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Патент USA US2407183

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2,407,133
Patented Sept. 3, 1946
UNITED STATES PATENT OFFICE
RUBBER COMPOSITION
Frank J. Soday, Swarthmore, Pa., assignor to The
i
United Gas Improvement Company, a corpora
tion of Pennsylvania
No Drawing. Application October 17, 1942,
_ Serial No. 462,411
17 Claims.
1
(Cl. 260-36)
2
.
This invention relates to‘ new compositions of
ylethyl alcoholareunusually Well adapted for use
matter comprising natural and/or synthetic rub
as softening agents for natural and/or synthetic '
ber and one or more esters of alkyl phenylethyl
alcohol.
rubber.
Particularly desirable results are ob
tained when such esters are incorporated in syn
More particularly, this invention pertains to
thetic rubber compositions.
rubber compositions comprising a mixture of one
or‘more natural and/ or synthetic rubbers or elas
tomers, and one or‘ more esters of alkyl phenyl
ethyl alcohols, either alone or in combination
‘
The excellent results obtained when esters of
the type described herein‘ are used as plasticizing
and/0r softening agents for natural and/ or syn
thetic rubber are largely due to the pronounced
solubility characteristics of such esters, and their
excellent compatibility with natural and/or syn
with other softening and/ or plasticizing agents.
An object of the invention is to provide’ natural
and/or synthetic rubber compositions suitable for
thetic rubbers and elastomers. This enables each
use as tire or tube stocks; for molding and‘ ex~
mill to operate at maximum.throughput, with a
truding purposes, for the fabrication of‘ printers’
very substantial saving in power.
rolls, hose, sheets, tubes, gaskets, and other‘ ob
The use of such esters in natural and/or syn
jects and specialties; for the preparation of ad
hesives and cements ; and for coating, impregnat
ing, Waterproo?ng, and other specialized uses;
thetic rubber compounding results in the produc
tion of uniform compounds and ?nished articles
remarkably free from bleeding, blooming, lea?ng,
comprising one or more natural and/ or synthetic
or lamination
rubbers and/ or elastomers and one or more esters 20
In addition the low viscosity characteristics of
of alkyl phenylethyl alcohols with or without the ‘ esters of the type described greatly assists in the
incorporation of other additives selected from a
milling and blending operations, and insures
list comprising sulfur, accelerators, pigments, res
rapid and complete penetration. Uniform stocks
ins, antioxidants, ?ller-s, extenders, and/or other
possessing ‘good calendering and extruding char
plasticizing and/or softening agents, such as 25 acteristics are thus obtained.
stearic acid, pine oil and pine tar. Another ob
Esters of the type‘described'are quite stable and
ject of the invention is the use of esters of alkyl
strongly resistant to thermal decomposition, thus
phenylethyl alcohol in conjunction with other in~
insuring the production of uniform compounds
gredients, such as resins, resinous materials, plas
and ?nished articles free from decomposition
tic product, and dibutyl phthalate, tricresyl phos 30 products. Such compounds, and the ?nished ar
phate, or other high boiling compounds, as sof
ticles prepared therefrom, possess very good aging
tening and/or plasticizing agents for natural
and/or synthetic rubber. Other objects and
advantages of the invention will be apparent to
characteristics.
those familiar withthe art upon an inspection of
the'speci?cation‘ and claims.
I
r
‘
These esters also contain substantially no free
carbon or other extraneous materials. This is of
considerable importance from the standpoint of
the preparation of clean, uniform rubber com
pounds and finished articles and from the stand
V
A considerable number of the softening and/or
plasticizing agents employed in rubber com
point of smooth, trouble-free mill operation.
pounds, and particularly synthetic rubber com
By a choice of the proper compounding ingre
pounds, at the present time suffer from many 40 dients and reaction conditions, rubber composi—
disadvantages, among which is their lack of com
tions possessing almost any desired property may
patibility with natural and, more particularly,
with synthetic‘rubber. This lack of compatibil
be obtained readily. Thus, products ranging
ity renders it extremely difficult to obtain a uni
form mixture or dispersion of the softener in the
hard rubbers may be obtained at will.
from very soft, mildly cured types to the so-called
rubber compound, resulting in the production of
non-uniform- objects or products.‘ In addition,
the use of'such ‘softening agents ‘frequently re
sults in the Iea?ng or‘ lamination of the ‘rubber
compound during the mastication or calendering 50
.
