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Biosourced Raw Materials - Moving the Farm into Polymers

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Biosourced Raw Materials - Moving the Farm into Polymers. Douglas A. Wicks Robert M. Hearin Support Foundation Professor The University of Southern Mississippi. Outline. Overview of Polymer Science Background Examples Generation of ethanol Vegetable Oil Macromonomers - PowerPoint PPT Presentation

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Page 1: Biosourced Raw Materials - Moving the Farm into Polymers
Page 2: Biosourced Raw Materials - Moving the Farm into Polymers

Biosourced Raw Materials - Moving the Farm into

Polymers

Douglas A. WicksRobert M. Hearin Support Foundation ProfessorThe University of Southern Mississippi

Page 3: Biosourced Raw Materials - Moving the Farm into Polymers

OutlineOverview of Polymer ScienceBackgroundExamples

Generation of ethanolVegetable Oil

MacromonomersSoy Bean Composites

Page 4: Biosourced Raw Materials - Moving the Farm into Polymers

School of Polymers and High Performance

Materials at

The University of Southern Mississippi

Page 5: Biosourced Raw Materials - Moving the Farm into Polymers

UndergraduateEducation

GraduateEducation

CommunityOutreach/Education

Research

Graduate Education

• PhD in Polymer Science and Engineering• 80 graduate students• Majority US Citizens• Diverse foreign contingent France, China, S. Africa, Turkey, S. Korea, Spain, Brazil, Columbia, Malaysia, Poland, India, Canada

Page 6: Biosourced Raw Materials - Moving the Farm into Polymers

UndergraduateEducation

GraduateEducation

CommunityOutreach/Education

Research

Undergraduate Education

• BS in Polymer Science• 4 Year degree program • 90 students• Comprehensive program

•Synthesis•Coatings•Processing

• Regionally drawn students•Mississippi, Louisiana, Alabama, Tennessee.

Page 7: Biosourced Raw Materials - Moving the Farm into Polymers

UndergraduateEducation

GraduateEducation

CommunityOutreach/Education

Research

Research Programs

$10MM in external fundingFederalStateIndustrialInternational

National NSF CentersIndustry/Univ. Coop Res CenterMaterials Research Center

Internationally recognized faculty

Page 8: Biosourced Raw Materials - Moving the Farm into Polymers

UndergraduateEducation

GraduateEducation

CommunityOutreach/Education

Research

Outreach Programs

International Coatings and Formulations Institute (ICFI)

Page 9: Biosourced Raw Materials - Moving the Farm into Polymers

CoatingsThames

Evans UrbanWicks Smith

Polymer Processing

HesterMooreMorganOtaigbe

Polymer Science Faculty

Page 10: Biosourced Raw Materials - Moving the Farm into Polymers

Polymer Physics

Synthesis

MauritzHoyleLochheadNazarenko

McCormickMathiasStoreyBoyes

Polymer Science Faculty

Page 11: Biosourced Raw Materials - Moving the Farm into Polymers

Long History of Natural Products in Polymers

Page 12: Biosourced Raw Materials - Moving the Farm into Polymers

Present Project ObjectiveDevelop a concentrated acid hydrolysis process that converts

softwood sawdust into sugars that can be fermented to ethanol.

The process must be economical. - minimize equipment cost

- maximize conversion to sugars

Hester

Page 13: Biosourced Raw Materials - Moving the Farm into Polymers
Page 14: Biosourced Raw Materials - Moving the Farm into Polymers

1 - motor 2 - transmission3 - sawdust feeder4- acid feed port5 - twin screw extruder6 - flow restricting orifice7 - static mixer & water port8 - hydrolysis reactor9 - product cooler 10 – product collector11 - water feed pump12 - acid feed pump13 – computer controller

123

45678910

USM Sawdust To Sugars Mini-Plant

11

12

13

Page 15: Biosourced Raw Materials - Moving the Farm into Polymers

Continuous Film Formation with Solventless Latex

Stage III: Hexagonal packingStage V: Crosslinked Film

Stage I: Aqueous latex Stage II: Close contact particles

Stage IV: Ambient Crosslinking

Thames Research Group

Page 16: Biosourced Raw Materials - Moving the Farm into Polymers

Vegetable Oil Macromonomer

O

O

O

O

O

O

O

O

O

O

O

O

Thames Research Group

Page 17: Biosourced Raw Materials - Moving the Farm into Polymers

Castor Acrylated Monomer(CAM) Acrylate

group reactswith growing

polymerradicals

Alkyl moieties provideinternal plasticization

Residual unsaturationprovides mechanism

forambient cure

O

H3COOO

H H

H H

Thames Research Group

Page 18: Biosourced Raw Materials - Moving the Farm into Polymers

CAM Incorporation Variable Tg (Var-Tg) latexes

MMA:BA ratio held constant, CAM added

Iso-Tg latexes MMA:BA:CAM ratios adjusted to achieve 5°C Tg

0 2 4 6 8 10 12 14 16

2

4

6

8

10

12

14

16

MFT

Tg

Te

mp

era

ture

(°C

)

