Redox for Main Polymerization of

Emulsion
Polymers
By Paul Fithian and Mike O’Shaughnessy,
polymerization, and what impact they would have on poly-
BruggemanChemical U.S., Inc., Newtown Square, mer properties, performance and monomer conversion.
PA; and Matthias Lubik and Stefan Mark, This article will present results comparing thermal ini-
L. Brüggemann GmbH & Co. KG, Heilbronn, Germany tiation of main polymerization to redox initiation at lower

I
temperatures. Two series of tests were performed – one using
t is well known that utilizing a redox pair is an a 45%-solids latex, the second using a 50%-solids latex.
effective way to reduce free monomer at the end For each series, acrylic latex of butyl acrylate, methyl
of an emulsion polymerization process. This is methacrylate and methacrylic acid was produced. Data
because a redox couple generates a large amount was developed comparing a thermally initiated latex to one
of free radicals capable of converting low levels of free using redox for the main polymerization. A redox chase
monomer. The ability to use redox chemistry for initia- was then performed for each case. Residual monomer levels
tion of main polymerization is also known to be effective. and polymer properties are shown to compare the perfor-
For some systems, these redox reactions can be done at or mance of each test.
below room temperature.
A new family of advanced sulfinic acid derivative reduc- Main and Post-Emulsion Polymerization
ing agents has been developed that offer higher reactiv- Many current emulsion polymer production recipes use a
ity when compared to conventional reducing agents in combination of thermal and redox radical generation, in two
the post polymerization. This work was undertaken to distinct steps in the process, main and post polymerization.
determine if they could be used for the initiation of main A typical main polymerization process utilizes a per-
sulfate to generate radicals, initiating and sustaining
polymerization. Heating the emulsion with the persul-
FIGURE 1 È Residual monomer level of reducing agent tests.
fate initiator to ~ 80 °C cleaves the persulfate molecule
Total Residual Monomer Level

into two radicals. Conversion of the monomer continues,

50,000 however the curve of monomer conversion is asymptotic,
40,000 resulting in a very long time for little monomer conver-
sion at the end of the main polymerization. Although this
30,000
results in 99% + conversion of the monomer, monomers
20,000 used in emulsion polymerization are VOCs and typically
10,000 have an offensive odor.
Post polymerization using redox chemistry is currently
0 No Fe(II)
utilized for most emulsion polymers. When introduced
Advanced 2 mL 1% Fe(II) into the system toward the end of monomer conversion
Ascorbic
Sulfinic Sodium
Acid SFS in the main polymerization period, a flood of radicals is
Acid Sulfite
Derivative introduced into the system, converting monomers into

