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Патент USA US3095408

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United States Patent 0 " we
Patented June 25, 1963
1
3,095,398‘
PROCESS OF INCREASING THE» PARTICLE SIZE
‘
0F SYNTHETIC RUBBER LATEX
Louis H. Howland, Water-town, ‘and Victor S.- Chambers,
, Naugatuck,‘ Coun., assignors to United States Rubber
2
monium alginate. It is preferred however, to increase
the solids content by evaporation concentration. Un
reacted monomers may be stripped from the latex by
the evaporation concentration. ,
Polyvinyl alcohols are generally graded by the viscosity
in centipoises of a 4% solution of the polyvinyl alcohol
in water at 20°’ C; Any of the conventional polyvinyl
er'sey
alcohols having a viscosity in 4% aqueous solution at 20°
No Drawing. Filed Jan; 28, 1960, Ser; No. 5,100
C. from 4. to 70‘ centipoises may be used in the present
16-Claims. (Cl. 260—29.7).
10 invention. An example of a commercial low viscosity
‘ This invention relates to the preparation of synthetic
type polyvinyl alcohol is one having a. viscosity of 4 to_6
rubber latices of large particle size, particularly to permit
centipoises in. 4% aqueous solution at 20° C. An ex
‘them to be concentrated‘ to ?uid latices of high solids
ample of a commercial medium viscosity type polyvinyl
content.
alcohol is one having a viscosity of 20' to 30 centipoises
We have found that treating a synthetic rubber latex 15 in 4% aqueous solution at. 20° C. An example of a
fompany, New York, N.Y., a corporation of New
containing unreacted polymerizable monomeric material
commercial high viscosity type polyvinyl alcohol is one
with a small amount of polyvinyl alcohol at a tempera
having a. viscosity of 45 to 70 centipoises in 4% aqueous
turn from 0° C‘. to 15° C. before removing unreacted
solution at 20° C.
monomers, results in a latex having a greatly increased
The synthetic rubber latex may be an aqueous emulsion
particle size over the same latex without the polyvinyl 20 polymerizate of one or more butadienes-1,3, for ex~
alcohol treatment. Such latices that have been treated
ample, butadiene-1,3, 2-methylbutadiene-l,3 (isoprene),
with polyvinylv alcohol in the presence of unreacted mon
2,3-dimethyl-butadiene-1,3, piperylene, or a mixture of
omers may readily be concentrated, preferably by evapora
one or more such butadienes- 1,3, with one or more other
tion concentration, to ?uid high solids latices.
polymerizable compounds which are capable of form
In carrying out the present invent-ion, the emulsion 25 ing rubbery copolymers with butadienes-1‘,3, for example,
of synthetic rubber forming monomers is polymerized
up to 70% by weight of such mixture of one or more
to a latex of a conversion of 60% to 95%, and the latex
monoethylenic compounds which contain a CH2=C<
is treated with a small amount of polyvinyl alcohol at a
temperature of 0° C. to 15° C. in the presence of at
group where at least one of the disconnected valences
is attached to an. electroenegative group, that is, a group
least 5% of unreacted polymerizable monomers based 30 which substantially increases the electrical dissymmetry
on the‘ weight of the original synthetic rubber forming
or polar character‘ of the molecule. Examples of com
monomers. The time of treatment is not critical. The
pounds which contain a CH2=C< group and are copolym
polyvinyl alcohol may be added to the latex with or
after the shortstopping agent after the desired conversion
erizable with butadienes-l,3 are aryl ole?nes, such as
styrene, vinyl toluene, alpha methyl styrene, chloro
styrene, dichlorosty-rene, vinyl naphthalene; the alpha
of 60% to 95%, and the residual monomers may then 35
be removed. If the polyvinyl alcohol is added to the
methylene carboxylic acids and-their esters, nitriles and
initial emulsion of monomers, it may be in contact with
amides, such as acrylic acid, methyl acrylate, methyl
the latex for a time to carry out the polymerization gen
methacrylate, acrylonitrile, methacrylonitrile, methac
erally not more than 24 hours. The polyvinyl alcohol
rylamide; vinyl pyridines, such as 2-vinyl pyridine, 2
may be added at any intemediate stage of the polymeriza 40 methyl-5-vinyl pyridine; methyl vinyl ketone; vinylidene
tion. The temperature of the treatment with polyvinyl
chloride. Such a synthetic rubber latex may be termed
alcohol should be between‘ 0° C. and 15° C. since treat
a ‘*butadiene polymer synthetic rubber latex.” The polym
ments at higher temperatures do not give appreciable in
erization receipe will contain the usual 2% to 15%
crease in particle size. Therefore, the invention is par
of one or a mixture of anionic surface-active dispersing
ticularly useful in low temperature polymerizations be 45 agents based on the weight of polymerizable monomers.
tween 0° C. and 15° 0, since it is dif?cult to cool a
When the polyvinyl alcohol is included in the polymeriza
high temperature polymerization batch fortreatment with
tion recipe, it is not the» emulsi?er for the rubber forming
polyvinvyl alcohol before stripping unreacted monomers.
