst may also be mixed in bulk with the substrate
material.
If the catalyst is mixed in bulk with the substrate material, it is preferably
exuded or
"bled" towards the surface of the substrate. One method for making such a
catalyst
containing substrate is to mix the catalyst in bulk with the substrate
material and then
form the resulting mixture into the substrate article via molding, extrusion
and the like.
Of course, the catalyst cannot be deactivated by the composition of the
substrate material
or by the method for making the substrate article.
Tyre present invention preferably does not require any pre-functionalization
of the
substrate surface prior to application of the catalyst. In other words, the
substrate surface
does not have to be reacted with any agent that prepares the surface for
receiving the
catalyst. For example, formation on the substrate surface of a so-called
monolayer or self-
assembling layer made from a material (such as a thiol) different than the
catalyst or the
metathesizable adhesive or coating is unnecessary. The catalyst can be applied
to be in
"direct contact" with the substrate surface. Of course, for metallic
substrates the substrate
surface can be pre-treated with conventional cleaning treatments or conversion
treatments
and for elastomer substrates the surface can be solvent-wiped.
18

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
'the catalyst may be dispersed, suspended or dissolved in the carrier fluid.
The
carrier fluid may be water or any conventional organic solvent such as
dichloroethane,
toluene, methyl ethyl ketone, acetone, tetrahydrofuran, N-methyl pyrrolidone,
3-methyl-2-
oxazolidinone, 1,3-dimethylethyleneurea, 1,3-dimethylpropyleneurea and
supercritical
carbon dioxide. Ruthenium, osmium and iridium catalysts are particularly
useful in polar
organic and aqueous carrier systems. The carrier fluid 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
the
metathesis polymerization. The amount varies depending upon a variety of
factors
including substrate type and desired properties but it could range from 0.001
to 10,
preferably, 0.01 to 5 and more preferably 0.1 to 5 mg/cm2 substrate surface
area.
The adhesive or coating of the invention offers numerous ease-of use
advantages.
The metathesis polymerization occurs under normal ambient conditions in air
regardless
of whether moisture is present. There is no need for an exterior energy source
such as
radiation, thermal or photochemical for curing to produce the adhesive or
coating. Thus,
the adhesive or coating will adhere to thermally or solvent sensitive
surfaces. In addition,
there are a minimal number of steps according to the invention. There is no
need to
initially react the substrate surface to form any particular type of
functional groups on the
surface. There is no need for multiple, carefully controlled steps required
for forming so-
called monolayers or self-assembling layers. The bond formed by the method of
the
invention displays remarkable adhesive strength considering the ease-of-use of
the
method.
A further significant advantage is that the method of the invention is
environmentally-friendly. The catalyst can be delivered to the substrate
surface with an
aqueous carrier fluid. Substantially pure or technical grade metathesizable
monomer/oligomer can be used and the monomer/oligomer is substantially 100%
reactive. Consequently, there are substantially no volatile organic solvents
used according
to one embodiment of the invention.
Although not bound by any theory, it is believed that the adhesive or coating
formed according to the invention achieves its remarkable bonding due to a
number of
factors. The monomer and/or catalyst diffuses readily into the substrate
surface,
particularly elastomeric substrates. As a result of this diffusion, an
interpenetrating
19

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
network develops between the polymer chains formed from the metathesizable
material
and molecular structure of the substrate material. Moreover, the metathesis
polymerization reaction may well also encourage the formation of strong
covalent bonds
formed between molecules of the metathesizable material and molecules of the
substrate.
A unique advantage of the coating is its excellent adherence to the substrate
surface.
The adhesive or coating is an addition polymer formed via the metathesis
reaction.
The resulting polymer should be capable of forming a continuous film. Olefin
melathesis
typically yields polymers having an unsaturated linear backbone. The degree of
unsaturation functionality of the repeat backbone unit of the polymer is the
same as that of
the monomer. With a norbornene reactant, the resulting polymer should have a
structure
represented by:
Catal
. V In
wherein n can be 1 to 20,000, preferably 1 to 500, more preferably 1 to 100,
and most
preferably 10 to 100. The molar ratio of norbornene reactant to catalyst
should range
from 20,000:1 to 1:1, preferably 500:1 to 1:1, and most preferably 100:1 to
10:1.
The resulting polymer film can be brittle, but surprisingly superior bonding
occurs
even with flexible substrates. It appears that any cracking of the film does
not propagate
into the substrate.
According to a preferred embodiment of the invention the liquid catalyst
(either by
itself or as a component of a rnulti-component catalyst composition) is
applied to the
substrate surface. The catalyst can be applied to achieve continuous surface
coverage or
coverage only in predetermined selected areas by any conventional
coating/printing means
such as spraying, dipping, brushing, wiping, roll-coating or the like. The
metathesizable
material can be contacted with the resulting catalyzed-coated surface when it
is still wet.
However, the catalyst carrier fluid preferably is allowed to evaporate and
then the
metathesizable material is applied to the dry catalyzed-coated surface.
Evaporation of the
catalyst carrier fluid can occur over time in normal ambient conditions or it
can be
accelerated by subjecting the catalyst-coated surface to heat or vacuum. A
noteworthy

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
advantage of the invention is that the dry catalyst-coated surface remains
stable and active
for an extended period of time. Although not wishing to be bound by specific
limits, it is
believed that the dry catalyst-coated surface should retain its activity for
at least five
minutes, preferably at least 24 hours, more preferably for at least 1 month,
and most
preferably for at least 6 months. This stability contributes to manufacturing
flexibility by
providing a relatively long time period during which the metathesizable
material may 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 metathesizable material can be simultaneously
spray
applied to the substrate surface.
Once the catalyst has been made available at the substrate surface, the
metathesizable material (whether in the form of a second substrate, coating or
adhesive) is
brought into contact with the catalyst on the substrate surface. The
metathesizable
material typically begins to react upon contact with the catalyst. Film
formation is caused
by the metathesis polymerization of the metathesizable material to form a
substantially
linear polymer. The film-forming rate could be accelerated by addition of
either
Br~nsted acids, Lewis acids or CuCI to either the catalyst composition or the
metathesizable composition. Methods for contacting the metathesizable material
to the
catalyst-coated substrate surface depend upon the intended application.
If the metathesizable material is itself intended to form a coating, then it
can be
applied in a liquid form under normal ambient conditions to the catalyst-
coated substrate
surface by any conventional coating/printing means such as spraying, dipping,
brushing,
wiping, roll-coating or the like. The metathesizable coating material also
could be applied
by extrusion if it is in the form of a molten material. The coating thickness
can be varied
according to intended use.
The metathesizable material, especially in the form of a monomer, can be
included
as a component in a mufti-component exterior coating formulation such as a
paint or
caulk. In such a system the catalyst could be included in a primer formulation
that is
applied prior to the exterior coating.
If the metathesizable material is intended to form an adhesive for adhering
two
substrates together, the metathesizable material can be applied in a liquid
fore under
normal ambient conditions directly to the catalyst-coated substrate surface by
any
21

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
conventional coating/printing means such as spraying, dipping, brushing,
wiping, roll-
coating or the like. The other substrate surface then is brought into contact
with the
metathesizable material before curing of metathesizable material is complete.
Preferably,
however, the metathesizable material is applied to the substrate surface that
is not coated
with the catalyst and the metathesizable adhesive-coated substrate and the
catalyst-coated
substrate can be brought into contact under normal ambient conditions to
effect the
adhesive bonding. The metathesizable material can be applied in a liquid form
under
normal ambient conditions directly to the non-catalyst-coated substrate
surface by any
conventional coating/printing means such as spraying, dipping, brushing,
wiping, roll-
coating or the like. The metathesizable material can be allowed to dry or
remain wet prior
to bringing the two substrates together. The metathesizable adhesive material
also could
be applied in both of these alternative methods by extrusion if it is in the
form of a molten
material. If the metathesizable material is a solid at room temperature, then
it should be
heated to at least partially melt or become a semi-solid in order to
facilitate bonding.
Pressure also could be applied to a solid metathesizable material to achieve a
micro liquid
surface layer.
The types of substrate surfaces that can be coated or bonded according to the
invention vary widely. The substrates, of course, are articles of manufacture
that are
themselves useful. Such substrates could include machined parts made from
metal and
elastomers, molded articles made from elastomers or engineering plastics,
extruded
articles such as fibers or parts made from thermoplastics or thermosets, sheet
or coil metal
goods, fiberglass, wood, paper, ceramics, glass and the like. As used herein
"substrate"
does not include conventional catalyst supports made from bulk materials such
as alumina
or silica. Conventional catalyst supports are useful only to support a
catalyst to effect
polymerization, but would not be useful by themselves without the catalyst.
Illustrative elastomer substrates include 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-dime terpolymer rubber ("EPDM"), butyl rubber,
brominated butyl rubber, alkylated chlorosulfonated polyethylene rubber,
hydrogenated
nitrite rubber ("I-INBR"), silicone rubber, fluorosilicone rubber, poly(n-
butyl acrylate),
thermoplastic elastomer and the like as well as mixtures thereof.
22

