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 (...)