Esters of the type desired maybe regarded as
derivatives of alcohols having the following struc
tural formula
process. Finally, the incorporation of such in-'
compatible softeners in rubber compounds results
in the production of ?nished objects which fre—
quently exhibit bleeding or blooming during use.
I have discovered that the esters of alkyl phen
inwhich one of the group consisting of a and b
55
is an hydroxyl. group, the other ‘being. hydrogen,
2,407,183
3
and
R is an alkyl group, and n denotes that from one
to ?ve alkyl groups may be present in the mole
cule. Alcohols of this type are readily esteri?ed
with acids to give esters which are unusually
CHzCHzOH
/
CHOH.CHa
stable, light in color, and possess exceptionally Ci
desirable odors.
Acids which maybe reacted with alcohols of
the type described include aliphatic monobasic
E!
acids, such as formic, acetic, propionic, butyric, _
E3
beta para tolylethyl alcohol
valeric, caproic, oenanthic, caprylic, pelargonic,
alpha para tolylethyl alcohol
are particularly desirable plasticizing agents for
resinous and plastic materials.
The preparation of alpha tolylethyl alcohol is
capric, and similar acids having a higher num- 7
her of carbon atoms; unsaturated acids, such as
acrylic acid, crotom'c acid, isocrotonic acid, meth
acrylic acid, vinylacetic acid, and the like; halo
genated fatty acids, such as chloroformic acid,
monochloroacetic acid, dichloroacetic acid, alpha
chloropropionic acid, and the like; hydroxy. acids,
such as glycollic acid, lactic acid, alpha-hydroxy
disclosed and claimed in my U. S. Patent 2,293,744,
dated Aug. 25, 1942.
The preparation of the acetic, propionic, butyr
i0, and valeric acid esters of tolylethyl alcohols
are disclosed and claimed in my copending appli
cations, Serial Nos. 313,342, ?led January 11,
butyric acid, and the like; amino acids, such as '
glycine, alanine, valine, leucine, and the like; 20 1940, now Patent 2,316,912, dated April 20, 1943;
and in my U. S. Patent 2,293,775, dated August
dibasic acids, such as oxalic acid, malonic acid,
25, 1942.
methyl malonic acid, succinic acid, maleic acid,
Such esters may be prepared by the reaction
fumaric acid, and the like; aromatic carboxylic
of the desired tolylethyl alcohol, or mixtures of
acids, such as benzoic acid, anthranilic acid, sali
cylic acid, phthalic acid, and the like; and aryl 25 tolylethyl alcohols, or derivatives of tolylethyl
alcohols containing an atom or group capable of
substituted aliphatic acids, such as phenylacetic
being replaced with an ester group correspond
ing to the desired acid or mixture of acids, with
acid, hydrocinnamic acid, phenyl propionic acid,
cinnamic acid, and the like.
~ »
-
the desired acid or anhydride, or salts or deriva
tives thereof.
Such esters may be regarded as having the fol
lowing structural formula
CH-CH:
/ \
\
a
The preparation of such esters may be illus
trated by the preparation of the valeric acid
esters of tolylethyl alcohols.
.
b
Valeric acid occurs in four isomeric forms, as
Rn
follows.
'
CHa.CH2.CH2.CHz.COOH
n-valeric acid
in which one of the group consisting of a and b
is'an —OOC—X group, in which X is hydrogen,
alkyl, alkenyl, substituted alkyl, substituted al
kenyl, aryl, substituted aryl, alkyl-aryl, substi
tuted alkyl-aryl, aryl-alkyl, substituted aryl
alkyl, the
/oH,-<lJH,
CHa\ CH.CHz.COOH
40
CH3
isovaleric acid
CH:.GH2.CH.COOH
Ha
'
active valeric acid.
group, or the
I
~
,
is
CHa.O-COOH
'
(‘m-on,
H3
'
7
(I.
The conversion of tolylethyl derivatives to tol
ylethyl esters of valeric acids may be carried out
in any suitable manner, and with any suitable
esteri?cation
group, the other of said group consisting of a and
b being hydrogen, R. is an alkyl group, and n
denotes that from one to ?ve alkyl groups may
be present in the molecule.
'
Esters of tolylethyl alcohols,
CH2.CH:OH
/
pivalic acid
CHOH.CHa
,
—CH;
—CH:
apparatus.
,
Y
1
Any suitable esteri?cation reagent, such as a
valeric acid, its anhydride, its salt or mixtures
thereof, may be employed as desired.
