new modified liquid pure mdi for case applications
TRANSCRIPT
New Modified Liquid Pure MDI for CASE Applications
Katie L. Skok and Roeland J. TuinmanAuburn Hills, Michigan
Polyurethanes
Latest Innovations
Huntsman has developed a new “liquid” pure MDI isocyanate SUPRASEC 9561.
Benefits include: Improved long term shelf
stability Improved low temp stability Extended clarity Maintain physical properties in
a variety of elastomer formulations
Polyurethanes
Outline
Overview of “liquid” pure technology Properties of Huntsman’s “liquid” pure type
isocyanates Temperature Stability Dimer and Haze determination Elastomer physical properties and reactivities Final comments and conclusions Acknowledgements
Your “ACE” Polyurethanes Specialists for the C.A.S.E. Markets
Polyurethanes
Liquid Pure Background
4,4’-MDI is a solid at room temp Difficult to handle Expensive to transport Safety concerns for melt out
Quasi-prepolymer techniques
2,4’-MDI modifications
Carbodiimide modifications
Other novel methods
Solid4,4’-MDI
Liquid 4,4’-MDI
CH2 NCOOCN
Polyurethanes
Typical Properties
H-High, M-Medium, L-Low
100016.118LL31.8Rubinate 9433
130015.730LL31.0Rubinate 9225
130016.233MM29.2Competitor
130015.936MM29.3Suprasec 9561
150015.840HH29.6Rubinate 1680
Prepol Visc. cps, 25ºC
Prepol NCO%
Visc. cps, 25ºCFn
4,4' IsomerNCO%
Prepols were reacted down to 16% NCO with Jeffol PPG 2000
Polyurethanes
Dimer and Haze Determination
Dimer Aromatic isocyanates undergo dimerization to form
uretidinedione Dimer is a white crystal that often precipitates out of the
product
% Haze % Haze helps quantify the clarity of the MDI A product that is hazy may appear cloudy Haziness in a product can often indicate shelf stability
concerns
Polyurethanes
Dimer Determination
% Dimer vs Time at 50°C
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Days
% D
imer
RUBINATE1680
RUBINATE9225
RUBINATE9433
SUPRASEC9561
Competitor
Suprasec 9561 forms dimer at a similar rate to Rubinate 1680
Suprasec 9561
Rubinate 1680
Polyurethanes
% Haze
% Haze vs Time at 25°C
0
10
20
30
40
50
60
70
80
90
100
0 10 20 30 40 50 60 70
Days
% H
aze
RUBINATE1680
RUBINATE9225
RUBINATE9433
SUPRASEC9561
Competitor
Suprasec 9561 showed the lowest % Haze
Suprasec 9561
Polyurethanes
% Haze
% Haze vs Time at 50°C
0
10
20
30
40
50
60
70
80
90
0 10 20 30 40 50 60 70
Days
% H
aze
RUBINATE1680
RUBINATE9225
RUBINATE9433
SUPRASEC9561
Comp
At 50ºC Suprasec 9561 has the lowest % Haze
Suprasec 9561
Polyurethanes
Temperature Study
75% solid25% solid 0°C
50% solid10% solidSmall crystals Small crystals100% solid1°C
90% solid2°C
Chunks form Turning solid3°C
Small crystals Chunks build up4°C
Chunks form Chunks form5°C
Small crystals Small crystals 6°C
7°C
8°C
9°C
10°C
Rubinate 9433Rubinate 9225CompetitorSuprasec 9561Rubinate 1680
Polyurethanes
Temperature Study
Rub 1680Rub 1680
Sup 9561Sup 9561
Comp
Rub 9225
Rub 9433
Comp
Rub 9225
Rub 9433
Room Temp 1ºC
Polyurethanes
Elastomers
Elastomers with 3 variations in hardness levels were evaluated in order to highlight the broad range of properties possible to achieve thru polyol selection.
