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KYMENE™ WET-STRENGTH RESIN INNOVATIONS
All statements, information and data presented herein are believed to be accurate and reliable, but are not to be taken as a guarantee, an express warranty or an implied warranty of merchantability or fitness for a particular purpose, or representation, express or implied, for which Solenis International, L.P. and its affiliates and subsidiaries assume legal responsibility. ®Registered trademark, Solenis or its subsidiaries, registered in various countries
™Trademark, Solenis or its subsidiaries, registered in various countries
*Trademark owned by a third party©2014, Solenis PC-0045
SolenisStrong Bonds. Trusted Solutions.
Solenis supplies specialty chemicals for water-intensive industries, including the pulp and paper, oil
and gas, chemical processing, mining, biorefining and power markets. Whether you want to increase
production, develop new products, reduce costs or simply do more with less, we can help. With our
innovative technologies, passionate people and unrivaled experience, Solenis is ready to deliver the
solutions you need.
Together, we’ll create strong bonds that ensure trusted solutions.
Global HeadquartersSolenis International, L.P. Wilmington, Delaware Tel: +1 302 594 5000
solenis.com
Wet-strength Production Facilities
Because of our global reach, we are capable of providing wet-strength
resins—efficiently and cost-effectively—to any mill, anywhere in the world.
Solenis Facilities
Licensees
The product was an instant commercial success, both
for its ability to function in neutral/alkaline papermaking
processes and for its novel wet-strength capabilities.
Like all PAE resins, the polymer in Kymene 557H
contains quaternary ammonium groups that adsorb onto
negatively charged paper fibers and that continue to
cross-link even as the paper dries and cures. That means
the wet strength of paper treated with Kymene wet-strength
resin continues to increase after it’s been put into storage.
Over the years, our researchers have modified the basic
chemistry to make stronger-performing resins with
reduced by-products, 1,3-dichloropropanol (1,3-DCP)
and 3-monochloropropan-1,2-diol (3-MCPD), as well
as aminochlorohydrin (ACH) and polymer-bound CPD
(PB-CPD). Solenis has led the industry in decreasing
the organic chlorine content of its Kymene wet-strength
resins without compromising their efficiency. Our
scientists have developed manufacturing processes
with greater control to maximize the efficiency of how
epichlorohydrin is used to generate azetidinium chloride
(AZE), the reactive portion of PAE resin, while minimizing
the levels of 1,3-DCP and 3-MCPD. We’ve also introduced
innovative technologies that can be applied after the
manufacture of the basic PAE resin to reduce harmful
by-products.
Global Wet-strength Leader
Kymene™ Wet-strength Resin PortfolioToday, PAE resins account for 90 percent of the wet-strength market. Of this market, nearly half bear the Kymene
brand name. One reason for the success of the product is a broad range of configurations that enable papermakers
to customize their wet-strength programs to satisfy regional demands and regulatory requirements. Solenis has
introduced market-leading technologies into each of the widely used industry descriptors of G1, G2, G2.5 and G3 PAE
resins, making it possible to address a full range of customer compliance needs while balancing cost-in-use.
Today, we offer the broadest portfolio in every region of the world and can provide solutions to satisfy even
the most rigorous regulatory guidelines, including environmental labeling established by Nordic Ecolabel and
recommendations issued by the German Federal Institute of Risk Assessment (Bundesinstitut fur Risikobewertung,
or BfR). Solenis’s wet-strength resins can be supplied in a wide range of solids content — from 13 percent total solids to
30 percent total solids — to help our customers balance freight costs, shelf life and product stability concerns.
We offer the broadest portfolio of
wet-strength resins in the world, with
different product configurations to
accommodate any mill’s compliance
standards, regardless of location.