For example, valeric acid or acid halides there
of may be employed for the conversion of tolyl
ethyl alcohols or metallic derivatives thereof to
valerates, and salts of valeric acid may be used
'for the conversion of tolylethyl halides to val
65 crates.
, Illustrative of the salts of valeric acid which
beta ortho tolylethyl alcohol‘
/
CHZCHzQH
CH:
beta meta tolylethyl alcohol
alpha ortho tolylethyl alcohol.
/
CHOEGH:
may be employed as esteri?cation reagents may
be mentioned sodium valerate, potassium val
erate, calcium valerate, iron valerate, lead val
70 erate and other salts. These salts may be the
normal valerates, or the isomeric valerates, or
——CH3
alpha meta vtolylethyl alcohol
any desired mixture thereof.
The esteri?cation reaction may be carried out
in the presence of a solvent, such as for exam
ple, benzene, if desired. '
2,407,188
5
6
Any suitable reaction temperature may be: ‘em
ployed, suchas: for‘ example,.the boiling pointed
tion. containing the desired proportion: of. the iso
meric:
Also: a‘ forms
mixture
of:oftolylethyl
‘valeric; acids
esters.
ororvalerie
.anhydrides", or
7
,
The esteri?cation reaction. may be carried out
derivatives. thereot, may be employed in?ore
at atmospheric, subatmospheric, or superatmos U! going processes.
pheric pressures, as desired.
When mixtures: oi isomeric forms. of. tolylethyl
Suitable esteri?cation catalysts, such as, for
esters: of Valerie acid are. obtained, they may it
example, sulfuric acid, phosphoric acid or anhy
desired. be separated into fractions‘: containing the
drous hydrogen chloride, may be ‘advantageously
individual‘ isomers by anysuitable. method, such
the solution.
employed in certain of the reactions. particularly 10.
in the conversion of tolylethyl alcohols to esters
of valeric acids.
The use of a system whereby any water formed
by the esteri?cation reaction can be continu
as for‘ instance. by fractionation.
lowing examples'are given?
be found advantageous: from the standpoint of
tolylethyl chloride:
time
,
>
‘
One suitable method for effecting the esteri?
‘
108 gram (0.7 mole)v portion 0! alpha, para
the yield of ester secured, as; well as from the.
necessary to complete the. reaction.
8
Example: 1
ously removed‘ from the system will, in‘general, 15v
standpoint. of. the considerablereduction
‘
illustrative of the methods for preparing
various‘ tolylethyl esters. of Valerie. acids, the 1.01.
onorom
20
cation processes of the present invention com
prises re?uxing the derivatives wih esteri?cation
reagents. tor a. period or several hours.
>
For example... salts of. yaleric. acids. may be re~.
?uxed, with tolylethyl halides to produce. the cor
was added with stirring to a mixture of 127 grams
(0.91 mole) of freshly prepared potassium n
valerate in 100 grams of n-valeric acid, the addi
tion being carried out in a 1-liter ?ask ?tted with
responding tolylethyl esters. This: reaction. may.
if. desired... be e?ected in the presence oi; the cor
responding valeric acid.
;/ ~
The tolylethyl esters thus produced may be
suitably separated from the. halogen salts in the
reaction mixture, for example,‘ by ?ltration.
a re?ux condenser. The mixture was heated to
140° C. by means of an oil-bath and maintained
If a valeric acid has been employed in the
esteri?-cation reaction, it may be removed such as
by distillation under reduced’ pressure. Any un
removed acid may then be: neutralized such as 35
with an. alkaline solution.
>
v
The tolylethyl esters obtained'by the processes
at this: temperature with good stirring‘ for a. pe
riod of ?ve hours.
It was allowed to cool‘. and.
then. treated with 10% sodium bicarbonate solu
tion to neutralize the unchanged Valerie. acid
present. The neutral mixture was then extracted
with ether and dried over anhydrous sodium
sulphate.
herein described may be isolated and puri?ed in
‘
After the ether had been. removed. by heating.
For example,_ the reaction mixture may,‘ if‘ de 40 on a hot- water bath. the ester was distilled in.
vacuo, giving 110' grams of alpha,‘ para-tolylethyl
sired, be repeatedly extracted‘ with any suitable
n-valerate. ‘l
_
i
solvent, ‘suchas ether or benzeneyto increase the
This compound had the following structural
yield and purity of." the tolylethyl esters, therein.
formula and physical properties:
The extracts maythen be‘combined and. dried
over a drying agent such‘as, for example, anhy
any desired‘ manner. '
‘
drous sodium sulfate, after which‘ the, extraction
solvent employed.’ may be removed by ,‘ distilla
tion at atmospheric pressure. The residue may
1 /C5.QIHT
.
oo oicormacni
then befractionally distilled invacuo to obtain a.
puri?ed tolylethyl‘ ester of valericacid.
