Transactions of the IMF

The International Journal of Surface Engineering and Coatings

ISSN: 0020-2967 (Print) 1745-9192 (Online) Journal homepage: http://www.tandfonline.com/loi/ytim20

Cross-linking organic coatings with blocked

isocyanates

R. Jones

To cite this article: R. Jones (2008) Cross-linking organic coatings with blocked isocyanates,
Transactions of the IMF, 86:2, 75-79, DOI: 10.1179/174591908X264464

To link to this article: http://dx.doi.org/10.1179/174591908X264464

Published online: 18 Jul 2013.

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 Cross-linking organic coatings with blocked
isocyanates
R. Jones*

Compounds used for cross-linking tri-functional, can be reacted with polyisocyanate component (often
organic coatings, and the mechanisms alcohols in the form of di and tri referred to as the ‘‘hardener’’). As such
by which this takes place are discussed. functional ‘polyols’ in the presence of a they have a limited open time, or pot
The choice of blocked isocyanates is suitable catalyst (often a tin complex) to life, as this reaction of isocyanate with
important in determining cure form the urethane polymer bond. hydroxyl functionality will proceed at
temperature and coating properties. (Fig. 1) room temperature.
Isocyanates used for cross-linking A further limitation is the reactivity of
are normally used in the form of the polyisocyanates with moisture
polyisocyanates or ‘trimers’ (Fig. 2). (either from the atmosphere or water –
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Introduction Due to the reactive nature of the in the case of water based coatings),
isocyanate they are applied as two- causing premature gellation and
Cross-linking is one of the fundamental
component coatings comprising a evolution of carbon dioxide gas (Fig. 3).
chemical processes which take place
hydroxyl functional component – This is a limiting factor for applications
when organic coatings are applied and
cured. Coatings are usually applied as generically referred to as a polyol (often such as electrodeposition. Most
low viscosity liquids comprising an acrylic polymer) and the commonly the isocyanates used for
polymeric materials, often in an inert
medium (solvent). During cross-linking,
molecular weight increases and a three
dimensional polymer matrix is formed.
The resulting coating comprises a
polymer with a vastly increased 1 Formation of urethane bond
molecular weight compared to the
polymers in the originally applied liquid.
There are a large number of cross
linking mechanisms and molecules
which can be used for cross linking, the
choice of which depends on many
criteria. Typically the choice of polymer
type and cross-linking chemistry will
depend on such things as performance
of the final coating (eg environmental
resistance, flexibility, hardness,
adhesion) ease of application (solvent
type and amount, viscosity of the
coating during application) and cost. In
many applications different cross-
linking chemistries are used together to
balance all these requirements. For
general information the reader is
referred to one of the many general
texts on organic coatings 1,2

Blocked isocyanate chemistry

Isocyanates are one of the basic
building blocks to provide Polyurethane
systems for use in coatings, adhesives,
sealant and elastomer applications.
These isocyanates, usually di- or

Group Technical Manager, Baxenden

Chemicals Ltd, Accrington BB5 2EL, UK
*Email richard.jones@baxchem.co.uk 2 Structures of common isocyanate crosslinkers

ß 2008 Institute of Metal Finishing

Published by Maney on behalf of the Institute
DOI 10.1179/174591908X264464 Transactions of the Institute of Metal Finishing 2008 VOL 86 NO 2 75
 BULLETIN

nature), and, in actual use, the most

important thing is the overall
combination of both molecular
processes resulting in overall time and
temperature of cure. Curing can be
3 Reaction with moisture effected at lower temperatures, if the
curing time is increased. The user must
take into account these factors when
developing a process, with dwell time
in ovens and temperature sensitivity of
substrates being key factors to
consider. It is possible to increase the
rate of overall cure reaction by using
appropriate catalysts. Typically, these
4 Blocking/unblocking reaction
are of the type which catalyse urethane
formation and so act on the reaction of
free isocyanate with polyol. The author
is not aware of any catalyst which acts
directly on the unblocking equilibrium
which would have the effect of
lowering the unblocking temperature.
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5 Unblocking and cure reaction

