Dow Surfactants. A guide to products and performance for emulsion polymerization

Dow Surfactants A guide to products and performance for emulsion polymerization

Dow Surfactants for Emulsion Polymerization Unmatched Innovation and Performance from the World s Leading Coatings Supplier No matter where you do business in the world, Dow Coating Materials can provide you with surfactants and formulation expertise to meet your current and changing needs in the emulsion polymerization market. Dow Coating Materials brings together two of the industry s strongest suppliers of coating solutions The Dow Chemical Company and Rohm and Haas. Together, we offer the leading portfolio of coatings innovations, including surfactant chemistries. Our broad and diverse portfolio of surfactants for emulsion polymerization includes these well-known surfactant products: TRITON specialty nonionic and anionic surfactants DOWFAX specialty anionic surfactants specialty and general purpose nonionic surfactants These products from Dow Coating Materials improve the manufacturing performance of styrene-butadiene latex, vinyl, acrylic and other copolymer resin systems. Latex manufacturers also rely on these surfactants to help achieve the desired mechanical properties and storage stability of final products. What s more, Dow Coating Materials offers formulators the industry s most comprehensive capabilities package: A wide range of available chemistries enables solutions that meet almost any performance requirement. Unsurpassed experience across the full range of paint and coatings means we can help you optimize surfactant performance in your formulation. Our industry knowledge and expertise fosters innovation and collaboration, bringing new products and technologies as we work with you to meet your current and future needs. Awareness of regulations and legislation allows us to provide you with the most up-to-date information as well as valuable assistance with product stewardship. Our global sales, distribution and technical support network means we are on the ground in your local area, ready to serve your surfactant needs. World-class surfactant manufacturing facilities contribute to the operational excellence of Dow Coating Materials, for high-performance products that are consistently high-quality and cost-effective. Our comprehensive portfolio of ingredients for paints and coatings offers you the convenience of focused supply, backed by our in-depth knowledge of other formulation components. Our Broad Range of Surfactant Chemistries Expands Your Possibilities Dow surfactants include many diverse products across several surfactant chemistries. The unique functional and economic characteristics of these materials open the door to innovative surfactant solutions for emulsion polymerization applications from efficient particle size control in resins and rubbers, to better color stability in PVC films. Dow offers almost 200 surfactant products. Described in the following pages are major families of Dow surfactants, their functional contributions and key applications. Please contact your Dow representative for additional information (contact information is provided on the back cover of this brochure). 2

Explore Your Nonionic and Anionic Surfactant Possibilities Secondary Alcohol Ethoxylates 15-S Series Surfactants TMN Series Surfactants 15-S Series nonionic surfactants feature a wide range of ethoxylation and HLB values and offer superior wetting and handling properties. Their excellent emulsion polymerization profiles parallel those of NPE and OPE stabilized emulsions. Phosphate Polyether Ester TRITON XQS-20 Surfactants TRITON QS-44 Surfactants TRITON XQS-20 anionic surfactant is an efficient electrostatic emulsion stabilizer with buffering ability and corrosion inhibition characteristics. TRITON QS-44 surfactant offers good water resistance and provides freeze-thaw stability for all acrylic-based systems. TMN Series nonionic surfactants are known for their superior wetting, penetrant and dispersant characteristics and excellent pigment stabilization properties. They offer outstanding emulsification for waxes, silicone, PTFE and other difficult-to-emulsify materials. Octylphenol Ethoxylate Surfactants TRITON X Series Surfactants TRITON X Series surfactant structures are versatile nonionic specialty surfactants that provide excellent emulsification performance in all polymer systems. They are important ingredients of primary emulsifier mixtures used in the manufacture of emulsion polymers and stabilizers in latex polymers. EO / PO Copolymers XD Nonionic Surfactants XD nonionic surfactant is an excellent high molecular weight steric emulsifier and stabilizer for a broad range of materials, including aromatic and chlorinated solvents. Nonylphenol Ethoxylates NP Series Surfactants NP Series surfactants cover a wide range of ethoxylation and HLB values. They are used as emulsifiers, wetting agents and dispersants in a variety of applications, including emulsion polymerization and paints and coatings. Sulfosuccinates TRITON GR Series Surfactants TRITON GR Series anionic surfactants feature excellent substrate wetting and rewetting properties as well as excellent emulsifying and dispersing ability. These versatile surfactants are available in a range of solvent compatibilities. Alkyl Diphenyl Oxide Disulfonates DOWFAX 2A1 Anionic Surfactants DOWFAX Structure Anionic Surfactants DOWFAX 8390 Anionic Surfactants DOWFAX 30599 Anionic Surfactants DOWFAX 3B2 Anionic Surfactants DOWFAX anionic surfactants offer excellent solubility and stability in acids, alkalis and salts. The line of DOWFAX surfactants includes products with performance attributes suitable for incorporation into a variety of latexes to provide increased mechanical stability, lower reactor waste and low critical micellization concentration (CMC). Sulfates and Sulfonates TRITON XN-45S Surfactants TRITON X-200 Surfactants TRITON XN-45S surfactant is an anionic emulsifier and stabilizer that offers excellent wetting and superior small particle size control. TRITON X-200 anionic surfactant is an excellent electrostatic stabilizer with excellent emulsification properties. 3

