Documente Academic
Documente Profesional
Documente Cultură
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
4. 5. 6. 7. 8.
PU adhesive composition Isocyanates and Polyols Additives and other raw materials Common formulations Current and future development
60 minutes
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
Chapter 1 - Introduction
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
10
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
11
HO~~~~~~~ OH
OCN R NCO
O
Polyurethane
~~~~O C NH R NH C O~~~~~
Urethane Group
Chapter 3 PU Chemistry
12
13
15
16
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
17
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
18
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
Polyester Polyol
Good adhesion High strength, modulus, and hardness Better resistance to oxidation, elev. temp. Linear to highly branched
Chapter 5 Isocyanates and Polyols
19
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
20
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
Comparison of PU Polyols
22
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
23
24
Crosslinkers
Low molecular weight compounds containing active hydrogen with a minimum functionality of 3
25
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.)
26
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
Others
Chapter 6 Additives and Other Raw Materials
27
28
29
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
30
31
32
33
Blocking agents include phenols, branched alcohols, methylethyl ketoxime and e-caprolactam
34
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
35
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
37
38
39
Can be cured at room temperature; however strength, adhesion, and water resistance are greater when dried for several minutes at 120-175C
40
41
43
44
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
45
47
Chapter 3 PU Chemistry
48
Chapter 3 PU Chemistry
49
Reaction Versatility
Isocyanates react with active hydrogen compounds in the order:
R2NH > R-NH2 > Ar-NH2 > R-OH > R2OH ~ H20 > Ar-OH > R-SH
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
50
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
51
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
52
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
Polyurethane Morphology
1 Flexible PUR 2- 40% rigid segments 3- 60% rigid segments 4- Rigid PUR
Chapter 3 PU Chemistry
54
55
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
57
Fillers
Fillers that reduce shrinkage, improve strength, reduce costs, adjust viscosity
Barytes Hydrated Alumina Clays Quartz Flour Slate Flour Fumed Silica
Flaky fillers are used for surface properties, appearance, etc. Fibrous fillers (organic and inorganic) reinforce PU; generally increase rigidity and elastic modulus
58
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
59
60
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
61
62
Other Stabilizers
Fungicides (most often required for polyester urethane)
Copper-8-quinolinolate N-(trichloromethylthio) phthalimide (e.g., Fungitrol 11 from Nuodex)
63
64
65
66
67
68