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Silicone Functions Polyurethane

This document discusses the role of silicone surfactants in polyurethane foam. Silicone surfactants lower the surface tension of foam components, improving compatibility and allowing for better nucleation of small, stable bubbles. They also help prevent bubble coalescence and stabilize the foam structure. The ideal surfactant depends on the foam application, with properties like molecular weight and silicone content varying for uses like flexible slab, molded, or rigid foams. Selecting the proper surfactant tailored to each system is key to producing high quality foam.

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663 views

Silicone Functions Polyurethane

This document discusses the role of silicone surfactants in polyurethane foam. Silicone surfactants lower the surface tension of foam components, improving compatibility and allowing for better nucleation of small, stable bubbles. They also help prevent bubble coalescence and stabilize the foam structure. The ideal surfactant depends on the foam application, with properties like molecular weight and silicone content varying for uses like flexible slab, molded, or rigid foams. Selecting the proper surfactant tailored to each system is key to producing high quality foam.

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ธนพล กัตติยบุตร
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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The Role of Silicone Surfactants

as Surface Tension Reducing Agents


in Polyurethane Foam
The Role of Silicone Surfactants
as Surface Tension Reducing Agents
in Polyurethane Foam

Presented by:
Masao Takase
Dow Corning Toray Co., Ltd.
Translated by:
KH Boo
2
Todays presentation
Component roles in the foaming process
Structure of silicone surfactants
Four roles of a silicone surfactant
Emulsification improving compatibility of raw materials
Nucleation of bubbles
Prevention of coalescence (slow-down of diffusion)
Stabilization
Attributes important to surfactant selection
Conclusions
3
Component roles in the foaming process

Control of physical
phenomena:
Static surface tension
Dynamic surface tension
Interfacial tension
Polyol
Isocyanate
Water
Amine Catalyst
Tin Catalyst
Blowing Agent
Surfactant
Chemical reaction:
Chain extension
Gas formation
Crosslink
Polymer
Cell
PU Foam
4
Types of structures
Branch Type
ABA Type
(AB)
n
Type
Siloxane Unit
Polyether Unit
Rake Type / Pendant Type
5
Surface tension of raw materials
Sur f ace Tension wit h and wit hout Silicone Sur f actant
0
10
20
30
40
50
60
70
Water +
NEM(0.1%)
TDI-80 PPG(Mw=3000) Blowing Agent Entire Sytstem
S
u
r
f
a
c
e

T
e
n
s
i
o
n

(
m
N
/
m
)
Without Surfactant
With Surfactant
Surface tension of silicone surfactant: 21.4[mN/m]; concentration of silicone surfactant: 1.0pphp.
6
The four roles of a silicone surfactant

Control of Interfacial Phenomenon


3. Prevention of coalescence
1. Improved compatibility
of raw materials
Stabilization of bubbles Support of mixing
2. Dispersion of inlet gas 4. Stabilization of bubbles
Cream time to gel time
Gel Polymer
Cells are formed
Mixing to cream time
Liquid
Cell is not formed
7
1. Improving compatibility of raw materials

Depending on the specific


system, it is possible for the
silicone polyether to improve the
compatibility between materials.
The surfactant acts at the
interfaces of the formulation
components.
Polyether pendants can be designed to
be soluble in different polar components
of the system.
The silicone backbone will drive
toward hydrophobic/nonpolar materials.
8
2. Nucleation
Many factors affect the rate of nucleation and bubble
growth in the system.
It has been shown, in theory and in practice, that lowering
the surface tension of the system leads to an increased
number of fine cells in the foam.
9
2. Nucleation - Dispersion of inlet gas
Less surfactant can lead to a higher surface tension, which can cause coarse cells.
1 Part Silicone Surfactant 0.3 Parts Silicone Surfactant
10
2. Nucleation of stable bubbles
According to classical nucleation theory, for a stable bubble
to form, there has to be enough Gibbs free energy to reach
a critical radius/nucleus.
(1)
2
P 3
tension surface * 16
radius critical a forming of Energy Free s Gibb'

=

This equation shows that lowering the surface tension also
lowers the amount of energy needed for nucleation!
1% Surfactant
No Surfactant
Carbonated Soda Shaken for 3 Seconds
Number of bubbles increased
Size of bubbles decreased
No Surfactant
1% Surfactant
12
The four roles of a silicone surfactant

Control of Interfacial Phenomenon


3. Prevention of coalescence
1. Improved compatibility
of raw materials
Stabilization of bubbles Support of mixing
2. Dispersion of inlet gas 4. Stabilization of bubbles
Cream time to gel time
Gel Polymer
Cells are formed
Mixing to cream time
Liquid
Cell is not formed
13
3. Prevention of coalescence
(slowing down diffusion)
Gas will diffuse from areas of high pressure to areas of low pressure.
Therefore, gas will flow from smaller bubbles into larger bubbles.
LaPlace and Young theorized the following:
P P P
gas gas
= =

