1

What techno-economic regime for sustainable chemistry?

The analysis of the impacts of the relationship between green chemistry and

doubly green chemistry in academic research and industrial innovation.

E. Garnier1 & R. Debref 2,

3 5

Introduction

Since the last two decade, pollutions and accidents due to chemical activities and the

rise of social demand for more “sustainable” activities lead the sector of chemistry to design 10

new practices and new products. This paper discusses on the characterization of a new techno-

economic regime of sustainable chemistry by studying relationships between the concept of

"Green chemistry", as it was defined by chemists [Anastas & Warner (1998)], and what we

called the doubly chemistry green (2GC) [Nieddu & al. (2010)].

15

An implementation of a new regime for sustainable chemistry which is difficult to apprehend

The development of "Green Chemistry" (GC) emerged thanks to two movements

which take into account the effects of chemicals on the environment and human beings. The

first movement is due to the awareness of hazardous activities. The second is due to the rise of 20

the concept of sustainable development in our society. Then, since the 2000s, sustainable

chemistry of biomass, that we have called the "Doubly Green Chemistry" (2GC), follows the

same structural changes. Compared to GV, 2GC includes two other fundamental

developments which impacts agricultural sectors and chemical sectors. Firstly, the agricultural

sector gets surpluses of its exploitations and searches out new valorizations of non-food assets 25

(1). Secondly, the chemical sector is confronted to the problems of peak oil and is in the

search of substitutes for petroleum-based products (2).Consequently, the concept of 2GC can

be considered as a solution for these two structural problems. It reduces needs in terms of

fossil resources by promoting sustainable processes from agricultural resources. More

detailed studies of these structural dynamics shows us that they do not have direct effects nor 30

homogeneous effects. Firstly each of those structural movements make "windows of

opportunity" [Nill (2003)] to achieve 2GC. Researchers are also guided by it by focusing on

specific issues which can be sometimes complementary, independent or mutually opposed.

Secondly, as it is the case with the 12 principles of GC - in which actors can adapt actions by

defining their own "green chemistry compromise"-, developing sustainable bio-based 35 chemistry seems to be so open that it open the way for actors to chose various position in

comparing these dynamics. In fine, even if the concept of 2GC is considered as a unique

solution to various structural problems, the way that the 2GC is implementing is difficult to

understand and the form taken by the new regime of sustainable chemistry is not obvious.

40

An analytical framework for the implementation of sustainable chemistry regime

1 Ph.D in economics - Laboratory REGARDS (EA 6292) - University of Reims Champagne-Ardenne and ATER

at the Technological University of Troyes (Centre de recherches et d’études interdisciplinaires sur le

développement durable) 2 Ph.D Student in economics - Laboratoire REGARDS (EA 6292) - University of Reims Champagne-Ardenne

3 This paper is sponsored by the project ANR APERC2V. We would like to thank Martino Nieddu, Bernard

Kurek, Christophe Bliard et Franck-Dominique Vivien for their thoughtful help.

2

The evolutionary works, which deals with "Sectoral Systems of Innovation and Production"

[Malerba (2002 & 2004); Oltra & Saint Jean (2007, 2009, 2010 & 2012)] and the theory of 45

"transition to sustainable developement" [Kemp (2001), Kemp & al. (1998), Geels (2002);

Green, Rotmans & Schot (2010)], provide an interesting analytical framework for analyzing

changes in chemical and agricultural industries while emphasizing how this new sustainable

chemistry regime is spreading. The most of these contributions points out dynamics of

changes and give us a better understanding of the emergence of this regime in the medium 50

and the long term. Basically, Geels and his Dutch colleagues [Green, Rotmans & Schot] who

work on the technological transition, emphasize that appearances and stabilizations of new

techno-economic regimes are made by dynamic having two-steps. The First is an exploration

of various possible technological development paths. Secondly is an exploitation of the most

relevant technological paths (i.e. the “winning technologies”). This stage of exploration is a 55 movement which takes place at the micro level of innovation into specialized niches. The

relevance of these niches (and thus their exploitations as “dominant design”) depends on

motions that are located at intermediate and macro-economical levels. In other words,

explorations vary according to 1) existing techno-economic regimes and 2) changes in the

global landscape. Thus these works emphasize the multidimensional nature of the forces of 60 changing in techno-economic sectoral regimes.

Figure 1 : Technology transition in a dynamic perspective

References : Geels (2002) 65

The two level study of sustainable chemistry techno-economic regime

We discuss the emergence of a new techno-economic regime from a dominant design and

winning technology. This paper questions if sustainable chemistry is making a beeline for a 70 single sustainable path as it is suggested by Geels’ canonical model or if it is moving toward a

variety of paths maintained over time. For this, we propose to discuss on these scenarios from

a peculiar force of regime changes. This force can be called "techno-scientific knowledge" by

Geels or "technologies and knowledge base" by Malerba, Oltra and Saint Jean. Its dynamics

will be analyzed at two places of the sector from a multi-level perspective. Firstly we shall 75

focus on academic chemistry level (I), then on industrial development level (II). The first part

(1) distinguishes two stages in the representation and in the development of the techno-

3

scientific knowledge of sustainable chemistry regime at the academic level. The first stage

deals with a period when the dominant vision of sustainable chemistry referred to the "Green

Chemistry" and defined by chemists. The second stage is a transition to green chemistry of the 80 biomass that we call the "doubly green chemistry" (2GC). Finally, our work will emphasize

that implementations of technological path for the 2CG do not converge at the academic level.

