European Polymer Journal 42 (2006) 21532160

EUROPEAN
POLYMER
JOURNAL
www.elsevier.com/locate/europolj

The crosslinking reaction of acrylic PSA using

chelate metal acetylacetonates
Zbigniew Czech *, Marta Wojciechowicz
Szczecin University of Technology, Polymer Institute, K. Pulaskiego 10, Pl-70-322 Szczecin, Zachodniopomorskie, Poland
Received 29 November 2005; received in revised form 9 March 2006; accepted 20 March 2006
Available online 22 May 2006

Abstract
In this work, metal chelate zirconium acetylacetonate (ZrACA) was added into acrylic polymers with self-adhesive
properties. These acrylic polymers, known as acrylic pressure-sensitive adhesives (PSA), were crosslinked with ZrACA
to obtain acrylic self-adhesives with which to study the crosslinking reaction between carboxylic groups of the polymer
chain and metal chelate crosslinking agent.
2006 Elsevier Ltd. All rights reserved.
Keywords: Crosslinking of acrylic PSA; Pressure-sensitive adhesives; Acrylic; PSA; Adhesives; Metal chelate zirconium acetylacetonate;
Acrylic pressure-sensitive adhesives

1. Introduction
Pressure-sensitive adhesives are composed of
long chain molecules conned by crosslinkages into
three-dimensional networks. They are, in uncrosslinked form, capable of sustaining very large reversible deformations at low stress. However, a few
tenths of a percent of crosslinking agent make it a
pressure-sensitive adhesive having viscoelastic uid
state and good mechanical and thermal properties.
Pressure-sensitive adhesives (PSA) are nonmetallic materials used to bond other materials, mainly
on their surfaces through adhesion and cohesion
[1]. Adhesion and cohesion are phenomena, which

*
Corresponding author. Tel.: +48 60 105 71 12; fax: +48 91
483 49 08.
E-mail address: psa_czech@wp.pl (Z. Czech).

may be described thermodynamically and chemically, but actually they cannot be measured precisely. It was shown [2] that the most important
bonding processes are via adhesion and adhering
with pressure-sensitive adhesives. The term PSA
has a very precise technical denition and was dealt
with extensively in the chemical literature [3]. The
function of PSAs is to ensure instantaneous adhesion upon application of a light pressure. Most
applications further require that they can be easily
removed from the surface to which they were
applied, through a light pulling force.
The most importance properties, which are essential in characterizing the nature of PSA comprise:
tack, peel adhesion and shear strength. The rst
measures the adhesives ability to adhere quickly,
the second its ability to resist removal through peeling and the third its ability to hold in position when
shear forces are applied [4].

0014-3057/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2006.03.022

Z. Czech, M. Wojciechowicz / European Polymer Journal 42 (2006) 21532160

2. Methods of crosslinking
The properties of pressure-sensitive adhesives
synthesized by copolymerization of acrylic monomers and formulated in organic solvent mixture
are determined, to a great extent, by the kind and
quantity of the crosslinking agent added to the
self-adhesive. As with molecular weight, crosslinking inuences the bulk properties of the lm and
builds shear, heat and chemical resistance, while
negatively impacting the tack and peel. It is necessary to achieve inter-chain crosslinking for heat
resistance, because the pressure-sensitive adhesive
polymers are operating in the region above their
glass transition temperature. Therefore, without
crosslinks, the polymer would readily ow under
heat, losing all cohesive strength. The crosslinking
also builds water and chemical resistance, as well
as nal adhesive construction properties to enhance
die cutting, slitting and roll stability [5].
An acrylic copolymer whose chains are only
crosslinked via hydrogen bonds or inter penetrating
systems (IPN) can hardly be cohesively loaded. But
a few tenths of a percent of crosslinking agent make
it a pressure-sensitive adhesive having good
mechanical and thermal properties.
Traditional methods of crosslinking polymers,
which include sulfur vulcanization, peroxide curing
and radiation curing, give networks whose crosslink
densities cannot be examined by simple means [6].
Crosslinking based upon amine, ether, ester or
amine bonds located at suitable sites along the polymer can be used as both stoichiometry and reaction
can be controlled [7]. For instance, the formation of

