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Patented Oct. 22, 1946
Paul C. Jones, near ChagrinFalls, and Roger A.
Mathes, Akron, Ohio, assignors. to The B. F.
Goodrich Company, New York, N. Y., a corpo
ration of New York
No Drawing. Application December 21, 1944,
Serial No. 569,278
6 Claims. (Cl. 260-302)
This invention relates to the addition prod
slurry is ?ltered and the precipitate dried. After
drying, there was obtained 103.5 grams of the
ucts formed by_ the reaction between alkylene
imines and zinc salts of heterocyclic nitrogen
product which represents a 92% yield.
containing mercaptans.
Other, three-membered ring alkylene imines
These products, the structure of which is not 5 that can be substituted for ethylene imine in the
above example are the homologous hydrocarbon
de?nitely known, are useful as accelerators and
substituted ethylene imines, such as propylene
activators of vulcanization of rubber, although
imines and the like, without departing from the
they may also be used as insecticides, fungicides,
Among the rubbers with which our new
scope of our invention.
Zinc salts of other Z-mercaptothiazolines as
compounds may be used are all varieties of natu 10
well as the zinc salts of mercapto alkyl thiazoles,
ral rubber, such as cautchouc, balata, gutta
percha, latex, reclaimed rubber, and such syn
mercapto arylene thiazoles, mercapto oxazolines,
mercapto quinolines, mercapto thiodiazoles, mer
thetic rubbers as can be vulcanized ‘with sulfur,
captoirnidazoles, xanthogenic acids, and dithio
such as polymers of’ butadiene, isoprene, 2,3-di
methyl butadiene, piperylene, and the like and 15 carbamic acids may be substituted as equivalents
copolymers of these compounds with acryloni
for the zinc salt of 2-mercaptothiazoline in the
above example to produce their respective addi
tion products with equally good results.
omers. These new compounds may be added to
The addition products of the reaction between
the rubber on a roll mill or an internal mixer or 20 the alkylene imines and zinc salts of heterocyclic
trile, styrene, methyl acrylate, methyl methacryl
ate, isobutylene, and other copolymerizable mon
by any other suitable method. Other com
pounding ingredients, such as any of the ordinary
pigments, ?llers, dyes, antioxidants, or other ac
nitrogen-containing mercaptans are all good ac
As an indication of the ability of these com
celerators of vulcanization may be employed to
pounds to accelerate vulcanization, the following
gether with our new materials.
Small quantities 25 example illustrates the effect produced in rub
general 0.1 to 5% or more, based on the rubber
ber by the product of the reaction between the
zinc salt of 2-mercaptothiazoline and ethylene
imine. A typical tire tread stock of the following
composition, may be used.
composition, in which the parts are by weight,
may be used to achieve the desired results, either
as vulcanization activators or accelerators.
According to ‘our invention these addition 30 was prepared:
products are prepared by reacting» an alkylene
imine with a zinc salt of a heterocyclic nitrogen
____ __
containing mercaptan, preferably in approxi
Zinc oxide __________________________ __
mately equimolecular proportions and in the
__. _____________________________ __
presence of any of the commonly used reaction 35 Pine oil ______________________________ __
Cotton seed fatty acid____-_ ____________ __
diluents such as water, benzene, alcohol, and the
Channel black _______________________ __
Antioxidant ____ -i ____________________ __
like. Under such conditions the addition prod
uct forms as a precipitate which is readily iso
lated. It has been found that alkylene imines
react, even at room temperature, with zinc salts
of heterocyclic nitrogen-containing mercaptans.
The reaction is generally smooth and the pro
cedure simple.
Above reaction product as accelerator____
After vulcanization in a press at 280° F., the
composition had the physical‘properties as shown
in the following table, in which T is the ultimate
tensile strength in lbs/sq. in. and E is the ulti
The following speci?c examples will serve more
mate elongation in percent:
fully to illustrate our invention.
The zinc salt of Z-mercaptothiozoline and eth
ylene imine are reacted in equimolecular propor
tions by slowly adding 21.5 grams of ethylene
Time of vulcanization in minutes
15 ___________________________________________ --
2, 950
imine to a suspension of 91.5 grams of the zinc
. .__
3, 640
3, 000
500 _
salt of 2-mercaptothiazoline in 500 cc. of benzene 50. 150 __________________________________________ .at 70° C. while stirring the reaction mixture.
The white precipitate that forms, consisting of
Without an accelerator the above stock could
particles of larger size than those of the zinc salt
be vulcanized in about three hours, but the re
of the 2-mercaptothiazoline suspension, is the
sulting tensile strength would be only about one
addition product of the reaction. The resulting 55. half of the above values. But equally good re
sults may be obtained using other similar addi
tion products of any of the alkylene imines with
having its imino nitrogen atom attached to two
any of the zinc salts hereinabove mentioned.
carbon atoms which are directly connected one
to another, with a zinc salt of a heterocyclic ni
The complex. formed by reacting the zinc salt
of Z-mercaptothiazoline and ethylene imine is
trogen-containing mercaptan.
not only a more active vulcanization accelerator
than the zinc salt of 2-mercaptothiazoline, but is
not as sensitive to the activating effect of fatty
acid. This complex gives good results in the ab
sence of fatty acid.
These new products are quite stable and. are
capable of being stored for long periods of time
at room temperature without deterioration.
2. The addition product of equimolecular por
tions of an alkylene imine having its imino nitro
gen atom attached to two carbon atoms which
are directly connected one to another, and a zinc
salt of‘ a heterocyclic nitrogen-containing mer
3. The addition product of ethylene imine and
a zinc salt of a heterocyclic nitrogen-containing
Although We have described the preparation of
4. The addition product of equimolecular por
these products carried out in benzene as the reac 15 tions of ethylene imine and a zinc salt of a het
tion diluent, any of the common reaction dilu
erocyclic nitrogen-containing mercaptan.
ents, such as water, alcohols, ethers, gasoline, etc.,
5. The addition product of ethylene imine and
the zinc salt of Z-mercaptothiazoline.
Although We have herein described speci?c em
6. The addition product of equimolecular por
bodiments of our invention, we do not intend to 20 tions of ethylene imine and the zinc salt of 2
may likewise be used as reaction diluents.
limit ourselves solely thereto, but only to the ex- .
tent indicated in the appended claims.
We claim:
1. The addition product of an alkylene imine
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