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Патент USA US2131245

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Patented Sept. 27, 1938
2,131,245 .
UNITED STATES
,
PATENT OFFICE
2,131,245
VULC'ANIZATION or RUBBER .
Ira' Williams, Woodstown, N. J., and Frank Rea
_ Mayo, Wilmington, Del., assignors to E. I. du
Pont de Nemours & Company, Wilmington,
DeL, a corporation of Delaware
No Drawing. Application August 8, 1935,
5
10
l5
20
Serial No._ 35,238
20 Claims. (Cl. 18-53)
This invention relates to rubber and more par
positions of matter and to advance. the art.
ticularly to accelerators for the vulcanization of Other objects will appear hereinafter.
rubber.
These objects may be accomplished in accord
It is well known that the vulcanization of rub
ance with our invention which comprises incor
her may be accelerated by the addition of ‘various ’ porating into the rubber mix prior to vulcanizamaterials to the rubber mix prior to vulcaniza- ’ tion a small amount of a certain class of quater
tion. A number of materials are available for nary ammonium compounds which produce little
such use. These materials fall roughly under the tendency to premature vulcanization in the mix
following classes:
and are relatively free from a tendency to discolor
(1) Inorganic accelerators such as lime, lith
the rubber or to- giveit a bad odor. This new
arge and caustic soda, or its equivalent such as class of accelerating compounds comprises the
sodium phenolate..
quaternary ammonium compounds in which one
(2) Organic amines such as alkyl amines, valence of the nitrogen is satisfied by an anion
guanidines, aryl amines, quinine and piperidine. and each of the remaining valences is satis?ed by
(3) Aldehyde amine reaction products such as a distinct carbon atom at least three of which
acetaldehyde ammonia, hexamethylene tetra
carbon atoms are aliphatic. Two or three of
mine, formaldehyde aniline and butyraldehyde such carbon atoms may be'members of a group
aniline.
,
'
which form, with the nitrogen, a heterocyclic nu
(4) Derivatives of acids or acid amides such as cleus as in piperidine which is not strictly an all
zinc ethyl xanthate, diethyl ammonium diethyl phatic compound but the carbon atoms of which
dithiocarbamate, lead dithio fuorate, tetra are aliphatic in nature- The fourth carbon atom
methyl thiuram' sul?des, formamide, ureas' and may be aliphatic or aromatic but preferably is
thioureas.
aliphatic. The anion may be any salt forming
(5) Arylene thiazoles such as mercaptoben
anion selected from the group of inorganic acids,
25 zothiazole and its derivatives._
It is well known that different types of rubber
mixes require the use of diiferent types of accel
erating materials having different characteristics.
Also, the type of accelerating material to be
30 chosen depends upon the object made from the
rubber and the use to which it is to be put. Each
of the above classes of accelerators has certain
characteristics which makes it suited to’ particular
types of application and the existence of several
35 classes of accelerator makes it possible to select
a type most useful for the particular purpose.
An object of the present invention is\to pro
vide a new class of accelerating compounds which
40 has new and distinctive characteristics. A fur
ther object is to provide accelerators which pro
duce no discoloration or odor in'the vulcanized
rubber. A still further object is to provide a
method for accelerating the vulcanization of rub
45 her.
Still other objects are to provide new com
5
10
15
20
organic carboxylic acids, phenols, alcohols, thio- 25
phenols and thioalcohols. By the term “alco
hols” as used herein, we mean aliphatic com
pounds of carbon, hydrogen and oxygen derived
from hydrocarbons containing even numbers of
hydrogen atoms by substitution of hydroxyl 30
groups for equal numbers of hydrogen atoms.
By the term “thioalcohols” as used herein, we
means alcohols in which oxygen atoms have been
replaced by sulfur atoms.
The compounds of our invention are, in gen- 35
eral, well known and may be prepared by any of
the various methods described in the literature.