10
20
60
50
40
75
10
50
10
20
50
40
70
70
80
90
100
Shore OO Shore A Shore D
80
•Shock and vibration dampeners
•Recoil pads
•Comfort applications
•Soft skateboard wheel
•Concrete stamping pad
•Door seals•Solid wheels
•Prototyping molds
•Industrial rollers
Polyurethanes
70 Shore A Elastomers
Polyol blends were degassed prior to use
Components were mixed together via a Flacktek centrifugal mixer for 30 seconds
Parts were casted into a ¼” thick aluminum mold preheated to 45ºC
Parts were allowed to set on the bench top for one week before testing
0.25BYK A 535
0.005Fomrez UL-1
0.25Jeffcat TD 33A
8Ethylene Glycol
91.5Jeffol G-31-35
PbwComponent
Hard block content~31%Index 100
Polyurethanes
Physical Results
70 Shore A Elastomers
0
50
100
150
200
250
R1680 S9561 Comp R9225 R9433
Lb/
In Die C Tear
HH MM MM LL LL
Polyurethanes
Physical Results
70 Shore A Elastomers
0
500
1000
1500
2000
R1680 S9561 Comp R9225 R9433
PSI,
%
Tensile
Elonga tion
HH MM MM LL LL
Polyurethanes
75 Shore OO Elastomers
0.25BYK A 535
0.025Fomrez UL-1
1Jeffcat TD 33A
1Ethylene Glycol
48.9Jeffol PPG 3709
48.9Jeffol G-31-35
PbwComponent
Hard block content~14%Index 105
Polyol blends were degassed prior to use
Components were mixed together via a Flacktek centrifugal mixer for 30 seconds
Parts were casted into a ¼” thick aluminum mold preheated to 45ºC
Parts were allowed to set on the bench top for one week before testing
Polyurethanes
Physical Results
75 Shore OO Elastomers
30
32
34
36
38
40
42
44
R1680 S9561 Comp R9225 R9433
Lb/
In
Die C Tear
MM LL LLHH MM
Polyurethanes
Physical Results
75 Shore OO Elastomers
0
100
200
300
400
500
600
R1680 S 9561 Comp R 9225 R9433
PS
I, % Tensile
Elongation
HH MM MM LL LL
Polyurethanes
80 Shore D Elastomers
0.25BYK A 535
0.01Fomrez UL-1
0.199Jeffcat TD 33A
4.9Ethylene Glycol
94.64Jeffol G-30-240
PbwComponent
Hard block content~47%Index 100
Polyol blends were degassed prior to use
Components were mixed together via a Flacktek centrifugal mixer for 30 seconds
Parts were casted into a ¼” thick aluminum mold preheated to 45ºC
Parts were allowed to set on the bench top for one week before testing
Polyurethanes
Physical Results
80 Shore D Elastomers
0
5
10
15
20
25
R1680 S 9561 Comp R 9225 R9433
Ft-
Lbs
/In
UnnotchedIzod
HH MM MM LL LL
Polyurethanes
Physical Results
80 Shore D Elastomers
39
40
41
42
43
44
45
46
47
48
R1680 S 9561 Comp R 9225 R9433
Tem
p C
Heat DeflectionTemperature @66psi
HH MM MM LL LL
Polyurethanes
80 Shore D Elastomers
DMTA Frequency Sweep at 1Hz Temperature range -100
ºC to 250 ºC Heating rate of 3ºC/min Glass transition
determined at the maximum tan d peak
48.5R 9433, LL
48.6R 9225, LL
51.5Comp, MM
51S 9561, MM
53.1R 1680, HH
Tg
Glass Transition Temp
Polyurethanes
Reactivities
15514475135R 9433, LL
14110072120R 9225, LL
123986090Comp, MM
125925980S 9561, MM
120905571R 1680, HH
80 shore
D
75 shore OO
80 shore
A
70 shore
A
Suprasec 9561 has a gel time just slightly slower than Rubinate 1680
Gel time in seconds
Reactivity slows with lower amounts of 4,4’-isomer
Polyurethanes
Conclusions
SUPRASEC 9561
Improved long term shelf stability
Improved low temp stability
Extended clarity Maintain physical
properties in a variety of elastomer formulations
Polyurethanes
Acknowledgments
Many thanks to:
ACE Team MembersAnita ConwayWeichen ChiAmy Valitutti
AH Physical Testing Group
AH Analytical Testing Group
HATC Analytical Testing Group
