Chempol® MPS Resins and Sefose® Sucrose Esters Enable High

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Chempol® MPS Resins and Sefose® Sucrose

Esters Enable High-Performance Low-VOC

Alkyd Paints and Coatings

Manuel Venegas, P&G Chemicals

Neal Rogers, CCP

P&G Chemicals

• Oleochemical Foundation– Glycerine

– Fatty Alcohols

– Methyl Esters

– Fatty Acids

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– Fatty Acids

– Tertiary Amines

• Food Ingredients

• SEFOSE®

• Flavors & Fragrance

Coating Resins: Coating Resins:

Providing broad product portfolio and

technical expertise in coatings and

structural resins

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Coating Resins: Coating Resins:

solvent-based, waterborne, powders, additives

Liquid Coatings Resins:

•CHEMPOL Alkyds, Polyesters,

Solution Acrylics

•SYNAQUA Dispersions

•CRAYMUL, ESICRYL Specialty

Acrylic Emulsions

Market Focus Areas:

•Industrial

•Architectural

•Marine

•Graphic Arts

•Floor Care

Outline

• Alkyd Coatings: Situational Analysis

• Sefose® Technology

• CHEMPOL® MPS Performance Benefits

– Environmental

– Health and Safety

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– Health and Safety

– Paint Performance

• Summary

• Acknowledgements

• Questions

U.S. Coatings

Resin Market (2006)1

2006 Coatings ResinTechnology

Segmentation by Pounds of Solid Resin

7%7%

42%

40%

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• Coatings: Solvent-based ≈ water-based

• 3.4 billion lbs of solvents used in U.S. coatings sectors

• 45% of solvents are hydrocarbons; aromatics (e.g. xylene, toluene), aliphatics (e.g.

hexane, decane)

Water-Based Solvent-Based Powder

100% Solids E-Coat Radiation Cured

What is an Alkyd Resin?

O

O

O

R2

O

O

R3

O

R1

+ HO OH

OH

Catalyst

OH

OH

O

R1,2, 3

O

Tryglyceride

Glycerine Mono-glyceride

R1,2,3

Polyol

Drying Oil

Fatty acid modified polyester

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• Drying oil selection (soybean, linseed, etc.) based on drying properties requirements; typically 30-70% of

the alkyd resin

• Soybean oil alkyds most common in U.S.

Tryglyceride

OH

OH

O

R1,2, 3

OO OO

+Catalyst

-H2O

O O

O O

O

O

O

O

O O

O*

*

O

R1,2,3

O

R1,2,3PhthalicAnhydride

Alkyd Resin

Polyacid

Relevance Of Alkyd Coatings

Key Attributes

• Cost effective

• Good penetration properties

• Better adhesion

Key Opportunities

• Eliminate solvents � Lower VOC levels

• Increase renewable content - “Greener”

• Enhance performance

Why are Alkyd-Based Coatings Still Used?

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• Better adhesion

• High gloss finish

• Hard, less permeable films

• Favorable drying profile

• Some RenewableRenewableRenewableRenewable content

• Enhance performance

• Easy clean up

Alkyds provide unique formulation, application, cost and dry film properties unmatched with other resin Alkyds provide unique formulation, application, cost and dry film properties unmatched with other resin Alkyds provide unique formulation, application, cost and dry film properties unmatched with other resin Alkyds provide unique formulation, application, cost and dry film properties unmatched with other resin

typestypestypestypes

Analysis of Alkyd Coatings

• 27% of resins for solvent-based coatings are alkyds, 540 MM lbs.