monomers but is in addition to the usual 2% to 15%
There must be at least 5% of unreacted polymerizable
anionic surface-active dispersing agent based on the
monomers, based on the weight of original synthetic rub 50 weight of polymerizable monomers. Thus the anionic
ber forming monomers, present in the latex at the time
surface-active dispersing agent will. be in amount at least
of treatment with the polyvinyl alcohol, otherwise in
equal‘ to the maximum amount of polyvinyl alcohol and
crease in particle size will not result. The u-nreacted
monomers present with the polyvinyl alcohol may be all
generally will be in amount greatly in excess of the
amount of polyvinyl alcohol used. Such anionic sur
the unreacted monomers after the desired conversion or 55 face-active dispersing agents may be water-soluble soaps
only part of them as where volatile monomers, such as
of soap-forming monocarboxylic acids, such as alkali
fbutadienc-LS are vented from the latex before addition
metal, ammonium or amine salts of higher fatty acids
of the polyvinyl alcohol, provided at least 5% of higher
boiling monomers, such as styrene, remain for the poly
having 10 to‘ 24‘ carbon atoms in’ the molecule or of rosin
acids, including hydrogenated, d‘ehydrogenated and dis
vinyl alcohol treatment, after which such higher boiling 60 proportionated' rosin acids.
monomers may be stripped from the latex as by steam
distillation. The amount of polyvinyl alcohol added to
the latex in the presence of at least 5% of unreacted
The. anionic surface-active
dispersing agents, may be sul?onated or sulfated com
pound‘v having the general formula R—SO3M or
‘Ii-0803M. where M represents alkali-metal, ammonium
polymerizable monomers based on the weight of original
synthetic rubber forming monomers will be from 0.02 to 65 or amine radical, and R represents an organic radical con
taining a group having 9 to 231carbon atoms, such as
2 parts, and preferably from 0.05 to 1 part, per 100 parts
alkyll sulfonates, e.g. dodecyl? sodium sulfonate; alkyl
of original rubber forming monomers. The latex conven
sulfates, e.g». sodium oleyl sulfate; alkyl aryl‘ sulfonates,
tionally have a. solids content of 20% to 50% and may
be concentrated to a solids content of 55% to 70%, giv—
e.g. dodecyl benzene sulfonate; alkyl sulfosuccinates, e.g.
ing a ?uid high solids latex. The latex may be concen 70 dioctyl- sodium sulfosuccinate; aryl? sulfonate-formalde
trated by increasing the solids content in known manner
hyde condensation products, e.g. condensation product of
as‘ by creaming with a vegetable mucilage, such as am
sodium naphthalenetsulfonate and formaldehyde;
3,095,398
'
3
The following examples illustrate the invention. All
parts and percentages referred to herein are by weight.
Example 1'
4
Example 3
This example shows that incorporating polyvinyl alco
hol and a salt in the latex before removing residual mon
omers will give a latex of greatly increased particle size
Three 24-ounce glass bottle reactors (A, B and C) 5 enlargement over the known enlargement in particle size
were loaded with the following ingredients: 70 parts of
due to the incorporation of the salt in the latex.
butadiene-l,3; 30 parts of styrene; 0.20 part of sodium
The same polymerization recipe was used for latices
formaldehyde sulfoxylate; 0.15 part of diisopropylben
G and H as was used for latices A, B and C in Example
zene hydroperoxide; 0.015 part of ferrous sulfate hepta
1, and the mixtures were agitated by end over end rota
hydrate; 0.030 part of the tetrasodium salt of ethylene 10 tion at 5° C. Latices G and H were polymerized to
diamine tetraacetic acid; 3.0 parts of potassium oleate;
75.8% and 75.3% conversion, respectively, at which time
0.50 part of a condensation product of sodium naph
0.2 part of potassium dirnethyldithiocarbamate short~
thalene sulfonate and ‘formaldehyde dispersing agent;
stop and 0.75 part of potassium sulfate in 20 parts of
0.03 part of sodium dithionite; 0.1 part of tertiary dodecyl
water was‘ added to bottle G, and 0.2 part of potassium
mercaptan; and 142 parts of water. The mixtures were
dimethyldithiocarbamate and 0.75 part of potassium
agitated by end over end rotation at 5° C. Latices A,
sulfate and 0.2 part of the low viscosity polyvinyl alcohol
B and C were polymerized to 74.5%, 771.0% and 71.5%
used in Example 1 was added to bottle H. Bottles G
conversion, respectively, at which time 0.2 part of potas~
and H were allowed to stand 4 hours before opening and
sium dimethyldithiocarbamate shortstop in 20 parts of
venting the unreacted butadiene.
water was added to latex A, 0.2 part of potassium di 20
The average particle diameters of the thus treated
methyldithiocarbamate and 0.2 part of polyvinyl alcohol
in 20 parts of water were added to latex B, and 0.2 part
latices G and H were 1250 and 1860 angstrom units re
spectively, showing the increase in particle size on addi
tion of the sodium sulfate (comparison of latex G with
polyvinyl alcohol in 20 parts of water were added to latex
latex A of Example 1), and the increase in particle size
C. The polyvinyl alcohol was a low viscosity type having 25 of latex D by addition of the polyvinyl alcohol to the
a viscosity of 4 to 6 centipoises in a 4% aqueous solu
latex before removing unreacted monomers as shown in
tion at 20° C. Bottles A and B were allowed to stand
latex H.
