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Energy Efficient Emulsification using Hydrophobically Modified
Alkali Swellable Amphipathic Polymers
Two Proprietary Rheology Modifiers from 3V Inc.
Presented to the Midwest Chapterof the Society of Cosmetic ChemistsJanuary 13, 2015
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A Primer on Emulsions
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Why emulsions?
• Delivery of active ingredients.
• Dilution of actives down to safe yet effective levels.
• Cost effective.
• Elegant aesthetics.
• Easy application.
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Definition
An emulsion is a dispersion of two or more immiscible liquids.
• O/W (oil-in-water) - oil is the internal or dispersed phase.
• W/O (water-in-oil) – oil is the external or continuous phase.
• Multiple phase emulsions.
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Is it an emulsion or, something else?Effect of Particle Size
• Dispersion
• Suspension
• Emulsion
• Solution
Largest – least stable
Smallest – most stable
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Types of emulsions• Macroemulsions
– Dispersed phase 0.2-50 µ– Kinetically stable but ultimately unstable due to the Second Law of
Thermodynamics. – Opaque– Relatively high energy input required
• Microemulsions– Dispersed phase 0.01-0.2 µ– Thermodynamically stable– Transparent since droplet size <25% of wavelength of visible light – Very low O/W interfacial tension due to very high surfactant levels– Requires lower energy input
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Typical O/W Macro EmulsionINGREDIENTS
FuntionalityWATER PHASE
Water . . . . . . . . . . . . . . . . . 60-90 Diluent
Humectant . . . . . . . . . . . . . 2-7 Cushion, prevent drying out
Preservative . . . . . . . . . . . 0.05-0.5 Product protection
Surfactant . . . . . . . . . . . . . 0.25-2.0 Emulsifier for stability
Thickener . . . . . . . . . . . . . 0.1-0.75 Improved stability
Emollient . . . . . . . . . . . . . . 0.5-2.0 Elegant skin feel
OIL PHASE
Esters . . . . . . . . . . . . . . . . . 1.0-7.5 Elegant skin feel
Cosmetic Oils . . . . . . . . . . 2.0-10.0 Elegant skin feel
Surfactant . . . . . . . . . . . . . 1.0-5.0 Emulsifier for stability
OTC Actives . . . . . . . . . . . By law Sunscreens, etc.
OTHER
Preservative . . . . . . . . . . . 0.1-1.0 Product Protection
Perfume . . . . . . . . . . . . . . 0.1-1.0 Consumer Preference
[Wgt %]
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Factors Effecting Settling Velocity & Emulsion Stability
Particle
• count
• size
• shape
• density
• charge
Suspending Medium
• density
• charge
• Rheology
• polymer properties
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Rheology Modifiers• Pseudoplastic
– Synthetic Polymers: Acrylic Acid Polymers, Carbomers, Hydrophobically Modifier Polymers
– Gums: Guar, HydroxypropylGuar, Xanthan, Carrageenan
– Clays: Hectorites, Bentonites, Mg/Al Silicates
– Cellulosics: HEC, HPC
– Silicas: Hydrated Silicas, Fumed Silicas
• Newtonian– Polyethylene Glycols
• Thixotropic– Gums: Karaya, Carrageenan
– Organoclays: Quaternium-18 Hectorites & Bentonites, Stearalkonium Hectorites & Bentonites, DisteardimoniumHectorites
– Polyethylenes
– Silicas: Hydrated Silicas, Fumed Silicas
– Trihydroxystearin
– Al/Mg Hydroxystearate
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Viscosity vs. Typical Shear Rates Experienced by Products
Shear Rate (s-1)
Thixotropic
Pseudoplastic
Vis
co
sit
y
Storage Shipping Dispensing Application Homogenization
Newtonian
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Stable Emulsions & Suspensions
Gravity
ViscosityYield Value
Why use rheology modifiers?
