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Патент USA US2380475

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2,380,475 i
Patented July 31, 19__45 V
dunno STATES PATENT OFFICE,
zssos'zs
._ careers-rs son rm: ennrnon nor-runn
IZA'I'ION. 0F, UNSA'l'UI-A'IID ORGANIC,
oossrormns
_
'
William n. Stewart, Akron. out,‘ adgnorto'l‘he
.
Company, New York, N. Y...a
FGoodrieh
eorporation‘oi New York
I.
No Drawing. Application February
"1am;
Said No. 379,115
sooum. (OI-M3)
'l‘hiainventionrelatestoth'epolymerisationoi
arealiphaticorganieccn
thedmundet-s-s-hunkssebondedbya
unsaturated organic compounds which are< ca
tainingthethiol (-BHLtheaulMe (-8-),01'
pable oi undergoing an addition mlymerimtion to
form high molecular weight linear polymers, more
single valencyto an-alipha?cradical containinl
'
' particularly to the polymerisation 'ot coniuiated
oneor more hydrophilic substituanissuchas car
boxysroims. amino sroumhydmsmunacsr
butadienes'either'_ alone, in mixtures with one 81.1
other or with other polymerimble comonomers
'bonylgroupasulionicacidcrmmlorthelike.
such as‘the vinyl and vinylidene compounds. The
principal object o! the invention'i's to provide a
Examples of such sulfurcontaining
are aliphatic compoimds cuntaininl a thiol link
ization by the me c! which improved Polymers
acid (thioslycollic acid). alpha tbiol pronionic
acid (thiolactic acid), alpha .thiol hutyric acid,
new class of catalysis or accelerators of polymer- 10' !80 and a‘ hydrophilic group such as thiolactlc
maybeobtainedinincreasedyicldandinamuch
shorter interval oi time..
‘ v
> _ I
alpha thiol ieobutyric
monothio ethylene
glycol (beta 'mercapto ethanol). beta thiol ethyl
It is known that addition
may
be accelerated or prom
by the presence of 15 amine (beta amino ethyl mercaptan), cysteine
various substances am '
which are oxygen and
(beta thiol alpha amino nrwionic acid), glutathi
one (glutamyl cysteinyl glyeme) and the like?
aliphatic compounds containing a suiiide linkage
oxide, bensoyl peroxide, and per-salts. vHowever,
—S- and an aliphatic radical containing a .hy-_
with the use oi-such known polymerisation initia
tors, considerable diiliculty is still experienced in 20 drophilic substituent such as thio dished. ethyl
oxygen yielding compounds such as hydrogen per
obtaining high yields oi.’ a desirable polymer in a '
short interval oi time. Particularly in the com
mercial‘ manufacture oi’ polymers by emulsion
j polymerisation,‘ the productlon schedule is he
quently-disrupted by slow reactions and long in_
duction periods beiore the polymerisation starts.
I have ‘now discovered a large number of sub
beta hydroxy ethyl sul?de, 2-3’ diamino diethyl
suliide,_ methyl beta amino ethyl suliide, diethol
gamma methyl thiol butyric acid). sugar mercap
tals such as dextrose ethyl mercavtal' and many
others; and compounds containing a disuliide
linkage, —S—8—, and an alinlntic radical con
taining a hydrophilic group such as dithio dill!
stances which have
termed redo: systems
coilic ‘ acid, beta die acid. cystin'e'
I
because of their property of catalyzing or promot
ing oxidation reduction reactiom, particularly 30 ltbetaqdithio-alnhap'diaminodiiimnlllllc acid) . and
many others.
those occurring in biological processes, which sub
As hereinabove
these sulinr eontaining_ ‘
stances are quite eil'ective in promoting addition
polymerisations and which are vastly superior to ,- compounds are e?e‘ctive in promoting polymeris
any previously described noiymerimt'ion initiators
or accelerators in that the polymerisation is car
_ ried out in], much shorter time, the induction
tions whencombinedwithaheavymetalsalt.
