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Патент USA US2409110

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Patented Oct. 8, 1946
2,409,109
UNlTED STATES PATENT OFFICE
2,409,109
DIARYL GUANIDINE ADDITION PRODUCTS
Arnold Rogers Davis, Riverside, Conn., assignor
to American Cyanamid Company, New York,
'N. Y., a corporation of Maine
No Drawing. Application August 7, 1944,
Serial No. 548,497
‘
(Cl. 260—306.6)
5 Claims.
1
.
.
.
2
'.
These new products are variously useful but, in
particular, are adapted for use in vulcanization
of rubber, both natural and synthetic. Both the
diarylguanidines and mercaptans and dithiocar
bamic acids are known. These have been previ
the reaction by gentle heating as on a steam
bath. Products of the reaction may be either
amorphous or crystalline, many of- them appear
ing as clear resins and others as clear white crys
tals. Whichever the form in which the product
is obtained it has a ?xed analysis, and in the case
of the crystalline forms, a de?nite melting point,
indicating that a true chemical compound is
formed by the reaction and not simply a complex
mixture.
The invention will be more fully illustrated in
ously used in vulcanization, for example, the’
diarylguam'dines and the zinc salt of mercapto
conjunction with the following examples which
are intended to be illustrative only and not by
benzothiazole, as well as the dithiocarbamates
way of limitation. All parts are by weight unless
This invention relates to a group of new chem
ical products. More particularly, the invention
relates to a series of chemical compounds which
constitute addition products of a diarylguanidine
and a zinc salt of a mercaptan or a dithiocar
bamic acid.
otherwise noted. In these examples the follow
have been used in conjunction with each other to
ing abbreviations are used for the sake of sim
obtain results which could not'be obtained using
pli?cation:
these agents alone. The present group of new
D. P. G.-diphenyl guanidine
chemical combines both types of agent into a sin
D. O. T. G.-—di-o-toly1 guanidine
gle compound, having the advantage that a plu
rality of agents need not be used by the industry 2,0 D. X. G.--dixylyl guanidine '
M. B. 'I'.—mercaptobenzothiazole
to obtain the desired results; The present appli
D. T. C.—dithiocarbamic acid
cation relates to the new products, per se, vul
canization processes using the same being set
forth in my copending application for United
States Letters Patent, Serial No. 548,498, ?led of 25
even date.
EXAMPLE 1
_
(D. P. G.)zZn(M. B. T.) 2
199 parts of the zinc salt of mercaptobenzo
thiazole and 211 parts of diphenyl guanidine were
heated together with stirring until they fused at
The new compounds of the present invention
are most simply described as reaction products
which may be designated by the formula
about 110“ C. A clear resin formed in a few min
AxZn(B)2. A represents such diaryl guanidines 30 utes. The fusion product was held at l00-110°
as diphenyl guanidine, ditolyl guanidines, par
C. for about 15 minutes after which the melt was
ticularly the diorthotolyl guanidine, the dixylyl
cooled, crushed, ground and remelted at about
guanidines, dinaphthyl guanidine, and the like.
In the present invention :1: represents the integers
1 and 2. The group designated as B may be quite 35
widely varied since Zn(B)2 represents salts of
both marcaptans and dithiocarbamic acids. In
100° C. A clear resin was formed.
EXAMPLE 2
/C3H1
(D. P. G.)1Zn(SSCN\ )
this group are such compounds as the zinc salts
C5H5
of mercaptobenzothiazole, the dialkyl dithiocar
bamic acids such as the dimethyl, diethyl, dibutyl 40 435 parts of zinc N,N-n-propyl, phenyl dithio
and 'bis-alkoxyalkyl; the alkyl, aryl dithiocar-'
carbamate and 211 parts of diphenyl guanidine
bamic acids such as the'N,N-propyl, phenyl and
were fused together and held at 95-l00° C, for
N,N-butyl, phenyl, dithiocarbamic acids and the
about 15 minutes. A clear liquid form which, on
like.
i
A
cooling. gave a clear resin.