Adopted from “The Rheology of Natural and Synthetic Hydrophilic Polymer Solutions as related to Suspending Ability” By RJ Meyer and L. Cohen (BF Goodrich Chem. Co.) Presented in Nov. 1958, NYC. Published in Journal of Cosmetic Chemists
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Stokes Lawpredictor of emulsion stability
V = 2r2g(D1-D2)/9µ
Where: V = the particle’s settling velocity (m/s)
r = the radius of the particle
g = the gravitational acceleration (m/s2)
D1 = the density of the particles (kg/m3)
D2 = the density of the fluid (kg/m3)
µ = the viscosity of the fluid (Pa s)
In words – A higher viscosity (denominator)
reduces the settling velocity. Therefore, the
emulsion or suspension will be more stable.
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Yield Value
Insufficient force
to induce flow
Enough force to overcome
yield value of the toothpaste
Yield Point (Pa) Viscosity (Pa·s)
Honey 0 11.0
Ketchup 14 0.1
Mayonnaise 85 0.6
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The Evolution of Emulsions
Increasing emulsion stability & energy savings
Water + Oil
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WATER & OIL DON’T MIX
Once mixing stops syneresis, coalescences, agglomeration, creaming happens very quickly.
Significant energy input is required to create a homogeneous dispersion of two immiscible liquids.
NEWS FLASH!
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The Evolution of Emulsions
Increasing emulsion stability & energy savings
SurfactantsWater + Oil
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Definition
• An emulsifier is a surface active agent (surfactant) which reduces the interfacial tension between the dispersed phase and the continuous phase.
• Emulsifiers may be also be hydrophilic colloids, finely divided solids (e.g. Pickering Emulsions), amphipathic polymers.
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The HLB SystemSurfactant Selection
• Griffin 1947 Hydrophilic-Lipophilic Balance
• HLB of surfactant = mole % of hydrophilic group / 5
• Maximum HLB = 20
• Required HLB of cosmetic oils
• Spans, Tweens, Poloxymers
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Bancroft’s Rule
• Where the emulsifier is the most soluble becomes the external phase by lowering the interfacial tension on that side of the film
• Hydrogen bonding between non-ionic emulsifiers confers their rigidity and stability to interfacial films why ethoxylated materials are great emulsifiers
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Emulsion Preparation
• Energy input required to reduce droplet size of internal/dispersed phase and create homogeneous mixture– Heat - increased temperature reduces viscosity and
decreases interfacial tension so favors emulsification over coalescence
– Mechanical agitation– Homogenization – high shear– Ultrasonic vibration
• Amount of work depends upon length of time energy is applied presence of emulsifiers
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April 22, 201545th Anniversary of Earth Day
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What can YOU do to help save the planet?
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Twelve Principles of Green Chemistry1. Prevention - It’s better to prevent waste than to treat or clean up waste afterwards.
2. Atom Economy - Design synthetic methods to maximize the incorporation of all materials used in the process into the final product.
3. Less Hazardous Chemical Syntheses - Design synthetic methods to use and generate substances that minimize toxicity to human health and the environment.
4. Designing Safer Chemicals - Design chemical products to affect their desired function while minimizing their toxicity.
5. Safer Solvents and Auxiliaries - Minimize the use of auxiliary substances wherever possible make them innocuous when used.
6. Design for Energy Efficiency - Minimize the energy requirements of chemical processes and conduct synthetic methods at ambient temperature and pressure if possible.
7. Use of Renewable Feedstocks - Use renewable raw material or feedstock rather whenever practicable.
8. Reduce Derivatives - Minimize or avoid unnecessary derivatization if possible, which requires additional reagents and generate waste.
9. Catalysis - Catalytic reagents are superior to stoichiometric reagents.
10. Design for Degradation - Design chemical products so they break down into innocuous products that do not persist in the environment.
11. Real-time Analysis for Pollution Prevention - Develop analytical methodologies needed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.
12. Inherently Safer Chemistry for Accident Prevention - Choose substances and the form of a substance used in a chemical process to minimize the potential for chemical accidents, including releases, explosions, and fires.
SOURCE: http://www.epa.gov/sciencematters/june2011/principles.htm
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Design for Energy Efficiency
6. Minimize the energy requirements of chemical processes and conduct synthetic methods at ambient temperature and pressure if possible.