The term heavy ‘metal as
is meant
to include metallicelemmts whichhave a density
period is largely eliminated, lower temperatures
for the polymerization may be employed and con
seouently a higher molecular weight more linear
vpolymer
o
more desirable properties is
>
..
“
'l'hisinvention isconcernedwiththeuseinad
dition polymerisations of those redo! systems
which comprise certain sulfur containing com
pounds havin: a heavy metal salt in combination
therewith.
The sulfur containing‘ compounds
which, when combined with a
metllllt.
have been found to be elective in promoting ad
dition polymerimtions are members oi the class
which may be-‘dennerL-laoadly, as-aliphatlc or
ganic compounds containingat least one but not
more than two divalent-smut atoms. having at
least one sulfur atom connected by a single val
ency to an aliphatic radical containing at least
onehydrophilicgroup. Includedinthisclauoi“ thcblendeleeil’eriodic;
amen
in the polymerization
and nickel, those in subgroup B of groups I and II
of'the llendeleef Periodic Table such as copper,
unsaturated or
ganic compounds which are capable of undergo
ing an addition polymerisation to form a high
silver, xinc, cadmium and mercury. and those in
subgroup Aof groups VI and VII of the Mendeleef
molecular weight linear Polymer. Included in,
Periodic Table such as chromium. manganese and ca this class of monomers are the cmlugated buta
dienes such as butadiene. isoprene, dimethyi buta
The class of redox systems of this invention is
diene, chloroprene. piperylene and the like all of
' meant to include broadly any of the heavy metals
mentimed above when combined with any of the
which
'
contain a
sulfur containing compounds mentioned above 10
/
‘
om=c
'insuchamannerthatthemetalispresentasone,
\ .
of its salts rather than in the elemental state.
The metal salt may be combined with the sulfur
group; monomer mixtures of two or more of these
butadienes such as a mixture of butadiene and-di
compound either as a salt or in acomplex com
polmd. of uncertain chemical structure. or com
methyl butadiene; andmonomer mixtures of one
its simple salts while the sulfur compound may
group‘ and copolymerize with mitigated buta
dienes such as mixtures of butadiene with vinyl
15 or more of these conjugated butadienes with one
or more other compounds which also contain a
binations of metallic salts with sulfur containing
not known to form complexes or salts
‘
cm==c/
;of a definite chemical structure may be used. In
the latter event the metal may. be added as one of
'
be added as such or as one of its simple salts.
The preferred redox systems are those which
contain an aliphatic compound having a thiol or
a disulilde linkage and also an amino, hydroxy or
carboxy group, in combination with a water solu 26
ble salt of a heavy metal occurring in, the 8th to
12th positions of the ?rst long period of the
' periodic table such as iron, cobalt. nickel, copper
and manganese. Particularly preferred are those
redox systems which are known to promote or
catalyse oxidation reduction reactions occurring
in biological processes such as heavy metal cyste
ine or glutathione systems.
,
4
\
compounds including aryl olefins and substituted
aryl ole?ns such as styrene, p-chloro styrene, p
methoxy styrene, vinyl naphthalene and the like,
acrylic and methacrylic acids, esters, nitriles, and
amides such as aerylicacld, acrylonitrile, metha
crylonitrile, methyl acrylate, methyl methac
rylate, butyl acrylate, methacrylamide ‘and the
like and other vinyl compounds such as vinyl ke
tones, vinyl ethersrvinyl carbaaole, vinyl furane
and the like. Monomer mixtures of butadienes
with‘ other compounds containing a
. '
In the prac?ce of this invention monomeric
compolmds or mixtures of monomers are poly
merized by well known methods of polymeriza- _
tion such as by Polymerization in homogeneous
systems or bypolymerization in emulsions in pres
group such as vinylidene chloride and the like
may alsobeused. 'Allthesemonomers and mono
mer mixtures when polymerized or copolymerized
in the manner herein
form high mo
(awe of catalytic amolmts of the redox systems of
this inyurtion. In the emulsion polymerization
process which is at present preferred, the mono
lecular weight linear polymers. when the con
lugated butadiene is the monomer or is the pre
mer or monomer mixture is emulsified in a non
polymers are rubbery in character.