In order to more clearly describe our invention,
the preferred modes of carrying the same into
e?ect and the advantageous results to be obtained 40
thereby, the following example is given:
Example 1
A base stock was prepared consisting of 100
parts by weight of smoked sheet rubber, 25 parts 45
2
2,181,245
of carbon black, 5 parts of zinc oxide, 3 parts or
stearic acid and 3 parts of sulfur. ' To this com
pound 1 part or accelerator was added and the
product is to be employed in the presence oi
moisture, to employ the native ion or an acid
stronger than water for the preparation or the
compound was vulcanized at 227° F. and at 287°
quaternary ammonium compound.
F. after which the physical properties were determined.
While we have disclosed the pregerred em
bodiments of our invention, it will be readily ap
Lbe./ln.l at 500 percent elongation
10
10
Accelerating material
MW 3‘ Min. cure at 257° F.
80
60
20
30
60
2, 300
15
15
Tetra methyl ammonium chloride .......... _-
'l‘etra ethyl ammonium bromide.:-._
Ethyl trimethyl ammonium chlorideBenzyl trimethyl ammonium chloride
Oetyl trimethyl ammonium bromide.
150
250
l, 475
l, 775
75
50
50
150
475
325
l, 375
l, 900
1, 550
l, 625 2, 325
2, 150 2, 675
1, B00 2, 325
..... __
Methyl ethyl piperidinium ch1oride..
_
225
Dimethyl iperidinium iormate ................... ..
Dimethyl enzyl cyclohexyl ammonium chlo
Dti?ghlh
1 clh
l ammon1um chio
t
on c
o
If? y p b y l y triijiih 1
ur
- any
y
p-methgflysgllate
ammo
l, 600
2, 225
425
25
l, 800
2, 100
2, 700
50
l, 575
l, 300
2, 050
Z 525
76 I'm L800 2'3“
25
125
250
nl
um
700
875 l, 175
Dimethyl piperidinium thiocyanate ........ _- Under-cured
l, 125
l, 475
Dimethyl piperidinium hydrosul?de. ....... -_
275
550
2, 275
2, 600
2, 875
Tetra ethy ammonium formats_____________ __
25
175
l, 850
2, 125
2, 550
25
l, 575
l, 775
2, 250
50
l, 600
1, 825
2, 325
25
150
l, 800
2, 125
2, 475
Tetra ethyl ammonium stearate- .
Tetra ethyl ammonium benzoateTetra ethyl ammonium phenolate __________ __
It is evident from the above results that a rather
wide variety 01' physical results are obtainable
and that the activity at low temperatures is not
su?lciently great to cause dimculty in processing
the rubber containing these accelerators.
We have also found, that these accelerators,
when milled into white mixes do not cause discol
oration either during or after vulcanization and
do not produce an unpleasant odor.
It is‘evident that the organic groups attached
to the pentavalent nitrogen may be greatly varied
and that compounds having many combinations
or these organic radicles may be employed.
Some of the organic radicles that are satisfac
tory and may be attached to the pentavalent ni->
45 tro'gen are methyl, ethyl, propyl, isopropyl, N
butyl, isobutyl, amyl, iso-amyl and other straight,
1, 975
parent that many variations and modi?cations 30
may be made therein without departing from the
spirit of our invention. Accordingly, the scope
of our invention is to‘ be limited solely by the
appended claims construed as broadly as is per
missible in view of the prior art.
We claim:
,
1. The method 01' vulcanizing rubber which
comprises incorporating into the rubber mix prior
to vulcanization, a small amount of a quaternary
ammonium compound in which one valence of
the nitrogen is satis?ed by an anion derived
from the group consisting oi inorganic acids,
organic carboxylic acids, phenols, alcohols, thio
phenols and thio alcohols, and each of the re
maining valences is satis?ed by a distinct car 45
bon atom at least three of which are aliphatic.
or branched chain aliphatic groups which may
be substituted with such groups as hydroxyl,
2. The method of vulcanizing rubber which
comprises incorporating into the rubber mix
halogens, amines, sulfhydryl, ether, sul?de, or
prior to vulcanization, a small amount of a
50 other groups.
