REDOX OPTIMIZATION FOR EMULSION

POLYMER POST REACTION:

NEW APPROACH TO REDUCE VOCS,
CYCLE TIME, AND COST

Creating the missing link.

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Contents

• Company
• Introduction
• Lab tests – setup - results
• Conclusions
• Outlook

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Our Company - L. Brüggemann GmbH & Co KG

• Reducing Agents
• Zinc Derivatives
• Polymer Additives
• Ethanol

Subsidiaries in

• Hong Kong
Site Heilbronn, Germany, 2018 • USA

• 220 employees
• 130 Mio. €/year sales
• Family owned since 1868
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Introduction

• State of the art technology for post reaction –

Can we do better?

• Optimization attempt by variation of the relevant variables

• Lab results confirmed by customer

• Cycle time reduction could be achieved

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Reducing Agents - Visualization
SEM pictures of an advanced reducing agent:

• Dust free microganules

• Readily water soluble

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Variables and Monomers

• Production latex using thermal persulfate for main polymerization

• 41% Solids
• 6°C Tg
• pH 2.6
• Total residual monomer ~ 30,000 PPM

• Monomers:
• Methyl methacrylate
• Styrene
• Methacrylic acid
• Butyl acrylate

• Goals:
1. Reduce residual monomers with redox post polymerization
2. Optimize dosage, cycle time, and redox amount used

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Redox components and test series for post polymerization

• Reducing agents
• Bruggolite® FF6 M
• Bruggolite® E28
• Reducing Agent TP 1646
• SMBS

• Oxidizer
• tBHP

• Test series at Brüggemann lab Heilbronn, Germany

• Uniform redox addition over 60 minutes
• Uniform redox addition over 30 minutes
• Compare different reducing agents
• One shot redox addition at time 0

• Essential Polymers tests in Merton, WI, to confirm Brüggemann results

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Test overview and equipment - Brueggemann

• 350 g latex

• Stabilize temperature to 60 °C

• Simultaneous uniform dosage of redox

with Metrohm dosimeters over time

• Dosage is on an "as solids basis" of total latex

• Take samples at various time points

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Test overview and equipment - Brueggemann

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Test overview and equipment - Brueggemann

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Monomer level determination

• Measure butyl acrylate – hardest to remove in this system

• Headspace-GC/MS
• Calibrate and confirm in house measurements vs. stock solutions of
butyl acrylate/styrene
30,00,000
Surface Peak

25,00,000

20,00,000

15,00,000

10,00,000

5,00,000

0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00
BA Content (ppm)

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Brueggemann results
• 60 minutes post polymerization results – Group 1
1,00,000
Residual BA Level, PPM

10,000

1,000

100

10

1
0
15
30
Time of Sample 45
60

0 15 30 45 60
0.2% FF6 / 0.2 % tBHP-1 30,095 1 1 1 1
0.2% FF6 / 0.2 % tBHP-2 31,042 1 1 1 1
0.2% tBHP 29,105 25,818 24,668 22,888 21,496
0.1% FF6 / 0.1% tBHP 29,180 2,672 976 536 517

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Brueggemann results
• 60 minutes post polymerization results – Group 2
1,00,000
Residual BA Level, PPM

10,000

1,000

100

10

1
0
15
30
Time of Sample 45
60

0 15 30 45 60
0.1% FF6 / 0.1% tBHP 29,180 2,672 976 536 517
0.1% TP1646 / 0.1% tBHP 28,392 2,463 113 1 1
0.1% E28 / 0.1% tBHP 28,960 532 152 1 1
0.1% SMBS / 0.1% tBHP 28,613 4,232 1,908 1,383 994

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Brueggemann results
• 30 minutes post polymerization redox feed results – Group 1
1,00,000
Residual BA Level, PPM

10,000

1,000

100

10

0
Time of Sample 15
30

0 15 30
0.1% FF6 / 0.1 % tBHP 28,000 1 1
0.1% tBHP 28,000 25,818 24,668
0.05% FF6 / 0.05% tBHP 28,000 2,672 976

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Brueggemann results
• 30 minutes post polymerization results – Group 2
1,00,000
Residual BA Level, PPM

10,000

1,000

100

10

1
0
15
Time of Sample
30

0 15 30
0.05% FF6 / 0.05% tBHP 28,000 2,672 976
0.05% E28 / 0.05% tBHP 27,906 532 152
0.05% TP1646 / 0.05% tBHP 26,518 2,463 113
0.05% SMBS / 0.05% tBHP 25,930 4,232 1,908

