Introduction to Polyurethane!

Chemistry and Structure-Property Relationships

05/07/16
Monomers and Polymers

•  Monomer (mono – one; mer – part): Small molecules

•  Polymer – Cons8tutes many monomers.
•  Polymeriza8on – Process of covalently (chemically) bonding many monomers
together. Can be few hundreds to thousands monomer units
 Polymer types

•  Polymers can be broadly classified into

•  Thermosets – Cannot be melted once formed
•  Elastomers (Natural Rubber, PU, SBR etc)
•  Rigid Thermosets (Epoxy, Vinyl ester etc)
•  Thermoplas8cs - Can be recycled
•  Engineered Plas8cs (PC, Nylon, Alloys such as Xenoy etc)
•  Commodity Plas8cs (HDPE, PP etc)

•  Choice of Polymer depends on
•  Hardness and other physical property requirements
•  Environmental factors (Exposure to oil, water, other fluids, Temperature etc)
•  Tooling cost (Injec8on molds vs open cast vs compression molds)
•  Mode of failure (Fa8gue, cut and tear, wear, compressive loads etc
What Are Polyurethanes?

•  Polyurethanes are organic polymers that contain the urethane group in the structure

•  Typically, polyurethanes are formed via the reaction of a Polyol (-OH group) with a Isocyanate (-NCO
group)

•  Polyureas contain the urea group in the structure

•  Compositions may be contain just urethane group or a combination of urea and urethane groups.

O O

HN O HN NH

R R R R

Urethane Group Urea Group

Polyurethane classifications

-  Linear polyurethanes
-  Castable polyurethanes
-  Millable polyurethanes
-  Thermoplastic polyurethanes
-  Cellular polyurethanes
-  Sprayable polyurethanes
-  Porometric polyurethanes
-  Spandex fibers


 Castable Polyurethanes

•  Represent only a small portion of the overall polyurethane industry

•  Made by mixing several ingredients, introducing into a mold, and heat curing at
temperatures (100-130°C)

•  The curing process operates by extending chains of a prepolymer made from a

macro diol and a diisocyanate

•  The full mechanical properties of the urethane are not realized until a posturing
operation is completed

•  Castable urethanes can be cured with amine or diol curatives. Special

formulations may use a combination of diols and amines as curatives.
 Material Hardness Comparison
POLYURETHANES

PLASTICS
RUBBERS

Polypropylene
Fluorocarbons

Polystyrene

Phenolics
Acrylics
Acetals
Nylons

Ultem
20 30 40 50 60 70 80 90 95
SHORE A DUROMETER
45 55 65 75 85
Rubber Car SHORE D DUROMETER
Band Tire
50 70 90 100 110 120 130 140 150
Tread
ROCKWELL R
Men’s
Shoe Golf Bowling
Heel Ball Ball
Polyurethane (A versatile compound)

Polyol Type
1) Polyether
Diisocyanate Type 2) Polyester
1) TDI 3) Polycaprolactone
CuraVve Type
2) MDI 4) Polycarbonate 1) MBOCA
3) PPDI 2) Butanediol
4) H12MDI 3) TMP
5) HDI 4) TIPA
6) TODI 5) Diethyltoluene Diamne

Part A, Cured
Prepolymer Polyurethane
Part B,
or “Resin” Cura8ve or
“Poly”
Diisocyanates used in Cast Urethanes

Aromatic
•  Toluene diisocynate (TDI) 2,4 & 2,6 TDI

•  4,4’ diphenylmethane diisocyanate

(MDI)

MDI
•  Paraphenylene diisocyanate (PPDI)

•  1,5-naphthalene diisocyanate (NDI)

PPDI
•  Reactivity: NDI> MDI> TDI
NDI
Diisocyanates (cont’d.)

Aliphatic
•  H12MDI H12MDI

•  1,6 Hexamethylene diisocyanate

(HDI)
HDI
•  Lower reactivity

•  Non-yellowing due to lack of

double bonds.

•  Lower volume in hot cast market

Polyols used in Hot Cast Urethanes

Polyethers
•  PTMEG or Poly THF(C4): Excellent mechanical properties, hydrolysis resistance and very low abrasion
loss.
•  PPG(C3)-cheaper with lower performance. More susceptible to oxidation

Polyester
•  Compounds formed by polymeric reaction of an acid (adipic acid) with a glycol (ethylene glycol). Water is
the by product
•  Better tear, abrasion and oil resistance but lower hydrolytic stability

Polycaprolactone (C6)
•  Subgroup of polyesters. More expensive
•  Hydrolysis resistance: Polyester< Polycaprolactone< PTMEG

Polycarbonate
•  Superior hydrolysis resistance
•  Excellent High Temperature properties
•  High viscosity polymers. Difficult processing.

