Note: Descriptions are shown in the official language in which they were submitted.
~26~476
-1- 24-51~ 6438 )A
ADHESION PROMOTERS CONT~INING -S-SO R GROUPS
BACKGROUND OF THE INVENTION
This application is a division of Canadian Patent
Application Serial No. 439,385 filed October 20, 1983.
This invention relates to the bonding of rubber to
metal.
Articles in which rubber is bonded to metal have
been known for many years, and since the introduction of
the steel-belted radial tyre, rubber/metal bonding has
been very extensively studied. It is known that certain
substances will act as adhesion promoters to improve the
initial adhesion level between the rubber and the metal
and the maintenance o~ the adhesion level during
accelerated laboratory ageing tests designed to simulate
conditions to which the article may be subjected during
its service life.
The main adhesion promoters currently used to
promote the bonding of brass-coated steel to rubber are
cobalt compounds, for example cobalt naphthenate, and
resorcinol-and/or melamine-formaldehyde resins used in
conjunction with hydrated silica. Both of these types
of adhesion promoters, which can be employed separately
or in combination, have disadvantages, and alternative
rubber/metal adhesion promoters to those currently
employed are therefore desirable. 5uch alternatives are
provided by the present invention.
BRIEF SUMMARY OF THE INVENTION
This invention provides, in one aspect thereoE,
compounds of the formula Rl-S-SO3-Ml or a hydrate
thereof, where Rl represents an organic radical and
represents cobalt or nickel.
Preferred compounds are where Rl represents a C3 20
alkyl group, a C2 20 chloroalkyl group, a C3_20 alkenyl
group, a phenyl (Cl 16 alkyl) group, a 2,5-dihydroxy-
phenyl group or a grouping o~ the ~ormula R700CR3- where
R7 is a Cl 1~ alkyl group and R8 is a Cl 12 alkylene
group, and M represents nick~l.
: ; .. - .. -, .,- ,~. :
~'~6847~i
-2- 24-51(6438)A
Another preferred aspec-t of the present invention
is where the compounds have Rl representing a C4 18
alkyl group, a C3 12 chloroalkyl group, a C3 12 alkenyl
group, a phenyl (Cl 6 alkyl) group or a grouping of the
formula R700CR8 where R7 is a Cl 8 alkyl group and R
is a Cl 8 alkylene group.
A still further preferred aspect of the present
invention is where Rl represents a C4 12 alkyl group, a
benzyl or 2-phenylethyl group or a grouping of -the
formula R7OoCR8 where R7 represents methyl or ethyl and
R8 represents ethylene or ethylidene.
In another aspect of the present invention, the
compounds have the formula R700CR8S203Na, or a hydrate
thereof, where R7 is a Cl 8 alkyl group and R is a Cl 8
alkylene group.
Preferred compounds are where R7 represents methyl
or ethyl and R~ represents ethylene or ethylidene.
The above compounds may be used in a composite
comprising a sulphur-vulcanisable rubber composition
containing a rubber/metal adhesion promoter, and a
component having a metal surface in contact with the
said composition, in which the adhesion promoter is a
substance containing the above compoundls).
DETAILED DESCRIPTION OF THE INVENTION
As disclosed in SN 439,3B5, the adhesion promoters
outlined therein are, in many instances, compounds in
which thiosulphate groups -S-SO2OM or thiosuIphonate
groups -S-SO2R are each linked to a primary carbon atom
of the organic radical R1, or polymers in which the
thiosulphate or thiosulphonate groups are linked to
primary carbon atoms in side chains attached to the main
polymer chain. The thiosulphate or thiosulphonate
groups therefore usually occur in the form ~CH2-S-SO2R.
This is because the starting materials required for
- : '
- ~- . . ,:
~: :
~Z6~3476
-3- 24-51~6438jA
the production of such promoters are generally the
most readily available. Functionally, however,
compounds in which a thiosulphate group is attached
to a secondary carbon atom of the radical Rl are
satisfactory.
When the adhesion promoter is a compound
having the formula R -(S-S02R)n in which n has th~
value of 1, the organic radical Rl can be, for
example, a monovalent aliphatic, cycloaliphatic,
aromatic or heterocyclic radical, or a radical which
is a combination of any two or more such radicals.
Monovalent aliphatic radicals from which
in the above formula may be selected include
straight- and branched-chain alkyl and alkenyl
groups, more especially such groups containing from 1
to 20 carbon atoms, for example, methyl, ethyl,
n-propyl, isopropyl, allyl, sec-butyl, isoamyl,
n-hexyl, hex-3-enyl, n-heptyl, n-octyl, 2-ethylhexyl,
and decyl, dodecyl, pentadecyl, hexadecyl and
octadecyl groups.
When Rl is monovalent cycloaliphatic, it is
usually a radical containing from 5 to 8 ring carbon
atoms, which may be saturated or contain one or two
olefinic bonds, for example a cyclopentyl, cyclohexyl
or cyclohexenyl group.
Monovalent aromatic radical R1 may be, for
example, phenyl, naphthyl or biphenyl, and a
- heterocyclic radical may be, for example, pyridyl,
imidazol-2-yl or thiazole-2-yl.
126~34~7~
-4- 24-51(6438)A
. Monovalent radicals which are combinations
of two or more of the foregoing radicals include
alkylcycloalkyl radicals, ~or example methylcyclohexyl;
alkaryl radicals, for example phenyl(Cl 16 alkyl)
radicals, preferably phenyl (Cl 6 alkyl) radicals,
such as benzyl and phenethyl; and fused-ring
aromatic-heterocyclic radicals, for example quinolyl,
benzimidazol-2-yl and benzothiazol-2-yl.
Also included are monovalent radicals having
substitutent atoms or groups, for example halogen such
as chlorine or bromine, or nitro, hydroxyl, alkoxy,
carboxy, alkoxycarbonyl, alkylcarbonyl, or
(phosphonomethyl) amino alkyl groups. Examples
include haloalkyl, for example C2 20 chloroalkyl such
as 2-chloroethyl; C2 20 alkoxyalkyl, for instance
butoxyethyl; C3_20 alkylcarbonyloxyalkyl, for instance
2-(propionyloxy)ethyl, C3 20 alkoxycarbonylalkyl, for
instance 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)
ethyl, l-(methoxycarbonyl)ethyl and l-(ethoxycarbonyl)
ethyl, bis(phosphonomethyl)amino C2 6 alkyl, chlorotolyl,
hydroxyphenyl, and carboxypyridyl.
'
' '
.
': ' ' ' ' ';'' ' ' ': ~ ,': '.- ' '. .: "`~ :
~1.26~34~7~
-5 24-51(6438)A
Compounds within the above formula where n
has the value 1 include a sub-class where R1 represents
a C3 20 alkyl group, a C~ ~0 preferably C3 12
chloroalkyl group, a C3_20 preferably C3_12 alkenyl
group, a benzyl group, a phenethyl group, a.C2 20
alkoxyalkyl group, a C3 20 alkylcarbonyloxyalkyl
group, or a 2,5-dihydroxyphenyl group. In a further
sub-class, R1 represents a grouping R700CR8- where R7
is a Cl 12 alkyl group, preferably a Cl 8 alkyl group
and R8 is a C1 12 alkylene group.
In a&esion promoters which are compounds
of the above formula in which n has a value of 2, 3
or 4, groups of the formula -S-S02R are linked by àn
organic bridging group. In compounds having two
groups -S-S02R, the bridging group is divalent, and
such compounds can be represented by the formula
R02S-S-X'-S-S02R.
In this formula X' can be, for example, a
straight- or branched-chain alkylene group, preferably
one containing 2 or from 5 to 40 carbon atoms, and
more preferably one containing 5 to 16 ~arbon atoms,
or an analogous group containing one or more double or
triple bonds, for example an alkenylene or alkadienylene
group. Examples of such groups are ethylene,
pentamethylene, hexamethylene, octamethylene,
nonamethylene, decamethylene, dodecamethylene,
3-methyl-1,5-pentylene, 1,4-but-2-enylene,
1,6-hex-2-enylene and 1,8-octa-2,6-dienylene. As a
variant, a divalent bridging group may be an alkylene
:. ,., :::
~L~6~7~
-6- 24-51(6438)A
or alkenylene group having one or more ar~l, for
example phenyl, su~stituents. An example of such a
radical is 2-phenyl-1,4-butylene.
