Protecting the Environment Green Additives for the Coatings Industry

David Torocsik – Borchers OM Group

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Environment in the 21st century reasons for being Green

Definitions of Being Green

“Green” Solutions to Being Environmentally Friendly

Raw Materials from Nature as Building Blocks

Environmentally Friendly Alternatives to Hazardous Chemicals

Conclusion

Content

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Environment in the 21st Century- Good Reason for Being Green

Pictures source: Wikipedia

Europian heat wave 2003 Pakistan floods 2010

Katrina 2005

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Several Definitions of “Green” Products

Low or No VOC’s

Bio-based AND Non-hazardous

The product contains a high percentage of bio-based components either as supplied, or 100% of the active substance is bio-based

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Use more Renewable or Sustainable Non-Hazardous raw materials

Reduce VOC Content by making Higher Solids formulations

Convert our Solventborne formulations to Waterborne with Equivalent Properties

Product Stewardship – Cradle to Grave Awareness

Recycle and Rework Paint Waste whenever possible

How to Become More Environmentally Friendly?

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Vegetable Oils – Triglycerides

Glycerol-Based Alkyds

Use More Raw Materials from Nature as Potential Building Blocks

O

O

O

O

O

O

OO

O

O

O

RO

n

R = Chain of linoleic acid

Chain of a-linolenic acid

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Fatty acids can be a source for metal soaps and alkyd binders

Alcohols can be used to make non-ionic surfactants and PU compounds

Use More Raw Materials from Nature as Potential Building Blocks

O

OH

OH

O

Stearinic acid

-Linolenic acid

OH OH

OO

OO

OH

Lauryl alcohol Stearyl alcohol

Ethoxylated cetyl alcohol

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Polyols: glycerol and sugar derivatives

APG – Alkyl Polyglycosides(biodegradable surfactants)

Use More Raw Materials from Nature as Potential Building Blocks

CH2

CH OH

OH

CH2 OH

Reaction with

HOOC R

OCN R

(Poly)ester

(Poly)urethane

CH2

CH OH

O

CH2 OH

C

O

C17H35

O

OHOH

O

OH

O

C17H33

Glycerol monostearate Sorbitan monooleate

O

OH

O

OH

OH

H

O CH2 CH3n m

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Epoxy Hardeners from Cashew Nutshell Liquid (CNSL)

Acrylic Compounds

Use More Raw Materials from Nature as Potential Building Blocks

OH

R

O

OH

OH

R

R =

Anacardic acid C15:3 Cardanol

OH

R

NH(CH2)nNH2

Phenalkamine

O

OO

OC18H37

O

Furfuryl acrylate Stearyl methacrylate

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What are Environmentally Friendly Additives?

Additives that help make High Solids, Bio-Based or Waterborne Binder alternatives possible

What options are available?

Cobalt Free Driers

Additives that contribute Zero VOC’s

Tin Free Catalysts

Additives Containing Sustainable Raw Materials

Additives with Universal Applications – Waterborne, Solventborne and Solvent Free Coatings that result in fewer Specialized Additives

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The original bio-renewable binder systems were based on natural and synthetic oils (alkyds). However, they had two major flaws that were driving them to extinction:

1. They needed to be dissolved in petroleum based solvents that contain (VOC’s)

2. Also that they needed hazardous metal based catalysts to accelerate crosslinking

Over time Alkyd binders have been developed that are soluble in water or exempt solvents. However, most still rely on metal based driers, which then face us with an even tougher challenge of “how replace metal catalysts considered to be hazardous?”

History of Bio-Renewable Systems

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Cobalt has been the metal drier of choice for binders that cure via oxidation for over 100 years. However, Cobalt carboxylates are on the verge of being labeled more hazardous in Europe which will eventually affect all countries that sell products to Europe making it a global concern

Cobalt carboxylates promote surface dry in coatings and without these surface driers – bio-based binders that cure via oxidation will not dry properly

Cobalt Driers – Regulatory Concerns

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New interim

classification since

June 2013Current Labeling Cobalt-bis(2-ethylhexanoate), Cobalt 2 neodecanoate, Cobalt naphthenateCAS Nr. 136-52-7, EINECS Nr. 205-250-6

DSD:Repr. Cat. 3; R62 - Possible risk of impaired fertilityXn; R65 - lung damage if swallowedR43 - May cause sensitization by skin contactN; R50/53 - Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environmentR66 – Repeated exposure may cause skin dryness or cracking

CLP:Repr. 2; H361f, Skin sens. 1; H317,Eye Irrit. 2; H319,Aquatic Acute 1; H400,Aquatic Chronic 1; H410

Labeling of Cobalt-Carboxylates

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Manganese driers by itself used in waterborne and solvent-borne alkyd systems

Accelerated Manganese driers

Also available are Iron-based complex compounds that work well in waterborne and solventborne alkyd systems, and some contain Zero VOC’s

What are some Cobalt Drier Alternatives?

