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Β-FARNESENE-BASED TACKIFIERSKeith A. Nelson, Principal ScientistNestor P. Hansen, Manager, Adhesive Applications
ASC Convention & ExpoApril 4, 2017
β
FROM HYDROCARBONS TO SPECIALTIES
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 2
LPG or
Light Naphtha
Production
Steamcracker
Ethane cracker
Gas
CrudeOil
Polypropylene
Polyethylene
Styrene Products
Benzene
Styrene
Toluene
ParaxyleneXylenes
Ethylene
REFORMER
Pyrolysis Gasolines
Heavy Naphtha
Butadiene
PropyleneFCC
Refinery
Piperylene
C4 Products
C5 Products
LONG TERM ENVIRONMENT
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 3
● Longer term R&D Projects must predict a new environment and adapt new product development to evolve the product portfolio
● Looking forward, NPD must take into account the realities of steam cracker output and feed availabilities
C2 C3 C4 C5 C9 STY AMS OTHER
Light cracking objective
Bio-derived Feedstocks
(replacement and new)
C2 C3 OTHER
Cracking & on-purpose routes
On purposeIsopreneby-product
Phenol by-product
FARNESENE BIOSYNTHESIS
● Developed by Amyris, yeast has been genetically modified to produce β-farnesene- Technically specified feed stock- Higher molecular weight, boiling point vs. C5 hydrocarbons
● Reactive moiety comparable to isoprene
● Additional reactive double bonds suggests novel structure-property profile
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 4
SUGAR SOURCE
YEAST CELLISOPRENOID PATHWAY
β−farnesene
trans-1,3-Pentadiene (trans-Pips)
cis-1,3-Pentadiene (trans-Pips)
2-Methyl-2-butene
AlCl3
R
R
R R
CATIONIC F-C POLYMERIZATION
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 5
● Hydrocarbon resins are- Low MW, poorly characterized polymers having high glass transition temperatures (Tg)- Monomers
• Diolefins: cis- and trans-pentadienes• Mono-olefins: 2-methyl-2 and/or 2-methyl-1-butene• Aromatics: Styrene, α-methyl styrene
● Complex polymerization mechanisms lead to a wide structural variety
R
R
R+
CATIONIC F-C FARNESENE POLYMERIZATION
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 6
● Farnesene adds new mechanistic routes to an already complex process
R+
R+
R+
R
+
R
R
R
R
R
R+R
R
FARNESENE 1H NMR
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 7
1H NMR
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 8
● Complex spectrum indicates a wide variety of structures- Singlets at 1.7 and 1.8 ppm suggest presence of unreacted “tail”- Disappearance of peaks at 5 and 6.2 ppm indicate reaction of the
conjugated double bonds
13C NMR
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 9
020406080100120140160
Farnesene 13C DEPT 45°
Observed Chemical Shifts
Methine Methylene Methyl124.0 26.5 15.8124.3 26.6 17.5130.9 31.3 25.5135.1 39.6138.9 112.8146.0 115.5
13C NMR
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 10
● DEPT 45° shows only carbons bonded to hydrogen- Disappearance of peaks at 113, 114, and 146 ppm with the appearance of
a new peak near 124 suggests conversion of the conjugated double bond to a single double bond
- Peaks at 16, 18, and 25 ppm suggest presence of un-reacted “tail”
NEW PRODUCT DEVELOPMENT
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 11
● Target: A functional equivalent of a commercially available, aromatic-modified, medium softening point resin
● Design of Experiments used to determine optimal resin composition and properties- Presented at the ASC Spring, 2016- Box-Behnken design- Monomer ranges (independent variables)
• β-Farnesene: 25 to 35% (% of total reactive monomers)• AMS: 6 to 8% (% of total reactive monomers)• Piperylenes/2MB2 ratio: 1.6 to 2.2
● Dependent variables (adhesive performance)- Glass transition temperature (Tg)- Cross-over temperature (Tx)- Viscosity @ 149° C (300° F)- Shear Adhesion Failure Temperature (SAFT) on stainless steel
NEW PRODUCT DEVELOPMENT
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 12
● Optimal composition predicted by DOE based on adhesive performance targets (dependent variables). - Optimal composition
• Farnesene: 30% of reactive monomers• AMS: 6.5% of reactive monomers
- Physical properties were allowed to “float”
● Two industrial trials have been successfully completed- Softening point and molecular weights of the commercially produced
farnesene resin were slightly above target.
