latest developments in bio plastics (thermosets)

Latest developments in bioplastics (Thermosets)

Jokin Hidalgo, TECNALIAAlvaro Tejado (TECNALIA), Maider Azpeitia (TECNALIA),

Alejandro Salvador (TECNALIA).

www.innobite.eu

20/02/2014Donostia - San Sebastian

http://www.innobite.eu/

Why we talk bio-plastics?

2

www.innobite.eu

Latest developments in bioplastics

3

www.innobite.eu

"Sustainable development is development that meets the needs of the present without compromising the ability of future generations to

meet their own needs.

(World Commission on Environment and Development, 1988)

“El desarrollo sostenible se define como el desarrollo que satisface las necesidades del mundo actual, sin comprometer las necesidades de las

generaciones futuras.”

(Comisión mundial del medio ambiente y del desarrollo, 1988)

Driving forces: Sustainability


Driving forces

4

www.innobite.eu

Task X.Y

Driving forces: Consumers


DuPont Industrial Biosciences, “China Green Living Survey,” 2012. http://biosciences.dupont.com/china-green-living-survey/

http://biosciences.dupont.com/china-green-living-survey/



5

www.innobite.eu

Driving forces: Governments - StandardsCountry Acronim Web

Austria ÖNORM www.as-search.at

Spain AENOR www.aenor.es

France AFNOR www.afnor.org

Germany DIN www.din.de

Italy UNI www.uni.com

Japan JIS www.jsa.or.jp/default_english.asp

UK BSI www.bsigroup.com

US ASTM www.astm.org

International ISO www.iso.org

Europe CEN www.cen.eu

Standardisation bodies associated with the production of standards of biodegradability of plastics


http://www.as-search.at/

http://www.aenor.es/

http://www.sciencedirect.com/science?_ob=RedirectURL&_method=externObjLink&_locator=url&_issn=18716784&_origin=article&_zone=art_page&_plusSign=+&_targetURL=http://www.afnor.org/

http://www.din.de/

http://www.sciencedirect.com/science?_ob=RedirectURL&_method=externObjLink&_locator=url&_issn=18716784&_origin=article&_zone=art_page&_plusSign=+&_targetURL=http://www.uni.com/

http://www.sciencedirect.com/science?_ob=RedirectURL&_method=externObjLink&_locator=url&_issn=18716784&_origin=article&_zone=art_page&_plusSign=+&_targetURL=http://www.jsa.or.jp/default_english.asp

http://www.bsigroup.com/

http://www.sciencedirect.com/science?_ob=RedirectURL&_method=externObjLink&_locator=url&_issn=18716784&_origin=article&_zone=art_page&_plusSign=+&_targetURL=http://www.astm.org/

http://www.sciencedirect.com/science?_ob=RedirectURL&_method=externObjLink&_locator=url&_issn=18716784&_origin=article&_zone=art_page&_plusSign=+&_targetURL=http://www.iso.org/

http://www.sciencedirect.com/science?_ob=RedirectURL&_method=externObjLink&_locator=url&_issn=18716784&_origin=article&_zone=art_page&_plusSign=+&_targetURL=http://www.cen.eu/

6

www.innobite.eu

Driving forces: Generally Accepted Ecolabels.


Driving forces

7

www.innobite.eu

Driving forces: Clear up misunderstandings






Driving forces

8

www.innobite.eu







Driving forces

9

www.innobite.eu


Confusion


Driving forces

10

www.innobite.eu


Confusion


Federal Trade Commission USA (FTC)

European Bioplastics

11

www.innobite.eu

Driving forces: Global interest

Ngram Viewer

Growing interest in all indexed books related to bioplastics and biocomposites.


