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Патент USA US2133782

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Patented Oct. 18, 1938
2,133,782
1 iUNlTED STATES PATENT OFFICE
2,133,782
VULCANIZATION OF v RUBBER
Joy G. Lichty, Stow, Ohio, assignor to Wingfoot
Corporation, Wilmington, Del., a corporation of
Delaware
No Drawing. Application June 30, 1936,
Serial No. 88,210
20 Claims.
This invention relates to the vulcanization of
rubber. More particularly it relates to the vul
canization of rubber in the presence of acceler-‘
ators which are the reaction products of mercap
; toaryl thiazoles and alpha chloracyl chlorides.
The objects of the invention include the provi
sion of a new class of vulcanization accelerators,
the vulcanization of rubber in the presence of
such new accelerators, and the obtainment .of
.
j
(CI. 18-53)‘
thiazole, 1-mercapto-4-nitrobenzothiazole, etc.
and the similar 1-mercaptonapthathiazoles. Pre
ferred are the l-mercapto aromatic thiazoles of
the benzene and naphthalene series, and, of those,
l-mercaptobenzothiazole.
Any of these may be reacted with chloracyl
chlorides conforming to the structural formula
previously given. Following are the structural
formulae of some speci?c representative com
10. rubber products by said vulcanization.
Other
objects and advantages will appear as the descrip
tion proceeds.
‘
10
_
Itis known‘that mercaptothiazoles and certain
derivatives of mercaptothiazoles are vulcanization
accelerators.‘ ‘These are widely used in the art.
'15
By the present invention, it has been discovered
that valuable accelerators are obtained when
mercaptoaryl thiazoles, preferably in the form of
anhydrous alkaline salts, are reacted with com
go
pounds having the formula
Alpha chlor beta chlor butyryl
Alpha-phenyl dichloro acetyl I
c hlorideZ
chloride
’
lie-(inn on“)
20
H 010
25
25
in which X in each case is a halogen atom, Y'is a
halogen atom or hydrogen, and R is an alkyl, aryl,
or aralkyl radical or hydrogen. These alkyl, aryl,
30._
or aralkyl groups may be either substituted or un
substituted.
The process of preparing the accelerators is
butyryl Beta-phenyl-beta-chloro-alpha,
simple although care must be ‘exercised. Thus, Beta methyl-alpha-chloro
.
chloride
7
alpha dichloro propionyl chloride
because of the fact that the alpha halo acyl
halides tend to hydrolyze in the presence of water, ' All ofthe foregoing compounds have one or two
35. the'reaction should be conducted under substan chlorine atoms substituted in the alpha position 35
tially anhydrous conditions. _Also, the reaction and another in the acyl group. These are the
is preferably carried out in a liquid medium, such reactive chlorine atoms. The materials may also
as benzene, which‘ will not react with the alpha containchlorine atoms on the beta or other posi
halo acyl halide under the conditions of the re
. action. Heating is generally desirable although
not always necessary.
Representative of the mercaptoaryl thiazoles,
45
, .
which preferably in the form of anhydrous alka
linesalts, may be used in the practice of the
invention
are
1-mercaptobenzothiazole,
l-mer
capto 5-nitrobenzothiazole, l-mercapto-S-methyl
benzothiazole, l-mercapto 3,5-dimethyl benzo
thiazole, l-mercapto-3-phenyl benzothiazole, 1
merCapt0-5-ethoxy benzothiazole, 1-mercapto-3
. methyl benzothiazole, lé-mercapto-‘l-chlorbenzo
tions. These are'not so reactive'as the alpha
chlorine atoms, and so tend to be inert. However, 40
their presence is not detrimental. The com
pounds listed are merely representative and not
limitative of the invention. Any , other alpha
chlor acyl chloride may be used in the practice
of the invention. Also, chlorine may be replaced
by other halogens, such as bromine. However,
the alpha chlor aliphatic acyl chlorides are pre
ferred,vand of these, the chlor acetyl chlorides
are particularly desirable in the practice of the
invention.