In other instances, X' has a structure
comprising two or more alkylene units, pairs of such
units being linked through an oxygen or sulphur atom,
through a group -S02-, -NH-, -NH2+-, -N(Cl-6 alkyl)-,
-NH (Cl 6alkyl)-, -CO-, -COO-, or -CONR6- where R6 is
hydrogen or Cl 6 alkyl, or through an arylerle or
cycloalkylene radical. Representative of such
structures are thos~ of the formulae
-(CH2)a~~(CH2)a
~(CH2)a-0~(cH2)a~~o-(cH2)a
-(CH2)b-CO-(CH2)b
-(CH2)c~cO~-(cH2)a
and
-(CH2)C-cOo-y-ooc-(cH2)c-~ where
each a, a' and c independently represents an integer
of from 1 to 20, each b independently represents an
integer of from 1 to 10, and Y represents a group
-(CH2)c- or a group -(CH2CH2O)dCH2CH2- where d
represents an integer of from 1 to 5. Preferred
values for a are from 1 to 8, for example from 3 to
8, preferred values for a' are from 1 to 6, preferred
values for b are 1 to 4, and preferred values for c
are from 1 to 18, more especially 1 to 12, for
example from 3 to 12.
Other examples of the group X' are those
having the formula ~(CH2)e-SO2-(CH2)e ~ ( 2 e
-(CH2)e-NH2 -(CH2)e- where each e independently has a
value from 2 to 20, preferably from 2 to 18, and more
preferably from 2 to 12.
~ ~- -::: ~ .. . : :,
.-, - . ~:~ : :. ., : ~ -:
... . ~ :. , .:.
:: ., ~` ~ ' ' !: ~ :: ' . ` :
,: . . .:: `.... : '
1~6~47~
-7- 24-51(6438)A
Where values of a, a', b, c or e exceed 2,
the polymethylene groups can be straight chain or
branched.
Adhesion promoters having two, three or
four thiosulphate or thiosulphonate groups include
those where two, three or four groups -CmH2m-S-S02R,
m typically having a value from l to 6, are
substituents in an aromatic nucleus, for example a
benzene or naphthalene nucleus, (which may also
contain other substituents), or as substituents in
one or more nuclei of a di- or t:ri-nuclear aromatic
compound, for example biphenyl, diphenyl ether,
diphenyl sulphone or ben20phenone. Other examples
are tri-N-substituted s-hexahydro triazines where the
substituent on each ,~itrogen atom is a group having
the formula -COCmH2m -S-S02R. The most readily
available of thexe hexahydrotriaæines are compounds
where R is OM, for instance ONa, and m has the value
2.
Further examples of trivalent bridging
groups are those of the formulae
-Al-OCH2CH(OAl-)CH20Al- and A-C(A OOCAl-)3 where ~ach
Al is independently an alkylene group, for example a
C2_l8, preferably a C2_12, alkylene group and A is
C1 6 alkyl; and also those of the formulae N~(CH2)e~3
and HN+ [(CH2)e33 where each e independently has a
value of from 2 to 20, preferably from 2 to 18, more
especially from 2 to 12.
Further examples of tetravalent bridging
groups are those having the formulae
C(Al)4, Si(A1)4 and (Al)3Si-o-Si(A1)3
where A1 has the same meaning as before; and those
having ~he formula
c[cH2oco(cH2)e]4
.. .:.. ,. .:,, . , ,:
lX6~3~7~i
-8- 24-51(6438)A
where each e independently has a value of from 1 to
20, preferably from 2 to 18 and more preferably from
2 to 12.
Examples of polymers are those of the
formulae
CH2-S-S02R
(-0-CH2CH-)n,
and esterified and partially esterfied polyvinyl
alcohols wherein the polymer chain is formed from
units selected from -CH-CH2-,
o~
-CH-CH2- , and -CH-CH2-
1; 0
Co CO
R' (CH2)e
S-S02R
where R' represents a Cl 12 alkyl group and e has an
integral value of from 1 to 20, and at least 10%,
preferably at least 20% for example from 25% to 75%,
of the units in the polymer are those containing the
group -S-SO2R.
The optimum number of carbon atoms in the
alkylene units to which the thiosulphate or
thiolsulphonate groups are attached to bridgi.ng
groups of the kind described above where two or more
alkylene units are linked through atoms or groups, or
where the thiosulphate or thiolsulphonate groups are
attached to units pendant from polymer chains, the
optimum value of m in the formula -CmH2m-S-SO2R, and
:, , . : ,
-- ;~ -. ~ , , :, ..
- ,,
: ,. :,
,
~6~476
-9- 24-51(6438)A
the optimum number of carbon atoms in the groups Al,
depend on the remainder of the structure of the
bridging group.
A further requirement is that the relative
locations of the thiosulphate or thiolsulphonate
groups should not be such that significant
intramolecular cyclisation can occur when a rubber
composition containing the adhesion promoter is
heated.
Thus, w1thin the class of compounds defined
above there will be found differing degrees of
adhesion promoter activity, but methods of evaluation
as subsequently described are conventional, and it is
therefore a matter of simple and minimum
experimentation for the person skilled in the art to
determine whether a particular compound will usefully
promote the rubber/metal adhesion.
When M in the above formula of the adhesion
promoter represents a monovalent metal, this can be
for instance an alkali metal, for example sodium,
lithium or potassium. For economic reasons, sodium
is the preferred alkali metal. M can alternatively
represent the equivalent of a multivalent metal, for
instance magnesium, calcium, barium, zinc, nickel,
cobalt, manganese or aluminum.
Where M represents a monovalent ion formed
by the addition of a proton to a nitrogenous base,
the nitrogenous base can be ammonia or a simple
primary, secondary or tertiary amine
R2NH R2R3NH or R2R3R4N where
each of R2, R ~ and R4 independently represents an
alkyl group, for example a C1_20 alkyl group, a C5_9
cycloalkyl or alkylcyclohexyl group, a benzyl group,
a phenyl group or a substituted phenyl group,
provided that no more than one of R2, R3 and R4 is a
phenyl or substituted phenyl group. ~`
~ .,. - - -:
; . . - :; - , : .
:: : .:: . ~ :
.: ~ ~ . - -
34~7~
-10- ~4-51(6438)A
Examples of such amines are the secondary amines
R2R3NH where one of R2 and R3 is a tert-alkyl group,
for instance a tert-alkyl group having from 4 to 12
carbon atoms, such as tert-butyl, tert-amyl or
1,1,3,3-tetramethylbutyl, and the other is a benzyl
group or a cyclohexyl or alkylcyclohexyl group.
Alternatively both R2 and R3 can be tert-alkyl
groups. Further examples are tertiary amines where
R2 is a tert alkyl group and R3 and R4 are benzyl
groups.
Other suitable amines are the primary
amines R2NH2 where R2 is a phenyl or substituted
phenyl group, and the secondary amines R2R3NH where
R2 is a phenyl or substituted phenyl group and R3 is
a Cl 20 alkyl group, preferably a Cl 12 alkyl group-
Examples of such amines are aniline, the toluidines,
N-methylaniline, N-butylaniline and
N-isohexylaniline. A special class of such secondary
amines comprises those where R represents a
secondary alkyl group, preferably a C3 12 secondary
alkyl group, or a cyclohexyl group, and R3 represents
a 4-phenylaminophenyl group. These amines include
compounds such as
N-isopropyl-N'-phenyl-p-phenylenediamine,
~5 N-sec-butyl-N'-phenyl-p-phenylenediamine,
N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine,
N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine and
N-cyclohexyl-N'-phenyl-p-phenylenediamine. Such
amines function as mono-acid bases despite the
presence of the second nitrogen atom in the
4-phenylaminophenyl group, because this second
nitrogen atom has virtually no basicity.
