CONCENTROL has conducted a study on 15 new surfactants used in formulations of rigid polyurethane foams to analyze the effect of the reactivity of the surfactant on their properties.

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RIGID FOAM ADDITIVES
Effect of the silicone surfactant
reactivity on the properties of
rigid polyurethane foams
Josep Nadal
Technical Manager for PU Additives

3. 1.- INTRODUCTION
2.- EXPERIMENTALS AND RESULTS
3.- CONCLUSIONS
UTECH North America 2016

4. 1.- INTRODUCTION
2.- EXPERIMENTALS AND RESULTS
3.- CONCLUSIONS
UTECH North America 2016

5. Rigid polyurethane (PU) foam is one of the best thermal insulation material
Applications are wide:
- Appliances: Domestic refrigerators and freezers, hot water tanks
- Building industry: Sandwich panels (walls and roofing panels), insulating boards,
slabstock or 2K spray in place.
- Industrial: tanks and containers insulation, pipe lines
Besides thermal insulation performance, other requirements have to be taken into account:
- flammability performance
- adhesion to different facing materials
- dimensional stability
UTECH North America 2016
1.- INTRODUCTION
Silicone surfactants play a substantial role on the foam properties

6. Silicone surfactants are silicone-polyether copolymers
UTECH North America 2016
1.- INTRODUCTION
EO
PO
PDMS

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reactivity (R) of some surfactants
1.- INTRODUCTION
Silicone surfactants are silicone-polyether copolymers

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Non-capped: -OH
Capped: -OCH3
Capped: -OCOCH3
1.- INTRODUCTION
Silicone surfactants are silicone-polyether copolymers
reactivity (R) of some surfactants

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CAPPED OH number
(mg KOH/g)
ISO
REACTIVITY
COST HYDROLITIC STABILITY
-OH varied ü $ ü
-OCH3 ü < 10 $ $ $ ü
-OCOCH3 ü < 10 $ $ $
CAPPED OH number
(mg KOH/g)
APPLICATIONS
-OH varied General purpose: lamination, appliances, spray,
block, high density, etc.
-OCH3 ü < 10 Specific: OCF, spray, lamination
-OCOCH3 ü < 10 Very specific: lamination
1.- INTRODUCTION
Is reactivity important (COST, ISO REACTIVITY, etc.)
?

10. UTECH North America 2016
CAPPED OH number
(mg KOH/g)
APPLICATIONS
-OH varied General purpose: lamination, appliances, spray,
block, high density, etc.
-OCH3 ü < 10 Specific: OCF, spray, lamination
-OCOCH3 ü < 10 Very specific: lamination
1.- INTRODUCTION
HAS THE REACTIVITY OF SILICONE
SURFACTANTS A MAJOR IMPACT IN A
PUR/PIR FORMULATION FOR
LAMINATION?

11. 1.- INTRODUCTION
2.- EXPERIMENTALS AND RESULTS
3.- CONCLUSIONS
UTECH North America 2016

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ü In the first part we will present new surfactants where the only difference is the
capping group (synthesis and characterization).
Polarity (cloud point analysis)
Infrared spectra
Molecular Weight by SEC
1H-NMR
ü In the second part, physical analysis of the foams prepared with the previously
synthesized surfactants will be shown. The aim is to establish trends which link the
chemical structure with the physical parameters analyzed.
Lambda values
Fire properties
Dimensional stability measurements
General appearance
2.- EXPERIMENTALS AND RESULTS

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2.- EXPERIMENTALS AND RESULTS
SYNTHESIS
and
CHARACTERIZATION
of
NEW SURFACTANTS

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POLYSILOXANE POLYETHER (EO %)
MW RAMIFICATION VERY HIGH EO HIGH EO MEDIUM EO
LOW
MEDIUM
HIGH
MEDIUM
LOW
MEDIUM
HIGH LOW
2.- EXPERIMENTALS AND RESULTS
TABLE OF COMPOSITIONS
Usual structures of surfactants for lamination

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POLYSILOXANE POLYETHER (EO %)
MW RAMIFICATION VERY HIGH EO HIGH EO MEDIUM EO
LOW
MEDIUM
U-110
U-111
U-112
HIGH
U-120
U-121
U-122
MEDIUM
LOW
U-210
U-211
U-212
MEDIUM
U-220
U-221
U-222
HIGH LOW
U-310
U-311
U-312
OH hydroxyl OCH3 methoxy OCOCH3 acetoxy
2.- EXPERIMENTALS AND RESULTS
TABLE OF COMPOSITIONS (15 EXPERIMENTAL NEW SURFACTANTS)

