ALTERNATE SURFACTANTS IN

AN “ANTI-APE” ENVIRONMENT

Steve DuPont

March 21, 2013

PERSPECTIVE

AGENDA

WHY ALTERNATIVES

- HISTORICAL PERSPECTIVE

- REGULATORY & ENVIRONMENTAL

PRESSURE

- MARKET PRESSURE

ALTERNATIVES

- ETHOXYLATED ALCOHOLS

- BIO-RENEWABLES

- CATIONIC/NONIONIC BLENDS

HISTORICAL PERSPECTIVE

APE INTRODUCTION – UK IN 1940s

WASTE WATER TREATMENT STUDIES

BIODEGRADABILITY - NOT READILY BIODEGRADABLE

TOXICITY OF DEGRADATION PRODUCTS

BIOACCUMULATION

ENDOCRINE DISRUPTORS

REGULATORY PRESSURE

CANADA & EUROPE BAN

CALIFORNIA STATUS

REGULATORY PRESSURE

CALIFORNIA STATUS

Table 94509(m)(3) Product Categories in which Use of Alkylphenol Ethoxylate Surfactants is Prohibited

Product Category Effective Date Sell-through Date

General Purpose Cleaner (nonaerosol)

12/31/2012 12/31/2015

General Purpose Degreaser (nonaerosol)

12/31/2012 12/31/2015

Glass Cleaner (nonaerosol) 12/31/2012 12/31/2015

Heavy-duty Hand Cleaner or Soap (nonaerosol)

12/31/2013 12/31/2016

Oven or Grill Cleaner 12/31/2012 12/31/2015

REGULATORY PRESSURE

• NP and NPE’s will soon be added to EPA’s new

Chemicals of Concern List Under the “Nonylphenol

(NP) and Nonylphenol Ethoxylates (NPEs) Action Plan

number [RIN 2070-ZA09].

• This will begin in 2014, and result in:

- Significant new use rules will be issued for

these materials even in existing formulations.

- The agency will add them to the list of Chemicals

that companies must report under the Toxics

Release Inventory (TRI)

TOXIC RELEASE INVENTORY (TRI)

ENVIRONMENTAL PRESSURE

DfE

ECO LOGO

GREEN SEAL

US EPA DfE Program / CleanGredients® “The U.S. EPA's Design for the Environment program helps consumers,

businesses, and institutional buyers identify cleaning and other products that

perform well, are cost-effective, and are safer for the environment.”

Surfactants in cleaning products are distinguished by their rate of

biodegradation, degradation products, and level of aquatic toxicity. The DfE

Criteria for Surfactants combine these hazard characteristics, and requires that

surfactants with higher aquatic toxicity demonstrate a faster rate of

biodegradation without degradation to products of concern.

US EPA DfE Home CleanGredients Home

9

Acute Aquatic Toxicity (L/E/IC50 Value)1

Rate of Biodegradation

≤1 ppm May be acceptable if biodegradation2 occurs within a 10-day window without products of concern3

>1 ppm and ≤10 ppm Biodegradation2 occurs within a 10-day window without products of concern3

>10 ppm Biodegradation2 occurs within 28 days without products of concern3

1. In general, there is a predictable relationship between acute aquatic toxicity and chronic aquatic toxicity for organic chemicals, i.e. chemicals that have high acute aquatic toxicity also have high chronic aquatic toxicity. Since acute aquatic toxicity data are more readily available, the DfE Criteria use these data to screen chemicals that may be toxic to aquatic life. 2. Generally, >60% mineralization (to CO2 and water) in 28 days. 3. Products of concern are compounds with high acute aquatic toxicity (L/E/IC50 ≤ 10ppm) and a slow rate of biodegradation (greater than 28 days).

AQUATIC TOXICITY

10

• DAPHNIA MAGNA (48 hours) - mg/L

NP – 0.035 (EC50)

NP-4 – 4.9-5.7 (LC50) 1.6-10 (EC50)

NP-9 – 9.3-21.4 (LC50)

NP-15 – 23.1-71.8 (LC50)

MARKET PRESSURE

MULTI-NATIONAL MANUFACTURERS & DISCOUNT STORES

WHAT ARE ALTERNATIVES

SURFACE ACTIVE PROPERTIES OF APE’s

• WETTING – FOR HARD AND “SOFT” SURFACES

• DETERGENCY – MULTI-APPLICATIONS

• EMULSIFICATION – OIL TO EMULSION POLYMERS

• DISPERSING, SOLUBILIZING, STABILIZING, COMPATABLIZING

ETHOXYLATED ALCOHOLS

SYNTHETIC AND NATURAL BASED

• CHEMISTRY - C -9-11, 11-15, 12-15, 12-13, 12-14, 12-16

LINEAR – KNOWN FOR WETTING

BRANCHED - KNOWN FOR EMULSIFYING

MOLES OF EO – 1 – 40

ETHOXYLATED ALCOHOLS

SYNTHETIC AND NATURAL BASED

• PROs FASTER WETTING

BETTER LOW TEMPERATURE DETERGENCY

BETTER COLD WATER SOLUBILITY -NARROW OR NO GEL RANGE

• CONS – LINEAR ALCOHOL ETHOXYLATES

MOST CASES APEs GIVE BETTER EMULSIFICATION

APE’s MORE EFFECTIVE SOLUBLIZERS

APE’s GIVE BETTER HIGH TEMPERATURE > 60C DETERGENCY

TRADENAMES

• RHODASURFS

• ECOSURFS

• BIOSOFT

• GENAPOL LA/UD/X

• SURFONIC

• TOMADOL

BIO-RENEWABLES

SUGAR-BASE

• CHEMISTRY -

ETHOXYLATED SORBITAN ESTERS BASED TYPICALLY ON C- 12, 16 & 18 FATTY ESTERS

MOLES OF EO – 4, 5, 20

ALKYL POLYGLUCOSIDES (APG)

SOME OF FIRST BIO-RENEWABLES

BIO-RENEWABLES

ETHOXYLATED SORBITAN ESTERS

• PROs EXCELLENT EMULSIFIERS

LOW TOXICITY

GIVES LUBRICANT PROPERTIES

• CONS COST

BIO-RENEWABLES

ALKYL POLYGLUCOSIDES

• PROs HIGHLY ALKALINE STABLE

HELP TO PREVENT STREAKING

GOOD DETERGENT AND WETTING PROPERTIES

• CONS COST

TRADENAMES

• ALKAMULS

• TWEEN

• SPAN

• S-MAZ

• TRITON BG/CG

• GLUCOPON

CATIONIC/ NONIONIC BLEND

SPECIFIC TO NP-9 (ALCOHOL ETHOXYLATE &

CATIONIC )

• PROs BETTER WETTER

EXCEEDS DETERGENT EFFICIENCY

COLD WATER SOLUBLE

• CONS COST

ANIONIC SURFACTANT INCOMPATIBILITY

TRADENAMES

• BEROL

• BURCOTERGE

APEs ARE BEING USHERED OUT

GREEN MOVEMENT HERE TO STAY

THERE ARE ALTERNATIVES

TRADEOFFS INEVITABLE

CONCLUSIONS

QUESTIONS ?