16 hours and bottle C was allowed to stand 4 hours
The amount of alkali salt electrolyte added to the
before opening and venting the unreacted butadiene.
polymerization recipe as shown in Example 2, and/ or the
The average particle diameters of the thus treated 30 amount of alkali salt electrolyte added to the latex before
latices A, B and C were 420, 1440, and 1470 angstrom
removing unreacted monomers as shown in Example 3,
units, respectively, showing the great increase in particle
where it is desired to add such salt, may be from 0.2%
size on addition of the polyvinyl alcohol to the latex
to 2%, based on the weight of original rubber forming
before removing unreacted monomers.
monomers. Such alkali salt electrolyte may be an alkali
35 (potassium, sodium, ammonium or amine) salt of an acid
Example 2
of potassium dimethyldithiocarbamate and 1.0 part of
This example shows that incorporating polyvinyl
such as carbonic, formic, acetic, sulfuric, hydrochloric,
alcohol before removing residual monomers from a large
particle size latex made in known manner by including
trolytes that may be used are ammonium carbonate, am
nitric or phosphoric acids. Examples of alkali salt elec
an alkali salt electrolyte in the polymerization recipe will 40 monium bicarbonate, methyl amine carbonate, dimethyl
amine carbonate, sodium formate, potassium acetate,
give a latex of greatly increased particle size enlarge
ment over the increase in particle size due to the salt.
Three 24-ounce glass bottle reactors (D, E and F) were
loaded with the following ingredients: 70 parts of buta
diene-l,3; 30 parts of styrene; 0.20 part of sodium
formaldehyde sulfoxylate; 0.15 part of di-isopropylben 45
zene hydroperoxide; 0.015 part of ferrous sulfate hepta
hydrate; 0.030 part of the tetrasodium salt of ethylene
diamine tetraacetic acid; 3.0 parts of potassium oleate; '
0.50 part of a condensation product of sodium naph 50
thalene sulfonate and formaldehyde dispersing agent; 0.75
part of sodium sulfate; 0.03 part of sodium dithionite;
0.1 part of tertiary dodecyl mercaptan; and 150 parts
sodium sulfate, potassium sulfate, sodium chloride, po
tassium chloride, sodium nitrate, and trisodium phos~
phate. Such alkali salt electrolyte is in addition to the
very small amounts of electrolyte that may be present in
the latex from the catalysts, activators, sequesting agents,
oxygen scavengers, emulsi?ers and stabilizers in the
polymerization recipe.
Example 4
In run J, a 24-ounce glass bottle reactor was loaded with
the following ingredients: 70 parts of butadiene-l,3; 30
parts of styrene; 0.10 part of sodium formaldehyde sul
foxylate; 0.10 part of di-isopropylbenzene hydroperoxide;
of water. The mixtures were agitated by end over end
0.015 part of ferrous sulfate heptahydrate; 0.030 part of
rotation at 5° C. Latices D, E and F were polymerized 55 the tetrasodium salt of ethylene diamine tetraacetic acid;
to 53.5%, 55.6% and 56.2% conversion, respectively, at
which, time 0.2 part of potassium dimethyldithiocar
bamate shortstop in 20 parts of water was added to bottle
D, 0.2 part of potassium dimethyldithiooarbamate and
0.2 part of polyvinyl alcohol in 20 parts of water were
added to ‘bottle E, and 0.2 part of potassium dimethyl
dithiocarbamate and 1 part of polyvinyl alcohol in 20
3.0 parts of potassium oleate; 0.50 part of a condensation
product of sodium naphthalene sulfonate and formalde~
hyde dispersing agent; 0.75 part of sodium sulfate; 0.005
part of hydroquinone; 0.1 part of tertiary dodecyl mer
captan; and 100 parts of water. The mixture was agi
tated by end over end rotation at 5° C. The conversion
of the monomers into polymer was followed by periodi
parts of water were added to bottle F. The polyvinyl
cally measuring the percent solids of the polymerizing
alcohol was the same as that used in Example 1. Bot
system. When the conversion had reached approximately
tles D and E were allowed to stand 4 hours and bottle F 65 36%, 20 parts of water were added. The polymerization
was allowed to stand 16 hours before opening and vent
was shortstopped with 0.2 part of potassium dimethyldi
ing the unreacted butadiene.
thiocarbamate after 10 hours at 88% conversion. A
The average particle diameters of the thus treated
very viscous latex of a viscosity over 3000 centipoiscs
latices D, E and F were 1050, 1520 and 1830 angstrom
measured at approximately 25° C. was obtained with a
units, respectively, showing the increase in particle size 70 solids content of 42.8%. The average particle diameter
was 720 angstrom units.