Polyols - Polyethers
O

CH2 - CH - CH3

Propylene Oxide

HO - (CH - CH2 - O)n - CH2 - CH - (O - CH2 - CH)n - OH

Polypropylene Glycol (PPG)
CH3 CH3 CH3

H2C CH2

H2C CH3

Tetrahydrofuran Poly(oxytetramethylene) glycol (PTMG)

HO - (CH2 - CH2 - CH2 - CH2 - O )n - CH2 - CH2 - CH2 - CH2 - OH

Polyols - Polyesters
O O
HO - CH2 - CH2 - OH + HO - C - CH2 - CH2 - CH2 - CH2 - C - OH
Ethylene Glycol Adipic Acid
-H2O

O O
HO - CH2 - CH2 - (O - C - CH2 - CH2 - CH2 - CH2 - C - O - CH2 - CH2)n - OH
Polyethylene Adipate Glycol
Curatives

MBCA (4,4'-Methylene bis (2-chloroaniline)
Cl Cl
MBOCA
H2N CH2 NH2

1,4 -Butanediol
BDO, 1,4-BD HO - CH2 - CH 2 - CH 2 - CH 2 - OH

Hydroquinone bis (beta hydroxyethyl) ether (HQEE, XA)

HQEE
HO - CH2 - CH 2 - O O - CH 2 - CH 2 - OH

CH2 OH
TMP Trimethylolpropane (TMP)
CH3 - CH2 - C - CH2 OH

CH2 OH
 Reactivity of Isocyanate group

•  Highly reactive, affected by electronic

structure

R"N=C=O •  “R” group effects the reactivity of the NCO

group
!OH H"O"H
!NH •  Also reactivity is driven by the compound
reacting with isocyanate group
•  Amines > Hydroxyls
•  Alipha8c Amines > Aroma8c amines
•  Primary Hydroxyls > Secondary Hydroxyls

Cast Polyurethane Types

•  Best Performance
Prepolymers •  Less forgiving on ra8o
•  Most expensive

•  Cheapest •  Higher monomer content

•  Lowest performance that prepolymer
•  EH&S issues due to monomer Cast •  Wide range of hardness from
handling Polyurethanes 3 components
•  Exotherm needs to be •  Processing can be challenging
managed

One Shot Quasi

Systems Prepolymers
Formation of Prepolymer

POLYOL
DIISOCYANATE

HO OH
+ OCN

R NCO

Further chain extension can occur as hydroxyl sites react with terminal
NCO groups.

URETHANE PREPOLYMER

O O

OCN R N C O O C N R
H H
NCO
Prepolymer Curing with Chain Extender

Chain extension with Urethane group: Polyurethane

Chain extension with Urea group: Poly (Urea-Urethane)

 Polyurethane Prepolymer Processing

Part A Prepolymer Metering Curative Part B

(Melting), Mixing Melting or

Warming & Warming
Degassing (Degassing)
Dispensing

Molding

Curing

Demold

Post-Cure

Finishing
 Choice of Polyurethane

•  Application specific performance

•  Ethers have beeer hydoly8c stability than esters
•  Esters have beeer oil resistance than ethers
•  Esters have beeer cut and tear resistance than ethers
•  Amine cured urethanes have beeer high temperature proper8es than diol cured
urethanes.
•  Processing
•  TDI systems are easier to process than MDI systems
•  Diols (such as 1,4 BD are liquid at room temperature) whereas certain amines (such as
MBOCA) need to be melted
•  Cost
•  MDI systems are generally cheaper than TDI systems
•  Esters are typically cheaper than ethers
•  Quasi systems are cheaper than Prepolymers
 Schematic of Polyurethane elastomer

•  Sof Segment
•  Hard segment
•  Hydrogen bonding

•  Self reinforcing structure of

PU
•  Performance can be
achieved by choosing right
raw materials
•  Performance enhancing
addi8ves rarely needed
What controls properties?
Hard Soft
Segment Segment

1. CONCENTRATION OF HARD SEGMENT

2. COMPOSITION OF SOFT SEGMENT
3. COMPOSITION OF HARD SEGMENT
4. SEGREGATION OF HARD SEGMENT
Phase segregation and effect on properties

