Recent Developments in 
Cationic Surfactants for 
Fabric & Car Care 
Andras Nagy, Ph.D. 
Applied Technology Manager 
House...
Agenda 
 Traditional and Unique Applications: Substantivity 
 Antibacterial agents/Corrosion inhibitors/Asphalt emulsion/O...
What Is a Cationic Surfactant (Quat) 
 Quats are positively charged ions, R being alkyl or aryl 
group(s) 
 Permanently ch...
An Important Property 
Substantivity 
 An attractive force is required to deposit caring 
agents from dilute formulations ...
Traditional and Unique Applications 
Antimicrobial Quats: 
 Disruption of intermolecular interactions (bacteriostatic, fun...
Page | 6 
Fabric Softening 
1. Overview 
2. Rinse Cycle Products 
3. Dryer Cycle Products 
Consumer Specialties | Business...
Fabric Softeners Overview 
Phase Behaviour of Quats 
Double-chain cationic surfactants 
form vesicles 
from: J.N. Israelac...
Page | 8 
Fabric Softening 
1. Overview 
2. Rinse Cycle Products 
3. Dryer Cycle Products 
Consumer Specialties | Business...
How Are Fabric Softeners Made? 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
- 
- 
“heat” quat to T...
How Are Fabric Softeners Made? 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
2. Dispersed into warm...
How Are Fabric Softeners Made? 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
2. Dispersed into warm...
How Do Fabric Softeners Work? 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
2. Dispersed into warm ...
How Do Fabric Softeners Work? 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
2. Dispersed into warm ...
How Do Fabric Softeners Work? 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
2. Dispersed into warm ...
Page | 15 
Fabric Softening 
1. Overview 
2. Rinse Cycle Products 
3. Dryer Cycle Products 
Consumer Specialties | Busines...
How Are Fabric Softeners Made? 
Dryer Cycle Fabric Softeners: 
1. Quats and other ingredients are heated and 
homogenized ...
How Are Fabric Softeners Made? 
Dryer Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
2. Poured on a hot pla...
How Are Fabric Softeners Made? 
Dryer Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
2. Poured on a hot pla...
How Are Fabric Softeners Made? 
Dryer Cycle Fabric Softeners: 
• Industrial process 
Supply Roll 
Doctor Blade 
Squeeze 
R...
How Do Fabric Softeners Work? 
Dryer Cycle Fabric Softeners: 
1. Quats are heated and homogenized 
2. Poured on a hot plat...
Page | 21 
Fabric Softener Actives 
1. Chemistry, Biodegradability 
2. Chemistry, Performance 
3. Physical State 
4. Impro...
Evonik – The Global Leader in 
Fabric Softener Actives 
Full Range of Softener Chemistry 
Dialkyl cationic surfactants 
 N...
Biodegradability 
Ester bonds as potential “breaking points”: 
O O 
- 
CH3 
O O 
N 
CH3 
O 
Consumer Specialties |P Bagues...
Environmental Impact of 
Quaternaries 
Dialkyl-dimethyl and Ester Quaternaries 
Biodegradation of Quaternaries 
%-Degradat...
Page | 25 
Fabric Softener Actives 
1. Chemistry, Biodegradability 
2. Chemistry, Performance 
3. Physical State 
4. Impro...
Nitrile Quats 
• Premium softening and anti-stat properties 
• Yellowing with age, limited biodegradability and rewet 
Key...
Amidoamines 
• Wide range of formulations: (up to 25% active) 
• Versatile: household, industrial  institutional, textile ...
Imidazoline Quats 
• Excellent antistatic benefits with good softening 
• Good for clear fabric softener formulation. 
Imi...
Ester Quats 
• Readily biodegradable (best in class) 
• Wide range of formulations: (up to 25% active) 
• Good fragrance i...
Rinse Cycle Quat Characteristics 
Product 
ADOGEN® 
442 
VARISOFT® 
475 
VARISOFT® 
222 
REWOQUAT® 
WE 28 E 
Type Nitrile ...
Page | 31 
Fabric Softener Actives 
1. Chemistry, Biodegradability 
2. Chemistry, Performance 
3. Physical State 
4. Impro...
Consumer Specialties | Business Line Household Care 
O O 
N 
OH 
O 
R 
O 
R 
CH3OSO3 
Ester Quat 
CH3OSO3 
N 
HN 
HN 
O 
R...
Consumer Specialties | Business Line Household Care 
TEA Ester Quats 
 Biodegradable 
 Globally accepted 
 Regional CAS nu...
Consumption of Surfactants for 
Fabric Softeners by Region 
Consumer Specialties | Business Line Household Care 
+3.8% 
+5...
Fabric Softener Actives 
Current Technology 
Fabric Softener Actives 
Paste or solid products require 
continuous heating ...
Fabric Softener Actives 
Paste or solid products require 
continuous heating which impacts 
 Storage time 
 Transportation...
Page | 37 
Fabric Softener Actives 
1. Chemistry, Biodegradability 
2. Chemistry, Performance 
3. Physical State 
4. Impro...
Consumer Specialties | Business Line Household Care 
Our Goal 
A new product that meets multiple 
requirements for process...
Fabric Softener Active 
Attempts to make a liquid product 
 Additives (solubilizers  emulsifiers) 
 Additional solvent 
 H...
Making a Liquid Active at RT 
with Appropriate Synthesis Conditions 
Clear, liquid, easy-to-process 
TEA ester quat 
 Liqu...
REWOQUAT® WE 45* 
Physical/Chemical Property Comparison 
Improved Ester 
Quat* 
Amidoamine Quat 
Traditional Ester 
Quat 
...
REWOQUAT® WE 45* 
Physical/Chemical Property Comparison 
Improved Ester 
Quat* 
Amidoamine Quat 
Traditional Ester 
Quat 
...
Fabric Softeners 
Using a Low Temperature Dispersible Quat 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogen...
Fabric Softeners 
Using a Low Temperature Dispersible Quat 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogen...