Mixtures of alpha and beta tolylethyl; deriva
tives, in any proportion, may be employed in the
preparation of mixtures of. alpha and beta tolyl-.
50
‘H:
.
Boiling range=126-127.° at 6 mm. Hg absolute
Density (d 20/4) =0.9697
'
ethyl esters of Valerie‘ acids."
Such mixtures of the alpha and beta forms of 55. Refractive index (n 20/d) =1.48805
para tolylethy1 esters or valeric. acids may be de
The yield was 71.4% of theoretical.
sired in orderto obtain a product‘ possessing a
The compound was a. colorless, somewhat vis
desired boiling range, or desired volatility char
cous liquid with a very pleasant odor.
acteristics, or other desired properties.
Example II
For example, a mixture containing the desired 60a
proportion of each of the isomeric forms of tolylé
A.'solution' ofpotassium n-valerate in‘ n-valeric
ethyl halides may be reacted with a salt of valeric
acid was" made by stirring 210 grams (1.5“ mols)
acid to obtain a tolylethyl ester fraction contain
of the fused salt into 250 grams of the anhydrous
ing the desired proportion of the isomeric forms.
acid heated to 100°‘ C. When a clear‘ syrupy
of tolylethyl esters of the acid. Mixtures con 65. solution was obtained, 199 grams (1 mol) of
taining the desired proportion of alpha. and beta
beta, para-tolylethyl bromide:
tolylethyl halides suitable, for use in my process
may be obtained, for example, by adding‘ a hy
drogen halide to methyl styrene under theprop
er conditions. to give the desired. mixture of iso~~
meric tolylethyl- halides.
.
Similarly, a. mixture of the isomeric forms of
other tolylethyliderivatives, such as for example
the tolylethyl alcohols, in the desired proportions,
may ‘bees‘teri?ed to obtain a tolylethyl ester trac
CH;
was added slowly through the ‘re?ux condenser
2,407,183
8
7
and the temperature was raised gradually to 170°.
Distillation under reduced pressure gave 166
This temperature was maintained for a period
grams of alpha, para-tolylethyl isovalerate:
of 13.hours, during-which time a ?neprecipitate
of potassium bromide separatedfrom the reac
tion mixture.
.
CH.CH;
CH:
‘
'
'
OOC.CH:.C
-
CH2
The mixture was cooled and ?ltered bysuction
to remove the potassium bromide and excess
potassium valerate, and the clear filtrate was
distilled under reduced pressure to remove the
"
Ha
'
major portion of the valeric acid which came over 10 _' This compoundv had the following physical
at a temperature of 50-60“. at 4 mm. pressure ab
properties:
solute. The potassium bromide and excess po
Boiling range=127~132° at ‘7 mm. Hg absolute
tassium valerate were dissolved in cold water and
Density (d 20/4) =Q.9642
extracted twice with ether to recover the small
amount of absorbed ester. This extract was 15 Refractiveindex ('n 20/d) =1.48532
combined with thecrude ester and treated with
10% sodium bicarbonate solution to, neutralize
the residual acid.
The yield was ‘75.5% based on the weight of
alpha, para-tolylethyl chloride used.
It was then extracted with
ether, dried with anhydrous sodium sulphate, and
distilled.
20
Distillation under reduced pressure gave 172
grams of beta, para-tolylethyl n-valerate:
This product was a colorless, somewhat viscous
liquid with an agreeable ester odor.
Example IV
A 210 gram portion (1.5 mols) of potassium
isovalerate was added with stirring to 250 grams
of isovaleric acid and heated to 100° C. until all
25 the salt was dissolved. To this clear, syrupy solu
tion was'added dropwise, with continued stirring,
200 grams (1 mol) of beta, para-tolylethyl bro
mide:
-
-
CH:
/
30
CH .011 B
I
I
' ‘This compound had the following physical
properties;
'
.
7
~
,
Boiling-.range-—§113-116v° at 4 mm. Hg absolute
Density (0! 20/4)=0.9720
,
v
'
35
in 50 minutes after which the temperature was
raised to 165°. The temperature was kept at
This represented a yield conversion of 78.2%,
based; on the amount of beta, para-tolylethyl
163-167“, producing mild re?uxing of the acid,
for aperiod of 14 hours. The reaction mixture
bromide used in the esteri?cation.