on incorporation of sodium sulfate in the polymerization
Run K was similar to run I except that at approxi
recipe (comparison of latex D with latex A of example
mately 41% conversion 0.1 part of polyvinyl alcohol as
1), andrthe increase in the particle size of latex D by
a 5% dispersion and a total of 20 parts of water were
addition of the polyvinyl alcohol to the latex before re
moving unreacted monomers as shown in latices E and F. 75 added. The polyvinyl alcohol dispersion had been pre-v
3,095,398
v
pared by stirring 50 grams of a'low viscosity type poly
2-0 parts of water were-added at‘ 71% conversion and‘ the
polymerization‘ was shortstopped after 8: hours at 86%
conversion. The average particle size after venting the
butadiene was 1560 angstrom units;
vinyl alcohol having a viscosity of‘ 4' to‘ 6 centipoises in a
4% aqueous solution at 20 °' C‘. intorabout- 500 grams of
cold water andheating the stirred mixture at 60°~70° C.
for about 30 minutes, and then diluting to one liter with
Run S was similar to run L except that 30 parts of
butadiene and 70 parts of styrene were used as the
more water. The polymerization'was shortstopped‘with
0.2 part of potassium dimethyldithiocarbamate after 10
hours at 82% conversion.
monomers and the 20 parts more of water were added
A ?uid latex was, obtained
at 79% conversion. The polymerization was short
stopped after 8 hours at 93% conversion; The average
The latex was concentrated by evaporation concentration 10 particle size after Venting the butadiene was 600 angstrom
in a' laboratory’ disc concentrator at 35 ° to 40° C. to a
units.
solids content of 60% and a viscosity of 540‘centipoises
Run T was similar to run S except that a 5% aqueous
measured at approximately 25° C.
dispersion of 0.1 part of polyvinyl’ alcohol along with
the 20 parts of water were added at 75% conversion.
Example 5
15 The polymerization Was'shortstopped after 8 hours at
In run L, a 24-ounce glass reactor was-loaded. with the
90% conversion. The average particle size after venting
following ingredients: 70 parts of butadiene-1,3; 30 parts
the butadiene was 1300 angstrom units.
whose average particle diameter Was-1l530‘angstr0nrunits.
of! styrene; 0520 part? of' sodium formaldehyde sulfoxylate;
Example 6
0.15" part of ‘ di-isopropylbenzene hydroperoxide;. 0.015
part of ferrous sulfate heptahydrate; 0.030part of the 203 This example shows that polyvinyl alcohol alone does
tetrasodium salt of ethylene diamine. tetraacetic acid} 31
not increase the particle’ size of synthetic rubberv latex
parts of potassium oleate; 0.5 part of a condensation prod,
from which the unreacted monomers have ‘been removed.
not of‘ sodium naphthalene- sulfonate and‘ formaldehyde
‘ A commerciallatex polymerized at"5° C. to 80% con
dispersing agent; 0:75 partlof sodiumisulfat‘e; 0:03f part of
version with the following recipe was used, the ?gures
sodium: dithionite'; 011‘ part of‘ tertiary dodecyl' mer 25 representing parts by weight; Butadi‘ene‘ 72', styrene 28,
captan; and. 130' parts‘ of water. The‘ mixture‘ was agi~
tated' by end over endirotation‘ at’ 5°‘
.Thehconversion
‘sodium formaldehyde sulfoxylate 0.12; diisopropyl Iben
zene' hydroperoxide. 0.1, ferrous sulfate heptahydrate
0.011, tetrasodium salt of ethylene diamine‘ tetraacetic
acid 0.044, potassium soap of disproportionated‘ rosin
ofv monomers in-to: polymer was followed_‘ as: described in.
Example‘ 1.. When the conversion had‘ reached‘ approxi
mately 42%, 20 parts of water‘were added. The con 30 acids. 1.75,. potassium ol'eate 2.75, condensation product
versionL was . shortstoppedf after 24- hours at. 76% conver
of sodium. naphthalene sulfonate and‘ formaldehyde di's
sion: with 0.2 part of potassium.dimethyldithiocarbamate'
persing agent 0.5,. potassium sulfate 0.5, sodium hydro
sul?de 0.03, mixed tertiary (C12 to. C16) mercaptans 0.09,
in 1.0"» partsof water. The reactor was allowed‘to stand
approximately 16 hours and the‘ unreacted‘butadiene was
‘and water 155 ‘ parts.
This 'was' shortstopped at about
then vented‘ off.‘ The averageparticle diameter of: the 35 80% conversion. with 0.2‘ potassium dimethyl dithiocar~
latex. was 620v angstrom units.
bamate and‘ 0.02 part potassium soap of higher fatty acids.
Run M was similar to run L except that after 24 hours
Unreacted butadiene was vented off and unreacted resi
at‘ 84% conversion: a solution‘ of 0.2 potassium dimethyl
dual‘ styrene was removed". by steam distillation in the
dithiocarb-amate shortstop, 0.2 part of polyvinyl alcohol
(as 5% dispersion prepared. asin Example 1); andl-a total
of l0:parts" of‘ water were added:
The reactor was. al
lowed to. stand approximately 16‘ hours and theunrcacted
butadiene was. then ventedi oif. The average particle di
ameter ofitheil-atex. was 1420 angstrom units.
‘
conventional‘ manner.
