Petrochemical Alcohol Derivatives in Personal Care Applications Shell Chemicals, April 2005 Authors R van der Meij, RJ Blanco, JE Carty, J Redican 1
Summary All Alcohols are synthetic Labeling and classification has been harmonized across petrochemical-derived and oleo-derived alcohols Performance of petrochemical based alcohol derivatives are in many applications comparable to oleo-based alcohol products and in some cases offer higher formulation flexibility Some specialty petrochemical alcohols have unique properties for specialty personal care applications
Content What is in a name? Pricing Performance Conclusion
Natural alcohol ethoxylates start from fresh palm trees and are made chemically Oleo-chemical derived alcohol value chain Palm Kernel- Coconut Oil Fatty Acid/ methylester Fatty Alcohol Alcohol Ethoxysulfates Even Carbon number, 99% linear EO & sulfation
Synthetic alcohols are produced with very old palm trees as the starting material Crude oil Petro-chemical derived alcohol value chain Naphtha Ethylene Higher olefins Alcohols Alcohol Ethoxysulfates EO & sulfation Odd/Even Carbon number, 80% linear Based on modified OXO process
Classification for alcohols has been harmonized in Europe From APAG letter Q4 2004: A CEFIC Sector Group representing European alcohol manufacturers. Company members are COGNIS, ECOGREEN, OLEON, PROCTER & GAMBLE, SASOL & SHELL CHEMICALS Revisions to the Classification and Labelling of C12 / C13 Alcohols & Associated Cuts and Blends The APAG Alcohols Group recently reviewed available data relating to the acute aquatic toxicity (daphnia, fish, algae) of fatty alcohols in the C8 to C18 range. Recognising the value of harmonised classification and labelling, additional testing was initiated on fatty alcohols in the C12 to C15 range to more accurately assess acute toxicity to aquatic species and to establish an appropriate hazard classification under Annex VI of the EC Dangerous Substance Directive (DSD) 2. After finalisation of the testing, all results were extensively reviewed by an APAG Expert Group. The conclusion of this activity was that the toxicity as defined by EC/LC 50 values of C12 & C13 alcohols is below 1 mg/l, and accordingly, under hazard classification provisions in the DSD, these products should be classified and labelled as Dangerous to the environment (N) with R50 (Very toxic to aquatic organisms). Additionally, the product label should show the hazard symbol Dead Fish and Tree. Synthetic Synthetic C12/13 C12/13 alcohols alcohols were were already already classified classified like like this this
Consumer labels are no longer a barrier to use Petrochemical derived products Consumer product labels (EU) can now show both laureth- and pareth-sulfate Pareth sulfate is a commonly used surfactant for shampoo & bodywash product other active ingredients are a.o. Water Sodium C1213 pareth sulfate (cleansing surfactant) Sodium lauramphacetate (mildness surfactant) Sunflower seed oil (emolliency) Isostearic acid (emolliency) Cocamide MEA, cocamidopropyl betaine (foam stabilizer/booster) Less than 2% numerous other ingredients, like glycols, sodium benzoate, citric acid, Acrylates copolymer, stearic acid etc Shampoo product label, purchased in NL, April 2005
So what s in a name? The terms synthetic and natural should not be used, Oleo derived and Petrochemical derived alcohols are better terms Although the starting material for natural alcohols is a renewable source, the final product is a highly chemical processed product Both are chemically derived products Both have INCI names and are approved for use in the CTFA Cosmetic Ingredients Dictionary Both require the same transport and labeling Both have the same APAG classification Published in-vitro and in-vivo eye irritancy data are the same for both HRIPT data shows both do not elicit skin sensitization CAS Descriptions and INCI names for Modified Oxo (NEODOL ) derivatives are listed : Europe (EINECS) Korea (TCCL) Japan (ENCS) China (IECSC)* Philippines (PICCS)* *C16-19 alcohols branched not yet included
Pricing Feedstock Manufacturing It is an ethoxylate!
Price volatility for feedstock is a common theme! 1000 900 800 PKO CNO ETHYLENE PKO/CNO 700 Price ($/MT) 600 500 400 300 ethylene 200 100 0 1990 1992 1994 1996 1998 2000 2002 2004 Current Current crude crude oil oil volatility volatility and and chemical chemical cycle cycle drive drive ethylene ethylene pricing, pricing, Source various industry databases (CMAI, import statistics etc)
Prices for oleo-based alcohols follow feedstock Price, USD/ton 1800 1600 1400 1200 1000 800 600 400 200 0 US oleoalcohol PKO/CNO EU oleoalcohol 1996 1998 2000 2002 2004 2005 2005 2005 trend trend is is a continuation continuation of of the the increasing increasing price price Oleo alcohol prices are based on import statistics
Ethylene Oxide is 20-40% of low mole products EO pricing (PCI) 1400 1200 USA 1000 USD/ton 800 600 400 200 West Europe 0 Q2-95 Q4-95 Q2-96 Q4-96 Q2-97 Q4-97 Q2-98 Q4-98 Q2-99 Q4-99 Q2-00 Q4-00 Q2-01 Q4-01 Q2-02 Q4-02 Q2-03 Q4-03 Q2-04 Q4-04 Local Local EO EO imbalances imbalances will will result result in in large large regional regional EO EO price price differences differences Source: PCI
Outlook for all alcohols pricing has many uncertainties Harvest uncertainty is a given, weather control is beyond man Agricultural intensity is under pressure, genetic modification on the rise (?) Food oil drive, the world population continues to grow and needs more food oils Clean Fuels drive in the world stimulates bio-fuels, but drives glycerine prices down Crude Oil pricing remains volatile for the years to come Ethylene pricing will be strong shorter term due to demand drive, longer term it will be cost driven Capacity announcement for oleo-derived alcohols are plenty, will they all be built and is the feedstock secured?