:: :
::
~2~i8~76
~ 24-51(6438)A
Other examples of nitrogenous bases which
form thiosulphate salts useful in the invention are
substituted isothioureas, for example those of the
formula
. .
SR5
NH=C-NH2
where R5 represents a C1 20 alkyl group, a C5 9
cycloalkyl or alkylcycloalkyl group or a benzyl
group. Specific examples of substituted isothioureas
are S-ethylisothiourea and S-benzylisothiourea.
Where M represents an equivalent of a
multivalent cation formed by the addition of two or
more protons to a nitrogenous base, the bases from
which such ions can be derived include alkylene
diamines, N,N'-disubskituted alkylene diamines,
phenylenedi~mines and N,N'-disubstituted
phenylenediamines of the formula R2NH-A-NHR2 where
A represents an alkylene radical ~(CH2)C- where c has
a value of from 2 to 20, preferably from 2 to 12, and
which may be straight chain or branched, or a
phenylene, for example a meta- or paraphenylene
radical, and each R2 independently represents an
alkyl group, for example a Cl_20 alkyl group, a C5_9
cycloalkyl or alkylcycloalkyl group, a benzyl group,
a phenyl gr~up or substituted phenyl group, provided
that neither R2 is a phenyl or substituted phenyl
group when A is a phenylene radlcal.
In preferred amines where A represents an
alkylene radical, R2 is a tert-alkyl group, for
example tert-butyl, t-amyl or
1,1,3,3-tetramethylbutyl, or a phenyl group.
~2~476
-12- 24-51(6438)A
Examples of such amines are N,N'-diphenylethylene
N,N'-di-tert-butyl-1,4-tetramethylene diamine and
N,N'-bis(1,1,3,3-tetramethylbutyl)-
1,6-hexamethylene diamine.
In preferred amines where A represents a
phenylene radical, R2 is a secondary alkyl group,
preferably a C3 12 secondary alkyl group or a
cyclohexyl group. Examples of such amines are
N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,3-
dimethylbutyl)-p-phenylenediamine, N,N'-bis(1,4-
dimethylpentyl)-p-phenylendiamine, N,N'-bis(l-ethyl-
3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-
methylheptyl)-p-phenylendiamine and
N,N'-dicyclohexyl-p-phenylendiamine.
Possible bases also include polyalkylene
polyamines of the formula
R2NH-(A'-NH)n-A'NHR
where A' represents an alkylene radical of from 2 to
8 carbon atoms, n has a value of from 1 to 5, and
each R2 independently represents a Cl ~0 aIkyl group,
a C5 9 cycloalkyl or alkylcycloalkyl group, a benzyl
group, a phenyl group or a substituted phenyl group.
In other instances, the nitrogen of the
nitrogenous base is part of a heterocyclic ring. The
base can be monocyclic, for example pyridine, or 2
compound in which the nitrogen-containing
heterocyclic ring is fused to another ring, as for
example quinoline. Moreover, the heterocyclic ring
can be saturated, as for example in morpholine or
piperidine, or it may contain one or more double
bonds, as for example in pyrroline or
1,2-dihydroquinoline.
'' ' . '
' ~ ' '" , ' ~ -
, :' " ' ' ''
8476
-13- 24-51(6438)A
of the compounds where M represents such a
base, those preferred for use as adhesion promoters
are compounds where M represents a 1,2-dihydroquino-
linium ion, which may optionally have ring
substituents. Examples of such ions are 2,2,4-
trimethyl-1,2-dihydroquinolinium, 2,2,4-trimethyl-6-
(Cl 12alkoxy)-1,2-dihydroquinolinium, for instance
2,2,4-trimethyl-6-ethoxy-1,2-dihydroquinolinium,
2,2,4-trimethyl-6-~C1 18 alkyl)-1,2-dihydroquinolinium,
for instance 2,2,4-trimethyl-6-clodecyl-1,2-
dihydroquinolinium, and 2,4-diethyl-2-methyl-1,2-
dihydroquinolinium. ..
Other classes of bases which form divalent
cations by the addition of two protons are
15 represented by the general formulae
~ 2
/ C-S-A -S-C\
NH2 and
NH ~NH
C-NH-A2-NH-C
NH NH2
where A2 represents a radical -(CH2)e~, where e is an
integer from 2 to 20, preferably from 2 to 12, and
the radical -(CH2)e- can be either straight chain or
branched or a C2 20 alkylene or alkadienylene
radical, for example a but-2-enylene or
octa-2,6-dienylene radical. These bases form
bis(isothiouronium) and bis(guanidinium) ions
respectively.
~. ` , - - : ":, '
:~ ~ .,; ,
:, . ' ~ : "
~X~8~76
-14- 24-51(6438)A
When R in the groups S-S02R of the adhesion
promoter is an organic radical, aliphatic radicals
from which R may be selected include ~traight- and
branched-chain alkyl and alkenyl groups, more
especially such groups containing from 1 to 20 carbon
atoms, for example, methyl, ethyl, n-propyl,
isopropyl, sec-butyl, tert-butyl, isoamyl, t-amyl,
n-hexyl, hex-3-enyl, n-heptyl, n-octyl, 2-ethylhexyl,
and decyl, dodecyl, pentadecyl and octadecyl groups.
When R is cycloaliphatic, it is usually a
radical containing from 5 to 8 ring carbon atoms,
which may be saturated or contain one or two olefinic
bonds, for example a cyclopentyl, cyclohexyl or
cyclohexenyl group.
An aromatic radical R may be, for example,
phenyl, naphthyl or biphenyl, and a heterocyclic
radical may be, for example, pyridyl, imidazol-2-yl
or thiazol-2-yl.
Radicals which are combinations of two or
more of the foregoing radicals include
alkylcycloalkyl radicals, for example methyl-
cyclohexyl; alkyaryl radicals, for example tolyl,
dimethylphenyl and ethylphenyl; arylalkyl radicals,
for example benzyl and phenethyl; and fused-ring
aromatic-heterocyclic radicals, for example quinolyl,
benzimidazol-2-yl and benzothiazol-2-yl.
Also included are radicals having
substituent atoms or groups, for example halogen such
as chlorine or bromine, or nitro, hydroxyl, carboxy,
carboalkoxyl or alkylcarbonyl groups. Examples
include chloroethyl, chlorotolyl, hydroxyphenyl,
carboxypyridyl and nitrobenzothiazolyl.
,. ;,'-- " ~ ' .' . ' '
. ~
::
.:: . ~ . .
,., - .
lX6847~i
-15- 2~-51(6438)A
Specific compsunds or classes of compounds
useful as adhesion promoters include the salts and
hydrated salts of n-butylthiosulphate, n-pentyl-
thiosulphate, isopentylthiosulphate, n-hexylthiosulphate,
isohexylthiosulphate, n-heptylthiosulphate, iso-
octylthiosulphate, 2-ethylhexylthiosulphate, and the
straight- and branched-chain dodecylthlosulphates,
hexadecyl thiosulphates and octadecylthiosulphates, of
prop-2-enylthiosulphate, but-2-enylthiosul~hate,
pent-3-enylthiosulphate, hex-3-enylthiosulphate,
oct-3-enylthiosulphate an~ dodec-4-enylthiosulphate,
of 3-chloropropylthiosulphate, 4-chlorobutylthio-
sulphate, 6-chlorohexylthiosulphate and
10-chlorodecylthiosulphate, of benzylthiosulphate, 1,
phenylethylthiosulphate, 2-phenylethylthiosulphate,
4-phenylbutylthiosulphate, 3-phenylpentylthiosulphate
and the various isomeric phenyloctyl-, phenylnonyl-
and phenyldodecylthiosulphates, of 2,5-dihydroxyphenyl-
thiosulphate, of ethylene bisthiosulphate, .
pentamethylene-1,4-bisthiosulphate, hexamethylene-
1,5-bis thiosulphate, heptamethylene-1,7-bis thiosulphate,
octamethylene-1,8-bis thiosulphate, nonamethylene-
l,9-bis thiosulphate, decamethylene-1,10-bis thiosulphate
dodecamethylene-1,12-bis thiosulphate and
hexadecamethylene-1,16-bis thiosulphate, of but-2-ene-
1,4-bis thiosulphate, pent-2-ene-1,5-bis thiosulphate,
hex-3-ene-1,6-bis thiosulphate, oct-4-ene-1,8-bis
thiosulphate, octa-2,6-diene-1,8-bis thiosulphate and
octa-3,5-diene-1,8-bis thiosulphate
;: .: , :
. , .. -.,,, ,:. - . -
, ~ ~: .
