EVONIK - PU Additives

Additives designed for NOP

containing PU foams

Martin Glos, Christian Eilbracht, Peter Hohl

April 2009
 1. Introduction
2. Difficult Mixtures with NOPs
3. Macromolecular Approach
4. Particle Approach
5. Conclusions

Seite | 2
1. Evonik Goldsch midt

Polyureth ane Additives

for Spray Foam
Increasing Renewable Content

Bio-based materials such as sugar, glycerin and sorbitiol have been

used for many years now in the production of polyols

But the polyurethane industry is looking more and more into increasing
its renewable content

New Natural Oil Polyols have been developed
in an attempt in increase the renewable
content in the finished PU foam

To date, NOP technology has been proven
in many PU construction applications

But what is the limit? How much
petroleum-based Polyol can be replaced
by NOPs?
3
Natural Oil Polyols Limitations in
PU Applications

The Pros:
 Technology exists
 Variety of new structures in polyols
 “Sustainable”
 Offers a solution to a growing demand for
Eco-Friendly Products

The Cons:

 Composition may vary from geographic area,

weather conditions
 Relatively low hydroxyl functionality
 Limited compatibility with conventional polyols
 ….Resulting in poor foam performance

4
What Role Can Additives Play?

Emuslifier
……..WILL NOT make NOPs more homogeneous
……..WILL NOT increase NOPs hydroxyl functionality
……..CAN maximize NOP usage by creating a stable emulsion

Time

+ Emulsifier

Time

Resulting in acceptable foam performance

…with maximum renewable content! 5
 1. Introduction
2. Difficult Mixtures with NOPs
3. Macromolecular Approach
4. Particle Approach
5. Conclusions

Seite | 6
1. Evonik Goldsch midt

Polyureth ane Additives

for Spray Foam
Difficult Polyole mixtures

Addressing miscibility problems of polyols

• Rigid Foam: Mixtures Polyesterpolyols + NOP (Castor oil)
• Flex Foam: Mixture of Polyetherpolyols + NOP (+ water)
• Palm-based, Soy-based, Castor Oil-based, etc.
• Mixtures of Polyetherpolyols (EO-rich/PO-rich) or
Polyesterpolyol/Polyetherpolyol
Different polarity leads to formation of 2 (or multi) phase system
 Task: Improve the Miscibility or “Compatibility” of Polyols
 Longer shelf life for systems containing NOPs
 Form a stable emulsion (with low water content)

Seite | 7
Solubility of NOP’s
Creates a Challenge

Unmodified NOP’s are Not Soluble in Aromatic Polyesterpolyols

8
Even Modified NOP’s Display
Limited Solubility!

Polyester-
99:1 95:5 90:10 80:20 50:50 NOP Type
polyol
Phthalic Anhydride

PA 1 + A Castor Oil

PA1 B mod. Soybean Oil

PA1 + B' mod. Soybean Oil

PA1 + + + + C mod. Soybean Oil

PA1 + + + + + C' mod. Soybean Oil

DMT 1 + A Castor Oil

DMT-based

DMT 1 B mod. Soybean Oil

DMT 1 B' mod. Soybean Oil

DMT 1 + C mod. Soybean Oil

DMT 1 + C' mod. Soybean Oil

PET 1 A Castor Oil

PET- based

PET 1 B mod. Soybean Oil

PET 1 B' mod. Soybean Oil

PET 1 C mod. Soybean Oil

PET 1 C' mod. Soybean Oil

9
Polarity Differences Result in
Poor Compatibility
Castor oil O

H2C O CH3
- hydrophobic O
OH
HC O CH3
O
OH
H2C O CH3
OH

hydrophilic
Arom. polyester polyol O O segments
O
HO O O O
- hydrophilic O H

Polyether polyol R R R
H hydrophobic
- hydrophilic H2C O O O n O
R R R segments
H
HC O O O O
n
R R R
H
H2C O O O O
n 10
Emulsifier Support Stable Emulsions

Primary- Coalesence
Emulsion Breaking

Emulsifier impact on the emulsification process:

• Coalescence is prohibited by a protecting layer of surfactant
molecules at the interface

• Emulsification
- requires less mixing energy,
- is faster and finer and
- the emulsion stability is increased !