40
To four samples U,.V, W, and X of this latex was added
2 parts per hundred of rubber latex solids of the con‘
densation product ‘of sodium naphthalene sulfonate and
‘formaldehyde dispersing agent as a 10% aqueous solu
tion. To three of these samples V, W, and X was added
Run Ni was-similar to run L except that the, shortstop 45 0.2, 1.0, and 9.0 parts per hundred? of latex solids of a
solution without any'polyvinyl“ alcohol was». added after
polyvinyl alcohol which has a viscosity in 4% aqueous
24 hours at 83% conversion and thepolyvinyl alcohol was
solution of 4 to 6 centipoises as a 10% solution. These
not added until after thebutadiene‘ was vented 011. The
mixtures were heated at 50° C. for one hour, cooled and
reactor was allowed to. stand’. approximately 16. hours‘.
the particle size determined. The particle sizes of the
The. average particle diameter. of the latex‘ was 1080 50 thus treated latices U, V, W, and‘ X were 820‘, 840‘, 830
angstrom units.
and‘ 850 angstrom‘ units, respectively, showing that poly
- Run 0 was similar to run L except that 1100 parts of
vinyl alcohol alone does not increase the particle size of
butadiene. was used in» place of the 70/30v 'butadiene/
synthetic rubber latex.
styrene mixture and the 20 parts more of water were‘
The latices of increased‘ particle size accordingly to the
added‘ at 43% conversion.’ The polymerization was 55 present invention, particularly of high solidscontent, may
shortstopped' after 10 hours. at 71% conversion with‘. 0.2
be used‘ in the usual applications of latices,
in foam
partiof potassium dimethyldithiocarbaniate and the aver
sponge manufacture, tire cord dipping, bonding and‘ im
age? particle size. was measured after venting the remain
pregnating various materials, preparation of adhesives,
ingnbutadiene monomer. The average particle diameter
and the like.
was 880tangstrom units.
This application is a ‘continuation-impart of our ap
60
RunP‘was. similar to. run 0 except'that a 5% aqueous
dispersion of 0:1' part of polyvinyl. alcohol along with’ the
20'parts of water weretadded at 43% conversion and the
polymerization was shortstopped. after 10 hours‘. at 69%.
plication Serial No. 776,743, ?led November 28, 1958,
now abandoned.
In view of the many changes and modi?cations that
may 1be made without departing from the. principles under
conversion. The; average particle diameter after venting 65 lying the invention, reference should be; made to the ap
‘the butadiene: was". 1560. angstrom. units
pended claims for an understanding of the scope of the
Run: Q was. similar to. run: L except. that 50 parts of
protection aiforded the invention.
butadiene‘ and 50? parts of styrene were used as the
Having thus described our invention, what we claim
monomers and? the 20 parts. more of water‘were added at
and desire to protect by Letters. Patent is:
78% conversion. The. polymerization was shortstopped 70
1. The method which comprises treating a synthetic
after. 8 hours at 93 %v conversion. The‘ average particle
rubber latex which is an aqueous emulsion. polymerizate
diameter: after venting the butadiene was. 560 angstrom
of synthetic rubber forming monomeric material selected
units;
~
from the group consisting of butadiene-1,3, isoprene, 2,3
Run Rmwa-s similar'to-run Q'ex-cept thatia 5% aqueous
dimethyl butadiene-1,3, and piperylene, and mixtures
dispersion.:of:0‘.l" part of‘ polyvinyl‘. alcohol along with the 75 thereof, and mixtures of such butadienes-l',3- with up to
3,095,398
5. The method which comprises treating a synthetic
70% by weight of such mixtures of monoethylenic com
rubber latex which is an aqueous emulsion polymerizate
pounds which contain a CH2=C< group and are co
of synthetic rubber forming monomeric material selected
from the group consisting of butadiene-1,3, isoprene, 2,3
dimethyl butadiene-1,3, and piperylene, and mixtures
polymerizable with butadienes-l,3, and Which has been
polymerized to a latex of 60% to 95% conversion, in
the presence of at least 5% of residual unreacted polym
erizable monomeric material based on the weight of the
thereof, and mixtures of such -butadienes-1,3 with up to
70% by weight of such mixtures of monoethylenic com
original synthetic rubber forming monomeric material
pounds which contain a CH2=C< group and are co
with 0.02 to 2 parts of polyvinyl alcohol per 100 parts
by weight of original synthetic rubber forming monomeric
material at a temperature from 0° C. to 15° C., said poly
polymerizable with butadienes-1,3, and which has been
10 polymerized at 0° C. to 15° C. to a latex of 60% to 95%
conversion, in the presence of at least 5% of residual
vinyl alcohol having a viscosity in 4% aqueous solution
at 20° C. from 4 to 70 centipoises, and then removing
unreacted monomeric material from the latex.