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Tack Free Dry Time (in hours)

0 2 4 6 8 10 12 14

CoCo replacement #1Co replacement #2

23°C – 55RH(standard conditions)

10°C – 30RH

10°C – 80RH

0 12108642

6264666870727476788082

withoutdrier

0.079% CoCo, Zr drier

0.00065% Fenew catalyst

Ligh

tnes

s (L

val

ue)

dark light

Cobalt Free Driers

Improved dry in cool damp conditions and less yellowing over time

Performance Advantages Involving Cobalt Alternatives

Lightness (L value) after 2 months of storage in the darkand in the light

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Coatings that cure via oxidation require additives to prevent skinning in the can during storage

The most common anti-skinning additive for Cobalt containing systems is the volatile complexing agent methyl ethyl ketoxime (MEKO)

What are some of the issues with MEKO?

Its toxicity and corresponding labeling issues It doesn’t always work well with a number of cobalt replacement

driers

Why Use Anti-Skinning Additives?

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Phenolic based anti-skinning additivesProduct Issues:

slow evaporation the radical absorber stays in the film and may cause yellowing

Other slow evaporating Anti-Skinning additives are aminic compounds dissolved in Fatty acid esters or glycolic solvents

Advantages: Works for all metal types Reduced toxicity Disadvantages: Dosage has to be experimentally determined to avoid excessive

amounts causing prolonged drying time

Anti-Skinning Additives that are possible replacements for MEKO

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polyisocyanate polyol polyurethane

Function to increase chemical reactivity of polyurethane systems

Polyurethanes are used in highly durable coatings, gel coats and other additives like rheology modifiers and dispersants

Catalysts in Polyurethane Based Coatings and Additives

+

R-N=C=O + R`-OH

MLn -

H O

R-N-C-O-R´ catalyst

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Catalysts Mechanism Application

alkylated tin compounds

(e.g. Dibutyltin dilaurate)

Lewis-acid-mechanismpolarization of isocyanateimproves electrophilic properties of carbonyl group

1K & 2K polyurethanesblocked isocyanates

metal carboxylates

(e.g. Bismuth or Lithium)

Lewis-acid-mechanismpolarization of isocyanateimproves electrophilic properties of carbonyl groupInsertion mechanismafter formation of alcoholate

1K & 2K polyurethanesblocked isocyanates

tertiary amines Lewis-base-mechanismincrease nucleophilic properties of OH compound

2K polyurethanesepoxy resins

Catalyst Options Types Used in Coatings

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HMIS rating:  DBTL on the ECHA (European Chemicals Agency - Reach) website has been registered with a GHS 1B reproductive toxicity classification as well as STOT (Specific Target Organ Toxicity) – single and STOT – Repeated Class 1 which could lead to a 3* HMIS rating as they are both chronic endpoints

The Dodd-Frank Act targets the sources of Cassiterite/Tin. There are many unrestricted sources of Tin available but proving the source of Tin is a continuous concern

Tin Catalysts: Hazardous Chemical for the Production of Polyurethane Coatings and a Conflict Mineral

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catalyst influence on the OH-NCO reaction:[OH-Acrylic (D'phen A 870) / Isocyanurate (D'dur N 3300);

concentration: 0.003% metal / binder]

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0:00 2:24 4:48 7:12 9:36 12:00 14:24

time [h]

NC

O-a

bso

rpti

on

DBTL Borchi Kat 24 catalyst 315 catalyst 320 catalyst 322OtherOctoateNeodecanoateAcid Blend

The Effect of different Bismuth carboxylates on OH-NCO reaction:OH-Acrylic (Desmophen A 870) / Isocyanurate ( Desmodur N 3300)

[catalyst concentration: 0.003% metal / solid binder]

PU Catalysts: Tin Based Compared to Bismuth Based on the Organic Components

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pot-Life of different catalyzed clear coats based on Desmophen A VP LS 2383

0

10

20

30

40

50

60

0h 1h 2h 3h 4h 5h 6h 7h

time [h]

visc

osity

[s]

DBTL Borchi Kat 24 Borchi Kat 0243NeodecanoateOctoate

Bismuth Catalysts - Extending Pot Life

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Branched polyurethane oligomer

For waterborne systems

More than 50% sustainable RM

The Smart Choice - Dispersants Based on Sustainable Raw Materials

Contains sugar, fatty alcohol and acid

90% active in water

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Dispersants Based on Sustainable Raw Materials (SRM)

SRM Dispersant Conventional ConventionalSRM Dispersant

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Dispersants Based on Sustainable Raw Materials

SRM Dispersant Conventional ConventionalSRM Dispersant

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The coatings industry uses huge amounts of raw materials and is facing the challenge to switch to renewable resources

Recent alternative additives support the continued use of bio-renewable resin systems where only hazardous materials were effective before

Many sustainable raw materials are already available

New “green” additives can generate equal or better properties to current hazardous agents

Cost effective alternative formulations are possible

Summary

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Questions?

OMG Americas, Inc. 811 Sharon Drive

Westlake, Ohio 44145-1522USA

440-889-2950880-321-9696

eMail: Cust.service@na.omgi.com

www.borchers.com www.omgi.com

Thank you for your attention