phm CAM

0 2 4 6 8 10 12 14

2

4

6

8

10

12

14

16

Tg

MFTTe

mp

era

ture

(°C

)

phm CAM

Var-Tg CAM Latexes Iso-Tg CAM Latexes

Page 19: Biosourced Raw Materials - Moving the Farm into Polymers

Textile Latex For Military Uniforms

Thames Research Group

Page 20: Biosourced Raw Materials - Moving the Farm into Polymers

Benefits

Permanent Press UniformsImproved wear resistanceImproved color retentionCost savings

100 Additional Jobs for Mississippi

Thames Research Group

Page 21: Biosourced Raw Materials - Moving the Farm into Polymers

Additional Usage

7,500 uniforms supplied to USAF for field trial

US Army testing permanent press uniforms

Thames Research Group

Page 22: Biosourced Raw Materials - Moving the Farm into Polymers

Environmentally Friendly CompositesComponents

Continuous PhaseSynthetic

Urea-formaldehyde Polyethylene

Agricultural Soybean protein Lignin

ReinforcementsSynthetic

Carbon Glass

Agricultural Plant fibers Wood

Thames Research Group

Page 23: Biosourced Raw Materials - Moving the Farm into Polymers

Commercial Adhesives

Advantages: Rapid cure time Water resistance Cure by crosslinking

Disadvantages: Increasing cost Formaldehyde

emissions

Prominent Adhesives Urea-formaldehyde (UF) Melamine-formaldehyde (MF) Phenol-formaldehyde (PF)

Thames Research Group

Page 24: Biosourced Raw Materials - Moving the Farm into Polymers

Formaldehyde

Toxic compoundInhalationContact with skinIngestion

Irritates all parts of the respiratory system

Thames Research Group

Page 25: Biosourced Raw Materials - Moving the Farm into Polymers

Soybean Adhesive Potential

Alternative to using petroleum resources

BiodegradableRenewableRelative low costEnvironmentally-

friendlyFormaldehyde-free

Thames Research Group

Page 26: Biosourced Raw Materials - Moving the Farm into Polymers

Soybean CompositionCarbohydrates (35%)

Protein (40%)

Oils (20%)

Ash (5%)

http://hubcap.clemson.eduhttp://www.nsrl.uiuc.edu

Thames Research Group

Page 27: Biosourced Raw Materials - Moving the Farm into Polymers

Formaldehyde-Free Biodegradable Wood Composites

RenewableBiodegradableFormaldehyde-free Environmentally-friendly

Page 28: Biosourced Raw Materials - Moving the Farm into Polymers

Future Looking Totally Derived from Crops

                                                                                                                                                                                                                 

Page 29: Biosourced Raw Materials - Moving the Farm into Polymers

PLLA Ionomers -Project Concept

Biodegradable ionomers (polymers containing ions) based on poly(L-lactic acid) (PLLA)

Ion groups raise glass transition temperature

Higher Tg opens new applications in food packaging and food service

Page 30: Biosourced Raw Materials - Moving the Farm into Polymers

Incorporation of Ionic Groups by Copolymerization

115oC, N2 atm

Sn(OBu)2+

O O

OBn

CH3

O

O

O

O

CH3O O

O

CH3OOBn

L,L-lactide MBC

O

O

O

O

O

O

-Caprolactone

O O

O

CH3OOBn

O O

OBn

CH3

O

O

O

O+

Al(OiPr)3

85oC, N2 atm

MBCBn = CH2Ph

110 oC, N2 atm

Sn(Oct)2

Storey, R.F., Mullen, B.D., Melchert, K.M. J. Macromol. Sci.-Pure Appl. Chem., 2001 A38(9), 897.

Page 31: Biosourced Raw Materials - Moving the Farm into Polymers

Enhancement of Glass Transition Temperature by Ion Incorporation

O O O

O

OCH3

O

OH

O O

OBn

CH3

O

O

O

O

CH3

Page 32: Biosourced Raw Materials - Moving the Farm into Polymers

Conclusions

Biosourced Products have a place in polymers

They can be included into high performance materials

The next generation will truly bring us back to the farm

Page 33: Biosourced Raw Materials - Moving the Farm into Polymers

Acknowledgements

The Thames Research GroupSouthern Diversified Products

Professor Roger HesterProfessor Robson StoreyThe US Department of Agriculture