Slide 1: Surfactants for Emulsion Polymerization
Surfactants for Emulsion Polymerization Presented by Bruno Dario June 20th, 2024
Slide 2: Agenda
AGENDA Surfactants for Emulsion Polymerization 1. Indorama Ventures 2. Origin and Sustainability 3. Polymers and Process 4. Stability and Surfactants 5. Case Studies 6. Quick Guide: Transition to APE-free 7. Q&A © Indorama Ventures 2024 2
Slide 3: Our Purpose
OUR PURPOSE We enhance our relationships Reimagining Chemistry Together to Create A Better World Constant Value creation search for through innovation sustainability Purpose word choice explanation: Why we exist
Slide 4: Over the last 20 years, IVL has acquired
One of the world's leading producers of PET with Over the last Presence in Combined PET* 20 years, IVL 35 countries Global leader in the production of PET and r-PET has acquired Consolidated revenues of *Combined PET - Feedstock, PTA, PET, Packaging and Recycling FIBERS and US$ 18.7 bi Polyester fib
Slide 5: Where We Are
Integrated Oxides & Derivatives Where WE ARE Where WHERE WEwe AREare EMEA AMERICAS • Belgium • Brazil APAC • Mexico • United States • Australia • Uruguay • China • India 18 industrial units 8 countries 9 R&D centers 3,700 employees Indovinya Indovinya R&D Industrial facilities Units © Indorama Ventu
Slide 6: Origin and Sustainability
Origin and Sustainability Emulsion Polymerization © Indorama Ventures 2024 6
Slide 7: Definitions
Definitions When we talk about EMULSION POLYMERIZATION it is important to remember that… EMULSION AS WE POLYMERIZE SO, TODAY • Liquid dispersed in another liquid • Monomers will create a polymer, You will hear me talking about: • E.g., Mayonnaise which is a solid stabilized in water. A DISPERSION or
Slide 8: Origins and Importance
Origins and Importance Emulsion Polymerization World War II – shortage of natural rubber • Solution: free radical polymerization Versatility • Several types of polymers that can be made • Wide variety of applications Advantages: • Remove the heat of polymerization • High control of particle size and
Slide 9: Sustainability Key Drivers
Sustainability Key Drivers CASE Market Reduce environmental Efficient use of Enhance durability and social impact resources of materials Reduce VOC emissions Energy efficiency in Enhance short & long-term production processes performance Biobased alternatives High performance in HSE friendly formula
Slide 10: Polymers and Process
Polymers Click to edit andMaster title style Process Click to edit Emulsion Polymerization Master subtitle style © Indorama Ventures 2024 10
Slide 11: General Formulation
General Formulation Emulsion Polymerization % Weight Ingredients Minimum Maximum Water 50.0 55.0 Surfactant 0.5 5.0 Monomer 40.0 50.0 Initiator 0.2 0.5 © Indorama Ventures 2024 11
Slide 12: Typical Monomers
Typical Monomers Emulsion Polymerization Monomer Tg (°C) Affinity for Water 2-Ethylhexyl acrylate -64 Hydrophobic N-butyl acrylate -54 Hydrophobic Methyl acrylate 8 Hydrophobic Vinyl acetate 32 Hydrophilic Styrene 100 Hydrophobic Methyl methacrylate 106 Hydrophilic © Indorama Ventures 2024 12
Slide 13: Application and Tg
Application and Tg Acrylic polymers POWDER COATINGS INDUSTRIAL COATINGS ARCHITECTURAL COATINGS SELANTS (CAULKS) ELASTOMERIC COATINGS PSA - 50 °C - 25 °C 0 °C 25 °C 50 °C 75 °C 100 °C - 58 °F - 13 °F 32 °F 77 °F 122 °F 167 °F 212 °F © Indorama Ventures 2024 13
Slide 14: Common Polymers applied in Architectural/Industrial Coatings
Common Polymers applied in Architectural/Industrial Coatings Styrene-acrylic Vinyl-acrylic All-acrylic • Excellent hydrophobicity • Low-VOC capable (hydroplasticization) • Premium resins • Excellent adhesion to • Good scrub resistance • Excellent durability / weatherability metal/plastic • Good bala