carbamates from isocyanates and hydroxyl groups

and the formation of ureas from isocyanates and
amines are both well known.
Polymers containing ionic crosslinks such as
carboxylates have been known for many years [8].
These ionomers, as they are called, tend to exhibit
both rapid stress relaxation and marked creep under
load. Nonetheless, ionic linkages are attractive for
crosslinking in that the reactions can be controlled
to achieve the desired properties. If the ionic crosslink is metal mediated, the metal salt might be chosen for some particular spectroscopic characteristic.
Past works by Yeh [9] with b-diketonate chelates
of transition metals incorporated in carboxylated
styreneisoprene (SIR), styrenebutadiene (SBR),
and polystyrene rubbers have opened new possibilities for identifying crosslinks, estimating crosslink
density and studying the nature of the chemical
bond in the polymer under varying conditions,
using commonly available instrumentation.
With the aid of chemical bonds during the chemical crosslinking, an increase in cohesion may be
accomplished during the drying of the PSA coating
in the drying step. Logically, the tackifying properties of the PSA coating, such as tack and adhesion,
decrease (Fig. 1) [10].
The transition metals having a coordination number greater than 2, typically 4, 6 or 8 (exemplied by
Zn, Ni, Mn, Fe, Co, Cr, Al, Ti or Zr), form with 2,4pentanedione (acetylacetone) chelate complexes [11]
known as acetylacetonates. The hydrogen atoms of
the methylene group CH2 accordingly the induction eect of the neighboring ketone group are very
mobile. Therefore, the acetylacetonates show the

Tack, Adhesion

Adhesion

Cohesion

Tack

Density of crosslinkage

Fig. 1. General eects of crosslinking to the PSA performances.

Cohesion

2154

Z. Czech, M. Wojciechowicz / European Polymer Journal 42 (2006) 21532160

keto-enol antimerism. The central hydrogen atom of

the chelate rings is accessible to electrophilic substitution [12,13].
The following chelating agents can also be used
as chelating b-diketones: 2-acetylhexanone, 1,3diphenyl-1,3-propandione, 1-phenyl-1,3-butandione,
1,3-diphenyl-1,3-pentandione, 2,4-hexandione, 3,5heptandione, 3-phenyl-2,4-pentandione, 2,2,6,6-tetramethyl-3,5-heptandione or 1,1,1-triuro-2,4-pentandione [14,15].
The equilibrium between the ketone and enol
form of the b-diketone stabilizes slowly at room
temperature. The two tautomeric forms have been
observed in IR and NMR spectra [16] (Fig. 2).
Metal chelates that react with the acrylic polymer
chains containing carboxylic groups are particularly
ecient as crosslinking agents; they have the following formula (Fig. 3).
Chelate-forming reactions are usually exothermic
and therefore, the liberated alcohol does not need to
be distilled to make the reaction complete. Indeed,
such is the physical nature of the chelates that it is
often more desirable to leave the liberated isopropanol in the product as a solvent to facilitate handling. Only capable of forming coordinate bonds
with two donor atoms is metal atom with maximum
valence six. The chelates are therefore manufactured
by adding up to two moles of chelating agent to one
of metal acidester. A typical example is metal chelate titanium acetylacetonate, which is formed by
reacting isopropyl titanate with two moles of acetylacetone, respectively.
Acetylacetone reacts in its enol form with organic
derivatives of Zn, Ni, Mn, Fe, Co, Cr, Al, Ti and Zr
to form metal acetylacetonate. This reaction is
shown in Fig. 4.