24 nnn AUGUST 2017 | W W W . P C I M A G . C O M

dimers, oligomers and short polymer chains. Since most All tests were performed in a 3 L glass-jacketed reactor
of the monomer has already been converted into desired fitted with a four-neck top. Inserted into the necks were
polymer in the main polymerization step, these oligomers inlets for oxidizer, reducer, stirrer, nitrogen, thermo-
are not viewed as detrimental to the formed polymer. It couple, monomer emulsion feed tube and condenser. Dur-
can be viewed as a “clean up” operation to reduce free ing polymerization, samples were analyzed for residual
monomer, resulting in lower VOCs and odor. monomers to measure effectiveness over time. Physical
Redox components used in production post polymeriza- properties of the final polymer were compared.
tions typically use the following: Two series of tests were performed, the first with a
45%-solids latex, the second with a 50%-solids latex.
Oxidizers: Hydrogen peroxide The process approach utilized a seed polymer and a
tert-Butyl hydroperoxide (tBHP) monomer pre-emulsion. In both series, for main polym-
Ammonium persulfate (AP) erization, thermal initiation run at 80 °C is compared to
40 °C redox initiation. In the second series, a third case
Reducing agents: Ascorbic acid (AA) was run with redox initiation at 20 °C. These lower-
Sodium formaldehyde sulfoxylate (SFS) temperature redox reactions were allowed to heat up
Sodium sulfite adiabatically to increase reaction rate, negating the need
Sodium metabisulfite (SMBS) for vessel preheating. Identical monomer feed profiles
Advanced sulfinic acid derivative were used in each case. For all cases, after the main
reaction step, an identical post polymerization step was
Comparison of Various Reducing Agents performed to reduce residual monomers.
for Redox-Initiated Main Polymerization
An earlier study by BrüggemannChemical screened sev- Series 1 Emulsions: 45%-Solids Latex
eral reducing agents to determine which one would pro- Monomer Emulsion Feed
duce the fastest and most complete conversion of mono- Deionized water and sodium lauryl sulfate (SLS) at
mer in a styrene-butyl acrylate system. 29.5% solids were added to a flask and mixed for 1 min.
The testing utilized an adiabatic system to correlate Under agitation, to this flask was added in the follow-
temperature rise with monomer conversion. Tests were ing order; butyl acrylate, methyl methacrylate and
conducted with and without the addition of an iron sulfate methacrylic acid. These monomer levels were chosen
heptahydrate solution. to produce a latex with a glass transition temperature
This reaction mixture was heated to 60 °C. Shots of the (Tg) of about 1 °C, common for latexes that are used in
redox couple (selected reducing agent + ammonium per- low- or zero-VOC paint formulations.
sulfate) were added initially and at the 60/120/180-min
marks. Both reducing agent and ammonium persulfate TABLE 1 » Feed profile for Series 1 emulsions.
solution concentrations were 56.24 g/L. Each shot con-
sisted of 10 mL of this solution, added simultaneously via Feed Profile Start Time Stop Time Rate (g/min)
separate feed lines. Pre-emulsion (Rate 1) 0 30 2.0
In both cases, an advanced sulfinic acid derivative Pre-emulsion (Rate 2) 30 240 4.2
showed the earliest and highest temperature rise, indicat- Oxidizer/reducer 0 240 0.22
ing faster and more complete conversion of monomer, Post oxidizer/reducer 255 315 0.43
with or without addition of an iron transition metal.
Virtually no temperature rise was observed with the TABLE 2 » Latex properties for Series 1 emulsions.
advanced sulfinic acid derivative with subsequent addi-
tion, with or without iron sulfate heptahydrate solution. 80 °C Thermal 40 °C Redox
This indicates full conversion with only one dose of the Initiation Initiation
advanced sulfinic acid reducing agent, showing it to be far Property
more effective than the others tested. pH
The other reducing agents showed far less activity, and Initial 6.7 6.4
needed three or four doses of the redox couple to start Final 8.0 8.0
polymerization and begin generating heat. In this test,
Particle size
Figure 1 reveals that an advanced sulfinic acid derivative
Dv 138 140
is much better at converting monomers than the other
three reducing agents tested. Dn 131 133
Da 136 138
Further Study of Thermal vs. Redox for Total solids (%, 50 °C) 45 45
Main Polymerization Viscosity (cps, LVT #3 spindle, 12 RPM) 2 2
The results of the earlier work from Figure 1 prompted Filterables, PPM
further study of the use of a redox couple to initiate 40 mesh 3 1
main polymerization in a new all-acrylic system. These 150 mesh 12 4
tests utilized standard industrial equipment, practices
Tg, °C 0 1
and materials that are common to most emulsion poly-
mer facilities. MFFT, °C <4 <4

PA I N T & C O A T I N G S I N D U S T R Y  25
 Redox for Main Polymerization of Emulsion Polymers

Reactor Charge tor charge reached the reaction set point, the oxidizer
Water was added to a separate flask for the initial charge was added to the reactor. Simultaneously, the
charge. Under agitation, to this flask was also added monomer pre-emulsion was started at the prescribed
sodium bicarbonate, SLS and seed latex (previously pre- rate using a piston pump. After 30 min, the monomer
pared) to form the initial reactor charge. The seed latex pre-emulsion feed rate was increased to the new set
amount was chosen to obtain the appropriate particle point. The overall feed time for the monomers was 4
size at the end of the reaction and also to reduce batch- hrs. The oxidizer and the reducer (where appropriate)
to-batch variation in particle size. were started simultaneously with the monomer feed.
These were fed at a constant rate, using a syringe pump.
Oxidizer and Reducer Charges When the reducer was not used in this feed, water allo-
The oxidizer and reducer solutions were made by dis- cated for the reducer was still fed into the reactor to
solving the appropriate amount of each ingredient in maintain consistent solids concentration for all runs.
water. They were made up just before the reactor contents For the 80 °C thermal initiation, the vessel was pre-
reached the starting temperature of the reaction. heated to 80 °C. Only ammonium persulfate (APS) was
used during the monomer feed since the temperature of
Reaction Procedure the reaction allowed for an appropriate flux of APS radi-
The initial charge was added to the reactor. The head- cals at 80 °C via the reaction [O3SO–OSO3]2− ⇌ 2 [SO4] •−.
space was purged rapidly with nitrogen for 1 min to After the 4-hr monomer pre-emulsion feed was com-
eliminate oxygen. The reactor contents were then plete, the reactor contents were cooled to 70 °C over 30 min
heated to the starting temperature. When the reac- to simulate transfer to a cooling tank. The redox of tBHP
and advanced sulfinic acid derivative was then fed over
60 min. Simultaneously the reactor was further cooled to
FIGURE 2 » Monomer levels of 80 °C thermal initiation. 60 °C. After this, the reaction was cooled to 20 °C.
END OF START OF POST END OF POST
The 40 °C redox initiation was preheated to 40 °C
PRE-EMULSION FEED REDOX FEED REDOX FEED and allowed to heat adiabatically to 60 °C during the
Monomer Level, PPM

