Natural Oil-based Thermosets and Composites - Iowa State University

Iowa State University 1

2012 Biopolymers & Biocomposites Workshop, 08/14/2012, Ames, IA

Natural Oil-based Thermosets and Composites

Rafael Lopes Quirino Chemistry Department

Georgia Southern University Statesboro, GA

2

Outline

•  Background

•  Conjugation of C=C in Vegetable Oils

•  Polymer and Composites from Vegetable Oils

•  Introduction

•  Inorganic fillers

•  Natural fillers

•  Conclusions

•  Acknowledgements

2

3

Background

O

O

O

R

R'

R"

O

O

O

glycerol unit fatty acid chains

R, R', R" = dictinct aliphatic hydrocarbon chains with varying length, number and position of carbon-carbon double bonds, and functional groups

3 Sustainable Composites and Advanced Materials, submitted

Background

HO

O

7 HO

O

7 4

HO

O

7 7 HO

O

7

OH

5

HO

O

7 3HO

O

3 4

arachidonic acid α-eleostearic acid

linolenic acid linoleic acid

oleic acid ricinoleic acid

4

5

Conjugation of C=C in Vegetable Oils

J Am Oil Chem Soc (2001) 78, 447

Conjugated oils are more reactive than non-conjugated triglycerides

J Agric Food Chem (2006) 54, 9535 5

Conjugation of C=C in Vegetable Oils

6 J Am Oil Chem Soc (2012) 89, 1113

7

Polymer and Composites from Vegetable Oils

Chem Soc Rev (2007) 36, 1788 Biomacromolecules (2003) 4, 1018 7

R R'O2, hν, CH2Cl2

meso-tetraphenylporphyrinNaBH4, MeOH, 0 oC

RR'

O

O

RR'

OHR

R'

OOHCl

O

Et3N, CH2Cl2, 0-25 oC

R R'O

H2O2 / AcOH

HO

O RR'

OH

O

O

OO OR

R'

O

O

O

OHO

O

R R'HO Nu

Nucleophile (Nu)

OCNR"

NCO

RO Nu

O

NH

R"NH

O

R'

ONu

R R'O NuH

Grubbs catalyst

R' R'

R R+

Introduction

8

Cationic polymerization mechanism:

BF3• Et2OH2O

BF3•

R R'

BF3• HO

R R'

R R'

R R'

R R'

BF3• HO R

R'

R

R'

x

HO

H


Free radical polymerization process:

R R'

R"OR R'

OR"

R R'

R R'OR"

R R'R

R'

OR" R

R'

x

R"O = Free radical initiator fragment

ACS Symposium Series (2011) 1063, 37

Introduction

9


Sustainable Composites and Advanced Materials, submitted

Conjugated Vegetable Oil(50 wt %)

+

Divinylbenzene (DVB)(15 wt %)

+

O

O

n-Butyl Methacrylate (BMA)(35 wt %)

O O (Free Radical Initiator)

orBF3•Et2O, ∆

O

O

O

O

O

O

77

84

82

Introduction

10

Characteristics of soybean oil polymers

Polymer Tg (oC)

e (mol/m3)

Tmaxa

(oC) E b

(MPa) b

c

(MPa) b

d

(%) Toughness

(MPa) Polyethylene (LDPE) -68 - 355 370 9.6 46 5.2 Polystyrene 90 - 420 1330 30.3 4 0.5 CLS45-ST47-DVB00-(NFO5-BFE3) e 10 1.0×102 448 12 1.3 300 2.0 CLS45-ST32-DVB15-(NFO5-BFE3) f 76 2.2×103 475 225 11.5 41 4.0 CLS35-ST39-DVB18-(NFO5-BFE3) g 82 3.4×103 477 500 21.0 3 0.8 SOY45-ST32-DVB15-(NFO5-BFE3) 68 1.8×102 468 71 4.1 57 1.7 LSS45-ST32-DVB15-(NFO5-BFE3) 61 5.3×102 470 90 6.0 64 2.9 CLS45-ST32-DVB15-(NFO5-BFE3) 76 2.2×103 475 225 11.5 41 4.0 a The temperature at the maximum degradation rate b Young's modulus c Break strength d Elongation at break e A typical elastomer f A ductile plastic g A rigid plastic

Polymer and Composites from Vegetable Oils Introduction

11

Polymer and Composites from Vegetable Oils Inorganic fillers

Continuous glass fibers Organoclays

E increased from 4.1 MPa to 873.6 MPa by adding 45% of glass fibers

1-2 wt % clay can significantly increase the mechanical properties.

Biomacromolecules (2006) 7, 2692 Macromol. Mat. Eng. (2007) 292, 1085

12

Polymer and Composites from Vegetable Oils Natural fillers – corn stover,

wheat straw

20 30 40 50 60 70 802

3

4

5

6

Amount of Corn Stover (wt %)

Tens

ile S

tren

gth

(MP

a)

200

400

600

800

1000

1200

Young's M

odulus (MP

a)

50 60 70 80 90

2

4

6

8

Amount of Wheat Straw (wt %)

Tens

ile S

tren

gth

(MP

a)

800

1000

1200

1400

1600

1800

2000

Young's M

odulus (MP

a)

Trib. Int. (2010) 43, 171

13


DVB = U$ 96.30/L and DCPD = U$ 52.00/L (Aldrich Catalog 2008) 13

Natural fillers - Soybean hulls

14


DVB15-BMA35 DVB10-DCPD5-BMA35

DVB5-DCPD10-BMA35

DVB15-DCPD10-BMA25

0

100

200

300

400

500

600

700

800Young's ModulusStorage Modulus at 25 ˚C

MPa

Matrix: CSO50-DVB-DCPD-BMA-TBPO5 Filler Particle Size < 177 µm 60:40 (filler/resin)‏

14


15


15

Entry

1 - -31 57 152

2 DVB15-BMA35 <425 -32 76 416

3 DVB10-DCPD5-BMA35 <425 -17 75 318

4 DVB5-DCPD10-BMA35 <425 -7 65 234

5 DVB15-DCPD10-BMA25 <425 -13 84 384

Samplea Particle Size (µm) Tg1 (oC) Tg2 (oC) E' at 25 oC (MPa)

Resinb

a All samples were prepared with a 60/40 filler/resin ratio. b DVB15-BMA35 without filler.

