® Carbopol Polymers
Overview
© The Lubrizol Corporation 2008, all rights reserved
Typical Properties of Powdered Carbopol ® Polymers Chemical Description: linear with
High molecular weight,nonpolyacrylic acid cross-linked polyalkenyl polyether
Physical Appearance:
White powder
Particle Size:
2 - 7 microns
Bulk Density:
176 - 208 kg/m3
pH (1% water dispersion)
2.5 - 3.0
Moisture Content:
< 2%
Equivalent Weight
76
4
Major Functions of Carbopol ® and Pemulen ® Rheology Modifiers •
Thickening with a wide range of flow properties
•
Suspension of insoluble ingredients
•
Stabilization Stabiliza tion of emulsions (Carbopol® polymers)
•
Emulsification (Pemulen ® polymers)
How Carbopol ® Polymers Thicken
Carbopol ® Powder
State I: Powder
State II: Hydrated
State III: Neutralized
State I: Powder
COO H
Before contact with water, cross-linked polyacrylic acid is tightly coiled
State II (Polymer Dispersion): Hydrated
COOH
When dispersed in water, cross-linked polyacrylic acid begins uncoiling
State III (Polymer Mucilage): Neutralized NH4+
NH4+
NH4+ NH4+ NH4+ u u
Neutralization with a base creates negative charges along backbone These repulsive forces uncoil polymer into an extended structure
Neutralization Ratio Chart - pH 7.0 Neutralizer Trade Name
Neutralizer INCI/CTFA Name
Manufacturer
Weight Ration Base/Carbopol® polymer
NaOH (18%)
Sodium Hydroxide
2.3/1.0
Ammonia (28%)
Ammonium Hydroxide
0.7/1.0
KOH (18%)
Potassium Hydroxide
2.7/1.0
L-Arginine
Arginine
Ajinomoto
4.5/1.0
AMP-95®
Aminomethyl Propanol
Angus
0.9/1.0
Neutrol® TE
Tetrahydroxypropyl Ethylenediamine
BASF
2.3/1.0
TEA (99%)
Triethanolamine
Tris Amino® (40%)*
Tromethamine
Angus
3.2/1.0
Ethomeen® C-25
PEG-15 Cocamine
Akzo
6.2/1.0
Diisopropanolamine
Diisopropanolamine
Dow
1.2/1.0
Triisopropanolamine
Triisopropanolamine
Dow
1.5/1.0
1.5/1.0
*Note: The 40% solution should be made from Tris Amino crystals from the manufacturer. Do not use the pre-dispersed solution from the manufacturer as it contains many impurities.
Thickening Hydroalcoholic Gels Carbopol® polymer will precipitate out of solution if neutralizer is not chosen correctly.
Recommended Neutralizers for Hydroalcoholic Systems Up to % Alcohol
Neutralizer
20%
Sodium Hydroxide
30%
Potassium Hydroxide
60%
Triethanolamine
60%
Tris Amino
80%
AMP-95*
90%
Neutrol TE
90%
Diisopropanolamine
90%
Triisopropanolamine
>90%
Ethomeen® C-25
Suspension of Particles in a Carbopol ® Polymer Gel
Suspended Particle
Swollen Microgel
Yield Value
Formulations thickened with Carbopol ® polymers have very high yield values
Yield value is the initial resistance to flow under applied stress
Yield value (rather than viscosity) is the dominant factor in determining suspending ability
Applications for Yield Value
Suspension
Vertical Cling
Foam Stability
Emulsion Stabilization
Viscosity vs. Yield Value Polymer (wt%)
Broolfield Viscosity (mPa s)
Brookfield Yield Value (dyn/cm2)
Sand Suspension
0.1-Carbopol® Ultrez 21 polymer
6,800
200
Permanent
0.5-Locust Bean Gum
22,800
80
8 Hours
1.5-Sodium CMC
5,900
36
3 Hours
1.5-Guar Gum
8,040
32
4 Hours
2.5-Sodium Alginate
8,360
16
2 Hours
pH = 6.3 - 7.5
Suspended Sphere Test Method u
Location of several spheres marked
u
Gels stored at room temperature for 3 days
u
Yield value associated with largest/densest sphere with no appreciable movement
0.5% Carbopol ® 980 polymer
2.3% CMC
2.1% Guar
Viscosity = 33,000 mPa·s
6.0% Xanthan
pH = 7.5
Measurement of Brookfield Yield Value
Brookfield Yield Value (dyn/cm2)=
(Brookfield Visc. @ 0.5 rpm – Brookfield Visc. @ 1 rpm) 100
Carbopol ® Polymers: Application Guide Acrylates/C10INCI/CTFA Designation 30 alkyl acrylate crosspolymer
Carbomer
Ultrez 21
PROPERTIES Flow characteristics Relative viscosity Suspending ability (yield value) Clarity Relative Ion Tolerance Relative Shear Tolerance APPLICATIONS Clear Gels Hydroalcoholic Gels Lotions Creams Personal Cleansers High Electrolyte Systems (aloe gels, etc.)