solvent liquid, usually water. with the aid of an
emulsifying agent and polymerization is then ef
dominant constituent of a misnomer mixture such
Other monomers or monomer mixtures which
- are capable of rmdergoing an addition polymer
fected in adding the heavy metal, sulfur contain 45 ization and which may be used in the processof
lng mi! of this invention together, if (112- .
siretL-wlth various other substances. the nature -
of whiclrwlll be described hereinafter. and agitat
ing the emulsion until polymer is found. The re
this invention are the above mentioned vinyl and
vinyldiene compounds as well as other vinyl com
pounds such as ‘vinyl chloride and vinyl acetate,
sulting polymerized emulsion‘ containing polymer
either alone or in mixtrnes with one another, all
particles dispersed in a liquid medium greatly re
a thermoplastic resinous character
sembles natural rubber latex and may be co
agulated in the usual manner to yield the soli
PM
.
-
of which polymerize toyield a linear polymer of
The sulfur containing
-heavy metal
redox systems of this invention may be used in
the polymerization of m
in emulsions
The amount of the redox system to be used in 55 prepared with various emulsifying agents and
polymerisation may be varied over rather wide
containing various other initiators, promoters,
limits provided that an excessive amount of the
accelerators or modi?ers of
tion. As
redox system does not inhibit or poison the poly
emulsifying agents, partially neutralized fatty
merization reaction. For most purposes only eat
acid‘ soaps such‘as 70-90% neutralized myristic
alytic amounts of the redox system. say less than
or palmitic acids are particularly eil'ective but
2% by weight based on the weight of the mono
other well known emulsifying agents including
mers are preferred and in most instances the poly
completely neutralized fatty acid soaps such as
meriza?on proceeds, most rapidly when from .01
sodium oleate and sodium palmitate and hymolal
to 1% of the redox system is present. when the
sulfates or sulfonates such as sodium lauryl sul
sulfur containing compound and heavy metal are 65 fate and sodium isolutyl naphthalene sulfonaies
added as separate compounds a mixture or about
may also be employed.
_
5% of the sulfur containing compound and .l%
of the heavy metal salt is- preferred. when using
some heavy metals. particularly copper and man
The redox systems containing an aliphatic sul
fur containing compound of the character de
scribed and a heavy metal are preferably used to
ganese, however, it is desirable to use even smaller 70 accelerate polymerizations initiated with the well
of the heavy metal salt. less than .
known oxygen yielding
such as hy
drogen peroxide. organic pernxids. potassium
21%, since these metals in higher concentra
persulfate. sodium perborate, potassium percar
tmd to inhibit the polymerization.
has been mentioned hereinabove; the redox v Ibonate and the like. but may'alaobemed in poly
p ofthisinventionmaybeusedgenerally
merisation induced
known vpolymeriza
3
2,880,475
-ization mixtures greatly accelerates the process
and also improves the quality of the polymeriza
tion initiators such as diazoamino benzene, tri
chloroacetic acid and carbon tetrachloride. They
tion products.
also may be used advantageously in the poly
merization of conjugated butadienes carried out
in presence of a peroxide and a peroxide activator
such as sodium pyrophosphate, amino acids and
saturated fatty acids, orv in presence of a sub;
stance which is a reducing agent such as sulfur
.
i
In order to illustrate the practice of this in
vention and to show the accelerating effect of the
redox systems herein disclosed upon polymeriza
tions, an emulsion containing the following in
gredients is prepared:
dioxide, or in presence of both an oxidizing and a
Butadiene _____________________ __grams__
reducing agent. They may also be used to 10 Acrylonitrile _
do
gether with other redox systems which contain
Hydrogen peroxide (til/2% solution) ___cc__
a heavy metal salt combined with other com
Emulsifying solution‘ (2‘/_:% aqueous solu
pounds including sodium pyrophosphate, levulinic
tion of myristic acid 85% neutralized
acid, quebrachitol and cholesterol such as are
with NaOH) _____________ -1 ______ __cc__
disclosed in copending applications of William D. 15 Polymerization modi?er _________ __grams_..