12

www.innobite.eu

Driving forces: Research - Patents

Bio-source


13

www.innobite.eu

Driving forces: Research - Patents

Bioplastic


14

www.innobite.eu

Driving forces: Market Bio - Chemicals


15

www.innobite.eu

Driving forces: Market Bio - Chemicals

2011


Investments

16

www.innobite.eu

Driving forces: Market

Global plastic production

Plastics


http://www.plasticseurope.es

http://www.plasticseurope.es/


17

www.innobite.eu

Driving forces: Market Thermoset


http://www.plasticseurope.es



18

www.innobite.eu

Driving forces: Market

20165800

Bio-plastic production

Each year breaking estimations are

better.

Bioplastics


Plastemart, “Bio based plastics on the rise” http://www.plastemart.com/upload/Literature/Demand-for-bio-based-plastics-rising.asp

http://www.plastemart.com/upload/Literature/Demand-for-bio-based-plastics-rising.asp

http://www.plastemart.com/upload/Literature/Demand-for-bio-based-plastics-rising.asp

19

www.innobite.eu

Driving forces: Future lack of resources


http://www.oilposter.org/



20

www.innobite.eu

History


21

www.innobite.eu

History


22

www.innobite.eu

History

▪ 1846 Christian Schönbein produced nitrocellulose.

Then Alexander Parkes get the Parkesine, and John Wesley Hyatt the celluloid

▪ 1839, Charles Goodyear and his brother Nelson discovered the vulcanization of natural rubber.

▪ 1907, Leo Hendrik Baekeland, an American of Belgian origin, developed the first truly synthetic polymer, a thermoset polymer resulting from the reaction of phenol with formaldehyde.


23

www.innobite.eu

History


Fully synthetic

24

www.innobite.eu

History


Bio-Plastic

25

www.innobite.eu

Bioplastics:


Is bio-based = bio-degradable?

http://en.european-bioplastics.org/



26

www.innobite.eu

Bioplastics: Market





27

www.innobite.eu

Bioplastics: Market

Biodegradable

Non biodegradable





28

www.innobite.eu

Biorefinery: Resources from renewable sources.


29

www.innobite.eu

Biorefinery: From almost everywhere…

We can extract raw materials to generate useful biopolymers, from almost all the tree of life, as we can read in the next articles:

Vegetables: “Polysaccharides from Wastes of Vegetable Industrial Processing”.

Animals: “Animal Waste for the Production of Biofuels and Biopolymers”.

Fungi: “Are mushrooms the new plastic?”

Micro algae: ”Making plastics from algae”.

Bacteriums: “Researchers Train Bacteria to Convert Bio-Wastes Into Plastic”.


30

www.innobite.eu

Biorefinery:Diagram of possible applications of polymers obtained from bio refining processes of cereals and pulses.


R. Wool and X. Sun, Bio-based polymers and composites. Elsevier, 2005

31

www.innobite.eu

Biorefinery:

Bio- Fuels &

New Bio-Materials

Joining efforts


32

www.innobite.eu

Task X.Y

Bio-based polymers:

Natural rubber Starch Poly (lactic acid) Poly (hydroxyalkanoates) Poly (butylene succinate) Poly (γ-glutamic acid) Glycosaminoglycans Proteins

Cellulose Hemicelluloses Lignin

Chitin / Chitosan

Most Bio degradable


33

www.innobite.eu

Task X.Y

Bio-based polymers:

Polyolefins

Polyesters

Polycarbonates

Polyamides

Methyl acrylate

Poly (vinyl chloride) Thermosetting resins: polyurethanes, polyester, epoxy, phenolic, alkydic.

Only Bio-based


Latest developments in bioplastics 34

www.innobite.eu

Task X.Y

Bio-based polymers:

http://www.nova-institut.de

http://www.nova-institut.de/

http://www.nova-institut.de/

35

www.innobite.eu

Bio-based polymers:

C2 containing

compoundsLatest developments in bioplastics

Building Blocks?

36

www.innobite.eu

Bio-based polymers:

C2 containing

compounds

Mono-Ethyleneglycol (MEG)


Building Blocks?