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
Illustrative engineering plastic substrates useful in the invention include
polyester,
polyolefin, polyamide, polyimide, polynitrile, polycarbonate, acrylic, acetal,
polyketone,
polyarylate, polybenzimidazoles, polyvinyl alcohol, ionomer,
polyphenyleneoxide,
polyphenylenesulfide, polyaryl sulfone, styrenic, polysulfone, polyurethane,
polyvinyl
chloride, epoxy and polyether ketones.
Illustrative metal substrates include 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 according to the invention the metal surface can be cleaned pursuant
to one or
more methods known in the art such as degreasing and grit-blasting and/or the
metal
surface can be converted or coated via pllosphatizing, electrodeposition, or
autodeposition.
Illustrative fiber substrates include fiberglass, polyester, polyatnide (both
nylon
and aramid), polyethylene, polypropylene, carbon, rayon and cotton.
Illustrative fiber-reinforced or -impregnated composite substrates include
fiberglass-reinforced prepreg ("FRP"), sheet molding compound ("SMC") and
fiber-
reinforced elastomer composites. In the case of fiber-reinforced elastomer
composites,
fiber substrates can be sandwiched between and bonded to outer elastomer
layers to form
a composite multilayer composite structure such as tires, belts for the
automotive
industry, hoses, air springs and the like. The metathesizable adhesive of the
invention
could be used to bond fiber reinforcing cord to lire 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
applied to the fiber or cord and then either a separate metathesizable
material is contacted
with the catalyst-treated fiber or cord so as to form an adhesive with the
composite matrix
material or the composite matrix material is itself metathesizable.
The invention is particularly useful to adhere two substrates to each other.
The
types of substrates mentioned above could all be bonded together according to
the
invention. The substrates can each be made from the same material or from
different
materials. The invention is especially useful in bonding post-vulcanized or
cured
elastomer, particularly to a substrate made from a different material such as
metal.
23

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
It has been found that superior bonding of cured elastomer substrates is
obtained if
the metathesizable material is applied to the cured elastomer substrate
surface and then
the adhesive-applied elastomer substrate is contacted with the catalyst-coated
other
substrate. This procedure is shown schematically in Figure I. This,preferred
method is
especially applicable to bonding 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 metathesizable adhesive is applied to the surface of the elastomer
substrate. The
catalyst-coated metal substrate and the adhesive-applied substrate are brought
together
under minimal pressure that is adequate simply to hold the substrates together
and in
place until the metathesis reaction initiated by contact with the catalyst has
progressed to
the point of curing sufficient to provide at least a "green strength" bond.
Depending upon
the rate of diffusion of metathesizable material into the substrate and the
rate of
evaporation of the tnetathesizable material, there may be a lapse of up to 30
minutes
before the two substrates are brought together, but preferably the lapse is
about 30
seconds to about 5 minutes. In the case of bonding cured EPDM to steel, green
strength
appears to develop within approximately five to ten minutes after the
substrates are
contacted together and sufficiently high bond strength appears to develop
within
approximately thirty minutes after the substrates are contacted together.
The bonding process of the invention is particularly useful for bonding a
substrate
made from a thermoplastic elastomer such as SANTOPRENE~ to another
thermoplastic
elastomer substrate or to a substrate made from a different material.
SANTOPRENED is
the trade designation of a thermoplastic elastomer ("TPE") commercially
available from
Advanced Elastomer Systems that consists of elastomer particles dispersed
throughout a
continuous matrix of thermoplastic material. Such TPE blends are described in
detail in
U.S. Patent No. 5,609,962, incorporated herein by reference. As used herein,
TPE also
includes thermoplastic olefins ("TPO") such as those described in U.S. Patent
No.
5,073,597, incorporated herein by reference.
Polyolefins are typically the thermoplastic material used as the continuous
matrix
of TPE. According to the '962 patent, they are desirably prepared from
monoolefin
monomers having 2 to 7 carbon atoms, such as ethylene, propylene, 1-butene,
isobutylene,
1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene, 4-methyl-I-pentene, 5-
methyl-I-
hexene, mixtures thereof and copolymers thereof with (meth)acrylates and/or
vinyl
24

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
acetates. Preferred are monomers having~3 to G carbon atoms, with propylene
being
preferred. The polypropylene can be highly crystalline isotactic or
syndiotactic
polypropylene.
A portion of the polyolefin component can be a functionalized polyolefin
according to the '962 patent. In other words, non-functionalized polyolefins
and
functionalized polyolefins can be blended or mixed together to form the TPE.
The
polyolefins of the functionalized polyolefins can be homopolymers of alpha-
olefins such
as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene and
copolymers of
ethylene with one or more alpha-olefins. Preferable among the polyolefins are
low-
density polyethylene, linear low-density polyethylene, medium- and high-
density
polyethylene, polypropylene, and propylene-ethylene random or block
copolymers. The
functionalized polyolefms contain one or more functional groups which have
been
incorporated during polymerization. However, they are preferably polymers onto
which
the functional groups have been grafted. Such functional group-forming
monomers are
preferably carboxylic acids, dicarboxylic acids or their derivatives such as
their
anhydrides.
The elastomer component of TPE is made from olefinic rubbers such as EPM,
EPDM, butyl rubber, copolymer of a C4_~ 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 the functionalized polyolefin is 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
the polyolefin,
rubber, functionalized polyolefin and optional additives.
The olefin rubber component is generally present as small, e.g., micro-size,
particles within a continuous polyolefin matrix. The rubber is partially
crosslinked
(cured) and preferably fully crosslinked or cured. The partial or full
crosslinking can be
achieved by adding an appropriate rubber curative to the blend of polyolefin
and rubber
and vulcanizing the rubber to the desired degree under conventional
vulcanizing
conditions. It is preferred that the rubber be crosslinked by the process of
dynamic

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
vulcanization wherein the rubber is vulcanized under conditions of high shear
at a
temperature above the melting point of the polyolefin component. The rubber is
thus
simultaneously crosslinked and dispersed as fine particles within the
polyolefin matrix.
The bonding method of the invention is also particularly useful for bonding an
elastomeric or plastic tire tread to an elastomeric or plastic tire carcass.
As described
above, tire tread replacement or retreading generally involves adhering a pre-
cured or
uncured retread stock directly to a cured tire carcass. The metathesizable
adhesive
material of the invention can be used to replace the adhesive cushion or
cushion gum
layer currently used in the retreading art.
The metathesis catalyst is applied to a bonding surface of either the tire
carcass or
a bonding surface of the tire tread and the metathesizable material is applied
to the other
bonding surface of the tire carcass or tire tread. Preferably, the catalyst is
applied to the
tire carcass and the metathesizable material is applied to the tire tread. The
carcass of the
used tire can be buffed by known means to provide a surface for receiving the
catalyst or
metathesizable material. It is preferred that the bonding surface is mildly
rough or only
lightly sanded. The catalyst or metathesizable material - coated retread stock
is placed
circumferentially around the catalyst or metathesizable-coated tire carcass.
The coated
surfaces then are contacted together with minimal pressure sufficient simply
to hold the
tread and carcass together. The tread stock and carcass can be held together
during curing
of the methathesis material by any conventional means in the retread art such
as stapling
or placing a cover or film around the tire assembly. Curing is initiated when
the surfaces
are contacted, green strength begins to develop within approximately five to
ten minutes,
and high bond strength begins to develop within approximately 15 minutes to
one hour.
The resulting tire laminate includes a tire carcass or casing, a tire retread
and a
metathesis polymer adhesive layer between the carcass and retread. The tire
laminate is
useful for various types of vehicle tires such as passenger car tires, light
and medium
truck tires, off-the-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 carcass.
The catalyst and metathesizable material typically are applied in liquid form.
Retread or tread stock is well known in the att and can be any cured or
uncured
conventional synthetic or natural c-ubber such as rubbers made from conjugated
dimes
having from 4 to 10 carbon atoms, rubbers made from conjugated diene monomers
having
26

