biobased adhesives and coatings from plant based … adhesives and coatings from plant based...
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Biobased adhesives and coatings from plant based polymers
Xiuzhi Susan Sun
Donghai Wang
Kansas State University
Manhattan, KS USA
European Coatings Conference-Biobased adhesives Feb 21-22, Düsseldorf, Germany
Sustainability
Plants
Amino acidsProteins
Fatty acidsOils
Industrial & Consumer Products
Adhesives & resins, Inks, paints & coating, surfactants & detergents,
tires & rubber goods, transportation fuels, solvents, pharmaceuticals, cosmetics,
Biodegradable polymers, New biotechnology products
CompositesBionano materials,
More ….
SugarCarbohydrates
Fig. 2. Biobased materials and products derived From plants for various applications
Solar energy
X
X X
?
Will We Have to Import These Materials 20 Years Hence ?
Economic Impacts
Comprehensive Bioeconomy Systems Portfolio
Feedstocks: breeding, genetics, production, logistics (i.e.,harvesting, handling, storage); Conversion: green processing, catalysis, fuels and Materials and co-products; Sustainability: life-cycle, land use,soil/water quality,climate change,environment health; Social impacts: farmers’ benefits, public acceptance, stakeholders’ supports …. Also: Develop predictive tools and methods for such systems!
Long Term Goal
Plant
Feed/food
Canned food
Straws
Building stuff
feed
Folk art
Manure
Direct Uses
FermentationChem Segregation
Dry milling
Wine
Drinks
Ethanol
vinegar
Miso
Other acids
Starch
Protein
Lipids
Food ingredient
Coating/sizing
sweeteners
papers
Adhesives
Plastics
substrates
Food ingredient
medicine
adhesives
Paints & inks
Plastics
Coating
Edible oils
detergent
Paint & ink
Diesel
adhesives
Plastics
MedicineSurfactant
Lubricant
Breads
Cakes
Noodles
Crackers
Feed
Chemicals
Fibers
Detergent
Cookies
Flour
Bran Adhesives
Carbon Backbone Building Monomers
Glucose
O
O
O
OO
O
Polysaccharides
HO
R1 C COH
NH2
Fatty Acids Amino Acids
Fat & Oil Protein
H HO O
R2 C C N C COH
NH2 H R1
Protein polymers with various structure and functions
Xanthan gumLinear β-1,4-D-glucose with trisacharide side Chains,
Highly pseudoplastic, rapidly regaining viscosity
Scheme1OH
O
ClCOCOClCH2Cl2;Glycerolpyridine(90%yield)
O
O
OO
O
O
O
O
OO
O
OO
O
OO
O
O
1918
Oleicacid
BH3•THF;H2O2,NaOH(lowyield)
OH
OH
OH
Scheme1OH
O
ClCOCOClCH2Cl2;Glycerolpyridine(90%yield)
O
O
OO
O
O
O
O
OO
O
Scheme1OH
O
ClCOCOClCH2Cl2;Glycerolpyridine(90%yield)
O
O
OO
O
O
O
O
OO
O
OO
O
OO
O
O
1918
Oleicacid
BH3•THF;H2O2,NaOH(lowyield)
OH
OH
OH
Dihydroxylization
Epoxidizedplant oil
Protein Polymers
Proteins are major polymeric materials for food, pharmaceuticals, medical tissue engineering, and industrial products.
Protein hydrophobic interaction has been
considered the most important factor dominating protein surface properties for folding, aggregation, gelling, self-assembly, adhesion, and cohesion properties.
Impact on Potential Applications of Soy Proteins or other proteins
Gelling, Thickeners Emulsification, Surfactants, Coatings, Adhesives Fiber spinning Plastics Protein films Protein based composites Drug delivery Tissue engineering
Electrostatic Potential map of soy glycinin protein. Red color represents high electrostatic potential (more charged and more hydrophilic), the blue color represents low electrostatic potential (less water soluble or more hydrophobic.
A schematic description of hydrophobic interactions and aggregates of soy globular proteins.
