Fluorochemicals used in paper and packaging - is the new C6 chemistry an advance on the problematic C8?

To the many of you who read the earlier blog on fluorochemicals and their use in paper, and any others with an interest in this topic, it may be worth reading the recent article by the Environmental Working Group (EWG).

EWG, 'Finds no evidence that the industry-touted replacement chemicals being rushed to market are safer -- and plenty of evidence that DuPont and other manufacturers are continuing a decades-long pattern of deception about the health risks of PFOA and related chemicals.'

EWG make the point that the move from C8 to C6 chemistry is,

'Greenwashing – claiming environmental benefits for a product that's little better than its replacement – at its worst. PFOA is so remarkably persistent in the environment and broadly toxic to living organisms that using it as a bar against which to judge "green chemistry" is like calling anything under 200 miles per hour a safe speed limit. For C6 replacements, the full extent of the public record on their safety consists of a PowerPoint presentation delivered by Asahi Glass Company to the Environmental Protection Agency. Public records show that DuPont, Asahi, and Clariant are all shifting from PFOA to C6 chemistries despite an absolute dearth of public safety data, and despite the fact that on 3 critical counts, C6 may be as great a concern as PFOA:

• C6, like all the other PFCs, is extraordinarily persistent in the environment (NAS 1972).
• C6 is potentially 3 to 5 times more toxic than C8 to aquatic organisms (Asahi 2006).
• C6 crosses the placenta to contaminate children before birth, according to an EWG study of umbilical cord blood from 10 newborn babies (EWG 2005). While many studies of thousands of people by CDC, industry, and academic university researchers show that PFOA contaminates nearly the entire U.S. population, industry has failed to publish even a single study of C6 in people. EWG's tests of cord blood show it to be potentially as great a concern as PFOA.

EWG certainly make some good points in amongst the sometimes emotive and hyperbolic writing. The fact remains, does it make sense to continue with fluorine chemistry? Surely this is an opportunity to develop and market fluorine-free alternatives.

The main companies involved in the manufacture and supply (directly or indirectly) of fluorine-based chemicals to the paper industry are: Arkema, Asahi, Ciba, Clariant, Daikin, DuPont, 3M/Dyneon and Solvay Solexis. There are others.

Fluorine-based chemicals are mainly used in paper and packaging to give grease-resistance (eg pizza boxes, burger wrap, butter wrap, soap wrap, pet-food bags). Alternative barriers are available for some of the current applications, but in some of the more demanding applications it has been difficult to find chemicals which perform as well as those containing fluorine with its unique physical properties. Finding fluorine-free alternatives is an opportunity.

California first to introduce a bill to ban the introduction of PFCs into food packaging - Why are they alone?

At last there has been a move somewhere in the world to challenge the lengthy, voluntary withdrawal of the use of fluorochemicals containing PFCs from use in applications such as food packaging. This topic has been covered before in this weblog and the question asked as to why there should be a voluntary agreement with the EPA to withdraw these products when there is clear evidence that they are harmful.

See the weblog on the EPA announcement that the big manufacturers are on track, or that on the recent DuPont study to produce evidence as to the fate of fluorochemicals in the environment.

The question remains, why wait until 2015? In many papermaking applications there are alternatives, but if there are not, then increased pressure will generate innovation.

Enviroblog covers this topic well and highlights the recent bill filed by California State Senator Ellen M. Corbett which would make California the first state to ban some PFCs in food packaging. The bill, sponsored by EWG, would prohibit more than trace amounts of two PFCs called PFOS and PFOA in any material used to package food, beginning in 2010.

The big producers working with the EPA include Arkema, Asahi, Ciba, Clariant, Daikin, DuPont, 3M/Dyneon and Solvay Solexis.

Nalco elects du Pont's Frywald to fill Joyce's large shoes

Nalco has elected J Erik Frywald to succeed Dr William H Joyce as Chairman, President and CEO, effective the 28th February, 2008. Since 2003, Fyrwald had been Group VP of the $6.8 billion Agriculture and Nutrition division at E.I. du Pont de Nemours and Company, where he reported to its Chairman and Chief Executive Officer.

Paper fluorochemicals and PFOA - new Du Pont study adds to debate on grease-resistance chemicals being source of PFOA

A recent publication by DuPont scientists adds to the current debate on whether paper chemicals (and other fluorotelomer-based products used in textiles, carpets etc) are a source of PFOA. This peer-reviewed report describes a long-term study of the degradation of perfluorinated polymers in soil. ES&T online have given a good review of the study and views on the validity of the conclusions and the opinions of key bodies such as the EPA.

The jury is still out:

• PFOA has been shown to cause liver damage, reproductive problems, which has seen it labelled a “likely carcinogen” by the Environmental Protection Agency EPA's Science Advisory Board.
• PFOA is bioaccumulative, has been found widely in the environment and is a big concern.
  
