Protection and Conservation of thè Cultural Hehtage of thè Mediterranean Cities

PREPARATION OF NEW FLUORINATED POLYMERIC ACRYLIC MATERIALS AND

THEIR USE IN STONE PROTECTION

Botteghi, C1., Matteoli, U?, Paganelli, S; Fassina, V' Castelvetro, V3; Aglietto, M.3
‘Dipartimento di Chimica, Calle Larga S. Marta 2137. 30123 Venezia, Italy
'Laboratorio Scientifico della Soprintendenza per i Beni Artistici e Storici, Cannaregio 3553, 30121 Venezia, Italy
3Dipartimento di Chimica e Chimica Industriale, via Risorgimento 35. 56126 Pisa. Italy

Polymeric materials based on esters of 2- of these compounds produces selectively 2-

fluoroacrylic acid show considerably superior fluoropropanal [9], which was converted in 3
physico-mechanical properties (transparency, steps into thè appropriate 2-fluoroacrylic esters
impact-, heat- and atmospheric agents in 20-25 % overall yields.
resistance) than those based on non fluorinated Radicai homopolymerization in bulk or in
monomers [1,2]. As a part of our continuing solution of either non fluorinated (e.g. dioxane)
efforts to develop new technologies and or fluorinated solvent, such as 1,3-bis-
Products in thè field of thè cultural heritage trifluoropropylbenzene, occurs readily at 50 - 60
protection [3-8], we have prepared °C in thè presence of azoisobutironitrile (AIBN)
homopolymers of some perfluoroalkylethyl 2- as initiator, yielding high molecular weight
fluoroacrylate (Fig. 1) and their copolymers polymeric materials [10], These monomers,
with different vinyl ethers and 2-propenyl ethers however, owing to thè highly electron poor
(Fig. 2). character of their vinyl group, are particularly
F suitable for thè copolymerization with such
electron rich monomers as vinyl ethers and -
olefins, which are known to homopolymerize
very poorly in thè presence of radicai initiators.
Indeed, high molecular weight copolymers were
COORf
obtained in good yields (50 - 80 % with respect
to thè fluoroacrylate) by radicai initiated bulk
with Rf = -(CH2)n-(CF2)m-CF3 polymerization at 60 °C in thè presence of an
equimolar amount of an alkyl alkenyl ether,
(n = 1,2,m = 0, 5). such as butyl vinyl ether, and of AIBN as
initiator. However, while in thè case of
Fig. 1
copolymerization of thè hexafluoroisopropyl
ester of 2-fluoroacrylic acid thè resulting
------ CH2----- CF------CH2—CR2------- copolymer had always an equimolar
composition, corresponding to an altemating
comonomer strutture [11], thè copoly-
RfOOC OR1 merizations of thè parent 2-fluoroacrylic esters
with R1 = n-C4H9, Ì-C4H9, t-C4H9, cyclohexyl with non fluorinated alkoxy group yielded 2/1 to
3/1 molar excess of thè acrylate in thè resulting
R2 = -H, -CH3
copolymer. This is presumably due to more
Fig. 2 efficient competition of fast fluoroacrylate
homopropagation with respect to poly­
2-Fluoroacrylic acid monomer is merization through charge transfer (donor-
commercially available in relatively large acceptor couples) mechanism, presumably
amount and it is obtained by electrofluorination yielding acrylate-rich copolymers with a
processes. We have developed a new segmented composition consisting of blocks of
preparative pathway starting from vinyl altemating comonomers strutture and blocks of
fluoride: rhodium-catalysed hydroformylation oligo-fluoroacrylate. Similar conversions of

5"' International Symposium on thè Conservation of Monuments in thè Mediterranean Basin. Seville. 2000. pp. 221-223