SOURCE: http://www.epa.gov/sciencematters/june2011/principles.htm
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Dr. T.J. LinLin, TJ, “Low-energy emulsification – I –principles and applications”, J. Soc. Cosmet. Chem., 29, p117-125, March 1978
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Important Emulsion Variables to Control
• Components (ingredients) = cV– Critical component of any emulsion are rheology
modifiers
• Process parameters and Equipment = pV
• Optimized emulsion property = Zp
“More is not always better. Sometimes, less is more.” - Dr. TJ Lin
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LOW-ENERGY EMULSIFICATION (LEE)
α Phase
β Phase Internal Phase
External Phase
Internal Phase
A Conventional Hot Process B LEE
H
h H
h
h + βHh + H
Lin, Dr. TJ, Manufacturing Cosmetic Emulsions: Pragmatic Troubleshooting and Energy Conservation,Allured Business Media, p. 124, 2010
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The Evolution of Emulsions
Increasing emulsion stability & energy savings
SurfactantsWater + Oil
Low Energy Emulsification (LEE)
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Evolution of Emulsions
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Low Energy Emulsification
• Reduces the amount of energy required to make a stable emulsion
• No need to change formula or buy new equipment
• Reduces processing time and increase plant capacity
• Saves money and reduces carbon footprint
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The Evolution of Emulsions
Increasing emulsion stability & energy savings
Surfactants
Non-Associative Polymers e.g. Carbomer
Water + Oil
LEE
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Synthetic Polymeric Thickeners(Homopolymers, Copolymers, Crosspolymers)
• Non-associative– Carbomer– Acrylates Copolymer– Polyquaternium-37
“Carbomer is the ‘ultimate crutch’ to fix an unstable emulsion.” – George Deckner
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Carbomer “Alkylated” Carbomer
Action Mechanism
Oil
Oil
Oil
Oil
Oil
Oil
Polymeric emulsion
• Oil
• Acrylates Vinyl Isodecanoate Crosspolymer
Traditional emulsion
• Oil
• Water
1. Increasing the viscosity of the continuous phase2. Steric and electrostatic repulsion among drops
• Emulsifier
• Carbomer
• Water
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The Evolution of Emulsions
Increasing emulsion stability & energy savings
Hydrophobically Modified Alkali-Swellable Polymers (HASPs)
Surfactants
Non-Associative Polymers e.g. Carbomer
Water + Oil
LEE
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Synthetic Polymeric Thickeners(Homopolymers, Copolymers, Crosspolymers)
• Non-associative– Carbomer– Acrylates Copolymer– Polyquaternium-37
• Associative
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Associative ThickenersAcrylates/Vinyl Isodecanoate Crosspolymer
Hydrophilic backbone
Thickening properties
Lipophilic Moiety
Emulsifying properties
Resistance to electrolyte
Sensorial improvement
Higher Yield Value
= Carbon
= Oxygen
= Hydrogen
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Carbomer “Alkylated” Carbomer
Mode of Action
Oil
Oil
Oil
Oil
Oil
Oil
Polymeric emulsion
• Oil
• Acrylates/Vinyl Isodecanoate Crosspolymer
Traditional emulsion
• Oil
• Water
1. Increasing the viscosity of the continuous phase2. Steric and electrostatic repulsion among drops. Higher BYV. Controlled release of oil phase actives.
• Emulsifier
• Carbomer
• Water
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Simple Making Procedure
3 steps cold process easy handling & cost
efficient
Network building phase - dispersion and swelling of the polymer particles in either the water or oil phase
Emulsification phase – addition of oil phase and emulsification with continued agitation.
CAUTION: Avoid excessive shear to prevent
polymer breakdown and loss of viscosity.