O
(3
7
unreacted polymerizable monomeric material based on
the weight of the original synthetic rubber forming
monomeric material with 0.05 to 1 part of polyvinyl
'
2. The method which comprises treating a synthetic
rubber latex which is an aqueous emulsion polymerizate
alcohol and 0.2 to 2 parts of alkali salt electrolyte selected
from the group consisting of potassium, sodium, am
monium and amine salts per 100 parts by weight of
of synthetic rubber forming monomeric material selected
from the group consisting of butadiene-l,3, isoprene, 2,3
dimethyl butadiene-l,3, and piperylene, and mixtures
original synthetic rubber forming monomeric material
at a temperature from 0° C. to 15° C., said polyvinyl
alcohol having a viscosity in 4% aqueous solution at
20° C. from 4 to 70 centipoises, and then removing un
reacted monomeric material from the latex.
thereof, and mixtures of such butadienes-l,3 with up to
70% by weight of such mixtures of monoethylenic com
pounds which contain a CH2=C< group and are co
polymerizable with butadienes-1,3, and which has been
6. The method which comprises treating a synthetic
polymerized at 0° C. to 15° C. to a latex of 60% to 95 %
conversion, in the presence of at least 5% of residual
unreacted polymerizable monomeric material based on
rubber latex which is an aqueous emulsion polymerizate
of a mixture of butadiene-1,3 and up to 70% of said
mixture of styrene, and which has been polymerized at
0° C. to ‘15° C. to a latex of 60% to 95% conversion,
in the presence of at least 5% of residual unreacted
the weight of the original synthetic rubber forming
monomeric material with 0.02 to 2 parts of polyvinyl
alcohol per 100 parts by weight of original synthetic
polymerizable monomeric material based on the weight of
the original synthetic rubber ‘forming monomeric mate
rial with 0.02 to 2 parts of polyvinyl alcohol per 100
rubber forming monomeric material at a temperature
from 0° C. to 15° C., said polyvinyl alcohol having a
viscosity in 4% aqueous solution at 20° C. from 4 to 70
parts by weight of original synthetic rubber forming
centipoises, and then removing unreacted monomeric
monomeric material at a temperature from 0° C. to
15 ° C., said polyvinyl alcohol having a viscosity in 4%
aqueous solution at 20° C. from 4 to 70 centipoises, and
material from the latex.
3. The method of making a synthetic rubber latex
which comprises treating a synthetic rubber latex which
is an aqueous emulsion polymerizate of synthetic rubber
then removing unreacted monomeric material ‘from the
latex.
forming monomeric material selected from the group con
sisting of butadiene-l,3, isoprene, 2,3-dimethyl butadiene
1,3, and piperylene, and mixtures thereof, and mixtures
7. The method which comprises treating a synthetic
C., said polyvinyl alcohol having a viscosity in 4% aque
poises, and then removing unreacted monomeric material
rubber latex which is an aqueous emulsion polymerizate
of such butadienes-1,3, ‘and which has been polymerized 40 of a mixture of butadiene~‘l,3 and up to 70% of said
mixture of styrene, and which has been polymerized at
at 0° C. to 15° C. with up to 70% by weight of such
0° C. to '15 ° C. to a latex of 60% to 95% conversion,
mixtures of monoethylenic compounds which contain a
in the presence of at least 5% of residual unreacted
CH2=C< group and are copolymerizable with butadienes
polymerizable monomeric material based on the weight
1,3 to a latex of 60% to 95 % conversion, in the presence
of the original synthetic rubber forming monomeric ma
of at least 5% of residual unreacted polymerizable
terial with 0.05 to 1 part of polyvinyl alcohol and 0.2
monomeric material based on the weight of the original
to 2 parts of alkali salt electrolyte selected from the group
synthetic rubber forming monomeric material with 0.02
consisting of potassium, sodium, ammonium and amine
to 2 parts of polyvinyl alcohol and 0.2 to 2 parts of alkali
salts per 100 parts by weight of original synthetic rub
salt electrolyte selected from the group consisting of
potassium, sodium, ammonium and amine salts per 100 50 ber forming monomeric material at a temperature from
0° C. to 15 ° C., said polyvinyl alcohol having a viscosity
parts by weight of original synthetic rubber forming
in 4% aqueous solution at 20° C. from 4 to 70 centi
monomeric material at a temperature from 0° C. to 15°
from the latex.
8. The method of making a concentrated synthetic
removing unreacted monomeric material (from the latex. 55
rubber latex which comprises treating a synthetic rub
4. The method which comprises treating a synthetic
ber latex which is an aqueous emulsion polymerizate
rubber latex which is an aqueous emulsion polymeriz
of synthetic rubber forming monomeric material selected
ate of synthetic rubber forming monomeric material
from the group consisting of butadiene-1,3, isoprene, 2,3
selected from the group consisting of butadiene-1,3, iso
ous solution at 20° C. ‘from 4 to 70 centipoises, and then
prene, 2,3-dimethyl butadiene~l,3, and piperylene, and
60
dimethyl butadienc-1,3, and piperylene, and mixtures
thereof, and mixtures of such butadienes-l,3 with up to
mixtures thereof, and mixtures of such butadienes-l,3
with up to 70% by weight \of such mixtures of mono
ethylenic compounds which contain a CH2=C< group
and are copolymerizable with butadienes-1,3, and which
70% of such mixtures of monoethylenic compounds
which contain a CH2=C< group and are copolymeriz
able with butadienes-1,3, and which has been polymerized
has been polymerized at 0° C. to 15 ° C. to \a latex of 65 to a latex of 60% to 95 % conversion and a solids con
tent of 20% to 50%, in the presence of at least 5% of
60% to 95 % conversion, in the presence of at least 5%
of residual unreacted polymerizable monomeric material
based on the weight of the original synthetic rubber
forming monomeric material with 0.05 to 1 part of poly
vinyl alcohol per 100 parts by Weight of original synthetic 70
residual unreacted polymerizable monomeric material
based on the weight of the original synthetic rubber
forming monomeric material with 0.02 to 2 parts of poly
vinyl alcohol per 100 parts by weight of original syn
rubber forming monomeric material at a temperature
from 0° C. to 15° C., said polyvinyl alcohol having a
viscosity in 4% aqueous solution at 20° C. from 4 to 70
thetic rubber forming monomeric material at a tempera
ture from 0° C. to 15 ° C., said polyvinyl alcohol having
a viscosity in 4% aqueous solution at 20° C. from 4
to 70 centipoises, and then removing unreacted mono
centipoises, and then removing unreacted monomeric
material from the latex.
