βΒ-FARNESENE-BASED TACKIFIERSmedia.mycrowdwisdom.com.s3.amazonaws.com/asc/2017... · in a...

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


● 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


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


● 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


● 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


1H NMR


● 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


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


● 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


● 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


● 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


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


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


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


01020304050607080


°C

PSTC-17 SAFT

SAFT (SS) SAFT (Kraft Paper)

0.0

1.0

2.0

3.0

4.0

5.0


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


1000

10000

100000

1000000

130 140 150 160 170 180

Bro

okfie

ld V

isco

sity

, °C

Temperature °C

Adhesive Viscosity



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


75-50 -25 0 25 50


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(�)




Tg difference ~ 5 °C


125-50 -25 0 25 50 75 100


10 2

10 3

10 4

10 5

10 6

10 7

10 8

10 9St

orag

e m

odul

us

� (P

a)




Slightly “stiffer” and more elastic as indicated by G’


12575 100


10 3

10 4

10 5

Stor

age

mod

ulus

�

(Pa)

Lo

ss m

odul

us

� (P

a)




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


ACKNOWLEDGMENTS


THANKS!

Our sincere appreciation to: • W. Paul Boggs for the adhesive data

• John Rhys for NMR analyses

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