Fabric Softeners 
Using a Low Temperature Dispersible Quat 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogen...
Fabric Softeners 
Using a Low Temperature Dispersible Quat 
Rinse Cycle Fabric Softeners: 
1. Quats are heated and homogen...
Fabric Softener Dispersion 
Lab Batch Process – Timeline 
Traditional Ester Quat 
Heat Water and Quat 
EVONIK TEA Ester Qu...
Fabric Softener Dispersion 
Softness Evaluation 
Panel Testing PHABROMETER® - Nu Cybertek, Inc. 
Consumer Specialties | Bu...
Fabric Softening Performance Comparison - Panel 
120 
100 
80 
60 
40 
20 
0 
Control EVONIK Brand A 
Consumer Specialties...
Fabric Softener Dispersion 
PHABROMETER® - Force vs. Displacement 
Extraction Curve(s) for Class: Unknown 
Evaluation Type...
Fabric Softening Performance Comparison - PHABROMETER 
140 
130 
120 
110 
100 
90 
80 
70 
Control Brand A EVONIK 
Consum...
REWOQUAT® WE 45 
Summary 
REWOQUAT® WE 45 offers 
Potential cost savings for 
 Storage and handling 
 Processing 
 Energy ...
Dryer Sheet Quats 
 Chemistry, Improved Biodegradability 
 Performance Test 
Consumer Specialties | Business Line Househol...
VARISOFT® Dryer Sheet Quats 
Active Type Dryer Cycle Product 
Actives 
(%) 
Anti- 
Static 
Biodegradability1 
Storage 
Tem...
VARISOFT® Dryer Sheet Quats 
Antistatic Testing Equipment (ASTM D 5237) 
Static Decay Meter 
Humidity Chamber 
Consumer Sp...
VARISOFT® Dryer Sheet Quats 
Antistatic Test Results 
4.00 
3.50 
3.00 
2.50 
2.00 
1.50 
1.00 
0.50 
0.00 
National Brand...
Ethoxylated Quats 
1. Antistatic Sprays 
2. Cleaner blends 
Consumer Specialties | Business Line Household Care Page | 57
Ethoxylated Quats 
Antistatic Sprays 
Product 
Actives 
(%) 
R 
(C2H5O)xH N+ (C2H5O)yH 
R’ 
x+y R R’ Counter Ion 
Adogen 6...
Antistatic Spray Performance: 
Ethoxylated Quats Work Well 
50.00 
40.00 
30.00 
20.00 
10.00 
0.00 
0.25 
0.20 
0.15 
0.1...
Ethoxylated Quats 
1. Antistatic Sprays 
2. Cleaner blends 
Consumer Specialties | Business Line Household Care Page | 60
Car Care Basics and Challenges 
- 
 Drying 
 Rinsing 
 Cleaning 
Hannah Carwash System 
Consumer Specialties | Business Li...
Car Care Basics and Challenges 
Cleaning 
- 
Major Factors of Cleaning 
1. Mechanical energy 
 Most carwashes do not use b...
Car Wash: Step I 
1. Removal of contaminants by using surfactants: 
Water 
Oil 
Paint 
Consumer Specialties | Business Lin...
REWOQUAT® CQ 100 G 
Multipurpose Surfactant Blend 
Composition 
 Specialty blend of cationic and nonionic surfactants 
Per...
REWOQUAT® CQ 100 G 
Hard Surface Cleaning Results 
Improved Detergency  Degreasing 
Kitchen soil Soap scum Engine soil 
Ra...
Rinsing (Anionic Scavengers) 
1. Car Care 
2. Fabric Care 
Consumer Specialties | Business Line Household Care Page | 66
Car Wash: Step II 
2. Rinsing with water: 
Water film adheres to the surface upon washing and rinsing 
Water 
- - - - - - ...
Car Care Basics and Challenges 
Rinsing 
- 
Major Challenges 
1. Anionic surfactants are efficient cleaners, but difficult...
Anionic Scavengers - Softergents 
Mechanism 
Anionic surfactant 
Anionic 
surfactant 
Anionic surfactant 
Cationic emulsif...
Rinsing (Anionic Scavengers) 
1. Car Care 
2. Fabric Care 
Consumer Specialties | Business Line Household Care Page | 70
Anionic Scavengers – Softergents 
Chemistry 
Recommendations: 
• Use level: 
 Depending on rinse efficiency 
 Use at least...
Drying, Protection 
1. Theory and Practice 
2. Organomodified Silicones 
3. Traditional and Biodegradable Systems 
Consume...
Car Care Basics and Challenges 
Drying 
- 
Major Factors of Drying 
1. Cleaned cars have a thin water film which sticks 
s...
Drying Agents / Rinse Aids 
What are they? 
They are oil in water microemulsions containing emulsifiers, hydrophobes, 
sol...
Drying Aids/Protectants: 
Microemulsions of Cationic Emulsifiers and Oils 
water film 1. Water film adheres 
surface 
Cons...
Drying Aids/Protectants: 
Microemulsions of Cationic Emulsifiers and Oils 
water film 
Consumer Specialties | Business Lin...
Drying Aids/Protectants: 
Microemulsions of Cationic Emulsifiers and Oils 
water film 
surface 
Consumer Specialties | Bus...
Drying Aids/Protectants: 
Microemulsions of Cationic Emulsifiers and Oils 
water film 
surface 
1. Water film adheres to 
...
Increasing the Contact Angle 
Why is It Beneficial? 
θ 
1 
Consumer Specialties | Business Line Household Care 
A1 
B1 
θ ...
Drying, Protection 
1. Theory and Practice 
2. Organomodified Silicones 
3. Traditional and Biodegradable Systems 
Consume...
Organomodified Silicones 
Compatibility Chart 
Siliconophilic 
Alkylsiloxanes 
Hydrophilic Lipophilic 
Polyether-siloxanes...