11
 1. Introduction
2. Difficult Mixtures with NOPs
3. Macromolecular Approach
4. Particle Approach
5. Conclusions

Seite | 12
1. Evonik Goldsch midt

Polyureth ane Additives

for Spray Foam
Conventional Emulsifiers Fail
to Stabilize !
Mixtures with 20% NOP A (Castor Oil),
Mixtures with 20% NOP A (Castor Oil),
76% PA 1 (Ester Polyol)
76% PA 1 (Ester Polyol)
4% Emulsifier
4% Emulsifier

Emulsifier / Surfactant Structure at 40°C at RT

O O H
H O O
n m n
EO-PO-EO < 4h <1d
O O H
H O O
n m n
EO-BO-EO < 4h <1d
SO3Na

Alkylsulfonate < 4h <1d

CH 3 CH 3
(H 3C)3Si O Si O Si O Si(CH 3)3
CH 3 n (CH 2) 3
O
C2 H4 x
O
C3 H6 y
OR m
PES < 4h <1d

Ortegol CPL 2 20-24 h > 14 d 13

NOP & Polyester Blend Stability
- Freshly Mixed -

None EO-PO-EO Ortegol CPL 2

14
NOP & Polyester Blend Stability
- 1 h after mixing -

None EO-PO-EO Ortegol CPL 2

15
NOP & Polyester Blend Stability
- 2h after mixing -
None EO-PO-EO Ortegol CPL 2

16
Novel Surfactant Boost Emulsion
Stability

Surfactant:
Surfactant:

conventional
Ortegol CPL 2

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Novel Surfactant Boost Emulsion
Stability

Surfactant:

Ortegol CPL 2

18
Conventional Emulsifiers Lack
Coalescence Prevention

The physiochemical background:

Repulsive forces pull surfactants with “mobility” to lower stress areas

19
Conventional Emulsifiers Lack
Coalescence Prevention

20
Conventional Emulsifiers Lack
Coalescence Prevention

21
Conventional Emulsifiers Lack
Coalescence Prevention

22
New Emulsifier Technology
Clusters to Reduce Coalenscence !

The physicochemical background:

Ortegols CPL 2 features high surface activity & substantially
reduced mobility

23
System Stability a Challenge for
Spray Foam Applications
Fine & Stable Polyol Premix / System

Polyol

NOP

24
 Example: Wall Spray Foam (8kg/m3)
The Experimental Setup

Spray System #1 – PET based Spray System #2 – PA based

Polyethylene Terephthalate Polyester 25.0 Phthalic Anhydide Polyester 25.0

Mannich-based Polyether Polyol 10.0 Mannich-based Polyether Polyol 10.0

Sucrose Initiated Polyether Polyol 5.0 Sucrose Initiated Polyether Polyol 5.0

Flame Retardants 30.0 Flame Retardants 30.0

Catalysts 8.5 Catalysts 8.5
Tegostab B8589 2.5 Tegostab B8589 2.5
Water 19.0 Water 19.0

Polymeric MDI 1:1 ratio Polymeric MDI 1:1 ratio

NOP Vegetable oil Chemical OH number functionality

modification
A Castor oil NO 200 -250 3
B Soybean oil YES 200 -230 >3
C Soybean oil YES 220 -250 >3

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Establishing New Limits with Ortegol CPL 2
< 30 Day Resin Side Stability >

Spray NOP
Surfactant
Emulsifier Max % replacement of Polyester
System (Tegostab B8589)

#1 none 2.0 pphp None < 5%

A 2.0 pphp Ort. CPL 2 45%

A 2.0 pphp II 10%
A 2.0 pphp III < 5%
A 2.0 pphp IV < 5%

#1 none 2.0 pphp None < 5%

B 2.0 pphp Ort. CPL 2 25%
B 2.0 pphp II < 5%
B 2.0 pphp III < 5%
B 2.0 pphp IV < 5%