Native Protein HBF < ESFrepell HBF = ESFrepell
HBF > ESFrepell HBF >> ESFrepellHBF >0, and
ESFattract > 0
Hydrophobic polypeptide
Hydrophilic polypeptide
βα
A
α'
BA
conglycinin
AB
Bfront view
Glycinin
BAB
AB AA B
side view
B
C
E
20nm50nm
250nm2 μm
II
I
HB/HL=0.22 Im=0.058 pH 5.4
HB/HL=1.8 Im=0.115 pH 5.4
HBF > ESFrepell
HBF >> ESFrepell
Sun, X. S., D. Wang, L. Zhang, X. Mo, Li Zhu, D. Boyle, Macromolecular Bioscience, 2007 (8), 295-303
I
II
100nm 100 nm
100 nm 250 nm
HB/HL=0.22 Im=0.058 pH 4.8 Solid 3%
HB/HL=1.8 Im=0.115 pH 4.8 Solid 38%
HB/HL=1.8 Im=0.115 pH 4.8 Solid 3%
HB/HL=0.22 Im=0.058 pH 4.8 Solid 38%
HBF ~ ESFrepell
HBF > 0, ESFattract >0 HBF ~ ESFrepell
HBF >0, ESFattract >0
Sun, X. S., D. Wang, L. Zhang, X. Mo, Li Zhu, D. Boyle, Macromolecular Bioscience, 2007 (8), 295-303
J. Shera, X. S. Sun, 2009, Biomacromolecules, 10(8): 2201-2206
Design protein model system (KKKFLIVIGSIIKKK) to prove our hypothesis
TEM pH=2.0
TEM pH=12.0
J. Shera, D.Takahashi, A. I. Herrera, O. Prakash, and X. S. Sun, 2010, J, Nanoscience and Nanotechnology, 10, 7981-7987
Model scheme
NMR Modeling structure
K3
Hcore
H
Secondary structures of oligopeptides by Far-UV Circular dichroism (250 µM)
P 2
pH12
pH12
pH6.8
pH6.8
pH2.2
pH2.2
P 1
Secondary structure and adhesion – pH as a trigger
Shen, X., R. Moore, X. Mo, S. J. Frazier, T. Iwamoto, J. M. Tomich and X. S. Sun*, 2006, J of Nanoscience and Nanotechnology 6: 837-844.
KKKFLIVIGSIIKKK pH=12.0
Biobased Adhesives from soy protein polymers Wood products, wood/straw particle boards, feed binders
Packaging sealant glue
With 40% less weight, Tensile strength ~70MPa (1,000 psi) MOR ~45 MPa MOE ~6 GPa
Soy binder was designed for foundry industry, Compressive strength range 2-9 MPa, No odor, no hazardous emission, Good shaking out property, and easier for recycling.
Foundry Binders
Children art works – food color compatible Glassy finish and edible, glue curing fast and wet tacky
It is also compatible with nonfood pigments for paints applications
Children Glues
Glass bottle labeling, other Kraft and plastic packaging and labeling for Food, feed, and pharmacy products.
Labeling binder
Plant Oil Polymers
Fatty Acid Distribution in Various Plant Oils.
Fatty Acid # C: # DB Canola Corn Cottonseed Linseed Olive Palm Rapeseed Soybean High Oleic* Myristic 14:0 0.1 0.1 0.7 0.0 0.0 1.0 0.1 0.1 0.0 Myristoleic 14:1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Palmitic 16:0 4.1 10.9 21.6 5.5 13.7 44.4 3.0 11.0 6.4 Palmitoleic 16:1 0.3 0.2 0.6 0.0 1.2 0.2 0.2 0.1 0.1 Margaric 17:0 0.1 0.1 0.1 0.0 0.0 0.1 0.0 0.0 0.0 Margaroleic 17:1 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 0.0 Stearic 18:0 1.8 2.0 2.6 3.5 2.5 4.1 1.0 4.0 3.1 Oleic 18:1 60.9 25.4 18.6 19.1 71.1 39.3 13.2 23.4 82.6 Linoleic 18:2 21.0 59.6 54.4 15.3 10.0 10.0 13.2 53.2 2.3 Linolenic 18:3 8.8 1.2 0.7 56.6 0.6 0.4 9.0 7.8 3.7 Arachidic 20:0 0.7 0.4 0.3 0.0 0.9 0.3 0.5 0.3 0.2 Gadoleic 20:1 1.0 0.0 0.0 0.0 0.0 0.0 9.0 0.0 0.4 Eicosadienoic 20:2 0.0 0.0 0.0 0.0 0.0 0.0 0.7 0.0 0.0 Behenic 22:0 0.3 0.1 0.2 0.0 0.0 0.1 0.5 0.1 0.3 Erucic 22:1 0.7 0.0 0.0 0.0 0.0 0.0 49.2 0.0 0.1 Lignoceric 24:0 0.2 0.0 0.0 0.0 0.0 0.0 1.2 0.0 0.0 Average # DB/triglyceride 3.9 4.5 3.9 6.6 2.8 1.8 3.8 4.6 3.0 * Genetically engineered high oleic acid content soybean oil (DuPont).