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
from 4 to 10 carbon atoms with vinyl substituted aromatic monomers having from
8 to 12
carbon atoms, and blends 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 stock can be in the form of a strip that is
placed around
the outer periphery of the concentric circular tire carcass or casing. 1'he
cured carcass is
similarly well known in the art and is made from conjugated dimes such as
polyisoprene
or natural rubber, rubbers made from conjugated dime monomers having from 4 to
10
carbon atoms with vinyl substituted aromatic monomers having from 8 to 12
carbon
atoms, and blends thereof. Such rubbers generally contain various
antioxidants, fillers
such as carbon black, oils, sulfur, accelerators, scearic acid, and
antiozonants and other
additives.
The invention will be described in more detail by way of the following non-
limiting examples. Unless otherwise indicated, the steel coupons used in the
examples
are made from grit-blasted, 1010 fully hardened, cold rolled steel, the cured
EPDM rubber
strips are available from British Tire and Rubber under the designation 96616
and all
bonding and coating was performed at normal ambient conditions.
Primary adhesion of the bonded samples was tested according to ASTM-D 429
Method B. The bonded samples are placed in an Instrotl and the elastomeric
substrate is
peeled away from the other substrate at an angle of 180° at 50.88mm (2
inches) per
minute. The mean load at maximum load and the mean energy-to-break point are
measured. After being pulled apart, the samples are inspected to determine the
failure
mode. The most desirable failure mode is rubber tear - a portion of the
elastomeric
material of one substrate remains on the other substrate. Rubber tear
indicates that the
adhesive is stronger than the elastomeric material.
Example 1 - Bonding of EPDM-to-Metal - Application of Catalyst by Drip or
Flooding
Process
A catalyst solution was prepared by dissolving 0.021 g of RuCl2(PCy3)2=CHPh
iri 1.5 ml of CH2C12. Three grit-blasted steel coupons were prepared by
pipetting 0.5 ml
of the catalyst solution via syringe onto each coupon to just cover its
surface (34.9 mm x
25.4 mm) and the solvent allowed to evaporate for three to four minutes in the
open
27

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
laboratory atmosphere. This gave >_7 mg of RuCl2(PCy3)2=CHPh per coupon. 'fhe
metal
coupons were usually washed with acetone and dried prior to application of
catalyst
solution, but this was not required. Lt this example, the coupons were
unwashed. EPDM
rubber strips were prepared by washing the bonding surface (34.9 tnm x 25.4
mm) with
acetone, drying at room temperature for 3 to 4 minutes, and then applying via
syringe 0.03
ml of ENB to each coupon and spreading it evenly with the needle tip. The
catalyst-
coated metal coupon was immediately placed on top of the ENB-coated EPDM strip
so
that both treated surfaces contacted each other and a weight of approximately
100 gm was
placed on top of the mated area. The samples sat at ambient conditions
overnight. All the
samples could not be pulled apart by hand. They were evaluated using a
180° peel test on
an Instron and showed only EPDM rubber tear on failure. 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 of EPDM-to-Metal
This testing was performed as preliminary screening to evaluate different
application methods for bonding EPDM-to-metal. The process described in
Example I
was used to apply the RuCl2(PCy3)2=CHPh catalyst solution or ENB to either a
grit-
blasted steel coupon or EPDM rubber strip. The results are shown below in
Table 1.
Based on these results, it appears that the best bonding method occurred when
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 is the substrate to which the
catalyst or
monomer is applied.
Table 1. Comparison Bondintr between Application Surfaces
Catal Monomer Bond Notes
st ~
metal Rubber ood Could not ull a art b hand
in tension.
metal Metal variableOne sample pulled apart while
the other
two could not be pulled apart
totally and
showed rubber tear.
metal8 Metals variableFresh catalyst soln used. One
sample pulled
apart while the other two could
not be
ulled a art totall and showed
rubber tear.
rubber Metal oor Adhesion to rubber was ood,
oor to
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CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
metal.
rubber Rubber poor Adhesion to rubber was good,
poor to
metal.
rubber Rubber poor Fresh catalyst soln used. Adhesion
to
rubber was ood, oor to metal.
a) Catalyst applied to metal surface followed by apptcaUOn of ENB before
mating.
b) Catalyst applied to EPDM surface followed by application of ENB before
mating.
Example 3 - Delayed Bonding of Substrates Coated with Catalyst
A catalyst solution was applied to grit-blasted metal coupons according to the
process described in Example 1, but the catalyst-coated coupons were allowed
to dry and
stand in ambient conditions in the laboratory (except for being covered from
dust) for 3,
10, 20 and 33 days before bonding to the EPDM with ENB. All samples showed
EPDM
rubber tear when subjected to the 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); 10 day
samples
had a mean load at maximum load of 298.32 (N) and a mean energy to break of
40.18 (J);
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
15 (N) and a mean energy to break of 48.48 (J).
Example 4 - Application of Catalyst to Substrate by Brush Process.
A catalyst solution was prepared by dissolving 0.021 g of RuCl2(PCy3)2=CHPh
20 to 1.5 ml of CH2Cl2 in a screw-cap vial under N2. 'This solution was
applied by brush to
three grit-blasted steel coupons over the surface to be bonded (34.9 mm x 25.4
mm) and
the solvent allowed to evaporate in the open laboratory atmosphere during the
brushing
process, thus leaving the catalyst powder evenly distributed over the metal
coupon
surface. After drying, all prepared samples were weighed to determine the
amount of
catalyst on the surface which was 5.8~1.8 mg per coupon. When the first-made
solution
was depleted, 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 at room
temperature for 3 to 4 minutes, and then applying via syringe 0.03 ml of ENB
to each
29

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
coupon and spreading it evenly with the needle tip. The catalyst-coated metal
coupon was
immediately placed on top of the ENB-coated EPDM strip so that both treated
surfaces
contacted each other and a weight of approximately 100 gm was placed on top of
the
mated area. The samples sat at ambient conditions overnight. The next morning,
no
failure was observed on attempted pulling the samples apart by hand. They were
evaluated using a 180° peel test on an Instron and showed evenly
distributed rubber tear
on the EPDM on failure. A total of 12 specimens were tested and showed a mean
load at
maximum load of 283.87 (N) and mean energy to break of 41.72 (J).
Example 5 - Application of Waterborne Catalyst to Substrate
A catalyst solution was prepared by dissolving 0.015 g of RuCl2(PCy3)2=CHPh
and 0.006 g of dodecyltrimethylammonium bromide ("DTAB") surfactant (0.488
w/w%)
in 1.21 g of water. The aqueous catalyst solution was brushed onto two grit-
blasted metal
coupons using the procedure described in Example 4 except that the coupons
were heated
on a hot-plate at 40°C to aid in water removal. The coupons were cooled
to room
temperature and bonded to EPDM with 0.04 tnl 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 of
RuCl2(PCy3)2=CHPh and 0.0024 g of DTAB (0.068 w/w%) in 3.5 g of water. The
aqueous catalyst solution was brushed onto three grit-blasted metal coupons as
described
above, cooled to room temperature, and bonded to EPDM with 0.04 ml of ENB as
described in Example 4. They were evaluated using a 180° peel test on
an Instron and
showed rubber tear on the EPDM on failure. A total of three specimens were
tested and
showed a mean load at maxirnutn load of 215.07 (N) and mean energy to break of
23.09
(J).
Example 6 - ENB Monomer Residence Time on EPDM Substrate
Bonding of EPDM to grit-blasted steel coupons was performed according to
Example I except that 0.04 m1 of ENB was allowed to stand on the EPDM surface
to be
bonded for 0, 2, and 4 minutes before bonding to the metal. For the 4 minute
sample, an