(1)

Characteristic for crosslinking systems containing metal chelates is the addition of alcohol as a stabilizer, after the vaporization of which (in the drying
channel together with other solvents) the crosslinking starts spontaneously. Pressure-sensitive adhesive
acrylics containing the above mentioned crosslinking agents are, therefore, called room temperature
crosslinking pressure-sensitive adhesives [17].
Most of the pressure-sensitive adhesives will benet from a short crosslinking time at a temperature
higher than the volatilization temperature of the
polymerization solvent and the solvent stabilizer.
The crosslinking time and temperature will depend
upon the particular required acrylate ester monomers used, the chelating agent, the optional copolymerizable comonomer used, if any, the metal chelate
used, the volatilization temperature of the reaction
by-product after crosslinking, and the required
end use for the acrylic PSA [18].
Crosslinking of the polymer chains with a view to
the selected composition of functional monomers
will only be aected by the functional carboxyl
groups and hydroxyl groups protruding out of the
chain. Consequently, the crosslinking agents will
react preferably with the most proton-activegroups, and these are the carboxylic groups of the
acrylic acid molecules being connected to the polymer chain. Crosslinking relevant for practical application can only be attained provided that the
polymer chain is equipped with acid groups.
3. Target of the investigations
The target of this work was the investigation of
the crosslinking mechanism of the acrylic pressuresensitive adhesives using metal chelate zirconium

O
H
(2b)

H
(2a)

Fig. 2. The tautomeric forms of a b-diketone.

(RO)a
M
(O)b

CH3

M central metal atom

a + b + c = n-metal valence
b = 0 or 1
R = alkyl group

CH
CH3

2155

c
Fig. 3. General formula of metal acetylacetonates.

O
H
(3)

2156

Z. Czech, M. Wojciechowicz / European Polymer Journal 42 (2006) 21532160

CH3

CH

CH3

CH3
CH
CH3

Ti

OH

CH3
CH
CH3

CH3

CH

CH3

acetylacetone (enol form)

CH
CH3
CH3
tetraisopropyl titanate
CH3
O

(i-C3H7O)2 Ti

CH
CH3

2 i -C3H7OH

titanium acetylacetonate (TiACA)

isopropanol

Fig. 4. Synthesis of titanium acetylacetonate.

acetylacetonate and later the manufacture of

solvent-borne acrylic pressure-sensitive adhesives
with high application performances.
4. Starting materials
All starting materials were obtained reagent grade
and were used without further purication unless
otherwise noted. All used crosslinking agents: zirconium acetylacetonate, aluminum acetylacetonate,
iron acetylacetonate and titanium acetylacetonate,
monomers, solvents and AIBN were purchased from
Aldrich (Table 1).
The basic solvent-borne pressure-sensitive adhesive was synthesized from 65 wt.% of 2-ethylhexyl
acrylate, 30 wt.% of methyl acrylate and 5 wt.% of
acrylic acid in the organic solvent ethyl acetate with
a boiling point temperature of about 77 C. 2,2-Azobis-diisobutyronitrile in the amount of 0.1 wt.% was
used as the thermal initiator to start radical polymerization. The nal synthesized solvent-borne basic
acrylic pressure-sensitive adhesive was, after addition of isopropyl alcohol stabilizer, characterized
by the following important properties:

Amount of solid materials

Viscosity
Weight average
molecular weight M W
Number average
molecular weight M n
Polydispersity P d M W =M n

45 wt.%
4.6 Pa s
712 000 Dalton
415 000 Dalton
1.72

Facing the high reactivity of the tested crosslinking agents with functional groups incorporated in
the polymer, the addition of the stabilizer, i.e. isopropyl alcohol, after polymerization is necessary.
5. Test methods and instrumentation
The inuence of the crosslinking agents or crosslinking methods is usually determined in relation to
the reaction time and to the concentration versus
adhesion properties, considering the properties:
tack, adhesion, cohesion and shrinkage. The rst
three properties were determined by standard
AFERA (Association des Fabricants Europeens de
Rubans Auto-Adhesifs) procedures. Exact details
can be found in AFERA 4015 (tack), AFERA

Table 1
Selected metal chelates
Crosslinkers

Chemical formula

Appearance

Solubility in

Aluminum acetylacetonate (AlACA)