' The ester was obtained as a colorless, somewhat
viscous liquid with an agreeable odor. ‘
Hz
'
Refractive index (n 20/d)-__—1.48855
' Example 111
A solution of potassium isovalerate in isovaleric
acid was made by stirring 210 grams (1.5 mols) of
freshly fused potassium isovalerate into 300
grams of the anhydrous acid at a temperature of
was then cooled and ?ltered to‘ remove the po
tassium ‘bromide and excess. potassium 'iso
valerate, and this solid matter was‘ dissolved in
water and extracted with ether to recover any
. absorbed ester. The clear ?ltrate was distilled to
remove‘ most'of the isovaleric acid which came
over at 491-51°at 3 mm.‘Hg absolute. The crude
ester,combinedwith the ether extract, ‘was treat
ed with 110 %, sodium bicarbonate solution to neu
When a clear syrupy solution was ob
tralize the residual acid. It was then extracted
tained, 155 grams (1 mol) of alpha para-tolyl
with ether, dried with anhydrous sodium sulphate
ethyl chloride:
and distilled.
90° C.
/
'
'
‘Distillation under reduced pressure gave 156
CHCLCH:
grams of beta, para-tolylethyl isovalerate:
,
I
)
CHa
‘ omcinoodomoé
'
’
'
OH:
111'
60
was added slowly through the re?ux condenser,
H:
and the temperature was raised gradually to 140°
C. The temperature was .kept at 140-145’ 'for
" This compound had the following physical
five hours with vigorous stirring, during which‘
properties:
‘
time a ?ne precipitate of potassium chloride sep 65
Boiling
range=99—104.5°
at 1 mm. Hg absolute
arated out as a by-product of the reaction. The
Density (d20/4).=0.9645 _
.
.
'
,
mixture was cooled and ?ltered by suction to re
Refractive index (11.20/01) =1.48527
move the potassium chloride and excess potas
sium isovalerate, and the clear ?ltrate was dis
This weight of product represented a yield of
tilled under reduced pressure to remove most of 70 ‘73.4%, based on the weight of beta, para-tolyl
the isovaleric acid. The higher boiling liquid
containing the ester was treated in the cold with
10% sodium bicarbonate solution to neutralize
the residual acid.
It was then extracted with
ether, dried and distilled.
ethyl bromide used in the esteri?cation. ‘
‘The ester was ‘obtained as a colorless, some
whatv viscous liquid with a very sweet odor. '
It .‘will be understood, of course, that tolylethyl
75 esters of Valerie acids may be prepared from
,9‘
2,407,183
10
pure methyl‘ styrene or ‘hydrocarbon fractions
such as light oil fractions containing methyl
styrene by processes which may be conducted
and phenyl-beta-naphthylamine (Neozone D);
reinforcing pigments, such as, for example, car
bon blacks, such as channel black, clay, and blanc
?xe; ?llers and/or diluents, such as, for exam
on a continual, continuous, semi-continuous, or
batch basis. For example, such a, process may
ple, lithopone, barytes, whiting, and asbestine;
other softeners and plasticizing agents such as,
for example, para?in wax, factice, dibutyl phthal
ate, tricresyl phosphate, pine oil, oils, fatty acids,
comprise ?rst converting the methyl styrene into
a tolylethyl derivative containing a substituent
capable of being replaced with an ester group
corresponding to the desired valeric acid, and
thereafter effecting esteri?cation ‘of said deriva
tive.
and synthetic or natural resins or resinous ma
terials.
A preferred embodiment of the invention is the
use of esters of the type described in conjunction
with resins, such as thosederived by the poly
merization of light oil vand/‘0r coal tar fractions
For example, a tolylethyl halide or a mixture
of tolylethyl halides may be, prepared from a
light oil methyl styrene fraction obtained by the
vcontaining coumarone and/orindeneor theresins
derived by the polymerization of the high-boil
distillation of light oil from oil gas and contain
ing meta, para and. ortho methyl styrenes and
these tolylethyl halides may then be .esteri?ed
ing monomeric materialderived from tar by ?ash
distillation and/or solvent extraction processes,
and/or other organic liquids, such as the high
acid.
