Adhesives Part I: Formulation How to Formulate Polyurethane Based Adhesives: A Complete Overview of Key Ingredients and Latest Formulation Techniques Edward M. Petrie (SpecialChem Expert Team) 2 Seminar Objectives Learn capability of polyurethane adhesives Learn about their versatility and breadth Learn the formulation possibilities Chapter 1 - Introduction 3 Seminar Contents - Part I 1) Slide Show Presentation Chapter 1. Introduction 2. Types of PU adhesives 3. PU chemistry Morphology and physical properties 4. PU adhesive composition 5. Isocyanates and Polyols 6. Additives and other raw materials 7. Common formulations 8. Current and future development Chapter 1 - Introduction 60 minutes 30 minutes 2) Questions and Answers On-line interaction 4 Chapter 1 Introduction 5 Definition PU adhesives contain a number of urethane groups in the molecular backbone or are formed during use Urethane group Many complex reactions can occur simultaneously or sequentially O N C O H Diversity Versatility Diversity Versatility Chapter 1 - Introduction 6 Why the Attraction to PU Adhesives? Good adhesion achieved through: Chemical bonding with water, hydroxyls on substrate surface Physical bonding through van der Waals forces and low surface energy Mechanical through low viscosity and diffusion into porous substrates Specific mechanical properties achieved through molecular composition Toughness and other viscoelastic properties Elasticity and modulus Crosslinking density Many types, methods of application, and cure speeds are possible Chapter 1 - Introduction 7 Advantages and Disadvantages of PU Adhesives Advantages Highly versatile chemistry Flexible, tough, or rigid Bonds a variety of plastics Can be formulated as 1 or 2 component system Slow to fast curing time Good low temperature properties Good environmental resistance Good chemical, oil resistance below 50C Disadvantages Moisture sensitivity during storage and application Only average bond strength to metal without a primer Precise mix ratio required for certain products Requires good mixing Maximum temperature of 100-150C for specially formulated PUs Hydrolytic stability is a problem for certain types Chapter 1 - Introduction 8 Chapter 2 Types of Polyurethane Adhesives 9 Classification of PU Adhesives and Sealants Polyurethane adhesives vary widely in composition and are used in many different applications and in various market segments Chapter 2 Types of PU Adhesives 10 Chapter 3 Polyurethane Chemistry 11 Polyurethane Chemistry Urethanes are generally produced from isocyanates, represented as: R N = C = O Properties revolve around the universal and rapid reaction between the NCO group and any organic compound containing an extractable hydrogen atom Reaction with a hydroxyl terminated polymer (e.g., alcohol, polyester or polyether polyol, derivatives of castor oil or hydrocarbons) H O | || R N = C = O + HO - R R N C O R (Isocyanate) (Alcohol) (Urethane) Chapter 3 PU Chemistry 12 Isocyanate Polyol Reaction Polyether or Polyester Diisocyanate Polyol HO~~~~~~~ OH + OCN R NCO O O
~~~~O C NH R NH C O~~~~~ Urethane Group Polyurethane Chapter 3 PU Chemistry 13 Chapter 4 Polyurethane Adhesive Composition 14 Polyurethane Adhesive Composition Isocyanate Active Hydrogen Compound Catalyst Chain Extender Additives Drying agents Antioxidant UV Inhibitor Antimicrobial Leveling agent Colorant Adhesion Promoters Fillers and Extenders Other Polymers Chapter 4 PU Adhesive Composition 15 Manufacture of Polyurethane Adhesives Urethane adhesive and sealants are generally made in a batch process Prepolymer is made in a standard mix tank Adhesive or sealant is made in a high torque mixer Mixer control is important for consistent viscosity It is necessary to avoid moisture contamination Reactions run under a nitrogen blanket or in a vacuum Reactors are always jacketed for temperature control Chapter 4 PU Adhesive Composition 16 Chapter 5 Isocyanates and Polyols 17 Isocyanates MDI (methylene diphenyl diisocyanate) TDI (toluene diisocyanate) Polymeric isocyanates used for crosslinking (e.g., polymethylene polyphenylene isocyanate) Prepolymers Isocyanate prereacted with