CA 02318711 2000-09-13
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additional 0.03 ml of ENB was applied onto two of the EPDM strips since the
liquid
absorbed into the EPDM. All samples exhibited EPDM rubber tear 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 break of 29.45 (J); 2 minutes samples had a mean load at
maximum
load of 273.12 (N) and a mean energy to break of 35.34 (J); and the 4 minutes
samples
had a mean toad at maximum load of 247.28 (N) and a mean energy to break of
22.82 (J).
Example 7 - EPDM-to-Metal Bonding Using Different Steel Substrates
Phosphatized and unprocessed 1010 steel were bonded to EPDM rubber
according to the procedure described in Example 1. Bonding strength was
reduced
compared to grit-blasted steel, but all the samples still exhibited some EPDM
rubber tear
when subjected to the 180° peel strength test. The phosphatized steel
samples had a mean
load at maximum load of 158.69 (N) and a mean energy to break 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 break of 19.88 (J).
Example 8 - Application of Catalyst to Substrate by Spray Process.
A catalyst solution was prepared by dissolving 0.5 g of RuCl2(PCy3)2=CHPh in
20 ml of CH2C12. The catalyst solution was sprayed onto 12 grit-blasted steel
coupons in
a sweeping pattern until even-appearing coverage of the surface to be bonded
(34.9 mm x
25.4 mm) was obtained. The solvent was allowed to evaporate 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, which was 9.0~0.95 mg per coupon. EPDM
rubber
strips were prepared by washing the bonding surface (34.9 mm x 25.4 mm) with
acetone,
drying at room temperature for 3 to 4 minutes, and then applying via syringe
0.06 ml of
ENB to each coupon and spreading it evenly with the needle tip. The catalyst-
coated
metal coupon was immediately placed on top of the ENB-coated EPDM strip so
that both
treated surfaces contacted each other and a weight of approximately 100 g was
placed on
top of the mated area. The samples sat at ambient conditions overnight. The
next
morning, all samples could not be pulled apart by hand and showed only EPDM
rubber
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tear after analysis on an Instron. A total of 12 samples were tested and
displayed a mean
load at maximum load of 352.47 (N) and a mean energy to break of 61.23 (J).
Example 9 - EPDM-to-Metal Bonding Using Other Metals
A catalyst solution was prepared by dissolving 0.030 g of RuCl2(PCy3)2=CHPh
in 2.5 ml of CH2Cl2. The catalyst solution was,applied to steel Q-panel,
aluminum, and
chromated aluminum metal coupons and the metal coupons were bonded to EPDM
rubber
strips with 0.04 ml of ENB monomer per coupon as described in Example 4. Three
separate but identical batches of catalyst solution were used to prepare the
metal coupons,
which resulted in 7.311.2 mg catalyst per coupon after weighing. The specimens
were
analyzed on an Instron with a 180° peel test. All three metals showed a
very small
amount of robber tear with adhesive failure as the primary failure mode as
most of the
ENB polymer film was attached to the rubber on failure. Higher bond strengths
were
observed with the chromated aluminum surfaces.
Table 2. 180° Peel Test Data for EPDM-to-Steel, -Aluminum, and -
Chromated
Aluminum Specimens.
Sam le T Load at Max. Load Energy to Break (J)
~ a (N
Steel -Panel81.08 3.91
Steel -Panel87.08 3.78
Steel -Panel79.95 3.04
Mean 82.71 3.58
A1 84.45 3.59
A1 82.03 4.37
AI 114.25 6.33
Mean 93.58 4.76
chrom. A1 173.28 13.00
chrom. A1 113.86 6.88
chrom. Al 144.55 8.54
Mean ~ 143.89 L 9.47
Example 10 - Santoprene~-to-Metal Bonding Examples
A catalyst solution was prepared by dissolving 0.030 g of RuCl2(PCy3)2=CHPh
in 3.0 ml of CH2Cl2. The catalyst solution was applied to grit-blasted steel
coupons and
the steel coupons were bonded to three samples of four types of Santoprene~
(101-64,
32

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201-64, 201-87 and 8201-90) with 0.08 ml of ENB monomer per coupon as
described in
Example 4. Weighing revealed on average that 9.4~1.2 mg of catalyst was
contained per
coupon. The rubber surface was sanded prior to application of monomer for each
type.
The bonded specimens were analyzed on the Instron with the 180° peel
test and the results
are shown below in Table 3. All three samples of both softer rubbers, 101-64
and 201-64,
showed excellent rubber tear while the stiffer rubbers, 201-87 and 8201-90,
showed no
rubber tear and adhesive failure was prominent with most of the ENB polymer
film
attached to the rubber after peeling these specimens apart. Good bond strength
data were
observed for all specimens.
Table 3. 180° Peel Test Data for Rubber-to-Metal Bonded Sanded
Santoprene4
Specimens.
Sam le T Load at Max. Load Ener to Break (J)
a (N)
101-64 106.60 2.49
101-64 98.75 5.60
101-64 105.32 2.25
Mean 103.56 3.45
201-87 ' 72.76 3.69
201-87 87.64 3.27
201-87 103.56 3.96
Mean 87.99 3.64
201-64 72.45 4.09
201-64 114.54 3.30
201-64 90.27 5.41
Mean 92.42 4.27
8201-90 165.54 4.35
8201-90 165.24 6.02
8201-90 230.06 8.54
Mean 186.94 6.30
Example 11 - Natural Rubber-to-Grit-Blasted Steel Bonding
RuCl2(PCy3)2=CHPh was applied to grit-blasted steel coupons and bonded with
0.10 ml of ENB monomer per coupon using the process described in Example 4.
Four
natural rubber samples were prepared. Two samples were sanded and two samples
remained unsanded. The mated specimens were allowed sit over a two day period.
On
the third day, the two specimens prepared from the sanded natural rubber
pulled apart by
hand. A thin ENB polymer film was left on the natural rubber strip and some
rubber tear
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was observed. The two specimens prepared froth unsanded natural rubber could
not be
pulled apart by hand and were analyzed on the Instron using a 180° peel
test. The bonded
specimens had a mean load at maximum load of 183.14 (N) and a mean energy to
break
of 12.20 (J). Rubber tear was observed for the sample with the higher values.
Example 12 - EPDM-to-Grit-Blasted Steel Bonding with MoTB Catalyst
A catalyst solution was prepared by dissolving 0.021 g of 2,6-diisopropyl-
phenylimido neophylidene molybdenum (VI) bis-t-butoxide (MoTB) in 2 ml of
CH2C12.
The catalyst solution was applied to grit-blasted steel coupons and then the
steel coupons
were bonded to EPDM rubber strips with 0.08-0.09 ml of ENB monomer per coupon
as
described in Example 4. Because of catalyst sensitivity to air and moisture,
all handling
of rubber and metal coupons 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
tests were performed. The original grit-blasted metal and rubber coupons had
been stored
in the glove box for several months to ensure complete removal of any water or
oxygen
contamination. This was later found to be unnecessary as bonding was observed
even
with samples that had only a few hours residence time in the glove box. It was
noted that
within 5 - 10 seconds after mating the two surfaces, the coupons could not be
moved
around on top of each other suggesting that polymerization had occurred. All
specimens
were analyzed on an Llstron using the 180° peel test. The results are
means for two
separate data sets: the original two bonded specimens (long residence time in
the glove
box) - mean load at maximum load of 46.57 (N) and mean energy to break of 1.54
(J) and
three new specimens (surfaces were thoroughly washed with acetone prior to
placing in
the glove box followed by washing with CI-12C12 in the box prior to addition
of monomer)
- mean load at maximum load of 139.26 (N) and mean energy to break of I 1.12
(J). Some
rubber tear was observed on all specimens except one.
Example 13 - EPDM-to-Grit-Blasted Steel Bonding using Homobimetallic Ruthenium
Catalyst.
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A catalyst solution was prepared by dissolving 0.030 g of RuCl2(p-cymene)-
RuCl2(PCy3)2=CHPh in 3.1 ml of CH2Cl2, The catalyst solution was applied to
grit-
blasted steel coupons and then the steel coupons were bonded to EPDM rubber
strips with
0.08 ml of ENB monomer per coupon as described in Example 4. The mated
specimens
were analyzed on the Instron using a 180° peel test. The bonded
specimens had a mean
load at maximum load of 226.60 (N) and a mean energy to break of 26.78 (J).
Rubber
tear was observed for all specimens.
Example 14 - EPDM-to-Grit-Blasted Steel Bonding using DCPD as Monomer.
A catalyst solution was prepared by dissolving 0.031 g of RuCl2(PCy3)2=CHPh
in 3.2 ml of CH2C12, The catalyst solution was applied to grit-blasted steel
coupons and
the steel coupons then were bonded to EPDM rubber strips with DCPD monomer as
described in Example 4. The procedure for application of the DCPD varied
slightly from
that with ENB. The EPDM surface was washed with acetone prior to application
of
DCPD monomer, which required gentle melting of the distilled dicyclopentadiene
with a
heat gun, pipetting the liquid onto the EPDM surface and spreading the liquid
with a
pipette. On 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 mated and weighted down with approximately 100 grams.
The
mated specimens were analyzed on the Instron using a 180° peel test.
The bonded
specimens had a mean load at maximum load of 290.78 (N) and a mean energy to
break
of 44.44 (J). Rubber tear was observed for all specimens.
Example 15 - EPDM-to-Grit-Blasted-Steel Bonding using Methylidenenorbornene as
Monomer.
A catalyst solution was prepared by dissolving 0.031 g of RuCl2(PCy3)2=CHPh
in 3.2 ml of CH2C12, applied to three grit-blasted steel coupons, and then the
steel
coupons were bonded to EPDM with 0.10 ml of methylidenenorbornene monomer per
coupon as described in Example 4. The mated specimens were analyzed on the
Instron