221
fluoroacrylate but increasingly alternating
structure was obtained when using excess vinyl
ether in thè feed.
All homo- and copolymers were
characterised in terms of Chemical composition
(FT-IR, NMR), molecular weight and molecular
weight distribution, thermal behaviour (glass
transition and thermal decomposition
temperature) and surface properties of their
films, by means of static contact angle with
water.
The polymeric materials obtained show good
technological properties and stability towards
thè atmospheric agents (U.V. and I.R.
irradiation) higher than that of analogous
copolymers containing non fluorinated acrylic
monomers [1].
Tests were carried out on three lithotypes,
different for their framework and porosity and
commonly used in thè manufacture of historical
monuments:
Dolomitic Marble from Yugoslav
Macedonian with a dolomite content over 99%.
Total porosity varies from 1.5 to 2.5% (low
porosity) and saturation index from 60 to 80%.
Vicenza Stone from Berici Hills. Biosparite
with an abundant skeletal material in thè fine
carbonatic matrix. Total porosity varies from 12
to 15% (medium porosity).
Serena Stone from Firenzuola (FI). A marly
arenaceous stone classified as feldspathic
greywacke with partially carbonatic and clayey
matrix composed by quarz, feldspar, micas and
clasts of eruptive and metamorphic rocks. Total
porosity varies from 3.5 to 6.0% and saturation
index from 60 to 80%.
The following water-repellent substances
were applied:
Rhoximat HD 224 (former trade name
Rhodorsil 224 by Rhone Poulenc Italia S.p.A.).
Polymethylsiloxane applied by white spirit as
solvent (7% in weight).
Fomblin S12 (traded by Syremont as
Akeogard BA). Mixture of isobuthylamide of a
perfluoropolyetheric acid (40%) and of neutral
perfluoropolyether (60%) applied by
trichlorotrifluoroethane as solvent (50% in
weight).
Paraloid B72 (traded by Rohm and Haas).
Copolymer methyl acrylate/ethyl methacrylate
in trichloroethane.
222
Five samples (5x5x2 cm) were used for each
lithotype and each produci. They were
conditioned for 24 hours at 25 °C and 50% of
RH before thè treatment which was carried out
by capillary rising System (13).
The assessment of thè hydrophobic
performances was carried out measuring on thè
same untreated and treated samples thè
following properties according to Normal
Recommendations:
water capillary absorption (14);
contact angle (15);
drying index (16).
Finally, thè protective efficiency of thè new
fluorinated polymer was compared to that of
other commercially available products generally
used in stone protection (2,17).
References
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223
The International Group far thè Conservation of Monuments in thè Mediterranean
Basin (IGCMM) was faunded in Bari (Italy) in 1989, under thè leadership of Prof.
Fulvio Zezza. Sirice its foundation thè Group has met three times more in Geneve
(1991), Venice (1994), Rhodes (1997) and now in Seville (2000). For each Meeting thè
Group proposed to focus thè work in an important, present, and significant topic for thè
conservation of monuments in thè Mediterranean cities. In Bari, thè centrai theme was
"The influence of Coastal environment and salt spray on limestone and marble" (F.
Zezza, 1989). In 1991 thè Group met around thè topic "Marble: origin, alteration and
conservation" (D. Decrouez, 1991). Three years later thè symposium was held in
Venice chaired by Dr. Vasco Fassina with thè title "Stane and monuments:
methodologies for thè analyses of weathering and conservation" (V. Fassina, 1994) and
thè last meeting, conducted by Prof. Tonia Moropoulou, held in Rhodes, focused thè
Symposium on "New concepts, technology and materials for thè conservation and
management of historical cities, sites and complexes". Now in Seville, following thè
changes introduced in thè Rhodes Symposium and according to thè new european
conservation phyllosophy and policy, thè title of this meeting is: "Protection and
Conservation ofthe Cultural Heritage of thè Mediterranean Cities".

The IGCMM will continue to meet in other Mediterranean Cities providing new
contributions and approaches to thè monument conservation problematic froni both
scientifica! and technical points ofview.

The Group is opened to everybody because we think that thè stane degradation and
preservation problems and thè conservation management of cities can only be
understood through interdisciplinarity.

Editorial Office: Departamento de Cristalografia,

Mineralogia y Quimica Agricola,
Facultad de Quimica
Universidad de Sevilla

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