Carbomer
Acrylates/C10-30 Carbomer alkyl acrylate crosspolymer
Ultrez 10
Ultrez 20 ETD 2020 1382 1342
2984/5984 934
980 940
ETD 2050 981 941
Short High
Short High
Short High
Long Low
Medium Medium
High
High
High
High
High
Very high Medium High
Low Low High
High Low High
High Medium Low
High High Low
◆ ◆ ◆
◆ ◆
◆ ◆
◆ ◆ ◆ ◆
Ultrez 10 = Carbopol ® Ultrez 10 Polymer Ultrez 20 = Carbopol ® Ultrez 20 Polymer Ultrez 21 = Carbopol ® Ultrez 21 Polymer
◆ ◆ ◆ ◆ ◆ ◆
934 = Carbopol® 934 Polymer 1382 = Carbopol® 1382 Polymer 940 = Carbopol® 940 Polymer 2984 = Carbopol® 2984 Polymer 941 = Carbopol® 941 Polymer 5984 = Carbopol® 5984 Polymer
◆ ◆ ETD2020 = Carbopol® EETD2020 Polymer ETD2050 Carbopol®
Compatibility of Carbopol ® Polymers PROPERTIES
Ultrez 21
Ultrez 10
Ultrez 20
Flow Type
Short
Short
Medium
Formulation compatibility High electrolytes
√√
√√√
Surfactants
√√
√√√
•
•
√
Cationics
•
Solvents
√
√
√√
*H2O2
**
√
**
High pH
√√
√
√√
√√√
√√√
√√√
•
•
•
Easy to disperse/use *Best H202 compatible = Carbopol ® 934 Polymer ** Not tested
Ultez 20 = Carbopol ® Ultrez 20 Polymer Ultrez 21 = Carbopol ® Utrez 21 Polymer Ultrez 10 = Carbopol ® Ultrez 10 Polymer
Ease of Processing Carbopol® Polymer Wetting Times at 25 C °
Carbopol ® Polymer
Wetting Time 0.5 wt % (minutes)
Ultrez 20
3
Wetting Time 3.0 wt % (minutes) 5
Ultrez 21
2-3
5
Ultrez 10
5
6
ETD 2020
20
> 3 hours
980
> 50
> 5 hours
Note: The above values are typical, not specifications Procedure: 0.5%: 2.5 g of powder sprinkled onto the surface of 500 mL DI water contained in a 800 mL beaker 3.0%: 3.0 g of powder sprinkled onto the surface of 100 mL DI water contained in a 250 mL beaker
Ultrez 20 = Carbopol® Ultrez 20 Polymer Ultrez 21 = Carbopol® Ultrez 21 Polymer Utrez 10 = Carbopol® Ultrez 10 Polymer ETD2020 = Carbopol® ETD2020 Polymer
Concentration Dependence of Dispersion Viscosity 20,000
) s · a P m ( , y t i s o c s i V
Carbopol® Ultrez 21 Polymer Carbopol® Ultrez 10 Polymer Carbopol® Ultrez 20 Polymer
10,000
Carbopol® 980 Polymer Carbopol® 940 Polymer
0 1.0 2.0 3.0 pH = 2.5 - 3.50.0 Polymer Concentration, wt % Brookfield RVT @ 20 rpm
4.0
5.0
Measurement taken @ 1 hour @ 25 C
Dispersion Preparation of Carbopol ® and Pemulen ® Polymer - Add slowly in finely divided particles by sifting polymers through 20 - 30 mesh stainless steel screen into water vortex - Add as early in formulation as possible
- Add small amount of inorganic acid to reduce viscosity and air entrapment - Neutralize near the end of the formula - Up to 2.0% polymer concentration recommended