some or all of the polyol (not all of the polyol is used) very low viscosity Chapter 5 Isocyanates and Polyols 18 Isocyanates Triphenylmethane triisocyanate (Desmodur R) Polymethylene polyphenyl isocyanate (PAPI) Aliphatic isocyanates - Less reactive, non-yellowing, more resistant to UV, slightly higher thermal resistance, lower resistance to oxidation, more expensive HDI (hexamethylene diisocyanate) IPDI (isophorone diisocyanate) O = C = N - - CH2 - - N = C = O MDI (methylene diphenyl diisocyanate) Chapter 5 Isocyanates and Polyols 19 Polyols Polyether Polyol Low temperature properties Hydrolysis resistance Lower cost Easier processing Low viscosity Not as reactive as polyester Polyester Polyol Good adhesion High strength, modulus, and hardness Better resistance to oxidation, elev. temp. Linear to highly branched R R HO (CH2-CH-O) n R (O-CH-CH2) m OH Polyether polyol R R HO (CH2-CH-O) n R (O-CH-CH2) m OH Polyether polyol OH R O (CO-R-CO-O-R-O) n H Polyester polyol OH R O (CO-R-CO-O-R-O) n H Polyester polyol Chapter 5 Isocyanates and Polyols 20 Polyols Polytetramethylene ether glycol (PTMG) Polycaprolactone glycol Polybutadiene (PolyBD) glycol Improved hydrolytic stability Lower moisture vapor transmission Lower tensile strength and modulus Others Polycarbonates Fatty alcohols Castor oil Polyester amide Chapter 5 Isocyanates and Polyols 21 Polyols Important factors in selection of a polyol: Flexible Rigid Molecular Weight 1000-6500 150-1600 Functionality 2 to 3 3 to 8 Hydroxyl value (mg KOH/g) 28-160 250-1000 Glass Transition Temperature -40 to 60C +60 to 40C NCO / OH Ratio Lower Higher Chapter 5 Isocyanates and Polyols Chemical type MW Functionality Chain structure Chemical type MW Functionality Chain structure 22 Comparison of PU Polyols Chapter 5 Isocyanates and Polyols 23 Prepolymers A prepolymer is a low molecular weight urethane polymer that retains the ability to react further Prepolymers are formed by partially reacting the available isocyanate groups with a curative Partial reaction is possible by controlling the ratios of the reactants Called xmers Important parameters in prepolymer design: Mc: average MW between crosslinks % NCO: if value is too high in one-part systems gassing can occur NCO/OH ratio control mole % of xmer formed Chapter 5 Isocyanates and Polyols 24 Chapter 6 Additives and Other Raw Materials 25 Catalysts, Chain Extenders, Crosslinkers Catalysts Tertiary amines (e.g., triethanol amine) Transition metals (e.g., dibutyl tin dilaurate, DBTDL) Chain Extenders (diamines or diols) Reacts with isocyanate then phase separates into domains (hard segments) Each extender molecule more than doubles the length of the rigid segment Used to produce stiffer hard segments Used to crosslink Crosslinkers Low molecular weight compounds containing active hydrogen with a minimum functionality of 3 Chapter 6 Additives and Other Raw Materials 26 Other Curatives Polythioethers React with isocyanate Provides some of the properties of polysulfide sealants Amines Aromatic amines provide rigid, hard adhesives Aliphatic amines (e.g., polyetheramine) are extremely reactive with isocyanates Necessary to slow down the rate of reaction for practical use; therefore, blocking agents are used Blocking Agents Reversibly react with isocyanates (phenols, methylethylketoxime, caprolactam, malonates, etc.) Chapter 6 Additives and Other Raw Materials 27 Additives Usually added to the polyol component Generally does not take part in the reaction All additives must be free of water (or foaming and poor adhesion); solvents must have a H 2 0 and alcohol content of less than 0.02% Stabilizers Antioxidant (e.g., phenolic) at a 2% level UV stabilizer Antimicrobial at a 0.3% level Hydrolysis stabilizer Adhesion promoters (e.g., organosilane) Fillers Drying agents at a 2-5% level Triethyl ortho formate Calcium sulfate Molecular sieves Zeolite Others Chapter 6 Additives and Other Raw Materials 28 Plasticizers, Extenders, and Solvents Not usually required urethane is typically flexible enough Plasticizers are used to improve elongation, reduce prepolymer viscosity, and lower hardness Phthalate type plasticizer