... .
- . , - ,.
476
-16- 24-51(6438)~
with the cations sodium, magnesium, calcium, barium,
zinc, cobalt and nickel;
with the cations
ammonium,
N(C4 12tert-alkyl~-N-~enzylammonium, for example
N-tert-butyl-N-benzylammonium and
N-(1,1,3,3-tetramethylbutyl)-N-benzylammonium,
N-isopropyl-N-(4-phenylaminophenyl~ammonium,
N-~1,3-dimethylbutyl)-N-54-phenylaminophenyl)ammonium,
N-cyclohexyl-N-(4-phPnylaminophenyl)ammonium,
2,2,4-trimethyl-1,2-dihydroquinolinium, guanidinium
and benzylisothiouronium;
with divalent cations of the formula
R2 NH2-A- NH2R2
where A represents paraphenylene and R2 is a C3 12
secondary alkyl group, for example a
1,4-dimethylpentyl group; and with divalent cations
of the formula
[(NH2)2 CS (CH2)c SC(NH2)2]
where c has any one of the integral values from 2 to
12 so that (CH2)C represents for example
tetramethylene, pentamethylene, hexamethylene,
octamethylene or decamethylene.
Other classes of compounds useful as
adhesion promoters in the present invention are those
having the following formulae and their hydrates:
R700CR3-S203M
where R7 is methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec-butyl, n-hexyl, or 2-ethylhexyl, and R8
is ethylene, ethylidene,:propylene, butylene,
: 2-methylpropylene, hexamethylene or decamethylene,
o[(cH2)as2o3M]2
where a has any one of the values 2, 3, 4, 5 and 6,
and the compound
, : : ~-: - :
.. ;. .. ,, .,. ::
.
:. :. ., ~ :.. . .
.. .. .
~.2~8'~
-17- 24-51(6438)A
CH3
o[cH2cH2cH CH2CH2S23M~2;
(CH2)a, [(CH2)a S23M]2
where a' has any one of the values 1, 2, 3 or 4 and a
has any of the values 2, 3, 4, 5 and 6.
3S2(cH2)c C(CH2)a S203M where c
has any one of the integral values from 1 to 10 in
combination with any one of the integral values 2, 3,
4, 5 and 6 for a;
M03S2(CH2)c COO(CH2)c,OOC(CH~)c S2 3
where each c' has any one of the integral values from
2 to 10 in combination with any one of the integral
values from 1 to 12 for c;
M03S2(CH2)c COO(CH2CH20)d CH2CH200C(CH2)c S203M
where each c has any one of the integral values from
1 to 10 in com~ination with any one of the values 1,
2 and 3 for d; the compounds
M03S2-(CH2)e~SO2~(CH2)e S23
where each e has an integral values from 2 to 8;
the compounds :
3S2 (CH2)b-C-(CH2)b-S23M
where each b has an integral value from 1 to 4; the
compounds
3S2 CmH2m-c6H4-cmH2m-s2o3M and
:
Mo3s2^cmH2m-cloH6-cmH2m S23
where each m has the value 1, 2 or 3 and C6H4
represents phenylene, for example meta- or
para-phenylene, and C1oH6 represents naphthylene, for
example 1,4-naphthyIene or 1,5-naphthylene;
~2~8476
-18- 24-~1(6438)A
where in each instance M represents sodium or an
equivalent of magnesium, calcium, barium, zinc, nickel
or cobalt, or is selected from the cations
N(C4 12tert-alkyl)-N-benzylammonium, for example
N-tert-butyl-N-benzylammonium and N-1,1,3,3-
tetramethylbutyl)-N-benzylammonium, N-isopropyl-N-
(4-phenylaminophenyl)ammonium,
N-(1,3-dimethylbutyl)-N-(4-phenylaminophenyl)ammonium,
N-cyclohexyl-N-(4-phenylaminophenyl)ammonium,
lo 2,2,4-trimethyl-1,2-dihydroguinolinum, 6-ethoxy-2,2,4-
trimethyl-1,2-dihydroquinolium, and benzylisothiouronium.
Many of the adhesion promoters referred to
herein are described in EP-A-0070413, where they are
shown to be useful vulcanisate stabilizers. Compounds
not referred to therein but which are useful according
to the present inven-~on as rubber-metal bonding
promoters and are new compounds, include those of the
formula Rl-S~S03M and their hydrates where Rl is an
organic radicaI and M represents an equivalent of
magnesium, calcium, barium, zinc, cobalt or nickel.
Specifically to be mentioned are those where Rl is a
C3 20 alkyl or C2 20 chloroalkyl group, a C3 20
alkenyl group, a phenyl(Cl_l6) group or a 2,5-
dihydroxyphenyl group or a grouping of the formula
R7OoCR8- where R7 is a Cl 12 alkyl group and R8 is a
Cl_12 alkylene group.
Also novel are compounds and their hydrates
where M represents an alkali metal, for exampl~
sodium, and R represents a C2 20 chloroalkyl group,
a C3 2~ alkenyl group or a grouping of the formula
R700CR - where R7 is a Cl 12 alkyl group and R8 is
a C1 12 alkylene group-
!
:,. , . , . -.
;: , ......
.
::
:: .-
. ~ ,~ :, -
~2~347~
-19- 24-51(6438)A
These compounds can be prepared by the
reaction of an organic chloride of the formula RlCl
with sodium or potassium thiosulphate using, for
example, procedures as described in EP-A-0070143,
followed by the conversion, where appropriate, of the
initially-formed alkali metal salt to the
corresponding magnesium, calcium, barium, zinc,
cobalt or nickel salt. Methods for such conversion
are described in EP-A-0070143. An alternative
procedure comprises mixing the alkali metal salt and
a nickel salt in a solvent in which both are at least
moderately soluble but in which the by-product sodium
chloride has low stability. Absolute methanol can be
used as such a solvent.
The adhesion promoters referred to above
are especially effective in compositions in which the
rubber is cis-polyisoprene, either natural or
synthetic, and in blends containing at least-25% by
weight of cis-polyisoprene with other rubbers.
Preferably the rubber, if a blend, contains at least
40% a~d more preferably at least 60% by weight of
cis-polyisoprene. Examples of other rubbers which
may be blended with cis-polyisoprene include
poly-1,3-butadiene, copolymers of 1,3-butadiene
with other monomers, for example styrene,
.... ,;.
- ,: : .. : . . . .
1~8~76
-20- 24-51(6438)A
acrylonitrile, isobutylene and methyl methacrylate,
ethylene-propylene-diene terpolymers, and
halogen-containing rubbers such as chlorobutyl,
bromobutyl and chloroprene rubbers.
In the compositions of the invention the
essential vulcanising agent is sulphur, but other
vulcanising agents such as amine disulphides need not
be excluded. The amount of sulphur in the
compositions is typically from 2 to 6 parts, for
example from 3 to 6, by weight per lO0 parts by
weight of rubber, but lesser or larger amounts, for
example from l to 7 or 8 parts on the same basis, may
be employed. A preferred range is from 2.5 to 4
parts per 100 parts by weight of rubber. An
advantage of the adhesion promoters of the invention
over the conventionally-used cobalt compounds is that
they are effective at lower sulphur levels. The
principal significance of this is that over the range
of sulphur levels that gives vulcanisates of
acceptable physical properties, those vulcanisates
prepared using lower levels of sulphur show greater
resistance to reversion and oxidative ageing than
those prepared using higher levels of sulphur.