2
2,133,782
The following examples will serve to illustrate
the practice of the invention.
EXAMPLE 1
formula in which they have been found by test to
yield good results.
Parts by weight
Extracted pale crepe _____ __' ____________ __ 100
A suspension of 113.4 grams of anhydrous so
dium benzothiazyl mercaptide in 600 cc. of dry
Zinc
benzene was stirred and maintained at a tem
Stearic acid ___________________________ __
1.5
Accelerator ___________________________ __
0.5
perature of 40° C. or below during the slow addi
tion of a solution of 33.9 grams of chloracetyl
10 chloride in 100 cc. of dry benzene. The resulting
solid was ?ltered off. It was then added to 550 cc.
of benezene, the mixture heated to boiling, and
the solid material remaining ?ltered off while hot.
This benzene extraction was repeated several
15 times after which the various benzene ?ltrates
were consolidated. Evaporation of these ben
oxide ____________________________ __
Sulphur
5
___
3
Representative materials were mixed with rub
ber in accordance with this formula. Samples 10
were cured and tested. ‘Typical results follow.
-
Tensile
Ult. elg.,
Cure in mm. at ° F.
.
kgsJcm,
percent
kMo/dulrgs in
gs‘ cm‘ a _
'
500%
15
700%
zene ?ltrates gave 45.3 grams of an impure red
dye, decomposing over the range of 97—150° C.
The benzene insoluble residue was then washed.
20 with water to remove the sodium salts after which
there were left 60.1 grams of a deep blue benzene
insoluble material decomposing at 205-215° C.
The total yield of organic material was 105.1
Benzene soluble portion of product of Example 1
40/285 ______________________ __
52
920
8
16
60 _________________________ ._
80 _________________________ __
120 ________________________ __
65
80
95
905
880
880
10
12
13
21
26
31
grams.
25
20
Benzene insoluble portion of product of Example 1
Attempts to purify these fractions led mainly
to the conclusion that the product was a com
50
81
95
88
plex mixture. The nature and quantities of the
constituent compounds were indeterminate.
900
915
920
875
8
11
12
13
18
23
27
29
However, there was some evidence to support the
v31) belief that one of the principal compounds pres
ent resulted from the reaction of the sodium ben
zothiazyl mercaptide at both chlorine atoms to
yield a material having the formula
33
0
It is readily seen from these data that there is
little difference in the accelerating properties of
these two portions of the reaction product of‘
chloracetyl chloride and sodium benzothiazyl
mercaptide, although they are distinguishable
materials" as is evidenced by the differences in
solubility," color, and decomposition tempera
ture.
Equally, good results are obtainable by
addingto the previous formula 0.2 part by weight
of diphenyl guanidine. The test data follow.
40
A suspension of 62.3 grams of anhydrous so
dium benzothiazyl mercaptide in 300 cc. of ben
zene was stirred during the slow addition of a
solution of 14.8 grams of dichloroacetyl chloride
~"?l in 100 cc. of dry benzene. The product _was then
45
heated on a steam bath under a re?ux condenser
for one hour. The solid was ?ltered from the
Modulus in
.
'
.
Q11!“ ,m mms.‘ at a F‘
'
'
Ult. elg.
lugs/cm.a at
,
500%
700%
45
Benzene soluble portion of product of Example 1 and diphenz/lquanidine
hot benzene solution. Evaporation of this solu
tion gave 39.6'grams of solid. An additional ex
*‘3 traction in hot chloroform of the solid which
failed to dissolve in the mother liquor gave 12.1
grams more of the crude product, making a total
yield of 51.7 grams.
.