Stewart, Serial Nos. 379,713, 379,714, 379,716 and
379,717 ?led Feb. 19, 1941. Moreover, the heavy
metal, sulfur containing compounds herein dis
closed may be used to effect pclymerizations car
ried out in the absence of any added initiator.
55
45
10
250
0.3
This ‘emulsion is then divided into equal parts
and various redox systems are added to the emul
sion. These emulsions containing added redox
20 systems together with a control are sealed in
separate: glass tubes and polymerized by rotating
It is quite surprising that the sulfur containing
at a constant temperature of 30° C. The follow
compounds of this invention in association with
ing table shows the yield of the rubber-like buta
a heavy ~metal should promote polymerizations»
diene acrylonitrile copolymer obtained, and the
inasmuch as most sulfur containing compounds
such as the well known natural rubber vulcaniza 25 time required for the polymerization for tubes
containing various redox systems and for the
tion accelerators like the thiazoles and dithio
control.
=
carbamates are generally inhibitors of polymer
ization and other sulfur containing compounds
Redox system
known as polymerization modi?ers such as di
Yield
Time
Per cent
Hour:
' , alkyl dixanthogens, diaryl disul?des and thiuram 30
disul?des which increase the solubility and plas
ticity of the polymer usually slow down the poly
merization reaction. Moreover, certain heavy
metal salts when used in concentrations greater
than about 0.1% also act to slow down the poly‘.
merization. However, the redox systems of this
None
_
.
.
_
_
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
_
_
_
.
..
.
. _
_
98
Cobalt chloride, 0.01% _________________________ -_ }
Cysteine hydrochloride, .10% _________________ _.
Cobalt chloride, 0.0l%.._..
Cystine, 0.10%
erric sulfate, 0.01%
5283
98
'
.. }
.}
98
__________________ __ }
95
99
Jystine, 0.10%.. _. _
Zinc sulfate, 0.01%.
invention containing a sulfur compound of the
character described combined with a heavy metal
Cystinc, 0.10% _____________ . _
Cuprous chloride, 0.001% ._
95
Cuprous chloride, 0.001%. .
97
B-mercaptoethanol, 0.50%.
salt, greatly accelerate the polymerization re
action. This phenomena is contrary to the nor
(control)
4.0
mally expected result.
Although the exact manner in which the redox
systems of this invention accelerate polymeriza
tions is not known with certainty, it is believed
that the redox system promotes or catalyzes an
oxidation reduction reaction which voxidizes or
activates the monomer molecules to such an ex
tent that they are then capable of initiating a
chain reaction which produces a linear polymer.
The redox system may directly catalyze the oxi
dation of the monomer by an oxidizing agent such
as a peroxide, if such is present, or it may be
auto-oxidizable, and be capable of inducing mono
mer oxidation or activation by an oxidation re
duction involving the redox system itself, or some
other mechanism may be responsible for the in
crease in the rate of polymerization andkfor the
improved properties of ‘the polymerization prod
Glutathione, 0.50% ______ ._
Nickel sulfate, 01%....
..
97
B-mercaptoethanol, .50%__
Mcrcuric chloride, .0l% ..__
B-mcrcaptoethanol, .50%__.
97
It may be seen that in all cases the use of the
redox systems of this invention decreases the
time required for the polymerization. Tests on'
the copolymers obtained also show that the prac
tice of this invention yields a product which is
more plastic, and which when vulcanized pro‘
duces improved vulcanizates.