Processing and Formulating Guidelines Carbopol ® Ultrez Polymers
Sprinkle polymer on surface of water and allow to self-wet (vigorous agitation produces foam)
Gently begin agitation
Can be pre- or post-neutralized (depending on application)
Keep agitation to a minimum (to avoid air entrapment) while adding remaining ingredients to formulation
Effect of pH on Viscosity Carbopol ® Polymer - 0.5 (wt %) 100,000
Carbopol ® Polymer 10,000 Carbopol® Ultrez 21 polymer
) s · a P 1,000 m ( , y t i s o 100 c s i V
Carbopol® Ultrez 10 polymer
10
Carbopol® Ultrez 20 polymer
1 3
4
5
NaOH - 18 (wt %) Brookfield RVT @ 20 rpm
6
7
8
pH
9
10
11
12
NaCl Effect on Carbopol ® Polymer Gel Viscosities Carbopol® Polymer - 1.0 wt% at pH 7.5 Carbopol ® Polymer
90,000 ) 80,000 s · 70,000 a P 60,000 m ( , 50,000 y t i 40,000 s o 30,000 c s i V 20,000 10,000 0
Carbopol® Ultrez 21 polymer Carbopol® Ultrez 10 Polymer Carbopol® Ultrez 20 Polymer
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Brookfield RVT @ 20 rpm
NaCl Concentration (wt %)
Measurements taken immediately
Clarity Vs. Concentration 100
Carbopol ® polymers
99 98 ) T % ( y t i r a l C
Carbopol® Ultrez 20 polymer
97 96
Carbopol® ETD 2020 polymer
95
Carbopol® Ultrez 21 polymer
94 93 92 91 90 0.0
0.2
pH = 6.0 Brookfield RVT @ 20 rpm
0.4
0.6
0.8
Polymer Concentration (wt %)
1.0
Measurements taken @ 1 hour @ 25 °C
Creating the Right Sensory with the Right Choice of Carbopol ® Polymers
Formulate with Confidence™
© The Lubrizol Corporation 2008, all rights reserved
Gel: Screening Formulation Comparable Viscosities (23,000-28,000 mPa .s) Part
Ingredients
A
INCI
Carbopol Ultrez 10 polyme
Carbomer
Carbopol Ultrez 20 polymer
Acrylates C10-C30 Alkyl Acrylate Crosspolymer
Carbopol Ultrez 21 polymer
Acrylates C10-C30 Alkyl Acrylate Crosspolymer
Carbopol 940 polymer
Carbomer
Carbopol 980 polymer
Carbomer
Carbopol 934 polymer
Carbomer
% Weight 0.23 0.60
0.23
0.20 0.25 0.45
Deionized Water
B
C
TEA(99%)
Glydant Plus Liquid
Qs to 100
Triethanolamine
DMDM Hydantoin (&) Iodopropynyl Butylcarbamate
QS to pH = 6.0 6.5 –
0.40
0.40
0.40
0.40
0.40
0.40
Gel: Effect of Electrolytes on Viscosity Comparable Viscosities w/ 0.01wt% NaCl
w/ 0.05wt% NaCl
20,000 ) ) S S • . a a P P m m ( ( y t i s o c s i V
10,000
0 U10 U10 = Carbopol® Ultrez 10 polymer U20 = Carbopol® Ultrez 20 polymer U21 = Carbopol® Ultrez 21 polymer
U20
U21
940
Rheology Modifiers
980
934
940 = Carbopol® 940 polymer 980 = Carbopol® 980 polymer 934 = Carbopol® 934 polymer
More electrolyte tolerant Carbopol polymers offer higher viscosity response in the presence of electrolytes.