Neutralization - with a suitable agent
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Evolution of Emulsions
Advantages: time saving, energy conservation and increased production capacity
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Acrylates / Vinyl Isodecanoate Crosspolymer
HLB Range Tested 7.5 - 13
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Mineral Oil (HLB 10)Up to 50%
Caprylic/Capric Triglyceride (HLB 11)Up to 30%
C12-15 Alkyl Benzoate (HLB 13)Up to 30%
Cyclopentasiloxane (HLB 7.5)Up to 30%
Associative ThickenerAcrylates/Vinyl Isodecanoate Crosspolymer
0.25% Polymer - 10% Oil - pH 6
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EFFECT OF OIL CONCENTRATION
0.25% Acrylates/Vinyl Isodecanoate Crosspolymer
(adjusted to pH 6 with NaOH)
0
5000
10000
15000
0 10 20 30 40 50
Cyclopentasiloxane %
mPa∙s
0
5000
10000
15000
0 10 20 30 40 50
C12-15 Alkyl Benzoate %
mPa∙s
0
5000
10000
15000
0 10 20 30 40 50
Mineral Oil %
mPa∙s
0
5000
10000
15000
0 10 20 30 40 50
Caprylic/Capric Trigl. %
mPa∙s
HLB 10
HLB 7.5
HLB 11
HLB 13
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EFFECT OF ADDED EMULSIFIERS
15% C12-15 Alkyl Benzoate
0.25% Acrylates/Vinyl Isodecanoate Crosspolymer + 1% Emulsifier
LIPOPHILIC EMULSIFIERS
mPa·s
Cetearyl Alcohol 7200Glyceryl Stearate 12000Methyl Glucose SS 15000Sorbitan Laurate 9800Sorbitan Palmitate 14500Sorbitan Stearate 31500
NON-IONIC O/W EMULSIFIERS
mPa·s
Polysorbate-20 3300Polysorbate-40 4250Polysorbate-60 4300Polysorbate-80 3700PEG-8 Stearate 8400PEG-20 Stearate 4300PEG-40 Stearate 4000PEG-100 Stearate 4500Ceteareth-20 3900Ceteareth-33 3900
ANIONIC O/W EMULSIFIERS
K Cetyl Phosphate 4700Na Cetearyl Sulfate 4750
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Reduced oil droplet size and increased whiteness.
Lipophilic emulsifiers: high viscosity but a jelly-like consistency.
Hydrophilic emulsifiers: lower viscosity but excellent appearance.
Acrylates Vinyl Isodecanoate Crosspolymer only
+ 1% Polysorbate-60
EFFECT OF TRADITIONAL EMULSIFIERS
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Synthetic Polymeric Thickeners(Homopolymers, Copolymers, Crosspolymers)
• Non-associative– Carbomer– Acrylates Copolymer– Polyquaternium-37
• Associative – Acrylates/Vinyl Isodecanoate Crosspolymer
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Associative Polymeric Network
HASE After Neutralization
with Base
Hydrophobic alkylation enhances performance in many systems
HASE = Hydrophobically Modified Alkali Swellable Emulsion
Drawing courtesy of Raymond Rigoletto
Acrylates/Palmeth-25 Acrylate Copolymer
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Acrylates/Palmeth-25 Acrylate Copolymer
Simple Emulsion Base A BIngredient Wgt % Wgt %
Cetearyl Glucoside & Cetearyl Alcohol 2.0 0.0
Ceteary Alcohol 0.0 2.0
Ethylhexyl Stearate 10.0 10.0
Dicaprylyl Ether 10.0 10.0
Caprylic/Capric Triglyceride 3.0 3.0
Potassium Cetyl Phosphate 0.0 0.5
Preserved Water QS to 100 % QS to 100%
Brookfield, RV 20 rpm, 25oC
Emulsion B(Anionic)
Emulsion A(Non-ionic)
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Acrylates Palmeth-25 Acrylates CopolymerHLB Range Tested 5-6 and 7.5-13
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Acrylates Palmeth-25 Acrylates Copolymer Oils of different HLB requirements
10% Polymer + 30% Oil
Ingredient F GDI Water 56 56Polymer (30%) 10 10C12-15 Alkyl Benzoate (HLB 13) 30 ---Cyclomethicone (HLB 7.5) --- 30NaOH (10%) QS QS
100 100pH 6.1 6.3
Viscosity (cps) @ 25C 72,000 75,000Viscosity (cps) @45C 39,000 41,000
QS to pH 6.25 +/- 0.25Brookfield RVT T-E spindle @ 10rpm
Procedure – Add polymer to water. Then add oil and homogenize for 5 minutes using Silverson L4RT-A at 4,000rpm. Neutralize with base to pH 6.25. 500 gram batch size.