Multiple modifications of plant oils
O
O
OO
O
OOH
OH
OH
O
O
R
Acrylation: Resins
Epoxidation Resins
Esterification: Bio-diesels Cosmetics
Pharmaceuticals Maleinization: Resins
Hydroxylation Resins
RR
O
RR
OHOH
RR
O
O
OH
RR
OOO
OH
Glycerol: Filler
Cosmetics Pharmaceuticals
Application as pressure sensitive adhesives
Adhesion vs. Cohesion
Reference: Gierenz G, Karmann W. Adhesives and Adhesive Tapes. Weinheim: Wiley-VCH: 2011
PSA composition
s
elastomers tackifiers
carriers Others
Natural rubber Acrylics
Styrenic copolymers Polyisobutylene
butyl rubber EVA copolymer
Silicone elastomers etc.
Rosins and derivatives Terpene resins Hydrocarbon resins etc.
Cellophane Polyrpopylene
Polyethylene PET PVC
Paper Foam Cloth
etc.
Plasticizers Stabilizers Fillers Wetting agents Rheology modifers Defoamers Fungicides etc.
PSA compositions
Chemical pathways of epoxidized and hydroxylated triglycerides with phosphoric acid (H3PO4) were revealed using fatty acid methyl esters model system. Besides catalyst function, H3PO4 facilitates phosphate ester linkages. Novel transparent tapes were developed based on this chemistry.
Proposed chemical pathways of plant oil polymers for pressure sensitive adhesives
Reactions of 5 and 6 in the presence of H3PO4: Main product distribution in Polymer-5-6-P,
Model system for analytical analysis - Methyl oleate fatty acid
a: 1H NMR, b: 1H -1H COSY NMR of Polymer-5-6-P; cross-peaks between at δ 4.04 and 3.5 from phosphate ester and its vicinity alcohol; between δ 3.5 and 3.31, 3.22 from ether and its vicinity alcohols
Concentrations of phosphate esters (δ4.07-4.32), ethers (δ 3.54-3.59),and dihydroxide 6 (δ 3.39) in Polymer-5-6-P
O
-(CH2)7 (CH2)7CH3O
-(CH2)7
O
(CH2)4CH3O
-(CH2)7
O O
CH2CH3
OOO
R2O
R3O
R1 O
-(CH2)16CH3, -(CH2)14CH3
HO OH
-(CH2)7 (CH2)7CH3
HO OH
-(CH2)7 (CH2)4CH3
OH OH
HO OH
-(CH2)7
OH OH
CH2CH3
OH OH
Hydroxylate Soybean Oil: R1, R2, R3 = mixtures of:-(CH2)16CH3, -(CH2)14CH3
Epoxidized Soybean Oil: R1, R2, R3 = mixtures of:
"Green processing"One potOne step
Quick reactionSustainable
Enviromentally-friendly
Inexpensivematerials and methods
H3PO4
Soybean Oil-based Pressure-sensitive Adhesive
for Tranparent Tape
O
O
O
O
OP
O
OXO
O
X = H or triglyceride
Ether Cross-Link
phosphate ester Cross-Link
Cross-Link-Structure
Under review in Macromolecules
Soybean oil based transparent resin for tapes and coatings
TGA curve of the ESO PSA Transmittance of the ESO PSA compared to glass, PP, and PE
Thermally Stable, Transparent, Pressure-Sensitive Adhesives from Epoxidized and Dihydroxyl Soybean Oil
Thermally Stable, Transparent, Pressure-Sensitive Adhesives from Epoxidized and Dihydroxyl Soybean Oil
Peel adhesion strength of commercial tapes and the bio-based PSAs controlled by ratio of ESO (1) to DSO (2) and H3PO4
UV-Curable PSA: ESO/DSO/RE based resin: Peel strength N/cm
UV-Curable PSA: ESO/DSO/RE based resin: Tack strength (N/cm), shear strength (min/1 kg)
UV-Curable PSA: ESO/DSO/RE based resin: Storage modulus (G') and loss modulus (G") as a function of frequency sweep (rad/s)
UV-Curable PSA: ESO/DSO/RE based resin: G” vs G’ plots
UV-Curable PSA: ESO/DSO/RE based resin: Glass transition
UV-Curable PSA: ESO/DSO/RE based resin: Thermal stability
DSO Potential Applications
Transparent tapes (scotch tape, duck tape, postit, labeling and packaging tapes)
Films (thin film, coatings, computer screen)
Formulation with other ingredients (hard and soft composites for various uses)
Pilot scale production of Biobased adhesives.
Acknowledgement
Financial Supports: National Science Foundation U.S. Department of Agriculture U.S. Department of Defense U.S. Department of Energy Consortium of Plant Biotechnology Research United Soybean Board Kansas Soybean Commission Industrial Partnerships (...)