100,000
reaction. The advanced sulfinic acid derivative reducer
10,000 was used to activate the APS at this low temperature. In
1,000
an effort to simulate adiabatic temperature rise in the
BA reactor, similar to industrial reactors, the glass reac-
100 MMA tor was insulated with packing cloth and covered with
10 MAA thick aluminum foil. Upon the start of the reaction,
the heating water in the jacketed reactor was drained
1
0 30 60 90
and the reactor contents were allowed to increase in
temperature solely due to the heat of the reaction. The
Time, Min. reaction temperature continued to increase throughout
the monomer pre-emulsion feed. It reached a maximum
of 60 °C at the end of the feed.
FIGURE 3 » Monomer levels of 40 °C redox initiation. After the 4-hr monomer pre-emulsion feed was com-
END OF START OF POST END OF POST
plete, the reactor contents were maintained at 60 °C for
PRE-EMULSION FEED REDOX FEED REDOX FEED 30 min. Then the redox of tBHP and advanced sulfinic
Monomer Level, PPM

100,000 acid derivative was fed over 60 min while the reactor
10,000 temperature was maintained at 60 °C. After this, the
reaction was cooled to 20 °C. Further details on feed
1,000
BA profiles are in Table 1.
100 MMA

10 MAA Results
The results were similar for both reactions in most proper-
1 ties. Table 2 describes observations of the latex properties
0 30 60 90
produced by both recipes used in the Series 1 tests.
Time, Min.
Monomer Level Profile During Reactions
TABLE 3 » Molecular weight of Series 1 emulsions. Samples for monomer levels were taken at four times dur-
ing the reaction per the following:
80 °C Thermal Initiation 40 °C Redox Initiation
1. End of pre-emulsion feed.
Peak 1
2. After 30-min hold to simulate transfer of the reactor con-
Mn 133,000 139,000
tents to a post reaction tank. This often occurs in indus-
Mw 274,000 269,000 trial processes. This is also the start of post redox feed.
3. Middle of redox feed.
Peak 2 4. End of redox feed.
Mn 483 557 As shown in Figure 2 and Figure 3, the reaction
Mw 519 602 run with redox initiation in the main feed produced

26  AUGUST 2017 | W W W . P C I M A G . C O M

lower total levels of monomers than the thermal ini- TABLE 4 » Gel content of Series 1 emulsions.
tiation. This is surprising since the redox reaction was
performed at lower temperatures. Lower temperatures 80 °C Thermal Initiation 40 °C Redox Initiation
usually result in slower polymer growth. In both cases % %
the post redox with tBHP and advanced sulfinic acid Sample 1 76 72
derivative was very effective in reducing total monomer
Sample 2 74 70
concentration in the reaction.
Average 75 71
Molecular Weight Analysis
Each of the latexes produced in Series 1 were analyzed for TABLE 5 » Feed profile for Series 2 emulsions.
molecular weight. HPLC conditions for molecular weight
analysis were: Feed Profile Start Time Stop Time Rate (g/min)
• Agilent 1100 system with RI detector. Pre-emulsion (Rate 1) 0 30 2.0
• Column PLGel mixed D 7.5x300 mm + PLGel mixed C
guard 7.5x50 mm. Pre-emulsion (Rate 2) 30 240 3.8
• Column Temperature: 60 °C. Oxidizer/reducer 0 240 0.22
• Mobile phase: THF.
Post oxidizer/reducer 270 330 0.22
• Flow rate: 1 mL/min, isocratic.
• 40 µL injection.
Both reactions produced similar molecular weight
polymers (Peak 1). Second peak (Peak 2) is a combination FIGURE 4 » Temperature profile of thermal and redox initiation.
of oligomers and surfactant. Table 3 shows the molecular END OF START OF POST
90
Temperature, ºC

weight analysis results. PRE-EMULSION FEED REDOX FEED

80
70
Gel Content Analysis 60 80 ºC Thermal Initiation
Dried latex specimens were weighed, placed in a 150 mesh 50 40 ºC Redox Initiation
40 20 ºC Redox Initiation
stainless steel pouch and then immersed in extracting 20 ºC Redox Initiation –
30 Extra Reducer
solvent (THF) for 3 days. After extraction, the specimens
20
were removed, dried and reweighed and the gel content 0 30 60 90 120 150 180 210 240 270 300 330
was calculated. The gel contents were similar between the Time, Min.
two reactions, shown in Table 4.

