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Патент USA US2110834

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2,i10,834
Patented Mar. 8, 1938
UNITED STATES PATENT osFi
2,110,834
ACCELERATION OF VULCANIZATION OF
RUBBER
Ludwig Orthner, Leverkusen-on-the-Rhine, and
Cologne-Mulheim-on-the
Ewald Zaucker,
Rhine, Germany, assignors to I. G. Farbenin~
dustrie Aktiengesellschaft, Frankfort-on-the
Main, Germany
No Drawing. Original application June 23,
1931, Serial No. 546,417. Divided and this ap
plication July 1, 1932, Serial No. 620,527. In
‘Germany June 28, 1930
1 Claim.
The present invention relates to a process of
vulcanizing rubber and to the vulcanizates ob
tainable by said process.
Mercapto arylene thiazoles have already been
suggested for accelerating vulcanization. This
class of substances, however, possesses the disad
vantage of an unfavorable critical temperature,
that is to say, the use; thereof involves the
danger of a premature commencement of the
10 vulcanization.
In accordance withthe present invention nat
ural rubber or arti?cial rubber-like masses ob
tainable, for example, by polymerizing butadiene
(CI. 18-53)
chloroformic acid isopropylester:
Cl.CO.OCI-I(CH3) z;
chloroformic acid butylester:
C1.C'O.OC4H9 ;
C1.C().OCH2.C'H2C1;
chloroiormic acid cyclohexylester:
Cl.CO.CeH11;
or another homologue or an analogue of buta
benzoylchloride:
diene, are vulcanized with the addition of vul
canization accelerators possessing considerably
more favorable critical temperatures, said new
para-nitrobenzoylchloride:
vulcanization accelerators having the probable
general formu1a:—
para-chlorobenzoylch1oride :
Cl-—CO.CsI-I4Cl;
20
C1—~CO.CsI-I5;
C1.CO.C6H4NO2;
2.4-dichlorobenzoylchloride :
Cl.CO.CeI-I3Cl2;
N/
para-methoxybenzoylchloride :
C1.CO.C6H4(OCH3) ;
\y
wherein R. stands for a benzene or naphthalene
2-chloro-5-nitrobenzoylchloride:
nucleus, which may be substituted by monovalent
Cl
substituents, for example, by alkyl, alkoxy, halo
gen or a nitro group, a: stands for a sulfur or
oxygen atom, and y stands for aryl, such as
phenyl or substituted phenyl, or an alkoxy group.
These new accelerators are obtainable by caus
30
ing an about molecular quantity of a compound
‘ of the probable general formula:
01.00.0613}
N02
nitro~para-toluylic acid chloride:
NO:
(11.00.0511;
CH3
J;
para—tolyl-2-benzoylchloride:
Eel-O
35
C1.CO.C6H4.C6H4.CH3 ;
y
wherein Hal stands for a halogen atom, :1: stands
for an oxygen or sulfur atom, and 1/ stands for a
halogen atom, aryl or alkoxy to react with at
least
an about molecular quantity of a c-mer~
4-0
capto arylenethiazole, as is more fully described
in the annexed examples.
‘
>
As suitable compounds of the general formula
45
Hal-O
y
example:-—
phosgene, chloroformic acid methylester:
C1—-CO—OCI-I3;
chloroformic acid ethylester:
C1.CO.OC2H5§
chloroformic acid propylester:
55
chlorobenzoyl-2~benzoylchloride:
Cl.CO.CsH4.CO.CsI-I4.Cl;
The new accelerators are generally colorless
to yellowish crystalline substances, insoluble in
water, soluble in the usual organic solvents, and
are particularly valuable in view of their favorable
critical temperatures.
For vulcanization purposes the new vulcaniza
tion accelerators are incorporated within the 45
rubber (which term is intended to include nat
¢Z
‘ ural rubber as well as arti?cial rubber-like masses,
coming into consideration for the purpose of the
invention, there may be mentioned by way of
-50
CI
chloroformic acid amylester:
C1.C0.0C5H11;
chloroformic acid benzylester:
C1.C0.0CH2.C6H5 ;
chloroformic acid beta- chloroethylester:
,
derived, for example, from, butadiene, isoprene,
dimethylbutadiene or another homologue or
analogue of butadiene) in any desired manner,
for example, by rolling or kneading. Obviously,
a vulcanizing agent, such as sulfur, agents being
able to split off sulfur, selenium etc. is likewise
added, and if desired, other ingredients known to
favorable in?uence rubber-vulcanization proc 55
2
2,110,834
esses or the properties of the vulcanizates ob
tainable may be admixed to the vulcanization
separates directly in the reaction; after washing
with water it shows the melting point of 276° C.
mixture. The latter is then vulcanized in the
usual manner by heating it to a temperature suffi
cient to perform vulcanization, for example, to
Example 3
The condensation product from ,u-mercapto
benzothiazole (sodium salt) and chloroformic
a temperature between about 100-170° C.