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Brueggemann results
• Compare 60 vs. 30 minutes post polymerization
60 minute vs. 30 minute post polymerization
results after 30 minutes
Residual Monomer Level, PPM

1,00,000

10,000

1,000

100
10
1
0
15
Time of Sample 30

0 15 30
60 Min 0.2% FF6 / 0.2 % tBHP-1 30,095 1 1
60 Min 0.2% FF6 / 0.2 % tBHP-2 31,042 1 1
60 Min 0.1% FF6 / 0.1% tBHP 29,180 2,672 976
30 Min 0.1% FF6 / 0.1 % tBHP 28,000 1 1

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Brueggemann results
• Dose all redox components at time zero
0.05% FF6 / 0.05% tBHP one shot

1,00,000
Residual BA Level, PPM

10,000

1,000

100

10

1
0
5
10
Time of Sample 15
30

0 5 10 15 30
0.05% FF6 / 0.05% tBHP One Shot-1 28,000 4,200 4,000 3,800 2,500
0.05% FF6 / 0.05% tBHP One Shot-2 32,311 4,000 4,162 3,859 2,000

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Post Reaction – Sampling

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Essential Polymers results
• 60 minutes post polymerization
Reducer comparison - 60 minutes at 60°C

100000

10000
Residual BA Level, PPM

1000

100

10

0.2%FF6/0.2%tBH 0.1%FF6/0.1%tBH 0.1%TP1646/0.1% 0.1%E28/0.1%tBH 0.1%SMBS/0.1%t

Untreated 0.2%tBHP
P P tBHP P BHP
Residual BA Monomer (ppm) 24490 1 1 21180 1 1 2020

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Essential Polymers results
• 30 minutes post polymerization
Reducer comparison - 30 minutes at 60°C
100000
Residual BA Level, PPM

10000

1000

100

10

0.1%FF6/0.1%t 0.05%FF6/0.0.5 0.05%TP1646/0. 0.05%E28/0.05 0.05%SMBS/0.0

Untreated 0.1%tBHP
BHP %tBHP 05%tBHP %tBHP 5%tBHP
Residual BA Monomer (ppm) 24490 1 383 22570 1 127.5 609

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Essential Polymers results
• Whitening test procedure

Goal: Test the coating resistance to whitening after 16 hours with half
of the substrate submerged in a water bath

Substrate: Red ceramic tile

Conditions: 2 coats with 2-hour curing time prior to 16-hour water bath

Pass: No whitening or loss of adhesion

Fail: Whitening and/or bubbling of the coating

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Essential Polymers results
• Whitening test results
FCE Code Redox Treatment Blush Test Result Recovery

Control Untreated material Pass Full recovery

FCE162 60 min - 0.2% FF6/0.2% tBHP Pass Full recovery

FCE163 60 min - 0.1% FF6/0.1% tBHP Pass Full recovery

FCE164 60 min - 0.2% tBHP Pass Full recovery

Not white but film not fully

FCE165 60 min - 0.1% TP1646/0.1% tBHP Fail
recovered

FCE166 60 min - 0.1% E28/0.1% tBHP Pass Full recovery

FCE167 60 min - 0.1% SMBS/0.1% tBHP Pass Full recovery

FCE168 30 min - 0.1% FF6/0.1% tBHP Pass Full recovery

FCE169 30 min - 0.05% FF6/0.0.5% tBHP Pass Full recovery

FCE170 30 min - 0.1% tBHP Pass Full recovery

FCE172 30 min - 0.05% TP1646/0.05% tBHP Pass Full recovery

FCE171 30 min - 0.05% E28/0.05% tBHP Pass Full recovery

FCE173 30 min - 0.05% SMBS/0.05% tBHP Pass Full recovery

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Reducing Agents – Solution Preparation

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Conclusions
• Butyl acrylate can be reduced to undetectable levels in
as little as 15 minutes

• The amount of redox components and time period of redox addition

were shown to be related

• Simultaneous redox addition over a shorter time period will minimize

residual monomers, redox dosage, and cycle time

• One shot addition of all redox components is ineffective

• Use of tBHP oxidizer without a reducing agent has no effect

• Use screening tests with different reducing agents to minimize

dosage, cycle time, and residual monomer content

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Outlook

• Similar test procedure with a variety of emulsion polymer systems

• Evaluate different variables like influence of pH, temperature, viscosity

• Investigate possibilities for the main reaction – can the dosage

process be improved with a similar effect of saving time and costs?

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Thank you!

Creating the missing

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link.
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