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SURFACTANT CLOUD POINT
(4% water)
U-110 158ºF (70ºC)
U-111 100ºF (38ºC)
U-112 129ºF (54ºC)
U-120 187ºF (86ºC)
U-121 124ºF (51ºC)
U-122 145ºF (63ºC)
HIGH EO %
SURFACTANT CLOUD POINT
(4% water)
U-210 104ºF (40ºC)
U-211 77ºF (25ºC)
U-212 88ºF (31ºC)
U-220 140ºF (60ºC)
U-221 127ºF (53ºC)
U-222 114ºF (46ºC)
MEDIUM EO %
SURFACTANT CLOUD POINT
(4% water)
U-310 100ºF (38ºC)
U-311 100ºF (38ºC)
U-312 97ºF (36ºC)
LOW EO %
2.- EXPERIMENTALS AND RESULTS
SURFACTANT ANALYSIS (POLARITY – CLOUD POINT)
OH hydroxyl OCH3 methoxy OCOCH3 acetoxy

17. 0
10
20
30
40
50
60
70
80
90
100
CP (ºC)
EO %
UTECH North America 2016
2.- EXPERIMENTALS AND RESULTS
- +
REMARKS
1) CAPPED surfactants
show lower CP
2) Higher is the
ramification, higher is
the CP
3) No measured
relation between
surfactant MW and CP
SURFACTANT ANALYSIS (POLARITY – CLOUD POINT)

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OH hydroxyl
OCH3 methoxy
OCOCH3 acetoxy
2.- EXPERIMENTALS AND RESULTS
SURFACTANT ANALYSIS (INFRARED SPECTROSCOPY)

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2.- EXPERIMENTALS AND RESULTS
OH hydroxyl
OCH3 methoxy
OCOCH3 acetoxy
SURFACTANT ANALYSIS (INFRARED SPECTROSCOPY)

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2.- EXPERIMENTALS AND RESULTS
OH hydroxyl
OCH3 methoxy
OCOCH3 acetoxy
SURFACTANT ANALYSIS (INFRARED SPECTROSCOPY)

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2.- EXPERIMENTALS AND RESULTS
SURFACTANT ANALYSIS (MW MEASUREMENTS – SEC)
Low MW
Medium MW
High MW

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2.- EXPERIMENTALS AND RESULTS
SURFACTANT ANALYSIS
(1H-NMR)
OCH3 methoxy

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2.- EXPERIMENTALS AND RESULTS
OCOCH3 acetoxy
SURFACTANT ANALYSIS
(1H-NMR)

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ü first part summary.
Using 4 different analytical techniques, accurate characterization can be obtained
of all the 15 new surfactants
Polarity (cloud point analysis)
Infrared spectra
Molecular Weight by SEC
1H-NMR
2.- EXPERIMENTALS AND RESULTS

25. RIGID PU FOAM
ANALYSIS
UTECH North America 2016
2.- EXPERIMENTALS AND RESULTS

26. FORMULATION
PUR/PIR formulation with pentaneas blowing agent
UTECH North America 2016
2.- EXPERIMENTALS AND RESULTS
% pphp
Polyester-polyol 23 90,2
Polyether polyol (long chain) 2,5 9,8
PMDI 64 251
TCPP 4 15,7
SURFACTANT 1 3,92
K-octoate catalyst 1,3 5,1
Amine catalyst (DMCHA) 0,3 1,18
Water 0,5 1,96
Pentane (iso 75% - n 25%) 3,8 14,9

27. FOAM MEASUREMENTS (GENERAL ASPECT)
UTECH North America 2016
2.- EXPERIMENTALS AND RESULTS
-OH
HYDROXYL
U-110 (2) U-120 (5) U-210 (8) U-220 (11) U-310 (14)
-OCH3
METHOXY
U-111 (3) U-121 (6) U-211 (9) U-221 (12) U-311 (15)
-OCOCH3
ACETOXY
U-112 (4) U-122 (7) U-212 (10) U-222 (13) U-312 (16)

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2.- EXPERIMENTALS AND RESULTS
-OH
HYDROXYL
U-110 (2) U-120 (5) U-210 (8) U-220 (11) U-310 (14)
-OCH3
METHOXY
U-111 (3) U-121 (6) U-211 (9) U-221 (12) U-311 (15)
-OCOCH3
ACETOXY
U-112 (4) U-122 (7) U-212 (10) U-222 (13) U-312 (16)
Low MW surfactants with
very high EO content
Bad performance
Capping group has no
clear effect
Ramification Medium High
FOAM MEASUREMENTS (GENERAL ASPECT)

