Training Courses on Polyurethane 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)

Seminar Objectives Learn capability of polyurethane adhesives Learn about their versatility and breadth Learn the formulation possibilities

Chapter 1 - Introduction

Seminar Contents - Part I

1) Slide Show Presentation
Chapter 1. Introduction 2. Types of PU adhesives 3. PU chemistry
Morphology and physical properties

4. 5. 6. 7. 8.

PU adhesive composition Isocyanates and Polyols Additives and other raw materials Common formulations Current and future development

60 minutes

2) Questions and Answers

On-line interaction

30 minutes
Chapter 1 - Introduction
3

Chapter 1 Introduction

Definition
PU adhesives contain a number of urethane groups in the molecular backbone or are formed during use Urethane group
O NCO H

Many complex reactions can occur simultaneously or sequentially

Diversity Diversity Versatility Versatility

Chapter 1 - Introduction
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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

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

Chapter 2 Types of Polyurethane Adhesives

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

Chapter 3 Polyurethane Chemistry

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Polyurethane Chemistry
Urethanes are generally produced from isocyanates, represented as:
RN=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)
R N = C = O + HO - R (Isocyanate) (Alcohol) H O | || R N C O R (Urethane)

Chapter 3 PU Chemistry

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Isocyanate Polyol Reaction

Polyether or Polyester Polyol Diisocyanate

HO~~~~~~~ OH

OCN R NCO

O
Polyurethane

~~~~O C NH R NH C O~~~~~
Urethane Group
Chapter 3 PU Chemistry

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Chapter 4 Polyurethane Adhesive Composition

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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
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Chapter 4 PU Adhesive Composition

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

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Chapter 5 Isocyanates and Polyols

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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

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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

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Polyols
Polyether Polyol
Low temperature properties Hydrolysis resistance Lower cost Easier processing Low viscosity Not as reactive as polyester
R R R R HO (CH2-CH-O)n R (O-CH-CH2)m OH R (O-CH-CH2) OH HO (CH2-CH-O)
n m

Polyether polyol Polyether polyol

Polyester Polyol
Good adhesion High strength, modulus, and hardness Better resistance to oxidation, elev. temp. Linear to highly branched
Chapter 5 Isocyanates and Polyols

OH R O (CO-R-CO-O-R-O)n H OH R O (CO-R-CO-O-R-O)n H Polyester polyol Polyester polyol

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Polyols
Polytetramethylene ether glycol (PTMG) Polycaprolactone glycol Polybutadiene (PolyBD) glycol
Improved hydrolytic stability Lower moisture vapor transmission Lower tensile strength and modulus Polycarbonates Fatty alcohols Castor oil Polyester amide

Others

Chapter 5 Isocyanates and Polyols

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Polyols
Important factors in selection of a polyol: Chemical type Chemical type MW MW Functionality Functionality Chain structure Chain structure
Flexible Molecular Weight 1000-6500 Functionality 2 to 3 Hydroxyl value (mg KOH/g) 28-160 Glass Transition Temperature -40 to 60C NCO / OH Ratio Lower
Chapter 5 Isocyanates and Polyols

Rigid 150-1600 3 to 8 250-1000 +60 to 40C Higher

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Comparison of PU Polyols

Chapter 5 Isocyanates and Polyols

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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

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Chapter 6 Additives and Other Raw Materials

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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
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Chapter 6 Additives and Other Raw Materials

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

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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 H20 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
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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

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Chapter 7 Common Formulations

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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

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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

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Typical Two Component PU Formulation

Chapter 7 Common Formulations

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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

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Blocked One Component Adhesives

Reaction is reversible, and generally temperatures of 120-160C are required for deblocking
OCN R NCO + 2BH O O || || B C HN R NH C B

Blocking agents include phenols, branched alcohols, methylethyl ketoxime and e-caprolactam

Chapter 7 Common Formulations

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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

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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
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Chapter 7 Common Formulations

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
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Chapter 7 Common Formulations

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

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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

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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

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Chapter 8 Current and Future Development

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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
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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

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End of Presentation for Session I

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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
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Backup Slides and Additional Material

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Common PU Adhesive Reactions

Chapter 3 PU Chemistry

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Common PU Adhesive Reactions

Chapter 3 PU Chemistry

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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 Polycaprolactones Polyglycols Natural and Hydroxyl Containing Oils

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

Chapter 3 PU Chemistry

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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

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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

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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
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Polyurethane Morphology

1 Flexible PUR 2- 40% rigid segments 3- 60% rigid segments 4- Rigid PUR

Chapter 3 PU Chemistry

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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

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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
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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

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Fillers
Fillers that reduce shrinkage, improve strength, reduce costs, adjust viscosity
Barytes Hydrated Alumina Clays Quartz Flour Slate Flour Fumed Silica

Particulate fillers increase density and hardness

CaCO3 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

Chapter 6 Additives and Other Raw Materials

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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 Bstage development

Chapter 6 Additives and Other Raw Materials

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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

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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) Zinc oxide Certain molybdates

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

Chapter 6 Additives and Other Raw Materials

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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

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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

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Polymers Sometimes Used with PU Adhesives

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Polyurethane Metal Adhesive

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Solvent-Free General Purpose Reactive Adhesive

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Solvent Based Reactive Adhesive

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Thermoplastic PU Contact Adhesive

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