Match One or More Dow Surfactants to Your Polymer System and Performance Requirements Dow surfactants include products designed to contribute a wide range of valuable functionalities to emulsion polymerization formulations. Refer to the table below to identify the Dow surfactant most likely to meet your functional requirements. (Numbers in parentheses refer to recipes on pages 6-10). Product Polymer System Features / Benefits Easy to handle 15-S Series Surfactants (Recipes 1,9) TMN Series Surfactants TRITON X Series Surfactants (Recipe 2) NP Series Surfactants Used in a wide variety of polymer systems Can be used during polymerization or post-added Used as a post-add in a variety of polymer systems Used in a wide variety of polymer systems Can be used during polymerization or post-added Used in a wide variety of polymer systems Can be used during polymerization or post-added APEO free Wide variety of HLBs and EO lengths (3-40 moles EO) Provides good monomer emulsion stability Improves colloidal stability - Ionic stability / Storage stability / Freeze-thaw stability handling properties Superior wetting EO lengths from 3 to 11 available APEO free Promotes film formation Highly branched hydrophobe for lower surface tension dispersant Low surface tension Provides excellent freeze-thaw stability Improves colloidal stability - Ionic stability / Storage stability / Freeze-thaw stability Easy to handle Provides good monomer emulsion stability Wide variety of HLBs and EO lengths (1.5-55 moles EO) Improves colloidal stability - Ionic stability / Storage stability / Freeze-thaw stability Easy to handle Provides good monomer emulsion stability Wide variety of HLBs and EO lengths (4-70 moles EO) Provides good monomer emulsion stability XD Nonionic Surfactants All polymer systems Can be used during polymerization or post-added Significant surface tension reduction Efficient at low concentrations Improves colloidal stability - chemical stability / Storage stability / Freeze-thaw stability TRITON XN-45S Surfactants (Recipe 3) Wide range of polymer systems Efficient nucleator stabilizer General purpose emulsion polymerization 4

Product Polymer System Features / Benefits Monosulfonate TRITON X-200 Surfactants (Recipe 4) Wide variety of polymer systems Can be used during polymerization or post-added Very low CMC Robust stability over a wide range of and temperatures Provides mechanical stability Provides freeze-thaw stability DOWFAX Anionic Surfactants (Recipes 5, 6) Wide variety of polymer systems Unique disulfonate gemini structure Provides excellent mechanical stability - Less reactor waste / storage stability Less foamy latex Robust stability over a wide range of and temperature Range of hydrophobicities stability during polymerization TRITON QS and XQS Phosphate Esters Surfactants (Recipes 7, 8) Wide variety of polymer systems Can be used during polymerization or post-added Uses pre-neutralized 9.0 Small particle sizes water resistance Provides freeze-thaw stability Enhanced mechanical and storage stability Helps inorganic pigment dispersion 5