,
In another example of this invention an emul
sion prepared as described above is polymerized
in presence of various redox systems, and the rate
of polymerization is measured by determining
the percent yield at various intervals during the
process. The accelerating effect of the redox
system is shown below:
ucts. The association of small amounts or heavy
metals with various “sulfur containing com CO
For
pounds” in biological systems which undergo oxi
Redo)‘ System
dation reduction reactions is well known and
many theories have‘ been propcunded for an ex
Per-
Per-
Pcr-
Per
“03 yie
‘*“ii yie
‘*ii yie
“"13 yield
"8"‘
after after after after after
we
7%
hrs.
10%
hrs.
12%
hrs.
23
hrs.
45
hrs.
planation of such biological oxidoreductions.
Since it is believed that the initiation of poly
l;‘1'one(control)_._...
.
. , . . . . ..
0
merization reactions may be quite similar to bio
guliate,
errous 0.05%
ammonium.
(c0ntrol)n._.. ...
} 0
crrous ammonium su ate, (1.05, _
logical oxidoreduction particularly as regards the
role of the redox catalyst, analogies of polymer
errous ammonium su ate, 0.05 .
2—2’ diamino diethyl sul?de, 0.509;. } 4g
ization. systems with biological systems have
Ferrous
sulfate, 0.05%. } 66
proved of great value in elucidating. the action of 70 Cysteineammonium
hydrochloride, 0.50%.. ..
FGlutathione, .50%.._..1,f.
the redox systems Of this invention. It is to be
understood however that the invention is not to -
be limited by any proposed theory since the in
clusion of the substances herein described and
herein designated as redox systems in polymer
..
..
m
0
0
7
38
83
93
85
92
B9
93
45
94
93 """ ' ' ' ' ' ' ‘ ‘ ' ‘ "
' ' ' “ ' - ‘'‘‘' "
""""" ' '
Ferrous ammonium sulfate, 0.05%.
Dieggél
0.
0 _
dithiosulio,
_
_
.
.
.
.
_
_
_
.
.
.
_
succinate,
.
.
.
_
_
_
_
_
.
_
.
B-mercaptoethanol,.0.50% .....
71
90
93 __________ __
90
94 """"" '
._
Ferrous ammonium sulfate- 0.05‘7 _
} 76
'
‘
‘2,880,475
4
‘The table shows that vwithv the redox systems
\ of this invention‘ polymerization is substantially
complete in 12% hrs. while with no redox system
45 hrs. is required and with ‘a heavy metal salt
alon'e‘23. hrs. is required; Other embodiments of
the invention in which-various ‘other redox sys
tems are used with various other monomers and
monomer mixtures, catalysts and emulsifying
meriz'able‘ coniugated-butadiene and at least one
other compound-which :- intains a ‘
Ch —0
~
‘
t
,
h
>
\
a
a
,
group and is copolymerizable therewith in aqueous
emulsion.
‘
‘
~
‘
i
agents also show that the polymerization velocity
4. The method which comprises subjecting a
mixture of a polymerizable conjugated butadiene
is increased by the practiceof this invention.
In the practice of theinvention it is sometimes
and at least one other compound which contains a
' desirable to add various substances other than
those mentioned above to ‘the polymerization
recipe. For example when employing redox sys
‘ terns which are very effective in‘catalyzing bi- '
ological exodoreduction reactions such as the
glutathione-heavy metal system it may be desir
able to add colloids which are usually present in
.
biological systems as “carriersmfor the vredox ‘
system such as proteins, polypeptides, peptides, or
other colloidal‘ material. It may also be desir
able to‘ add materials which in?uence the quality
of - the ?nished polymer such as plasticizing or
groupand is copolymerizable therewith in aqueous
emulsion, to ,polymerizationlin aqueous emulsion
in the presence of a catalyst comprising a water
soluble heavy metal salt combined with an ali
phatic organic compound containing a single di
valent sulfur .atom connected by one of. its va
lences to a ‘hydrogen atom and by the other of its
valences to an aliphatic radical containing at
least one hydrophilic group, the total‘ concentra
tion of the heavy metal salt and the said aliphatic
, organic compound being less‘than 2% by weight .
stabilizing agents for the polymer.