Series 2: 50%-Solids Latex FIGURE 5 » Monomer levels of 80 °C thermal initiation reaction.

Reaction Procedure
All procedures were the same as in Series 1, except that 100,000
Monomer Level, PPM

tests were performed starting at 40 °C and 20 °C. Feed BA

10,000
profiles used are listed in Table 5. MMA
Note that the data presented in this series shows pro- MAA
1,000
gression of temperature and residual monomer levels
over the entire reaction. This is different than the data 100 END OF
presented in the Series 1 reactions, which show only the PRE-EMULSION
FEED
variables after the end of pre-emulsion feed. 10 START OF
POST
REDOX FEED
Results 1
Figure 4 shows a profile of temperature for all recipes. 30 60 90 120 150 180 210 240 270 300 330

Note the temperature rise for the redox-initiated latexes Time, Min.
as the reaction heats the vessel adiabatically. During the
first test with the 20 °C redox initiation, some evidence of FIGURE 6 » Monomer levels of 40 °C redox initiation.
monomer pooling was observed, as can be seen in the flat
spots of the temperature curve. To eliminate monomer 100,000
Monomer Level, PPM

pooling, additional reducer was used in the first 30 min.

10,000
Amount of reducer added during this time was doubled,
an increase of 0.1125 grams, for a total amount of reducer 1,000 BA
in the main polymerization of 1.0125 grams. On a per-
MMA
centage basis, the amount of reducer went from 0.16% 100
END OF MAA
on monomer solids to 0.17%. Weight ratio of oxidizer to PRE-EMULSION
FEED
reducer went from 3.88/1 to 3.46/1 10 START OF
POST
REDOX FEED
Monomer Level Profile During Reactions 1
30 60 90 120 150 180 210 240 270 300 330
Samples for monomer levels were taken 11 times during
the reaction: Time, Min.

PA I N T & C O A T I N G S I N D U S T R Y  27
 Redox for Main Polymerization of Emulsion Polymers

1. Every 30 min during monomer pre-emulsion feed (7

FIGURE 7 » Monomer levels of 20 °C redox initiation. samples).
100,000 2. End of pre-emulsion feed.
Monomer Level, PPM

3. After 30-min hold to simulate transfer of the reactor con-

10,000
tents to a post reaction tank. This often occurs in indus-
trial processes. This is also the start of post redox feed.
1,000 BA 4. Middle of redox feed.
100
MMA 5. End of redox feed.
END OF
PRE-EMULSION MAA The 40 °C redox initiation reaction produced lower
FEED
10 START OF
total levels of monomers than the 80 °C thermal initiation
POST reaction. This is surprising since the redox reaction was
REDOX FEED
1 performed at lower temperatures. Lower temperatures
30 60 90 120 150 180 210 240 270 300 330
usually result in slower polymer growth. The 20 °C redox
Time, Min. initiation produced slightly higher residual monomers,
however when extra reducer was used, it resulted in the
lowest total free monomer level.
FIGURE 8 » Total free monomer comparison. In all cases the post redox with tBHP and advanced
100,000
sulfinic acid derivative was very effective in reducing total
monomer concentration in the reaction. Data for these
Monomer Level, PPM

reactions are presented in Figures 5, 6 and 7.

10,000
Combining the data to look at total free monomer for
this series, and including the run with extra reducer for
1,000 the 20 °C redox-initiated case, it is shown in Figure 8 that
the redox-initiated main polymerization shows a signifi-
100 cant reduction in total free monomer level.
80 ºC Thermal Initiation
40 ºC Redox Initiation Latex Property Results
10 END OF START OF 20 ºC Redox Initiation
PRE-EMULSION POST The results were similar for all three reactions in most
FEED REDOX FEED 20 ºC Redox Initiation– Extra Reducer
properties. It should be noted that the filterable solids
1
240 270 300 350 were very low and the reaction vessels were easily
Time, Min.
cleaned. Table 6 describes observations of the latex prop-
erties produced by both recipes used in the Series 2 tests.