SP (C°) Mn Mw Mz MWD
Predicted 105 840 1560 2900 1.8
Lab 104 990 1780 3200 1.8
Plant 108 1130 2440 4930 2.2
ADHESIVE EVALUATIONS
● The farnesene resin (Farnesene30) was evaluated in a general purpose Hot Melt Pressure Sensitive Adhesive (HMPSA)
● A commercial aromatic modified C5 resins (Resin C5/C9) was used as the control
● Adhesives were mixed batch-wise in a sigma-blade mixer under N2
● Adhesives were coated at 20 µ thick and laminated to 50 µ PET for testing
● Samples were conditioned and tested in a controlled temperature and humidity room
● All testing conformed to PSTC Test Methods
HMPSA FormulationComponent Weight %SIS 40Resin 50Oil 10
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 13
TestingPSTC-1 Peel AdhesionPSTC-5 Quick StickPSTC-7 Shear AdhesionPSTC-16 Loop TackPSTC-17 SAFT
ADHESIVE PERFORMANCE - TACK
● For adhesives made with both resins the Loop Tack was essentially equivalent.- Loop Tack Values off SS and HDPE
were within 1 standard deviation of each other
- 0.3 lbs for SS, 0.1 lbs for HDPE● The difference of 0.5 lbs in Quick
Stick off of SS is slightly larger than the standard deviation of 0.2 lbs- Most of the previous testing did not
show this large of a difference between adhesives
● The Quick Stick off of HDPE is essentially equivalent as it is within the standard deviation of the testing
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 14
0.0
0.5
1.0
1.5
2.0
2.5
Commercial C5/C9 Farnesene30
PSTC-5 Quick Stick
Quick Stick, Stainless Steel Quick Stick, HDPE
0.0
1.0
2.0
3.0
4.0
5.0
Commercial C5/C9 Farnesene30
Poun
ds
PSTC-16 Loop Tack
Loop Tack, Stainless Steel Loop Tack, HDPE
ADHESIVE PERFORMANCE – PEEL & SAFT
● The Peel Adhesion for the Farnesene containing adhesive is significantly higher than for the control.
● The SAFT of the Farnesene30 adhesive is essentially the same as the control off of SS
● The SAFT off of Kraft Paper is significantly higher for the farnesene sample- This trend is not unusual and has
been seen in other lots of resin
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 15
01020304050607080
Commercial C5/C9 Farnesene30
°C
PSTC-17 SAFT
SAFT (SS) SAFT (Kraft Paper)
0.0
1.0
2.0
3.0
4.0
5.0
Commercial C5/C9 Farnesene30
Poun
ds
PSTC-101 Peel Adhesion
Peel Adhesion, Stainless Steel Peel Adhesion, HDPE
ADHESIVE PERFORMANCE
● This production lot resulted in an adhesive with a higher viscosity than the control C5/C9- This is a little unusual- Previous batches were more
similar- A result of the higher SP and
MW than the target and control
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 16
1000
10000
100000
1000000
130 140 150 160 170 180
Bro
okfie
ld V
isco
sity
, °C
Temperature °C
Adhesive Viscosity
Commercial C5/C9 Farnesene30
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 17
125-50 -25 0 25 50 75 100
Temperature � (°C)
10 1
10 2
10 3
10 4
10 5
10 6
10 7
10 8
10 9St
orag
e m
odul
us
� (P
a)
Loss
mod
ulus
�
(Pa)
3.0
0.0
0.3
0.6
0.9
1.2
1.5
1.8
2.1
2.4
2.7
Tan(delta) tan(�)
Adhesive with Commercial C5/C9
Adhesive with Farnesene30
Adhesive DMA - Temperature Sweep
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 18
75-50 -25 0 25 50
Temperature � (°C)
3.0
0.0
0.3
0.6
0.9
1.2
1.5
1.8
2.1
2.4
2.7
Tan(delta) tan(�)
Adhesive with Commercial C5/C9
Adhesive with Farnesene30
Adhesive DMA - Temperature Sweep
Tg difference ~ 5 °C
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 19
125-50 -25 0 25 50 75 100
Temperature � (°C)
10 2
10 3
10 4
10 5
10 6
10 7
10 8
10 9St
orag
e m
odul
us
� (P
a)
Adhesive with Commercial C5/C9
Adhesive with Farnesene30
Adhesive DMA - Temperature Sweep
Slightly “stiffer” and more elastic as indicated by G’
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 20
12575 100
Temperature � (°C)
10 3
10 4
10 5
Stor
age
mod
ulus
�
(Pa)
Lo
ss m
odul
us
� (P
a)
Adhesive with Commercial C5/C9
Adhesive with Farnesene30
Adhesive DMA - Temperature Sweep
2 °C Difference in crossover temperature
SUMMARY & CONCLUSIONS
● Successfully developed a hydrocarbon resin containing a significant amount of sustainable feedstock, β-Farnesene
● The physical properties of the commercially produced resin are close to targets… - Commercially produced resin had slightly higher SP, mw, and Tg than the
laboratory produced resin
● But yet yielded a HM PSA with surprisingly similar performance- Resin property differences are evident in the slightly higher adhesive
viscosity and adhesive Tg than expected- Rheological results are consistent with the observed adhesive
performance
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 21
ACKNOWLEDGMENTS
β-Farnesene-Based Tackifiers, ASC Convention & Expo, April 4, 2017 22
THANKS!
Our sincere appreciation to: • W. Paul Boggs for the adhesive data
• John Rhys for NMR analyses