Introduction of PU Catalyst

Ryohei Takahashi
(Tosoh R&D)
Dec. 21, 2018
 What is Polyurethane?

Polymer formed by reacting a polyol with a isocyanate

Used in a wide variety of applications

because of its unique properties
- Flexible foams : Bedding, Furniture, Seat
- Rigid foams: Insulating material (Appliance, Board)
- Semi-rigid foams: Wheel, Armrest, Headrest
- Others: Elastomer, Adhesive, Coating, Sealant, Shoe sole
 Polyurethane Foam
System (premix)
Polyol
Isocyanate
Blowing agent
Catalyst
Silicone
Others

Polyurethane
 Raw material of PU

Polyol Polyether, Polyester, Polymer polyol

Isocyanate TDI, MDI, TM blend, Aliphatic Isocyanate

Water, Freon(CFC11, 141b, 245fa, 365mfc),

Blowing agent
Cyclopentane, Pentane, Methylene chloride,

Amine (TEDA&TOYOCAT),
Catalyst
Metal (Tin, Lead, Potassium salt)

Silicone Surfactant

Others Cross-liking agent, Fire retardant

 The Role of PU Catalyst
1. Control the polyurethane foaming reactions
Reaction Profile, Cure Speed (Surface/Core)
2. Moldability and cell structure of PUF
Flowability, Voids and Defects, Skin Peeling,
Cell Structure (Size, Anisotropy, Openness)
3. Foam properties
General: Density, Odor and Emission
Rigid: Compressive Strength, Dim. Stab. ,
K-factor, Adhesion, Flame Retardancy
Flex.: Elongation, Durability,
Foam Tightness
 TEDA&TOYOCAT®
Ethylene amines derivatives

Crystal
TEDA N or
(Triethylenediamine) N Glycol Solutions

N N N
N N

TOYOCAT® TE DT
t-Amines for Polyurethanes N
N N N
N
NP DMI
 TEDA&TOYOCAT®
TERTIARY AMINE CATALYST for POLYURETHANE

Gelling Catalyst O
H
R NCO R' OH R N C O R' Urethane

Blowing Catalyst O
H H
2 R NCO H 2O R N C N R CO2 Urea

O R
Trimerization Catalyst
N
3 R NCO R N O Isocyanurate
N
O R
 TEDA&TOYOCAT®
Basic Product Lines for Polyurethane Foams

N
N

H
O
N
N
N

N
N

N
N N

N
N

N
N

N
N
DM70 TE TRC RX5

N
N

TEDA-L33 MR NP DT

0.1 1.0 10.0 100.0

Gelling Log[k2w/k1w] Blowing
 Cream Time & Gel Time
Polyol
System Isocyanate

Stir a mixture Pour into Start foaming Stop foaming Turn into
of polyol system cup/mold a gel
and isocyanate

Cream Time (=CT)

Gel Time (=GT)

 Thermo-sensitiveness
1. Cyclic Amines: Generally thermo-sensitive
N
N N N N
N N

2. Blocked Amines: Thermo-sensitive

R' OH R R' OH R
N N
O R R heat O R R

Inert Active
3. Linear Amines: Generally less thermo-sensitive

N N N N
N N N
Thermo-sensitiveness
Activation Energies for Gel and Blow Reactions
E(Kcal/mol)
TDI-DEG TDI-H2O
Cyclic Amines N
N
5.3 5.8
N

N
N
6.4 4.5
N N
5.8 7.5

Linear Amines N
N 4.2 1.1
N
N
N 3.2 1.6
N
N 3.2 3.0
 Gel/Blow Balance and Foaming
High
Large
Adhesive
Flowability

Cream Time
Density
Isotropic cell
Small

Cell size
Low

K-Factor Shrinkage (Dim. stab.)

Gelling Catalytic Activity Blowing

 Gel/Blow Balance and Cell Structure
Rise profile
Blowing
Cat.
Gelling Cat.
Rise height
Pressure

Foaming pressure
Gelling Cat.
Blowing Cat.

Gel Time
Blow Cat. Large, Isotropic cell

Gel Cat. Small, Anisotropic cell

 Reactive Amines
General Amine Catalyst/Non-reactive
e.g.
Free TEDA cause
TEDA O O emission related
H H H N problems, such as
R N C N R N C O R2
1 1
N Odor, PVC staining.
Urea Urethane
Reactive Amine Catalyst (RACs)
t-Amine with reactive sites (NH2/NH/OH) toward NCO
e.g. DMEA
O O O
N H H H H
O C N R N C N R N C O R2
1 1

N Urea Urethane
OH

RACs can be incorporated into polymer network and stabilized.

 TOSOH’s Special Amine Catalyst
Application Product Advantages

CX20 Less Corrosive Delayed Action Catalyst

Flexible CX40 Surface Cure Catalyst for Low Mold Temperature

CX60 Cell Opening Gelling Catalyst, A300 replacement

F94 Provides Better Adhesion even at Higher H2O Level

Rigid M50 Gelling Surface Cure Catalyst with High Acitivity

TR40 Trimerization Catalyst, Improves Fire Performance

MC12 Longer Cream Time & Faster Cure

Footwear F24 Improves Abrasion Resistance

S10 Reduces Foam Density, Maintains Foam Properties