Slide 15: Diverting a little bit from the topic…
Diverting a little bit from the topic… How do acrylics compare to other polymers applied in Architectural / Industrial Coatings? Chemical Resin UV Resistance Hardness Flexibility Heat Resistance Cost Resistance Air Dry Alkyd G to VG P to G G to VG P to G P to G VG to E Alkyd Melamine G to VG G to VG
Slide 16: Emulsion Polymerization
Emulsion Polymerization Simplified setup All-Acrylic Recipe Example 1. Prepare Initial charge and add to the reactor. 2. Heat up the reactor to 80-85°C under N2 atmosphere. 3. Charge 5 wt.% of Monomer Pre-emulsion in the reactor. 4. After this, add the First Initiator Batch in the reactor. 5. Keep t
Slide 17: Parameters and Properties of Emulsion Polymers
Parameters and Properties of Emulsion Polymers Emulsion Polymerization Common Process Issues Emulsion Polymer Properties • Clot dispersed in the latex • Residual Monomer • Polymer buildup on reactor surface • pH • Conversion time • Solid Content • … • Particle Size • Viscosity • Molecular Weight • T
Slide 18: Stability and Surfactants
Stability Click to edit andMaster title style Surfactants Click to edit Emulsion Polymerization Master subtitle style © Indorama Ventures 2024 18
Slide 19: Colloidal Stability
Colloidal Stability All- Acrylic < Styrene Acrylic Source: M. El-Aasser and P. Lovell, Emulsion Polymerization and Emulsion Polymers, Wiley, West Sussex, 1997 © Indorama Ventures 2024 19
Slide 20: Surfactants – Surface Active Agents
Surfactants – SURFACE ACTIVE AGENTS Anionic Charged Cationic Hydrophilic Polar Head (Affinity with water) Neutral Aromatic Hydrophobic Nonpolar Tail (No affinity with water) Aliphatic *Linear or Branched © Indorama Ventures 2024 20
Slide 21: Alkylphenol Ethoxylate
When talking about surfactants... The most “famous” one: Alkylphenol Ethoxylate Hydrophobe Hydrophile n • Polarizable Aromatic Ring • Dense electronic cloud • Creates a soft transition from hydrophobic to hydrophilic © Indorama Ventures 2024 21
Slide 22: Anionic Surfactants
Anionic Surfactants (A) Function: • Monomer emulsification • Particle Nucleation (B) Nc ∝ [Surfactant]0.6 • Polymerization speed • Particle size distribution • Clot formation • Shelf-life stability • Sensitive to salt concentration (C) (A) Sodium salt of sulfated lauryl alcohol (D) (B) Sodium dodecy
Slide 23: APE-free Anionic Surfactants
APE-free Anionic Surfactants Tailoring surfactants to fit our customer’s needs OXIMULSION® OXIMULSION® OXIMULSION® PROPERTIES 1228 1328 APH 11230 (A) EO Content* Low Low Medium Appearance Liquid Liquid Liquid Solids, wt.% 28 28 28 CMC, g/L 0.27 0.28 0.34 (B) S.T., 0.1%, 35 38 46 mN/m (A) sodium salt
Slide 24: Nonionic Surfactants
Nonionic Surfactants H3C O H O n 40n= 9 - 40 n= 9 - 40 CH3 Function • Electrolytic Stability • Stability during neutralization • Mechanical Stability • Freeze-thaw Stability • Shelf-life Higher steric repulsion is obtained when: • Thick and dense layers • Strong adsorption • Complete coverage © Indo
Slide 25: APE-free Nonionic Surfactants
APE-free Nonionic Surfactants Tailoring surfactants to fit our customer’s needs Hydrophobe Type Size Structure Distribution Sourcing • Fatty Alcohols • EO • Synthetic • # of Carbons • Linear • Broad range • Natural • PO Alcohols • EO units • Branched • Narrow range • Synthetic • EO/PO • Sorbitan est
Slide 26: Alcohol Ethoxylates: Degree of Ethoxylation
Alcohol Ethoxylates Tailoring surfactants to fit our customer’s needs Branched 40 C13 O/W Emulsifier C10 High Steric Repulsion Degree of Ethoxylation 20 2-PH Branching C13 – C15 12 High Surface Activity C11 6 C9 – C11 3 Cetearyl Stearyl Alcohol Alcohol Oil Soluble Lauryl Alcohol Linear 1 10 11 12 13
