Formaldehyde is an extremely useful industrial chemical but also
one that has long been known to cause environmental health problems
in some circumstances. A major route for human exposure is inhalation
of formaldehyde gas emitted from urea- and phenol-formaldehyde resins
used as adhesives in engineered woods such as plywood and particleboard.
Industrial workers are exposed to significantly higher amounts of formaldehyde
than the general public, although residents of new homes built with
engineered wood materials often experience symptoms, especially soon
after moving in. Formaldehyde concentrates in indoor air, with known
and suspected human health effects ranging from eye irritation to cancer.
Now a new adhesive using soy protein, processed
to resemble the protein that allows mussels to cling to rocks, is
enabling some manufacturers to make formaldehyde-free engineered
woods. Developed by Kaichang Li, an associate professor in the wood
science and engineering department at Oregon State University in
Corvallis, the soy adhesive is being hailed by many as a nontoxic,
economically attractive, and renewable solution to a long-standing
environmental health issue.
Formaldehyde Figures
Soy adhesives are not new, having been used
in commercial wood products as early as the 1920s. But like other
vegetable glues, they were water-soluble and too chemically unstable
to provide the necessary durability. The 1930s saw the introduction
of urea- and phenol-formaldehyde adhesives derived from petroleum
and natural gas. When cured using heat and pressure, these formaldehyde
adhesives easily outperformed the soy glues of the time. The construction
and wood products industries embraced the formaldehyde-based adhesives
wholeheartedly.
According to the National Toxicology Program’s 2004 Report
on Carcinogens, 11th Edition (ROC), the amount of formaldehyde
manufactured has steadily risen over the last 75 years, and in 1998
(the latest year for which figures are available), 11.3 billion pounds
of formaldehyde were produced in the United States. An overview of
the formaldehyde market in the 12 June 2002 issue of Chemical
Week, an industry publication, noted that the formaldehyde used
in wood adhesives make up half of all formaldehyde made.
More than 1.8 million U.S. workers are exposed to formaldehyde on
the job, according to the National Institute for Occupational Safety
and Health (NIOSH) “current intelligence bulletin” on formaldehyde.
Embalmers, laboratory workers, and textile workers making permanent-press
fabrics are the most highly exposed, but wood industry workers are
also high on the list.
Among the general public, the 2.2 million people who live in mobile
homes made with engineered wood products make up the largest formaldehyde-exposed
group, according to the ROC. That’s because these structures
are more airtight than conventional homes and thus concentrate whatever
fumes occur in them. Further, conventional homes tend to be built with
more solid wood compared to manufactured homes (although some residents
of conventional homes have also been exposed to high levels of formaldehyde--during
the 1970s a urea-formaldehyde foam was used in insulation; use of this
foam was discontinued in the early 1980s, however, and most of the
foam’s formaldehyde has long since dissipated). Many consumer
products, including nail polish remover, permanent-press fabrics, and
deodorants, also contain formaldehyde.
Formaldehyde from both natural and man-made sources is generally
present at about 0.03 parts per million (ppm) in both indoor and outdoor
ambient air, according to the Consumer Product Safety Commission document “An
Update on Formaldehyde: 1997 Revision.” This is much lower than
the worker exposure limits of 0.75 ppm over an 8-hour period and 2.0
ppm over a 15-minute period set by the Occupational Safety and Health
Administration.
There is wide variation in individuals’ sensitivity to formaldehyde.
According to a 1995 International Agency for Research on Cancer monograph
on wood dust and formaldehyde, concentrations above 0.5-1.0 ppm can
cause irritation of the eyes, skin, nose, throat, and lower airways.
Acute or long-term exposure may lead to other problems. In rats, ingestion
of high doses produces problems such as breathing difficulties and
vomiting. In humans, ingestion can also corrode and trigger hemorrhaging
in the gastrointestinal tract, as well as cause cardiovascular collapse
and convulsions, according to a review in the 19 June 2000 issue of Human
and Experimental Toxicology.
Rodent studies have established a link between formaldehyde exposure
and cancer of the nasal cavity, and human epidemiologic studies have
found associations between formaldehyde and nasopharyngeal, nasal,
prostate, lung, and pancreatic cancers as well as leukemia, although
other studies have not always borne out these associations.
Despite these discrepancies, the potential for human health risks
has spurred a number of health organizations to err on the side of
caution. In 2004 the ROC listed formaldehyde as “reasonably
anticipated to be a human carcinogen,” and the International
Agency for Research on Cancer changed its rating of formaldehyde from
a “probable” to a “known” human carcinogen
in 2004.
Clued In to a Better Glue
Li’s new soy adhesive is an ingenious chemical construct, something
of a Holy Grail in the search to make vegetable proteins that are strong
enough and water-resistant enough to hold up in industrial applications.
In a report published in the September 2002 issue of Macromolecular
Rapid Communications, Li noted the fine complementarity between
the features of marine adhesive proteins (like those that make clinging
mussels such a threat to boat hulls) and soy proteins. Marine adhesive
proteins stick to wet and irregular surfaces, bind very strongly, and
degrade very little, but are burdensome and costly to synthesize; soy
proteins are abundant, renewable, and affordable, but are relatively
weak and easily degraded.