29. UTECH North America 2016
2.- EXPERIMENTALS AND RESULTS
-OH
HYDROXYL
U-110 (2) U-120 (5) U-210 (8) U-220 (11) U-310 (14)
-OCH3
METHOXY
U-111 (3) U-121 (6) U-211 (9) U-221 (12) U-311 (15)
-OCOCH3
ACETOXY
U-112 (4) U-122 (7) U-212 (10) U-222 (13) U-312 (16)
U-120 (5) U-210 (8) U-220 (11) U-310 (14)
U-121 (6) U-211 (9) U-221 (12) U-311 (15)
U-122 (7) U-212 (10) U-222 (13) U-312 (16)
Medium MW surfactants with
high EO content
Acceptable performance
Capping group has no
clear effect
No benefit is observed
Ramification Low Medium
FOAM MEASUREMENTS (GENERAL ASPECT)

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2.- EXPERIMENTALS AND RESULTS
-OH
HYDROXYL
U-110 (2) U-120 (5) U-210 (8) U-220 (11) U-310 (14)
-OCH3
METHOXY
U-111 (3) U-121 (6) U-211 (9) U-221 (12) U-311 (15)
-OCOCH3
ACETOXY
U-112 (4) U-122 (7) U-212 (10) U-222 (13) U-312 (16)
U-220 (11) U-310 (14)
U-221 (12) U-311 (15)
U-222 (13) U-312 (16)
High MW surfactants with
medium EO content
Very good performance
Capping group has no
clear effect
No benefit is observed
Ramification Low
FOAM MEASUREMENTS (GENERAL ASPECT)

31. FOAM MEASUREMENTS (DIMENSIONAL STABILITY)
UTECH North America 2016
OH hydroxyl OCH3 methoxy OCOCH3 acetoxy
2.- EXPERIMENTALS AND RESULTS
0,00
0,50
1,00
1,50
2,00
2,50
3,00
3,50
compression
(Kg/cm2)
parallel compression
vertical compression

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OH hydroxyl OCH3 methoxy OCOCH3 acetoxy
2.- EXPERIMENTALS AND RESULTS
0,00
0,50
1,00
1,50
2,00
2,50
3,00
3,50
compression
(Kg/cm2)
parallel compression
vertical compression
FOAM MEASUREMENTS (DIMENSIONAL STABILITY)

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OH hydroxyl OCH3 methoxy OCOCH3 acetoxy
2.- EXPERIMENTALS AND RESULTS
0,00
0,50
1,00
1,50
2,00
2,50
3,00
3,50
compression
(Kg/cm2)
Compression values are
more related to
surfactant composition
(EO, PO, Siloxane %)
Rather that influence of
capping
parallel compression
vertical compression
FOAM MEASUREMENTS (DIMENSIONAL STABILITY)

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OH hydroxyl OCH3 methoxy OCOCH3 acetoxy
2.- EXPERIMENTALS AND RESULTS
26
27
28
29
30
31
32
33
34
density (Kg/m3)
density
High degree of variability
D (OH) = 1,86 lb/ft3 (29,8 kg/m3)
D (OCH3) = 1,89 lb/ft3 (30,2 kg/m3)
D (OCOCH3) = 1,87 lb/ft3 (29,9 kg/m3)
No tendency is observed
FOAM MEASUREMENTS (DENSITY)
average

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2.- EXPERIMENTALS AND RESULTS
0,00
1,00
2,00
3,00
4,00
5,00
6,00
inches B2 test (DIN 4102)
In all cases, flammability
results are well above the
maximum established by B2
Test (DIN 4102)
PIR formulation
15,7 pphp TCPP
FOAM MEASUREMENTS (FLAMMABILITY – B2 TEST)

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2.- EXPERIMENTALS AND RESULTS
10,00
15,00
20,00
25,00
30,00
35,00
U-110
U-111
U-112
U-120
U-121
U-122
U-210
U-211
U-212
U-220
U-221
U-222
U-310
U-311
U-312
mW/mK Lambda value/ thermal conductivity (λ)
Thermal conductivity
decreases with higher MW
surfactants with lower EO
content
No direct relation with the
capping group
AGED
RECENT
FOAM MEASUREMENTS (THERMAL CONDUCTIVITY-LAMBDA)

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3.- CONCLUSIONS
IN THE CHOSEN PUR/PIR FORMULATION FOR LAMINATION, BIGGER
DIFFERENCES IN PERFORMANCE HAD BEEN SEEN RELATED TO
THE CHEMICAL COMPOSITION OF THE SURFACTANT
(EO, PO, SILOXANE %) RATHER THAN THE EFFECT OF THE CAPPING GROUP
HAS THE REACTIVITY OF SILICONE
SURFACTANTS A MAJOR IMPACT IN A
PUR/PIR FORMULATION FOR
LAMINATION?

38. UTECH North America 2016
Thank you for your time.
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