Page | 82 
Basics of Silicone Quats 
+ 
+ / 
+ + 
Consumer Specialties | Business Line Household Care
Silicone Quats 
Strong Bond Between Surface and Molecule 
Consumer Specialties | Business Line Household Care Page | 83
Silicone Quats 
Strong Bond Between Surface and Molecule 
Surface 
Consumer Specialties | Business Line Household Care Pag...
Silicone Quats 
Strong Bond Between Surface and Molecule 
Two anchor points 
Silicone Backbone 
Surface 
Consumer Specialt...
Silicone Quats 
Strong Bond Between Surface and Molecule 
Two anchor points 
Silicone Backbone 
Surface 
TEGOPREN® 6922 (s...
Silicone Quats 
Miracles Can Happen….. 
What a difference!!! ☺ 
Consumer Specialties | Business Line Household Care Page |...
Drying, Protection 
1. Theory and Practice 
2. Organomodified Silicones 
3. Traditional and Biodegradable Systems 
Consume...
Drying Agent / Rinse Aid Trends 
HISTORICAL EVOLVING 
 Fast drying 
 Spot free 
surface 
 Visual: 
Aesthetics 
 Low price ...
Biodegradable Rinse Aids 
Drying and Protection of Surfaces 
Goal: 
Develop an emulsifier that enables the formulation of ...
Traditional and New Emulsifiers 
Dialkyl Quats: 
 good performance, stable products 
 low biodegradability 
 (high di-fatt...
Traditional and New Hydrophobes 
Mineral Seal Oil: 
 good performance, stable products 
 low biodegradability 
 unpleasant...
Performance Comparison 
“Split-hood” test 
Consumer Specialties | Business Line Household Care Page | 93
Readily Biodegradable Emulsifier 
Carspray 800 
MDEA Ester Quat emulsifier for vehicle rinse aids/drying agents 
to addres...
Acknowledgements 
BL Household Care – Hopewell, Virginia 
• Dennis Parrish 
• Miyako Hisamoto 
• Gonglu Tian 
• Erin King ...
Consumer Specialties | Business Line Household Care Page | 96
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Desenvolvimentos Recentes em Surfactantes Catiônicos para Fabric Care e Car Care – Andras Nagy – Evonik

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Desenvolvimentos Recentes em Surfactantes Catiônicos para Fabric Care e Car Care – Andras Nagy – Evonik

  1. 1. Recent Developments in Cationic Surfactants for Fabric & Car Care Andras Nagy, Ph.D. Applied Technology Manager Household Care/CS NA
  2. 2. Agenda Traditional and Unique Applications: Substantivity Antibacterial agents/Corrosion inhibitors/Asphalt emulsion/Ore flotation Fabric softeners Vehicle drying agents Emulsifiers/surfactants: cleaning/drying aids/protectants Anionic Scavengers – Softergents: car care - fabric care Silicone Quats: special organomodified silicones Latest Developments: Smart molecules Low temperature dispersible fabric softener quat Readily biodegradable emulsifier for vehicle rinse aids Consumer Specialties | Business Line Household Care Page | 2
  3. 3. What Is a Cationic Surfactant (Quat) Quats are positively charged ions, R being alkyl or aryl group(s) Permanently charged, independent of the pH of their solution. Cationic surfactants are salts of quaternary ammonium cations with an anion. Made by alkylation of tertiary amines Have hydrophobic tail(s), polar head(s) with positive charge(s) and counter-anion(s) with negative charge(s) X- - + - Consumer Specialties | Business Line Household Care Page | 3
  4. 4. An Important Property Substantivity An attractive force is required to deposit caring agents from dilute formulations to the target surface Most surfaces are negatively charged mainly due to oxidation The Coulomb attraction between cationic surfactants and surfaces can be used as a deposition mechanism - - - - - - - - Consumer Specialties | Business Line Household Care Page | 4
  5. 5. Traditional and Unique Applications Antimicrobial Quats: Disruption of intermolecular interactions (bacteriostatic, fungistatic, algistatic, antiviral activity) Corrosion Inhibitors: Substantivity of the cationics will create protective coatings Ore Flotation: Quats will form monomolecular films on negative particles. Air bubbles will float the hydrophobic components Asphalt Emulsions: Cationic emulsions will coat inorganic particles and metal surfaces even in wet conditions (highway construction, vehicle undercoating) Miscellaneous Applications: Cosmetics, Hair conditioners, Pigment dispersants, etc. Consumer Specialties | Business Line Household Care Page | 5
  6. 6. Page | 6 Fabric Softening 1. Overview 2. Rinse Cycle Products 3. Dryer Cycle Products Consumer Specialties | Business Line Household Care
  7. 7. Fabric Softeners Overview Phase Behaviour of Quats Double-chain cationic surfactants form vesicles from: J.N. Israelachvilli et al., J. Chem. Soc., Faraday Trans. II, 72 (1976) 1525-1568 + Consumer Specialties | Business Line Household Care Page | 7
  8. 8. Page | 8 Fabric Softening 1. Overview 2. Rinse Cycle Products 3. Dryer Cycle Products Consumer Specialties | Business Line Household Care
  9. 9. How Are Fabric Softeners Made? Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized - - “heat” quat to T °C T °C Homogenize Consumer Specialties | Business Line Household Care Page | 9
  10. 10. How Are Fabric Softeners Made? Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Dispersed into warm water T °C Disperse quat into water at T °C; mix Consumer Specialties | Business Line Household Care Page | 10
  11. 11. How Are Fabric Softeners Made? Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Dispersed into warm water 3. Cooled down while being mixed t °C Cool to t °C; mix Consumer Specialties | Business Line Household Care Page | 11