CA 02318711 2000-09-13
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using a 180° peel test. The bonded specimens had a mean load at maximum
load of 40.55
(N) and a mean energy to break of 1.48 (J).
Example 16 - EPDM-to-EPDM Bonding
A catalyst solution was prepared by dissolving 0.030 g of RuCl2(PCy3)2=CHPh
in 2 ml of CH2CI2. The catalyst solution was applied to two EPDM strips. Each
catalyst-
coated EPDM strip was bonded to another EPDM strip with 0.02 ml of ENB monomer
per strip as described in Example I. The EPDM rubber strips were washed with
acetone
and allowed to dry prior to application of either catalyst solution or ENB
monomer. Two
strips were bonded in a lap-shear configuration surface (34.9 mm x 25.4 mm);
examination of the specimens on the next day revealed they could not be pulled
apart by
hand. They were then analyzed by a lap shear tensile test on an Instron after
three months
of standing at ambient conditions and showed an average load at break of
419.42 (N).
A catalyst solution was prepared by dissolving 0.027 g of RuCl2(PCy3)2=CHPh
in 2.5 ml of CH2C12. The catalyst solution was applied to three EPDM strips.
Each
catalyst-coated EPDM strip was bonded to an EPDM strip with 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 prior to application of either catalyst
solution or ENB
monomer. Six specimens were bonded in 180° peel test mode. Three were
sanded before
bonding. All specimens bonded and could not be pulled apart by hand and were
analyzed
on an Instron using a 180° peel test. The sanded specimens had a mean
load at maximum
load of 166.51 (N) and a mean energy to break of 25.56 (J); and the unsanded
specimens
had a mean load at maximum load of 176. l6 (N) and a mean energy to break of
26.97 (J).
Failure analysis showed that the sanded specimens had rubber tear but the
unsanded
specimens had deeper rubber tear with chunks torn away.
Example 17 - EPDM-to-EPDM Bonding with MoTB Catalyst
Two separate catalyst solutions were prepared to self-bond unsanded and sanded
EPDM specimens. The first solution was prepared by dissolving 0.0216 g of 2,6-
diisopropylphenylimido neophylidene molybdenum (VI) bis-t-butoxide (MoTB) in 2
ml
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of CH2C12. The catalyst solution was applied to two unsanded EPDM rubber
strips that
were then bonded to EPDM rubber strips with 0.08 ml of ENB monomer per coupon
as
described in Example 12. The second solution was prepared by dissolving 0.0211
g of
2,6-diisopropylphenylimido neophylidene molybdenum (VI) bis-t-butoxide (MoTB)
in
0.7 ml of CH2C12. The catalyst solution was applied to sanded EPDM rubber
strips that
were then bonded to EPDM rubber strips with 0.13 ml of ENB monomer per coupon
as
described in Example 12. All specimens were analyzed on an Instron using the
180° peel
test. The results are means for two separate data sets: the original two
unsanded bonded
specimens (long residence time in the glove box) - mean load at maximum load
of 9.4I
(N) and mean energy to break of 0.27 (J) and two new specimens (surfaces were
sanded
prior to placing in the glove box followed by washing with CH2C12 in the box
prior to
addition of monomer) - mean load at maximum load of 12.97 (N) and mean energy
to
break of 0.76 (J). No rubber tear was observed on any specimen.
Example 18 - EPDM-to-EPDM Bonding using Hotnobimetallic Ruthenium Catalyst and
ENB.
A catalyst solution was prepared by dissolving 0.031 g of RuCl2(p-cymene)-
RuCl2(PCy3)2=CHPh in 3.1 ml of CH2C12. The catalyst solution was applied to
three
EPDM rubber strips that were then bonded to EPDM rubber strips with 0.16 ml of
ENB
monomer per coupon as described in Example 4. The mated specimens were
analyzed on
the Instron using a 180° peel test. The bonded specimens had a mean
load at maximum
load of 126.28 (N) and a mean energy to break of I 1.38 (J). Rubber tear was
observed for
all specimens.
Example 19 - EPDM-to-EPDM Bonding using DCPD as Monomer.
A catalyst solution was prepared by dissolving 0.031 g of RuCl2(PCy3)2=CHPh
in 3.1 ml of CHZCl2. The catalyst solution was applied to three EPDM strips
that were
then bonded to EPDM strips with DCPD monomer as described in Examples 4 and
14.
The mated specimens were analyzed on the Instron using a 180° peel
test. The bonded
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specimens had a mean load at maximum load of 181.75 (N) and a mean energy to
break
of 26.46 (J). Rubber tear was observed for all specimens.
Example 20 - Rubber-to-Rubber Bonding Using Differently Cured Rubbers
A catalyst solution was prepared by dissolving 0.031 g of RuCl2(PCy3)2=CHPh
in 3.2 ml of CH2C12. This solution was applied to three rubber strips that
were then self
bonded with ENB monomer (see Tables 4 and 5 for the amount of ENB applied to
each
specimen) as described in Example 4. Once this catalyst solution had been
depleted,
another identical batch was prepared and used to bond another three specimens.
Both
EPDM and natural rubber A225P strips were molded and cured to different
extents of
cure as shown in Tables 4 and 5. The extent cure is shown as a percentage that
was
determined on a Monsanto Oscillating Disk Rheometer (for example, T9o = lime
at 90%
of maximum torque). Surface pretreatment of both surface types involved
washing with
acetone. The A225P was sanded while the EPDM remained unsanded. The EPDM was
cured at 100, 70 and 40% and the A225P was cured at 100, 90, 70 and 40%.
Instron
results from the 180° peel test are shown in Tables 4 (EPDM) and 5
(A225P).
Table 4. 180° Peel Test Data for Extent of Cure Study for EPDM-to-EPDM
Specimens.
Sample TypeAmount of Load at Max. Energy to Break
Monomer (ml) Load (N) (J)
100% 0.16 178.58 24.87
100% 0.16 162.50 23.44
100% 0.16 173.38 24.99
Mean 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
Mean 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
Mean 219.11 55.62
All samples showed excellent rubber tear. However, no deep rubber tear was
observed. The 40% EPDM samples showed better rubber tear when compared to the
70
and 100% samples.
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Table 5. 180° Peel Test Data for Extent of Cure Study for A225P-to-
A225P Saecimens.
Sample TypeAmount of Load at Max. Energy to Break
Monomer (ml) Load (N (J)
100% 0.10 375.01 40.07
100% 0.10 304.20 29.16
100% 0.10 396.97 46.42
Mean 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
Mean 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
Mean 291.06 47.26
40% 0.10 328.91 59.14
40% 0.14 356.18 63.42
40% 0.16 420.21 ?6.88
Mean 368.44 66.48
The 100% A225P showed good rubber tear; and the 90, 70 and 40% A225P
showed deep rubber tear. It should be noted that the 100% A225P strips were
approximately twice as thick as those for the other three types of cured
rubber.
Example 21 - Santoprene0-to-Santoprene~ Bonding
A catalyst solution was prepared by dissolving 0.030 g of RuCl2(PCy3)2=CHPh
in 2.5 ml of CI-i2C12. This solution was applied to three strips of four types
of
Santoprene~ (101-64, 201-64, 201-87 and 8201-90), and self-bonded with ENB
monomer as described in Example 4. The amount of ENB applied depended on the
Santoprene~ surface treatment: 0.06 ml for unsanded and 0.16 rnl for sanded
specimens.
Once this catalyst solution had been depleted, another identical batch was
prepared and
used to bond another three specimens. The bonded specimens were analyzed on an
Iostron with the 180° peel test and the results are shown in Tables 6
and 7. All unsanded
samples showed no rubber tear and displayed adhesive failure as a polymer film
was
observed on much of the rubber surface. All three 101-64 sanded samples showed
excellent rubber tear, two 201-64 samples showed excellent robber tear, and
both stiffer
rubbers, 201-87 and 820'1-90, showed no rubber tear.
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Table 6. 180° Peel Test Data for Rubber-to-Rubber Using Unsanded
Santoprene~
Specimens.
Santo rene~ T Load at Max. Lvad (N) Ener to Break (J)
a
201-G4 9.55 0.46
201-64 6.58 0.38
201-64 5.58 0.30
Mean 7.24 0.38
201-87 9.14 0.43
201-87 5.45 0.27
201-87 3.39 0.19
Mean 5.99 0.30
1 O 1-64 4.39 0.29
101-64 7.98 0.43
101-64 7.79 0.30
Mean 6.72 0.34
8201-90 7.16 0.14
8201-90 3.68 0.17
8201-90 3.00 0.15
Mean 4.62 0.15
Santo reneO T Load at Max. Load Ener to Break J)
a (N)
101-64 85.49 3.38
101-64 93.01 3.11
1 O 1-64 58.47 3.59
Mean 78.99 3.36
201-64 48.52 2.61
201-64 107.29 4.29
201-64 60.50 3.40
Mean 72.10 3.43
201-87 67.95 4.00
201-87 63.76 4.03
201-87 73.98 4.36
Mean 68.56 4.13
8201-90 29.85 1.69
8201-90 31.91 1.81
8201-90 21.82 1.28
Mean 27.86 I .60
Table 7. 180° Peel Test Data for Rubber-to-Rubber Using Sanded
Santoprene~
Specimens.
Example 22 - Tire Retread Applications
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A catalyst solution was prepared by dissolving 0.031 g of RuCl2(PCy3)2=CHPh
in 3.1 ml of CH2Cl2. Three types of bonding were performed: (1) tread-to-tread
(2)
carcass-to-carcass and (3) carcass-to-tread. For carcass-to-tread specimens,
the catalyst
was applied to the carcass and ENB monomer to the tread. The bonding procedure
was as
described in Example 4. Once the catalyst solution had been depleted another
identical
batch was prepared. The amount of ENB applied depended on the specimen and is
shown
in Tables 8 and 9. Mechanical properties were obtained on both unsanded and
sanded
combinations of carcass and tread stock. The bonded specimens were analyzed on
an
Instron with the 180° peel test. Table 8 shows data for the unsanded
specimens. All
unsanded samples showed rubber tear. The tread-to-tread samples showed some
superficial rubber tear. The carcass-to-carcass and carcass-to-tread samples
showed deep
rubber tear.
Table 8. I80° Peel Test Data for Rubber-to-Rubber Bonding Using
Unsanded Carcass
and Tread Stocks.
Sample Type Amount of Load at Max. Energy to Break
MonoW er (ml) Load (J)
(N)
Tread/Tread 0.06 72.84 6.08
Tread/Tread 0.06 60.79 4.90
Tread/Tread 0.08 71.18 7.73
Mean 68.45 6.24
Carcass/Carcass0.10 261.83 36.81
Carcass/Carcass0.14 205.64 20.79
Carcass/Carcass0.16 349.31 48.82
Mean 272.27 35.47
Carcass/T'read0.06 186.91 29.43
Carcass/Tread 0.08 134.94 17.99
Carcass/Tread 0.10 140.14 16.36
Mean ~ 154.00 21.26
Table 9 shows data for sanded specimens. These all showed rubber tear as well.
However, rubber tear was deeper when compared to the unsanded specimens. The
tread-
to-tread samples showed the least amount of tear but still snore than the
unsanded version.
The carcass-to-carcass samples showed excellent, deep rubber tear. Finally,
the carcass-
to-tread samples also showed excellent rubber tear but not as good as the
carcass-to-
carcass samples.
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Table 9. 180° Peel Test Data for Rubber-to-Rubber Bonding Using Sanded
Carcass and
Tread Stocks.
Sample Type Amount of Load at Max. Load Energy to Break
Monomer (ml) (N) (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
Mean 136.93 26.72
Carcass/Carcass0.16 362.55 50.16
Carcass/Carcass0.16 421.78 53.61
Carcass/Carcass0.16 296.06 45.30
Mean 360.13 49.69
CarcasslTread 0.14 287.73 58.74
CarcasslTread 0.14 300.87 56.43
CarcasslTread 0.15 218.00 43.35
Mean 268.86 52.84
Example 23 - Metal-to-Metal Bonding
A catalyst solution was prepared by dissolving 0.021 g of RuCl2(PCy3)2=CHPh
in 1.5 ml of CH2Cl2. The catalyst solution was applied to three grit-blasted
steel coupons
that were then bonded to other grit-blasted steel coupons with 0.02 - 0.03 ml
of ENB
monomer per coupon as described in Example l, except that the monomer was
applied to
the catalyst coated metal coupon. The other steel coupon was immediately mated
to the
treated surface and weighted down with a 100 g weight. After three days of
sitting at
ambient conditions, all three samples could not be pulled apart by hand. The
samples
were analyzed on an Instron using a lap shear tensile test and showed a mean
load at break
of 375.99 (N).
Example 24 - Glass-to-Glass Bonding
A catalyst solution was prepared by dissolving 0.040 g of RuCl2(PCy3)2=CHPh
in 3.0 ml of CH2Cl2. The catalyst solution was applied to three glass
microscope slides
that were then bonded to other glass microscope slides with 0.15-0.20 ml of
ENB
monomer per slide as described in Example 1, except that not all the catalyst
solution was
used - just a sufficient amount 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
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CA 02318711 2000-09-13
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surface. Immediately, the other glass slide was mated onto 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 - Paper-to-Paper Bonding
A catalyst solution prepared from 0.040 g of RuCl2(PCy3)2=CHPh in 3 ml of
CH2C12 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 mated
and held in place with a 100 g weight. After 1.5 hours, the two paper pieces
were
examined and found to be held together and could not be pulled apart.
Example 26 - Spray Application of RuCl2(PCy3)2=CHPh and Coating Formation
using
ENB on Various Substrates
A catalyst solution was prepared by dissolving 0.75 g of RuCl2(PCy3)2=CHPh in
ml of CH2Cl2. This solution was then spray applied onto a 7.62 cm x 15.24 cm
substrate surface, which had been previously wiped with acetone to remove any
surface
20 contamination, in a sweeping pattern until even-appearing coverage was
obtained. The
solvent was allowed to evaporate for 30 minutes in the open laboratory
atmosphere
leaving the surface coated with catalyst. Black Santoprene~, manila
Santoprene~,
acrylonitrile butadiene styrene (ABS), polypropylene, polymethylmethacrylate
(PMMA),
aluminum, chromated aluminum, stainless steel, polycarbonate sheet, Delrin
acetal resin
25 sheet, Mannington Classic uncoated embossed polyvinyl (PVC) flooring
(designated
"MC"), and Tarkett/Domco polyvinyl flooring (designated "T") were sprayed with
ENB
monomer and allowed to dry. Both static and kinetic coefficients of friction
of all the
coated specimens were measured by determining drag resistance on an Instron
(see P.R.
Guevin, "Slip Resistance," in Paint and Coatin T~ estinQ Manual. Fourteenth
Edition of
the Gardner-Sward Handbook, J.V. Koleske, ed., ASTM Manual Series: MNL 17,
AS'fM, Philadelphia, 1995, Chapter 50.) The results are shown below in Tables
10 and
1 I. For all samples the static and kinetic coefficients of friction were
lower after spray
43