Product performance Petrochemical derived alcohols perform as well as oleo-derived alcohols, and even better in some applications, and there are unique commodities as well
Petrochemical based alcohol derivatives are comparable to oleo derivatives Surface-active properties for typical personal cleansing surfactant Chemical Description cmc, ppm Surface Tension, dynes/cm Krafft Temp., C Calcium Tolerance, ppm N 145-2S 50 33 0 >20000 C1214-2S 300 31 0 >20000 N 145-S 1100 25 36 440 C1214-S 1400 36 16 400 Petrochemical Petrochemical and and oleo-derived oleo-derived alcohol alcohol sulfates sulfates and and alcohol alcoholethoxysulfates ethoxysulfateshave have similar similar surfactant surfactant properties properties and and have have similar similar sensitivity sensitivity to to water water hardness hardness
Petrochemical based alcohol derivatives are comparable to oleo derivatives 18000 Cleansing formulation properties C1214-2S Typical liquid handsoap formulation Component %wt Viscosity, cps 9000 N145-2A N145-2S Water Alcohol Sulfate Alcohol Ethoxysulfate Cocamidopropyl betaine q.s. to 100 6.2 5.4 1.2 LMMEA 1.0 Sodium Chloride Varies (0-5%) 0 0 2 4 6 %NaCl Petrochemical Petrochemical alcohol alcohol ethoxysulfates ethoxysulfateshave have comparable comparable peak peak viscosity, viscosity, while while requiring requiring less less salt salt to to thicken thicken than than oleo-derived oleo-derived alcohol alcohol ethoxysulfates ethoxysulfates
Petrochemical based alcohol derivatives provide more formulation options through carbon chain flexibility C1214-2S C1115-2S C1213-2S 800 Effect of Silicone Conditioner on Shampoo Lather Lather Volume, ml 600 C1214-2S N145-2S N23-2S C1214-2S N145-2S N23-2S N23-2S and C1214-2S have comparable lather performance No Additive Dimethicone (conditioning agent) Lather Drainage, ml/min 20 15 10 C1214-2S N145-2S N23-2S C1214-2S N145-2S N23-2S N145-2S drains more rapidly with better actives to hair delivery and higher actives retention No Additive Dimethicone Petrochemical Petrochemical derived derived alcohol alcohol ethoxysulfates ethoxysulfates provide provide formulation formulation flexibility flexibility (cleansing (cleansing priority priority or or 2-in-1 2-in-1 products) products) Method: WTC Lather Test - 0.01 % Additive, 0.4%w AES,25 C, 200 ppm hardness, 0 NaCl
A specialty high molecular weight emollient alcohol like NEODOL 67 has unique skin-care attributes NEODOL 67 is a monomethyl branched C1617 alcohol -16 C pour point 95% methyl branched Odor free Shell s NEODOL 67 has unique characteristics: Excellent handling characteristics, liquid at room temperature Solubilizes a wide variety of organic sun-care ingredients Excellent inorganic sunscreen pigment dispersability Excellent skin moisturization and sensorial after-feel characteristics Excellent HRIPT no response results
NEODOL 67 demonstrates excellent dispersability maintaining good product attributes for sunscreen application TARGET SUNSCREEN VISCOSITY - 10,000 CPS ISOHEXADECANE CAPRYLIC/CAPRIC TRIGLYCERIDE MINERAL OIL DIOCTYL SEBACATE ESTER NEODOL 67 C1617 ALCOHOL BRANCHED 0 10 20 30 40 50 60 WEIGHT SUNSCREEN PIGMENTADDED, (gm) Eusolex T2000 Z-COTE NEODOL NEODOL 67 67 demonstrates demonstrates excellent excellent dispersability dispersability (vs. (vs. other other common common emollients) emollients) on on two twopigment types types while while maintaining maintaining good good finished finished product product viscosity viscosity and and good good rub-in rub-in afterfeel afterfeel
These excellent properties explain the growth of NEODOL application in Personal Care NEODOL volume applied in Personal Care use (bodywash, shampoo etc.) expected 2003 2004 2005
Conclusions Petrochemical based alcohol derivatives are a good raw material for Personal Care applications Labeling and classification have been harmonized across petrochemical-derived and oleo-derived alcohols Performance of petrochemical based alcohol derivatives are in many applications comparable to oleo-based alcohol products and in some cases offer higher formulation flexibility Some specialty petrochemical alcohols have unique properties for specialty personal care applications