Typical Latex Recipes Using Dow Surfactants 1. 15-S Styrene / Butylacrylate Latex Recipe Recipe Parts bom 81.3 50.0 47.5 1.5 0.5 19.0 0.1 0.7 Seed Latex Monomer Mixture (4 hours feed) Butylacrylate Styrene Acrylic Acid Methacrylic Acid Aqueous Mixture (4 hours feed) DOWFAX 2A1 (45%) 15-S-20 (80%) Sodium Hydroxide (20%) (4 hours 10 min feed) Potassium Persulfate 1383.5 13.9 850.2 807.7 25.5 17.0 19.7 11.8 338.4 8.5 340.1 11.9 Feed monomer mix and aqueous mix feeds during mentioned addition time, maintain temperature at 80 C. After addition, hold for 30 minutes at 80 C. Cool below 30 C, adjust to 7.0 with ammonia. Units 15-S-12 15-S-15 15-S-20 15-S-30 15-S-40 3.5 3.3 4.2 3.5 3.0 % 43.8 44.1 44.2 44.4 44.5 % 99.5 99.5 99.0 99.7 99.8 Wet Coagulum 100 Mesh g/l 1.451 0.823 0.023 0.319 0.256 nm 155 155 145 150 148 Brookfield Viscosity RV #50 rpm mpas 30 31 40 31 36 Dynes/cm 41.9 42.3 41.6 45.6 45.3 Mechanical Stability Poor Chemical Stability CaCl 2 (10%) CaCl 2 (20%) CaCl 2 (30%) Freeze-Thaw Stability -15ºC 9.0 1-5 Cycles 2 2 4 5 5 Resistance Poor 6 Coagulum can be reduced by pre-emulsifying monomers

2. TRITON X-405 Styrene / Butylacrylate Latex Recipe 3. TRITON XN-45S Styrene / Butylacrylate Latex Recipe Recipe Parts bom Recipe Parts bom 81.3 50.0 47.5 1.5 0.5 19.9 0.1 0.7 Seed Latex Monomer Mixture (4 hours feed) Butylacrylate Styrene Acrylic Acid Methacrylic Acid Aqueous Mixture (4 hours feed) DOWFAX 2A1 (45%) TRITON X-405 (70%) Sodium Hydroxide (20%) (4 hours 10 min feed) Potassium Persulfate 1383.5 13.9 850.2 807.7 25.5 17.0 19.7 11.8 338.4 8.5 340.1 11.9 Feed monomer mix and aqueous mix feeds during mentioned addition time, maintain temperature at 80 C. After addition, hold for 30 minutes at 80 C. Cool below 30 C, adjust to 7.0 with ammonia. Wet Coagulum 100 Mesh Chemical Stability Mechanical Stability Freeze-Thaw Stability -15ºC 9.0 TRITON X-405 2.8 45.0% 99.8% 0.8 g/l 145 nm 35 cps 46.2 dynes/cm 5 cycles 61.4 0.2 86.0 12.0 2.0 1.3 25.0 0.5 TRITON XN-45S Feed into reactor: Monomer Mixture Butylacrylate Methylmethacrylate Methacrylic Acid Aqueous Mixture TRITON XN-45S Sodium Persulfate 1125.6 6.1 1577.3 220.1 36.7 39.7 366.8 458.5 9.2 Feed 7% of monomer feed and surfactant feed, and 15% of persulfate feed, from 0 to 10 minutes. Hold for 10 minutes. Feed rest of monomer feed, surfactant feed, and persulfate feed over 3 hours, and maintain temperature at 80 C. After additions, hold for 30 minutes at 80 C. Cool below 30 C, adjust to 7.0 with ammonia. Wet Coagulum Mechanical Stability TRITON XN-45S 2.1 47.3% 99.8% none 99.5 nm 45 cps 46.1 dynes/cm 7