Regarding our second part (2), we will focus on industrial developments of the sector of

resilient floorings, a sub-sector of chemistry. We will observe the coexistence of technological

development paths from "Green Chemistry" and "Doubly Green Chemistry". 85

1 - The representation and the development of techno-scientific knowledge

at academic level

In a context of coming regime change, techno-scientific knowledge is a central element in 90

economic actors' strategies who aim to ensure their reproduction over time [Nieddu et al.,

(2010)]. From this point of view, we need to understand how Science - the activity producing

knowledge - imagines the concept of sustainable chemistry and develops knowledge : the

roots of this new techno-economical regime. The first subsection will be presented as follows

(1). Firstly, at the wake of sustainable chemistry, the latter takes various forms and many 95

names before to be stabilized thanks to the concept of "Green Chemistry" (GC) in the

academic world (1.1). Then, this concept has been formalized by 12 principles by including

the use of biomass (1.2). Finally, this formalization and this interest of agricultural assets has

allowed a “flexible” conceptualization of 2GC (1.3).

100 The second subsection (2) will show that during the 2000s the domination of the concept of

GC has been gradually weakened until a trend reversal. At this time, the academic world has

increasingly turning its efforts toward the development a sustainable chemistry based on the

renewable biomass (2.1). The most of tools used in GC have been re-expended to serve 2CG. It is due to technological expectations and hopes [Brown et al. (2003)], market, the respect for 105 the environment and various productive heritages (2.2).

1.1-The lack of techno-scientific dominant design for sustainable chemistry

regarding its declension in terms of green chemistry

110 From the emergence to the domination of the concept of green chemistry

In the wake of the 1990s, the development of sustainable chemistry begin in the U.S.

[Linthorst (2009), Garnier (2012)]. Confronted to environmental issues and assessments of

millions of tons of pollutants and annual productions of waste, the U.S. Department of the 115

Environment (EPA) considers that there are significant opportunities for industry to reduce or

prevent pollution instead of giving a priority to "end of pipe" technologies. That is why this

institution ratifies it and the "Pollution Prevention Act". So, regarding its position in the

economy and its relations with other industries, the chemical sector became the first sector

involved in this policy based on a principle of prevention. Many names and scientific 120

concepts was implemented in order to achieve a sustainable chemistry. Beside the

"Environmental Chemistry", the "Sustainable Chemistry", the "Clean Chemistry", the "Begnin

Chemistry" [Woodhouse and Breyman, (2005)] or the "Soft Chemistry" [Livage, (2009)], the

"Green Chemistry" make also a breakthrough, even if its foundations and the supremacy of

this notion was not stabilized established yet. 125

4

Indeed, on the one hand, the history of GC is based on a specific institutional construction,

from a multi-step orientation toward Science, in the United States. Firstly these steps are

developed thanks to national grant for research in GC4. Then organizations of competition

reward the most relevant actors and processes for green chemistry5. Finally one Institute 130

dedicated to green chemistry that will be attached to "American Chemical Society"6.

On the other hand, since 1998, two main events crystallize the concept and the name of GC

until achieving a dominant point in the world of chemical research7. The first event deals with

the publication of "Green Chemistry: Theory and Practice" published by Anastas and Warner. 135 This book provides the most resumption definition of GC. It includes also a statement of 12

principles of GC to be followed. These proposals is a real success since the concept of green

chemistry will be disseminated until being in the landscape of this science. Secondly, still in

1998, the English network of the University of York writes an article which will be very

much cited within the scientific community [Macquarrie & Clark (1998)]. Henceforth, the 140 keyword “GC” appears and this successful context opens the way for the creation of a new

journal the next year : "Green Chemistry".

The GC, a concept based on priorities and compromises

The success of the concept of GC from academic chemical community at the international 145 level can be explained in two ways. The first one comes from the importance of the United

States in the world of research. The second one depends on the formulation of the concept

from the list of principles. The GC, as it has been thought by Anastas and Warner in 1998, is

presented such as a roadmap based on the respect of these principles "as far as possible" in

order to move towards a sustainable chemistry. The 12 principles contained in the list below 150 (Figure 3) aim to integrate modes of reasoning in order to get a new chemistry’s philosophy

of the 21st century (Figure 2). In fact, the academic world has a tool which is both marked by

a very strong symbolic and that is very malleable.

Figure 3 : The 12 principles of GC 155

1. It is better to prevent waste than to treat or clean-up waste after it is formed.

2. Synthetic methods should be designed to maximize the incorporation of all materials used in the process to the final

product.

3. Whenever practicable, synthetic methodologies should be designed to use and generate substances that possess little or

no toxicity to human health and the environment. 160 4. Chemical methods should be designed to preserve efficacy of function while reducing toxicity.

5. The use of auxiliary substances (e.g. solvents, separation agents, etc.) should be made unnecessary whenever possible

and, innocuous when used.

6. Energy requirements should be recognized for their environmental and economic impacts and should be minimized.

Synthetic methods should be conducted at ambient temperature and pressure. 165 7. A raw material or feedstock should be renewable rather than depleting wherever technically and economically

practicable.