Gel: Stress Sweep 1000
1000
Rest plateau
Critical Strain 100.0
100.0
10.00 G ' ( P a s. )
G 10.00 ' ( P a s. )
Rest plateau Yield Stress
1.000
0.100
Yield Stress
1.000
Carbopol Ultrez 10 Polymer CarbopolUltrez 20 polymer Carbopol Ultrez 21Polymer Carbopol 940 Polymer Carbopol 980 Polymer Carbopol 934 Polymer
0.100
0.010
Critical Strain
Carbopol® Ultrez 10 Polymer + NaCl Carbopol® Ultrez 20 Polymer + NaCl Carbopol® Ultrez 21 Polymer + NaCl Carbopol® 940 Polymer + NaCl Carbopol® 980 Polymer + NaCl Carbopol® 934 Polymer + NaCl
0.010 0.1000
1.000
10.00
osc. stress (Pa)
100.0
1000
0.1000
1.000
10.00
100.0
osc. stress (Pa)
Lower values for yield stress result in easier-to-break structures. The longer the “rest plateau”, the higher the stress needed to break the structure .
1000
Gel: Sensory Attributes of Carbopol ® Polymers (Forced Ranking Method) Cushion
*
Carbopol® Ultrez 10 Polymer Carbopol® Ultrez 20 Polymer
*
* Afterfeel Intensity
Quickness of Break -9E +2 63
Carbopol® Ultrez 21 Polymer Carbopol® 940 Polymer
Carbopol® 980 Polymer
HSD95
Spreadability
Wetness
*
*with significant difference
Each polymer has its own sensory fingerprint.
Carbopol® 934 Polymer
Gel: Range of Aesthetics for Carbopol ® Polymers Light
Heavy
Wet Watery
Creamy
Quick Break
Long Playtime
Ultrez 10
Ultrez 21
980
Ultrez 20
Carbopol ® Polymers Taken from the forced ranking sensory data of tested Carbopol ® Polymers Ultrez 10 = Carbopol® Ultrez 10 polymer Ultrez 21 = Carbopol® Ultrez 21 polymer 980 = Carbopol® 980 polymer Ultrez 20 = Carbopol® Ultrez 20 polymer
Gel: Summary of Sensory Evaluation •
Carbopol ® Ultrez 20 polymer offers luxurious feel and longer playtime – a melting sensory. Good for rich cushiony and non watery sensory gel formulations.
•
Both Carbopol ® Ultrez 10 and Carbopol ® Ultrez 21 polymers provide refreshing sensory in initial rubout. Good for refreshing formulations.
•
Carbopol ® 980 polymer provides in-between sensory characterized by slippery and lighter initial cushiony feel. Good for medium to rich formulations with non-tacky afterfeel.
Emulsion: Sensory Attributes of Carbopol ® Polymers QDA Rating Method Cushion
*
Afterfeel Intensity
* HSD95
*
Quickness of Break
-9 E + 26
Spreadbility
Wetness
*
Carbopol® Ultrez 10 Polymer
Carbopol® Ultrez 20 Polymer
Carbopol® Ultrez 21 Polymer
Carbopol® 940 Polymer
Carbopol® 980 Polymer
Carbopol® 934 Polymer
*
Emulsion: Range of Aesthetics for Carbopol ® Polymers Light
Heavy
Low residual feel
High residual feel
Non-lingering afterfeel
Ultrez 10
980
Lingering afterfeel
Ultrez 21
Ultrez 20
Carbopol ® Polymers Ultrez 10 = Carbopol® Ultrez 10 polymer Ultrez 21 = Carbopol® Ultrez 21 polymer 980 = Carbopol® 980 polymer Ultrez 20 = Carbopol® Ultrez 20 polymer
Emulsion: Summary of Sensory Evaluation •
Even with the complexities of emulsion formulations, Carbopol polymers still provide sensory influence in the resulting emulsions. –
Carbopol® Ultrez 20 polymer provides luxurious, melting rubout sensory and highest afterfeel intensity.