Tensile
kgs./em.z percent’
144
194
204
210
805
755
730
725
18
32
41
43
70
117
174
183
Benzene insoluble pom'on ofproduct of Example 1 and diphenylgnanidine
Other mercaptoaryl thiazoles and other alpha
‘ Y1 chlor acyl chlorides may be substituted for the
55 materials of the examples. The mercapto aryl
40 _________________________ __
60;. ________________________ __
thiazoles are preferably used in the form of the
188
210
s25
740
720
21 7
82
39
s4
144
174
212
715
47
193
55
sodium salts, as in the examples, or as other re
active salts, such as the potassium, calcium, and
‘'1 magnesium salts. The free mercapto aryl
thiazoles also may be used, generally in con
junction with a suitable catalyst.
Other products typical of the invention are the
reaction product of sodium 5-nitro benzothiazyl
'1 mercaptide and alpha chlorbenzyl acetyl chloride,
the reaction product of potassium 5-ethoxy ben
zothiazyl mercaptide and alpha chloropropionyl
The combined use of the products of the inven
tion and diphenylguanidine is shown to yield
excellent cures.
\'
It is to be understood that the invention in
cludes the use of the accelerating reaction prod
ucts as such or separated into components. It
also includes the use of the reaction products by
themselves or in combination with other acceler
ators, particularly, the basic nitrogen-containing
chloride, the reaction product of sodium beta
accelerators, such as di ortho tolyl guanidine,
napthathiazyl mercaptide and .beta-furfuryl
beta-chloro-alpha-chloropropiony1 chloride, the
reaction product of potassum 4-chlor benzothiazyl
p-p’ diamino diphenyl methane, butyl ammo
niumoleate, diphenyl guanidine neutral phthal
chloride,
ate, urea and 2-4 diamino diphenyl amine.
Thus while only the preferred forms of the
etc.
The compounds of the invention may be em
ployed as accelerators in most of the ordinary
rubber formulae. The following is one speci?c
invention have been described in detail, it will
be apparent to those skilled in the art that vari
ous modi?cations may be made therein without
departing from the spirit of the invention or the
mercaptide - andv alpha-chlorobutyryl
05
2,133,782
scope of the appended claims in which it is in
tended to cover by suitable expression all forms
of patentable novelty residing in the invention.
I claim:
1. The reaction product obtainable by reacting
a mixture consisting of a mercaptoaryl thiazole
of the benzene and naphthalene series and an
alpha chloracyl chloride under substantially
anhydrous conditions.
10
2. The reaction product obtainable by react
ing a mixture consisting of a mercapto aryl thia
zole of the benzene and naphthalene series and
a compound having the formula
15
R is selected from the group consisting of alkyl,
aralkyl, and aryl groups, and hydrogen.
11. The process of treating rubber which com
prises vulcanizing it in“ the presence of an ac
celerator which is a reaction product of a mix
ture consisting of anhydrous-sodium benzothiazyl '
mercaptide and an alpha chlor aliphatic 'acyl
chloride.
12. The process of. treating rubber which com
prises vulcanizing it in the presence of an ac
celerator which is a reaction product of a mix
10
ture consisting of an anhydrous alkali metal salt
of a mercapto aryl thiazole of the benzene and
naphthalene series and a compound having the
15
formula
Y
in which X is halogen, Y is selected from the
group consisting of halogens and hydrogen, and
20 R is selected from the group consisting of alkyl,
aralkyl, and aryl groups and hydrogen, the said
reaction being conducted under substantially
anhydrous conditions.
3. The reaction product obtainable by reacting
25 a mixture consisting of a mercapto aryl thiazole
of. the benzene and naphthalene series and an
alpha monochloracyl chloride under substan~
tially anhydrous conditions.
4. The reaction product obtainable by reacting
a mixture consisting of a mercapto aryl thiazole
of the benzene and naphthalene series and an
alpha dichloracyl chloride under substantially
anhydrous conditions.
5. The reaction product obtainable by reacting
35 a mixture consisting of a mercapto benzo thia
zole and chloracetyl chloride under substantially
anhydrous conditions.
6. The reaction product obtainable by reacting
a mixture consisting of a mercaptobenzothiazole
40 and dichloracetyl chloride under substantially
anhydrous conditions.