commonly used Extenders are used to primarily lower cost Aromatic oils Asphalts Coal tars Solvent containing adhesives are formulated with dry organic solvents Ketones, lower alkyl esters (e.g., acetates), methylene chloride and trichloroethylene Certain flow agents (cellulose acetate butyrate, vinyl acetate copolymers, etc.) can be added Chapter 6 Additives and Other Raw Materials 29 Chapter 7 Common Formulations 30 PU Adhesive Formulation Reactive Polyurethane Adhesives One-component adhesives (solvent, water, and 100% solids) Two-component adhesives (solvent, water, and 100% solids) Reactive hot melts Wood binders Non-Reactive Polyurethane Adhesives Solvent borne adhesives Hot melt adhesives Water based adhesives Chapter 7 Common Formulations 31 Two Component Reactive Adhesives Generally composed of a diisocyanate terminated prepolymer as one component, and a polyol and polyamine crosslinking agent and catalyst as a second component Solventless and low solvent content adhesives Function as an adhesive or sealant Chapter 7 Common Formulations 32 Typical Two Component PU Formulation Chapter 7 Common Formulations 33 Moisture Cured One Component Adhesives Moisture cure Ambient conditions, shelf life, and foaming can be a problem Can be applied either with or without solvent Chapter 7 Common Formulations 34 Blocked One Component Adhesives Reaction is reversible, and generally temperatures of 120-160C are required for deblocking O O || || OCN R NCO + 2BH B C HN R NH C B Blocking agents include phenols, branched alcohols, methylethyl ketoxime and e-caprolactam Chapter 7 Common Formulations 35 Other One Component PU Adhesive Types Anaerobic Prepared by reacting hydroxyethyl methacrylate with TDI or an NCO terminated prepolymer; a hydroperoxide is added, and the mixture stored in an oxygen permeable container with air Polymerization takes place when access to oxygen is eliminated in the joint Solid Polyol A solid polyol, such as pentaerythritol, is simply mixed into the adhesive/sealant. When heated, the polyol melts and reacts with the isocyanate Chapter 7 Common Formulations 36 Reactive Hot Melt (HMPUR) Adhesives Solid polyether or polyester polyol mixtures are reacted with an excess of diisocyanate to produce a prepolymer The prepolymer is cooled into a hot melt product that can flow at relatively low temperatures 85-140C Molten prepolymer has a high degree of green strength Once applied the residual non-reacted isocyanate groups react with moisture to form a thermosetting structure Prepolymer contributions: Higher NCO/OH ratio: lower melt viscosity, lower elongation, higher tensile modulus and extended open times Lower NCO/OH ratio: thermoplastic characteristics with improved flexibility and toughness Chapter 7 Common Formulations 37 Isocyanate Wood Binders, Primers, Solutions Aromatic isocyanates (predominantly MDI) used for manufacture of: Oriented strand board (OSB), Medium density fiberboard (MDF), and Particleboard Isocyanates solutions can be used as primers for coatings and adhesives Isocyanates solutions can be blended with various types of elastomers (solvent blends) as rubber cements SBR Natural Rubber Neoprene Nitrile Chapter 7 Common Formulations 38 Solvent Based and Hot Melt Non-Reactive Adhesives Thermoplastic polyurethanes such as Estane (Goodrich) and Desmocoll (Bayer) Solvent systems can either be applied directly (permeable substrate), as a contact adhesive, or as a coating and then hot pressed Hot melt adhesives are most commonly applied as an extruded film for laminating applications Properties depend on formulation and selection of diisocyanates, polyols, chain extenders, and plasticizers Chapter 7 Common Formulations 39 Water Based Adhesives PU lattices can be prepared in various ways: Special monomers are polymerized in an aqueous medium to produce a thermoplastic PU Thermoplastic PU is dissolved in solvent and emulsified in water, then the solvent is removed Isocyanate terminated PU prepolymer is blocked and emulsified in water together with a crosslinking agent. Chapter 7 Common Formulations 40 Water Based Adhesives Aqueous polyurethane dispersion usually contain: 