Slide 27: Alcohol Ethoxylates: Branching
Alcohol Ethoxylates Tailoring surfactants to fit our customer’s needs Branched C13 C10 Lower Cloud Points Better Handling Better Wetting Odor 2-PH Branching Better Emulsification Lower Odor C13 – C15 Lower Solidification Point Good Handling Longer solubilization Time Good Wetting C11 Good Emulsifica
Slide 28: What to consider when choosing surfactants
What to consider when choosing surfactants Performance Sustainability Attributes • Clot Formation ↑ BIODEGRADABILITY • Particle Size and Control during the ↓ TOXICITY process ↑ [Renewable Content] ↑ Electrolyte Stability ↑ Ease of processing / energy savings ↑ Mechanical Stability ↑ Water Resistance
Slide 29: Anionic Surfactants
Click to edit Master title style Anionic Surfactants Click to edit Emulsion Polymerization Master subtitle style © Indorama Ventures 2024 29
Slide 30: Anionic Surfactants
Anionic Surfactants OXIMULSION® OXIMULSION® OXIMULSION® OXIMULSION® PROPERTIES 1228 1328 APH 11230 2742 Description Sulfated Sulfated Sulfated Phosphate EO content* Low Low Medium Low Appearance Liquid Liquid Liquid Liquid Solid Content, wt.% 28 28 28 > 95 Solvent Water Water Water Water pH 7 11 8 3
Slide 31: Two Step Process
Two Step Process Emulsion Polymerization 1° STEP | Generation of Seeds MONOMERS Anionic Surfactant SC ~ 10 wt% < 50 nm 2° STEP | Growth of Seeds MONOMERS Anionic Surfactant 1018 seeds/L SC ~ 50 wt% < 200 nm Source: Asua et. Al., Langmuir 2003, 19, 3212 - 3221. © Indorama Ventures 2024 31
Slide 32: Formulations: Two Step Process
Formulations Emulsion Polymerization Two Step Process Components (phm) Step 1 Step 2 Methyl methacrylate 50 50 Butyl acrylate 48 48 Methacrylic acid 1 1 APE-free anionic surfactant 25 2 Buffer 0.7 0.7 • Thermal initiator: 4h at 80 °C Ammonium persulfate 0.6 0.6 • Redox initiator: 1h at 60 °C Oxidizi
Slide 33: Formulations: Seeded Process
Formulations Emulsion Polymerization Seeded Process OXIMULSION® OXIMULSION® OXIMULSION® OXIMULSION® Properties Benchmark 1228 1328 APH 11230 2742 Solid Content, wt.% 50 50 50 50 50 pH 9 9 9 9 9 Viscosity, 25°C, cP 300 281 235 186 185 Zeta Potential, mV -77 -60 -59 -58 -56 Freeze-thaw stability (Cycl
Slide 34: Effect of surfactant on coagulum formation
Effect of surfactant on coagulum formation in the reactor 1000 200 170 173 800 150 155 148 Particle Size (nm) Filterable Soids (ppm) 150 600 100 400 331 200 50 0 0 0 0 OXIMULSION® OXIMULSION® OXIMULSION® OXIMULSION® 0 1228 1328 APH 11230 2742 Benchmark OXIMULSION®OXIMULSION®OXIMULSION®OXIMULSION® 12
Slide 35: Effect of surfactant on mechanical stability
Effect of surfactant on mechanical stability 3000 60 CaCl2 Concentration (mmol.L-1) Filterable Solids (ppm) 2000 40 2000 28 20 1000 12 0 0 0 51 45 46 25 0 0 Benchmark OXIMULSION® OXIMULSION® OXIMULSION® OXIMULSION® Benchmark OXIMULSION® OXIMULSION® OXIMULSION® OXIMULSION® 1228 1328 APH 11230 2742 12
Slide 36: Effect of surfactant on wet scrub resistance
Effect of surfactant on wet scrub resistance of 30% PVC paint Emulsion Polymerization ASTM D2486 800 726 Number of Cycles 700 672 651 628 600 569 500 400 Benchmark OXIMULSION® OXIMULSION® OXIMULSION® OXIMULSION® 1228 1328 APH 11230 2742 © Indorama Ventures 2024 36
Slide 37: Effect of surfactant on blocking and dirt pickup
Effect of surfactant on blocking evolution of 30% PVC paint Dirt Pickup ASTM D4946 Rating: 1-11 / (1=Best) 10 12 11 10 8 10 8 8 6 Grade Grade 4 4 4 6 4 3 4 4 3 2 2 2 2 2 2 2 2 2 2 2 1 2 0 0 Benchmark OXIMULSION® OXIMULSION® OXIMULSION® OXIMULSION® Benchmark OXIMULSION® OXIMULSION® OXIMULSION® OXIMUL
Slide 38: Nonionic Surfactants