Representatives of this new class of accelera
tors, which possess too low a velocity on hot vul
canization, can be adjusted to give more favor
acid methylester (I in the table) was tested as
accelerator in the following mixture:10
10 able times of heating by combination with stearic
Parts by weight
acid and/or with appropriate accelerators of
15
classes other than that of the present invention
Crepe _______________________________ __ 100
especially basic accelerators while preserving a
Zinc oxide _________ __‘ ________________ __
5
satisfactory critical temperature.
su’lfur _________________ __ ____________ __
3
The following examples will illustrate the invention without, however, restricting it thereto :+~
stearic acid _________________________ __
Accelerator ___________________________ __
1_5
L03
Example 1
the condensation product from ,u-mercapto
benzothiazole (sodium salt) and chloroformic
To a solution of 100 grams of wmercapto
benzothiazole and 24 grams of sodium hydroxide
in 200 cos. of methyl alcohol, 65 grams of chloro
formic acid ethylester (I) or 56,5 grams of
acid ethylester (II in the table) was tested in the 20
following mixture:
chloroformic acid methylester (II) are dropped,
30
Parts by weight
the reaction mixture is boiled for 5 minutes and
poured on to ice. After recrystallization from
petrolether the condensation product obtained
with the ethylester (I) has the melting point of
C'fepe -------------------------------- -- 100
Zinc oxide ___________________________ __
5
Sulfur _______________________________ __
3
Stearic acid _________________________ __
1.8
66° 0., the condensation product obtained with
Accelerator __________________ _.'_ ______ __
NJ Si
1.15
the methylester (II) has the melting point of
56° C. The reaction proceeds according to the
the condensation product from n-mercapto
following equation:
benzothiazole (sodium salt) andphosgene (III
35
Example 2
in the table) was tested in the following mix
ture:—
Into a solution of 100 grams of n-mercapto
benzothiazole and 24 grams of sodium hydroxide
Crepe
in 200 cos. of acetone, 84 grams of benzoylchloride
Zinc (gig;""""""""""""""""""" "
5
sulfur
3
45 are dropped in slowly.
On diluting the reaction
'40
Parts by wags“
“““““““““““““““““““““““ "
mixture with water the reaction product of the
stearig'aai: -------------------- "
1.5
formula
Accelerator ___________________________ --
0-3
the condensation products from ,p-mercapto
benzothiazole (sodium salt) and benzoylchloride
and having a melting point of 130° C. is precipi~
tated
When substituting the 8(1 grams of benzoyl-
Parts by weight I
C_rePe--_ ------------------------------ —- 100
‘
chloride
Zmc oxldea ------------------- -~* ----- n
5
sulfu.r--"f --------- *- """""""""" "
3
by
111
grams
of
para-nitrobenzoyl-
chloride, the compound of the formula
N
/ \ C 8 CO
/ ' '
1.5
Accelerator ___________________________ __
1.0
.
The following
values were obtained
_NO
'
Steanc acid __________________________ __
‘
A=tensile strength in kg. per sq. cm.
\s
B=stretch in percent.
65
Heating
,
I
II
III
IV
V
Press.
Minutes
7
ab.
A
B
A
B
A
B
A
B
A
B
atm
70
75
in
(IV in the table) and para-nitrobenzoylchloride
(V in the table) were tested in the following mix
ture:-—
30
0.5
20
2.0
105
1015
0a
1000
____ _.
00
2.0
____ _.
150
933
100
91s
.... ..
15
3. 0
. . _ . ._
102
887
35
3. 0 ______________________ _.
133
852
__ _ _ _.
43s
____ __
5n
________________________________ -.
Not tested
........ _
Nottestad
115
________ ._
004
1118
139
868
60
2,110,884
With the mixture:
Parts by weight
Crepe ________________________________ __ 100
Zinc oxide ____________________________ __
-5
Sulfur ________________________________ __
3
Stearic
10
acid __________________________ __
1
Diphenylguanidine ____________________ __
0.2
Accelerator ___________________________ __
0.8
II
Minutes
Pressahatm.
a0
10
20
60
0.5
3.0
3.0
3.0
This is a division of our co-pending applica
tion Serial No. 546,417, ?led June 23, 1931.
We claim:—
The process of treating rubber which comprises
vulcanizing a rubber mix to which has been added
diphenylguanidine and a product obtainable by
reacting a Z-mercaptobenzothiazole with ethyl
chloroformate.
LU'DWIG ORTHNER.
EWALD ZAUCKER.
the following values were obtained:
Heating
3
IV
A
B
A
B
19
159
102
153
1130
940
842
856
141
168
159
940
870
864
10
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