Titanium acetylacetonate (TiACA)
Zirconium acetylacetonate (ZrACA)
Iron acetylacetonate (FeACA)

Al(C5H7O2)3
Ti(C5H7O2)2(C3H7O)2
Zr(C5H7O2)4
Fe(C5H7O2)3

Powder
Liquid
Powder
Powder

Toluene, acetone, ethyl acetate

Isopropyl alcohol, toluene, ethyl acetate
Toluene, ethyl alcohol, acetone
Toluene, acetone, ethyl alcohol

Z. Czech, M. Wojciechowicz / European Polymer Journal 42 (2006) 21532160

4001 (peel adhesion) and AFERA 4012 (shear

strength). Administrative address: 60, rue Auber94408 Vitry Sur Seine Cedex, France.
Shrinkage presents the percentage or millimeter
change of dimensions of the PVC foil covered with
PSA after PSA crosslinking and attached to the
glass after keeping it 1 week at temperature of
70 C. With shrinkage greater than 0.5% or greater
than 0.5 mm other properties were neglected.
The viscosity of the investigated solvent-borne
acrylics pressure-sensitive adhesives was determined
with a Rheomat RM 189 from Rheometric Scientic, with spindle No. 3 at 23 C.
The amount of solid materials was found according to DIN EN 12092, the residual of monomers
were measured with gas chromatograph Unicam
610, J&W DB-1 column, FID detector and integrator Unicam 4815.
The molecular weight studies were performed in
tetrahydrofurane with a liquid chromatograph
LaChrom system: RI Detector L-7490 and LaChrom
UV Detector L-7400 from Merck-Hitachi, equipped
column from HewlettPackard.
with a PLgel 106 A
The volatile by-product acetylacetone was identied with the aid of gas chromatograph Varian CP3800.
6. Crosslinking mechanism of acrylic PSA using
zirconium acetylacetonate (ZrACA)
Our former examinations [19] proved that the
crosslinking reaction of acrylic pressure-sensitive
adhesives with the aid of metal acetylacetonates

CH3
O

Zr

+ CH2

CH3

proceeds only if the polymer chains of PSA contain

carboxylic groups as reactive crosslinking centers.
The presence of hydroxyl groups does not lead to
crosslinking and gives unsatisfactory cohesion
increase (cohesive failure in the adhesive layer, yet
under a little load).
The crosslinking reaction of acrylic PSA runs
similarly to the reaction between zirconium acetylacetonate and the carboxylic group of the acrylic
acid, built in the acrylic polymer chain (Fig. 5).
The formation of the zirconium acrylate has been
proven by elementary analysis; the volatile acetylacetone was identied with the aid of gas chromatography.
In order to explain the crosslinking reaction of
acrylic PSA, by the use of zirconium acetylacetonate, the following mechanism of crosslinking process is to be assumed by the author (Fig. 6).
In the rst step of the crosslinking reaction, the
carboxylic group provided by the acrylic acid unit
of PSA copolymer reacts with zirconium acetylacetonate (with its mesomeric form (2) (Fig. 6)) in the
following way (Fig. 7).
In the second stage of the crosslinking reaction of
carboxylated acrylic PSA the following rearrangement proceeds provided by the acyl cation (Fig. 8).
The carbocation acyl cation split o is stabilized
by the p electrons of the oxygen heteroatom. The
oxygen atom interacts with the neighboring electron
attracting the cationic centre of the carbon atom,
due to its free electron pairs. The formed oxonium
ion is unstable, and in the second step of crosslinking the following rearrangement proceeds (Fig. 9).

CH

CH

OH

2157

CH2

CH

O
O

Zr

+ CH3

O
CH2

CH3

ZrACA

acrylic acid

zirconium acrylate

acetylacetone

Fig. 5. Reaction between zirconium acetyacetonate and acrylic acid.

CH3

CH3
O

Zr

CH
CH3

zirconium acetylacetonate

- O

C
+

Zr

CH
(1)

CH3

+
C

- O

Zr

CH3
CH

(2)

CH3

+
O

- O

Zr

CH3

CH

mesomeric stabilization of internal complex

Fig. 6. Intramolecular mesomeric stabilization of zirconium acetylacetonate.