–
Carbopol® Ultrez 21 polymer provides melting, lighter rubout sensory and medium to light afterfeel intensity.
–
Carbopol® Ultrez 10 polymer provides refreshing, short rubout sensory and light afterfeel intensity.
–
Carbopol® 980 polymer provides light, lubricating rubout sensory and velvety
afterfeel.
Carbopol ® Polymers: Application Guide Acrylates/C10INCI/CTFA Designation 30 alkyl acrylate crosspolymer
Carbomer
Ultrez 21
PROPERTIES Flow characteristics Relative viscosity Suspending ability (yield value) Clarity Relative Ion Tolerance Relative Shear Tolerance APPLICATIONS Clear Gels Hydroalcoholic Gels Lotions Creams Personal Cleansers High Electrolyte Systems (aloe gels, etc.)
Carbomer
Acrylates/C10-30 Carbomer alkyl acrylate crosspolymer
Ultrez 10
Ultrez 20 ETD 2020 1382 1342
2984/5984 934
980 940
ETD 2050 981 941
Short High
Short High
Short High
Long Low
Medium Medium
High
High
High
High
High
Very high Medium High
Low Low High
High Low High
High Medium Low
High High Low
◆ ◆ ◆
◆ ◆
◆ ◆
◆ ◆ ◆ ◆
Ultrez 10 = Carbopol ® Ultrez 10 Polymer Ultrez 20 = Carbopol ® Ultrez 20 Polymer Ultrez 21 = Carbopol ® Ultrez 21 Polymer
◆ ◆ ◆ ◆ ◆ ◆
934 = Carbopol® 934 Polymer 1382 = Carbopol® 1382 Polymer 940 = Carbopol® 940 Polymer 2984 = Carbopol® 2984 Polymer 941 = Carbopol® 941 Polymer 5984 = Carbopol® 5984 Polymer
◆ ◆ ETD2020 = Carbopol® EETD2020 Polymer ETD2050 Carbopol®
Trademarks •
•
Carbopol and SilSense are registered trademarks of The Lubrizol Corporation. Fixate, Glucam, Glucamate, Glucate, Glucquat, Hydramol, Merquat, Novemer, Pemulen, Schercemol and Sensomer are trademarks of The Lubrizol Corporation.
•
Hydrolite is registered trademark of Symrise.
•
Euxyl is a registered trademark of Schülke & Mayr GmbH
•
Olympus is a registered trademark of Olympus corporation
•
Fucosorb is a trademark of Sensient
•
Lipopearl and Liposphere are trademarks of Lipo Technologies, Inc.
Disclaimer The information contained herein is believed to be reliable, but no representations, guarantees or warranties of any kind are made as to its accuracy, suitability for a particular application or the results to be obtained herefrom. Lubrizol Advanced Materials, Inc. ("Lubrizol") cannot guarantee how any products associated with this information will perform in combination with other substances or in your process as the "user". Often, the information is based on laboratory work with small-s cale equipment. Due to variations in methods, conditions and equipment used commercially in processing materials, the information does not necessarily indicate end product performance or reproducibility. As such, no warranties or guarantees are made as to the suitability of the information or products referenced hereunder for any applications disclosed to Lubrizol. Full scale testing and end product performance are the responsibility of the user. Further, any formulations presented should be used only as a suggested starting point. Lubrizol shall not be liable and the user assumes all risk and responsibility for, any use or handling of any material beyond Lubrizol's direct control. THE SELLER MAKES NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, BUT NOT LIMITED TO, THE IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. Nothing contained herein is to be considered as a permission, recommendation, or as an inducement to practice any patented invention without permission of the patent owner. © Copyright, Inc. 2012 Lubrizol Advanced Materials