40% thermoplastic resin (for aqueous inertness) Aliphatic diisocyanate polymer (for light stability), and An anionic surfactant Can be cured at room temperature; however strength, adhesion, and water resistance are greater when dried for several minutes at 120-175C Chapter 7 Common Formulations 41 Chapter 8 Current and Future Development 42 Recent Development Activities Examples of development: Hybrid PU adhesives Ethylene / vinyl acetate copolymers Epoxy Acrylics Blocked isocyanates Pressure sensitive acrylic prepolymers Urethane toughened acrylate adhesives Reactive hot melts Pressure sensitive Anaerobic and radiation curing mechanisms Non-sagging without fillers Chapter 8 Current and Future Development 43 Reactive Epoxy Urethanes Mixture of epoxy and polyurethane oligomers with pendant epoxy groups Curing of epoxy groups unites the urethane and non-urethane components Tough, durable adhesive films Good adhesion to oily surfaces and plastics Chapter 8 Current and Future Development 44 End of Presentation for Session I 45 Seminar Contents - Part II Selecting and Applying Polyurethane Adhesives: Overview of major applications and key performances to match your end-use requirements 1. Introduction Markets and applications Comparison to other adhesive systems Range of types and properties 2. Application variables Health and Safety 3. Reaction rates 4. Types of polyurethane adhesives and their use 5. Stability in various environments Part II: Wed May 26, 2004 47 Backup Slides and Additional Material 48 Common PU Adhesive Reactions Chapter 3 PU Chemistry 49 Common PU Adhesive Reactions Chapter 3 PU Chemistry 50 Reaction Versatility Isocyanates react with active hydrogen compounds in the order: R2NH > R-NH2 > Ar-NH2 > R-OH > R2OH ~ H20 > Ar-OH > R-SH Isocyanate coreactants of commercial significance are: Polyester Polyols Polyether Polyols Amines Polymerization and/or crosslinking will occur depending on the amount and nature of the diisocyanates, stoichiometric amount and type of comonomer, and conditions of curing As with other polymers, additives are used to further modify the systems for specific end-use properties Polycaprolactones Polyglycols Natural and Hydroxyl Containing Oils Chapter 3 PU Chemistry 51 Crosslinking Capability Linear, thermoplastic PUs are obtained by using compounds with two reactive groups such as diisocyanates and diols Crosslinking occurs when: Polyols with three or more hydroxyl groups (i.e., a functionality of 3 or more) are reacted with an isocyanate, or when Isocyanates with three or more Isocyanate groups are reacted with a polyol. There is an excess of isocyanates (linkages of allophanate and biuret). The amount of crosslinking determines the stiffness of the polymer, strength, and resistance to environmental factors Chapter 3 PU Chemistry 52 Crosslinking Polyurethanes exhibit both chemical crosslinking and physical crosslinking Physical and chemical crosslinking sometimes overlap Crosslinking does not always produce the expected effect because of disruption of the domain structure (especially at low levels of crosslinking) Chapter 3 PU Chemistry 53 Polyurethane Morphology PU molecule consists of two separate phases or microdomains (pseudocrosslinking) Hard segment polyisocyanate and low molecular weight hydroxy compound (a short chain polyol or a diamine chain extender) Crosslinks the soft segment Soft segments Hydroxy terminated diols Greater flexibility and elongation, resistance to low temperature Lower hardness, modulus, abrasion resistance At elevated temperatures two phases become one amorphous, soft phase Chapter 3 PU Chemistry 54 Polyurethane Morphology 1 Flexible PUR 2- 40% rigid segments 3- 60% rigid segments 4- Rigid PUR Chapter 3 PU Chemistry 55 Polyisocyanates Provide Varied Adhesion Properties Isocyanates react readily with a variety of other functional groups Di- and polyisocyanates can undergo self-polymerization to form three dimension resins in situ Isocyanates are quite soluble in many organic substances, and due to their small molecular size readily permeate insoluble porous structures The reaction of di- and polyisocyanates with hydroxyl