(3)

CH3

2158

Z. Czech, M. Wojciechowicz / European Polymer Journal 42 (2006) 21532160

O

+
C

- O

CH3

Zr

+ H O

CH

CH3

Zr

CH

CH3

CH3

Fig. 7. The rst step of the reaction between ZrACA and carboxylic group of the PSA polymer.

CH3

Zr

CH
CH3

CH3

O
Zr +
O

CH
C

CH3

Fig. 8. The second step of the reaction between ZrACA and carboxylic group of the PSA polymer (acyl cation abstraction).

O
C

CH3

Zr

CH

CH3

Zr

CH3

+
4

O
CH3

OH
CH

O
CH3

CH2

CH3

acetylacetone
(enol-form)

zirconium acrylate

oxonium-ion

CH3

O
CH2

CH3

acetylacetone
(ketone-form 15 %)

acetylacetone
(enol-form 85 %)

Fig. 9. The end phase of the reaction between ZrACA with the polymer chain containing acrylic acid and the tautomeric forms of
acetylacetone.

ethyl acetate

acetylacetone

t = 25C
p = 1.2 bar

Start

The acetylacetone by-product formed in the reaction between metal acetylacetones and acrylic PSA
containing acrylic acid carboxylic group has been
identied by gas chromatography (Fig. 10). During
the crosslinking, the acrylic acid was represented by
carboxylic groups available in the acrylic PSA polymer chain.

Retention time [min]

Fig. 10. Retention peaks of reaction mixture of zirconium

acetylacetonate and acrylic PSA containing carboxylic groups.

7. Use of metal chelate crosslinking agents after the

polymerization
The solvent-borne acrylic pressure-sensitive
adhesives crosslinkable with metal chelates must
be stabilized by an addition of alcohols into the

Z. Czech, M. Wojciechowicz / European Polymer Journal 42 (2006) 21532160

2159

25.0
basic polymer containing 1.0 wt.% of metal chelate
and stabilized with 30 wt.% of isopropyl alcohol

22.5

Viscosity [Pas]

20.0
17.5

ZrACA
FeACA

15.5
12.5

TiACA

10.5
7.5
5.0

AlACA

2.5
0.0
0

10

20

30

40

50

Pot-life [days]

Fig. 11. Inuence of type of metal chelates on the viscosity of crosslinked acrylic PSA during storage.

14
ZrACA
TiACA
AlACA
FeACA

Tack [N/2.5cm]

12
10
8
6
4
0.2

0.4
0.6
0.8
Amount of crosslinker [wt.%]

1.0

Fig. 12. Tack of various crosslinked acrylic PSA.

18
Peel adhesion [N/2.5 cm]

polymer solution. The stabilizer has been chosen

taking into account to its price and its boiling point.
Most often, isopropyl alcohol is used.
The pot-life test has been carried out with an
acrylic PSA containing 1.0 wt.% aluminum, titanium, iron or zirconium acetylacetonate, stabilized
with 30 wt.% of isopropyl alcohol (Fig. 11).
As can be seen from Fig. 11 it is very dicult to
stabilize the PSA crosslinkable with ZrACA. The
pot-life of such an acrylic adhesive has been no
longer than a few days. The other metal acetylacetonates have changed the viscosity of the PSA
solution during the rst 30 days. After one month
of storage time of the best stabilization has been
observed for acrylic PSAs that contained AlACA
and TiACA. The conducted tests established the
lower reactivity of aluminum acetylacetonate.
The investigated metal chelates have been used in
concentrations of 0.2, 0.4, 0.6, 0.8 and 1.0 wt.% as
referred to the acrylic polymer solids.
The inuence of the tested metal chelates on the
performance characteristics of the acrylic pressuresensitive adhesive is illustrated in Figs. 1214.
As can be seen from the data of Figs. 1214, the
investigated metal acetylacetonates with dierent
central metal atoms are excellent crosslinking
agents, which essentially improve the cohesion of
crosslinked acrylic pressure-sensitive adhesives.
The best values of tack and peel adhesion have been
observed in the case of zirconium acetylacetonate
(ZrACA). The shear strength at 70 C of acrylic
adhesives crosslinked with 1.0 wt.% of zirconium,
titanium, aluminum and iron acetylacetonate has
been measured between 30 and 40 N.