7. The reaction product of a mixture consist
ing of an anhydrous alkali metal salt of a mer
capto aryl thiazole of the benzene and naphtha
45 lene series and a compound having the formula
x o
50 in which X is halogen, Y is selected from the
_ group consisting of halogens and hydrogen, and
R is selected from the group consisting of. alkyl,
'
8. The reaction product of a mixture consisting
55 of an anhydrous alkali metal salt of a mercapto
aryl thiazole of the benzene and naphthalene
series and an alpha chloracyl chloride.
9. The process of treating rubber which com
prises vulcanizing it in the presence of an ac
60 celerator which is a reaction product of a mix
ture consisting of an anhydrous alkaline salt of
a mercapto aryl thiazole of the benzene and
naphthalene series and an alpha chloracyl
chloride.
13. A rubber product which has been vulcan
ized in the presence of an accelerator which is a 25
reaction product obtainable by reacting a mix
ture consisting of a mercapto aryl thiazole of the
benzene and naphthalene series and an alpha
chlor acyl chloride under substantially anhydrous
conditions.
14. A rubber product which has been vulcan
so
ized in the presence of an accelerator which is a
reaction product of a mixture consisting of an
anhydrous alkaline benzothiazyl mercaptide and
a compound having the formula
35
XO
Y
in which X is halogen, Y is selected from the 40
group consisting of halogens and hydrogen, and
R. is sleoted from the group consisting of alkyl,
aralkyl, and aryl groups, and hydrogen.
’
15. A rubber product which has been vulcan
ized in the presence of. an accelerator which is 45
a reaction product of a mixture consisting of an
thiazole of the benzene and naphthalene series '
it
65
aralkyl, and aryl groups, and hydrogen.
anhydrous alkali metal salt of a mercapto aryl
R- —(“]—X
aralkyl, and aryl groups and hydrogen.
in which X is halogen, Y is selected from the 20
group consisting of halogens and hydrogen and
R is selected from the group consisting of. alkyl,
'
10.v The process of treating rubber which com
prises vulcanizing it in the presence of. an ac
celerator which is a reaction product of a mixture
consisting of an anhydrous mercaptobenzothia
zole and a compound having the formula
and an alpha chloracyl chloride.
16. A rubber product which has been vulcan
reaction product of a mixture consisting of an
anhydrous alkali metal salt of a mercapto aryl
thiazole of the benzene and naphthalene series
and a compound having the formula
55
x o
R_t_t_X
t
in which X is halogen, Y is selected from the
group consisting of halogens and hydrogen and
R is selected from the group consisting of alkyl,
aralkyl and aryl groups, and hydrogen.
17. The process of treating rubber which com
prises vulcanizing it in the presence of an ac 65
celerator which is'the benzene insoluble portion
of the reaction product of a mixture consisting
of anhydrous sodium benzothiazyl mercaptide
and chlor acetyl chloride.
18. The process of treating rubber which com
prises vulcanizing it in the presence of. an ac
70
50
ized in the presence of an accelerator which is a
70
celerator which is the benzene soluble portion
of the reaction product of. a mixture consisting
in which X is halogen, Y is selected from the
75 group consisting of halogens and hydrogen and
of anhydrous sodium benzothiazyl mercaptide
and chlor acetyl chloride.
75
4
1 s;
2,133,782
19. The process of producing aryl thiazyl su1-‘
phide derivatives which comprises reacting under
20.‘ The process of producing benzothiazyl sul
phide derivatives which comprises reacting under
substantially anhydrous conditions and in a
liquid medium a mixture consisting of an alkali
substantially anhydrous conditions and in a
medium of benzene a mixture consisting of. sodi
um benzothiazyl mercaptide and a chlor acetyl
chloride.
JOY G. LICH‘I'Y.
['1 metal salt of a l-mercapto aryl thiazole of the
benzene and naphthalene series with an alpha
chlor acyl chloride.
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