10% Polymer + 30% C12-15 Alkyl Benzoate 10% Polymer + 30% Cyclomethicone
Photomicrographs 500X
Cold Process
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10% Polymer & Mineral Oil increased from 20% to 40%
Ingredient Wgt % Wgt %DI Water 66 46Polymer (30%) 10 10M.O. 20 40NaOH (5%) QS QS
100 100pH 6.5 6.7
Viscosity (cps) @ 25C 34,500 106,000Viscosity (cps) @ 45C 21,500 57,000
QS to pH 6.25 +/- 0.25Brookfield RVT T-E spindle @ 10rpm
Photomicrographs 500X
Acrylates /Palmeth-25 Acrylates Copolymer Effect of Increasing Oil Phase
10% Polymer + 20% M.O.
Procedure – Add polymer to water. Add M.O. homogenizing for 5 minutes using Silverson L4RT-A at 4,000rpm. Then neutralize to about pH 6.5 with sweep agitation. 500 g batch size.
10% Polymer + 40% M.O. 5% Polymer + 10% M.O.(Batch B diluted 50:50)
Procedure – Dilute Batch B 50:50 with DI Water after the emulsion is formed.5,000 cps @ 25C1,000 cps @ 45C
Cold Process
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Acrylates /Palmeth-25 Acrylates Copolymer Effect of Polymer Concentration
Decrease polymer concentration from 5.0% down to 1.25% keeping M.O. constant at 20%
Ingredients J K LWgt % Wgt % Wgt %
DI Water 74.5 78.0 78.0 78.00Polymer (30%) 5.0 2.5 1.25M.O. 20.0 20.0 20.0NaOH (5%) QS QS QS
100.0 100.0 100.0pH 6.2 6.6 6.5 Viscosity (CPS) @ 25C 86,500 21,000 1,000Viscosity (CPS) @ 45C 46,500 14,000 400QS to pH 6.25 +/- 0.25Brookfield RVT T-E spindle @ 10rpm
5% Polymer 2.5% Polymer 1.25% Polymer
Photomicrographs 500X
NOTE: A viscosity drop of 20% for every 10C above 25C is a general accepted norm.
Cold Process
Procedure – Add polymer to water. Add M.O. homogenizing for 5 minutes using Silverson L4RT-A at 4,000rpm. Then neutralize to about pH 6.5 with sweep agitation. 500 g batch size.
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Acrylates Palmeth-25 Acrylates CopolymerEmulsification of Low HLB Oils
Ingredients Wgt % Wgt % Wgt % DI Water 67.0 67.0 67.0Polymer (30%) * 10.0 10.0 10.0M.O. (HLB 10) 20.0 - - - - - -Almond Oil (HLB 6) - - - 20.0 - - -Dimethicone (HLB 5)) - - - - - - 20.0NaOH (5%) QS QS QS
100.0 100.0 100.0pH 6.2 6.3 6.5
Viscosity (cps) *** @ 25C 74,500 92,500 53,000
Photomicrographs 500X
Mineral OilHLB 10
DimethiconeHLB 5
Almond OilHLB 6
QS to pH 6.25 +/- 0.25Brookfield RVT T-E spindle @ 10rpm
Procedure – Add polymer to water. Add M.O. homogenizing for 5 minutes using Silverson L4RT-A at 4,000rpm. Then neutralize to about pH 6.5 with sweep agitation. 500 g batch size.