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CA 02318711 2000-09-13
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coating with ENB compared to the control (e.g., shown in the Table as Aluminum-
C) of
that sample except in a few cases. Lower static and kinetic coefficients of
friction
indicate improved surface lubricity.
Table 10. Static and Kinetic Coefficient of Friction Results for Metal
Substrates Spray
Coated with
ENB.
_
Sample ID Static COF Static COF Kinetic COF
Kinetic COF
_Mean _ Std Dev Mean Std Dev
Aluminum-1 0.440 0.086 0.107 0.011
Aluminum-2 0.307 0.078 0.155 0.017
Aluminum-3 0.277 0.041 0.143 0.013
Aluminum-4 0.244 0.047 0.154 0.042
Aluminum-C 0.746 0.150 0.242 0.118
Chromated 0.263 0.093 0.112 0.025
Aluminum-1
Chromated 0.287 0.039 0.162 0.018
Aluminum-2
Chromated 0.341 0.076 0.095 0.018
Aluminum-3
Chromated 0.256 0.042 0.152 0.014
Aluminum-4
Chromated 0.755 0.430 0.233 0.138
Aluminum-C
Stainless 0.397 0.062 0.119 0.013
Steel-1
Stainless 0.297 0.049 0.119 0.005
Steel-2
Stainless 0.259 0.031 0.131 0.015
Steel-3
Stainless 0.256 0.063 0.121 0.005
Steel-4
Stainless 0.244 0.008 0.184 0.006
Steel-C
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CA 02318711 2000-09-13
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Table 11. Static and Kinetic Coefficient of Friction Results for Plastic
Substrates
Saran Coated with BNB.
Sample ID Static Static Kinetic COF Kirtetic
COF COF COF
Meart Std Dev Mean Std Dev
ABS-1 0.216 0.068 0.073 0.011
ABS-2 0.436 0.224 0.075 0.048
ABS-3 0.343 O.I08 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-1 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 0.4 I 9 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
Polycarbonate-1 1.364 O.I42 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-1 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
Polypropylene-C 0.394 0.056 0.225 0.057
Black Santoprene-10.369 0.064 0.143 0.009
Black Santoprene-20.332 0.026 0.145 0.064
Black Santoprene-30.290 0.022 0.100 0.027
Black Santoprene-40.253 0.008 0.099 0.021
Black Santoprene-C2.581 0.033 2.204 0.115
Manila Santoprene-I0.282 0.021 0.080 0.011
Manila Santoprene-20.364 0.026 0.107 0.072
Manila Santoprene-30.272 0.023 0.112 0.021
Manila Santoprene-40.287 0.037 0.080 0.010