Typical Latex Recipes Using Dow Surfactants 4. TRITON X-200 All Acrylic Recipe 5. DOWFAX 2A1 Styrene/Butadiene Latex Recipe Recipe Parts bom Recipe Parts bom 80.5 0.1 Sodium Persulfate Monomer Mixture (3 hours 40 minutes feed) 1198.0 1.5 116.8 Seed Latex Monomer Mixture (3 hours 40 minutes feed) 1376.6 96.0 2.0 2.0 30.0 0.5 0.2 Methyl Methacrylate Methacrylic Acid Acrylic Acid Aqueous Mixtures (4 hours 20 minutes feed) Sodium Persulfate (4 hours 20 minutes feed) TRITON X-200 (28%) Sodium Hydroxide 1427.4 29.7 29.7 446.0 7.4 53.1 279.4 29.7 40.0 56.0 4.0 0.2 1.2 15.0 0.75 0.2 Butylacrylate Styrene Acrylic Acid Mercaptan Aqueous Mixtures (5 hours 30 minutes feed) Sodium Persulfate (5 hours feed) DOWFAX 2A1 (45%) Sodium Hydroxide 471.86 660.62 35.39 9.4 14.1 176.8 19.6 11.8 235.7 Start surfactant feed. Feed 10% of monomer feed and 10% of persulfate feed. Hold 10 minutes at 80 C. Monomer mix and aqueous mix feeds are then added during mentioned addition time, maintaining temperature at 80 C. After additions, hold for 30 minutes at 80 C. Cool below 30 C, adjust to 7.0 with sodium hydroxide. Start monomer mix and aqueous mix feeds. Feed during mentioned addition time. Maintain temperature at 80 C. After additions, hold for 60 minutes at 80 C. Cool below 30 C. TRITON X-200 5.6 DOWFAX 2A1 42.9% 3.4 99.9% 45.0% Wet Coagulum 100 Mesh < 1 g/l 99.0% 295 nm Wet coagulum 100 Mesh 0.02 g/l 17 cps 134 nm 39.6 dynes/cm 32 cps Mechanical Stability 45.3 dynes/cm Freeze-Thaw Stability -15ºC 9.0 5 cycles Mechanical Stability Freeze-Thaw Stability -15ºC 9.0 5 cycles 8

Recipe Parts bom 69.7 0.2 88.0 10.0 2.0 30.0 0.5 6. DOWFAX 30599 All Acrylic Recipe Sodium Persulfate Pre-Emulsion Mixture (4 hours feed) 2-Ethyl Hexyl Acrylate Methacrylic Methacrylate Methacrylic Acid DOWFAX 30599 (45%) Aqueous Mixtures (4 hours feed) Sodium Persulfate 943.8 2.7 1190.8 135.3 27.06 45.1 405.9 270.6 14.1 Feed 10% of pre-emulsion feed and 10% of persulfate feed. Hold 10 minutes at 80 C. Pre-emulsion feed and persulfate feed are added during mentioned addition time. Maintain temperature at 80 C. After additions, hold for 30 minutes at 80 C. Cool below 30 C. Wet Coagulum 100 Mesh DOWFAX 30599 4.8 43.1% 99.95% < 0.5 g/l 237 nm 22 cps Recipe Parts bom 72.5 2.34 0.15 49.0 49.0 2.0 1.5 30.0 3.1 0.35 5.0 0.15 7. TRITON QS-44 All Acrylic Recipe TRITON QS-44 surfactants must be neutralized before use. A 25% solution of TRITON QS-44 surfactants are prepared by neutralization with sodium hydroxide. TRITON QS-44 surfactants are stirred with water until dissolved and neutralized to 9.0 with caustic 20%. TRITON QS-44 (25%) Feed into reactor: Ammonium Persulfate Monomer Mixtures Ethylacrylate Methylmethacrylate Methacrylic Acid Aqueous Mixtures TRITON QS-44 (25%) Ammonium Persulfate Iron (II) Sulfate 7 H2O 913.5 68.67 29.5 1.9 616.9 616.9 25.2 75.5 377.7 39.3 4.5 63.0 1.9 Add persulfate shot. Start monomer feed, surfactant feed, persulfate feed, and iron sulfate feed after persulfate shot. Feed over 3.5 hours, maintaining temperature at 70 C. After addition hold for 30 minutes at 70 C. Cool below 30 C, adjust to 7.0 with ammonia. Wet Coagulum 100 mesh Spot Resistance Freeze-Thaw Stability -15ºC 9.0 TRITON QS-44 6.3 44.8% 99.95% 0.5 g/l 80 nm 52 cps 45.6 dynes/cm 5 cycles 9