37

www.innobite.eu

Bio-based polymers:

C2 containing

compounds

Other C2 based building blocks:

Acetic acid

Dichloroethane (formed by chlorination of ethane)

Vinylchloride (formed by dehydrochlorination of dichloroethane)

Ethylene oxide (oxidation of ethylene)

Ethylenediamine (reaction of 1,2-dichloroethane and ammonia)


Building Blocks?

38

www.innobite.eu

Bio-based polymers:

C3 containing

compounds


Building Blocks?

39

www.innobite.eu

Bio-based polymers:

C3 containing

compounds

Ethyl Lactate

Green Solvents


Building Blocks?

40

www.innobite.eu

Bio-based polymers:

Propylene Glycol (1,2-Propanediol)

Unsaturated polyester resins, coolants and antifreeze, hydraulic and brake fluid, aircraft de-icing fluid, heat transfer fluids, paints and coatings.


Building Blocks?

41

www.innobite.eu

Bio-based polymers:

C3 containing

compounds

1,3 Propanediol

DuPont formed a joint venture with agriculture products company Tate & Lyle

Susterra® PDO: products from textiles to coatings and engineering plastics. Susterra® PDO is co-polymerised with terephthalic acid to produce poly(trimethylene) terephthalate (PTT) sold by DuPont under the trade name Sorona® .Sorona® PTT has been targeted at clothing, carpet and automotive textile markets.

Cerenol™ polyols based on PDO can be used in variety of applications from personal care and functional fluids to performance coating and elastomers.


Building Blocks?

42

www.innobite.eu

Bio-based polymers:

C3 containing

compounds

Epichlorohydrin

Production of resins and polymers (mainly epoxy resins (76%) )


Building Blocks?

43

www.innobite.eu

Bio-based polymers:

Epichlorohydrin

Glycerol


Building Blocks?

44

www.innobite.eu

Bio-based polymers:

C3 containing

compounds

Isopropanol

Isopropanol production via fermentation and its conversion into propylene have been reported by Mitsui Chemicals, INC.

Propylene


Building Blocks?

45

www.innobite.eu

Bio-based polymers:

C3 containing

compounds

n-Propanol

Recently a Braskem patent was published which describes the fermentative production of n-propanol and the subsequent dehydration into propylene.

Propylene


Building Blocks?

46

www.innobite.eu

Bio-based polymers:

C3 containing

compounds

Acrylic acid

Coatings, adhesives, sealants, textiles, fibres, polymer additives/impact modifiers, super absorbent polymers…


Building Blocks?

47

www.innobite.eu

Bio-based polymers:

C4 containing

compounds

n-Butanol

Succinic Acid

Methyl methacrylate


Building Blocks?

48

www.innobite.eu

Bio-based polymers:

C4


Building Blocks?

49

www.innobite.eu

Bio-based polymers:

C4 Succinic Acid


Building Blocks?

50

www.innobite.eu

Bio-based polymers:

C5 containing

compounds

Furfural Levulinic acid Isoprene

Xylitol


Building Blocks?

51

www.innobite.eu

Bio-based polymers:

C6 containing

compounds

Lysine Adipic acid

Glucaric acid


Building Blocks?

52

www.innobite.eu

Bio-based polymers:

C6 containing

compounds

2,5-Furandicarboxylic acid (FDCA)

Building Blocks?

53

www.innobite.eu

Task X.Y

Bio-based polymers:

C6 containing

compounds

SorbitolIsosorbide


Building Blocks?

54

www.innobite.eu

Bio-based polymers:

Cn containing

compounds

p-Xylene


Building Blocks?

55

www.innobite.eu

Bio-based polymers:

Cn containing

compounds

Fatty Acid derivatives

Lubricants, metal-working fluids, fuel additives, personal care products, corrosion inhibitors, rheology modifiers…


Building Blocks?

56

www.innobite.eu

Bio-based polymers:


Building Blocks?

CompaniesBigDevelopment

s

57

www.innobite.eu

Task X.Y

Bio-based polymers: Thermosets


http://www.compositesworld.com/articles/green-resins-growng-up

58

www.innobite.eu



Tannin-based adhesives

Bark of various trees.