25 .‘of the material polymerized; and‘the concentra
The practice of this invention also allows poly
tion of the heavy metal salt being such that the,
merizations to proceed rapidly under conditions
polymerization proceeds more rapidly than in the
where-polymerization would ordinarily be im
. absence of the heavy metal salt. »
. possible, because the great accelerating effect of
5. The method of claim 4(in which the heavy
the redox system more than counteracts the in‘ 80 ‘metal salt is a‘ salt'wof a heavy- metal occurring
hibiting'effect of other substances which would
in the 6th to 12th positions of the ?rst long period
of the periodic. table.
‘.
prevent the polymerization. Many such inhibit
6. The method of claim 4 in which the heavy
ing substances are di?lcult to exclude from the
metal salt is a salt of aheavy metal occurring in
polymerization batch because they are present
as impurities in the monomers or in other essen 85 the 6th to 12th positions ofthe ?rst long period
of the periodic table; and the aliphatic organic
tial materials.
compound is an hydroxy-substituted aliphatic,
Although various embodiments "of the invention
have been herein disclosed, it is not intended
7. The method of claim 4 in which the material
that the invention be limited solely thereto for it
mercaptan.
.
..
.
_
.
- will be obvious to those skilled in the art that ‘0 polymerized is a mixture of butadiene-1,3 ‘and
many modi?cations and variations are within the
spirit and scope of the invention as de?ned by
the appended claims.
I claim:
.~
‘
at least one copolymerizable vinyl compound ;' the
heavy metal salt is a salt of a heavy metal occur
ring in groupVIII'and the ?rst long period of the
periodic table; and the aliphatic organic com
pound is an‘ hydroxy-substituted aliphatic mer
1. The method which comprises subjecting ‘a 45
polymerizable material consisting of at least one
» 8. The method of claim 4 in which the'mate
unsaturated organic compound which contains a
rial polymerized is a- mixture of butadlene-1,3 and
at least one copolymerizablevinyl compound; the
captan.
‘
I
_
‘
50 heavy metal salt is a salt of a heavy metal oc
curring in group ‘VIII and the first long‘period of
group and which undergoes in aqueous emulsion
the periodic table‘; and the aliphatic organic com
an addition polymerization to form a high molec
pound ,is beta-mercapto ethanol.
.
.
'
'
ular weight linear polymer, to polymerization in
‘9. ‘Themethod of claim 4 in which the mate
aqueous emulsion ‘in the presence of a catalyst
. rial polymerized is a mixture of butadiene-1,3 and
comprising a water-soluble heavy metal salt com
bined with an aliphatic organic compound con
taining at least one but not more than two diva
lent sulfur atoms each of which is connected by its
capto ethanol and a water soluble cobalt salt. ‘
' 10. The method which {comprises subjecting a
acrylonitrile and the catalyst comprises beta mer
‘mixture of a polymerizable conjugated butadiene
two valences to two different atoms, and having 60 and at least one othercompound which contains a
at‘ least one of said sulfur atoms connected by
CHFC/ .
at least one of 'its two valences to an aliphatic
radical containing at least one hydrophilic group,
the total concentration of the heavy metal salt
and the said aliphatic organic compound being
less than 2% by weight of the material polymer
sion in the presence of a catalyst comprising. a.
ized, and the concentration of the heavy metal
salt being such that the polymerization proceeds
water-soluble heavy metal salt combinedwith an
aliphatic organic 'compoundcontaining a single
more rapidly than in‘ the absence of the heavy
metal salt.
v
‘
i
,
.
I
’
‘
group and is copolymerizable' therewith in aque
ous emulsion, to polymerization in aqueous emul—
divalent sulfur atom connected‘ byvone of its va
70 lences‘ to a hydrogen atom and by the other of its
valences to an aliphatic radical containing at least
one amino group and at least one‘carboxy group.
conjugated butadiene.
the total concentration‘ of the heavy metaljsalt
and the aliphatic organic‘ compound being less
3. The method of claim 1 in which the material
subjected to polymerization is a mixture of a poly 75 than 2% by ‘weight of the material polymerized
and the concentration of the heavy metal salt be
2. The method of claim 1 in which the mate
rial subjected to polymerization is a polymerizable
.