The type and nature of blocking
agents vary greatly but they have one
cross-linking are derived from aliphatic isocyanate reforms on cooling. While, common characteristic in that they
isocyanates – hexamethylene conventionally, users of blocked contain an active hydrogen atom within
diisocyanate (HDI) or isophorone isocyanates refer to the deblocking the molecule. Most contain only one
diisocyanate (IPDI). Aromatic temperature, this can be misleading. It active hydrogen atom (an exception
isocyanate derivatives – based on must also be remembered that the being diethyl malonate, which has a
toluene diisocyanate (TDI) or overall process which takes place reactive methylene group containing
diphenylmethane diisocyanate (MDI) during curing is the result of two two active hydrogen atoms).
are less commonly used, though different molecular processes: ie. the
alcohol blocked TDI derivatives are unblocking equilibrium reaction and the Blocking agents
used in electrodeposition processes. subsequent reaction of the unblocked The most commonly used blocking
HDI and IPDI based cross-linkers have isocyanate with polyol. Thus the agents are shown in Fig. 6
the significant advantage of light deblocking temperature is not a fixed Many molecules have been
stability over the aromatic isocyanates temperature (due to the equilibrium assessed as blocking agents for
It is, however, possible to control the
reaction between isocyanates and
polyols by masking the isocyanate
groups thus preventing both reaction at
room temperature - only allowing it to
take place at elevated temperatures –
and reaction with moisture. This is
done by carrying out a reaction
between the isocyanate and a suitable
‘blocking agent’ before mixing with the
polyol, normally OH terminated
polyesters or acrylics (Fig. 4).
These so called ‘blocked
isocyanates’ are stable at room
temperature even when mixed with
polyols and only become reactive once
the system is heated. As the
temperature rises the isocyanate
unblocks liberating NCO groups which
are then free to react with polyols to
form the urethane polymer. The free
blocking agent then either remains in
the coating or is removed by
evaporation (Fig. 5).
A significant feature is that the
blocking/unblocking reaction is a
chemical equilibrium. In the absence of
any co-reactant (polyol), or loss of
volatile blocking agent, the blocked 6 Blocking agents commonly used in coating formulations

76 Transactions of the Institute of Metal Finishing 2008 VOL 86 NO 2

 BULLETIN
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7 DSC traces showing unblocking temperatures of DEM, DMP and MEKO blocked HDI biuret

isocyanates, only those most of techniques. In Table 1, the systems used in the coatings industry,
commonly used industrially are deblocking temperatures are obtained diethyl malonate (DEM), dimethyl
discussed here. The type and nature of using a differential scanning calorimetry pyrazole (DMP) and methyl ethyl
blocking agents varies greatly but they (DSC) technique. The blocked ketoxime (MEKO). Considering DMP
have one common characteristic in that isocyanates are mixed in a 1:1 molar and MEKO, the peak exotherms are
they contain an active hydrogen atom ratio ( based on functional groups) with separated by some 40uC (122uC for
within the molecule. Most blocking a trifunctional amine (Jeffamine T403 DMP and 163uC for MEKO),
agents contain a single active hydrogen from Huntsman Corporation). The demonstrating that DMP blocked
(an exception being diethyl malonate, temperature is increased at a rate of isocyanates will unblock at lower
which has a reactive methylene group 10uC min21 in a dry N2 atmosphere temperature than MEKO blocked
containing two active hydrogen groups, from 25uC to 250uC. While no isocyanates.
although only one normally reacts with exotherm occurs due to the unblocking The other blocked isocyanate shown
the NCO groups). The most common itself, the exotherm of the reaction of is diethyl malonate which reacts, as can
blocking agents used in coatings are the unblocked isocyanate with amine is be seen from the shape of this curve, in
shown in Fig. 6 and the features of observed. a somewhat different manner to DMP
each blocking agent are shown in The major effect that is illustrated is and MEKO. A small exothermic
Table 1. the difference between different reaction appears to start at about 40uC
The key feature of the different blocking agents on the same which then continues until it peaks at
blocking agents is the effect on isocyanate (Fig. 7). Here HDI biuret has 120uC. DEM blocked systems are
deblocking temperature. The effects been blocked with three commonly commercially available with a quoted
can be easily screened using a number used blocking agents for aliphatic ‘unblocking temperature’ of 90–100uC,