Typical Latex Recipes Using Dow Surfactants 8. TRITON XQS-20 Vinylacetate / Butylacrylate Recipe TRITON XQS-20 surfactants must be neutralized before use. A 25% solution of TRITON XQS-20 surfactants are prepared by neutralization with sodium hydroxide. TRITON XQS-20 surfactants are stirred with water until dissolved, and neutralized to 9.0 with caustic 20%. TRITON XQS-20 surfactants avoid utilization of protective colloid for vinylacetate systems. 9. Post-Additions of Nonionic Surfactants Several nonionic surfactants have been added to a finished styrene butyl acrylate latex stabilized with 0.5 parts of DOWFAX 2A1 to improve colloidal stability at a level of 1 part (bom). Recipe Parts bom 43.7 2.34 0.15 80.0 2.6 30.0 10.0 0.35 TRITON XQS-20 (25%) Feed into reactor: Ammonium Persulfate Monomer Mixtures Vinylacetate Butylacrylate Aqueous Mixtures TRITON XQS-20 (25%) Ammonium Persulfate 890.10 81.35 47.59 3.05 1627.1 406.8 211.5 610.2 203.4 7.2 CaCl 2 (10%) CaCl 2 (20%) CaCl 2 (30%) Spot Resistance (1 hr) MFFT Freeze-Thaw Unit ml/100g ml/100g Deg C Cycles 15-S-20-19 5 15-S-30 19 5 15-S-40 20 4 Add persulfate shot over five minutes. Start monomer feed and surfactant feed after persulfate shot. Feed over 3 hours 25 minutes, start persulfate feed after 30 minutes and feed over 3 hours. After addition hold for 30 minutes at 90 C. Reactor Wet Coagulum 100 Mesh Chemical Stability TRITON XQS-20 4.8 50.7% 99.8% 0.4 g/l 128 nm 412 cps 45.4 dynes/cm 10