  12. 12. How Do Fabric Softeners Work? Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Dispersed into warm water 3. Cooled down while mixed 4. Fragrances and other additives are added Add dye, fragrance, etc.; mix thoroughly Consumer Specialties | Business Line Household Care Page | 12
  13. 13. How Do Fabric Softeners Work? Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Dispersed into warm water 3. Cooled down while mixed 4. Fragrances and other additives are added 5. These liquid softeners are added during the rinse cycle in the washing machine Consumer Specialties | Business Line Household Care Page | 13
  14. 14. How Do Fabric Softeners Work? Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Dispersed into warm water 3. Cooled down while mixed 4. Fragrances and other additives are added 5. These liquid softeners are added during the rinse cycle in the washing machine 6. The positively charged molecules are attached to the negative fibers to make them soft, and antistatic Consumer Specialties | Business Line Household Care Page | 14
  15. 15. Page | 15 Fabric Softening 1. Overview 2. Rinse Cycle Products 3. Dryer Cycle Products Consumer Specialties | Business Line Household Care
  16. 16. How Are Fabric Softeners Made? Dryer Cycle Fabric Softeners: 1. Quats and other ingredients are heated and homogenized - - “Melt” ingredients at T °C T °C Homogenize Consumer Specialties | Business Line Household Care Page | 16
  17. 17. How Are Fabric Softeners Made? Dryer Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Poured on a hot plate (lab process) 3. Nonwoven substrate is put on the plate 4. Quat is spead evenly with a roller Consumer Specialties | Business Line Household Care Page | 17
  18. 18. How Are Fabric Softeners Made? Dryer Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Poured on a hot plate (lab process) 3. Nonwoven substrate is put on the plate 4. Quat is spead evenly with a roller 5. Coated substrate is lifted to solidify 6. Dryer sheet quat is ready for use Consumer Specialties | Business Line Household Care Page | 18
  19. 19. How Are Fabric Softeners Made? Dryer Cycle Fabric Softeners: • Industrial process Supply Roll Doctor Blade Squeeze Roll Heating Cans Cooling Cans Cutting Blade Heated Dip Tank Take-up Roll Consumer Specialties | Business Line Household Care Page | 19
  20. 20. How Do Fabric Softeners Work? Dryer Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Poured on a hot plate, 3. Nonwoven substrate is put on the plate 4. Quat is spead evenly with a roller 5. Coated substrate is lifted to solidify 6. Dryer sheet quat is ready for use 7. The positively charged molecules are attached to the negative fibers to make them soft, and antistatic Consumer Specialties | Business Line Household Care Page | 20
  21. 21. Page | 21 Fabric Softener Actives 1. Chemistry, Biodegradability 2. Chemistry, Performance 3. Physical State 4. Improvement: Room Temperature Dispersible Quat Consumer Specialties | Business Line Household Care
  22. 22. Evonik – The Global Leader in Fabric Softener Actives Full Range of Softener Chemistry Dialkyl cationic surfactants Nitrile (ADOGEN® 442) Amidoamine (VARISOFT® 222) Imidazolinium (VARISOFT® 475) Ester Quat (REWOQUAT® WE 45) Monoalkyl Quats Anionic scavengers Softening boosters ADOGEN® 471 Organomodifed Silicones (II) Fabric care benefits Easy ironing Reduced wrinkling Faster drying REWOQUAT® SQ 1 2-in-1 Softener Additives ADOGEN® 477 D Consumer Specialties | Business Line Household Care Page | 22
  23. 23. Biodegradability Ester bonds as potential “breaking points”: O O - CH3 O O N CH3 O Consumer Specialties |P Baguesi n| e2s3s Line Household Care O R O R CH3 X N X OH O R O R R O R' Smaller molecules are more easily accessible by microorganisms Fatty acids are readily biodegradable The other molecular fragments are also completely biodegradable* * Puchta et al: Tenside Surf. Det. 30 (1993) 3
  24. 24. Environmental Impact of Quaternaries Dialkyl-dimethyl and Ester Quaternaries Biodegradation of Quaternaries %-Degradation 100 10 1 0.1 EC50 [mg/l] Consumer Specialties | Business Line Household Care Page | 24 100 80 60 40 20 0 Dialkyl-dimethyl Ester OECD 301 E (5 d) OECD 301 C (30 d) Aquatic toxicity of Quaternaries 0.01 Dialkyl-dimethyl Ester OECD 201 (Algae) OECD 202 (Daphnia) OECD 203 (Fish) Ester quaternaries yielded significantly better data than the standard dialkyl-dimethyl quaternaries
  25. 25. Page | 25 Fabric Softener Actives 1. Chemistry, Biodegradability 2. Chemistry, Performance 3. Physical State 4. Improvement: Room Temperature Dispersible Quat Consumer Specialties | Business Line Household Care
  26. 26. Nitrile Quats • Premium softening and anti-stat properties • Yellowing with age, limited biodegradability and rewet Key Product Offerings ADOGEN® 442 75% Tallow based AROSURF® TA 100 Powder, for warm water wash Consumer Specialties | Business Line Household Care Page | 26
  27. 27. Amidoamines • Wide range of formulations: (up to 25% active) • Versatile: household, industrial institutional, textile • Good softening and rewet Key Product Offerings VARISOFT® 222 LM 90% Cold water processable Consumer Specialties | Business Line Household Care Page | 27
  28. 28. Imidazoline Quats • Excellent antistatic benefits with good softening • Good for clear fabric softener formulation. Imidazolinium VARISOFT® 475 75% Paste, tallow VARISOFT® 3690 Liquid, oleyl VARISOFT® 3696 Liquid, 100% active, ethyl sulfate Consumer Specialties | Business Line Household Care Page | 28
  29. 29. Ester Quats • Readily biodegradable (best in class) • Wide range of formulations: (up to 25% active) • Good fragrance impact Key Product Offerings REWOQUAT® WE 16 E Tallow based w/ ethanol REWOQUAT® WE 18 E US High viscosity version w/ ethanol REWOQUAT® WE 28 E US Vegetable based w/ ethanol REWOQUAT® WE 45 Clear, liquid, easy to handle Consumer Specialties | Business Line Household Care Page | 29
