Convenient synthesis of tributylsilyl methacrylate

Article abstract of DOI:10.1080/00397910701462757

To replace antifouling paints containing organotin compounds and to develop self-polishing coatings free of toxicity, we describe here the synthesis of a new polymerizable molecule containing silicon: tributylsilyl methacrylate. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910701462757

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Convenient Synthesis of Tributylsilyl
Methacrylate
David Mancardi a , Michèle Sindt a , Jean‐Michel Paul b & Jean‐Luc
Mieloszynski a
a Laboratory of Chemistry and Methodology for the Environment (LCME) ,
Paul Verlaine‐Metz University , Metz, France
b Arkema, Research and Development Centre (CRDE) , Saint-Avold, France
Published online: 19 Oct 2007.
To cite this article: David Mancardi , Michèle Sindt , Jean‐Michel Paul & Jean‐Luc Mieloszynski (2007)
Convenient Synthesis of Tributylsilyl Methacrylate, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 37:21, 3873-3878, DOI: 10.1080/00397910701462757
To link to this article: http://dx.doi.org/10.1080/00397910701462757
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Synthetic Communicationsw, 37: 3873–3878, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701462757
Convenient Synthesis of Tributylsilyl
Methacrylate
`
David Mancardi and Michele Sindt
Laboratory of Chemistry and Methodology for the Environment (LCME),
Paul Verlaine-Metz University, Metz, France
Jean-Michel Paul
Arkema, Research and Development Centre (CRDE),
Saint-Avold, France
Jean-Luc Mieloszynski
Laboratory of Chemistry and Methodology for the Environment (LCME),
Paul Verlaine-Metz University, Metz, France
Abstract: To replace antifouling paints containing organotin compounds and to
develop self-polishing coatings free of toxicity, we describe here the synthesis of a
new polymerizable molecule containing silicon: tributylsilyl methacrylate.
Keywords: acrylic acid, acrylic anhydride, catalyst, silane
INTRODUCTION
Antifouling paints are used in aquatic media and particularly protect ships’
shells against fouling.[1] This phenomenon is characterized by the development
of marine organisms as mussels, algae, or barnacles on submerged surfaces and
has important consequences for the industries concerned. Fouling creates an
additional charge for ships and an overconsumption of fuels to maintain
speed. The ancestral techniques of Greek (copper nails) are now replaced by
Received in Poland October 4, 2006
`
Address correspondence to Michele Sindt, Laboratory of Chemistry and Method-
ology for the Environment (LCME), Paul Verlaine-Metz University, Metz, France.
E-mail: sindt@univ-metz.fr
3873

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D. Mancardi et al.
antifouling paints. Their action consists of the liberation of biocides included in
the formulation. In the case of self-polishing paints, the biocide is copper or tin
and is linked to an acrylate copolymer by covalent ester bond.
However, between 1976 and 1981, the high ecotoxicity of organotin
compounds was established[2] and constitutes a real menace for the environ-
ment. Regulation,[3] which prohibits the use of tributyltin acrylate, obliges
scientists to find a substitute.
To this end, a solution consists in the replacement of stain by silicon,
using the ability of silylated ester to rapidly hydrolysize. We selected trial-
kylsilyl (meth)acrylic copolymers. This kind of paint has a self-polishing
effect, but silylated compounds have no biocide properties. It will be
necessary to introduce a toxic as copper oxide to bring biocide potential in
the formulation.
The synthesis of trialkylsilyl(meth)acrylate is described in the literature
as early as 1960,[4] using acrylic acid salts and chlorosilanes. The use of
catalysts[5] such as crow ether or N,N-diethylaniline improves the yields.
Other silane derivatives can be used: acrylic or methacrylic acid reacts with
H-alkylsilanes in the presence of catalysts (Cu,[6] Pd[7]), with silanols in
presence of TiCl4, or with hexamethyldisilazane.[8]
Our contribution is to propose a convenient synthesis of a polymerizable
molecule containing silicon, tributylsilyl methacrylate 1, chosen for its good
propensity for hydrolysis.[9]
RESULTS AND DISCUSSION
After organohalosilanes, organo(organooxy)silanes are the most interesting
compounds in the chemistry of silicone. Besides, the use of methoxytributyl-
silane affords organoacyloxytributylsilanes.[10] The reaction of methoxytribu-
tylsilane with acrylates monomers (Scheme 1) has been studied in the
presence of different catalysts (paratoluenesulfonic acid (PTSA), Zr(Acac)4,
ZnCl2, Amberlyst 15, 1-methylimidazole (1-MIM), 4-dimethylaminopyridine
(DMAP)).
Using methylmethacrylate, none of the catalysts tested gave the
expected compound. Starting from methacrylic acid, yields were very low
(3–25%) (Table 1), and different by-products were observed, such as
hexabutyldisiloxane.
Scheme 1. Reaction of methoxytributylsilane with methylmethacrylate or
methacrylic acid.