Table 1 Characteristics of blocking agents

Approximate peak
Blocking agents unblocking temp- uC* Key Features

Caprolactam 180 Solid-melt point 70–72uC. Often used in powder coating blocked isocyanates
MEKO 150 Liquid-boiling point: 59–60uC at 15 mm Hg ( 152uC at 76 0mm Hg); toxicity
concerns
3,5-dimethyl pyrazole 120 Solid melt point 107–109uC boiling point 216uC
Diethyl malonate 120 Liquid – reacts via transesterification
Alcohols .180 Very stable blocked isocyanates, usually used in cationic electrodeposition
applications with epoxy/amine resins
Phenols .140 Often used for wire coating enamels; toxicity/environmental concerns
*Determined by differential scanning calorimetry using blocked aliphatic isocyanate

Transactions of the Institute of Metal Finishing 2008 VOL 86 NO 2 77

 BULLETIN

temperature with a lower deblocking

temperature being observed for a
blocked TDI prepolymer (Fig. 9),
compared to an aliphatic isocyanate
blocked with the same blocking agent.
This may be a useful feature when light
stability is not required.

8 Reaction of DEM blocked isocyanates via transesterification

Considerations when
formulating with blocked
isocyanates
which is different from that estimated blocked prepolymers. With the major
from the peak observed on the DSC. exception of wire coating, the majority This ability to formulate stable
However, it should be noted that DEM of these applications are in non-metal one-component systems gives the
blocked isocyanates do not react in the coating applications and often used in formulator the scope to develop
same way as conventional blocked conjunction with amines. Those systems for varied applications utilising
isocyanates. The cross-linking reaction applications using phenol itself as a solvent-borne, water-based and
takes place via transesterification of the blocking agent should be specifically powder coating technologies. These
ester groups on the DEM moiety and engineered to avoid release of phenol blocked isocyanate systems can be
the system does not unblock or to the environment and contact with used for automotive, OEM, coil, textile,
regenerate free isocyanate. Equally the employees. electrostatic spraying and
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product of cross-linking is not a electrodepostion applications, all of

urethane but an amido-ester (see which are readily adaptable to
Fig. 8).
Isocyanate type one-component heat curing systems.
Alcohol blocked isocyanates are A further influence on the unblocking While much of the foregoing text
almost exclusively used in cationic temperature is the nature of the refers to unblocking temperature, it is
electrodeposition coatings, where the isocyanate itself. As noted above, crucial to remember that the whole
thermal stability allows their use in isocyanates are conventionally cure process is the result of both the
water based systems using very separated into two distinct types, so unblocking and the cross-linking
reactive amine/epoxy resin as a called aromatic isocyanates and reactions. Thus, once the isocyanate is
co-reactant. The unblocking aliphatic isocyanates. Aromatic unblocked the overall cure reaction will
temperature varies with the nature of isocyanates are those in which the not be instantaneous. Typically overall
the actual alcohol used. isocyanate function is directly bonded cure times are of the order 20 minutes
Phenols are widely used in to an aromatic ring, as in TDI or MDI. to 1 hour at the unblocking
production of blocked isocyanates or This has an influence on unblocking temperature, with the fastest times