Cold Process
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The Evolution of Emulsions
Increasing emulsion stability & energy savings
HASP Polymeric Emulsifiers
Surfactants
Non-Associative Polymers e.g. Carbomer
Acrylates/Vinyl Isodecanoate Crosspolymer (powder)Acrylates/Palmeth-25 Acrylate Copolymer (liquid)
Water + Oil
LEE
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The Greening of Emulsions
Increasing emulsion stability & energy savings
HASP Polymeric Emulsifiers
Surfactants
Non-Associative Polymers e.g. Carbomer
Acrylates/Vinyl Isodecanoate Crosspolymer (powder)Acrylates/Palmeth-25 Acrylate Copolymer (liquid)
Water + Oil
LEE
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Evolution of Emulsions
Advantages of Cold Process Emulsification: time saving, energy conservation and increased production capacity
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One Pot Process Possible• Acrylates/Vinyl Isodecanoate Acrylates Crosspolymer (powder)
– Direct Addition• Add Polymer to Water Phase in main mix tank• Add Oil Phase to the main mix tank with rapid agitation / homogenization • Add suitable to neutralize to pH 5-7
– Indirect Method• Add Polymer to Oil Phase in side kettle. Do not heat above 60oC• Add Oil Phase to Water Phase containing sufficient neutralizing base to pH 5-7
with rapid agitation in main mix tank • Do not over homogenize
• Acrylates/Palmeth-25 Acrylates Copolymer (liquid)– Add Polymer to Water Phase in main mix vessel– Add Oil Phase with homogenization– Neutralize with suitable base to pH 6-7
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Acrylates Vinyl Isodecanoate Crosspolymer
• Properties– Amphipathic polymer (powder form) for emulsification & thickening– High suspending properties & improved electrolyte tolerance– Enhanced water-resistance for sunscreen actives
• Applications– O/W emulsions– Clear styling gels– Surfactant systems– Clear hydroalcoholic hand sanitizers
• Easy to use– May be dispersed either into water following the normal procedure for Carbomer or
into the Oil Phase of emulsions. – Functional over a broad pH range. Neutralization can be carried out with alkali
(NaOH, KOH or NH4OH) or with hydrophilic organic amines (such as TEA, AMP, TrisAmino).
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Acrylates/Palmeth-25 Acrylate Copolymer• Properties
– Hydrophobically modified associative thickener and emulsifier– Liquid 30% polymer solids water-thin white emulsion
• Applications– O/W emulsions– Clear sulfate-free surfactant systems– Styling products– High pH products depilatories and relaxers
• Easy-to-use– Adds instantly to water
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ReviewTips to Improve Emulsion Stability
• Prevent particle interaction
• Increase viscosity & yield value of continuous phase.
• Add polymer(s).
• Increase concentration of dispersed phase.
• Low levels of electrolytes.
• Reduce particle/droplet size of dispersed phase.
• Increase mechanical and/or heat energy.
• Emulsifier selection and concentration.
• Avoid aeration.
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SUMMARY
Hydrophobically modified amphipathic polymers are one way to making even lower energy emulsions.
Cold process emulsification provides greater savings, increased manufacturing capacity and . . .
Helps save the environment.
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Marketing Sustainability
British Standardfrom
Carbon Trust
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3V cares about the environmenthttp://www.3vgreeneagle.com/en
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References1. Lin, Dr. TJ, Manufacturing Cosmetic Emulsions: Pragmatic Troubleshooting
and Energy Conservation, Allured Business Media, 2010
2. Klein, Ken, Formulating Cosmetic Emulsions, SCC Continuing Education Course, 1998.
3. Deckner, George and O’Lenick, Tony, Lamellar Gel Network Lab Workshop, C&T Summit Philadelphia, June 2014
4. www.epa.gov, 12 Principals of Green Chemistry originally published by Paul Anastas, Ph.D. and John Warner, Ph.D. in Green Chemistry: Theory and Practice (Oxford University Press: New York, 1998),
5. “STABYLEN 30: A Thickening, Suspending and Emulsifying Agent for Emulsions and Surfactant Systems”, 3V Technical Report No. 1 – Edition 2/1
6. “Formulation of O/W Emulsions with STABYLEN 30”, 3V Technical Report –Edition 1/2
7. “SYNTHALEN® W2000: A Liquid Thickener for Cosmetic Applications”, 3V Technical Report No. 6 - Edition 4/2