8. Unnecessary derivatization (blocking group, protection/deprotection, temporary modification of physical/chemical

processes) should be avoided whenever possible.

4 The program « Alternative Synthetic pathways for pollution prévention» established in 1991 and enlarged and

renamed in 1993. 5 « Presidential Green Chemistry Challenge » in 1995

6 The « Green Chemistry Institute » established in 1997, joined to the « American Chemical Society » for

the« American Chemical Society Green Chemistry Institute » in 2001

7 At the same time, in 1998; Europe initiates discussions which will lead to the development of the REACH

directive. A study demonstrates the need for an overhaul of existing regulatory instruments Europeans on the

chemistry within the limitations of existing regulations on the issue.

5

9. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. 170 10. Chemical products should be designed so that at the end of their function they do not persist in the environment and

break down into innocuous degradation products.

11. Analytical methods needed to be further developed to allow for real time, in process monitoring and control prior to

the formation of hazardous substances.

12. Substances and the form of a substance used in a chemical process should be chosen so as to minimize the potential 175 for chemical accidents, including releases, explosions, and fires.

Source : Anastas et Warner (1998), p.30

Figure 2 : Comparison between chemistry of 20st and 21st century 180

The 20st century chemistry (Pétrochemistry)

(1) Start with a petroleum-based feedstock.

(2) Dissolve it in solvent.

(3) Add a reagent.

(4) React to form an intermediate chemical.

(5) Repeat (2)-(4) serval times until the final product is obtained; discard all waste

and spent reagent; recycle solvent where economically viable.

(6) Transport the product worldwide, often for long-term storage.

(7) Release the product into the ecosystem without proper evaluation of its long-

term effects

The 21st century chemistry (GC)

(1) Design the molecule to have minimal impact on the environment (short

residence time, biodegradable).

(2) Manufacture from renewable feedstock (e.g. carbohydrate).

(3) Use a long-life catalyst.

(4) Use no solvent or a totally recyclable benign solvent.

(5) Use the smallest possible number of steps in the synthesis.

(6) Manufacture the product as required and as close as possible to where it is

required.

Source: Clark (2002), in Clark & Macquarrie (ed.), p.2

The flexibility of this roadmap appreciated by scientists is due to the fact that these principles

do not have to be applied simultaneously since simultaneous applications are impossible 185 [Anastas & Warner (1998), Lancaster, (2002)]. Consequently the selection of these 12

precepts and their organization into a hierarchy confirm the fact that the GC can be based on

priorities and compromises. Regarding this situation, scientists can selected some of them8 in

order to apply the concept of green chemistry while decreasing instabilities as much as

possible. For instance, scientific can get significant progress on principles such as the atom 190 economy, the catalysis, or the energy conservation (searched for economic reasons by

industry), without making non-toxic products or processes (the first uses of catalysis focused

on the production of war gas). Thus the sustainable biomass chemistry is well into the logic of

GC (the seventh principle, Figure 3), this case does not propose necessarily a convergent view

of the form that it would take since this framework is confronted to the variability of 195

compromises too.

The heterogeneity of the position of biomass chemistry in GC

Chemistry of biomass appears from the 12 principles of GC since the seventh precept 200

calls for the use of renewable resources. Communications of the ACS Symposium about

green chemistry carried out in the 1990s provide a justification of it. As a matter of fact the

interest for biomass is due to the decreases of dangers and risks. Renewable assets would

substitute synthetic molecules which are designed ex nihilo without knowing toxicity by non-

8 It leads to excesses that can be linked to green washing practices as it has been reported by researchers

interviewed for our ANR project. They have emphasized the trend that a scientific is in GC dynamic from the

moment they mobilized simultaneously two principles.

6

toxic and biodegradable peculiarities. For instance the sector of agriculture is one of the main 205 activities that contributes to the spread of hazardous molecules in nature that is why proposing

relevant alternatives for substituting synthetic molecules petroleum-based would be relevant.

The valorization of agricultural products would be one place where the application of GC

could allow the reduction of spread of dangerous molecules in nature, and the levels of

pollution generated by the inputs of industrial agriculture. The study of chemists national 210 networks dedicated to GC9 and of reference books on the global concept10 shows that biomass

valorization is well included into the peculiarities of GC based on the establishment of

priorities and compromises. From the chemists research networks level, some of them give

priority to the seventh principle of GC while making compromises with other principles :it is

the case of Canadian, Brazilian, Spanish and Japanese networks. Yet other networks such as in 215 the United States and the United Kingdom associate the conversion of biomass to other

principles without giving a clear priority to one or other of principles. These differences are

observable in the books studied. Some numbers of the ACS Symposium Series deal with GC

without quoting biomass valorization even if Paul Colonna's book entitled "La chimie verte"

(2006) argues that the GC and the biomass chemistry are completely joined. 220

Moreover the study of these empirical insight emphasizes if compromises of this 12 principles

are made in favor of biomass valorizations, else the coupling solutions with other principles

of GC would be multiple. Thus, no trajectories of 2GC developed has been identified such as

a dominant design. For instance, some scientists have tried to implement the concept of 2GC 225 by associating biodegradability questions (10th principle). It is the case of starch and the

valorization of lignocelluloses 11. Then others scientists tried to associate uses of biomass to

alternatives of polluting solvents and of auxiliary synthesis (5th principle)12. Finally others

worked on catalysis or on atom-efficient reactions. Thus the conceptualization of the

sustainable chemistry points out the important role of biomass. Yet it does not have give a 230

definition of a dominant technological path for characterizing a techno-economical

sustainable chemistry regime.