5
2,880,475
ing such that the polymerization proceeds more
wherein x is an aliphatic radical containing a
rapidly than in the absence of the heavy metal
carboxy group.
salt.
11. The method of claim 10 in which the ma
terial polymerized is a mixture of butadiene-1,3
and a copolymerizable vinyl compound; and the
heavy metal salt is a salt of a heavy metal occur
ring in the 6th to 12th positions of the ?rst long
16. The method of claim 14 in which the heavy
metal salt is a salt of a heavy metal occurring in
the 6th to 12th positions of the ?rst long period of
the periodic table; and the aliphatic organic com
pound is a compound of the formula
period of the periodic table.
wherein X is an aliphatic radical containing at
least one carboxy group and at least one amino
12. The method of claim 10 in which the mate
rial polymerized is a mixture of butadiene-1,3 and
a copolymerizable vinyl compound; the heavy
group.
.
~
17. The method of claim 14 in which the mate
rial polymerized is a mixture of butadiene-1,3 and
metal salt is a salt of a heavy metal occurring in
the 6th to 12th positions of the ?rst long Period
of the periodic table; and the aliphatic organic 15 a. copolymerizable vinyl compound; the heavy
metal salt is a salt of a heavy metal occurring in
compound is glutathione.
group VIII and the ?rst long period of the peri
13. The method of claim 10 in which the ma
odic table; and the aliphatic organic compound
terial polymerized is a mixture of butadiene-1,3
is cystine.
and acrylonitrile; and the catalyst comprises
18. The method of claim 14 in which the mate
glutathione and a water soluble copper salt.
20
rial polymerized is a mixture of butadiene-l,3
14. The method which comprises subjecting a
and acrylonitrile and the catalyst comprises
mixture of a polymerizable conjugated butadiene
cystine and a water soluble iron salt.
19. The method which comprises subjecting a
and at least one other compound which contains a
mixture oi.’ a polymerizable conjugated butadiene
and at least one other compound which contains a
group and is copolymerizable therewith in aqueous
emulsion, to polymerization in aqueous emulsion
in the presence of a catalyst comprising a water
soluble heavy metal salt combined with an all
phatic organic compound of the formula
30 group and is copolymerizable therewith in aqueous
emulsion, to polymerization in aqueous emulsion
in the presence of a catalyst comprising a com
wherein X is an aliphatic radical containing at
least one hydrophilic group, the total concen
tration of the heavy metal salt and the aliphatic '
organic compound being less than 2% by weight
plex compound of a heavy metal and an aliphatic
organic compound containing at least one but not
more than two divalent sulfur atoms and having
at least one of said sulfur atoms connected by a
single valence to an aliphatic radical containing
of the material polymerized and the concentra
‘at least one hydrophilic group, the concentration
tion of the heavy metal- salt being such that the
of the complex compound being less than 2% by
polymerization proceeds more rapidly than in the 40 weight of the material polymerized and such that
absence of the heavy metal salt.
the polymerization proceeds more rapidly than
15. The method of claim 14 in which the heavy
in the absence of the complex compound.
metal salt is a salt of a heavy metal occun'lng in
20. The method of claim 19 in which the heavy
the 6th to 12th positions of the first long period
metal is a metal occurring in the 6th to 12th posi
oi the periodic table; and the aliphatic organic
tions of the ?rst long period of the periodic table.
compound is a compound of the formula
Z—B—B—X
_
(
Patent No. 2,380,475.
‘WE-LIAM D. S'I'E'WART.
’
Certi?cate
of Correction
July 31, 1945.
WILLIAM D. STEWART
It is hereby certi?ed that error appears in the rinted speci?cation of the above
numbered patent requiring correction as follows: Iil'age 1, second column, line 10
for “thiolactic” read th'iolacetic; 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 4th day of June, A. D. 1946.
law-l
LESLIEFRAZEB,
>
FirstZAseistant Gommiuiomr of Patents.