• Alkyd coatings contribute to VOC emissions

• Existing Low VOC-capable resins compromise on performance:

– Low molecular weight alkyds� Slow dry

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– Low molecular weight alkyds Slow dry

– Exempt solvents are expensive and/or w/ undesired odor / performance

– Acrylic emulsion resins offer low VOC solution but have short open times, low gloss, and

reduced corrosion resistance; i.e. undesired attributes for many applications

Breakthrough Innovation

Sucrose polyesterSucrose polyesterSucrose polyesterSucrose polyester tailoredtailoredtailoredtailored to work to work to work to work synergisticallysynergisticallysynergisticallysynergistically with alkyd resinswith alkyd resinswith alkyd resinswith alkyd resins

CCP and P&G � SOLUTION: CHEMPOLCHEMPOLCHEMPOLCHEMPOL®®®® MPSMPSMPSMPS

� New family of alkyd resins using Sefose® Sucrose Polyesters

� Enable low VOC solventborne coating formulations

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Sucrose polyesterSucrose polyesterSucrose polyesterSucrose polyester tailoredtailoredtailoredtailored to work to work to work to work synergisticallysynergisticallysynergisticallysynergistically with alkyd resinswith alkyd resinswith alkyd resinswith alkyd resins

� Co-reactant that becomes an integral part of coating film � auto-oxidative cross-

linking

� Provides optimal viscosity control even for high solids finished products

� Renewable non-volatile modifier of traditional alkyds

� Non-persistent, non-toxic and 100% biodegradable

What is Sefose® ?

• A highly esterified sucrose polyester (SPE) made from sugar and vegetable oils.

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Triglyceride � Mw 800-1000 SPE � Mw 2400-2800, unique molecular

architecture and tailorable reactivity &

physical properties

SPE Process Summary

Refining,

Hardening and

Deodorizing

Methyl Ester Making and

Distillation

SPE Reaction

System

Refining,

Drying and

Filtration

Methyl Ester

Evaporation

and Stripping

Methanol

Water

Glycerin

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Filtration and Stripping

and other

Sucrose

reactants

Sucrose Polyester

O

O

O

O

O

O

O

O

O

O

OO

O

O

O

OO

O

O

Vegetable Oil:

• soybean

• safflower

• rapeseed

• canola

• cottonseed

• sunflower

• etc

SPE Reaction

Two Stage Esterification ReactionTwo Stage Esterification ReactionTwo Stage Esterification ReactionTwo Stage Esterification Reaction

Stage 1 – Form Sucrose Partial Esters

Sucrose + 1 - 4 RCOCH3

O

K2CO3

K+ Stearate

(emulsifier)

SE1-4 + 1- 4 MeOH

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O (emulsifier)

• Sucrose insoluble in FAME

• Soap used as emulsifier to bring FAME

and sucrose together

• Formed sucrose mono- & di-esters

further emulsify sucrose

• More sucrose reacts, speeding up

reaction

SPE Reaction

Key Process Parameters

• 275oF

• Good mixing

• Minimize “charring”

Soap/Sucrose

and FAME

Catalyst & FAME

Nitrogen &

Methanol

Vacuum System

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• Minimize “charring”

• Remove MeOH

• Low moisture, low O2

Nitrogen

RadialFlowImpeller Sucrose

partial esters

SPE Reaction

Stage 2 – Convert Sucrose Partial Esters to Sucrose Octaester

SE1-4 + RCOCH3

O

Base CatalystSE8 + 1- 4 MeOH

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• Uses excess FAME and MeOH removal

to drive reaction forward

• Column reactor used (atmospheric)

• Reaction is complete when

– > 70% octaester (SE8)

– < 0.5% sucrose pentaester

• Downstream processing of crude SPE

to remove: soap, catalyst, excess FAME,

color

SPE Design Versatility

OO O

Fatty Acid Chain LengthControlled via:

• FAME blend

Functionalization

Site

Tailor Made To Deliver Superior Performance

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O

O

O

O

O

O

O

O

HO

O

O

O

O

O

OO

O

O

UnsaturationControlled via:

• Oil selection

• Hydrogenation

Functionalization

Site

Degree of EsterificationControlled via:

• Chemical process

Chempol MPSChempol MPSChempol MPSChempol MPS®®®®

Performance BenefitsPerformance BenefitsPerformance BenefitsPerformance Benefits

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CHEMPOL® MPS

Performance Benefits

• Paint formulations were

constructed with Chempol® MPS

resins to demonstrate

Environmental and Performance

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Environmental and Performance

benefits

Environmental Impact

1.1.1.1. VOC ReductionVOC ReductionVOC ReductionVOC Reduction – if widely adopted for usage in long oil alkyd coatings,

Chempol MPS would

• Reduce VOC emissions from coatings by up to 87,000 tons87,000 tons87,000 tons87,000 tons VOC per year