• The DuPont study concludes that the PFOA and PFCAs come from impurities, also known as residuals or precursors, in the fluoropolymer product they tested (stain repellant solution). As a result, they conclude that the polymer degrades very slowly, with a half-life of 1200–1700 years and degrades too slowly to be a current source of PFOA in the environment. Others disagree with the conclusions and have raised a number of valid ponits regarding the interpretation of the results and conclusions drawn from the study.
  

Time for a quick summary of where the paper chemical supply industry is with perfluorinated chemicals (PFCs) such as PFOS (perfluorooctyl sulphonate) and PFOA (perfluorooctanoic acid). Perfluorinated chemicals (PFCs), gained notoriety in the paper chemicals industry when in the late 1990's, 3M Corporation announced they would withdraw their successful Scotchban fluorochemicals from the market. These chemicals were sold for use in grease-resistant paper and board and it became clear that PFOS (perfluorooctyl sulphonate) was detected widely in the blood of humans - PFOS is a PFC and is classified as persistent, bioaccumulative and toxic (PBT). The details and history of PFOS are outlined on the EPA website or in a number of environmental-concern sites (eg EWG). Although the production of products containing PFOS has been stopped, ongoing blood sampling continues to reveal the presence of PFOS (eg WWF and The Co-operative Bank).

The findings on PFOS led the EPA in 2000 to review similar chemicals, including PFOA (perfluorooctanoic acid) to determine whether they might also present concerns. In essence, PFCs accumulate in the environment and have been found in a wide range of wildlife, as well as in humans. There is evidence to suggest that exposure to perfluorinated chemicals such as PFOS and PFOA may cause birth defects, adversely affect the immune system and disrupt thyroid function, which during pregnancy, can lead to many developmental problems (there are a number of references but for example see the WWF or the very effective Environmental Working Group's web sites). The US Environmental Protection Agency also considers both PFOS and PFOA to be carcinogenic and occupational exposure to PFOS has been correlated with increased incidence of bladder cancer.

The generation of PFOS was linked to the electrolytic process used by 3M and a Japanese manufaturer and it was known that the other process used by companies such as DuPont, called telomerisation would not generate PFOS. However, in producing a number of fluorine-based chemicals (not paper chemeicals), PFOA is used as a processing aid and later science showed how PFOA could be produced as an unintentional by-product.

Where are we now with the EPA investigation:

• There is evidence to suggest that exposure to PFCs may cause birth defects, adversely affect the immune system and disrupt thyroid function, which during pregnancy, can lead to many developmental problems.
• PFOS is a by-product of the electrolytic process used originally by 3M and ..... PFOS is classified as persistent, bioaccumulative and toxic (PBT). Paper chemicals produced using the electrolytic process has been withdrawn.
  
• The US Environmental Protection Agency (EPA) "invited" eight companies (DuPont, 3M, Arkema, Asahi Glass, Ciba Specialty Chemicals, Clariant, Daikin and Solvay) to participate in the 2010/15 PFOA Stewardship Program, by pledging to reduce PFOA releases from manufacturing and in products by 95% by 2010, and to work toward the elimination of PFOA and its precursors from emissions and products no later than 2015. All emissions figures are based on a 2000 baseline and the commitments will apply to both to US and global operations. Chemical intermediates that break down to PFOA in the environment are also included as are similar perfluorinated compounds with longer carbon chains.
• PFOA is formed as degradation products of small polymers called fluorotelomers and as the unintended by-product of their manufacture. Fluorotelomers are used in a range of commercial products, including fire fighting foams, as well as soil, stain and grease resistant coatings for carpets, textiles, leather, paper, including fast food packaging, as well as personal care and cleaning products.
• Once released into the environment, perfluorochemicals including PFOA persist and are now widely distributed throughout the global environment. They are reported to be found in food samples and have been detected in almost all human blood samples tested.
• Studies show that PFOA does not break down by any known environmental degradation mechanism that is by hydrolysis, photolysis, or biodegradation.

So, are paper chemical manufacturers and suppliers continuing to sell fluorochemicals containing PFCs or PFC precursors?

• The answer is yes.
• Trademarks of fluoropolymers used to give grease-resistance in the paper and board industry: Zonyl (DuPont), Lodyne (Ciba), Cartafluor (Clariant).

Many environmental-concern groups have worked hard to expose and bring an end to the release of PFOS and PFOA and significant pressure has been put on manufacturers to develop PFC-free alternatives. The big question is why, when it is known that PFOA is persitent, bioaccumulative and toxic, that its release into the environment is not stopped immediately. Reducing emissions between now and 2015 is at least a start.

Are there alternatives to PFC-containing products?

• Fluorine is a unique compound with unique properties so changing to chemistries such as silicone bring a loss of performance. In some applications this lower level of performance could be sufficient. Solvay has an alternative to fluorine. In some applications it is possible to use barrier coatings based on latex formulations and/or waxes.
  