  30. 30. Rinse Cycle Quat Characteristics Product ADOGEN® 442 VARISOFT® 475 VARISOFT® 222 REWOQUAT® WE 28 E Type Nitrile Imidazolinium Amidoamine TEA Ester Quat Softening Fragrance Impact Static Control Range of Formulation Biodegradation **** = most favorable Consumer Specialties | Business Line Household Care Page | 30
  31. 31. Page | 31 Fabric Softener Actives 1. Chemistry, Biodegradability 2. Chemistry, Performance 3. Physical State 4. Improvement: Room Temperature Dispersible Quat Consumer Specialties | Business Line Household Care
  32. 32. Consumer Specialties | Business Line Household Care O O N OH O R O R CH3OSO3 Ester Quat CH3OSO3 N HN HN O R O R ((CH2)2O)nH Amidoamine N N CH3OSO3 NH R R O Imidazolinium Nitrile R N R Cl Page | 32 Fabric Softener Actives
  33. 33. Consumer Specialties | Business Line Household Care TEA Ester Quats Biodegradable Globally accepted Regional CAS numbers Descriptor matches fatty acid Complex mixture Mono, di, tri ester quats Esteramines Typical concentration of 90% Paste or solid at 25 °C O O N OH O R O R CH3OSO3 Ester Quat CH3OSO3 N HN HN O R O R ((CH2)2O)nH Amidoamine N N CH3OSO3 NH R R O Imidazolinium Nitrile R N R Cl Page | 33 Fabric Softener Actives
  34. 34. Consumption of Surfactants for Fabric Softeners by Region Consumer Specialties | Business Line Household Care +3.8% +5.7% Global Demand (t) 328,000 (2009) 361,000 (2014) +2.5% -0.1% XX% CAGR 2009 – 2014 *CAGR 2011 – 2016 +6.0%* Sources: SRI Consulting, Coimbra Consultoria Representações Comerciais Ltda
  35. 35. Fabric Softener Actives Current Technology Fabric Softener Actives Paste or solid products require continuous heating which impacts Storage time Transportation Color and odor Solvent level Consumer Specialties | Business Line Household Care Page | 35
  36. 36. Fabric Softener Actives Paste or solid products require continuous heating which impacts Storage time Transportation Color and odor Solvent level Fabric Softener Formulations Paste or solid products impact Processing and handling conditions Energy use Cycle time Consumer Specialties | Business Line Household Care Page | 36 Fabric Softener Actives Current Technology
  37. 37. Page | 37 Fabric Softener Actives 1. Chemistry, Biodegradability 2. Chemistry, Performance 3. Physical State 4. Improvement: Room Temperature Dispersible Quat Consumer Specialties | Business Line Household Care
  38. 38. Consumer Specialties | Business Line Household Care Our Goal A new product that meets multiple requirements for processing and use Easy-to-handle and transport Room temperature processing Biodegradable Globally accepted Wide range of stable formulations Competitive softening performance Fabric Softener Actives Paste or solid products require continuous heating which impacts Storage time Transportation Color and odor Solvent level Fabric Softener Formulations Paste or solid products impact Processing and handling conditions Energy use Cycle time Page | 38 Fabric Softener Actives Proposed Technology
  39. 39. Fabric Softener Active Attempts to make a liquid product Additives (solubilizers emulsifiers) Additional solvent Highly unsaturated fatty acid raw materials Partially hydrogenated fatty acids Fatty Acid Blends None of these reached the goal! Consumer Specialties | Business Line Household Care Page | 39
  40. 40. Making a Liquid Active at RT with Appropriate Synthesis Conditions Clear, liquid, easy-to-process TEA ester quat Liquid at room temperature Ethanol solvent Freeze/thaw stable Dispersible at room temperature No heating (or cooling) required As low as 18 °C Robust formulation range Formulates from 5% to 20% actives Base formulas are stable Softening equal to competitive products Consumer Specialties | Business Line Household Care Page | 40
  41. 41. REWOQUAT® WE 45* Physical/Chemical Property Comparison Improved Ester Quat* Amidoamine Quat Traditional Ester Quat Appearance @ 25 °C (77 °F) Clear Liquid Opaque Liquid / Paste Solid Quaternary 84-88% 89-91% 89-91% Flash Point 24 °C (76 °F) 24 °C (76 °F) 24 °C (76 °F) Consumer Specialties | Business Line Household Care Page | 41
  42. 42. REWOQUAT® WE 45* Physical/Chemical Property Comparison Improved Ester Quat* Amidoamine Quat Traditional Ester Quat Appearance @ 25 °C (77 °F) Clear Liquid Opaque Liquid / Paste Solid Quaternary 84-88% 89-91% 89-91% Flash Point 24 °C (76 °F) 24 °C (76 °F) 24 °C (76 °F) Storage Temperature 20 °C (68 °F) 38 °C (104 °F) 45 °C (113 °F) Pumping Temperature 25 °C (77 °F) minimum 45 °C (113 °F) minimum 55 °C (131 °F) minimum Consumer Specialties | Business Line Household Care Page | 42
  43. 43. Fabric Softeners Using a Low Temperature Dispersible Quat Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized - - “heat” quat to T °C T °C Homogenize Consumer Specialties | Business Line Household Care Page | 43
  44. 44. Fabric Softeners Using a Low Temperature Dispersible Quat Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Dispersed into warm water T °C Disperse quat into water at T °C; mix Consumer Specialties | Business Line Household Care Page | 44
  45. 45. Fabric Softeners Using a Low Temperature Dispersible Quat Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Dispersed into warm water 3. Cooled down while mixed t °C Cool to t °C; mix Consumer Specialties | Business Line Household Care Page | 45