J Appl Polym Sci (2009) 112, 2033



Resin composition: 50 wt% of conjugated soybean oil 35 wt% of n-butyl methacrylate

15 wt% of divinylbenzene 5 wt% of t-butyl peroxide

Filler/resin ratio: 50/50 Filler particle size: <425 µm

B: cryofractured sample; F: cut sample

16 16 J Appl Polym Sci (2009) 112, 2033


17


17

Natural fillers - Rice hulls

18


OO O

OH

COOHO

O∆

Matrix: CLO50-DVB15-BMA-MA-TBPO5 70/30 (filler/resin)‏

J Appl Polym Sci (2011) 121, 2050


19


A

SEM of: CLO50-BMA35-DVB15 composite (A), and CLO50-BMA20-DVB15-MA15 composite (B).

SEM of CLO50-BMA35-DVB15 composite (A), and X-ray map of line Si Ka for the same composite (B).

B

J Appl Polym Sci (2011) 121, 2039 J Appl Polym Sci (2011) 121, 2050

19


20


20 J Appl Polym Sci (2011) 124, 1520

Natural fillers – Wood flour

21

A = CSO-BMA-DVB; B = CSO-BMA-DVB-MA; C = TUN-BMA-DVB; D = TUN-BMA-DVB-MA


21 J Appl Polym Sci (2012) 126, 860

Natural fillers - Bagasse

22


cure sequence: 5h (160 ˚C) + 2h (180 ˚C) - post-cure resin composition: 50 wt% oil, 20 wt% BMA, 15 wt% DVB, 15 wt% MA, 5 wt% TBPO pressure: 600 psi filler particle size: 1 mm (diameter)‏ filler has been dried overnight

Green Chem (2012), 14, 1398

Oil Tensile Strength ElongationUsed (MPa) at break (%)

CCO 0.6 ± 0.1

CLO

TUN 0.6 ± 0.1

CFO

E (GPa)

2.2 ± 0.4 10.0 ± 1.1

2.7 ± 0.5 12.8 ± 1.8 0.6 ± 0.1

2.9 ± 0.5 13.4 ± 2.6

2.2 ± 0.5 10.1 ± 2.1 0.5 ± 0.1

22

Natural fillers - Oat hulls

Conclusions

23

Filler (70 wt %) Resin (30 wt %)

soybean hulls CSO50-BMA35-DVB15 0.8 2.6 278

rice hulls CLO50-BMA20-DVB15-MA15 2.3 9.1 613

wood flour CLO50-BMA20-DVB15-MA15 4.3 17.6 2244

2.3 18.4 1051

TUN50-BMA20-DVB15-MA15 3.9 16.2 1180

oat hulls TUN50-BMA20-DVB15-MA15 2.9 13.4 1073

E (GPa) Tensile strength (MPa) E' at 130 ˚C (MPa)

wood fibera CLO50-BMA20-DVB15-MA15a

sugar-cane bagasse

a Filler/resin ratio = 50/50

Material

0.8 – 4.3 2.6 – 18.4 686 – 4882

HDPE 0.8 17.9 – 33.1 -

PP 1.5 – 2.0 29.0 – 38.0 1560

PET 2.0 – 2.7 172.0 -

PS 3.0 – 3.5 42.0 -

70% glass fiber/epoxy 40.0 – 45.0 55.0 – 800.0 2700

70% carbon fiber/epoxy 181.0 - 2340

E (GPa) Tensile strength (MPa) E' at RT (MPa)

bio-based composites

24

Acknowledgements

l  RRTTC (UNI)‏

l  CBiRC

l  Dr. Larock

l  Dr. Kessler

l  Dr. Pfister

l  John Woodford, Yixin Ma

24

Supporting Info

25

Reaction coordinate

Pote

ntia

l ene

rgy

Ea

thermoset polymer

Reaction coordinate

Pote

ntia

l ene

rgy

Ea

thermoset polymer

R R'

1

2

3

4

RR'

O

R R'

RR'

O

Where:

1 =

2 =

3 =

4 =

Sustainable Composites and Advanced Materials, submitted

26

Supporting Info

Resin: CSO50-DVB15-BMA35 Filler/Resin ratio: 50:50 Partial cure: 130 oC (4h), 276 psi Full cure: 130 oC (5h), 276 psi + 150 oC (2h)‏

J Appl Polym Sci (2009) 112, 2033 26

Soybean hulls

Supporting Info

27

Resin composition: 50 wt% of conjugated soybean oil 35 wt% of n-butyl methacrylate 15 wt% of divinylbenzene 5 wt% of t-butyl peroxide

27 J Appl Polym Sci (2009) 112, 2033

Soybean hulls

Supporting Info

28

A-BMA35-DVB15 B-BMA35-DVB10-MA5 C-BMA30-DVB15-MA5 D-BMA20-DVB15-MA15

Rice hulls

Natural Oil-based Thermosets and Composites - Iowa State University

Documents

Transcript of Natural Oil-based Thermosets and Composites - Iowa State University