1.2- The reversal of perspective despite the preservation of diversity of

technological pathways 235

Reversal of perspective reversal which considers biomass chemistry as a central element

Regarding the special case of the book "La chimie verte" written by Paul Colonna quoted

above, we argue that the publication of such book confirms a substantial shift since the uses 240

of renewable resources is important in chemistry. Moreover other indicators follow this trend.

Let’s take some examples. Firstly working on these renewable resources becomes more and

9 The Canadian Green Chemistry Network (CGCN), le WWVerde - Quimica verde no Brasil, l’Interuniversity

National Consortium « Chemistry for the Environment » (INCA) (Italia), the Green Chemistry Network (GCN)

(United Kingdom), the Red Espanola de quimica sostenible (REDQS), the’Hellenic Green Chemistry Network

et le Green & Sustainable Chemistry Network (Japan) 10

The ACS Symposium Series publications since 1998, Green chemistry : Theory & Practice [Anastas &

Warner (1998)], Handbook of Green Chemistry [Clark & Macquarrie (2002)], La chimie verte [Colonna (2006)] 10

e.g. all teh publicatiosn on the ionic liquides : Rogers et al. (ed.) (2002) ; Rogers et al. (ed.) (2005-a) (2005-b) ;

Malhotra. et al. (ed.) (2007), and on the supercritical carbon: Gopalan A.S. et al. (ed.) (2003) 11

Glass et al. (ed.) (1998) ; Rowell et al. (ed.) (1998) ; Scholz et al. (ed.) (1998) 12

Rogers et al. (ed.) (2002) ; Turner et al. (ed.) (2006)

7

more important according to the " Presidential Green Chemistry Challenge "13

. Secondly the

historical journal "Green Chemitry" and the most recent journal "Chemsuschem" follow the

same trend14. Thus, we argue that the relationship between GC and biomass chemistry is more 245 than an simple assimilation : it is a reversal of perspective.

Sustainable chemistry is a holistic approach which aims to get an ultimate objective in

achieving sustainability [for our society] thanks to chemistry. Of course it includes the

concept of GC (see above), but “ in a general framework and a vision centered on the 250 balance between economic growth and development, environmental preservation and

promotion of society (health protection and quality of life), in which innovation plays the role

of driver to achieve this balance” [Centi et Perathoner (2009)]. Since the 2000s evolutions are

based on carbon chemistry because renewable carbon resources is the only one alternative to

fossil carbon. Finally this issue emphasizes the level of scientific and of technical challenges 255

that is required to be stored in the inventory of scientific knowledge and know-how15.

Biomass chemistry can be defined as follows: biomass chemistry may be more "dirty"

because of impurities, co-products and variability of the raw material. Then a significant

portion of synthetic reactions on biomass based on "stoichiometric reactions" has low rates of 260 reaction yields whereas "catalytic reactions" has been provided by petroleum industry for

optimizing its processes. Many examples in scientific literature reviews dealing with biomass

point out this perspective shifting in which renewable resources is the core of its devices

[Kamm & Kamm (2004), Clark & Dewarte (2008), Bozelle & Petersen (2010), Sheldon

(2011), Gallezot (2012)]. As says Gallezot, "A major objective of this review (…) is to address 265 critically the environmental sustainability of biomass-to-chemical value chains. The use of

renewable feedstock is #7 in the list of green chemistry principles, but biomass conversion

processes should not ignore the 11 other principles" [Gallezot (2012, Forthcoming), our own

translation]. In other words, Scientific have to wonder how they can make biomass chemistry

which is both "green and sustainable" thanks to biomass by modifying the tools of GC in 270

order to link economic issues and environmental sustainability (Figure 4). Finally our

question dealing with technological path which implement the sustainable chemistry is clearly

presented.

275

280

13

Of the 15 first prizes (issued in 1996, 1997, 1998) only two can be linked to biomass chemistry in reference to

the seventh principle (so in the sense of fossil carbon substitution) . Over the past three years, 11 prices of 15 can

be directly traced to biobased products in reactions or in substrates. 14

In the case of "Green Chemistry", end of 2011, 57 of 63 articles published on the website of the journal as

"advanced section" (forthcoming in 2012) present the seventh principle of GC whereas it would be hard to find

just one article about this topic in the first issue. In the case of "Chemsuschem", the first two issues published in

2008 have no article referenced with the keyword "biomass." By somewhere else, any items containing the term

"renewable resources" were present in this review before the eighth number. Nowadays 103 articles do have it

on their first keyword and 88 in the second despite the fact that 41 articles have been referenced with the

keyword "green chemistry" all over the existence of this review (Last consultation - 13st December, 2011). 15

Example taken from the book edited by Colonna in 2006 or from the book edited by Clark and Deswarte in

2008

8

Figure 4 : The tools of Green Chemistry recomposed around biomass in order to achieve 285

Doubly Green Chemistry

Garnier (2012)

Technological path of 2GC defined by economic issues, environmental concerns and 290 productive heritages