bearing polyesters and polyethers produce the strong, polar, hydrogen bonded flexible PUs which wet substrates very well Isocyanates provide elastomer- metal bonds with flexible to rigid gradation in physical properties between the elastomer and metal which provides superior fatigue life 56 Polyols and Hydrolytic Stability Hydrolysis Resistance as a Function of Change in Stress at Break All polyurethane elastomers: 80 shore A, immersed in water at 80C Chapter 5 Isocyanates and Polyols 57 Polyols Properties of Adhesive Films Based on Mixtures of Polyols Polyol PO1 = 5% hydroxyl content Polyol PO2 = 1.3% hydroxyl content A = modulus at 100% elongation B = tensile strength C = elongation at break Chapter 5 Isocyanates and Polyols 58 Fillers Fillers that reduce shrinkage, improve strength, reduce costs, adjust viscosity Barytes Hydrated Alumina Clays Particulate fillers increase density and hardness CaCO 3 has a catalytic effect on isocyanate reaction Aluminum hydroxide reduces flammability Carbon black reinforces and provides UV protection Colloidal and microexpanded silica are thixotropic agents Flaky fillers are used for surface properties, appearance, etc. Fibrous fillers (organic and inorganic) reinforce PU; generally increase rigidity and elastic modulus Quartz Flour Slate Flour Fumed Silica Chapter 6 Additives and Other Raw Materials 59 Thixotropy Thixotropic agents are used to provide non-sag properties or to reduce penetration in absorbent substrates Usually fumed silica or bentonite is used as an additive to provide thixotropy However, carbon black, fibers, and treated clays can also increase thixotropy Bayer has developed amine terminated prepolymers (ATEP) that provide fast B-stage reaction for thixotropy Generally need automated meter, mix, and dispense equipment for fast B- stage development Chapter 6 Additives and Other Raw Materials 60 Silane Primer / Additive Improves Moisture Resistance Adhesion promoters can be applied as a primer or as a component in the adhesive formulation Generally silanes are used to provide: A chemical bridge between the surface and organic polymer or between organic polymers A barrier to prevent moisture penetration into the interface Effective dispersion of fillers and reduction in the apparent viscosity of the system Isocyanate Terminated PU, Adhesion to Al (1. Urethane is Adiprene L-100, 2. Substrates degreased and etched, 3. Most commonly recommended for pot life) Chapter 6 Additives and Other Raw Materials 61 UV Stabilizers and Antioxidants Required with aromatic isocyanates and polyether polyols UV absorbers and stabilizers are commonly employed when PU is exposed to light Carbon black Titanium dioxide Tinuvin P (Ciba-Giegy) Antioxidants neutralize free radicals that are formed by the reaction of various chemical bonds with oxygen Iganox 1010 (Ciba-Giegy) Hindered phenols and amines UV stabilizers and antioxidants work synergistically, so they are often used together Zinc oxide Certain molybdates Chapter 6 Additives and Other Raw Materials 62 Stabilizers Hydrolytic Stability Improved hydrolytic stability (most often required for polyester urethanes) Carbodiimide (e.g., Staboxal P from Bayer) Satrastab developed by SATRA (Shoe and Allied Trades Assoc., Kettering, England) Elimination or reduction of ester groups in the polyol Hydrolysis resistance increases in the order of ether > polycaprolactone > polyester Chapter 6 Additives and Other Raw Materials 63 Other Stabilizers Fungicides (most often required for polyester urethane) Copper-8-quinolinolate N-(trichloromethylthio) phthalimide (e.g., Fungitrol 11 from Nuodex) Improved heat resistance Non-stabilized PU are not recommended for service temperatures greater than 100C Heat resistance can be improved through exclusion of catalyst residues from the polymer and by tailoring the polyurethane structure Antioxidants and hybrid with epoxy and other resins Chapter 6 Additives and Other Raw Materials 64 Polymers Sometimes Used with PU Adhesives 65 Polyurethane Metal Adhesive 66 Solvent-Free General Purpose Reactive Adhesive 67 Solvent Based Reactive Adhesive 68 Thermoplastic PU Contact Adhesive