ALTERNATE SURFACTANTS IN AN "ANTI-APE" ENVIRONMENT - MARCH 21, 2013 STEVE DUPONT

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       12/31/2012                      12/31/2015
(nonaerosol)
General Purpose Degreaser     12/31/2012                      12/31/2015
(nonaerosol)
Glass Cleaner (nonaerosol)    12/31/2012                      12/31/2015
Heavy-duty Hand Cleaner or    12/31/2013                      12/31/2016
Soap (nonaerosol)
Oven or Grill Cleaner         12/31/2012                      12/31/2015

REGULATORY PRESSURE
 TOXIC RELEASE INVENTORY (TRI)
• 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)

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

      Acute Aquatic Toxicity                         Rate of Biodegradation
      (L/E/IC50 Value)1
      ≤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).

                                                                                                                                                                                                            9

AQUATIC TOXICITY

• 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)

                                          10

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

CONCLUSIONS

 APEs ARE BEING USHERED OUT

GREEN MOVEMENT HERE TO STAY

THERE ARE ALTERNATIVES

TRADEOFFS INEVITABLE

QUESTIONS ?