• Equivalent to VOC emissions from 7,000,000 cars

• Equivalent to 648,000 barrels of crude oil

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• Equivalent to 648,000 barrels of crude oil


2.2.2.2. Ground Level Ozone ReductionGround Level Ozone ReductionGround Level Ozone ReductionGround Level Ozone Reduction

• Determined by analyzing the Maximum Incremental

Reactivity values of common solvents used in alkyd

coatings

• 2.47 tons of ground level ozone per day are generated

per ton of VOC used in coatings 2

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per ton of VOC used in coatings 2

• Broad use of Chempol MPS would lead to elimination

of 589 tons ground level ozone formed per day

(enough to fill 96 hot air balloons)


3. Increase Renewable Content• CHEMPOL® MPS paints require less petroleum-based feedstock materials than

other low VOC paints

Paint From: % Renewable Content

Chempol MPS > 40

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• Conversion to CHEMPOL MPS could potentially

– Save 34,900 tons of petroleum-based alkyd feedstock chemicals (pentaerythritol, phthalic

anhydride, etc.)

– Equivalent to reduction of 260,000 barrels of crude oil

Chempol MPS > 40

Conventional Alkyd 20-25

Acrylic Latex 0

Raw Materials for Alkyd Resins

Mineral oil - Natural gas

Reformate

o,m,p-xylene

Propylene

Iso-or –n-butyraldehyde

Methanol

Formaldehyde

Ethanol

Acetaldehyde

Propylene

Allyl Chloride

Epichlorohydrin


Reformate

o,m,p-xylene

Propylene


Methanol

Formaldehyde

Ethanol

Acetaldehyde

Propylene

Allyl Chloride

Epichlorohydrin

Vegetable Oils


Reformate

o,m,p-xylene

Propylene


Methanol

Formaldehyde

Ethanol

Acetaldehyde

Propylene

Allyl Chloride

Epichlorohydrin


Reformate

o,m,p-xylene

Propylene


Methanol

Formaldehyde

Ethanol

Acetaldehyde

Propylene

Allyl Chloride

Epichlorohydrin

Vegetable Oils

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Phthalic acids

Neopentyl

Glycol

PentaerytritolTrimethylolPropane

Glycerol

Alkyds

EpichlorohydrinSolvents

Phthalic acids

Neopentyl

Glycol


Glycerol

Alkyds


Phthalic acids

Neopentyl

Glycol


Glycerol

Alkyds


Phthalic acids

Neopentyl

Glycol


Glycerol

Alkyds


Alkyd building blocks originate from petroleum-based and vegetable-based

oil feedstocks. The use of Sefose sucrose polyesters decreases the overall

quantity of petroleum-based materials required.

Health and Safety

• Common petroleum hydrocarbon solventshydrocarbon solventshydrocarbon solventshydrocarbon solvents are toxic, have low flash points, are

combustible and show adverse health effects; i.e. asthma, neurological effects.

• Sefose has very high flash point and is non-toxic

• Over 3 million interior architectural coatings project sites per year could see reduced

pollutant levels as a result of CHEMPOL® MPS alkyd paints.

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Safety Parameters and Codes

Solvent

Flash

Point, oC

NFPA Codes:

H, F, R

Exposure

Limits, ppm Toxicity

Mineral Spirits 41 1, 2, 0 TWA 100

Lungs. Eyes. Skin. May

cause cancer.

Xylene 25 2, 3, 0

TWA 100;

STEL 150

Nerves. Liver. Kidney. Blood.

Eyes. Heart. Bone Marrow.

n-Butyl Acetate 23 2, 3, 0

TWA 150;

STEL 200 Central nervous system.

Sefose > 250 0, 1, 0 Non volatile Non Toxic

Paint Performance

• Paint performance results demonstrate advantages of Chempol MPS technology for

Dry, film toughness, and application viscosity.