Non Total Chlorine Free
BfR XXXVI /1/2/3 BfR XXXVI Non BfR
0 1 10 100 1000 10000
1,3-DCP ppm (wet basis)
%AO
X1 (wet
basis
)
1.00%
0.10%
0.01%
G3
G2
G2.5
G1
Total Chlorine Free
Compliance Standards for Kymene Wet-strength Resins
Solenis invented the modern era of wet-strength paper manufacturing with the introduction of Kymene™ 557 wet-strength resin, the first polyamido-amine-epichlorohydrin (PAE) resin ever brought to the market.
1 Adsorbable organic halogen
In the late 1950s, Solenis researchers began a quest to
find new wet-strength resins that could demonstrate
good performance under neutral pH conditions. Their
efforts led to polyamido-amine-epichlorohydrin (PAE)
resin. Solenis filed its first patent application for PAE resin
technology in 1957, and just two years later, it began to
market Kymene™ 557 wet-strength resin effective at pH
levels between 5 and 8.
But our researchers didn’t just invent the PAE resin:
They have continued to refine the chemistry to reduce
the by-products of the manufacturing process. In
Kymene wet-strength resin synthesis, those by-products
include 1,3-DCP and 3-MCPD, as well as ACH and
PB-CPD. Both 3-MCPD and 1,3-DCP are considered
hazardous substances and are possible human
carcinogens. And all of the chlorine-containing by-
products, taken together, increase adsorbable organic
halogen (AOX) levels in the effluent of paper mills.
As a result, the use of PAE resins is highly regulated
and allowable levels of by-products vary greatly from
country to country. Government regulators also provide
stringent requirements for the use of wet-strength
resins in food-packaging applications.
The Synthesis of Kymene Wet-strength Resins Although the basic reactions in the
synthesis of wet-strength resins are
well understood, we have introduced
advanced process control and
purification techniques to increase
the efficiency of our products while
lowering their environmental impact.
A History of Chemical Innovation
NN
NO-
O
O
H
H
HC l
O
C l C l
O H
H O C l
O H
Epichlorohydrin
N N
N O
O
O
C l
O H
C l
H O
H H
Aminochlorohydrin (ACH)
N N
N O
O
O
C l
O H
O H
H H +
C l -
Azetidinium (Aze)
1,3 -dichloropropanol (1,3-DCP)
3 -monochloropropan -2 -ol (3 -MCPD)
Resin synthesis By-product formation
Polymer -bound CPD (PB -CPD)
Another first is launched—the first G3 resin allowing papermakers to manufacture products with reduced or non-detectable levels of 3-monochloropropan-1,2-diol (3- MCPD) and 1,3-DCP.
Membrane separation technology is perfected, making it possible to manufacture higher-solids, higher-efficiency G3 wet-strength resins.
The G1 portfolio gets updated to have much lower 1,3-DCP and 3-MCPD.
The G2.5 and G3 portfolio gets refreshed with the introduction of Kymene LHP, GHP and XHP wet-strength resins.
1957
1990
Development begins on products containing less than 1,000 parts per million (ppm) of 1,3-dichloropropanol (1,3-DCP).
1980s
1993
1999
A completely new wet-strength resin category—G2.5—is created when Kymene 217LX wet-strength resin launches.
2005
2008
2010
2012First patent application filed for polyamido-amine-epichlorohydrin (PAE) resin technology, ushering in a new era with Kymene 557 wet-strength resin.
Kymene SLX wet-strength resin—a G2 resin with less than 1,000 ppm 1,3-DCP—launches in Europe.
A History of Chemical Innovation
Kymene ULX wet-strength resin is introduced in Europe. This product takes advantage of “biodehalogenation” to become the first G3 wet-strength resin.
Membrane Separation TechnologyA decade of research has led to revolutionary membrane
separation technology, which can help paper mills decrease
levels of both 1,3-DCP and 3-MCPD and overall AOX.