'
The proportions in which the diaryl guanidine
45
EXAMPLE 3
and the zinc salt are combined may be quite
widely varied. In general, however, it has been
found preferable to use from'one to two mol parts
of the diaryl guanidine with one mol part of the
zinc salt, The products may be readily produced 50
by heating the reactants to the fusion point and, ‘ ‘
continuing the‘ heating until reaction is complete.
Alternatively’, the reacti'on'may be carried‘ out by
suspending ‘or dissolving diaryl guanidine in a
volatile solvent such as benzene and carrying out
..
(D. P. G.) lZll<SSON
The process of Example 2 ‘was repeated, using
513 parts of zinc N,N-n-butyl, phenyl dithiocar
bamate and 211 parts of diphenylguanidine. As
in Example 2,. a clear liquid was formed which
455
give a clear ?lm on cooling.
'
' ' ‘
I
‘21469, 10s .
4
3
Optically, the product shows’crystals di?ering'
EXAMPLE 4
from either di-o-tolyl guanidine or zinc merc'ap- '
(D. P. G.)Zn(M. B. T..)2'
The procedure of Example 1 was repeated,
using 199 parts of the zinc mercaptobenz-othiazole
tobenzothiazole.
EXAMPLE 11
47.8 parts of di-o-tolyl guanidine were suspend
and 106 parts, diphenylguanidine. The mass
ed in 500'parts of ,benzol and 39.8 parts of zinc
fused at 125-130‘? C. and after being cooled,
mercaptobenzothiazole added thereto. Both ma
. crushed, and ground, melted at about 130° C.
terials dissolved on'heating to about ‘YB-80° C.,
The product was a light brownish-yellow resin.
the temperature being held at this point until
10. about one-half the benzol was evaporated. On
EXAMPLE 5
' standing for about one hour,’ crystals formed and
the‘ mass solidi?ed-1 About 250 parts of ben'zol
were added to dissolve the crystals, the solution
"was ?ltered and cooled, crystals separated out,
513 parts of zinc butylphenyldithiocarbamate .. »washed with benzol and dried in air for about 48
and 211 parts of diphenylguanidine were fused v ‘ hours.‘ ‘The product was ahomogeneous crystal
together for about 15 minutes at 95° C. A sub-r _' line mass melting at 152'-153° C. and having a
~ nitrogen content of 12.30% and a sulfur content
stantially water-white resin was formed. '
EXAMPLE 6
of 13.81%.
20
'
C2135
.
~
~
'.EXAMPLE 1.2
_
_~The same lamountsof material used in EXain-V
/
\czHs
2
The procedure of Example 5 was repeated using
107 parts of dixylylguanidine and '7 3 parts of zinc
diethyldithiocarbamate.
1
ple 11 ‘were fused together at 170° C. and heated"
at 153-155‘? Cgu-ntil the melt was clear. A glassy
amorphous product-was obtained.
25
7 .
After about one-half
EXAMPLE 13
~
Exam-ch11 was repeated using 51.3. parts of
hour’s heating at 100-105° C. a clear, resinous
zinc N-propyl. nhenyl dithiocarbajmate and 422
product was obtained.
' parts of diphenyl guanidine...‘ After .30 minutes
30 of heating, the'solution allowed crystals of the
u).
EXAMPLE '7
product to form when cooled.
;
,,
' .
EXAMPLE 14 _
Example 11 was repeated using 39.8‘partsof ,lzinc Q
The procedure in Example 6 was repeated using 3.5 mercaptobenzothiaz‘ole and 147.8 parts of. di-'o:-,t_ol_e
yl guanidine 500 ‘parts of benzol. A cleanse
half the quantity of zinc diethyldithiocarbamate.
lution formed‘v after aboutvone-ha-lf hour" at '70‘:
A similar appear resin vwas obtained. .
