Improved Utilization of Downstream Corn Oil from Bioethanol Industry: Super Performed Sustainable

Flame Retardant for Engineering plastic-based Biocomposites in Automotive Applications

Boon Peng Chang, Suman Thakur, Amar K. Mohanty and Manjusri Misra

Bioproducts Discovery and Development Centre, Department of Plant Agriculture; School of Engineering, Thornbrough Building, University of Guelph, Canada.

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Bioethanol industry

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Sustainability Low Carbon Cost Effective

From Biomass to Advanced Biofuels and Bioproducts

A biofuel is a type of renewable fuel whose energy derived from biological carbon fixation.

Corn Sugarcane Cellulosic

CO2

BioFuel

Fig. 1. Biofuel for a sustainable future (Life Cycle).

Downstream Corn Oil (Bioethanol Industry)

3[Ref 1] Renewable Fuels Association (RFA), Ethanol Co-products, https://ethanolrfa.org/resources/industry/co-products/ (Accessed August 2019).

Corn Distillers Oil Production

20173,575

[Ref 2]

CO2DDGS

Corn Oil

Co-Products

Bioethanol Production

Distillation

Fermentation

Product Recovery

Corn Starch Enzymatic Hydrolysis

Fig. 2. Bioethanol Production.

Fig. 3. Corn Distillers oil production (one of the largest co-product from bioethanol industry) from 2005 to 2017. (Adapted from [Ref. 1])

Vegetable Oils• Soybean Oil

• Castor Oil

• Corn Oil

• Tung Oil

• Linseed Oil

• Coconut Oil

• Sunflower Oil

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Triglyceride of long chain fatty acid

Recent Research Fields and Applications as Polymer Additives

Lubricant Plasticizer Toughening Agent

Hydrophobic Coating Biobased Epoxy Resin

Flame Retardant

Why use flame retardant?

• Slow down polymer combustion, fire propagation or fire extinction

• Reduce smoke emission

• Avoids dripping

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❑ Flame retardant additives in polymers for automotive parts can

resist fire propagation and burning.

❑ Hence, the driver or passenger have time to escape in the event

of a vehicle on fire.

Flame Retardant for Automotive and Transportation

• Flame-retardants (FR) - largest group of plastics additives, are playing a major role in the plastics industry by improving life safety.

• FRs were consumed accounting for 27% of the total plastics additives market (~8.5 bn) in the year of 1997 [2] .

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Fig. 4. Worldwide plastic additives. Market distribution ($8.5 bn 1997). Figure adapted and redrawn from [Ref 2].

[Ref 2]: Georlette, P., 2001. Applications of halogen flame retardants. Fire retardant materials, pp.264-292.

Global Consumption of Flame Retardant (FR) by Type

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[Ref 3]: Additives used in Flame Retardant Polymer Formulations: Current Practice & Trends, Clariant

“Fire Retardants and their Potential Impact on Fire Fighter Health” Workshop at NIST Gaithersburg, MD USA, 30 Sep 2009

https://www.nist.gov/sites/default/files/documents/el/fire_research/2-Reilly.pdf (Accessed August 2019)

Halogen (Br > Cl)P-containing SystemMineral FR System

Effectiveness

Non-Halogen based Flame Retardant

Toxic hydrocarbon gas – HBr, HCl

Fig. 5. Global consumption of FRs in the year 2007. Figure adapted and redrawn from [Ref 3].

Biobased flame retardant

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Lignin

Chitosan

Vegetable oil

[Ref 4] Prieur, B., 2016. Modified lignin as flame retardant for polymeric materials (Doctoral dissertation, Lille 1).

[Ref 5] Hu, S., Song, L., Pan, H. and Hu, Y., 2012. Thermal properties and combustion behaviors of chitosan based flame retardant combining

phosphorus and nickel. Industrial & Engineering Chemistry Research, 51(9), pp.3663-3669.

[Ref 6] Heinen, M., Gerbase, A.E. and Petzhold, C.L., 2014. Vegetable oil-based rigid polyurethanes and phosphorylated flame-retardants derived

from epoxydized soybean oil. Polymer degradation and stability, 108, pp.76-86.

Phosphate esters [Ref. 6]

Phosphorylated lignin [Ref. 4]

Byproduct from pulping industry as flame retardant for polymeric materials (polylacticacid (PLA) and acrylonitrile butadiene styrene (ABS)).

Intumescent flame retardant nickel chitosan phosphate [Ref. 5]

Improved the flammability and thermal properties of poly(vinyl alcohol) (PVA) and the nickel can take its synergistic effect on thermal stability of PVA.

Phosphorylated polyols as flame retardant for rigid polyurethane foams.

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❖ Exceptional dimensional stability.❖ Excellent electrical properties.❖ Very good heat and heat ageing resistance.❖ Very low creep, even at elevated temperatures.❖ Very good colour stability.❖ Excellent wear properties

Engineering polyesters

Polyester is a category of polymers that contain the ester functional group in their main chain

Ester bond

Properties of engineering polyesters

Engineering polyesters

❖Polyethylene terephthalate (PET)

❖Polytrimethylene terephthalate (PTT)

❖Polybutylene terephthalate (PBT)

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PET PTT

PBT

Polybutylene terephthalate (PBT)

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PBT is highly flammableFlame Retardant is very important additives for PBT

o The projection trend of Global Automotive GF/PBT Market increasing every yearfrom 2013 to 2024 (including long fiber, short fiber/PBT) [7].

o Some of the application of PBT in automotive include Roof Panel, Body Panels, Chassis and others [7].