.
5
2,880,475
ing such that the polymerization proceeds more
wherein x is an aliphatic radical containing a
rapidly than in the absence of the heavy metal
carboxy group.
salt.
11. The method of claim 10 in which the ma
terial polymerized is a mixture of butadiene-1,3
and a copolymerizable vinyl compound; and the
heavy metal salt is a salt of a heavy metal occur
ring in the 6th to 12th positions of the ?rst long
16. The method of claim 14 in which the heavy
metal salt is a salt of a heavy metal occurring in
the 6th to 12th positions of the ?rst long period of
the periodic table; and the aliphatic organic com
pound is a compound of the formula
period of the periodic table.
wherein X is an aliphatic radical containing at
least one carboxy group and at least one amino
12. The method of claim 10 in which the mate
rial polymerized is a mixture of butadiene-1,3 and
a copolymerizable vinyl compound; the heavy
group.
.
~
17. The method of claim 14 in which the mate
rial polymerized is a mixture of butadiene-1,3 and
metal salt is a salt of a heavy metal occurring in
the 6th to 12th positions of the ?rst long Period
of the periodic table; and the aliphatic organic 15 a. copolymerizable vinyl compound; the heavy
metal salt is a salt of a heavy metal occurring in
compound is glutathione.
group VIII and the ?rst long period of the peri
13. The method of claim 10 in which the ma
odic table; and the aliphatic organic compound
terial polymerized is a mixture of butadiene-1,3
is cystine.
and acrylonitrile; and the catalyst comprises
18. The method of claim 14 in which the mate
glutathione and a water soluble copper salt.
20
rial polymerized is a mixture of butadiene-l,3
14. The method which comprises subjecting a
and acrylonitrile and the catalyst comprises
mixture of a polymerizable conjugated butadiene
cystine and a water soluble iron salt.
19. The method which comprises subjecting a
and at least one other compound which contains a
mixture oi.’ a polymerizable conjugated butadiene
and at least one other compound which contains a
group and is copolymerizable therewith in aqueous
emulsion, to polymerization in aqueous emulsion
in the presence of a catalyst comprising a water
soluble heavy metal salt combined with an all
phatic organic compound of the formula
30 group and is copolymerizable therewith in aqueous
emulsion, to polymerization in aqueous emulsion
in the presence of a catalyst comprising a com
wherein X is an aliphatic radical containing at
least one hydrophilic group, the total concen
tration of the heavy metal salt and the aliphatic '
organic compound being less than 2% by weight
plex compound of a heavy metal and an aliphatic
organic compound containing at least one but not
more than two divalent sulfur atoms and having
at least one of said sulfur atoms connected by a
single valence to an aliphatic radical containing
of the material polymerized and the concentra
‘at least one hydrophilic group, the concentration
tion of the heavy metal- salt being such that the
of the complex compound being less than 2% by
polymerization proceeds more rapidly than in the 40 weight of the material polymerized and such that
absence of the heavy metal salt.
the polymerization proceeds more rapidly than
15. The method of claim 14 in which the heavy
in the absence of the complex compound.
metal salt is a salt of a heavy metal occun'lng in
20. The method of claim 19 in which the heavy
the 6th to 12th positions of the first long period
metal is a metal occurring in the 6th to 12th posi
oi the periodic table; and the aliphatic organic
tions of the ?rst long period of the periodic table.
compound is a compound of the formula
Z—B—B—X
_
(
Patent No. 2,380,475.
‘WE-LIAM D. S'I'E'WART.
’
Certi?cate
of Correction
July 31, 1945.
WILLIAM D. STEWART
It is hereby certi?ed that error appears in the rinted speci?cation of the above
numbered patent requiring correction as follows: Iil'age 1, second column, line 10
for “thiolactic” read th'iolacetic; 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 4th day of June, A. D. 1946.
law-l
LESLIEFRAZEB,
>
FirstZAseistant Gommiuiomr of Patents.
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