Protecting the Environment Green Additives for the Coatings Industry David Torocsik – Borchers OM...
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Transcript of Protecting the Environment Green Additives for the Coatings Industry David Torocsik – Borchers OM...
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
3
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
5
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?
6
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
7
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: [email protected]
www.borchers.com www.omgi.com
Thank you for your attention