C. 7, Heating was continued for one hour, ‘followed,
by ?ltrationg-l» On cooling, no crystals V'for/m d.
About one-half the solvent was then evaporated. ,
EXAMPLE 8
40
The crystals forrnegl afterevaporating part ofthe
solvent were redissolved inr-benzol'an'd recrystal-lv
lized. The resultant crystals ‘formed were washed
twiceinbenzol and ‘dried at 100° C. for’about'
534 parts of dixylyl guanidine were added to a
solution of 362 parts of zinc diethyldithiocar
bamatein benzene at 30° C. The temperature
Was raised to 75-78” C. and held for about 40
minutes after which the solution was filtered,
the ?lter washed with hot benzene and the wash
ings added to the original ?ltrate. The ?ltrate
was rapidly evaporated to about ‘one quarter its
original volume and then allowed to stand in air
one hour. The crystalline product had a melting
point of 15,5—157° C; and the following analysis: ‘
"
(D. P. G.)Z11(SSCN\
)
C2H5OG3H7 2
60
119 parts of.zinc mercaptobenzctmhiazole~ and
143 parts of di-o-tolyl guanidine were fused to
gether at 125.‘? 9, to give, a clear melt which 'was
cooled, crushed and ground and again-heated at,
125° C- for about 15 mmlites. elite: which the fur‘
sion product was allowed to stand overnight.
‘.
'
~
'EXAMPLE15V'.1'N,rT..
A portion of ‘zinc mcrcaptobenzothiazolev was’
the mass was c00led.;er0und and; r@m§1ted;1;h¢
temperature beinecheldat 1.57:?‘ qguntilreec?en
clarity of the melt; T
211 parts of diphenyl guanidine, for a suficient .
time to form a clear liquid. ‘ On cooling 2. thick
EXAMPLE10
‘
appeared tube: oinp16te,"a$ evideneedjhy lthel
bamate were fused together at about 100° C. with
talline growth.
7.44
Washed inyhexane. benzol and. acetone “1193
parts of washed salt was fused with‘ 143.5 parts of
di-o-tolyl euanidine at 1.25%‘)? C, .,,Aft§1'.fll5i<m
297 parts of zinc bis-ethoxypropyldithiocar
light colored paste was formed indicating crys
7.26
eating that auniform product was'obtained.‘
EXAMPLE 9
/c'2H5ooaH1
14.60
%'___.____v______ __ 7.1-1. _____ __ 14.40
A second bath. of crystals recovered from the
mother liquor had the same melting point ‘indie
55
1
12.78
s,
50 Zn, a’
(0 ---- --V-_--_---' _____________ -__"
at room temperature. No crystals appeared
even after long standing. The product is a soft
resin.
N,',%'___V _____ __'_____' _______ __.____ 12.74
1
65
.
.
-
V
EXAMPLE.
1.6
.
,
wléaniéa?ée '11} bitty-l‘ rubzlii ‘ r1; P; 2.‘:
'The product of Example-‘3 "(DZ 1’:
(NZN
C.) 2 was, rfn'ade intof-t'he fol
lowing’ composition bywinilli“ :' the comp hents
butyl, phenyl" Di
0 togetherz" ’
3
~»
‘Butyl B‘ (containsisa, .z'rlo‘,i1.5%' gm
Stearioaci?
j
Pelletexr black. "
75 Accelerator '
~
“
'
f __
2,409, 105
.
6
5
After curing for 60 minutes at 153° C. the prod
present invention are prepared by fusion or by
uct was found to be a Shore Hardness of 44.
EXAMPLE 17
the solvent process, the compositions shown in
the following table were prepared and tested. It
was made up into the following composition:
G. R.-S ______________________ __ 100
will be noted that substantially equivalent results
Vulcanization of Buna S
5 were obtained.
