New Generation of FluoroTechnology

Why are users switching to alternative chemistries? What is driving the change?

FluoroCouncil member companies are moving away from traditional long chain perfluorinated chemicals (LCPFCs) toward alternative chemistries such as short-chain fluoroproducts that offer similar application properties, but with improved environmental and biological profiles.

This movement has been driven by multiple factors and on multiple fronts. In general, stewardship concerns relative to LCPFCs, particularly bio-persistence, started the change. This fostered global regulatory activities which have encouraged the transition away from LCPFCs and supported the introduction of alternative chemistries. This has also resulted in a general regulatory direction toward greater restrictions and bans for LCPFCs. Debate by and information from international organizations such as the Stockholm Convention on Persistent Organic Pollutants (POPs), the United Nations Environment Programme (UNEP), the Strategic Approach to International Chemicals Management (SAICM), and the Organisation for Economic Cooperation and Development (OECD) have reinforced this movement.

Importantly, many downstream users of these products, including major consumer retailers and brands, are beginning to indicate an understanding of these issues and a preference for products that are not produced with or do not use LCPFCs.

Environmentally conscious companies are supporting this transition toward more sustainable chemistries. These companies have engaged with governments and regulators at the national and international level to facilitate this global transition. These companies embraced the US EPA’s 2010/2015 PFOA Stewardship Program, a global partnership between the U.S. Environmental Protection Agency (US EPA) and industry. The partnership is based on voluntary commitments to corporate goals to reduce human and environmental exposure to PFOA, precursors and higher homologues by eliminating those chemicals from facility emissions and product content by the end of 2015. These Stewardship Companies have made significant investments in the development of alternative chemistries that use new technologies to improve their environmental and biological profile.

What are the alternatives to long-chain perfluorinated chemistries?

Alternatives to LCPFCs fall into two broad categories:

Fluorinated Products:

  • Short-chain fluorotelomer-based 6 fluorinated carbon functionality compounds
  • Electrochemical fluorination-based 4 fluorinated carbon functionality compounds – perfluorobutane sulfonate (PFBS) [Shorter chain perfluoroalkyl sulfonates]
  • Mono- and poly-fluorinated ether functionality compounds (e.g., CF3 or C2F5 or -CF(CF3)CF2-fluoroalkyl polyethers)
  • Fluorinated oxetanes
  • Other fluorinated polymers

Non-Fluorinated Products:

While non-fluorinated products are available for some current uses of LCPFCs, e.g. certain surfactants, they are generally not suitable for the majority of applications because they do not provide the required performance in use.

  • Propylated naphthalenes or biphenyls
  • Fatty alcohol polyglycol ether sulfate
  • Sulfosuccinate
  • Hydrocarbon surfactants
  • Naphthalene derivatives
  • Siloxanes and silicone polymers
  • Other proprietary non-fluorinated materials

The most widely successful fluorinated alternatives have been materials in two classes:

Surfactants:

  • Converting from ≥ 6-Carbon to 4-Carbon-based sulfonate chemistry
  • Converting from ≥8-Carbon to 6-Carbon fluorotelomer chemistry
  • Converting from 8- and 9-Carbon perfluorocarboxylate polymerization aids (PFOA/PFNA) to certain mono- and poly-perfluoroethers or other substances.

Surface Modification Polymers:

  • Converting from ≥6-Carbon to 4-Carbon-based sulfonate chemistry
  • Converting from ≥8-Carbon to 6-Carbon fluorotelomer chemistry

How are the alternative short-chain perfluorinated chemistries different from the older, long-chain perfluorinated chemistries?

A primary consideration in identifying alternatives to LCPFCs is whether data indicate that the alternatives offer reduced bio-persistence and a reduced environmental footprint. When evaluating alternatives, another priority difference is whether they maintain efficacy in use, to ensure continued production of high performance fluoroproducts that provide critical benefits to society. Cost-effectiveness and minimal customer disruption are also considered in evaluating alternatives.

The alternative short-chain chemistries offered by FluoroCouncil member companies offer significantly reduced bio-persistence and a reduced environmental footprint as well as maintaining efficacy in use.

Do the alternatives perform as well as the long-chain chemistries?

FluoroCouncil member companies understand that performance is a key priority in evaluating alternatives to long-chain perfluorinated chemicals (LCPFCs). Each company has worked to design alternatives that meet the high performance needs demanded by industries that rely on the unequaled properties of FluoroTechnology. Alternatives to PFOA are now available that allow the manufacture of fluoropolymers products with equal or improved performance. Long-time users of C8/long-chain products also continue to switch to alternative chemistries such as C6/short-chain fluoroproducts to meet their performance needs and sustainability goals.

Are there alternatives for all of the applications for which the older chemistries were used?

Alternatives now exist for most of the uses of the LCPFCs.

Are there non-perfluorinated products available?

While non-fluorinated products are available for some current uses of LCPFCs, e.g., certain surfactants, they are generally not acceptable for the majority of applications because they do not provide the required performance in use. The most widely successful alternatives have been fluorinated materials.

Will there be access to the newer chemistries, particularly in countries with developing economies?

Yes, the new chemistries will be available worldwide as regulatory approvals are obtained where required.