  46. 46. Fabric Softeners Using a Low Temperature Dispersible Quat Rinse Cycle Fabric Softeners: 1. Quats are heated and homogenized 2. Dispersed into warm water 3. Cooled down while mixed 4. Fragrances and other additives are added Add dye, fragrance, etc.; mix thoroughly Consumer Specialties | Business Line Household Care Page | 46
  47. 47. Fabric Softener Dispersion Lab Batch Process – Timeline Traditional Ester Quat Heat Water and Quat EVONIK TEA Ester Quat Consumer Specialties | Business Line Household Care Cool Quat Salt Fragrance Preservative Quat Salt Fragrance Preservative Time (min) 20 40 60 80 100 Time (min) 20 40 60 80 100 Page | 47
  48. 48. Fabric Softener Dispersion Softness Evaluation Panel Testing PHABROMETER® - Nu Cybertek, Inc. Consumer Specialties | Business Line Household Care Page | 48
  49. 49. Fabric Softening Performance Comparison - Panel 120 100 80 60 40 20 0 Control EVONIK Brand A Consumer Specialties | Business Line Household Care Softness Score Fabric Softener Dispersion Softening Performance – Panel Test Methodology – Panel Test and Statistics Fabric samples prepared according to ASTM Method D 5237 Statistical differences reported at 95% confidence level (Friedman Simple Rank) Brand A is based on TEA Ester Quat technology Softer EVONIK TEA Ester Quat and Brand A are statistically equal Page | 49
  50. 50. Fabric Softener Dispersion PHABROMETER® - Force vs. Displacement Extraction Curve(s) for Class: Unknown Evaluation Type: Hand Density Type: Heavy Fabric (H) 3440 μg/cm 2.5 2 1.5 1 0.5 0 1 5 9 13 17 21 25 29 33 37 41 45 49 53 Control REWOQUAT® WE 45 Brand A 57 61 65 69 73 77 81 85 89 93 97 101 105 Force Displacement Consumer Specialties | Business Line Household Care Page | 50
  51. 51. Fabric Softening Performance Comparison - PHABROMETER 140 130 120 110 100 90 80 70 Control Brand A EVONIK Consumer Specialties | Business Line Household Care Softness Score Fabric Softener Dispersion Softening Performance – PHABROMETER® PHABROMETER® – Nu Cybertek, Inc. Quantitative fabric softness comparison Fabric samples prepared according to ASTM Method D 5237 Average of five replicates per sample Statistical differences reported at 95% confidence level Brand A is based on TEA Ester Quat technology Softer EVONIK TEA Ester Quat and Brand A are statistically equal Page | 51
  52. 52. REWOQUAT® WE 45 Summary REWOQUAT® WE 45 offers Potential cost savings for Storage and handling Processing Energy use cycle time Formulation flexibility and performance Ability to produce both non-concentrated and ultra formulas Stable formulations from 5% to 20% Softening and anti-stat equal to other ester quats Patent pending technology Consumer Specialties | Business Line Household Care Page | 52
  53. 53. Dryer Sheet Quats Chemistry, Improved Biodegradability Performance Test Consumer Specialties | Business Line Household Care Page | 53
  54. 54. VARISOFT® Dryer Sheet Quats Active Type Dryer Cycle Product Actives (%) Anti- Static Biodegradability1 Storage Temperature (° F) TEA Ester Quats VARISOFT® DS 355 65 **** Readily (OECD 301) 155-165 VARISOFT® DS 362 65 **** Readily (OECD 301) 160-170 Dialkyldimethyl VARISOFT® DS 136-100 70 *** Inherently 150-170 VARISOFT® DS 150 50 *** Inherently 135-150 Amidoamine VARISOFT® DS 110 70 **** Inherently 155-165 Consumer Specialties | Business Line Household Care Page | 54
  55. 55. VARISOFT® Dryer Sheet Quats Antistatic Testing Equipment (ASTM D 5237) Static Decay Meter Humidity Chamber Consumer Specialties | Business Line Household Care Page | 55
  56. 56. VARISOFT® Dryer Sheet Quats Antistatic Test Results 4.00 3.50 3.00 2.50 2.00 1.50 1.00 0.50 0.00 National Brand VARISOFT® DS 355 VARISOFT® DS 362 Static Decay Time (s) Antistatic tests performed on polyester fabrics (ASTM Method D 5237) Shorter decay times indicate better performance Control samples exceeded 300 seconds (not shown on graph) Product coating weights were 1.4 grams Consumer Specialties | Business Line Household Care Page | 56
  57. 57. Ethoxylated Quats 1. Antistatic Sprays 2. Cleaner blends Consumer Specialties | Business Line Household Care Page | 57
  58. 58. Ethoxylated Quats Antistatic Sprays Product Actives (%) R (C2H5O)xH N+ (C2H5O)yH R’ x+y R R’ Counter Ion Adogen 66 100 15 CH2CH3 Tallow Ethyl Sulfate Variquat K 1215 100 15 CH3 Coco Methyl Chloride Rewoquat CPEM 100 5 CH3 Coco Methyl Sulfate Variquat 638 100 2 CH3 Coco Methyl Chloride Consumer Specialties | Business Line Household Care Page | 58
  59. 59. Antistatic Spray Performance: Ethoxylated Quats Work Well 50.00 40.00 30.00 20.00 10.00 0.00 0.25 0.20 0.15 0.10 0.05 0.00 Static Guard Varisoft 137 90 Varisoft 222 LM Static Decay Time (s) Static Guard Varisoft 137 90 Varisoft 222 LM 90 90 WE 45 Rewoquat WE 45 Rewoquat CPEM CPEM Adogen 66 Static Decay Time (s) Adogen 66 Consumer Specialties | Business Line Household Care Page | 59
  60. 60. Ethoxylated Quats 1. Antistatic Sprays 2. Cleaner blends Consumer Specialties | Business Line Household Care Page | 60
  61. 61. Car Care Basics and Challenges - Drying Rinsing Cleaning Hannah Carwash System Consumer Specialties | Business Line Household Care Page | 61
  62. 62. Car Care Basics and Challenges Cleaning - Major Factors of Cleaning 1. Mechanical energy Most carwashes do not use brushes anymore to protect the car finish “Touchless” systems are getting more popular 2. Time Longer reaction time: better cleaning, but higher chance of damaging the car finish Longer time → less capacity → time is money 3. Temperature Higher temperature: better cleaning, but higher chance of damaging the car finish, higher energy cost 4. Chemistry Most important factor Should be highly efficient, safe, economical Environmental friendly: minimum waste (water/chemical) Consumer Specialties | Business Line Household Care Page | 62