Typical Physical Dow Nonionic Surfactants Product Cloud Point (1) HLB (2) Moles EO TERGITOL 15-S Secondary Alcohol Ethoxylates CMC (3) / Surface Tension (4) Foam Height (5) Pour Point (6) Form / Color (7) 15-S-12 89 14.5 12 110 / 31 170 / 84 20 Semi-Solid White 15-S-15 >100 15.4 15 180 / 34 127 / 8 28 S White 15-S-20, 80% >100 16.3 20 280 / 35 120 / 55 0 L Colorless 15-S-30 >100 17.4 31 710 / 39 118 / 28 39 S White 15-S-40, 70% >100 18.0 41 / 42 57 / 10-9 L Colorless TERGITOL TMN Branched Secondary Alcohol Ethoxylates TMN-6, 90% 36 13.1 8 580 / 26 118 / 21-29 L Colorless TMN-10, 90% 76 14.4 11 940 / 27 162 / 26-16 L Pale Yellow TERGITOL Ethylene Oxide / Propylene Oxide (EO / PO) Copolymers XD 74 PRT / 38 106 / 31 35 S White TRITON X Octylphenol Ethoxylates X-165, 70% >100 15.5 16 360 / 28 150 / 130 23 L Pale Yellow X-405, 70% >100 17.6 35 / 41 150 / 40-3 L Pale Yellow X-705, 70% >100 18.4 55 / 39 140 / 135 4 L Pale Yellow TERGITOL Nonylphenol Ethoxylates NP-15 >100 15.0 15 / 36 100 / 60 24 L NP-30 >100 17.1 30 / 44 100 / 60 41 S NP-30, 70% >100 17.1 30 / 44 5 L NP-40 >100 17.8 40 / 45 100 / 95 48 S NP-40, 70% >100 17.8 40 / 45 9 L NP-50, 70% >100 18.2 50 12 L NP-55, 70% >100 18.3 55 15 L NP-70 >100 18.7 70 21 S Dow Anionic Surfactants (4) Product Cloud Point (1) HLB (2) Moles EO Neutral Alkaline Foam Height (5) Pour Point (6) Form / Color (7) DOWFAX Alkyldiphenyloxide Disulfonate Salts 2A1 >100 >40 0 34 35 140 / 130 L Amber 3B2 >100 >40 0 37 38 135 / 135 L Light Brown 8390 >100 >40 0 44 46 120 / 25 L Light Brown 35099 >100 >40 0 33 34 154 / 145 L Yellow / Brown TRITON GR Dioctyl Sulfosuccinates GR-5M 0 26 NR (8) 190 / 180-48 L - Colorless TRITON Phosphate Esters QS-44 Proprietary 38 39 130 / 65 6 L Amber XQS-20 Proprietary 46 46 145 / 130-29 L Amber TRITON Sulfates and Sulfonates X-200 Proprietary 28 29 182 / 182-1 L Opaque White XN-45S Proprietary 33 32 170 / 165-45 L Amber (1) Cloud point: C, 1 wt% aqueous solution (2) HLB Range: 3.5-10.5 w/o emulsifer, 10-15 good wetting, 10.5-18 good w/o emulsifer, 12-15 detergents (3) Critical micelle concentration: ppm at 25 C (4) Equilibrium surface tension: dynes/cm at 1 wt% actives, 25 C (5) Ross-Miles foam height: mm at 1 wt% actives, 25 C, initial / 5 minute (6) Pour point: C (7) Form at 25 C: L = Liquid, S = Solid (8) NR = Not Recommended; can hydrolyze under some alkaline conditions 11

In addition to Dow Surfactants, The Dow Chemical Company also supplies a variety of other high-performance formulating ingredients for paints and coatings, including: CARBITOL, CELLOSOLVE, DOWANOL Glycol Ethers Biocides POLYOX -Soluble Resins Emulsion Polymers Specialty Alkanolamines Ethylenamines ETHOCEL Ethylcellulose METHOCEL Cellulose Ethers CELLOSIZE Hydroxyethyl Cellulose CYRACURE Cycloaliphatic Epoxides DAXAD Dispersants TONE Caprolactones Hydrocarbon Resins Polyvinyl Acetate Nitroparaffins Epoxidized Products Redispersible Powders Solution Vinyl Resins Acrylic Acid Acrylate Esters Amino Alcohols Visit our web site: www.dow.com/coating or call From the United States and Canada: Phone: 1-800-447-4369 Fax: 1-989-832-1465 email: CUSTINFOGRP@dow.com In Europe: Toll-free Phone: +800 3 694 6367 Phone: 32-3-450-2240 In Latin America: Phone: 55-11-5188-9222 In Asia Pacific: Phone: 60 3 7965 5392 All Pacific countries except Indonesia & Vietnam: Toll-free Phone: 800 7776 7776 Toll-free Fax: 800 7779 7779 Toll free from Austria (00), Belgium (00), Denmark (00), Finland (990), France (00), Germany (00), Hungary (00), Ireland (00), Italy (800 783825), The Netherlands (00), Norway (00), Portugal (00), Spain (00), Sweden (00), Switzerland (00) and the United Kingdom (00). www.dow.com/coating www.dow.com Contract Manufacturing (Fine Chemicals) NOTICE: No freedom from any patent owned by Seller or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for Customer s use and for ensuring that Customer s workplace and disposal practices are in compliance with applicable laws and other governmental enactments. Seller assumes no obligation or liability for the information in this document. Published January 2010 Printed in the United States Form No. 884-00377-0114-NAR-EN-BBI NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED. The DOW Diamond Logo and Human element and design are trademarks of The Dow Chemical Company 2010 Trademark of The Dow Chemical Company ( Dow ) or an affiliated company of Dow