What will be the transition period from old to new chemistries?

Short-chain alternatives are available for a broad range of applications, and regulatory approvals are being obtained. FluoroCouncil member companies are working closely with customers to meet their needs and to fulfill the Stewardship Program commitments to virtually eliminate the old chemistry by the end of 2015.

The FluoroCouncil has also continuously worked with regulators and others to encourage non- Stewardship Program companies to adopt the Program’s principles and goals to eliminate PFOA and related chemicals from facility emissions and product content. Such commitments would further facilitate the transition to new, improved chemistries.

Why is it important for users to convert to the alternatives?

FluoroTechnology producers and users with a stewardship focus are acting now to transition toward alternative chemistries such as short-chain fluoroproducts that offer similar application properties, but with improved environmental and biological profiles. Global regulatory activities are encouraging the transition from LCPFCs and supporting the introduction of alternative chemistries. This has resulted in a general regulatory direction toward greater restrictions and bans for LCPFCs. International organizations such as the Stockholm Convention on Persistent Organic Pollutants (POPs), the United Nations Environment Programme (UNEP), the Strategic Approach to International Chemicals Management (SAICM), and the Organisation for Economic Cooperation and Development (OECD) have reinforced this movement.

Unfortunately, not all FluoroTechnology manufacturers have made the same stewardship commitments as the members of the FluoroCouncil and other participants in the PFOA Stewardship Program. Production and use of the old chemistry continues by companies in China, India, and elsewhere, without commitments to reduce emissions or product content. This lack of action stands to threaten the global emissions and body burden gains seen through the success of the Stewardship Program. The FluoroCouncil has continuously worked with regulators and others to encourage the entire industry to adopt the principles of the Stewardship Program and maintain these successes.

What is the position of downstream customers relative to the conversion to alternatives?

Based on stewardship commitments and educational efforts of the FluoroCouncil member companies, many downstream users of these products, including major consumer retailers and brands, are beginning to understand of these issues and a preference for products that are not produced with or do not use LCPFCs. In fact, more and more customers are converting. There is also an understanding that fluorinated chemistries, such as the short-chain products, are necessary to provide required performance in most applications.

Have data on the C6/short-chain alternatives been generated?

Recognizing questions about long-chain PFCs, regulatory authorities have increased their scrutiny during assessment of proposed alternatives. The C6/short-chain products currently on the market designed to replace long-chain PFCs have been rigorously evaluated by industry and assessed by regulators. FluoroCouncil members have worked with U.S. EPA in its review of alternatives to long-chain PFCs, providing data on their improved safety and effective use. To date, EPA has reviewed over 150 alternatives. As part of their strong, ongoing commitment to product stewardship, FluoroCouncil members are also continually developing additional data on the toxicological and biological profiles for C6/short-chain products.

What is the safety profile of the newer chemistries?

A primary consideration in identifying alternatives to LCPFCs is whether data indicate that the alternatives offer improved biological and environmental profiles (for raw materials, impurities, potential degradation products and the commercial products). Alternative materials are evaluated for these human health and environmental considerations and safety in use and are being approved for use by regulators around the world.

Have the alternatives been thoroughly reviewed by competent regulatory authorities?

For the newer alternatives such as short-chain fluoroproducts, supporting data have been submitted for detailed regulatory reviews to obtain necessary approvals. These approvals generally require detailed data sets to robustly define hazard and exposure profiles.

Can the C6/short-chain products break down to PFOA, PFOS or PFHxS?

A considerable number of studies have been conducted to identify the degradation products associated with the alternatives. Based on these studies, it has been determined that short-chain products cannot degrade to long-chain substances such as PFOA, PFOS or PFHxS.

Are the C6/short-chain alternatives expected to be harmful to human health or the environment?

A significant volume of data supports the conclusion that C6/short-chain substances are not expected to be harmful to human health or the environment. Many C6/short-chain alternatives are high molecular weight polymers that are not bioavailable.

An important degradation product associated with the C6/short-chain alternatives is perfluorohexanoic acid (PFHxA). According to the U.S. Environmental Protection Agency,1 PFAC chemicals with fewer than eight carbons, such as perfluorohexanoic acid (PFHxA), are not considered long-chain PFAC chemicals. These shorter-chain PFAC chemicals are not part of [the long-chain perfluorinated chemicals] action plan because data in non-human primates indicate that they have substantially shorter half-lives in these animals than PFOA and are less toxic than long-chain PFAC chemicals.

1 U.S. EPA refers to this broad class of chemicals as perfluoroalkyl carboxylates or PFAC chemicals.

How quickly is PFHxA eliminated from the body?

PFHxA has been evaluated in a considerable number of environmental and toxicity studies. A significant volume of data supports the conclusion that C6/short-chain substances such as perfluorohexanoic acid (PFHxA) are readily eliminated from the body. Studies used to model half-life in humans show that the half-life of PFHxA in humans is approximately two orders of magnitude less than the half-life of PFOA. This supports the sustainability goals of the apparel industry and regulators by addressing concerns about the long elimination half-life of the long-chain PFCs used in the past.

An assessment of available data on the persistent organic pollutant (POP) characteristics of several short-chain substances and PFHxA can be viewed here.

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