75 meric material from the latex and creaming the latex to
‘3,095,398
a solids content of 55% to 70% with a vegetable mucilage
creaming agent.
9. The method of making a concentrated synthetic
rubber latex which comprises treating a synthetic rubber
latex which is an aqueous emulsion polymerizate of syn
10
thetic rubber forming monomeric material selected from
the group consisting of butadiene-1,3, isoprene, 2,3-di
methyl butadiene-l,3 and piperylene, and mixtures there
of, and mixtures of such butadienes-LS with up to 70%
of such mixtures of monoethylenic compounds which con
thetic rubber forming monomeric material selected [from
tain a CH2=C< group and are copolymerizable with
the ‘group consisting of butadiene-1,3, isoprene, 2,3-di
butadienes-1,3, and which has been polymerized to a latex
methyl butad-ieneaLS, and piperylene, and mixtures there
of ‘60% to 95 % conversion and .a ‘solids content of 20%
of, and mixtures of such butadienes-LB with up vto 70%
to 50%, in ‘the presence of at 'least 5% of residual un
of such mixtures of monoethylenic compounds which 10 reacted polymerizable monomeric material based on the
contain a CH2= C< group and are copolymerizable with
weight of the original synthetic rubber forming mono
butadienes4l,3, and which has been polymerized to a
meric material with 0.05 to 1 part of polyvinyl alcohol
latex of 60% to 95% conversion and a solids content
and “0.2 to 2 parts of alkali salt electrolyte selected from
of 20% to 50%, in the presence of at least 5% of residual
the group consisting ‘of potassium, sodium, ammonium
unreacted polymerizable monomeric material based on
and ‘amine salts ‘per 100 parts by weight of original syn
the weight of the original synthetic rubber forming mono~
thetic rubber forming monomeric material 'at a tempera
meric material with 0.02 to 2 parts of polyvinyl alcohol
ture from 0° C. to 15° C., said polyvinyl alcohol having
per 3100 parts by weight of origin-a1 synthetic rubber form
a viscosity in 4% aqueous solution at 20° C. from 4 to
ing monomeric material at a temperature from 0° C. to
70 centipoises, and then removing unreacted monomeric
‘15° C., said polyvinyl alcohol having a viscosity in 4% 20 material from the latex and evaporating water from the
aqueous solution at 20° C. from 4 to 70 centipoises, and
latex until the latex is concentrated to a solids content of
then removing unreacted monomeric material from the
55% to 70%.
latex ‘and evaporating water ‘from the latex until the latex
13. The method of making a concentrated synthetic
is concentrated to a solids content of 55% to 70%.
rubber latex which comprises treating a synthetic rubber
10. The method of making a concentrated synthetic 25 latex which is an aqueous emulsion polymerizate of a
rubber latex which comprises treating a synthetic rubber
mixture of butadiene-1,3 and up to 70% of said mixture
latex which is an aqueous emulsion polymerizate of syn
of styrene, and which has been polymerized at 0° C. ‘to
thetic rubber forming monomeric material selected from
15° C. to a latex of 60% to 95 % conversion and a solids
the group consisting of butadiene-1,3, isoprene, 2,3-di
content of 20% to 50%, in the presence of at least 5% of
methyl butadiene -1,3, and piperylene, and mixtures there
residual unreacted polymerizable monomeric material
of, and mixtures of such butadienes-L3 with up to 70%
based on the weight of the original synthetic rubber form
of such mixtures of monoethylenic compounds which
ing monomeric material with ‘0.02 to 2 parts of polyvinyl
contain a CH2=C< group and are copolymerizable with
alcohol per 100 parts by weight of original synthetic rub
butadienes-l,3, and which has been polymerized to a latex
ber forming monomeric material at a temperature from
of 60% to 95% conversion and a solids content of 20% 35 0° C. to 15 ° C., said polyvinyl alcohol having a viscosity
to 50%, in the presence of at least 5% of residual un
in 4% aqueous solution at 20° C. from 4 to 70 centi
reacted polymerizable monomeric material based on the
poises, and then removing unreacted monomeric material
weight of the original synthetic rubber forming mono
from the latex and evaporating water from the latex until
meric material with 0.02 to 2 parts of polyvinyl alcohol
the latex is concentrated to a solids content of 55% to
and 0.2 to 2 parts of alkali salt electrolyte selected from 40 70%.