• The smaller molecule, fluorosurfactant-based products were of immediate concern as they would be more likely to be adsorbed by animals. Therefore, an approach has been to favour higher molecular weight fluoropolymers. This does not necessarily remove the hazard as by-products can be generated in the manufacturing process and the polymer itself has the potential to degrade in the environment and generate PFOA (it was this hypothesis which the DuPont scientists were studying).
• Some companies have put effort into C4 and C6 fluorotelomers rather than the traditional C8 chemistry with the view that the environmental and toxicological effects would be reduced. However, there have been no breakthroughs in producing cost-effective paper chemicals so far.
  

Some additional reading:
C&EN article
ACS article
CEE Food Industry Article

ICI frustrated with Akzo Nobel ....... request put-up-or-shut-up order

To continue the story from an earlier blog, the FT has reported that, "ICI has asked that the Takeover Panel issue Akzo Nobel with a “put-up-or-shut-up” order. ICI rejected the £7.2bn (€10.7bn) takeover by Akzo but has had no formal contact with the Dutch company since.

The FT report states that, "ICI’s leading shareholders have said that any offer for the company should be above 700p. But some analysts warned that at that price the deal would destroy value for Akzo. The offer of 600p a share is equal to a multiple of about 11.5 times earnings before interest, tax, depreciation and amortisation. At 700p, this multiple rises to 12.5 times. Recent deals in the sector have been at similar, if not higher, levels."

The FT report goes on to state that, "A second approach could trigger competing bids from rivals including BASF, DuPont and Dow Chemical, and possibly from private equity. Akzo has repeatedly said it would not overpay for ICI. The company is sitting on a large cash pile after it sold its pharmaceuticals business to Schering-Plough, the US drugs group, for £11bn in cash in March.

Shares in ICI have risen more than 40 per cent in the past six months on takeover speculation. Some analysts say the antitrust issues, as well as ICI’s large pension, deficit would be a hurdle for any takeover, but not an insurmountable barrier."

The relevance for paper chemicals is that Akzo Nobel own Eka Chemicals and ICI own National Starch.

Akzo Nobel make a strong move to acquire ICI ........ where would this leave Eka Chemicals and National Starch?

In the future, will Eka Chemicals and National Starch both be owned by Akzo Nobel?

Akzo Nobel confirmed this morning that it approached the board of ICI with a view to entering into discussions about a cash offer for ICI. The 600p a share (GBP 7.2 bn bid) offer was rejected by ICI, but the door is left open for a higher offer coming from Akzo Nobel (see articles in the Financial Times and Wall Street Journal). There is also the sensitive issue of the ICI pension fund to resolve and today the trustees made it clear that they have the power to determine the size of the pension deficit which could range from GBP500 mio to GBP 2.2 bn and that the trustees would expect discussions with any serious suitor (see FT article).

Many analysts consider 600p to be an attractive price, and feel this approach could start competing bids from rivals including BASF, DuPont, Dow Chemical, and even possibly from private equity companies.

Regarding the paper chemicals activities of Eka Chemicals and National Starch, there would have to be a question as to whether the business fits with the core activities and future focus of Akzo Nobel.

"In parallel, Akzo Nobel will continue its share buy-back program of €1.6 bn launched on May 3, 2007 and will further evaluate tax efficient options of returning cash to shareholders and optimizing its capital structure consistent with its growth strategy."

For further comments, and a warning to ICI against rejecting Akzo's approach just to protect its old ICI pride when Akzo could be the best option it has see the FT Lex article. Although, Forbes thinks otherwise, and through the day ICI share value has increased.

Bioploymers from renewable resources .......

Using renewable resources has hit the top of the science agenda and now is the time for all the old paper chemical products developed from renewable resources to be put back on the table. There have always been projects based on renewable resources but most were before their time and rejected in favour of traditional, lower cost materials based on petrochemicals. In the early days of Biopol, a biodegradable 'plastic', there were many efforts to develop applications in papermaking (eg biodegradable barrier coatings) but the projects struggled to be commercially viable.

Paper chemicals suppliers had started to replace mineral oils (eg emulsion retention aids, defoamers) with plant oils; there have always been surfactants based on plant or animal-derived fatty acids; steric acid has been widely used in de-inking; and there are many other examples of the use of renewable resourced-based paper chemicals. With the increased cost of oil and the 'climate change' drive to using bio-rawmaterials there has never been a better opportunity to engineer new bioproducts. There are exciting advancements in engineering new biopolymers (see the DuPont announcement), and an opportunity to commercialise many new pulp and paper biochemicals in the future.

Just a word of caution - there is no guarantee that raw materials from plant origin will provide a cost-effective and 'green' source of raw materials. The biofuel story remains controvertial and there are questions regarding the environmental impact and sustainability of making more land available for producing biofuel - prices of raw materials from bio-sources have increased so the price balance between petrochemicals and renewable sources will determine the future competitiveness and viability of the two sources.