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
Manila Santoprene-C1.050 0.063 1.065 0.562
T-1 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 scoring a crosshatch pattern with a
razor blade lightly into the coating surface. Five lines approximately 3.2 mm
apart and
another five lines approximately 3.2 mm apart in crossing pattern. A 50.8-63.5
mm long
strip of 25.4 mm width Scotch masking tape (2500-3705) was applied over the
crosshatched area and pressed smooth with a finger. After a second or two the
tape was
pulled quickly from the surface. An adhesion ranking scale was set up with 1
being the
best and 5 being the worst (see Table 12).
Table 12. Crosshatch
Adhesion Test Definitions.
Value ,_ Description
1 Very excellent-nothing on tape
2 Excellent just crosshatch pattern
3 Good-crosshatch pattern and
specks at edges
4 Fair-crosshatch and between
lines
5 Poor-evervthing hulled uD
Adhesion ratings of poly(ENB) coating to rubbery substrates such as
Santoprene~ and EPDM are shown in Table 13. They show that both Santoprene~
specimens gave excellent adhesion with only crosshatch pattern seen on the
tape. EPDM
adhesion was only a 4 with a single poor coating and 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. Crosshatch Adhesion Test Results for Poly(ENB)
Coatin s on Various Substrates.
Sample ID Adl2esion rating Type of Substrate
Manila Santoprene-4 2 rubbery
Black Santoprene-1 2 rubbery
EPDM-1 4 rubbery
EPDM-4 I rubbery
Aluminum-4 2 metal
Chromated Aluminum-4 2 metal
Stainless Steel-4 1 metal
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CA 02318711 2000-09-13
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Polypropylene-4 2 plastic
ABS-4 1 plastic
Propylene Carbonate-4 1 plastic
PMMA-1 2 plastic
MC-4 5 flooring
T-2 5 flooring
Delrin-2 5 flooring
Silicon Wafer 2 inorganic
Teflon 1 - 2 lastic
Example 27 - Spray Application of RuCl2(PCy3)2=CHPh and Formation of Layered
Coatings
A catalyst solution was prepared by dissolving 0.75 g of RuCl2(PCy3)2=CHPh in
25 ml of CH2CI2. This solution was then spray applied onto the surface of four
7.62 cm x
15.24 ctn pieces of EPDM, which had been previously wiped with acetone to
remove any
surface contamination, in a sweeping pattern until even-appearing coverage was
obtained.
The solvent was allowed to evaporate for 30 minutes in the open laboratory
atmosphere
leaving the surface coated with catalyst. The samples were then sprayed with
ENB
monomer and allowed to stand in the open laboratory atmosphere until not
tacky. More
ENB was applied to EPDM-4 and the sample allowed to dry overnight. The
catalyst and
resultant polymer levels are reported in Table 14. The increase in coating
weight after the
second spraying of ENB on EPDM-4 demonstrated that layers of poly(ENB) could
be
built up on previous a EPDM surface and that the catalyst remained active.
Table 14. Catalyst and Monomer Levels for Catalyst/ENB
Coated EPDM Sam les.
Sample ID Substrate wt (g) Catalyst wt (g) Ist Polymer wt (g) 2nd Polymer wt
(g)
EPDM-1 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
Example 28 - Spray Application of RuCl2(PCy3)2=CHPh and Formation of Coatings
with
Other Monomers
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CA 02318711 2000-09-13
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A catalyst solution was prepared by dissolving 0.75 g of RuCl2(PCy3)2=CHPh in
25 ml of CH2C12. This solution was then spray applied onto the surface of an
ABS
specimen (10.16 cm x 15.24 cm), which had been previously wiped with
isopropanol to
remove any surface contamination, in a sweeping pattern until even-appearing
coverage
was obtained. The solvent was allowed to evaporate for 30 minutes in a fume
hood in the
open laboratory atmosphere leaving the surface coated with catalyst. The
samples were
then sprayed with DCPD, with rnethylidenenorbornene (MNB), and cyclooctene
(CO)
monomers and allowed to stand in the open laboratory atmosphere for 2.5 hours
before
weighing. The catalyst and resultant polymer levels are reported in Table 15.
Coefficient
of friction data and cross-hatch adhesion data are reported in Tables 15 and
16,
respectively. For the cyclooctene specimen, no polymer formation was observed;
the
cyclooctene appeared to volatilize from the surface.
Table I5. Coefficient of Friction Data for Different Monomers S ra A lied to
ABS
Monomer CatalystPolymer StaticStatic KineticKinetic
wt
wt (g) (g) COF COF COF COF
Mean std dev Mean std
dev
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
Table
16.
Cross-Hatch
Adhesion
Data
for
Different
Monomers
S ra
A lied
to
ABS.
Monomer Adhesion Ratin
DCPD 1
MNB 3
a) 1
= Excellent-nothing
on
tape;
2 =
Excellent-just
crosshatch
pattern;
3 =
Cood-crosshatch
pattern
and
specks
at
edges;
4 =
Fair-crosshatch
and
between
lines;
5 =
Poor-everything
pulled
up.
Example 29 - Coating Formation using MoTB Catalyst and ENB
A catalyst solution was prepared by dissolving 0.1692 g of 2,6-diisopropyl-
phenylimido neophylidene molybdenum (VI) bis-t-butoxide (MoTB) in 5 ml of
CH2Clz.
The catalyst solution was applied to 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
roughened with
thick brush marks because the solvent dissolved the ABS surface. Using a
pipette, ENB
monomer was applied in front of a 1 mil draw down bar and the bar was pulled
down
48