Li was able to get the best of both worlds by coaxing soy protein
to cross-link with the adhesive’s second major ingredient--a
proprietary resin known as kymene--in a similar manner to mussel adhesive.
Cross-linking organizes large molecules into a mesh-like configuration.
In Li’s soy adhesive, this occurs after the glue is applied to
the wood, during curing (the chemical and physical process by which
ingredients are united into a stable form). The cross-links in Li’s
adhesive are so strong that it can be boiled for hours without degrading,
he says.
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Shell game. Mussels stick to rocks,
boat hulls, and piers through the strength of a tightly
bonding adhesive that adapts to wet and irregular surfaces.
A new adhesive inspired by the tenacity of mussels
combines those qualities with the affordability and
renewability of soy protein.
image: Anna Colls/Alamy |
The commercial formulation now on the market has been patented by
Oregon State University and licensed to Wilmington, Delaware-based
Hercules Incorporated, the resin manufacturer that produces kymene.
Columbia Forest Products, a manufacturer of veneer-core hardwood plywood
based in Portland, Oregon, is the first wood products company to convert
a manufacturing process to a completely formaldehyde-free soy adhesive.
Both companies worked with Oregon State University to develop the commercial
formulation.
The soy adhesive is comparable in cost to the urea- and phenol-formaldehyde
adhesives, says Charles Grabiel, commercialization manager for the
consulting firm Omni Tech International and an adviser to the United
Soybean Board. This group of soybean farmers advises the Secretary
of Agriculture on ways to increase the utilization of U.S. soybean
products.
Optimizing the Innovation
So far, the commercialization of the new adhesive affects only a
subset of the very large engineered wood market, since Columbia Forest
Products produces decorative hardwood plywood exclusively for interior
applications. But work is under way at Oregon State University to commercialize
the patented formaldehyde-free wood adhesive for production of particleboard,
medium-density fiberboard, exterior-grade oriented strandboard, and
plywood.
There is less pressure to convert exterior-grade wood products because
they use phenol-formaldehyde resins, which offgas formaldehyde at a
much lower rate than the urea-formaldehyde resins. Adhesives in exterior
wood products must also meet stricter moisture-proofing standards set
for certification by industry organizations such as the Engineered
Wood Association, says Grabiel.
Since Li’s soy formulation has demonstrated strength and water-resistance,
its certification for use in exterior products is expected to go smoothly.
However, the method of applying adhesives differs by product type,
Grabiel says. For plywood, glue can be rolled onto the panels before
they are pressed, but to form composite products out of small wood
pieces and sawdust, the adhesive must be reformulated to a sprayable
consistency. Grabiel estimates it will take at least two years to resolve
these manufacturing issues so that exterior wood products and other
composite types can become formaldehyde-free.
With new products, there is always the chance that “the cure
is worse than the disease,” but there are no immediate indications
that soy adhesives pose as great or greater health threats than their
predecessors. One potential concern is allergies. Soy products are
known to cause allergic reactions in some people (mostly infants),
including digestive, respiratory, and skin reactions. Soy also contains
plant estrogens, which are bioactive when ingested. However, owing
to extensive processing, these compounds are unlikely to be present
in the isolated proteins used in the adhesive.
Before curing, the soy protein used in the wood adhesive is nonvolatile,
is not a hazardous air pollutant, and may be handled with basic protective
gear such as gloves and safety glasses, according to the United Soybean
Board’s “Soy-Based Wood Adhesives and the Environment” information
sheet. Grabiel adds, “The soy protein in the resin is tightly
bound to wood and to itself, so will not degrade readily. The ultimate
result of the degradation of the soy resin should be no different than
the degradation products of soy flour.”
Although many wood products and resin adhesive manufacturers have
significantly reduced their use of formaldehyde, and the industry is
displaying a lively ingenuity in seeking alternative products, not
everyone is on the formaldehyde-free bandwagon. “We’re
not considering moving to a formaldehyde-free system,” says Rob
Schmidt, senior vice president for market applications at Dynea North
America, a subsidiary of the world’s largest producer of formaldehyde
resins. “It’s not something we consider necessary from
a toxicity or cost-benefit point of view,” Schmidt says, because
of the “minimal hazard associated with using formaldehyde adhesives.” Thus,
the uneasy tug-of-war between formaldehyde’s industrial convenience
and its health effects will likely continue until further study can
elucidate the physiological fate of the highly functional chemical.
In the meantime, fans of the soy-based approach are finding new ways
to employ the bean in wood products. A hybrid adhesive combining soy
protein with phenol-resorcinol-formaldehyde is being used by one company
to make finger-joined wood products from green (undried) lumber, Grabiel
says. Using soy protein in the adhesive mix reduces by half the amount
of formaldehyde required. In addition, adhesives using soy protein
require less time and use less energy to cure before use. A number
of chemical manufacturers are also using similar chemical processes
to create adhesives made with other alternative components, including
wheat, corn, casein (a dairy protein), and seed gums.
Valerie J. Brown