Examples o vulcanisation accelerators
which can be used in the present invention are the
thiazole-based accelerators, for example
2-mercaptobenzothiazole, bis(2-benzothiazolyl)-
disulphide, 2(2',4'-dinitrophenylthio)benzothiazole,
benzothiazole-2-sulphenamides for instance
N-isopropyl-benzothiazole-2-sulphenamide, N-tert-
butyl-benzothiazole-2-sulphenamide,
, ,
- ., :
. ~
. . - ~-, :
~: . ,, , : , ...
~L2~8~6
-21- ~4-51(6438)A
N-cyclohexylbenzothiazole-2-sulphenamide, and
2(morpholinothio)benzothiazole, and thiocarbamyl-
sulphenamides, for example N,N-dimethyl N',N'-
dicyclohexylthiocarbamoyl-sulphenamide and
S N(morpholinothiocarbonylthio)morpholine. A single
accelerator or a mixture of acclerators may be used.
Best results are usually obtained using the
benzothiazole-2-sulphenamides, especially those with
relatively long induction times, for example
N,N-dicyclohexyl-benzothiazole-2-sulphenamide and
2(morpholinothio)benzothiazole. In the compositions
of the invention, these are usually used in amounts
of from 0.3 to 2, for example from 0.3 to 1.5,
preferably from 0.4 to 1.0 and more preferably from
0.5 to 0.8, parts by weight per 100 parts by weight
of rubber.
The adhesion promoters defined above are
very effective in promoting bonding between rubber
and brass, for example the bonding between rubber and
brass-coated steel. The brass typically has a copper
content of from 60 to 70% by weight, more especially
from 63 to 68% by weight, with the optimum percentage
depending on the particular conditions under which
the bond is formed. The brass coating on
brass-coated steel can have a thickness of, for
example, from 0.05 to 1 micrometre, preferably from
0.07 to 0.7 micrometre, for example from 0.15 to 0.4
micrometre.
Rubber can also be bonded effectively to
alloys of copper and zinc containing small amounts of
one or more other metals, for example cobalt, nickel
or iron.
~, ;:. ,
: , . . .
,~ :. ;.; ~ , :
, . ~ .~, . ..
, . ~.
: . .- . ;: -, . .
76
22- 24-51(643~)A
For bonding rubber to ~inc, as for example
in bonding rubber to zinc-coated steel cords (which
are widely used in the manufacture of conveyor
belting) cobalt compounds have been used as adhesion
promoters. Examples of such compounds are cobalt
- naphthenate and the cobalt-boron complexes described
in GB-A-2 022 089. The thiosulphate and thiosulphonate
adhesion promoters described above, other than the
cobalt thiosulphates, generally show only weak promoter
activity for the bonding of rubber to ~inc when used
alone. However, mixed adhesion promoters in which,
for example, the alkali metal or nickel thiosulphates
described above, partially replace the conventional
cobalt compound, show improved promoter effect over
the conventional cobalt compound alone.
An aspect of the present inven~ion is thus
a rubber-metal composite in which the metal surface
is zinc, the rubber composition contains a compound
of the formula Rl-(S-SO3M)n as defined above and the
composite also contains a cobalt compound, which may
be a compound of the above formula in which M
- represents an equivalent of cobalt, or another cobalt
compound.
The amount of adhesion promoter employed in
2S the present invention is usually from 0.1 to 6 parts
by weight, and preferably from 0.5 to 4, for example
from 2 to 4, parts by weight per 100 parts by weight
of rubber.
The adhesion promoters used in this
invention can be incorporated into rubber by
conventional mixing procedures, for example by adding
them in a Banbury mixer or by adding them to the
rubber on a mill. Ordinarily, with liquid or low
. .,...:- ,., . :
.. . .
~8476
-23- 24-51(6438)A
melting solid additives, no special ~recautions are
necessary for obtaining good dispersions. However,
when using higher melting solids it is recommended
that they be ground to a fine powder, preferably 70
micrometre particle size or less, to ensure adequate
dispersion. In certain instances, it is convenient
to add a solid adhesion promoter as a predispersion
of particulate material in a r~lbber-compatible
hydrocarbon oil or polymer, for example EPDM rubber.
Additives which are conventionally present
in rubber compositions which are to be bonded to
metal are normally used in the vulcanisable
compositions of the present invention. Such
additives include carbon black, usually a carbon
black of the N300 series such as N347 or N326, which
typically is used in an amount of from 40 to 70 parts
by weight per 100 part~ by weight of rubber. Other
such additives are, for example, zinc oxide, which
may be used in an amount of, for instance, from 2 to
10 parts by weight per 100 parts by weight of rubber;
stearic acid at a level of, for instance, from 0.5 to
2, for example from 1 to 2, parts by weight per 100
parts by weight of rubber; hydrocarbon softeners and
extender oils; antidegradants, for example
N-alkyl-N'-phenyl-p-phenylendiamines; and
tackifiers. Other fillers may be used, for example
silica, and the rubber stocks may also contain metal
oxide activators other than zinc oxide, for example
magnesium oxide, phenolic, resorcinol and/or melamine
adhesive resins, and prevulcanization inhibitors, for
instance N-cyclohexylthiophthalimide. The metal
surface to which the rubber is to be bonded can be
subjected to various pre-treatments, for example to
ensure complete cleanliness or to confer corrosion
resistance.
::`.:` ::" . :, ~
: - .,. :
.. ...
: ~ .
.:.- : . ~. . . .
3 26~347~
-24- 24-51(6438)A
Evaluation of the adhesion promoters was
carried out using a vulcanisable rubber composition
of a type known as "skimstock" as follows:
Parts bY Weight
Natural Rubber 100
HAF Carbon Black 55
Zinc Oxide 8
Stearic Acid 2
Process oi l 3
Tackifier 3
Antiozonant(1) 2
Antioxidant(2 )
Sulphur 4
Accelerator(3) 0.7
~onding Promoter 3( 4 )
(1) N-1,3-dimethylbutyl-N'-phenyl-p-
phenylenediamine
( 2 ) Polymerised 2,2,4-trimethyl-1,2-
dihydxoguinoline
(3) 2tmorpholinothio)benzothiazole
except where indicated in Table l
by xx, when the accelerator was
N,N-dicyclohexylbenzothiazole-2-
sulphenamide
( 4 ) In comparative experiments using :
cobalt naphthenate as bonding
promoter, 1.5 parts by weight of
cobalt naphthenate containing 10%
by weight of cobalt were used.
Mixing of the components except sulphur and
accelerator was done in a laboratory scale Banbury
mixer having a capacity of 1.57 litre and operating
at a filling factor of about 0.8 and a rotor speed of
117 r.p.m., according to the following schedule:
~26~476
-25- 24-51(6438)A
Time(mins.)
0 Rubber placed in a mixer and
rotors started.
1 Half carbon black and zinc oxide
added.
2.5 Remainder of carbon black,
stearic acid, process oil,
tackifier, cmtiozonant,
antioxidant, bonding promoter
added.
4 Sweep.
Dumped at temperature
150 i 5C.
The batch was then transferred to a mill at 75-70'~C
for sheeting off. Sulphur and accelerator were added
to portions of the masterbatch on a mill as
required.
The metal component was a typical
brass-coated steel tyre cord havins the construction
3 + 9 -~ 15 x 0.175 + 1. In most cases the cord had a
0.20 micrometre-thick coating of brass having a
copper content of 63.5 ~ 3% by weight. Results
marked with an asterisk were obtained using cord with
a 0.18 micrometre-thick coating of brass having a
copper content of 67.5 $ 3%.
Rubber/metal bond strengths~were measured
using the adhesion test described by R. C. Ayerst and
E. R. Rodger, Rubber Chem. Technol. 45, 1497(1972).
In this method, adhesion blocks are prepared in a
similar manner to that specified in ASTM D-2229, but
using clamping plates to hold the cords in the mould
to maintain alignment during cure, and a frame for
pre-loading and uniformly stressing the cord be~ore
mould bulding. The adhesion block comprises a strip
~: ::
::
::
~''; ~ :
. . .