Compounds
The same accelerator produced in Example v3
Buna S_
100
5
Zinc oxide ____________________ __
5
5
5
10 E. P. C. black _________________ __
50
50
Sulfur _______________________ __.
2
2
Coal tar softener _____________________ __
Zinc oxide
E. P. C. black
5
50
Sulfur ______
Above accelerator_____' ________________ __
2
0.65
14) ________________________ __
Modulus
minutes
°C.
15
30
60
141
141
141
Tensile
15) _______________________ __
490
985
1, 295
61
59
Mod. at 300%________________ 1,150
Shore hardness (30") _______ __
1,100
Tensile ____________________ __ 3,050
2° Elongation % ______________ __
580
2,950
600
elong.
1,945
3, 090
2, 750
0.90
Cured 55 minutes at 141° C.
Per cent
@ 300% strength
0.90
(D. O. T. G.)2Zn (M. B. T02 (Ex.
15
Temp"
5
(D. O. T. G.)2Zn(M. B. T.)2 (Ex.
C1116
Time’
100
Bardol (coal tar softener) _____ __
710
605
490
Set at break, % _____________ .._
26
26
280° F ___________________ __
.168
.174
DeMattra out growth rate
mils./kc__
Effect of varying proportions of diaryl guanidine 25
33
27
Torsional
hysteresis
“K”
at
EXAMPLE 18
0n vulcanization
I claim:
1. A reaction product of one to two mols of a
In order to show the distinction between the
use of diaryl guanidine in the ratio of l and 2
diaryl-guanidine and one mol of a zinc salt hav
parts of diaryl guanidine per part of zinc salt, 30 ing the formula Zn(X)z in which X represents a
member of the group consisting of the
the following compositions were prepared and
tested and the results shown in the table were ob
tained.
N
’
_SC//
\S
Compounds
G. R.-S _____________________ __ 100
Bardol (coal tar softener) ____ __
5
Zinc oxide __________________ __
5
100
5
5
E. P. C. black__________________
50
50
Sulfur _____________________ _..
2
2
(D. P. G.)zZn(M. B. T02 ______ __
35
40
.89
.90—
60' cure at 141° 0.
60
61
Mod. at 300% ______________ __ 1,070
755
Tensile ____________________ __ 2,610
Elongation ________________ __
535
2,285
590
Torsional
hysteresis
“K”
at
280° F ____________________ __
.180
alkyl
;
phenyl
ethoxyalkyl
(From Example 4)
Shore hardness _____________ __
/alkyl
; —SSCN
and
(From Example 1)
D. P. G.Zn(M. B. T02 _______ __
/alkyl
; -—SSCN
.184
--SSCN
ethoxyalkyl
radicals.
2. A reaction product of one to two mols of a
diaryl-guanidine and one mol of a zinc mercap
45 tobenzothiazole.
3. A reaction product of one to two mols of di
phenylguanidine and one mol of zinc mercapto
benzothiazole.
4. A reaction product of one to two mols of di
5 0 o-tolyl guanidine and one mol of zinc mercapto
benzothiazole.
5. A reaction product of one to two mols of
Comparison of solvent as. fusion products
dixylyl guanidine and one mol of zinc mercap
In order to show that substantially the same 55 tobenzothiazole.
ARNOLD ROGERS DAVIS.
results are obtained whether the products of the
EXAMPLE 19
/
///
Certi?cate of Correction
Patent No. 2,409,109.
October 8, 1946.
ARNOLD ROGERS DAVIS
It is hereby certi?ed that error appears in the printed speci?cation of the above
numbered patent requiring correction as follows: Column 4, line 59, Example 15, for
“125-104° C.” read 125-140" 0.; and that the said Letters Patent should be read with
this correction therein that the same may conform to the record of the case in the
Patent O?ice.
Signed and sealed this 15th day of July, A. D. 1947.
'
[am]
LESLIE FRAZER,
First Assistant C’ommissioner of Patents.
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