Technical Paper

Polyurethanes

Scavenge moisture and

cut pinholes in a trice
Oxazolidine latent hardeners in polyurethane systems

Contact: Neil Carter duction of methanol in silane-cured systems),, better

Dr. Neil Carter substrate adhesion and ease of subsequent coating.
Incorez
The popularity of polyurethane chemistry in con- The traditional method of curing PU sealants is to use
T +44 1772 201964
[email protected] struction sealants is growing. However, moisture the reaction of the terminal isocyanate groups of the
ingress and pinholing can be a problem. Oxazolidine polyurethane binder with moisture. This process requires
latent hardeners can overcome these drawbacks. a high level of isocyanate to give effective cure, which
in turn leads to toxicity issues concerning residual isocy-

W
hilst there have been a number of technical ad- anate monomer. Another problem is the production of
vances in the resins used in construction seal- carbon dioxide during the reaction. This results in pin-
ants, polyurethane (PU) chemistry continues to holing, a phenomenon which can then compromise the
offer the best balance between cost and performance. integrity and aesthetics of the finished coating.
The chemistry is highly versatile, with aromatic and ali- An effective way to eliminate such gassing and improve
phatic prepolymers offering the formulator a range of the cure performance of the sealant is to introduce an
properties to meet differing performance requirements. oxazolidine latent hardener. Such a product allows the
The addition of oxazolidine latent hardeners reduces the formulator to combine the benefits of this type of hard-
negative effects of moisture and speeds up reaction. ener with a prepolymer at a much lower isocyanate lev-
The main advantages PU offers over other technologies el. Typically, this can be reduced by as much as 10-15 %.
are better mechanical strength the absence of toxic by The benefits of introducing oxazolidine latent hardeners
products of the cure mechanism (in contrast to the pro- into aromatic PU sealants are:

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 Technical Paper
Polyurethane chemistry

»»Elimination of gassing
»»E xcellent through cure in thick film applications (com-
pared to moisture cure/aldimine systems)
»»Retention of good workability of the sealant (skinning
control)
»»E xcellent early hardness development, as measured by
Shore, through hardener crosslinking
»»No significant negative impact on mechanical strength
or shrinkage through crosslinking at recommended
levels of addition of the hardener
»»No detrimental effect on UV resistance
When handling PU prepolymer mixes containing oxazoli-
dine latent hardeners, it is vitally important to keep mois- Figure 1: MDI prepolymer cured without oxazolidine (left), cured with 2 % hard-
ture ingress to a minimum. It is good practice to purge of ener A (centre) and cured with 2 % hardener B (right)
all mixing reactors with nitrogen and to reduce as much as
possible exposure to atmospheric moisture during handling.
a level of 2 % w/w, compared to the same prepolymers
Gassing eliminated cured only with moisture.
The addition of an oxazolidine latent hardener not only
Traditionally, PU sealants are cured by the reaction of ter- eliminates sealant defects created by gassing, but also
minal isocyanate groups with moisture. A side product of promotes faster through-cure (see Figure 3). This reflects
this reaction is the generation of carbon dioxide. This re- the ability of oxazolidine latent hardeners to hydrolyse
mains trapped in the cured sealant system. Figures 1 and quickly and crosslink the PU prepolymer compared to the
2 illustrate cured aromatic PU prepolymers (MDI & TDI) water-isocyanate reaction.
mixed with two oxazolidine latent hardeners, hardener A The addition of an oxazolidine latent hardener does not
(“Incozol LV”) and hardener B (“Incozol EH”), typically at have a significant impact on PU-prepolymer viscosity
and, consequently, does not affect the workability of the
sealant. The initial viscosities of the oxazolidine/prepoly-
mer blends shown in Figure 4, indicate the influence of
the latent hardeners on the systems. Hardener A either
reduces or retains the viscosity whilst hardener B increas-
Results at a glance es it slightly. These differences offer options for formula- European Coatings
There are a range of advantages in introducing tors to retain the desired workability of the system. Conference
oxazolidine latent hardeners into aromatic PU sealant As regards storage stability, as expected, TDI-based mixes “Polyurethanes for
formulations. are more stable than MDI systems due to the increased high performance
reactivity of MDI prepolymers. For TDI systems, mixing coatings”
The ability of oxazolidine latent hardeners to act with a latent hardener shows an initial viscosity rise when 25-26 September
as moisture scavengers ensures that the reaction moisture ingress during mixing and handling occurs. How- 2012
between any moisture present and the isocyanate ever, stability is excellent, with little rise in viscosity, as Berlin, Germany
is prevented, thereby preventing the generation of long as the containers are sealed from the atmosphere. www.european-
carbon dioxide which would result in sealant defects. In the case of MDI mixes, the stability is lower than with coatings.com/
TDI. The data in Figure 5 reflects the inclusion of 2 % oxa- events
The addition of an oxazolidine latent hardener into zolidine in MDI prepolymer mixes. Dilution of the binder
a formulation will promote faster through cure than
that achieved by moisture alone. This is due to the
ability of the latent hardener to hydrolyse quickly
and crosslink the PU prepolymer in preference to the
water and isocyanate reaction.