We argue that scientists select their own peculiarities in function of economical and

technological expectations. Also it means that the tools of GC are adapted (new substrates,

new solvents, new catalysts, etc.). No technological dominant path emerge. It is confirmed by 295 the appearance of new specialized journals (as « Polymers from Renewable Ressources »

(2009), « Biofuels, Bioproducts and Biorefining » (2007)). In fact this field of application is

explored from a specific way by scientists since they have to be able to manage situations

while wondering where original reactions developed in fundamental research could be

inserted in various outlets of biomass valorizations. The "PIR Ingenotech" program is a 300 relevant example. This program is managed by chemists and economists. Firstly they observe

together how fundamental research is spreading in industrial uses. Secondly they analyze how

this same reaction can find many applications such as a catalyst plant substrate, glycerol-

based solvents or products (surfactants). Thus scientists cannot stay at one level of principles

applied in the laboratory. Instead they select the concept of 2GC from a broader context by 305 designing their innovations from environmentally and economically point of view.

Moreover, we argue that many technological paths taken over by scientists depend mainly on

the concept of "productive heritages"[Nieddu et al. (2011 & 2012), Garnier (2012)]. Working

in collaboration with our colleagues of INRA and CNRS (APERC2V ANR project) has 310 emphasized that each strategies of research and development dealing with fractionating and

biomass processing is based on knowledge and skills which are controlled in other areas. That

is why knowledge and skills are used to make the transition from petrochemistry to bio-based

chemistry. The concept of "Productive heritages" has been validated by other chemists (in

particular during a workshop in 2011) and was the subject of communications16. We will 315

present these heritage as follow. The first heritage (HP1) refers to a complete thermal

16

Lund Symposium [Nieddu et al. (2011)] and Strasbourg Symposium [Bliard et al., (2011)].

Biomass

valorizations

Reduction of materials

used

Reduction of risks and

hazards

Reduction of energy

required

Waste minimization and economy of atoms

Need of

protection

catalytic

solution

Inherently safe design

Alternative

solvant

Intensification

process

Improving energy

efficiency

Alternative

energy source

9

deconstruction of biomass. It is a process of thermochemical biomass pyrolysis for getting a

synthetic gas instead of getting it by coal gasification. The second heritage (HP2) corresponds

to enzymatic deterioration of compounds of biomass in ester (compounds of synthetic

polymers). The third heritage refers to valorization of naturally occurring compounds from 320

biomass after its extraction and limited chemical transformation (eg valorization of modified

fatty acids to produce polymers). Finally, the last heritage corresponds to the extraction in the

state of complex organic compounds and of their functionality.

Regarding this first part of our work, We have shown that there is no convergence to a single 325 technological pathway from an academic-level for implementing a techno-economic regime

of sustainable chemistry. However, this last subsection lessons points out that the diversity of

technological paths are not "anarchic" since we can classify it (Figure 5 for the technological

path of 2GC). We propose to confirm our assumptions about diversity and classification by

focusing on technological paths of techno-economic regime of sustainable chemistry at an 330 industrial level.

Figure 5 : The classification of the diversity of technological path of the doubly green

chemistry

335 Biomass

chemistry

logic

Economic logic Productive heritages Environmental logic in GC optic

Destructuring fractionation

Integrate the supply chain of petrochemical

through "modular

innovations" and by

delivering the

appropriate

intermediates (Top 10 U.S.)

Mobilization of thermochemical processes

related to traditional

chemistry (HP1)

Gasification Homogeneous and heterogeneous catalysis

Pyrolysis Break in the systems (plasma)

Hybridization of petrochemicals with

biochemical processes related to food (HP2)

Fermentation processes

Enzymatic or microbial catalysis

Non-destructuring

fractionation

Or limited fractionation

Use of existing supply chain in the food and

stationery by passing

traditional suppliers of chemical intermediates

Mobilization food and stationery’s skill in terms

of treatment of living

biomass materials complexity and of non

destructuring treatment

biomass raw materials (HP3 et HP4)

One pot cascade catalysis

Economy of steps and therefore energy, continuous processes

Photochemistry

Reactive

Extrusion

2 The dynamics of technico-scientific regime of doubly green chemistry at

an industrial level : the case of resilient floorings

The diversity of ways in Science for achieving and for applying the concept of 2GC will be 340 confirmed from an industrial level. For this, we focus in this part on upstream of the sector of

chemistry by analyzing innovation strategies of three main actors of the market of resilient

floorings in Western Europe. A short historical overview (2.1) will emphasize easier our

understanding of evolutions of strategies which call for the concept of green chemistry (2.2).

Finally we show that the families of product of resilient floorings are based on the coexistence 345 of paths from biomass valorizations (biomass path and a hybrid path) to petroleum-based

products.

2.1 The sector of resilient flooring, environmental issues and

evolutions of products by the most important industrial groups in 350

Western market.