TABLE 6 » Latex properties for Series 2 emulsions. Molecular Weight Analysis

HPLC conditions for molecular weight analysis were:
40 °C 20 °C • Agilent 1100 system with RI detector.
80 °C Thermal
Redox Redox • Column PLGel mixed D 7.5x300 mm + PLGel mixed C
Initiation
Initiation Initiation guard 7.5x50 mm.
Property • Column temperature: 60 °C.
• Mobile phase: THF.
pH
• Flow Rate: 1 mL/min, isocratic.
Initial 6.6 6.6 6.6 • 40 µL injection.
Final 8.23 8.14 8.04
The reactions produced higher MW as a function of
Particle size decreasing temperature of reaction as expected from
Dv 137 131 140 theory (Peak 1). The Mw increased by over 50% when
the temperature was reduced from 80 °C to 20 °C. This
Dn 128 123 133 is expected to produce improved properties such as
Da 134 128 138 scrub resistance. Second peak (Peak 2) is a combina-
tion of oligomers and surfactant, and remains constant
Total solids (%, 50 °C) 50 50 50 for the three reaction temperatures. Molecular weight
Viscosity observations are in Table 7.
10 9 9
(cps, LVT #3 spindle, 12 RPM)
Gel Content Analysis
Filterables, PPM Dried latex specimens were weighed, placed in a 150
40 mesh 9 3 11 mesh stainless steel pouch and then immersed in
extracting solvent (THF) for 4 days. After extraction, the
150 mesh 15 7 19
specimens were removed, dried and reweighed, and the
Tg, °C 1 0 0 gel content was calculated. The gel contents were similar
between the three reactions. Gel content observed can be
MFFT, °C <4 <4 <4
found in Table 8.

28  AUGUST 2017 | W W W . P C I M A G . C O M

TABLE 7 » Molecular weight of Series 2 emulsions. Expected Areas of Value Creation
• Elimination of the heating step of initial reactor charge, reduc-
80 ˚C Thermal 40 ˚C 20 ˚C ing energy consumption and time.
Initiation Redox Initiation Redox Initiation
• Adiabatic temperature rise during reaction, allowing for faster
Peak 1 cycle time since less cooling is required.
Mn 62,755 89,400 96,100 • A reduction in reactor fouling is anticipated since the reactor is
Mw 184,600 243,850 282,500 always in cooling mode. This should reduce “baked on” latex on
the sides of the reactor, increasing time between cleanings and
Peak 2
shortening time needed to clean reactor.
Mn 202 199.5 200 • Value of yet-unknown properties of latex polymer, although
Mw 206 201.5 203 higher Mw usually results in improved toughness and abrasion
resistance. 
TABLE 8 » Gel content of Series 2 emulsions.
For more information:
80 °C Thermal 40 °C 20 °C L. Brüggemann GmbH & Co KG
Initiation Redox Initiation Redox Initiation Heilbronn, Germany
% % % [email protected]
Sample 1 79 76 75
Sample 2 76 74 78
BrueggemannChemical Asia Ltd.
Hong Kong
Average 78 75 77 [email protected]

FIGURE 9 » ASTM D 2486 scrub resistance comparison. BruggemannChemical U.S., Inc.

Newtown Square, PA
160
Average % of control [email protected]
140
Percent of Control

120

100

80

60

40

20

0
80 ºC 40 ºC 20 ºC
Thermal Initiation Redox Initiation Redox Initiation

Scrub Data Comparison of Latexes

Resins produced in the 50%-solids cases were formulated into
paint. Scrub data for each were compared, using ASTM D 2486
protocol. Results can be seen in Figure 9, revealing a much higher
scrub resistance for the latexes produced via low-temperature
redox initiation.

Conclusions
There was good process control for both the thermal system
reacted at 80 °C and the redox system started at 40 °C. There
was no monomer pooling or temperature variation other than
a slow rise in temperature from 40 °C to 60 °C. When starting
at 20 °C, additional reducer should be introduced in the early
stages to prevent monomer pooling.
Similar latex polymer properties were obtained using the
redox during the monomer feed starting at 40 °C and 20 °C. The
Mw of the latex polymers increased with lower starting reac-
tion temperatures. This resulted in more-durable latex paints.
Scrub resistance for the paint formulated with low-temperature
redox-initiated latexes was higher than thermal-initiated latex,
an increase of 52% for the Series 2 case run at 20 °C. This is due
to the increase in molecular weight.

PA I N T & C O A T I N G S I N D U S T R Y  29