Review of existing bioresins and their Applications (Jim Dewar)2007

59

www.innobite.eu

Task X.Y



Lignin: PF resin, and adhesives.

Lignin: 5-50% of the wood.

(For PF) Barrier to commercial development if different blends and source of lignins are going to give different properties.

Review of existing bioresins and their Applications (Jim Dewar)2007

60

www.innobite.eu



R. J. A. Gosselink, “Lignin as a renewable aromatic resource for the chemical industry,” 2011.

61

www.innobite.eu



Lignin: PU resin

Plasticsengineeringblog, “Rumplestiltskin Wanted,” Plasticsengineeringblog, http://plasticsengineeringblog.com/2012/11/12/rumplestiltskin-wanted/

http://plasticsengineeringblog.com/2012/11/12/rumplestiltskin-wanted/

http://plasticsengineeringblog.com/2012/11/12/rumplestiltskin-wanted/

62

www.innobite.eu



Cashew Nut Shell Liquid (CNSL)

Novolac, epoxy and PU.

Review of existing bioresins and their Applications (Jim Dewar) 2007

63

www.innobite.eu



Triglycerides

Chemistries available for turning such oils into useful polymeric products (Amines, monoglycerides, polyols, maleates, acrylates , epoxy, hydroxyl, and maleate half esters .

Triglycerides consist of three fatty acids (i.e., carbon numbers from 22 down to 14 and double bonds down from 3 to 0) covalently linked to a central glycerol.

64

www.innobite.eu

Bio-based polymers: Commercial Thermosets


UPS: from Soya Oil …

UPS: Bio 1,3-propanediol from corn dextrose via fermentation…

UPS: Variety of renewably sourced raw materials.

UPS: From renewable resources like corn, linseed oil, soy, canola…Isosorbide, propylene glycol, glycerin, industrial ethanol and ethylene glycol…

65

www.innobite.eu

Bio-based polymers:


Poly furfuril alcohol (PFA) Prepregs: sustainable, fire retardant prepregs suitable for composite applications. Similar performance to phenolic.Derived from hemicellulose crop waste such as sugar cane bagasse.

Epoxy resin derived from naturally occurring pine oil.

Commercial Thermosets

Bio-based UPS (ortho-, iso-, and terephthalic, dicyclopentadiene (DCPD) modified and bisphenol A fumarate) and vinyl esters.

66

www.innobite.eu

Bio-based polymers:


Polyols for PU.

Dimer diamine for use in both thermoplastic polyamides as well as curative in thermoset epoxy and polyurea systems.

Polymerised fatty acids. Dimer diol building block with high di-functionality provides good colour, water repellency, flexibility, thermo-oxidative and UV stability and outstanding hydrolysis / chemical resistance for polyurethane and polyester coatings, adhesives and elastomers.

Commercial Thermosets

Novolac, epoxy and PU resins from cardanol [Industrial oily alkyl-phenolic product obtained by vacuum distillation of "cashew nut shell liquid" (CNSL)].

67

www.innobite.eu

Bio-based polymers:


Companies commercializing novel pathways to biobased commodity

chemicals:

February 2014 / Pathways to novel chemicalshttp://www.aocs.org/Membership/informArticleDetail.cfm?itemnumber=19304

http://www.aocs.org/Membership/informArticleDetail.cfm?itemnumber=19304

http://www.aocs.org/Membership/informArticleDetail.cfm?itemnumber=19304

68

www.innobite.eu

Task X.Y

Bio-based polymers:


Catalysts&

Enzymes&

Microorganisims

Main ways:

69

www.innobite.eu

Bio-based polymers:


WORLD’S FIRST BIOBASED FAÇADE

Bioresin combined with hemp fibres

http://materia.nl/article/worlds-first-biobased-facade/

Real Cases



70

www.innobite.eu

Task X.Y

Bio-based polymers:


Real Cases

71

www.innobite.eu

Task X.Y

Bio-based polymers:


Real Cases

72

www.innobite.eu

Task X.Y

Bio-based polymers:


Real Cases

73

www.innobite.eu

Task X.Y

Bio-based polymers:


http://abcnews.go.com/Technology/ford-makes-car-lined-coke-bottle-material/story?id=20904665http://www.dieselpowermag.com/tech/ford/1109dp_fords_bio_plastic_techology/photo_01.html

Real Cases

74

www.innobite.eu

Task X.Y

Bio-based polymers:


Soybean Car1941

en.wikipedia.org

Real Cases

But time before…

http://en.wikipedia.org/wiki/Soybean_Car

Thank you

INNOBITE is co-funded by the European CommunitySeventh Framework Programme for European Research and

Technological Development (2012-2015)

www.innobite.eu

http://www.innobite.eu/

76

www.innobite.eu

Presentation TitleTask X.Y

Driving forces: Governments - Standards

Title Mandate TC Publication DateCEN/TR 16208:2011 Biobased products- Overview of standards M/429 ___ 2011-05-04

CEN/TR 15932: 2010 Plastics - Recommendation for terminology and characterisation of biopolymers and bioplastics

___ CEN/TC 249 2010-03-24

CEN/TS 16137:2011 Plastics - Determination of bio-based carbon content

M/430 CEN/TC 249 2011-04-27

CEN/TR 16227:2011 Liquid petroleum products – Bio-lubricants – Recommendation for terminology and characterisation of bio-lubricants and bio-based lubricants

M/430 CEN/TC 19 2011-08-10

CEN/TS 16295:2012 Plastics - Declaration of the bio-based carbon content

M/430 CEN/TC 249 2012-02-15

CEN/TS 16398:2012 Plastics - Template for reporting and communication of bio-based carbon content and recovery options of biopolymers and bioplastics- Data sheet

M/430 CEN/TC 249 2012-10-31

ftp://ftp.cen.eu/CEN/Sectors/List/bio_basedproducts/M_429.pdf

http://www.cen.eu/cen/Sectors/TechnicalCommitteesWorkshops/CENTechnicalCommittees/Pages/default.aspx?param=6230&title=Plastics




http://www.cen.eu/cen/Sectors/TechnicalCommitteesWorkshops/CENTechnicalCommittees/Pages/default.aspx?param=6003&title=Gaseous%20and%20liquid%20fuels,%20lubricants%20and%20related%20products%20of%20petroleum,%20synthetic%20and%20biological%20origin.





77

www.innobite.eu

Presentation TitleTask X.Y

Driving forces: Governments - Standards Title Mandate TC Expected

Publication Date

prEN 16575 Bio-based products - Vocabulary M/492 CEN/TC 411 2014-12-30FprCEN/TS 16640 Bio-based products - Determination of the bio-based carbon content of products using the radiocarbon method

M/492 CEN/TC 411 2014-02-22

CEN/TR xxxxx Bio-based products - Overview of available and possible methods and techniques for determination of the total bio-based content of products

M/492 CEN/TC 411 2014

TS xxxxx Bio-based products - Bio-based solvents - Requirements, application classes and test methods

M/491 CEN/TC 411 2015

EN xxxxx Bio-based products - Sustainability criteria M/492 CEN/TC 411 2016

EN xxxxx Bio-based products - Life Cycle Assessment M/492 CEN/TC 411 2016

EN xxxxx Bio-based products - Determination of the bio-based content - Method based on the 14C content and elemental analysis

CEN/TC 411 2016


http://www.cen.eu/cen/Sectors/TechnicalCommitteesWorkshops/CENTechnicalCommittees/Pages/default.aspx?param=874780&title=Bio-based%20products












latest developments in bio plastics (thermosets)

Technology

survey latest developments

marketlatest developments

orglatest developments

ylatest developments

forces consumers forces

misunderstandings forces

dupont industrial biosciences

china green living survey