4t7~j
-26- 24-51(6438)A
o rubber havlng one end of each of several
unifor~ly-spaced lengths of cord embedded in one edge
of the strip, and a similar array of lengths of cord,
each length having one end embedded in the edge of
the strip opposite the first edge and in staggered
relationship to the cords in the first edge. Pullout
adhesion is measured on a tensille tester by arrangin~
the adhesion block so that the cords are vertical and
the rubber strip horizontal, and by holding two lower
wires and pulling out the upper wire between them at
a crosshead speed of 5 cm/min. The pullout force
recorded is the mean of the values for each of the
several lower cords except those at each end of the
strip, which are not taken into account in order to
eliminate possible end effects. Where the pullout
force exceeds the breaking load of one or more of the
wires in the test procedure, this is signified in the
Tables by the symbol >. Rubber coverage on the
pulled out cord is assessed on the scale 0 (bare
cord) to lO (100% coverage) by comparison with
standard samples. High coverage values indicate
failure in the rubber phase rather than at the
rubber-metal interface, and may mean that the rubber
has poor physical properties unless accompanied by
high pullout force.
The results given in the tables below under
the headings "Initial Adhesion", "Air Ageing", "Steam
Ageing" and "Salt Bath Ageing" were obtained on
adhesion blocks where ~he rubber was cured at 145C
for Tgo + 5 minutes, "Tgol' being the time in minutes
taken for a sample of the same rubber cured in a
rheometer (British Standard Test Method 1673 Part 10)
to reach 90% of the maximum modulus. Blocks that
were "air aged" before testing were subjected at 85C
. " ., ~ .
'',: , . ,
" ~- . ' : '~
-27- 24-51(6438)A
to the conditions of British Standard Method 903,
Part A.lg (1975) after curing. Those that were
"steam aged" were kept in steam under pressure at
120C for 8 hours and those that were "salt bath
aged" were immersed in a 5% sodil~ chloride solution
at 90C after curing and before testing. Results
shown under the heading "2 Tgol' were obtained on
blocks that were cured twice the Tgo time, i.e. were
"overcured".
In "Steel Cord: Analysis of Used Truck
Tires and Simulation of the Found Phenomena in
Laboratory Experiments" an article in "Tire
Reinforcement and Tire Performance", ASTM STP 694,
R. A. Fleming and D. I. Livingston, Eds, American
Society for Testing and Materials, 1979, pp. 69-86,
C. C. J. de Jong concludes that in evaluating tyres
and other composites containing metal cord
reinforcement, attention should be paid to aged
adhesion rather than to initial adhesion. The ageing
conditions mentioned above are similar to those
proposed by de Jong to simulate, at an enhanced
level, various conditions which might be encountered
during the service life of a tyre.
..
,. . ,:
-: ~
, . .. .
~2~L76
-28- 24-51(6438)A
In Table 1, the adhesion promoters are di- or ..
tri-sodium salts as follows:
Formula
(Excluding possible water Promoter number in
of crYstallisation Table 1
NaO3S2 ( CH2 ) 5S23
NaO3S2(cH2)6~2O3 2
NaO3S2 ( CH2 ) 10S23
NaO3S2-(CH2)4--(CH2)4S23N
3 2 (CH2)4-O-cH2-o-(cH2)4s2o3Na 5
3S2 (CH2)2-O-CH2-O-~cH2)2s2o3Na 6
O
aO3S2 (cH2)3-c-o-(cH2)~s2o3Na 7
[NaO3S2(CH2)l0coo(cH2)2]2o 8
NaO3S2CH2 ~CH2s203Na
~ CH2S23Na 10
CH2 S23Na
~ CH2 S203Na 11
CH2 S23Na
NaO3S2(CH2)2sO2(cH2)2s2o3N 12
O = C(CH2S2O3Na)2 13
R-N ~ N-R 14
R
(R is -COCH2CH2S2O3Na)
:~2~
-29- 24-51- (6438)A
oo _ ~
o oooooo~ooooooooooo
h ~0 ~ O 0~ C10 0 1-- --~ C~l C10 ~D 3 ~ ~ ~ ~ C~
00 ~ _ _ _ _ _
~n C~ O OOOOOOOOOOO~OOOOO
~J 00
C ~ ~ A
~1 ~ `D ~
3:1 ~O O O O O O O O O O O O O O O O O O O
C
00 ~ `D ~ ~ ~ ~ ~ J ~ ~ ~ ~ t~ ~ ~ c~ c~
C~ O OOOOOOOOOOOOO~OOOO
Ql O~ C~ ~O 00 ~ ~ ~ ~ O ~ 1--C~ t`J
C`~U~ t`J ~ ~ ~ ~ ~) cr~ ~ U'~ ~ ~ ~t ~ ~ ~ ~) 4'
e '~ ,~ ô ~ o ,~ O~ t~ ~O c~ c~ 00 ~ ~
O OOOOOOOOOOOOOOOOOO
: ;t
o _ _ _ _ _ _ ~
~:1 ~ OO O O O O O O O O O O O O O O O O O
E a o ~o ~ o o o~ ~ o o oo ~ ~ ~J ~ ~ ~ ~ ~o r~
'1: C~o
Z 4~ _, __~________,____,_ _,
C ~ O O O O 0 0~ 0 0 0~ 0 C~ C~~ ~ ~ ~~ r~ O
.,, C ~ U~ ~ ~ ~ ~ ~ `$ ~ '5 C" ~ ~ ~ ~ ~ ~ ~ ~
~ :
o
.,, ~ _ _ _ ______ _~___
o oooooooooooooooooo
u~ u~ C~ V C~ ~ C~l O r~ o V ~ O ~ ,, .
~ C
co o o o o o o o o o o o o o o o o o o
_I C ~ ~~D c~ c~ ~ ~ ~O ~ u'~ r~
o~ :
c ~ :
oo ~
c~ c ~ ~
~-- Clo 2; ~ Z ~ ~ 'I ~ t~ ~ ~ ~
O ~D
e ~ c~ c ~
o ~
~Z _, 0~,
u~o In o
~ _I ~
:
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: ~ . . ... .
,: :. . . :
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-30- 24-51~6438)A
In Table 2, the adhesion promoters are mixtures of
nickel salts and the corresponding sodium salts of
bis thiosulphates as follows:
Formula of Nickel Salt
(Excluding possible water Promoter number in
of crystallisation _ Table 2
[ O3S2(CH2)5S2O3 ]Ni
[ 3S2(cH2)6s23 ]Ni 2
[ o3S2(cH2)los2o3 ]N
[ 3S2 (CH2)4-O-(CH2)4S2o3 ]Ni++
[ 3S2 (CH2)3CQO(CH2)4S2o3 ]Ni++ 5
[[ 3 2 (CH2)l0-COO(cH2)2]2o] Ni+~ 6
[ 3S2(CH2)2O-CH2-O(CH2)2S2O3 ]Ni++ 7
[ 3S2(cH2)2s2(cH2)2s23 ]Ni 8
[ 3S2cH2 ~ CH S O -~Ni++ 9
~CH2S203 ~ 10
CH2S203
The mixtures were prepared by passing a solution of
the sodium salt through a column of cation exchange
loaded with nickel and evaporating the eluate. :
Elemental analyses of the products showed that about
50% of the original sodium had been displaced by
nickel with the exception of Promoter No. 2 where
only about 30% of the sodium had been displaced.
, ", ~
, .. : ". "
- : . ~ ~ : . . -
.: : ;: ~
- .,-
~L2~8A~76
-31- 24-51 (6438)A
~ ~ ~ A ~_
h ~ O O o o o o o o --_ _
C
U~ 00 _ _ ~
O~ ¢ ~ O O O O O O O O O O O
c
~ a
C
O~
~_~ ~'_ A ~ A _~
V~00 O OOOOOOOOOO
04
h
O E h _ _ _ _ _ _ _ _ _ _ _
U O O O O O O O O O O O
8 ~ ~ ~ ~
o -- --o o o o o o o o o
:~ o ~ ~ ) ~ ~ - ~ o c~ ~ o
`5
E
~ C
E--~ ~r~
C
V ~ _ ~ A _ _ _ _ A A A
Z ~r~ _ `_____`_____
C eS ~
O
cr c
~n ~ o o o o o o o o o o o
U
~ .
