33 33 Oral The Road to Green Coatings MATTHIAS LUBIK...

Matthias Lubik

01.09.2013 2

Heilbronn Site / Headquarters

01.09.2013 3

BrüggemannChemical Asia, Ltd.Hong Kong

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BrüggemannChemical U.S., Inc.

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USA and Asian Subsidiaries

01.09.2013 4

Business Activities

Matthias Lubik, Lecture 33 ABRAFATI 2013 – September 16th

The Future of Emulsion Polymerization with Bruggolite®FF6 M

ASC Spring Convention

5

VOC and Formaldehyde Free Initiator Systems –

The Future of Emulsion Polymerization with Bruggolite ®FF6 M

The Road to Green Coatings




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- Polymer dispersions are widely used in the coatings industry due to their better environmental profile

- Binders based on water borne polymer dispersions continue to replace solvent borne system globally in all coatings segments

- The main ingredients for the polymerization process are water, monomers, surfactants and an initiator system

Introduction – Polymer Emulsions




7





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Mechanism:

Initiation: I → 2R• (Decomposition of initiator)M + R• → R─M•

Propagation: R─M(n)• + M → R─M(n+1)•

Termination: R─M(n+1)• + R• → R─M(n+1)R





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Reducing agents together with oxidizing agents are the source of free radicals that are generated and start the respective free radical reaction.

Below is an example highlighting the reaction of sodium sulfite (Na2SO3) as the reducing agent with ammonium persulfate ((NH4)2S2O8) as the oxidizing agent:

Introduction – Reducing Agents

Na2SO3 (NH4)2S2O8

.+Na2SO3 NH42 +

SO4

2 -SO4

. -+ +++

Na2SO3

.++ (NH4)2S2O8 Na2SO4 NH42 +

SO4

2 -SO4

.-+ +++ H2O + 2 H

+

Reducing agents are the substances in a redox reaction that donate electrons to another species

Oxidizing agents are the substances in a redox reaction that accept electrons from another species




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Formaldehyde is currently described as a known human carcinogen

Legislation in Europe and North America bans formaldehyde for several uses

ECHA (European Chemicals Agency) will recommend a classification as "substance which is presumed to have carcinogenic potential for humans” starting in 2015 which represents another tighter regulation of formaldehyde use

Introduction Formaldehyde Toxicity




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Why Reduce Monomers ?

- Reduce VOC and odors/toxicity- Improve conversion yield - Improve polymer performance, appearance, and hardness- Reduce grits

What Types of Monomers are to be Considered?Most hydrophobic monomers such as 2-ethylhexyl acrylate, butyl acrylate, lauryl methacrylate, and vinyl neodecanoate (VeoVa™)…Typical water based systems like X-NBR/SBR, vinyl acetate, vinyl acetate ethylene (VAE), styrene acrylics, acrylics, hybrid systems,…

How?Process technique and novel reducing agent to obtain < 200 ppm residual monomer content

Introduction




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Main Polymerization- Water- Surfactant- Monomers- Acrylic Acid- Persulfate- Other

Post Polymerization

Water -Reducing Agent -

Oxidizing Agent (tBHP) -

Ammonia –

Reducing Agents – AA (Sodium salts of isoascorbic or erythorbic acid); SFS (Sodium formaldehyde sulfoxylate); FF6 M

Process Chemistry




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Reducing Agents - Comparison

Na+O S

O

C

H

H

OH

Hydroxymethyl sulfinicacid sodium salt

Na+O S

O

HC

O

HH

Na+O S

O

C

H

OH

CO

O

Na+

Na+O S

O

HC

O

H

CO

O

Na++

90 °C

Sodium sulfinate Formaldehyde

FF6

2-Hydroxy-2-sulfinatoacetic acid disodium salt

65 °C

+

Sodium sulfinate Sodium glyoxalate

(Sodium Formaldehyde Sulfoxylate)

SFS




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- Stay in the Green Zone

- Optimize for your Specific Chemistry

- Initial Charge Shot of Reducer

Process Factors for Bruggolite ®FF6 M

FF6 M Solution Concentration 3-5%

20°C




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Vinyl acetate Emulsion Polymer Formula:

Example Polymerization Data - VA




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Emulsion polymerization of Vinyl acetate at 20 °C a nd pH=5