' Likewise, a mixture of tolylethyl alcohols may 201 boiling aromatic oils derived by the flash distilla
tion and/or solvent extraction of tar, as soften
be prepared from such a methyl styrene frac
ing agents ‘for natural and/or synthetic rubber.
tion, after which the tolylethyl alcohols may be
A preferred embodiment of this invention is the
converted into tolylethyl esters of valeric acid by
to form the desired tolylethyl esters of valeric
use of an‘aromatic oil of the type described in
'
The use of fatty acid ormixed ‘fatty acid'es 25 combination with one or more resinous materials
esteri?cation.
and an ester of the type described as a softener
ters of a mixture ‘of m-, ‘p- and o-tolylethyl also
for natural and/ or ‘synthetic rubber compositions.
hols as a plasticizing agent or agents for natural,
and more particularly synthetic, rubber is a pre
ferred embodiment of this invention.
Examples of the rubber or rubber-like mate
rials with which esters of the type described
herein may be compounded are the various grades
and types of natural rubber and rubber-like ma
A preferred resin for incorporating with the ester
and aromatic oil is the resin obtained by the
polymerization, by thermal, and/or catalytic
methods, of certain high-boiling monomeric ma
terial separated in monomeric form from tar
formed during the production of combustible gas
by processes involving the pyrolytic decomposi
terials, and synthetic rubbers or elastomers, such
as, for example, those ‘obtained by ‘the polymeri
tion of petroleum oil with or without the aidof
catalysts. Such resins may be formed in situ in
zation of one or ‘moreqd-iole?n'es, >or substituents
thereof,--such ias butadiene, isoprene, piperylene,
Z-chlorobuta-dienmand the-like, either :alone or
aromatic oils of the type described herein.
terials such as ole?nes, unsaturated nitriles, acids,
fractions containing indene and/or coumarone.
Other desirable ingredients which may be
blended with an ester'of the type described either
Another desired resin ‘which may be incor
porated in the ester as a softener for natural
in admixture, or in‘lcombination with one or'm‘ore
and/or synthetic rubber‘ isnthe resin derived by
unsaturated‘and/or‘reactive compounds ‘0r ‘ma: 40 the
polymerization of petroleum and/or coal tar
estersgethers, ‘ketones, aldehydes, and/or substit
uents thereof, such ‘as, :for example,‘ styrene,
acrylic nitrile, isobutylene, acrylic ‘esters, and?the
like; Important examples of [synthetic rubbers
41) alone or in combination with one or more resinous
or ‘elastomers :are those ‘obtained by the cop'oly
materials and/or aromatic oils, as a softener for
merization of onevsor more diole?nes with (1’)
dimers of petroleum or coal tar fractions con
natural ‘and/or synthetic rubber include the
acrylic nitrile, ‘(29 styrene lorsubstituents thereof,
taining indene and/or coumarone, dibutyl
phthalate, tricresyl phosphate, and pine oil.
and/ or ‘(3) isobutylene or similar “ole?nes'; These
materials are known in the art under different
‘Reclaimed rubber is also included among the
materials which may be. plasticized with the esters
trade names, such as, for example, Buna, .Buna
S; Buna .N, Perbunan; Chlorop'rene, Neoprene,
herein described, together with natural and/or
Ameripol, Hycar, Buty’ltrubber, and _the like.
synthetic rubber, and with or without other in
The‘ ouantitywof esters of “the type described
herein which :may be incorporated in natural or
synthetic rubbers, or elastom'er-s, may be ‘varied
over very wide limits, depending upon the ‘prop?
gredients.
The ester or esters, and other ingredientamay ‘
be mixed or compounded with the natural rubber
and/or synthetic rubber onmixing or compound
ing rolls or mills, ‘or they may be compounded by
erties wdesired. . Thus, for example, quantities
varying from a few percent, or less, to an amount
any other method known in the art. The rubber
equal to, or greater ‘than, the quantity ofvrub 6%) composition then may be vulcanized, if desired,
her, "or rubber mixture, employed in the‘ l'com
by any of the methods employed for this pur
position, m'aybeused.‘
Q
, ,
posein the art.
In addition to‘esters of the type described ‘here
Examples of rubber compositions containing
in, other ingredients which may be incorporated
esters of the type described herein are as follows:
in natural rubber and/or synthetic ‘rubber com
Example 5
positions “include rvulcanizin-g agents 'and/ or ac
celera‘tors, such as, for example, sulfur or sulfur
Component
containing compounds such‘ as tetramethyl
thiuram disul?de ‘mje'rcaptoa‘rylenethiazoles, such
as mercaptobenzothiazole, benzothiazyl disul?de,
litharge, and dithio carbamates; pigments, such
1322211?’