Also, such organic radicles may
be any of the various aralkyl and heterocyclic
organic radicles such as benzyl, phenylethyl,
quaternary ammonium compound in which one 50
valence of the nitrogen is satis?ed by an anion
derived from the group consisting of inorganic
naphthylmethyl, naphthylethyl, biphenylmethyl,
acids,>organic carboxylic acids, phenols, alco
biphenylethyl, anthracylmethyl, piperidyl, mor
hols, thio phenols and thio alcohols, and each of
the remaining valences is satis?ed by a distinct 55
carbon atom, at least three of the carbon atoms
being aliphatic and not more than two of them
forming part of a heterocyclic nucleus.
3. The method of vulcanizing rubber which
comprises incorporating into the rubber mix
prior to vulcanization, a small amount of a
quaternary ammonium compound in which one
valence of the nitrogen is satis?ed by an anion
derived from the group consisting of inorganic
55 pholyl and the like.
As heretofore indicated, one of the carbon
atoms attached to the pentavalent nitrogens may
be in an aromatic ring. Suitable aromatic rings
are phenyl, tolyl, xylyl, xenyl or other substituted
60 phenyl groups, naphthyl, substituted naphthyl,
anthracyl, substituted anthracyl and higher aro
matic groups.
The anion is also subject to wide variation and
may consist of such negative groups as phenoxy,
65 alkoxy or sul?de which may constitute various
organic groups connected to the nitrogen by
means of sulfur such as thiophenol, thioalcohol
or various organic carboxylic acids such as acetic
acid, chloracetic acid, propionic acid, butyric acid,
70 oxalic acid, palmitic acid, oleic acid, tartaric
acid, maleic acid, phthalic acid, benzoic acid
acids, organic carboxylic acids, phenols, alco
aliphatic carbon atom not more than two 01.’
which form with the nitrogen part of a hetero
cyclic nucleus.
70
4. The method of vulcanizing rubber which
and the like. Or the anion may be inorganic
comprises incorporating into the rubber mix
such as phosphate, nitrate, cyanide, carbamate,
prior to vulcanization, a small amount 01' a
carbonate, bicarbonate, and suli'hydryl radicles.
75 In general, it is desirable, especially when the
65
hols, thio phenols and thio alcohols, and each of
the remaining valences is satis?ed by a distinct
quaternary ammonium compound in which one
valence of the nitrogen is satis?ed by an anion 75
3
2,131,245
derived from the group consisting of inorganic
acids, organic carboxylic acids, phenols, alco
phatic carbon atom not more than two of which
form with the nitrogen part of a heterocyclic
hols, thio phenols and thio alcohols, and each of
nucleus.
the remaining valences is satis?ed by a distinct
aliphatic carbon atom in a separate and distinct
aliphatic group.
11. Rubber having incorporated therein as a
vulcanization accelerator a small amount of a
quaternary ammonium compound in which one
valence of the nitrogen is satis?ed by an anion
5. The method of vulcanizing rubber which
comprises incorporating into the rubber mix
prior to vulcanization, a small amount of a
10 quaternary ammonium compound in which one
valence of the nitrogen is satis?ed by an anion
derived from the group consisting of inorganic
acids, organic carboxylic acids, phenols, alco
derived from the group consisting of inorganic
acids, organic carboxylic acids, phenols, alcohols,
thio phenols and thio alcohols, and each of the 10
remaining valences is satis?ed by a distinct ali
phatic carbon atom in a separate and distinct ali
phatic group.
_
hols, thio phenols and thio alcohols, and each of
15 the remaining valences is satis?ed by a, distinct
carbon atom, at least three of the carbon atoms
being aliphatic and not more than two of them
forming with the nitrogen part of a heterocyclic
nucleus, all of the groups, other than the anion,
12. Rubber having incorporated therein as a
vulcanization accelerator, a small amount of a
quaternary ammonium compound in which one
valence of the nitrogen is satis?ed by an anion
derived from the groupconsisting of inorganic
attached to the nitrogen consisting of carbon
thio phenols and thio alcohols, and each of the
and hydrogen.
'
acids, organic carboxylic acids, phenols, alcohols,
remaining valences is satis?ed by a distinct car- _
6. The method or vulcanizing rubber which
comprises incorporating into the rubber mix
prior to vulcanization, a small amount of a
quaternary ammonium compound in which one
valence of the nitrogen is satis?ed by an anion
derived from the group consisting of inorganic
acids, organic carboxylic acids, phenols, alco
bon atom, at least three of the carbon atoms be
ing aliphatic and not more than two of them
forming with the nitrogen part of a heterocyclic
nucleus, all or the groups, other than the anion,
attached to the nitrogen consisting of carbon and
hydrogen.