0

20

40

60

80

100

0 5 10 15 20 25 30 35 40

Conversion [%]

Time [min]

Bruggolite®FF6 M

SFS

AA




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Vinyl acetate and VeoVa Formula:


VeoVa™ (Source: Momentive)




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Emulsion polymerization of Vinyl acetate and VeoVA TM using H 2O2 oxidizer

Example Polymerization Data - VeoVa™

0

300

600

900

1200

1500

1800

2100

2400

0 30 60 90 120

Residual monomer level [ppm]

Time [min]

Vinylacetate VeoVa

11043 ppm




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High Reactivity of FF6 M

20°C 40°C 60°C

0

1000

2000

3000

4000

5000

6000

7000

8000

Residual Monomer Content [ppm]

Model System Vinyl Acetate – Main Polymerization

Temperature [°C]

50% FF6 M Dosage

AA (Ascorbic Acid) FF6 M




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High Reactivity of FF6 MPost Polymerization; Acrylic Latex, 60°C, FF6 M / TBHP, weight basis; Residual Monomer: 2-Ethyl hexyl acrylate




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Reduction of Oxygen in Water at 20 °C and pH = 5, with 1.0% Reducing Agent

Effectiveness of Reducing Agents

0,00

2,00

4,00

6,00

8,00

10,00

12,00

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Oxygen [ppm]

Time [min]

Bruggolite FF6 M

SFS

AA




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Measuring Redox Potential




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Prevention of Polymer Yellowing

Vinyl acetate – Main Polymerization

Styrene acrylate – Main Polymerization

3 d / 30°C 2 h / 50°C 2 h / 75°C 1 h / 100°C 1 h / 120°C

FF6M

AA

FF6M /Iron salt

AA /Iron salt

FF6M /No Iron

after3 weeks / 40°C




Hydrophobicity – Monomers - Polymers

Monomer Water Solubility at

20°°°°C (g/100g)

Vinyl neodecanoate <0.001

2-ethylhexyl acrylate 0.01

Styrene 0.03

Butyl acrylate 0.16

Methyl Methacrylate 1.5

Ethyl Acrylate 1.8

Vinyl acetate 2.5

Methyl acrylate 5.2

Water Solubility as Indicator of Hydrophobicity

D. R. Bassett, "Hydrophobic Coatings from Emulsion Polymers," Journal of Coatings Technology,

January 2001

� Main requirement for protective and exterior coatings is to provide effective barriers against water

� This can be done by increasing the hydrophobicity of the binders used

� The use of very hydrophobic monomers in emulsion polymerization can result in slow monomer transport and low reactivity leading to high residual monomer content

9/1/2013




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Food Contact Status

Formaldehyde Standards for Composite Wood Products Act – July 2010

FDA “Food Contact Notification” since 10/2005

§175.105 (Adhesives)§177.2600 (Rubber articles for repeated use)§176.170 (Paper and board/aqueous and fatty food)§176.180 (Paper and board / dry food)

BfR “Food Contact Notification” since 05/2005

VI (Styrene polymers, polystyrene mixtures)XIV (plastic dispersions)XXXIV (Vinylidene copolymers)




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Future Chances with Bruggolite FF6 M

Main polymerization – Idea Stage

- More controlled reactions with FF6 M based redox system

- Tailor-made polymers with improved physical properties

- Soft-start-polymerization with no retardation - Lower temperature initiation for free radical

generation- Avoiding of side reactions and cross-linking - Controlled molecular weight distribution




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Future Chances with Bruggolite FF6 M

Post polymerization

- Replacement of physical stripping- Less energy consumption- No recycling of monomer streams- Higher throughput- Overall higher process equipment utilization




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Conclusions and Results

-Residual monomer content can be reduced from 2,000 to < 200 ppm by using Bruggolite® FF6 M

-Most applicable to hydrophobic monomers

-Process conditions will be different than for SFS or AA

-Formaldehyde free system

-Non-yellowing

-Less reactor time to achieve specific monomer content

• Questions?




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� Brenntag Quimica Brasil Ltda.� Cristiane Freitas at [email protected]� Phone: 551155452119� www.brenntagla.com

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33 33 Oral The Road to Green Coatings MATTHIAS LUBIK...

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