70
as, for example, magnesium erode, zinc oxide,
and lead oxide; antioxidants, such as, tor-exam
ple phenyl-alpha-naphthylamine (Neozone ,A), 75,
Natural rubber _______________________________________ ._
109
Butyric acid esters of a mixture of 0-, m-, and p-tolyl
ethyl alcohol
Zinc. __.,__ ,
Sulfur ____ ,.
Iercaptobenzothiazole ...... _.
-
10
-
5
2.5
0- 3
2,407,183,
12
Example 6
Component
Example 12
ragga}?!
Pale crepe rubber ____________________________________ __
Zinc oxide ........ __
Parts by 3
Component
weight
100
Butadiene-isobutylene rubber ________________________ . _
45
Sulfur _______________________________ _ _
Butyric acid ester of tolylethyl alcohol _______________ ._
2. 5
Resin obtained from monomeric material boiling above
Resin obtained from monomeric materia
210° C. and isolated from petroleum tar.
Butyric acid esters of a mixture of 0', In
210° C. and isolated from petroleum tar ____________ ..
Carbon black __________________________ _.
Sulfur .
10
Stearic acid _______ __
_ _ _ _ . _ _ .
_ _ . . __
lvlercaptobenzothiazole. . _ I . ._- _
to
»
Phenyl-alpha-naphthylamine.__
Zinc oxide
Example 7
ov-lyernm
to
meal
Eaiample 13
A natural rubber tire tread mix may be com
pounded as follows:
Parts by'
Weight
Component
Parts by
Component
weight
Perbunan ____________________________________________ _ .
Zinc oxide __________ _ _
Smoked sheet rubber ________________________________ _,
Channel black ________ __
H
was
20 Sul
Zinc oxide: __________________________________________ _.
Valerie acid esters of a mixture of 0-, m-, and p-tolyl
ethyl alcohols ______________________________________ _.
Resin obtained from monomeric material boiling above
210° C. and isolated from petroleum tar
Sulfur ____________________ __
_
cNgoriwn
Stearic aci_d__.::::::::::: .... ..
Valerie acid ester of tolylethyl alco
_
Stearic acid
25
Mercaptobenzothiazole ______________________________ -_
Example 8
A synthetic rubber tire tread mix may be com
pounded as follows:
Component
Neoprene ____________________________________________ .1
Parts by
weight
100
Zinc oxide ____________ 1
Mercaptobenzothiazole.
The foregoing compositions may be sheeted
out, shaped and vulcanized, if desired, such as
by the application of a temperature of, say, 140°
C. in a press for a period of,v say; 45 minutes.
Other procedures may, of course, be used if de
30 sired.
Rubber-ester compositions of the type de
scribed, either as such or with the incorporation
of other ingredients such as the resin and/or
aromatic oil derived from monomeric material
35 boiling above 210° C. and isolated from petroleum
tar, may be used for a variety of purposes, such
as for the manufacture of tires; tubes, and other
Channel black ________________ __
Valerie acid ester of tolylethyl al
Phenyl-alpha-naphthylamine_
objects, and as adhesives, coating, impregnating,
and waterproo?ng agents. Such compositions
Sulfur _________________________ . .
40 may or may not be vulcanized prior to, ‘during,
Example 9
or subsequent to the use thereof.
'
' I
While various procedures and formulas have
Component
been particularly described these are of course
subject to considerable variation. Therefore, it
will be understood that the foregoing speci?c ex
amples are given by way of illustration, and that
Buna S ______ __
Plantation crep
Zinc oxide. _ _
Channel blac _
changes,
Age Rite resin
Pine tar _____ _.
Valerie acid ester of phenylethyl alcohol
Stearie acid_
Sulf
50
omissions,
additions,
substitutions
and/or modi?cations might be made within the
scope of the claims without departing from the
spirit of the invention.
’
'
I claim:
1. A new composition of matter comprising an
Example 10
Component
ester of alkyl phenyl ethyl alcohol in which said
Parts
by
weight
alkyl substituent appears on the ring, and rub
55 ber selected from the group consisting of natural
rubber and rubber-like polymers of butadiene,
isoprene, piperylene, and 2-chlorobutadiene.
Butadiene-styrene rubber ____________________________ __
Butyric acid ester of tolylethyl alcohol ______________ 1. '
2. A new composition of matter vcomprising a
vulcanized mixture of an ester of alkyl phenyl
60 ethyl alcohol in which said alkyl substituent ap
pears on the ring and rubber selected from the
group consisting of natural rubber and rubber
Resin obtained from monomeric material boiling above
210° C. and isolated from petroleum tan...‘ ........ .,
Carbon black __________________________ _.