10

Presentation of the sector and issues in terms of sustainable development

What is a resilient flooring? 355

The resilient flooring is a peculiar chemical-based product family for buildings. This products

is able to resist manipulations during processes of installation and maintenance. Its

peculiarities can be basic or complex in order to correspond to various functionalities. The

European Resilient Flooring’s Manufactures Institute (ERFMI) identifies eight families. 360

Every one depends on raw materials and processes (ERFMI, 2005). Unlike homogeneous

PVC flooring, heterogeneous PVC is made by many layers in order to respect the quality of

comfort and design. Then PVC foam aims to reduce noise and safety PVC provide high

resistance against sliding. This situation is similar to cushioned PVC and semi-flexible

products. Finally, there is also thermoplastic polymers declined in only one family. Thus the 365 use of PVC, and so petroleum, can be highly declined. Despite this diversity, two other

families of products exists. The first one is called linoleum flooring and is based on biomass

valorization and extrusions since it is feed by linseed oil, limestone, sawdust, natural resin,

mineral, natural pigments and a burlap frame ( Larsson, 1908; Gorrée et al. 2002; Potting and

Blok 1995). Consequently Linoleum is made from complex molecules by including 370 lignocelluloses. The second one is rubber which is the result of the vulcanization of natural

resin. These products belongs to the productive heritage 4 that we has seen above. Finally,

regarding the domination of PVC and the use of biomass, we conclude that these two kind of

raw material -petroleum and biomass - are in the core of Western European market.

375

Who are the leaders in the Western European market?

The origins of industry groups specialized in the production of these resilient flooring are

mainly French. First of all, Tarkett Group is the result of a joint venture between two

industrial groups which do have a parallel history. The first one is the swedish group Tarkett 380

which was elaborated in the nineteenth century in order to produce wooden flooring until

shifting its production towards PVC flooring after the World War II. Always during the same

period, the second one is the french group Sommer specialized in the production of felt and

textiles until diversifying its production for PVC floorings. The second industrial operator that

we take as an example is the Swiss group Forbo International. It begins its activity in the 385

1920s in France by producing linoleum and by uniting its activities with other European

specialists. Finally some years before World War II the french group Gerflor focus its

production on vinyl flooring in the Rhone region, a region where chemical activity is still a

large cluster. Thus regarding these histories these groups are well concerned by segmentations

of products between PVC and linoleum. As a matter of fact these segmentations emphasize 390 various competitive landscape because it depends on specializations in PVC or linoleum of

each company. Firstly, Tarkett Group gets more than one-third of market share in Western

Europe while Gerflor and Forbo International do have 10% and 5%. However, this

domination is reversed in the market of linoleum since Forbo International is an European

leader, Tarkett is a small actors and Gerflor is only a distributor17 (Interviews, 201218

). Thus 395 the various competitive advantage of theses manufacturers means that challenges of

sustainable development would be different also.

17

According to Bertrand Chammas, CIO of Gerflor (Bâtiweb, 2011). 18

Our data come from confidential interviews organizing since 2011 in the sector of resilient floorings

11

400

The sustainable issues in the sector of resilient floorings

Contributions dealing with life cycle analysis of resilient floorings learn us that PVC and

linoleum has been confronted to criticisms. Firstly criticisms about PVC floorings took place

in the 1970s because of hazardous materials. Manufacturers have been forced to find 405 alternatives by some European government, including Sweden, in order to avoid the use of

asbestos, cadmium, solvents, chlorinated paraffin forced (Schwartz, 2006; Tarkett 2006).

Even if criticisms about these adjuvants was a real issue, chlorine, a central element in the

composition of PVC, was actively contested in the late 1980s. (Schwartz, 2006). More

recently, flooring manufactures have to solve various problems. Firstly managing dangers of 410

phthalates which are endocrine disruptors in spite of giving the resiliency of products (Vinyl

2010). Secondly decreasing emissions of volatile organic compounds (VOCs) from

dissipating into the air and PVC and linoleum products are concerning (Jönsson, 1999). These

compounds could be dangerous since they are directly closed to consumers while being

located in confined areas (Jönsson , 1999; European Commission, 2004). Thirdly 415 manufacturers have to take into account the availability of petroleum for producing from PVC

and of biomass for linoleum. Fourthly, concerning energy and resources saving during life

cycle of products. For instance, by focusing on these two main families of resilient products,

the ERFMI tells us that there are similarities between them in terms of surface treatments

because their own peculiarities need less and less detergents, water and energy (EPD of 420

ERFMI, 2005; Pluijmert et al, 2008). These surface treatments have been developed for PVC

products the 1970s (Tarkett, 2006). Then, other surface treatments have emerged and have

been applying for linoleum products in order to avoid the risks of pathogens wetlands (ie

moisture). Thus, regarding environmental and health issues and our problematic, we have to

understand how biomass could be a solution to solve them. That is why, we shall describe it 425 in the relationship between products developed and relations to the environment in time by

focusing on the strategies of Tarkett, Forbo International and Gerflor.

2.2 The role of biomass in the strategies of flooring manufacturers : the

analyze of relationships between products and environmental concerns in

long period 430

The interest of petroleum resources and of biomass in the sector of resilient floorings by

manufacturers is not linear since the 19st century. Facing environmental issues, manufacturers

have developed peculiar products. We propose to emphasize three periods in order to study

strategies of these operators.

The 1st period : the environment and the use of local assets 435

Echoing the presentation of the three main actors, the first period of evolution shows that

these companies have developed their activities in function of available resources closed to

production sites. In 1870, the Swedish company Tarkett produced wood parquets from wood

which is still a very important resource in the region of Blekinge (Tarkett Environmental

Report, 2006). At the same time, Sommer, specialized in felt and textiles, was based in the 440 Ardennes in France in an area rooted in this kind of activities. Then the group Forbo

International, located in the Marne in France, began its activity by producing linoleum

product thanks to limestone which is abundant in this region. Finally, Gerflor, specialized in

vinyl flooring, is based in the Chemical Valley, a famous and a powerful area today. The first

12

period finished in the wake of the World War II and emphasizes that theses three market 445 leaders have different skills - wood, textiles, PVC and linoleum - and their relationship

between products and the environment was based on the exploitation locally available

resources (Interviews, 2012).