  63. 63. Car Wash: Step I 1. Removal of contaminants by using surfactants: Water Oil Paint Consumer Specialties | Business Line Household Care Page | 63
  64. 64. REWOQUAT® CQ 100 G Multipurpose Surfactant Blend Composition Specialty blend of cationic and nonionic surfactants Performance Excellent degreasing and soap scum removal Good emulsification, anti-redeposition Provides antistatic property Easy rinsing, quick drying Imparts gloss Ease of Formulation Good surfactant compatibility (even with anionics) 100% active liquid, easy to process No solvent or hydrotrope needed Moderate foaming High/low pH, temp., hard/soft water Consumer Specialties | Business Line Household Care Page | 64
  65. 65. REWOQUAT® CQ 100 G Hard Surface Cleaning Results Improved Detergency Degreasing Kitchen soil Soap scum Engine soil Rating “2” National Brand All Purpose Cleaner 10.9 % active Rating “8” CQ 100 G based All Purpose Cleaner 2.0 % active Rating “3” National Brand Tub Tile Cleaner 3.5 % active Rating “8” CQ 100 G based Tub Tile Cleaner 1.0 % active Rating “2” National Brand Traffic Film Remover 10.9 % active Rating “9” CQ 100 G based Traffic Film Remover 2.0 % active Consumer Specialties | Business Line Household Care Page | 65
  66. 66. Rinsing (Anionic Scavengers) 1. Car Care 2. Fabric Care Consumer Specialties | Business Line Household Care Page | 66
  67. 67. Car Wash: Step II 2. Rinsing with water: Water film adheres to the surface upon washing and rinsing Water - - - - - - - - Paint Consumer Specialties | Business Line Household Care Page | 67
  68. 68. Car Care Basics and Challenges Rinsing - Major Challenges 1. Anionic surfactants are efficient cleaners, but difficult to rinse them off from surfaces. 2. Carry over anionics can react with quaternary emulsifiers –Car care drying agents will work less efficiently 3. Insoluble soap scums ruin the final aesthetics Step 1. Cleaning (Anionic) Step 2. Rinsing (Water) Step 3. Drying - Softening Anionic carry over Insoluble scum Consumer Specialties | Business Line Household Care Page | 68
  69. 69. Anionic Scavengers - Softergents Mechanism Anionic surfactant Anionic surfactant Anionic surfactant Cationic emulsifier Scavenger (monoquat) Scavenger (diquat) Inactive, insoluble Inactive, soluble Net positive charge Active, soluble (cationic emulsifier) A B C Consumer Specialties | Business Line Household Care Page | 69
  70. 70. Rinsing (Anionic Scavengers) 1. Car Care 2. Fabric Care Consumer Specialties | Business Line Household Care Page | 70
  71. 71. Anionic Scavengers – Softergents Chemistry Recommendations: • Use level: Depending on rinse efficiency Use at least the same amount as the anionic carry-over concentration • Chemistry: Monoalkyl diquats are the most efficient CH3 Cl N CH3 Cl R CH3 N R CH3 CH3 Cl N CH3 CH3 CH3 R (CH2-CH2-O)xH N CH3 2CH3OSO3 (CH2-CH2-O)yH (CH2-CH2-O)zH N CH3 R = tallow, x, y, z 1 Consumer Specialties | Business Line Household Care Page | 71
  72. 72. Drying, Protection 1. Theory and Practice 2. Organomodified Silicones 3. Traditional and Biodegradable Systems Consumer Specialties | Business Line Household Care Page | 72
  73. 73. Car Care Basics and Challenges Drying - Major Factors of Drying 1. Cleaned cars have a thin water film which sticks strongly to the surface 2. Manual (towel) drying is very inefficient, slow and costly 3. Blow drying is inefficient due to the stubborn water film 4. Water needs to be beaded for Easy and quick water removal Dryer, shinier cars Customers associate semi-wet cars with poor cleaning: they can easily be resoiled, water droplets leave spots after drying Consumer Specialties | Business Line Household Care Page | 73
  74. 74. Drying Agents / Rinse Aids What are they? They are oil in water microemulsions containing emulsifiers, hydrophobes, solvents/coemulsifiers and water How do they work? They are diluted and sprayed on wet surfaces to make the surface hydrophobic and to enhance the removal/draining of water Consumer Specialties | Business Line Household Care Page | 74
  75. 75. Drying Aids/Protectants: Microemulsions of Cationic Emulsifiers and Oils water film 1. Water film adheres surface Consumer Specialties | Business Line Household Care to the surface upon washing and rinsing Water - - - - - - - - Paint Vehicle Rinse Aids Page | 75
  76. 76. Drying Aids/Protectants: Microemulsions of Cationic Emulsifiers and Oils water film Consumer Specialties | Business Line Household Care rinse aid 2. Sprayed -on rinse aid penetrates through water film and spreads over the surface surface 1. Water film adheres to the surface upon washing and rinsing Water + + + + + + + + - - - - - - - - Paint + + + + ++ + + + + + + Page | 76
  77. 77. Drying Aids/Protectants: Microemulsions of Cationic Emulsifiers and Oils water film surface Consumer Specialties | Business Line Household Care hydrophobic film water film rinse aid 3. Rinse aid displaces water film, deposits hydrophobes (Sheeting) 2. Sprayed-on rinse aid penetrates through water film and spreads over the surface 1. Water film adheres to the surface upon washing and rinsing Water + + + - - - - - - - - + + + + + + Paint + + + + ++ + Page | 77
  78. 78. Drying Aids/Protectants: Microemulsions of Cationic Emulsifiers and Oils water film surface 1. Water film adheres to the surface upon washing and rinsing hydrophobic film Consumer Specialties | Business Line Household Care hydrophobic film water film rinse aid water droplets 3. Rinse aid displaces water film, deposits hydrophobes (Sheeting) 2. Sprayed-on rinse aid penetrates through water film and spreads over the surface Water beads up, smaller droplets combine to bigger ones (Beading) and removed by a blower Water +-+ +- +-+ +- +- + -+ +- + +- Paint Page | 78