#1 none 2.0 pphp None < 5%

C 2.0 pphp Ort. CPL 2 30%
C 2.0 pphp II 10%
C 2.0 pphp III < 5%
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C 2.0 pphp IV < 5%
Establishing New Limits with Ortegol CPL 2
< 30 Day Resin Side Stability >

Spray NOP
Surfactant
Emulsifier Max % replacement of Polyester
System (Tegostab B8589)

#2 none 2.0 pphp None < 5%

A 2.0 pphp Ort. CPL 2 15%

A 2.0 pphp II 10%
A 2.0 pphp III < 5%
A 2.0 pphp IV < 5%

#2 none 2.0 pphp None < 5%

B 2.0 pphp Ort. CPL 2 25%
B 2.0 pphp II < 5%
B 2.0 pphp III < 5%
B 2.0 pphp IV < 5%

#2 none 2.0 pphp None < 5%

C 2.0 pphp Ort. CPL 2 15%
C 2.0 pphp II < 5%
C 2.0 pphp III < 5%
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C 2.0 pphp IV < 5%
 1. Introduction
2. Difficult Mixtures with NOPs
3. Macromolecular Approach
4. Particle Approach
5. Conclusions

Seite | 28
1. Evonik Goldsch midt

Polyureth ane Additives

for Spray Foam
Going beyond molecules

Solid particles with surface active properties

Water-based mixtures known as “Pickering” emulsions
• Very stable water based emulsions are known
Particles need to have the right surface tension
Coalesence of droplets is further reduced
Tasks:
• Find appropriate particles for Polyol mixtures
• Easy to handle products are needed

Seite | 29
Particles as Surfactant
– How can this work?

The physicochemical background:

Particles are sitting at the interfacial surface and prohibit coalesence

Seite | 30
 Particles as Compatibilizers –
Storage Results

No Particle
Polyol mixtures Ratio Additive Addtive shelf life

Polyester Polyol (PA 1)/Castor Oil 80/20 < 1d 3% >14 d

Polyester Polyol (PET 1)/Castor Oil 80/20 < 1d 2% >14 d

Polyether Polyol / NOP / Water 50/50/4 < 1d 2% >7 d

Good storage stability can be achieved with particles as emulsifiers!

Seite | 31
Particles as Compatibilizers –
Storage Results
Storage of a blend: Polyetherpolyol/NOP/Water = 50/50/4
Result after 24 hours

With
Without
Particle
additives
Additive

Seite | 32
Particles as Compatibilizers –
Foam Results in Flex Foam

Formulation containing NOP

Polyetherpolyol 50.0
NOP 50.0
Water 4.0
Methylene chloride 2.5
TEGOSTAB BF 2370 1.0
DMEA 0.2
Kosmos 29 0.2
TDI (T-80) 62.0

Seite | 33
Particles as Compatibilizers –
Foam Results in Flex Foam

No Particle
Foaming result Additive Additive
Blow Off weak weak
Rise Time 195 sec 193 sec
Settling - 0.1 cm - 0.1 cm

Porosity (back pressure) 44 mm 23mm

NO disadvantages in foaming caused by particles!

Seite | 34
 1. Introduction
2. Difficult Mixtures with NOPs
3. Macromolecular Approach
4. Particle Approach
5. Conclusions

Seite | 35
1. Evonik Goldsch midt

Polyureth ane Additives

for Spray Foam
Conclusions:

The solubility & compatibility limitations of NOPs are real and

can have a profound impact on final foam performance.

Even “modified-NOPs” have their limitations.

To better utilize NOP technology one must first create a uniform state
(resin blend/reaction mixture).

Macromolecules like Ortegol CPL 2 can support the use of NOP technology

Specially designed particles show promissing results

Helping to create a uniform resin blend (fine & homogeneous emulsion)

Improved resin blend stability (days not hours)

Maximize NOP usage – from a system compatibility standpoint

Also applicable to non-NOP miscibility problems

Ongoing work: Particle Design and Product Development

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