_l O
' _ _ _ _ _ _ _
8 ~ ~ ~ ~I
G
~ _I . .
~ Ll
Z ~C
O
~ ~ O
E C
o
:4 C~
U~ o U~
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4~76
-32~ 24-51(6438)A
Table 3 shows results obtained with various adbesion
promoters as follows:
Formula or Name
(Excluding possible waterPromoter Number
of crvstallisation _in Table 3
[C2H500CCH2C~2S203 ] 2Ni
Mixture of [CH3(cH2)3s23 ]2
[CH3(cH2)3s2o3 ]2Na 2 2
[ 03S2(CH2)6S203 ]Co 3
[ 03S2(CH2)6S203 ]A2 4
where A is N-benzyl-N-
1,1,3,3-tetramethylbutylammonium
Nickel laurate 5
Mixture of 2 parts by weight nickel 6
laurate and 2 parts by weight
UaO3S2~CH2)65203
:
, .. . .
7~i
-33 24-51 (6438)A
,~
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`D O
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c
h ~J ~S) CO r~ ~ ~
~1 ~ o _ O O O O O O O
a:~ _.
C _~
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C _ _, _ _ _ _
C CO O O O O O O O
.
~ u~
0
h
~0
O E C _ _ ~_ _ _ _
C~ ~ O O O O O O O
~1: ~ ~ ~ ~ ~ ~
h
r
~ I_ oO cO ~ 00 ~ ~
C~ . O _ _~ _ _ _ _ _
O ~ C~ O ~O 1~ ~0
~1 EC
~1: 3~
E~ C~
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U~ O O O O O O O
c ~ co ~ r~ ~D X u~
.,, ~ ~ ~ '$ `J
:~
~r O _ _ ~ V~
:o O o O o o o o
._~ ~ u~ cr~ u~
v ~ In u~ ~ ~ ~ u~
U
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rl
n u~ Cl~ ~ ~
O O O O O O O
C ~ ~ In In ~ 00 ~
S~
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:~ C
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-34- 24~51(6438)A
The results listed in Table 1 show that
while the known adhesion promoter cobalt naphthenate
gives higher initial adhesion values than the control
it actually has an adverse effect on vulcanised
composites that are subject to steam ageing and salt
bath ageing. In contrast, the adhesion promoters of
the present invention improve initial adhesion
relative to the control and show good retention of
adhesion on ageing.
The results listed in Table 2 show ~he
adhesion promotion effects of nickel organic
thiosulphates. Improvement in initial adhesion and
salt bath ageing is particularly significant.
There is evidence from the above results
that in the bonding of rubber to brass, adhesion
promoters where M represents a mixture of sodium and
nickel ions are more effective than analogous
compounds where M represents sodium alone.
Comparison of the results obtained with nickel
laurate (Promoter No. 5 in Table 3) with those
obtained with the nickel organic thiosulphates of
the present invention show, however, that the latter
have advantages over the prior art nickel compound
(USA 3991130), in respect to air ageing and steam
ageing.
The results obtained with Promoter No. 6 in
Table 3 again show that an improvement over the use
alone of a promoter of this invention where M is
sodium (Promoter No. 2 in Table 1) can be achieved by
using a mixture of such a promoter with a prior art
: ' ~''''` . '' . '"' "`'' .'" '`'`, `' ~ i "
8~76
-35- 24-51(6438)A
nickel compound. The result also shows that such a
mixture is better than the prior art nickel compound
alone. A similar result would be expected where M in
the promoter of this invention is, for example, an
alkali metal other than sodium, an alkaline earth
metal or zinc.
Comparison of the results obtained with
Promoter No. 3 in Table 3 with those obtined with
cobalt naphthenate (Table 1), shows that the adverse
effect on ageing is avoided when the cobalt is
present in association with an organic thiosulphate
anion.
The results shown in Table 4 were obtained
using the vulcanisable rubber composition described
above, with N,N-di-cyclohexylbenzothiazole-2-
sulphenamide as the accelerator, and using the cord
with a coating of brass having a copper content of
63.5 + 3% by weight.
The adhesion promoters of Table 4 are set
out below:
.,. ~ . , .
... :.. :.
~2~76
36- 24-51t6438)A
Formula or Name (Excluding
Possible Water of Promoter Number
Crystallisation In Table 4
l(a)
CH300C CH S203Na
Hexamethylene-1,6-bis(thiosulphale) 2
2,2,4-trimethyl-1,2-dihydroquinolinium
salt
Hexamethylene-1,6-bistthiosulphate) 3
N-isopropyl-N'-(p-phenylaminophenyl)-
10 . ammonium salt
fCH - CH2-(CH - CH2)2-CH - CH2 1 4*
LOCOCH3 OH C(cH2)ss~3Na~ n
[ 03S2CH2CH = CH CH2S203 ] 2Na 5
Hexamethylene-1,6-bis(thiosulphate)Ba 6
salt
Hexamethylene-1,6-bis(thiosulphate)Mg 7
salt
Hexamethylene-1,6-bis(thiosulphate)Zn 8
salt
Mixture of 3 parts by weight hexa- 9
methylene-1,6-bis(thiosulphate) :
disodium salt and 1 part by weight
nickel chloride
Nickel chloride 9A(b)
-.:,: :- . : ; . .
-37- 24-51(6438~A
[CH300C CH S203 ]2 Ni 1O(c)
OH 11(d)
23 Ni
OH
_ 2
[C6H5CH2S203 ]2 Ni l2(e)
[C6HScH2s23 ]2 Co 13(f)
[n C7H15S203 ]2 Ni 14(g)
(a) At 1.6 phr
(b) At 1.0 phr
(c) At 1.41 phr
(d) At 1.31 phr
(e) At 1.33 phr
(f) At 1.36 phr
(g) At 1.36 phr
*Average formula
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-39- 24-51(6438)A
The results in Table 4 show that all the
compounds tested have significant metal rubber
promoter activity relative to the controls. Nickel
chloride (9A), which is disclosed in FR-A-2053749 as
a promoter for rubber-metal bonding, is included for
comparison with the mixture of nickel chloride and
hexamethylene-1,6-bis(thiosulphate) disodium salt
(9). The presence of the latter results in a marked
improvement in the resistance of the composite to salt
bath ageing.
The results shown in Table 5 were obtained
using a vulcanisable rubber composition having
components the same as that described above except
that the rubber was a mixture of 80 parts by weight
of natural rubber and 20 parts by weight of
polybutadiene 1220 rubber and the accelerator was
N,N-dicyclohexylbenzothiazole-2-sulphenamide at 1.0
part phr. In Experiments 1, 2, and 3, the cord was
made from steel wire coated with brass having a
copper content of 63.5%, and in Experiments 4, 5 and
6 the cord was made from steel wire coated with a
ternary alloy of copper 70%, cobalt 4% and zinc 26%.
: :: . , - .
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. . . 1 ,
.. . .
476
-40- 24-51 (6438)A
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-41- 24-51(6438)A
The results in Table 6 were obtained with a
rubber compositions as follows:
Natural Rubber 30
Polybutadiene Rubber 1220 25
Oil~Extended Styrene-Butadiene 67.5
Rubber 1712 (37.5% oil)
Carbon Black 60
Zinc Oxide 5
Stearic Acid 1.5
Process Oil 10
Antidegradant(l) 2
Antioxidant(2)
Sulphur 4
Accelerator(3)
Bonding Promoter 3
(1) N-1,3-dimethylbutyl-N'-phenyl-
p-phenylenediamine
(2) Polymerised 2,2,4-trimethyl-
1,2-dihydroquinoline
(3) N,N-dicyclohexylbenzothiazole- :
2-sulphenamide
347~
-42- 24-51 (6438)A
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-43- 24 51(6438~A
Table 7 gives the results of experiments
designed to investigate the effect of variations in
the amount of sulphur in the vulcanisable
compositions. The adhesion promoter was
1,6-hexamethylene bis(thiosulphate) nickel salt,
hexahydrate at 1.0 part by weight: per 100 parts of
rubber. Otherwise, except for the results marked
with an asterisk, and except where the accelerator
was N-tert-butylbenzothiazole-2-sulphenamide, the
composition was the same as that used in obtaining
the results of Table 1. The brass coating on the
cord contained 63.5 $ 3% by weight of copper. The
results marked with an asterisk were obtained with a
composition containing 0.5 parts of stearic acid per
100 parts by weight of rubber. The results show
optimum properties at 3-4 parts by weight of sulphur
per 100 parts by weight of rubber.