Introducing an oxazolidine latent hardener allows

the formulator to use a prepolymer with reduced
isocyanate content. Typically, the isocyanate level
can be reduced by as much as 10-15 %.

Oxazolidine latent hardeners, such as hardener A

and hardener B, bring added benefits to both aro-
matic and aliphatic PU sealant formulations. They do
this without affecting the physical properties of the
system. There is no significant detrimental impact on
the workability of the sealant, the tensile strength
and the elongation.
Figure 2: TDI prepolymer cured without oxazolidine (left) and cured with 2 %
hardener A (right)

www.european-coatings.com 06 l 2012 European Coatings J OURNAL 19

 Technical Paper
Polyurethanes

and curing agent in fully formulated systems with dry,

inert fillers affords improved stability.
The addition of latent hardeners does not significantly
alter physical properties such as hardness and tensile
strength in the cured PU system. Crosslinking at low lev-
els does not detrimentally alter sealant performance.
In general, hardener B slightly increases the hardness
and tensile strength of PU polymer, while hardener A
somewhat reduces the hardness and tensile strength.
This is due to the nature of their respective backbones.

Formulation hurdles
Today, formulators using polyurethane also face a number
of hurdles when trying to achieve the desired film prop-
erties and appearance. Whether the target is a high-gloss
finish for a volatile organic component -compliant coating, a
fast curing adhesive or a strong, flexible defect-free sealant,
the issues facing formulators when attempting to develop
Figure 3: The figures of hardness development indicate faster cure when oxa- new technologies with PU include:
zolidines are blended, resulting in increased concentration of reactive groups as »»Retaining and improving performance cure and physical
well as faster hydrolysis of oxazolidines properties of PU systems
»»Meeting legislation demands such as volatile organic
component reduction
»»Reducing toxicity by decreasing isocyanate concentration
One of the biggest issues is the ongoing battle to deal with
the presence of moisture often attracted through hydro-
scopic polyols and solvents or present in pigments, fillers
and plasticisers. The reaction of moisture with isocyanate
can seriously compromise performance (for example, prop-
erties such as film strength). Furthermore, appearance prop-
erties can be affected by the generation of carbon dioxide.
The oxazolidine technology offers an alternative low-toxicity
solution to formulators of both one and two-component
polyurethane systems in overcoming moisture-related for-
mulation issues. All oxazolidine products are triggered by
the reaction with moisture and it is their preferential reac-
tion that helps the formulator limit the moisture-isocyanate
reaction problem. Oxazolidine products can be used in
aliphatic and TDI-based prepolymers. A number of grades
are suitable for use in MDI systems. However, oxazolidine
products offer benefits over and above just inhibiting the
Figure 4: Initial viscosities of oxazolidine/MDI systems reaction with moisture. Some of these are described below
in more detail.
Formulators of sealants, adhesives and high-build elasto-
meric coatings are always striving to improve performance
properties. Traditionally, polyurethane systems incorporate
a high level of isocyanate to speed up the cure rate to an
effective level. This often requires the incorporation of toxic
catalysts such as lead, mercury and, more recently, variants
using tin. Oxazolidine technology however, offers a number
of routes forward. For example, high-solid, one-component
systems can incorporate oxazolidines in a number of ways.
The presence of an oxazolidine not only reduces the prob-
lems associated with CO2 generation and subsequent gas-
sing, but also enables PU manufacturers to reduce the level
of isocyanate present in the formulation. This is achieved
by activating the oxazolidine, initially latent in the formula-
tion, by mixing it with the formulation components to yield
in-can stability. On application, and subsequent exposure
to moisture, the oxazolidine-moisture reaction yields ami-
no-alcohol functionality which can affect a through cure
Figure 5: Storage stability of oxazolidine/MDI systems at 23 °C at much lower isocyanate concentrations, by a so-called