Key Characteristics

• High mechanical strength,

• Good dimensional stability,

• Rapid crystallization rate (desirable for injection molded part) and

• High heat deflection temperature.

[Ref 7] Global Automotive Glass Fiber Reinforced PBT Market Market Evolving Opportunities with Top Industry Players Profiles | BASF, Lanxess, DSM, SABIC,

PolyOne. https://majoreports.com/global-automotive-glass-fiber-reinforced-pbt-market-market-evolving-opportunities-with-top-industry-players-profiles-basf-

lanxess-dsm-sabic-polyone/127910/

Synthesis of phosphorylated downstream corn oil

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Epoxidization of Corn oil Process

+ Formic acid+ H2SO4

+ Hydrogen Peroxide

Phosphorylated Corn Oil

Ring Opening Reaction

Fig. 6. Synthesis of phosphorylated epoxidized downstream corn oil

Epoxidized Corn oil

@60 °C for 6 hours

Down Stream Corn oil

Materials

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No. Materials Grade and Trade

name

Company

1. Poly(butylene terephthalate)

(PBT)

Celanex 2000-3 Calenese (Ticona)

2. Poly(trimethylene terephthalate)

(PTT)

Sorona Dupont

3. Downstream Corn Oils N/A IGPC Ethanol Inc.

(Ontario, Canada)

Processing temp: 250°C Melt mixing @100 rpm Screw Speed

DSM Explore Co-rotating Twin Screw Micro-compounder

Processing

Fire Test UL-94: Horizontal Burning Test

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PBT/Phosphorylated Corn Oil

SamplesTime to

Extinguish (s)Dripping

UL-94

Class

Neat PBT Burnt completely Yes NR

PBT/PCO(92.5/7.5) Not Burning N/A HB Passed

CompositionCorn Oil FR/polyester

(wt%)Rating Results

Neat PBT NR Burnt through Clamp

Corn Oil/PBT Blends V-2 Not Burning

Neat PTT V-2Not Burning

Corn Oil/PTT Blends V-2Not Burning

(Burning time reduced as compared to neat PTT)

• At only small amount of the corn oil/PBT and corn oil/PTT blends showed significant flame retardancy.

• The fire class of PBT changed from non-rating (NR) burning fire class to not burning fire class (V-2).

• The time to stop the propagation of fire was reduced significantly after incorporation of modified corn-oil in PTT.

Fire Test UL-94:Vertical Burning Test

Conclusions1. Downstream corn oils from bioethanol industry was successfully

modified and utilized as a sustainable feedstocks for the synthesis of biobased flame retardant for engineering plastics.

2. The flame retardancy of the engineering plastics i.e. poly(butylene terephthalate) and poly(trimethylene terephthalate) were improved significantly after incorporation of our synthesized functionalized biobased flame retardant from downstream corn oil.

3. Unlike conventional flame retardant, the incorporation of small amount (<10 wt%) of these biobased flame retardant changing the UL-94 fire class of PBT from non-rating (NR) burning class to not burning fire class (V-2).

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Acknowledgement1. Ontario Ministry of Agriculture, Food and Rural Affairs

(OMAFRA)/University of Guelph - Bioeconomy for Industrial Uses Research Program (Project # 030251);

2. The Agriculture and Agri-Food Canada (AAFC) and IGPC Ethanol, Canada through Bioindustrial Innovation Canada (BIC) Bioproducts AgSci Cluster Program (Project # 053786 and 054015);

3. and The Natural Sciences and Engineering Research Council (NSERC), Canada Discovery Grants Project # 401111 and 400320.

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List of References1. Renewable Fuels Association (RFA), Ethanol Co-products,

https://ethanolrfa.org/resources/industry/co-products/ (Accessed August 2019).

2. Georlette, P., 2001. Applications of halogen flame retardants. Fire retardant materials, pp.264-292.

3. Additives used in Flame Retardant Polymer Formulations: Current Practice & Trends, Clariant “Fire Retardants and their Potential Impact on Fire Fighter Health” Workshop at NIST Gaithersburg, MD USA, 30 Sep 2009 https://www.nist.gov/sites/default/files/documents/el/fire_research/2-Reilly.pdf(Accessed August 2019)

4. Prieur, B., 2016. Modified lignin as flame retardant for polymeric materials (Doctoral dissertation, Lille 1).

5. Hu, S., Song, L., Pan, H. and Hu, Y., 2012. Thermal properties and combustion behaviors of chitosan based flame retardant combining phosphorus and nickel. Industrial & Engineering Chemistry Research, 51(9), pp.3663-3669.

6. Heinen, M., Gerbase, A.E. and Petzhold, C.L., 2014. Vegetable oil-based rigid polyurethanes and phosphorylated flame-retardants derived from epoxydizedsoybean oil. Polymer degradation and stability, 108, pp.76-86.

7. Global Automotive Glass Fiber Reinforced PBT Market Market Evolving Opportunities with Top Industry Players Profiles | BASF, Lanxess, DSM, SABIC, PolyOne. https://majoreports.com/global-automotive-glass-fiber-reinforced-pbt-market-market-evolving-opportunities-with-top-industry-players-profiles-basf-lanxess-dsm-sabic-polyone/127910/ (Accessed August 2019) 18

Thank you Thank you !

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