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0

2

4

6

8

10

VOC

% Organic Renewable

Application FlowBlock Room Temp

Block Elevated Temp

Paint Performance

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Dry Set to Touch

Dry HardScrub Resistance

Solvent Resistance

CHEMPOL MPS 801-4460 Conventional Long Oil Alkyd

• CHEMPOL MPS 801-4460 outperforms conventional alkyd paint on most performance criteria.

• Scrub Resistance and Solvent Resistance benefits attributed to the high density functionality and

reactivity of Sefose®.

0

2

4

6

8

10

VOC

% Organic Renewable

Application FlowBlock Room Temp

Block Elevated Temp

Paint Performance

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Dry Set to Touch

Dry HardScrub Resistance

Solvent Resistance

CHEMPOL MPS 801-9000 High Solids / Low MW Alkyd

• CHEMPOL MPS 801-9000 outperforms the High Solids Low MW Alkyd on most performance

criteria.

• Dramatic faster dry times for CHEMPOL MPS.

Comparative Screening

Life Cycle Assessment (LCA)

0%

20%

40%

60%

80%

100%

120%

Photochemical oxidation

Marine aquatic ecotoxicity

Fresh water aquatic ecotox.Eutrophication

Ozone layer depletion (ODP)

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• Chempol MPS paints show significant (>10%) environmental improvements on multiple environmental

indicators vs. conventional alkyd paint.

Human toxicity

Acidification

Terrestrial ecotoxicity

Abiotic depletion

Global warming (GWP100)

Paint-solvent based CCP

Paint-sefose based -CCP

Summary

• Commercial Introduction of CHEMPOL® MPS alkyd resins

will…

– Enable low VOC alkyd paints with no performance trade offs

– Provide positive environmental impact by significantly reducing

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– Provide positive environmental impact by significantly reducing

� VOC emissions

� Formation of Ground-Level Ozone

� Use of hazardous solvents

� Petroleum consumption by using renewables

References

1 “The U.S. Paint & Coatings Industry 2006-2011: A Multiclient Study”by

Kusumger, Nerlfi & Growney, One DeBaun Ave. C, West Caldwell, NJ

07006

2 Estimates developed by Technology Sciences Group (TSG); multi-

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2 Estimates developed by Technology Sciences Group (TSG); multi-

disciplinary consulting firm providing scientific and regulatory expertise

Acknowledgments

P&G TeamP&G TeamP&G TeamP&G Team

Victor Arredondo

Roger Berger

Debbie Back

Rob Starghill

Samir Verma

CCP TeamCCP TeamCCP TeamCCP Team

Del Eslinger

Dennis Ryer

Jeff Lackey

Mike Gromacki

Dennis Hoover

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Samir Verma

Amita Kanti

Bob Enouen

Ross Holthouse

Don Versteeg

Dennis Hoover

Steve Voeks

Mary Bain

SPECIAL Thank You toSPECIAL Thank You toSPECIAL Thank You toSPECIAL Thank You to:

• U.S. EPA for the Recognition, and the

• ACS for their support to the Green Chemistry Program

Thank you!

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Thank you!

The Environment

& The Consumer

• Consumers demanding greener and sustainable products w/ no tradeoffs

• VOC’s from solvent borne paints contribute to ozone & smog formation, and are linked

VOC Limit [g/L]

Category EPA AIM

Rule

OTC

Flat 250 100

Non-Flat 380 150

Non-Flat High Gloss 380 250

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smog formation, and are linked to health ailments

• VOC limits set by many regional and state agencies are already lower than the federal limits

• EPA working to adopt lower OTC VOC limits to amend current AIM rule

Non-Flat High Gloss 380 250

Quick Dry Enamel 450 250

Primer 350 200

Quick Dry Primer 450 200

Specialty Primer 350 350

Stains 550 250

Varnish 450 350

Floor 400 250

Industrial Maint. 450 340

Documents

Chempol® MPS Resins and Sefose® Sucrose Esters Enable High