.. . .. . . ..
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-44- 24-51 (6438)A
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-45- 24-51(6~38)A
Table 8 gives the results of experiments
designed to investigate the effect of variations in
the amount of the rubber-metal bonding agent, in this
instance 1,6-hexamethylene-bis(thiosulphate) nickel
salt, hexahydrate (HTSNi). The rubber composition
was otherwise the same as that used in obtaining t~e
results of Table 1, with 2(morpholinothio)benzothiazole
as the accelerator.
Values in parentheses were obtained with
cord having a brass coating containing 67.5 ~ 3% by
weight of copper. The other values were obtained
with cord having a brass coating containing 63.5 ~ 3%
by weight of copper.
High rubber-metal bonding promoter activity
is shown with as little as 0.75 part of HTSNi per 100
parts by weight of rubber, and the optimum is at 1.0
part by weight of HTSNi.
- - -., .. - .. ~ '
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47- 24-51~6438)A
In other experiments reported in Table 9,
1,6-hexamethylene bis(thiosulphate) nickel salt,
hexahydrate (HTSNi) was compared with other nickel
compounds as a brass-rubber adhes:ion promoter. The
adhesion promoter was used at a level of l.O part by
weight per 100 parts by weight of rubber. otherwise
the rubber composition was the same as that used in
obtaining the results given in Table 1, with
N,N-dicyclohexylbenzothiazole-2-sulphenamide as
accelerator. The cord has a brass coating containing
63.5% ~ 3% by weight of copper.
HTSNi showed better overall performance
than other nickel compounds particularly during salt
bath ageing.
: : ,. ::,": . ; :- :
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-48- 24-51 (6438)A
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476
-49- 24-51(6438)A
Details of the preparation of nickel
benzylthiosulphate are given below:
Sodium benzylthiosulphate (57.5 g) and anhydrous
NiC12 (14.2 g) were mixed in absolute methanol (150
ml) at room temperature, and the mixture was stirred
for 24 hours. It was then filte.red, and methanol was
evaporated from the filtrate. The residue was
treated with water (50 ml) to displace the residual
methanol, and the resulting solution was evaporated
to dryness under vacuum, at a temperature not
exceeding 50C.
The residue analysed as follows:
Ni (by titration) 10.23%
Benzylthiosulphate (Nmr spectrum) 68.8%
Water (Nmr spectrum) 21.2%
This analysis corresponds approximately to the
formula
[C6H5cH2s23 ~ Ni .7H20.
The yield was 62%.
Table 10 gives results obtained in the
evaluation of various rubber/metal bonding promoters
as set out below. The adhesion promoter was used at a
level of 1.0 part by weight per 100 parts by weight
of rubber. Otherwise the rubber composition was the
same as that used in obtaining the results given in
Table 1, with 2(morpholino3benzothiazole as
accelerator. The cord had a brass coating containing
63.5 i 3% by weight of copper.
..
. .
~ 47t;
-50- 24-51(6438)A
Promoter Number Formula (excluding
in Table 10 possible water of crystallisation
12H25 23
( C12H25S23 ) 2N
3 C16H33S23Na
4 CH2=CHCH2S203Na
CH3
CH3CHCH2CH2S203Na
6 ~C6H5CH2CH2s203)2
7 Cl(CH2)3S23Na
8 [3S2(CH2)6s23] Mn
:: . - :.,
,~
.. .
- .
.. ....
~L~`~'71~
-51- 24-51(6438)A
TABLE lO
Pull-out Force in Newtons/cm
Initial SteamSalt Bath Ageing
Promoter Adhesion A~einq_~48 Hours)
l 490 470 310
2 490 500 390
3 570 520 230
4 520 600 360
590 480 240
6 500 420 420
7 >500 ~530 300
8 520 560 320
Details of the preparation of various novel
monothiosulph=tes ar- given below:
:
~ :
7~i
-52- 24-51(6438)A
Nickel benzylthiosulPhate
Sodium benzylthiosulphate (57.5 g) and
anhydrous NiCl2 (14.2 g) were mixed in absolute
methanol (150 ml) at room temperature, and the mixture
was stirred for 24 hours. It was then filtered, and
methanol was evaporated from the filtrate. The
residue was treated with water (50 ml) to displace the
residual methanol, and the resulting solution was
evaporated to dryness under vacuum, at a temperature
not exceeding 50C.
The residue analysed as follows:
Ni (by titration) 10.23%
Benzylthiosulphate (Nmr spectrum) 68.8%
Water (Nmr spectrum) 21.2%
15 This analysis corresponds approximately to the formula
[C6H5cH2s23-] 7H20-
The yield was 62%.
By a similar procedure there were prepared
Cobalt ben~ylthiosulphate
Nickel n-heptylthiosulphate
Nickel 2,5-dihydroxyphenylthiosulphate
(from the potassium salt described in
D.R.P. 175070~
Nickel dodecylthiosulphate
Nickel l-(methoxycarbonyl)ethyl-l-thiosulphate
Nickel n-butylthiosulphate, nickel
2-(ethoxycarbonyl)ethyl-l-thiosulphate and nickel
2-phenylethyl thiosulphate were prepared by the
ion-exchange method described in EP-A-0070143 from
the sodium salts.
. . .
,:,, ;.~ ~
,
~Z68476
-53- 24-51(6438)A
Sodium allylthiosulPhate
A mixture of allyl bromide (100 g~, sodium
thiosulphate (212.5 g), ethanol (90 ml) and water (40
ml) was stirred and heated to reflux for 15 minutes,
giving a homogeneous solution. The solution was
allowed to cool somewhat, and ethanol and water were
then evaporated under vacuum.
The solid residue was added to absolute ethanol, and
the solvent was then evaporated under vacuum to
remove more water. The residue was stirred with hot
ethanol (800 ml), and the suspension thus obtained
was filtered. On cooling, the filtrate deposited a
white solid (109.2 g).
The NMR spectrum of the sold showed that it consisted
of 80% by weight of sodium allylthiosulphate, 11% by
weight of water and 9% by weight of inorganic salt.
Sodium 3-chloropropylthiosulphate
This was obtained by the reaction of
1-iodo-3-chloropropane with sodium thiosulphate
pentahydrate in aqueous ethanol solution under
conditions resulting in the preferential replacement
of the iodine atom of the starting material, although
the product contained some propane bis thiosulphate,
sodium salt.
IR spectrum 1610 - 1430 - 1200 - 1030 - 640 cm
- . :,. . :
:: ,.: ~ :
- -, :-, : :,
,: ~. .
. : :: :: .. .
47~i
-54- 24-51(6438)A
Sodium 2-(ethoxycarbonyl)ethylthiosulphate
This was obtained by the reaction of ethyl
3-chloropropionate and sodium thiosulphate in aqueous
ethanol, and isolation of the product by evaporation
of the solvents under reduced pressure, extraction of
the residue with hot ethanol, and evaporation of the
ethanol extract after filtration. The IR spectrum
was consistent with the expected structure, and
titration with HgC12 showed the presence of 97.1% of
the theoretical of S203Na group content.
Sodium 1-(methoxycarbonYl)ethylthiosulphate
This was obtained by the reaction of methyl
2-chloropropionate with sodium thiosulphate in
aqueous ethanol, and isolation of the product by a
procedure similar to that described for sodium
2-(ethocycarbonyl)ethylthiosulphate above. NMR
analysis showed the presence of 77.3% thiosulphate,
2.2% water, 0.7% methanol and the balance a mixture
of inorganics and organic impurities.
,
..
- : ...... ,. ,, ~ :