Click to edit Master title style Surfactants Nonionic Click to edit Emulsion Polymerization Master subtitle style © Indorama Ventures 2024 38
Slide 39: Vinyl-Acrylic Emulsion
Vinyl-Acrylic Emulsion SURFONIC® NB-407 OXITIVE® 7110 OXITIVE® 7140 Physical-Chemical Properties Physical-Chemical Properties Physical-Chemical Properties • Nonylphenol ethoxylated • Fatty alcohol ethoxylated • Synthetic alcohol ethoxylated • 40 EO • Medium degree of ethoxylation • High degree of et
Slide 40: Vinyl-Acrylic Emulsion
Vinyl-Acrylic Emulsion SURFONIC® NB–407 OXITIVE® 7110 OXITIVE® 7140 Components Weight (%) Components Weight (%) Components Weight (%) Initial Charge Initial Charge Initial Charge Water 34.6 Water 34.6 Water 34.5 0.2 Buffer 0.2 Buffer 0.2 Buffer HEC HEC 0.2 HEC 0.2 0.2 ® ALKOPON® NNP 940 HS 0.2 OXIMU
Slide 41: Total Filterable Solids
Effect of different nonionic surfactants Reactor Cleanliness 500 410 400 • Clot formation < 500 ppm for Total Filterable Solids (ppm) all formulations. 300 224 200 • Longer ethylene oxide chain in the nonionic improved the 98 100 performance even compared against reference. 0 NP-4EO-SNP-40EO / NP-40
Slide 42: Average Particle Size
Effect of different nonionic surfactants Particle Size 450 400 379 • Acceptable particle size range is 200 350 – 400nm. Average Particle Size (nm) 300 250 208 • Longer ethylene oxide chain 190 200 in the nonionic surfactant 150 tends to decrease the particle size. 100 50 0 ® ® NP-4EO-S /NP-40EO NP-4
Slide 43: Mechanical Stability
Effect of different nonionic surfactants Mechanical Stability 6000 5000 4396 Mechanical Stability (ppm) 4000 2795 3000 • Longer EO chain in the 2000 1600 nonionic improved the mechanical stability; 1000 0 NP-4EO-SNP-40EO / NP-40EO (5:95) L2S / L20®(5:95) OXITIVE 7110 L2S / B40®(5:95) OXITIVE 7140 ©
Slide 44: Emulsion Polymer Formulation
Emulsion Polymer Formulation Goal: to evaluate different ratios of nonionic to anionic surfactants: 95:5 / 85:15 Monomer Mix Initiator Components (phm) Formulation 1 4.0h 4.5h Vinyl Acetate 80 % Butyl acrylate 20 % Active Content (phm) OXITIVE® 7110 3.74 – 4.18 OXIMULSION® 1228 0.22 – 0.66 Upfront C
Slide 45: Total Filterable Solids
Effect of different ratios of nonionic to anionic Reactor Cleanliness 500 410 400 • Clot formation < 500 Total Filterable Solids (ppm) 300 ppm for all formulations. 224 200 158 • New ratio of anionic to nonionic reduced clot formation. 100 0 ® ® NP-4EO-S NP-4EO-S / (5:95) / NP-40EO OXIMULSION 1228 /
Slide 46: Average Particle Size
Effect of different ratios of nonionic to anionic Particle Size 450 400 379 382 350 • Acceptable particle size range Average Particle Size (nm) 300 is 200 – 400nm. 250 200 190 150 • Low impact in particle size. 100 50 0 NP-4EO-S ® NP-4EO-S / NP-40EO/ (5:95) OXIMULSION L2S / L20 (5:95)1228 / ® L2S /
Slide 47: Mechanical Stability
Effect of different ratios of nonionic to anionic Mechanical Stability 6000 5000 4396 • Less than 1.0% clot formed Mechanical Stability (ppm) 4000 under shear stress. 3000 2598 • New ratio of anionic to nonionic reduced clot formation after 2000 1600 mechanical stress. 1000 0 ® ® NP-4EO-SNP-4EO-S /
Slide 48: Wet Scrub Resistance
Vinyl-Acrylic Paint Scrub Resistance – ASTM D2486 7000 6000 6000 5260 Wet Scrub Resistance (cycles) 5000 4233 3564 4000 2609 3000 1996 2000 1000 0 ® BENCHMARK Benchmark BENCHMARK Latex APE BENCHMARK LATEX Benchmark Latex APE- NP-4EO S / NP-40EO NP-4EO-S NP-40EO OXIMULSION 1228 / L2S / L20 (5:95) L2S
Slide 49: Reactive Surfactants
Click to edit Master title styleSurfactants Reactive Click to edit Emulsion Polymerization Master subtitle style © Indorama Ventures 2024 49
Slide 50: Why does it happen?
