Keith A. Nelson, Principal Scientist Nestor P. Hansen, Manager, Adhesive Applications. ASC Convention & Expo April 4, 2017

Size: px

Start display at page:

Download "Keith A. Nelson, Principal Scientist Nestor P. Hansen, Manager, Adhesive Applications. ASC Convention & Expo April 4, 2017"

Patricia Crawford
5 years ago
Views:

1 ββ-fanesene-based TACKIFIES Keith A. Nelson, Principal Scientist Nestor P. Hansen, Manager, Adhesive Applications ASC Convention & Expo April 4, 2017

FOM HYDOCABONS TO SPECIALTIES Gas Ethylene Polyethylene Crude Oil Production Ethane cracker efinery Propylene Polypropylene FCC LPG or Light Naphtha Steamcracker Butadiene Piperylene C4

2 FOM HYDOCABONS TO SPECIALTIES Gas Ethylene Polyethylene Crude Oil Production Ethane cracker efinery Propylene Polypropylene FCC LPG or Light Naphtha Steamcracker Butadiene Piperylene C4 Products C5 Products EFOME Heavy Naphtha Pyrolysis Gasolines Benzene Styrene Styrene Products Toluene Xylenes Paraxylene β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

LONG TEM ENVIONMENT Longer term &D Projects must predict a new environment and

NPD must take into account the realities of steam cracker output and feed

on-purpose routes Isoprene by-product On purpose Phenol by-product Bio-derived

3 LONG TEM ENVIONMENT Longer term &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 OTHE Light cracking objective Cracking & on-purpose routes Isoprene by-product On purpose Phenol by-product Bio-derived Feedstocks (replacement and new) β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

FANESENE BIOSYNTHESIS Developed by Amyris, yeast has

Technically specified feed stock - Higher molecular

C5 hydrocarbons β farnesene YEAST CELL ISOPENOID

SOUCE Additional reactive double bonds suggests novel

4 FANESENE 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 β farnesene YEAST CELL ISOPENOID PATHWAY eactive moiety comparable to isoprene SUGA SOUCE Additional reactive double bonds suggests novel structure-property profile β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

Aromatics: Styrene, α-methyl styrene Complex polymerization mechanisms lead to a wide structural variety

5 CATIONIC F-C POLYMEIZATION 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 trans-1,3-pentadiene (trans-pips) AlCl 3 cis-1,3-pentadiene (trans-pips) 2-Methyl-2-butene β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

6 CATIONIC F-C FANESENE POLYMEIZATION Farnesene adds new mechanistic routes to an already complex process β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

7 FANESENE 1H NM β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

8 1H NM 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 β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

9 13C NM Observed Chemical Shifts Methine Methylene Methyl Farnesene 13C DEPT β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

10 13C NM 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 β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

11 NEW PODUCT DEVELOPMENT Target: A functional equivalent of a commercially available, aromaticmodified, medium softening point resin Design of Experiments used to determine optimal resin composition and properties - Presented at the ASC Spring, 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) C (300 F) - Shear Adhesion Failure Temperature (SAFT) on stainless steel β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

12 NEW PODUCT 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 Lab Plant β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

13 ADHESIVE EVALUATIONS The farnesene resin (Farnesene30) was evaluated in a general purpose Hot Melt Pressure Sensitive Adhesive (HMPSA) A commercial aromatic modified C5 resins (esin C5/C9) was used as the control Adhesives were mixed batch-wise in a sigma-blade mixer under N 2 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 Formulation Component Weight % SIS 40 esin 50 Oil 10 Testing PSTC-1 Peel Adhesion PSTC-5 Quick Stick PSTC-7 Shear Adhesion PSTC-16 Loop Tack PSTC-17 SAFT β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

14 ADHESIVE PEFOMANCE - 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 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 Pounds PSTC-16 Loop Tack Commercial C5/C9 Farnesene30 Loop Tack, Stainless Steel Loop Tack, HDPE PSTC-5 Quick Stick Commercial C5/C9 Farnesene30 Quick Stick, Stainless Steel Quick Stick, HDPE β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

15 ADHESIVE PEFOMANCE PEEL & SAFT The Peel Adhesion for the Farnesene containing adhesive is significantly higher than for the control. Pounds PSTC-101 Peel Adhesion 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 C 0.0 Commercial C5/C9 Farnesene30 Peel Adhesion, Stainless Steel Peel Adhesion, HDPE PSTC-17 SAFT Commercial C5/C9 Farnesene30 SAFT (SS) SAFT (Kraft Paper) β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

16 ADHESIVE PEFOMANCE Adhesive Viscosity 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 Brookfield Viscosity, C Temperature C Commercial C5/C9 Farnesene30 β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

17 Adhesive DMA - Temperature Sweep Adhesive with Commercial C5/C9 (Pa) 10 8 Adhesive with Farnesene Storage modulus (Pa) Loss modulus Tan(delta) tan( ) Temperature ( C) β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

18 Adhesive DMA - Temperature Sweep Tg difference ~ 5 C Adhesive with Commercial C5/C9 Adhesive with Farnesene Tan(delta) tan( ) Temperature ( C) β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

19 Adhesive DMA - Temperature Sweep Storage modulus (Pa) Slightly stiffer and more elastic as indicated by G Adhesive with Commercial C5/C9 Adhesive with Farnesene Temperature ( C) β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

20 Adhesive DMA - Temperature Sweep 10 5 Adhesive with Commercial C5/C9 Adhesive with Farnesene30 Storage modulus (Pa) Loss modulus (Pa) C Difference in crossover temperature Temperature ( C) β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

21 SUMMAY & 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 - esin property differences are evident in the slightly higher adhesive viscosity and adhesive Tg than expected - heological results are consistent with the observed adhesive performance β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

22 ACKNOWLEDGMENTS THANKS! Our sincere appreciation to: W. Paul Boggs for the adhesive data John hys for NM analyses β-farnesene-based Tackifiers, ASC Convention & Expo, April 4,

Viscosity, 25 C. Mn, g/mol. Wingtack

Viscosity, 25 C. Mn, g/mol. Wingtack Wingtack 10 A Unique Liquid Tackifying Resin Benefits Tackifying hydrocarbon resin Low-color liquid resin Broad compatibility Polymeric plasticization Enhanced flexibility Low-temperature tack and adhesion