•  Phase segrega8on requirements are applica8on specific

•  A processor can control phase segrega8on by choosing
•  Chemistry (Iso/Polyol/cura8ve package)
•  TDI/PTMEG/MOCA = Good. TDI/PTMEG/BD = Bad
•  Ra8o of cura8ve
•  >100% theory = more linear = beeer fa8gue resistance.
•  Too much excess cura8ve (>120%) disrupts phase segrega8on
•  Processing condi8ons
•  Higher mold temperatures (below degrada8on) leads to smaller crystal size = lower hardness

•  Typically suppliers are able to provide application specific chemistry but a general
knowledge of urethane chemistry helps in understanding why certain choices are made
•  Good phase segregation leads to
•  High temperature proper8es
•  Beeer dynamics (less heat build under dynamic loads)
•  Fa8gue proper8es
•  Cut and tear resistance
•  Certain applications may also require “not to great” phase segregation
•  Dead blow hammer – cura8ve packages inten8onally disrupt natural phase segrega8on.

Structure property relationships

ApplicaVon Chemistry Comments

requirements
High cut and tear Polyester backone Hydrogen bonding leads to cut growth
resistance

High rebound PTMEG backbone High levels of phase segrega8on. Beeer

rebound

Sof compounds Triol cures Triol cures disrupt phase segrega8on

leading to lower hardness

Clear compounds Alipha8c Lower phase segrega8on. Saturated double

bonds – no free radical genera8on

More in “What Urethane Where” presenta8on

Reactions of Prepolymers
•  Reac8ons of isocyanates are all exothermic
•  Liquid Prepolymers can React With:
- Hydroxy Compounds
- Amines
- Water
- Ureas and Urethanes
-And can Dimerize (isocyanate polymeriza8on)

Reaction with Water

2 H2O+ OCN-R-NCO H2N-R-NH2 + 2CO2

•  The reaction with water provides the primary source of gas for
blowing in the manufacture of low density flexible foams.
•  Can be an issue in hot cast where bubbles/foam is not needed
•  Water can be introduced while
•  Drum handling
•  Curative handling
•  Processing
Isocyanate Polymerization Reactions


O

C

R’-NCO + OCN-R’ R’-N N-R

C

O
Uretidinedione (dimer)

•  Dimer reac8on is more common with MDI prepolymers with high monomer
content
•  Happens at all temperature but more prevalent at higher or lower temperatures
•  Shelf life cri8cal in many compounds with high monomer content
 Hydrolysis Reactions

O O
~ R C O R ~ + H2O ~ R C OH + HO R ~
Ester Acid Alcohol

O O
~ R NH C NH R ~ + H2O ~ NH C OH + H2N R ~
Urea Carbamic Acid Amine

O O
~ R NH C O R ~ + H2O ~ NH C OH + HO R ~
Urethane Carbamic Acid Alcohol

•  Ester hydrolysis common issue when using Polyester based PU in hot moist
environments (Example: TDI/Ester/Amine cure in Asia)
•  Diol cures less suscep8ble than amine cures
 Additives
Plasticizers:
–  Non-Reactive Diluents (Do Not Change Ratio of Curative/Prepolymer)
–  Benzoflex 9-88SG: 10pph Lowers Hardness 5-6 Points With Esters
–  Usually Preblend with Prepolymer; With Curative Sometimes
–  Typically used to soften or reduce cost

Fillers
–  No Reinforcing Action in Urethanes
–  Must Be Dry
–  Cost reduction in Conjunction with Plasticizers
–  10 pph Increases Hardness About 2 Points
–  Not common to use fillers
Catalysts and Other Additives

Catalysts Other Additives

–  Amine Cures (e.g., MBCA, E 300) –  Degassing Aids – SAG-47
•  Azelaic, Adipic, Oleic Acids
–  0.2% Azelaic in MBCA –  Internal Lubricants – Graphite,
Reduces Pot Life and MoS2 , Silicones, etc.
Demold by Factor of 2
–  Antistatic Agents – Catafor, Carbon
–  Diol/Triol Cures (e.g., 1,4-BD, Blacks
HQEE, TMP)
•  Niax A-33, Fomrez C-2, –  Stabilizers – Stabaxol for Esters,
SUL-4, UL-32 Antioxidants, UV Stabilizers
–  Highly Active in MDI

Systems

Ques8ons