.
hols, thio phenols and thio alcohols, and each of
the remaining valences is satis?ed by a distinct
aliphatic carbon atom not more than two of
13. Rubber having incorporated therein as a
vulcanization accelerator, a small amount of a
quaternary ammonium compound in which one
valence of the nitrogen is satis?ed by an anion
which form with the nitrogen part of a hetero
cyclic nucleus, all of the groups, other than the
derived from_ the group consisting of inorganic
anion, attached to the nitrogen consisting of
carbon and hydrogen.
thio phenols and thio alcohols, and each of the
remaining valences is satis?ed by' a distinct ali
"7. The method of vulcanizing rubber which
phatic carbon atom not more than two of which
acids, organic carboxylic acids, phenols, alcohols,
comprises incorporating into the rubber mix prior torm with the nitrogen part of a heterocyclic
to vulcanization, a small amount of a quaternary nucleus, all of the groups, other than the anion,
ammonium compound in which one valence of attached to the nitrogen consisting of carbon and
the nitrogen is satis?ed by an anion derived from hydrogen.
the group consisting of inorganic acids, organic
14. Rubber having incorporated therein as‘ a
carboxylic acids, phenols, alcohols, thio phenols
and thio alcohols, and each of the remaining
valences is satis?ed by a distinct aliphatic car
bon atom in a separate and distinct aliphatic hy
drocarbon
group.
.
a
.
.
'
vulcanization accelerator, a small amount of a
quaternary ammonium compound in which one
valence of the nitrogen issatis?ed by an anion
derived from the group consisting of inorganic
acids, organic carboxylic acids, phenols, alco
8. Rubber having incorporated therein as a
hols, thio phenols and thio alcohols, and each of
the remaining valences is satis?ed by a distinct
' vulcanization accelerator, a small amount of a
quaternary ammonium compound in which one aliphatic carbon atom in a separate and distinct
50 valence of the nitrogen is satis?ed by an anion aliphatic hydrocarbon group.
derived from the group consisting of inorganic
15. The methodof vulcanizing rubber which
acids, organic carboxylic acids, phenols, alcohols,
comprises incorporating into the rubber mix prior '
thio phenols and thio alcohols, and each of the
to vulcanization, a small amount of tetra methyl
ammonium chloride.
16. The method of vulcanizing rubber which
remaining valences is satis?ed by a distinct car
55 bon atom at least three of which are aliphatic.
9. Rubber having incorporated therein as a
vulcanization accelerator, a small amount of a
quaternary ammonium compound in which one
valence of the nitrogen is satis?ed by an anion
60 derived from the group consisting of inorganic
comprises incorporating into the rubber mix prior
to vulcanization, a small amount of tetra ethyl
ammonium formate.
17. The method of vulcanizing rubber which
remaining valences is satis?ed by a distinct car
comprises incorporating into the rubber mix prior
to vulcanization, a small amount of dimethyl pi
peridinium formate.
18. Rubber having incorporated therein as a
bon atom, at least three of the carbon atoms being
vulcanization accelerator a small amount of tetra
acids, organic carboxylic acids, phenols, alcohols,
thio phenols and thio alcohols, and each of the
65 aliphatic and not more than two of them forming methyl ammonium chloride.
65
with the nitrogen part of a heterocyclic nucleus. '
19. Rubber having incorporated therein as a
10. Rubber having incorporated therein as a
vulcanization accelerator, a small amount of a
quaternary ammonium compound in which one
70 valence of the nitrogen is satis?ed by an anion
derived from the group consisting of inorganic
acids, organic carboxylic acids, phenols, alcohols,
thio phenols and thio alcohols and each of the
remaining valences is satis?ed by a distinct ali
vulcanization accelerator a small amount of tetra
ethyl ammonium formate.
20. Rubber having incorporated therein. as a
vulcanization accelerator dimethyl piperidinium 70
formate.
-
IRA WILLIAMS.
FRANK REA MAYO.
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