CA 02318711 2000-09-13
Attorney Docket No. IR-2588(ET)
across the catalyst coated area. Upon attempting to draw down the bar a second
time, the
newly formed coating scratched because the monomer polymerized so quickly.
This gave
a wrinkled, dark brown coating in the catalyst coated area and a chalky yellow
edge were
the ENB monomer did not touch.
To eliminate this surface dissolution problem, another MoTB catalyst solution
(0.1192 g of MoTB in 3 ml CH2C12) was again applied to a surface, but this
time to a
10.16 cm x 15.24 cm chromated aluminum (AC) substrate. A more uniform coating
of
poly(ENB) formed on the surface. The chromated alumina coated specimen (AC)
showed
a static coefficient of friction of 0.4410.03 and a kinetic coefficient of
friction of
0.1410.05. These data were obtained for the AC specimen only as the ABS
surface was
too rough as described above. Cross-hatch adhesion data for both specimens are
reported
in Table 17.
Table 17.
Cross-Hatch
Adhesion
Data for
Different
Monomers/Substrates.
Monomer Substrate Adhesion Ratin
ENB ABS 4
ENB AC 3
a) 1
= Excellent-nothing
on tape;
2 = Excellent
just crosshatch
pattern;
3 = Good-crosshatch
pattern
and
specks at
edges;
4 = Fair-crosshatch
and between
lines;
5 = Poor-everything
pulled
up.
Example 30 - Coatings by Application of Catalyst or Monomer in a Polymer
Matrix
A matrix solution was prepared (2 g of PMMA, 0.1 g of RuCl2(PCy3)2=CHPh,
and 50 ml of CH2Cl2) and applied by spray application to a PMMA substrate. The
coating was not uniform so three to four drops of the above matrix solution
were applied
to the PMMA substrate and spread out using a glass rod. On drying, a clear
uniform
coating formed which was sprayed with ENB.
Changes in surface tension of the coatings were evaluated using a set of Accu-
Dyne solutions. These solutions are used to match their surface tensions with
the surface
in question. A match in surface tension is determined when the applied
solution wets the
surface being tested. The surface tension of the solution then correlates with
the surface
tension of the surface.
No change in surface tension was observed before and after spraying ENB on
the PMMA/RuCl2(PCy3)2=CHPh matrix described above (y= 38 dynes/cm). More
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RuCl2(PCy3)2=CHPh was added to the PMMA/RuCl2(PCy3)2=CHPh matrix thus bringing
the total to 0.35 g catalyst in the PMMA matrix. This new solution was coated
onto new
5.08 cm x 5.08 cm PMMA substrate, dried, and then sprayed with ENB. The
surface
tension remained 38 dynes/cm. Again, another addition of catalyst brought the
new total
to 0.55 g RuCl2(PCy3)2=CHPh in the PMMA matrix. This surface, which was
processed
as described above, displayed 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 of RuCl2(PCy3)2=CHPh in I S ml of CH2C12 was
sprayed onto a 10.16 cm x 15.24 cm PMMA substrate surface to provide 0.0384 g
of
catalyst onto the surface on drying. The overcoat PMMA/ENB matrix (2 ml of
ENB, 1
gm of PMMA, in 10 ml of CH2C12) was applied by glass rod to the catalyst
coated surface
and the resulting surface tension was 46 dynes/cm). This compares to a surface
tension of
36 dynes/cm for a control uncoated PMMA substrate.
Example 3 I - Coating Paper by Spray Application of RuCl2(PCy3)2=CHPh and
Different
Monomers
Commercial filter paper (Whatman #41 ) samples were cut into fifteen dogbone-
shaped specimens ( 11 cm overall length, 40 x 7.2 mm draw area) and spray
coated with a
solution of RuCl2(PCy3)2=CHPh as described in Example 8. After drying in the
laboratory air for 30 minutes, the specimens were weighed, and then five
specimens were
spray coated with DCPD (5 ml), five specimens were spray coated with
ethylidenenorbornene (8 ml), and five specimens were spray coated with
cyclooctene (5
ml) on one side of the paper. After drying for 16 hours in the fume hood, the
specimens
were weighed to determine the amount of reacted monomer and their tensile
properties
determined on an Instron (Table 18). Poly(ENB) and poly(DCPD) coated paper dog-
bones showed increased maximum load values, while poly(cyclooctene) did not.
Statistical analysis (t-test) revealed increased displacement at maximum load
for DCPD at
the 95% confidence level. Little poly(cyclooctene) formed likely as a result
of its high
volatility vs ROMP rate.
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CA 02318711 2000-09-13
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Table 18. Tensile Strength Data for Paper Dog-Bone Specimens°.
ID Monomer catalystcoatingDisplacement Load at
amt (g) amt at max load
(g) max load (Kgf)
(mm) [meanlsd]
[mean/sd]
A ENB 0.0072 0.0941 0.624 0.187 2.636 0.190
B DCPD 0.0066 0.0949 0.644 0.083 3.401 0.661
C C clooctene0.0060 0.0018 0.574 0.047 0.894 1.064
D - - - 0.514 0.051 1.024 0.189
a) W hatman #41 filter paper, 5 samples each.
Example 32 - Fiber Coating by Application of RuCl2(PCy3)2=CHPh and Monomer
Kevlar~, NomexO, and nylon threads (size 69, 0.2032 mm) were cut into 30.48
cm lengths, soaked in a solution containing approximately 0.04 g of
RuCl2(PCy3)2=CHPh
in 5 ml of CH2Cl2 for one minute, and allowed to dry in a straight position.
After 20
minutes the threads were sprayed with 8 ml of ENB. After two hours the threads
appeared straight and stiff. Tensile properties for these specimens were
cvtnpared to
uncoated threads on an Instron (Table 19). No real differences in tensile data
were
observed. However, each thread was thicker providing evidence that the threads
were
indeed coated.
Table 19. Tensile Properties of ENB Cnaterl anti T Itt~t~atPr~ ThrP~rlc
Thread Load @ Max Max. % Strain Thickness
Load (K ) (mm)a
Kevlar 3.94711.089 9.31012.354 0.27
Kevlar - coated4.3300.008 10.65911.056 0.31
N lop 2.63310.477 59.06917.614 0.26
N lop - coated2.60110.651 31.15418.324 0.30
Nomex 1.89310.129 31.28913.006 0.27
Nomex - coated2.01810.260 30.45216.182 0.28
a~ r nese measurements were mane wttn caapers and then vended with a thickness
gauge.
Example 33 - Fabric Coating by Application of RuCl2(PCy3)2=CHPh and Monomer
Strips of cotton, fiberglass, polyester, and aramid fabric were cut to 2.54 em
x
15.24 cm geometries, dipped in a solution containing 1.0 g of
RuCl2(PCy3)2=CHPh in 100
ml of CHZC12 for one minute, and allowed to dry. It was noted that excess
catalyst wicked
to the fabric surfaces during the drying process. The excess catalyst was
shaken froth
51

CA 02318711 2000-09-13
Attorney Docket No. IB-2688(ET)
each fabric. All fabrics had a purple color showing that catalyst had adsorbed
onto the
surface. Approximately ~30 ml of ENB was sprayed onto both sides of the fabric
strips.
All fabric samples stiffened as the polymerization occurred. Tensile
properties were
determined for six of each coated and uncoated specimen on an Instron (Table
20). While
stiff, the fabrics could easily be bent like uncoated fabric.
By coating poly(ENB) on the polyester fabric the load at peak almost doubled,
but differences in displacement or % strain were slight. This suggests that
the strength of
the tightly woven polyester fabric is increased strictly by addition of
poly(ENB). Aramid
and cotton fabrics showed displacement and % strain at peak to be halved and
load at
peak to be slightly increased or no change, respectively. Thus, these fabrics
lose some of
their stretchability by the addition of poly(ENB), but lose none of their
strength. For
fiberglass, the load at peak and energy to break increase significantly, while
displacement
and % strain at peak show no change.
Table 20. Tensile Properties of ENB Coated and T lnrnatPrl Fahrirca
ll~ l~IaterialDisplacement % Strain Load Energy
Type at at at to
Peak Peak Peak Break
(mm) (%) (kN) (J)
mean/sd mean/sd] [mean/sdJ [mean/sd
Control Pol ester10.8820.481 42.8411.892 0.889 0.048 7.036 0.577
8165-27 Pol ester11.5750.181 45.5710.712 1.511 0.076 7.723 0.866
A
Control Aramid 15.5000.746 61.4172.937 0.168 0.008 1.397 0.072
8165-27 Aramid 8.282 1.616 32.6056.364 0.237 0.019 1.758 0.289
B
Control Cotton 6.972 0.404 27.4481.590 0.702 0.022 2.102 0.218
8165-27 Cotton 3.380 0.470 13.3071.850 0.805 0.106 1.951 0.227
C
Control Fiber 2.925 0.034 11.5161.197 0.641 0.085 1.841 0.858
lass
~ 8165-27Fiberglass3.050 0.166 12.0080.653 _ 0.203 8.669 3 042
D ~ ~ ~ ~ ~ ~ 1.917
tl) LGlGlll(1)ICU USIII~ spa i x o s~nps or eacn tadnc.
5 'Z

Representative Drawing