ZrACA
TiACA
AlACA
FeACA

16
14
12
10
8
6

0.2

0.4
0.6
0.8
Amount of crosslinker [wt.%]

1.0

Fig. 13. Peel adhesion of various crosslinked acrylic PSA.

Summarizing, aluminum and zirconium acetylacetonates have turned out to be the best metal
chelates as crosslinking agents, useful for industrial
crosslinking of solvent-borne acrylic pressuresensitive adhesives. The acrylic PSA crosslinked

Z. Czech, M. Wojciechowicz / European Polymer Journal 42 (2006) 21532160

45
40
35
30
25
20
15
10
5
0

ZrACA
TiACA
AlACA
FeACA

3.0
2.5
Shrinkage [%]

Shear strength [N]

2160

ZrACA
AlACA
TiACA
FeACA

2.0
1.5
1.0
0.5
0.0
0.0

0.2

0.4
0.6
0.8
Amount of crosslinker [wt.%]

1.0

Fig. 14. Shear strength of various crosslinked acrylic PSA.

with ZrACA has the advantages of a high tack, high

peel adhesion and moderate shear strength for concentrations between 0.2 and 0.6 wt.% ZrACA. The
excellent balance between adhesion and cohesion
for acrylic PSA containing ZrACA is the knowhow in the case of industrial use in the areas of
self-adhesive labels and PVC decorative lms.
8. Inuence of investigated crosslinking agent metal
chelates referring to the shrinkage resistance of
solvent-borne acrylic PSA
The target of this investigation was the development of solvent-borne acrylic PSA for PVC sign
and marking lms with high performance and low
shrinkage. In this case, the greatest attention was
attached to the shrinkage parameter. With acrylic
PSA shrinkage greater than 0.5% other evaluated
PSA properties were neglected.
The inuence of the concentration of the external
crosslinker metal chelates zirconium acetylacetonate
(ZrACA), aluminum acetylacetonate (AlACA), titanium acetylacetonate (TiACA) and iron acetylacetonate (FeACA) on shrinkage of the synthesized
solvent-borne acrylic PSA is described in Fig. 15.
As expected, the amount increase of the tested
metal chelate crosslinking agents ZrACA, AlACA,
TiACA and FeACA corresponds with the decrease
of shrinkage of solvent-borne acrylic PSA. By using
ZrACA in comparison to AlACA or TiACA a
slightly better shrinkage resistance was observed.
For this reason the TiACA in PSA technology is
becoming more and more replaced by ZrACA or
AlACA as a crosslinker for solvent-borne acrylic
PSA. Up to 0.2 wt.% ZrACA or 0.2 wt.% AlACA
the shrinkage values of 0.5% and 0.55% were not satisfactory. Above this amount of both metal acetylacetonates the shrinkage level dropped under 0.5%.

0.2

0.4
0.6
0.8
Amount of crosslinker [wt.%]

1.0

Fig. 15. Shrinkage performances of various crosslinked acrylic

PSA.

9. Summary
Almost all the properties of tested acrylic PSA
presented in this paper show that the mentioned representatives of the investigated metal chelates are
good alternative crosslinking agents to those usually
used. This publication can be used by the producer
of solvent-borne acrylic pressure-sensitive adhesives
to promote the selected metal chelates as modern,
eective crosslinking agents for the future.
Especially the fourfunctional zirconium acetylacetonate (ZrACA) and threefunctional aluminum acetylacetonate (AlACA) guarantee in the PSA technology
several excellent properties and the best balance performance of crosslinked self-adhesive acrylics.
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