Sulfur _ _ _ _ _ _ _ _ _
v
_ _ _ _ _ . __
ltfercaptobenzothiazole. _ _ . .
Zinc oxide ________________ __
Phenyl-alpha-naphthylamine ________________________ . _
like polymers of butadiene, isoprene, piperylene,
Example 11
and 2-chlorobutadiene.
65
Component
Butadiene-acrylic nitrile rubber ______________________ ..
Valerie acid ester of tolylethyl alcohol ________________ ._
Resin obtained from monomeric material boiling above
210° C. and isolated from petroleum tar
Carbon black
Parts by
'
3. A new composition of matter comprising an
ester of tolyl ethyl alcohol, and rubber selected
from the group consisting of natural rubber and
_ weight
rubber-like polymers of butadiene, isoprene,
piperylene, and 2-chlorobutadiene.
70
4. A new composition of matter comprising a“
vulcanized mixture of an ester of tolyl ethyl alco-1
hol, and rubber selected from the group consist
ing of natural rubber and rubber-like polymers
of butadiene,‘ isoprene, piperylene, and z-chloro-j
Zine oxide __________ _ _
Phenyl-alpha-naphthylamin
75
butadiene,
13
2,407,183
14
5. A new composition of matter comprising at
least one fatty acid ester of tolyl ethyl alcohol,
and rubber selected from the group consisting of
natural rubber and rubber-like polymers of buta
diene, isoprene, piperylene, and >2-chlorobuta4
diene.
6. A new compostion of matter comprising a ‘
vulcanized mixture of at least one fatty acid ester
of tolyl ethyl alcohol, and rubber selected from
12. A new composition of matter comprising a
vulcanizate of a mixture containing butadiene
acrylic nitrile copolymer rubber and an ester of
alkyl ‘phenyl ethyl alcohol in which said alkyl
the group consisting of natural rubber and rub
10 substituent appears on the ring.
ber-like polymers of butadiene, isoprene, piper
ylene,and 2-chlorobutadiene.
i
11. A new composition of matter comprising
the vulcanizate of a mixture which comprises
butadiene-isobutylene copolymer rubber and an
ester of alkyl phenyl ethyl alcohol in which said
alkyl substituent appears on the ring.
13. A new composition of matter comprising a
-
7. A new composition of matter comprising [a
vulcanized mixture of a propionic acid ester of
tolyl ethyl alcohol, and rubber selected from the '
group consisting of natural rubber and rubber;
like polymers of butadiene, isoprene, piperylene, >
and 2-chlorobutadiene.
8. A new composition of matter comprising a
vulcanized mixture of a butyric acid ester of tolyl
ethyl alcohol, and rubber selected from the group
consisting of natural rubber and rubber-like
vulcanized mixture of butadiene-styrene copoly-'
mer rubber, and a fatty acid ester of tolyl ethyl
alcohol.
14. A new composition of matter comprising
vulcanized material selected from the group con‘
sisting of natural rubber and rubber-like poly
mers of butadiene, isoprene, piperylene, and 2
chlorobutadiene, said vulcanized material being
plasticized with a fatty acid ester of tolyl ethyl
alcohol.
15. A new composition of matter comprising a
polymers of butadiene, isoprene, piperylene, and
2-chlorobutadiene.
vulcanized mixture of butadiene-styrene copoly
mer rubber, and propionic acid ester of tolyl ethyl
9. A new composition of matter comprising a 25 alcohol.
vulcanized mixture of a valeric acid ester of tolyl
16. A new composition of matter comprising a
ethyl alcohol, and rubber selected from the group
consisting of natural rubber and rubber-like
polymers of butadiene, isoprene, piperylene, and
2-chlorobutadiene.
10. A new composition of matter comprising
vulcanized mixture of butadiene-isobutylene co
polymer rubber, and butyric acid ester of tolyl‘
ethyl alcohol.
30
copolymer rubber, and valeric acid ester of tolyl
ethyl alcohol;
alkyl phenyl ethyl alcohol in which said alkyl sub
stituent appears on the ring.
17. A new composition of matter comprising a
‘ vulcanized mixture of butadiene-acrylic nitrile
the vulcanizate of a mixture comprising buta
diene-styrene copolymer rubber and an ester of
35
FRANK J. SODAY.
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