The 2nd period : the convergence on petroleum-based technologies and the emergence

of issues related to safety product 450

At the end of World War II the relationship between products and environmental concerns

emerge. It is due to lower prices of petroleum, higher prices of wood and the need to rebuild a

devastated Europe. Consumer society and industrial activities has expand business portfolios

of manufacturers by providing PVC products and linoleum (Potting and Blok 1995, Schwartz 455 2006). Yet during this period, the production of PVC has a peculiar interest. Indeed, in 1947,

Tarkett Ronneby reorganized its production processes towards PVC flooring thanks to Willy

Sen, Swiss chemist, (Tarkett, 2006, Schwartz 2006). Gerflor and Forbo International follow

this trend without forget linoleum. Year after year, the maturity of the production process of

PVC was so important that the first wastes (loose laying) during installations has been 460 recovered and recycled by Tarkett in 1956 (Tarkett, 2006). Yet this prosperous period has

been questioned because of environmental concerns. That is why, in the wake of the 1990s,

collective strategies emerged in order to applying the concept of sustainable chemistry (Ibid).

The 3st period : collective actions for moving towards a sustainable chemistry 465

In the wake of the 1990s, many disciplines converge in order to solve environmental issues.

While economists were questioning the concept of sustainable development, chemists

developed the concept of green chemistry (Anastas & Warner, 1998) and engineers applied

the concept of industrial ecology (Frosch & Gallopoulos, 1989). These contributions drive the 470 sector of resilient floorings by reviewing innovation projects in order to respect the concept of

green chemistry and applying it on an industrial scale. What are the consequence of it? As a

matter of fact collective actions has been needed for applying the 12 principles of green

chemistry. Saving wastes, energy and the substitution of hazardous substances are priorities.

In the early 1990s solving these issues was determined by European manufacturers, including 475 Tarkett, Forbo International and Gerflor, that is called European PVC Flooring

Manufacturers. Then, it becomes the European Resilient Flooring Manufacturers' Institute

(ERFMI) and follow until fourteen manufacturers19 in Western Europe. Moreover, the

maturity of these collective actions helped the sector for being integrated in a bigger project :

the European project Vynil 2010. This project includes the market of plastics and recycling 480 programs (EPFLOOR for resilient floorings). (The European PVC Industry's Sustainable

Development Programme 2011). The ERFMI coordinates the European meanwhile the

French Union (SFEC) manages the project called Sol PVC (European Commission, 2004; Sol

PVC pro, 2012). Manufacturers can manage flows of materials and energy in order to

minimize the amount of waste of energy required thanks to these recycling centers which are 485 closed to production sites. In parallel, these collaborations help each members for finding

alternatives to phthalates and VOC (The European PVC Industry's Sustainable Development

Program 2011). Thus, we argue that these collective actions converge towards a sustainable

chemistry (green chemistry). Yet the role of biomass is not clearly identified.

19

ERFMI members in 2011 are : The Altro Group plc, Amorim Revestimentos, S.A. Amtico International,

Armstrong DLW GmbH, Beauflor, Forbo International, S.A. Gerflor S.A., IVC, Juteks d.d., Mondo S.p.A, Nora

Systems, GmbH Polyflor Ltd., Tarkett SAS, Upofloor Oy

13

490

PVC and biomass, two assets for the quest of the doubly green chemistry for resilient

floorings

PVC and linoleum floorings are different. Waste and energy saving minimization while

reducing the risks by substitutions are the common challenges of the sector in order to be on 495 the same wavelength of the principles of green chemistry. Yet a better understanding of the

design of linoleum and PVC products show that biomass is becoming the core of new design

processes in order to applied the concept of doubly green chemistry. Moreover this quest open

the way to diversity.

500

Various development path for resilient floorings coming from 2GC

First of all, in the case of Tarkett, the productive heritage 4 dealing with linoleum is located in

Italy and is base on a local production wherein linseed oil comes from for animal feed20. This

initiative is due to the “Cradle to Cradle” certification that has been followed also by Forbo

International in 2012 . It means that this old Bio-based product has been able to to resist 505

competitions with PVC. This product is difficult for recycling because of its complexity. That

is why it is not allowed in the program specifically EPFLOOR. Yet it can be transformed in

compost or incinerated thanks to its high energy capacities (ERFMI, 2005). Thus regarding

the role of biomass in linoleum products we argue that they can be based on the concept of the

doubly green chemistry. Then, during the 2000s, manufacturers link PVC products to the 2GC 510 from a peculiar path. REACH regulation EC 1907/2006 in 2007 forces them to adopt free

phthalates products while decreasing of volatile organic compounds (European Commission,