Next-generation ResinsTo help papermakers meet compliance standards and
government regulations, Solenis further developed and
then incorporated ‘’biodehalogenation’’ into its wet-
strength resin manufacturing. This process relies on
naturally occurring microorganisms to convert 1,3-DCP
and 3-MCPD to glycerol, a simple sugar alcohol that the
same microorganisms then use for food. Unlike other
physiochemical methods used to reduce and remove
epichlorohydrin residuals, biodehalogenation consumes
very little energy, requires no additional chemicals and
generates no additional waste stream. It does, however,
limit the solids and level of functionality of the resins
that can be purified this way, requiring papermakers to
compromise on performance.
This led Solenis scientists to search for even better
purification techniques. In recent years, they have
developed and perfected membrane separation
technology, which takes finished Kymene™ resin and
passes it through a nanofiltration device, essentially
removing all by-products. At the same time, membrane
separation overcomes some of the limitations of the
biodehalogenation process related to solids and levels of
functionality. As a result, Solenis has been able to produce
new high-solids, high-efficiency G2.5 and G3 resins with
even higher levels of azetidinium (AZE) functionality.
Papermakers who use our G3 resins produced with
membrane separation technologies are able to maximize
wet-strength performance while decreasing levels of
both 1,3-DCP and 3-MCPD and overall AOX.
Solenis’ ongoing commitment to wet strength reflects an
increasing demand among consumers for paper products
that remain strong even when wet. Today, any grade of
paper that needs to maintain its integrity after becoming
wet relies on the application of a wet-strength agent.
These grades include tissue (facial, kitchen towel, wipers,
napkins and tableware), packaging (liquid packaging,
aseptic container, carrier board, and other forms of food
packaging), and specialty (tea bag, coffee filter, labels,
currency, laminating grades, etc.).
Solenis’ PAE resin inventions established the modern
wet-strength platform and helped to clarify the
fundamental chemistry. Wet-strength resins are a class
of chemicals that adhere to pulp fibers and form linkages
between fibers through covalent bonding. These linkages
supplement and reinforce the natural hydrogen bonding
in the dry sheet and, because they’re covalent, cannot be
broken by soaking in water and are resistant to cleaning
chemicals. Papers treated with these resins, such as kitchen
towels and wipers, typically have a wet breaking strength of
30 percent or greater of their dry breaking strength.
Wet Strength: Satisfying Consumer Demand
Wet Strength by the Numbers
28% Towel/Wipers
16% Liquid Packaging Board
17% Facial Tissues
8% Carrier Board
6% Cup and Plate
24% Other Specialty Papers
Wet-strength papermaking is vitally important because of the prominence these grades have in day-to-day consumer activities and because
governments carefully monitor any paper and board that comes into contact with food.
Kymene™ Wet-strength Resin: Active Patents
Biodehalogenation:
US5470742
US5843763
US5871616
G2.5 and G3:
US6554961
EP1189972
EP1770109
AU755277
CA2375694
JP4666853
US7175740
EP1337576
EP1770110
US7303652
EP1337576
CA2398630
JP4266635
CN1293122
US7081512
CA2526093
KR101168773
G3 via membrane separation:
US7932349
US8101710
EP2064265
CA2663054
The Future of Wet StrengthAll of these innovations will lead to a better Kymene
product line that helps our customers adapt to changing
industry requirements, deliver products that are both
functional and safe for consumers, increase sustainability
and minimize associated environmental impacts.
As consumer needs and regulatory requirements
continue to evolve, wet-strength chemistry must evolve
with it, which is why the Kymene story is far from being
over. Solenis scientists continue to explore and refine
the chemistry we invented at the same time that we
research commercially viable alternatives, with the goal of
introducing next-generation wet-strength products that:
• Increase solids so significantly that paper mills can cut their deliveries by half, thereby significantly improving sustainability.
• Improve functionality to significantly increase the wet-strength-to-dry-strength ratio papermakers can achieve.
• Remain far ahead of all regulatory compliance issues by further reducing 1,3-DCP, 3-MCPD and total AOX.