  79. 79. Increasing the Contact Angle Why is It Beneficial? θ 1 Consumer Specialties | Business Line Household Care A1 B1 θ 2 A2 B2 If the contact angle increases: θ 2θ 1 the face area increases: A2A1 higher droplet profile (“larger sail”), easier water removal by the blower or driving wind the footprint decreases: B2B1 less contact between the droplet and the surface: less sticking, easier water removal by the blower or driving wind Page | 79
  80. 80. Drying, Protection 1. Theory and Practice 2. Organomodified Silicones 3. Traditional and Biodegradable Systems Consumer Specialties | Business Line Household Care Page | 80
  81. 81. Organomodified Silicones Compatibility Chart Siliconophilic Alkylsiloxanes Hydrophilic Lipophilic Polyether-siloxanes Ionic Siloxanes Silicone Oil Alkylpolyether-siloxanes Consumer Specialties | Business Line Household Care Page | 81
  82. 82. Page | 82 Basics of Silicone Quats + + / + + Consumer Specialties | Business Line Household Care
  83. 83. Silicone Quats Strong Bond Between Surface and Molecule Consumer Specialties | Business Line Household Care Page | 83
  84. 84. Silicone Quats Strong Bond Between Surface and Molecule Surface Consumer Specialties | Business Line Household Care Page | 84
  85. 85. Silicone Quats Strong Bond Between Surface and Molecule Two anchor points Silicone Backbone Surface Consumer Specialties | Business Line Household Care Page | 85
  86. 86. Silicone Quats Strong Bond Between Surface and Molecule Two anchor points Silicone Backbone Surface TEGOPREN® 6922 (shorter silicone backbone) TEGO® Polish Additiv Q70 (longer silicone backbone) Consumer Specialties | Business Line Household Care Page | 86
  87. 87. Silicone Quats Miracles Can Happen….. What a difference!!! ☺ Consumer Specialties | Business Line Household Care Page | 87
  88. 88. Drying, Protection 1. Theory and Practice 2. Organomodified Silicones 3. Traditional and Biodegradable Systems Consumer Specialties | Business Line Household Care Page | 88
  89. 89. Drying Agent / Rinse Aid Trends HISTORICAL EVOLVING Fast drying Spot free surface Visual: Aesthetics Low price Unlimited water Environmental, Safety concern is low Nitrile Quats Mineral Seal Oil Fast drying Spot free surface Visual cues Competitive price / performance Waste water restrictions Environmental, Biodegradability, Safety issues New regulations Ester Quats Ester Oils PERFORMANCE ENVIRONMENTAL FORMULATIONS Consumer Specialties | Business Line Household Care Page | 89
  90. 90. Biodegradable Rinse Aids Drying and Protection of Surfaces Goal: Develop an emulsifier that enables the formulation of rinse aids/drying agents to address the needs of the evolving market Biodegradability Environmental friendliness (low aquatic toxicity) Formulation versatility (for both traditional and biodegradable ingredients) Water reclaim system friendly formulations (due to droughts) Performance: improved drying/protection for less spotting Safety: low toxicity Raw materials from renewable resources Price/performance advantages Consumer Specialties | Business Line Household Care Page | 90
  91. 91. Traditional and New Emulsifiers Dialkyl Quats: good performance, stable products low biodegradability (high di-fatty-alkyl content) Ester Quats: TEA type: medium performance, limited formulas good biodegradability, low toxicity (1:2:1 mixture of mono-, di- and tri-fatty-alkyl ratio) MDEA type: good performance, versatile formulas good biodegradability, low toxicity (enhanced di-fatty-alkyl content) CH3 R N R CH3 R=Fatty Alkyl CH3 O O N (+ monoquat and triquat) (R = Fatty Alkyl) CH3 X O - X X OH O O N CH3 O R R O O R R (+ monoquat) (R = Fatty Alkyl) Consumer Specialties | Business Line Household Care Page | 91
  92. 92. Traditional and New Hydrophobes Mineral Seal Oil: good performance, stable products low biodegradability unpleasant odor (aromatics) source dependent characteristics Ester Oils: Alkyl Laurate, Palmitate, Stearate, etc. good performance, versatile formulas good biodegradability low toxicity low odor Aliphatic petroleum naphtas (Middle distillate) O R O R' R = Fatty Alkyl R'=straight or branched Alkyl C5 Consumer Specialties | Business Line Household Care Page | 92
  93. 93. Performance Comparison “Split-hood” test Consumer Specialties | Business Line Household Care Page | 93
  94. 94. Readily Biodegradable Emulsifier Carspray 800 MDEA Ester Quat emulsifier for vehicle rinse aids/drying agents to address the needs of the evolving market: Readily Biodegradable Environmental friendly, safe (low toxicity) Formulation versatility (for both traditional and biodegradable ingredients) Water reclaim system friendly formulations Performance: improved drying/protection for less spotting Raw materials from renewable resources Price/performance advantages Patented technology O O N CH3 - O R O R CH3 (+ monoquat) (R = Fatty Alkyl) X Consumer Specialties | Business Line Household Care Page | 94
  95. 95. Acknowledgements BL Household Care – Hopewell, Virginia • Dennis Parrish • Miyako Hisamoto • Gonglu Tian • Erin King • Jennifer Goodyear • Saiid Mohammed • Phuong Le • Dana Nystrand Evonik Industries – Janesville, WI, Mapleton, IL BL Household Care – Hanau, Germany Interfacial Technology – Essen, Germany Evonik Degussa Brasil Ltda Consumer Specialties | Business Line Household Care Page | 95
  96. 96. Consumer Specialties | Business Line Household Care Page | 96

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