the group consisting of potassium, sodium, ammonium
14. The method of making a concentrated synthetic
and amine salts per 100 parts by Weight of original syn
rubber latex which comprises treating a synthetic rubber
thetic rubber forming monomeric material at a tempera
latex which is an aqueous emulsion polymerizate of a
ture from 0° C. to 15 ° C., said polyvinyl alcohol having
mixture of butadiene-1,3 and up to 70% of said mixture
a viscosity in 4% aqueous solution at 20° C. from 4 to 45 of styrene, and which has been polymerized at 0° C. to
7'0 centipoises, and then removing unreacted monomeric
15° C. to a latex of 60% to 95% conversion and a solids
material from the latex and evaporating water from the
content of 20% to 50%, in the presence of at least 5%
latex until the latex is concentrated to a solids content of
of residual unreacted polymerizable monomeric material
55% to 70%.
based on the weight of the original synthetic rubber form
11. The method of making a concentrated synthetic 50 ing monomeric material with 0.02 to 2 parts of polyvinyl
rubber latex which comprises treating a synthetic rubber
alcohol and 0.2 to 2 parts of alkali salt electrolyte se
latex which is an aqueous emulsion polymerizate of syn
lected from the group consisting of potassium, sodium,
thetic rubber forming monomeric material selected from
ammonium and amine salts per 100 parts by weight of
the group consisting of butadiene-1,3, isoprene, 2,3-di—
original synthetic rubber forming monomeric material ‘at
methyl -butadiene-1,3, [and piperylene, and mixtures there 55 a_ temperature from 0° C. to 15° C., said polyvinyl alco
of, and mixtures of such butadienes-1,3 with up to 70%
hol having a viscosity in 4% aqueous solution at 20° C.
of such mixtures of monoethylenic compounds which con
‘from 4 to 70 centipoises, and then removing unreacted
tain a CH2=C< group and are copolymerizable with
monomeric material from the latex and evaporating water
bu|tadienes-1,3, and which has been polymerized ‘at 0° C.
from the latex until the latex is concentrated to a solids
to 15° C. to a latex of 60% to 95% conversion and a 60 content of 55 % to 70%.
solids content of 20% to 50%, in the presence of at least
5% of residual unreacted polymerizable monomeric ma
terial based on the weight of the original synthetic rubber
forming monomeric material with 0.02 to 2 parts of poly
15. The method of making a concentrated synthetic
rubber latex which comprises treating a synthetic rubber
latex which is an aqueous emulsion polymerizate of a
mixture of butadiene-l,3 and up to 70% of said mixture
vinyl alcohol per 100‘ parts by weight of original synthetic 65 of
styrene, and which has been polymerized at 0° C. to
rubber forming monomeric material at a temperature
15° C. to a latex of 60% to 95% conversion and a solids
from 0° C. to 15° C., said polyvinyl alcohol having a
content of 20% to 50%, in the presence of at least 5%
viscosity in 4% aqueous solution at 20° C. from 4 to 7'0
of residual unreacted polymerizable monomeric material
centipoises, and then removing unreacted monomeric ma
based on the weight of the original synthetic rubber form
terial from the latex and evaporating water from the 70 ing monomeric material with 0.05 to 1 part of polyvinyl
latex until the latex is concentrated to a solids content of
alcohol per 100 parts by weight of original synthetic rub
55 % to 70%.
ber forming monomeric material at a temperature from
12. The method of making a concentrated synthetic
0° C. to 15° C., said polyvinyl alcohol having a viscosity
rubber latex which comprises treating a synthetic rubber
in 4% ‘aqueous solution at 20° C. from 4 to 70 centi
latex which is an aqueous emulsion polymerizate of syn‘ 75 poises, and then removing unreacted monomeric material
3,095,398
11
from the latex and evaporating water from‘ the latex until
12
original synthetic rubber forming monomeric material at
16. The method of making a concentrated synthetic
rubber latex which comprises treating a synthetic rubber
a temperature from 0° C. to 15° C., said polyvinyl al
cohol having a viscosity in 4% aqueous solution at 20° C.
from 4 to 70 centipoises, and then removing unreacted
monomeric material from the latex and creaming the
latex which is an aqueous emulsion polymerizate of a mix
ture of butadiene-l,3 and up to 70% of said mixture of
latex to a solids content of 55% to 70% with a vegetable
mucilage creaming agent.
styrene, and which has been polymerized at 0° C. to 15°
References Cited in the ?le of this patent
UNITED STATES PATENTS
the latex is concentrated to a solids content of 55% ‘to
70%.
-
C. to a latex of 60% to 95% conversion and a solids con
tent of 20% to 50%, in the presence of at least 5% of 10
residual unreacted polymerizable monomeric material
2,138,073
based on the weight of the original synthetic rubber form
ing monomeric material with 0.05 to 1 part of polyvinyl
2,444,801
2,481,876
2,897,168
3,004,942
alcohol and 0.2 to 2 parts of alkali salt electrolyte se
lected from the group consisting of potassium, sodium, 15
ammonium and amine salts per 1100 parts by weight of
Schweitzer __________ __ Nov. 29,
Arundale _____________ __ July 6,
Rhines ______________ __ Sept. 13,
Brown _______________ __ July 28,
Brown _______________ __ Oct. 17,
1938
1948
1949
1959
1961
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