Why does it happen? LATEX Fragile Film STAGE I T>MFFT Continuous and STAGE II Transparent Film T>Tg STAGE III Coalesced Film © Indorama Ventures 2024 50
Slide 51: OXIMULSION REACT N1
OXIMULSION REACT® N1 H2C [ ]m A [ O ] O n H APEO-free Partially Bio- Concentrated Product VOC ≤ 5 g/L based Solid content >99 wt.% Air Water Liquid HLB of 15 Behave as conventional Compatible with surfactants all latexes © Indorama Ventures 2024 51
Slide 52: Two Step Process
Two Step Process Emulsion Polymerization 1° STEP | Generation of Seeds MONOMERS O O – S + H3C O O Na SC ~ 10 wt% n O 40 - 50 nm 2° STEP | Growth of Seeds MONOMERS O H H2C A O m n O O – S + H3C O O Na SC ~ 45 - 50 wt% 1018 seeds/L n O ~ 100 nm Source: Asua et. Al., Langmuir 2003, 19, 3212 - 3221. © I
Slide 53: Emulsion Polymerization Starting Formulations
Emulsion Polymerization Starting Formulations Components w/w Methylmethacrylate (MMA) 0.75 SEEDED SEMI-BATCH PROCESS Butyl acrylate (BA) 0.72 Latex seed (Previously Methacrylic acid 0.03 prepared) Anionic surfactant* 0.38 Ammonium persulfate 0.004 Methylmethacrylate (MMA) 23 Butyl acrylate (BA) 22 P
Slide 54: Effect of Surfactant Composition on Coagulum Formation
Effect of Surfactant Composition on Coagulum Formation in EP 75 wt% REACT® N1 67 wt% REACT® N1 50 wt% REACT® N1 25 wt% Anionic Surfactant 33 wt% Anionic Surfactant 50 wt% Anionic Surfactant Coagulum in Reactor Thermocouple C Impeller Dispersed coagulum in 800 ppm 834 ppm 805 ppm latex © Indorama Ven
Slide 55: Incorporation of Reactive Nonionic Surfactant
Incorporation of Reactive Nonionic Surfactant Surfactant Incorporation = Total Surfactant - Free Surfactant 120 100 100 Incorporation (wt%) 80 60 40 20 0 0 2 phm AS 1 phm AS + 1 phm REACT N1 © Indorama Ventures 2024 55
Slide 56: Water Absorption
Water Absorption Latex films with 2 phm of coalescent immersed in water at 25°C Commercial AS/REACT N1 AS 100 WATER ABSORPTION (WT%) 80 60 40 20 0 0 5 10 15 20 25 30 IMMERSION TIME (DAYS) © Indorama Ventures 2024 56
Slide 57: Whitening
WHITENING Latex films with 2 phm of coalescent immersed in water at 25°C after 4 days Commercial AS / REACT® N1 (1:1) © Indorama Ventures 2024 57
Slide 58: Transition to APE-free Surfactants
Transition Click to edit toMaster APE- title Surfactants free style Click to edit Emulsion Polymerization Master subtitle style © Indorama Ventures 2024 58
Slide 59: APE-FREE Alternatives to APE-based Nonionic Surfactants
APE-FREE Alternatives to APE-based Nonionic Surfactants Emulsion Polymerization APE-FREE HLB APE-based Nonionic HLB Alternatives OXITIVE® 7254 13.4 SURFONIC® N-95 13.1 OXITIVE® 7110 16.9 SURFONIC® NB-307 17.1 OXITIVE® 7130 17.4 SURFONIC® NB-307 17.1 OXITIVE® 7140 18.0 SURFONIC® NB-407 17.8 OXITIVE®
Slide 60: Replacement of APE-based for APE-FREE Surfactants
Replacement of APE-based for APE-FREE Surfactants Emulsion Polymerization Replacement of APE for APE-FREE Surfactants in Styrene-Acrylic Latex APE-based APE-free solution Replacement of APE for APE-FREE Surfactants in Vinyl-Acrylic Latex OXIMULSION® B1000 NP 9.5 EO SULFATED + NP 23 EO APE-based APE-
Slide 61: Q&A Session
Q&A Session Surfactants for Emulsion Polymerization Contact Click to edit Master Bruno Dario title style Research Scientist II – CASE & Performance Products +1 (346) 413-1152 (mobile) Click to edit Master subtitle style bruno.dario@us.indorama.net Indorama Ventures – Indovinya 8401 New Trails Dr., S
Slide 62: Disclaimer
Disclaimer This presentation and its content (“Material”) is proprietary to Indorama Ventures Public Company Limited (“Indorama Ventures”) and/or its affiliates (collectively, the “Group”) and may not be, in whole or in part, reproduced or disclosed, published, distributed or released to any other p