20 European Coatings J OURNAL 06 l 2012 www.european-coatings.com

 Technical Paper Milling
Polyurethanes Grinding
‘moisture-triggering’ route. This approach allows formula- Dispersing
tors to reduce prepolymer total-isocyanate contents from
typically 10-15 % to much lower toxicity levels of 2-5 %.
Therefore oxazolidine products can help formulators
achieve this aim with their selection based on property
requirements. Furthermore, the oxazolidine latent-curing
agent imparts an increased level of crosslinking through its
four-functionality structure (two secondary-amine and two
primary-hydroxyl groups). This helps formulators improve
cure rate and impart additional tensile strength to the coat-
ing, adhesive or sealant.
Other routes are also available to formulators through the
use of oxazolidines. The reaction of a hydroxyl-functional
oxazolidine enables PU formulators partially to end-cap the
isocyanate groups in the prepolymer further to reduce iso-
cyanate content. This approach also imparts other benefits
such as early tensile-strength development through latent
in-situ crosslinking on exposure to moisture.
Continued legislative pressure is forcing polyurethane for-
mulators to find ways of significantly reducing the amount
of solvent used in products to make them more environ-
ment friendly. Low-viscosity, oxazolidine-reactive diluents
such as hardener A, allow the design of two-component,
PU, high-solid systems, with the added benefit of eliminat-
ing gassing. Hardener A is a four-functional, bis-oxazolidine
curing agent that significantly reduces hydrogen bonding
through its carbonato-link and has a low viscosity of 50cps.
This allows formulators effectively to reduce the viscosity of
the product mixture. Therefore, formulators can continue to
use the same application tools. Thus eliminating the need
to retrain operators or dispose of the contaminated waste
associated with using alternative water-based products.

The G e r m an
q u a l i t y
Better film appearance
i t o f
The addition of an oxazolidine to a product can also im-
prove coating appearance. The elimination of carbon
dioxide pinholes from coatings, which occur as a result
spir since 1854
of the moisture-isocyanate reaction, by the preferential
reaction of a moisture scavenger, provides further signifi-
cant benefits for the formulator.
Pinhole defects lead to problems such as downglossing
or more significantly can compromise film integrity lead-
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ing to weaknesses such as loss of film strength or ease
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Oxazolidine technology has been adopted in a wide ar-
ray of polyurethane coating, sealant and adhesive ap-
plications. The polyurethane-coatings sector has chosen
this technology for use in two-component, high-solid
systems for applications in the automotive, marine,
wind-turbine and aerospace sectors. The use in one-
component polyurethane coatings is restricted to the
it us
industrial-maintenance sector. Please visnd 2,
June 201 ,
Oxazolidines are widely used in one-component aliphatic 18th – 22 Frankfurt/Main
and aromatic polyurethane cartridge sealants. These ACH E M A 42
Stand B
high-performance, elastomeric, polyurethane sealants Hall 6.0,
require no mixing and typically no priming to promote
adhesion to many substrates, including concrete and ma-
sonry.
There is a growing interest in the use of oxazolidines in More than 155 years:
the production of one-component, reactive, hot-melt ad- SIGMUND LINDNER GmbH
hesives, where they accelerate the cure rate and improve Oberwarmensteinacher Str. 38 · 95485 Warmensteinach / Germany
both green strength and crosslink density. í Phone (+49) 92 77 - 99 40 · Fax (+49) 92 77 - 9 94 99
E-Mail: [email protected]

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