2007). Innovation projects propose to hybridize PVC with platform molecules from biomass

while being recyclable, renewable and less dangerous. For instance, Tarkett produces IQ

homogeneous products derived from natural castor oil (Tarkett 2012). It is the same case for 515 Forbo International who has invested in Bio-based resins (ARD, 2010). Finally, Gerflor call

for the uses of Bio-based molecules Polysorb produced by Roquette Group - at a conference

in 2011 called Plant Based Chemistry in 2020 [Convers and Thumerel (2011), Formule Verte

(2011a), p.6; Formule Verte (2011b), p.38]. These Bio-based molecules are polymers

designed by thermochemical or biochemical process. Therefore, we argue that these new 520 hybrid products are productive heritage 1 or 2. These products are available only through

cohabitation between biomass and PVC and reduce the risks and health hazards while

providing a degree of recyclability, thereby enhancing and saving energy and matter. In

conclusion, we have here a mixed strategy between doubly green chemistry and green

chemistry. 525

One development path for resilient floorings coming from green chemistry without

biomass valorization

Some adaptations of products taking into account a sustainable chemistry do not follow this

last trend. Indeed even if recycling and energy saving are improved thanks to hybrid PVC

flooring, pure PVC products take on other path and stay over time. As a matter of fact, PVC 530 products are maintained in function of the complexity of their functionalities most of them do

have a single layer such as homogenous products while heterogeneous have nine layers

[ERFMI, (2005)]. Consequently, processes of dematerialization are more or less easy. In 2004

about 7.5% of recycled materials in 2004 was include in new product in order to saving fossil

20

For more information, see the environmental performance of linoleum products by Tarkett

14

resources (ERFMI , 2005). Today, nearly 25% or more are included[Tarkett (2012), The 535 Architect's Newspaper, Gerflor, (2011)]. Beside, new products emerge from this strategy. For

example, Gerflor is able to inject 32% 53% 55% and 100% of recycled products in order to

propose a variety of solutions for consumer needs. Thus these cases emphasize the fact that

PVC products melted by thermochemical process to preserve assets are based on the

principles of green chemistry. 540

Finally strategies in the sector of resilient floorings show three period that can be

characterized by various relationship between products and environmental concerns and by

various interests for biomass valorization. These evolutions show the emergence of

collaborative actions in order to achieve sustainable chemistry. Details point out the fact that

current strategies were developed for getting the coexistence of diversity of paths. On the one 545 hand trajectories based on the concept of green chemistry (without priorities of biomass

valorization) and on the other hand trajectories based on the quest of doubly green chemistry :

this diversity of products can be summarizes in the table below.

Figure 7 : The principles of diversities in the adoption of GC and the 2GC for PVC and

linoleum products in the sector of resilient floorings (made by ourself) 550

Conclusion and Discussion

This paper discusses on the emergence of a new techno-economic regime by studying the

concept of dominant design and of winning technology. We wondered if the sector of 555

Identity of

products Bio-based (1) Hybrides (2) Petroleum-based (3)

Compositions

Biomass Petroleum

natural resin Fibers Wood Linseed oil

Platform

molecules

Recycled

materials

Pure

materials

Functionalities Surface treatments (energy and material saving)

Family of

products

Linoleum

Productive heritage 4

Biobased PVC

products

Productive

heritage 1 and

2

PVC products

Strategies Doubly green chemistry (2GC) Mixed strategy

(2GC and GC) Green chemistry

Manufacturers Tarkett, Forbo International

Tarkett, Forbo

International ,

Gerflor

Tarkett, Forbo International

, Gerflor

Diversity Maintaining and new characteristique in terms of

maintanace Yes Yes

15

sustainable chemistry was moving towards a single and a dominant technological path, as it

has been suggested by Geels’ canonical model, or if variety of technological paths was

maintaining over time. For this, our work is based on a multi-level perspective. More

precisely at two places in this sector. First of all we focused on academic chemistry. Then we

analyzed industrial developments. 560

Regarding the academic sphere, the concept of sustainable chemistry emphasizes two steps in

terms of representations and of development paths. Firstly, after having taken various names

and many forms, this concept has been reinforced thanks to the concept of "Green Chemistry"

in which the valorization of plants was included but not really stabilized. Secondly, during the

2000’s, the dominance of this concept was disturbed until a real turnaround. Indeed, at that 565

time, the academic world has concentrate its development efforts on a sustainable chemistry

which is based on the recovery of plant resources. This is the reason why the most of tools of

"Green Chemistry" have been redeployed for it and we called it "doubly green" (2GC) (ie a

sustainable chemistry of the plant) whose takes various forms.

Then, regarding the sphere of industrial developments, we analyzed one peculiar case of 570

chemistry: the domain of resilient floorings. Our work emphasized the coexistence of the

concept of the "Green Chemistry" in which is included the concept of "Doubly Green

Chemistry". Basically our work points out are three families of products. The first one is

based on plastic products which are designed by melting PVC and recycled PVC (GC

strategy). The second one is the linoleum which is a former product and designed from Bio-575 based products since it requires, for instance, sawdust and linseed oil (2GC strategy). The

third one is a hybrid product because it mobilizes PVC, PVC recycled and Bio-based

plasticizers in order to avoid hazardous products (i.e phthalates) while managing the elasticity

of assets (mix-strategy between GC and 2GC).

In a nutshell our results point out that there is no emergence of a single dominant 580 technological path for sustainable chemistry as it is suggested by Geels’ canonical model.

Instead, there is a variety of technological path maintained over time.

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