) 2 ( ) 1 (
(2) (1)
radius
1
radius
1
* Tension Surface * 2
The rate at which the gas diffusion takes place is proportional to P.
(2)
Therefore, decreasing the surface tension decreases P, which
decreases the diffusion rate.
Lower
Pressure
Higher
Pressure

=
ra rb
P
1 1
2
PB
PB
r
P

=
Both are very stable foams.
Larger Pressure Drop Smaller Pressure Drop
Lower
Pressure
Example of
coalescence!
3. Prevention of coalescence (slowing down diffusion)
Higher
Pressure
15
4. Stabilization
There are many theories as to how a surfactant helps
stabilize a foam:
Gibbs
Marangoni
Ewers & Sutherland
Plateau
We will highlight a few.
16
Marangoni effect on stabilization:
Fluid flows from low surface tension to high.
Higher-tension
area created
Liquid flow pushes fluid back to
stabilize the thinned wall.
4. Stabilization by
Surfactant Migration
Surfactant will flow from an
area of high to low
concentration!
This will not only drop the
surface tension of the newly
formed area, but it also will
drag with it some of the
entangled liquid layer
(theorized by Ewers/
Sutherland).
(2)
18
Does surface tension control everything?
?
No, it does not.
Other important variables that impact performance and
surfactant selection:
Solubility characteristics
Molecular weight differences
Reactivity differences
etc.
19
Surface tension is
only one of the
many variables!
This foam completely
collapsed in seconds
with an ultra-low
surface tension
surfactant!
Surfactant
21 Dynes/cm
Surfactant
30 Dynes/cm
20
Important roles of silicone surfactant by application

Flexible Slab HR Molded Rigid


Improving Raw Material
Compatibility
Medium Medium High
Dispersion of Inlet Gas Medium Medium High
Prevention of
Coalescence
Medium Medium Medium
Stabilization High Low Medium
21
Structural components of silicone surfactant

1. Type of structure
2. Siloxane Mw
3. Modified polyether Mw
4. Number of modified polyether unit
5. EO / PO ratio of polyether
6. End unit of polyether
7. Copolymer Mw
8. Silicone content of copolymer
Si O
CH
3
O
C
3
H
6
O(EO)
a
(PO)
b
R
Si
CH
3
CH
3
m
Si O
CH
3
CH
3
CH
3
Si
CH
3
CH
3
CH
3
n
22
Flexible slab and hot mold

Si O
CH
3
O
C
3
H
6
O(EO)
a
(PO)
b
R
Si
CH
3
CH
3
m
Si O
CH
3
CH
3
CH
3
Si
CH
3
CH
3
CH
3
n
High Mw of siloxane and polyether
O-R capped polyether
EO/PO ratio of polyether is approximately 50 to 50
Silicone content of copolymer is lower
23
HR mold
Si O
CH
3
O
C
3
H
6
O(EO)
a
(PO)
b
R
Si
CH
3
CH
3
m
Si O
CH
3
CH
3
CH
3
Si
CH
3
CH
3
CH
3
n
Low Mw of siloxane and polyether
Various kinds of polyether
Silicone content is wide range
24
Rigid refrigerator/construction
/
Si O
CH
3
O
C
3
H
6
O(EO)
a
(PO)
b
R
Si
CH
3
CH
3
m
Si O
CH
3
CH
3
CH
3
Si
CH
3
CH
3
CH
3
n
Medium Mw of siloxane and polyether
High EO content of polyether
25
Conclusions
Physical phenomena such as Emulsification, Nucleation of
bubbles, Prevention of coalescence, and Stabilization are
significantly influenced by the selection of the silicone
surfactants.
Selection of the right surfactant is a key to your success!
Dow Corning knows which is the ideal molecule to
help you meet the requirements of your system.
For more information:
Please visit the Dow Corning booth #818
Visit our website, www.dowcorning.com/polyurethane
Or e-mail us at [email protected]
26
References
1. Lee, S.T., & Ramesh, N.S. (2004). Polymeric Foams:
Mechanisms and Materials, p 81. New York: CRC Press LLC.
2. Herrington, Ron, & Hock, Kathy. (1997). Dow Polyurethanes:
Flexible Foams, p 3.12 and 3.17. USA: The Dow Chemical
Company.
Some of your Dow Corning polyurethane foam team DC PUA
Some of your Dow Corning polyurethane foam team DC PUA
Vicky J ames,
Masao Takase,
Stephanie Gathman
Bee Yung, Chris Velasquez
Kuang Hoe "KH" Boo

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