9 DSC trace showing unblocking temperature of DMP blocked TDI prepolymer

78 Transactions of the Institute of Metal Finishing 2008 VOL 86 NO 2

 BULLETIN

achieved using catalysis. It is possible It is also important to consider all enable the formulator to produce
to cure faster at temperatures above ingredients of the coating formulation storage stable isocyanate cross-
the unblocking temperature, (provided on the ultimate properties, linked one component products for
the cured coating does not thermally performance and cost. The polyol thermal curing. The choice of
degrade). In use, the balance of cure component (for instance whether it is a blocking agent influences the cure
speed, vs energy requirement vs high hydroxyl functionality acrylic polyol temperature. By suitable choice of
temperature sensitivity of the substrate or a low hydroxyl functionality polyester blocked isocyanate cross-linker and
needs to be considered. or polyether polyol) will influence the polyol component a wide range of
Low unblocking temperature properties of the coating in terms of properties can be achieved in the final
products, such as those blocked with flexibility and solvent resistance. The cured coating on a variety of
Dimethyl Pyrazole can be used to cure choice of isocyanate will also influence substrates.
at temperatures as low as 120uC using this with IPDI trimer based blocked
cure times around 30 minutes. isocyanates giving harder chemically
resistant coatings, which may suffer
References
However, the same product can also be
used at higher temperatures where from brittleness, or more flexible 1. A. Goldschmidt and H-J.
cure times can be much reduced, for coatings based on HDI trimer or biuret. Streitberger: ‘BASF Handbook
instance cure times of tens of seconds In practice the formulator will achieve on Basics of Coating Tech-
can be achieved in a coil coating line the desired coating properties by nology’, 2003, Hannover, Vincentz
with peak metal temperatures of 220– balancing all the requirements to Network.
240uC. Indeed, these products are achieve the desired properties. 2. Z. W. Wickes Jr, F. N. Jones, S. P.
often exploited, not for their lower Papas and D. A. Wickes: ‘Organic
Downloaded by [Orta Dogu Teknik Universitesi] at 06:59 19 April 2016

temperature cure possibilities, but for

Summary Coatings: Science and Technology’,
the increased production speed which Use of blocked isocyanates as 3rd edn, 2007, Hoboken, NJ, Wiley
is achievable. cross-linkers in coating formulations Interscience.

Book Review

Glow Discharge Optical Emission to form a crater which may have a of the GDOES and the quality of the
Spectroscopy : A practical guide by diameter of 2–4 mms and a depth of results in dedicated applications, there
Thomas Nelis and Richard Payling. 20–40 microns. The shape of the crater is an expectation of similar certainty in
Published by the Royal Society of may give an indication of the relative casual application to samples of poor
Chemistry, in RSC Analytical sputtering rates for different components provenance. This book would make
Spectroscopy Monographs (ed. N W of the sample material. All of this good cautionary reading.
Barnett), Cambridge UK, 2003. ISBN 0- becomes clear as the reader delves into The text is presented in 13 Chapters.
85404-521-X. Price £85 (Discount for RSC the book; it is a pity that a simple There is a rather precipitative start, on
Members, sales@rsc.org) pp. xi plus 299. overview was not provided at the outset. the preparation and maintenance of
Having made the criticism, it must be instruments and on samples selection
GDOES is a technique for the said that this is an extremely useful and preparation followed by the
analysis of bulk solids, for the depth handbook for the working analytical optimisation of source and analytical
profiling of thin surface films and laboratory. GDOES is often acquired for parameters. Calibration is covered well,
coatings. The specimen forms the a specific analytical purpose, e.g. in four chapters including a treatment of
cathode of the glow discharge system monitoring the composition of a drift in the spectrometer itself. These
in which argon and electrons interact to particular alloy, material surface or chapters and that on bulk analysis
form a plasma. Argon ions and sample surface coating. Issues of precision in contain a good deal of practical statistics
ions are driven by an electrical bias to measurement calibration and accuracy and the book may well share a place on
collide with the sample surface with have to be tackled and are intimately the shelf with the RSC’s monograph on
enough kinetic energy to cause related to good laboratory procedures, ‘Statistics for the Quality Control
sputtering. Once excited in the plasma, instrument and sampling management. Chemistry Laboratory’ by E Mullins
sputtered atoms emit photons with However, once installed, the [reviewed in a later issue – Ed.]. Bulk
characteristic wavelengths that are usefulness of GDOES in ‘jobbing’ work, analysis leads to an account of depth
detected and quantified often in the provision of rapid semi- profiling and thence, belatedly, to the
spectrometrically. Specimens have to quantitative analysis of a wide range of theory of the G D Source and the
be large enough to be mounted as the materials, makes it a popular technique. selection of wavelengths for the optical
cathode although special holders are How often is the analytical chemist analysis. The final chapter is practical, on
available for mounting small samples faced with more-or-less urgent pleas to trouble shooting. There are two
and there are techniques for handling ‘analyse this’ from desperate appendices of optical lines used in
powders and the curved surfaces of colleagues across their companies? GDOES and a bibliography.
rods, wires and tubes. The actual Some response can usually be made.
analysis is made on material emanating The danger is that, given the sensitivity J P G Farr

Transactions of the Institute of Metal Finishing 2008 VOL 86 NO 2 79