Tributylsilyl Methacrylate
3875
Table 1. Synthesis of tributylsilyl methacrylate 1 from methacrylic acida
Entry
Catalyst
Yield (%)
1
2
—
3
12
15
5
Paratoluenesulfonic acid (PTSA) (0.5%wt)
Paratoluenesulfonic acid (PTSA) (1%wt)
Zr(Acac)4 (0.5%wt)
3
4
5
Zr(Acac)4 (1%wt)
7
6
1-Methylimidazole (1-MIM) (0.5%wt)
1-Methylimidazole (1-MIM) (1%wt)
4-Dimethylaminopyridine (DMAP) (0.5%wt)
4-Dimethylaminopyridine (DMAP) (1%wt)
Zinc chloride (ZnCl2) (0.5%wt)
Zinc chloride (ZnCl2) (1%wt)
10
13
7
7
8
9
9
10
11
23
25
aReaction conditions: methoxytributylsilane: 10 mmol, acrylate: 11 mmol, EMHQ:
2000 ppm, catalyst: 0.5 or 1% weight, temp: 1008C, time: 6 h.
The use of acetoxytributylsilane instead of methoxytributylsilane consti-
tutes an alternative: we observed that it can react with methacrylic acid in the
presence of ZnCl2 to produce 1 (88%). Acetoxytributylsilane is obtained by
reaction between methoxytributylsilane and acetic anhydride. Starting from
this synthesis, we develop a protocol leading to 1 in very good yields
(Scheme 2).
Methoxytributylsilane and acetic anhydride in the presence of a catalyst
are stirred at 100–1108C; when methylacetate is formed, it is removed from
the media and acrylic acid is added at the same time. The tributylsilyl metha-
crylate 1 is obtained with 95% yield (Table 2) and 99% purity (catalyst
Amberlyst 15).
Because the methacrylic anhydride is prepared by reaction of acetic acid
and methacrylic acid, we turned to a direct reaction of methoxytributylsilane
with this one (Scheme 3).
This reaction also affords the compound 1 in very good yields (95%)
(Table 3). However, the nature of the catalysts has an influence on the final
purity of 1.
We observed that traces of 1-MIM or DMAP persist even after distillation
and give a yellow color to the product. With ZnCl2, a rapid hydrolysis of 1 is
Scheme 2. Reaction of methoxytributylsilane with acetic anhydride and methacrylic
acid.

3876
D. Mancardi et al.
Table 2. Synthesis of tributylsilyl methacrylate 1 from acetic anhydride and
methacrylic acida
Entry
Catalyst
Temp (8C)
Yield (%)
1
2
Zinc chloride (ZnCl2) (1%wt)
Amberlyst 15 (1%wt)
100
80
94
95
aReaction conditions: methoxytributylsilane: 10 mmol, acetic anhydride: 10 mmol,
acrylic acid: 12 mmol, BHT, Topanol A: 2000 ppm, catalyst: 1% weight, temp:
80–1008C, time: 2–6 h.
observed: it seems that hydrochloride acid is generated in the media, leading
to this phenomenon. Furthermore, we observed the formation of a dimere of
methacrylic anhydride during the distillation step. Only when using
Amberlyst A15 is compound 1 colourless, with 99.5% purity.
EXPERIMENTAL
1H NMR and 13C NMR spectra were recorded on a Brucker AC-250 (250-
MHz) spectrometer with deuterated chloroform (CDCl3) as solvent with
chloroform (7.26 ppm) as internal reference. Chemical shifts are reported in
parts per million (ppm): s: singlet, d: doublet, t: triplet, q: quartet, m:
multiplet, and coupling constants (J) are in Hertz. Mass spectra were
recorded on a Hewlett-Packard (model 5971 A) in electronic impact
Scheme 3. Reaction of methoxytributylsilane with methacrylic anhydride.
Table 3. Synthesis of tributylsilyl methacrylate 1 from methacrylic anhydridea
Entry
Catalyst
Temp (8C)
Yield (%)
1
2
3
4
1-Methylimidazole (1-MIM) (1%wt)
4-Dimethylaminopyridine (DMAP) (1%wt)
Zinc chloride (ZnCl2) (1%wt)
100
100
100
75
95
95
94
95
Amberlyst 15 (1%wt)
aReaction conditions: methoxytributylsilane: 10 mmol, methacrylic anhydride:
11 mmol, Topanol A: 2000 ppm, catalyst: 1% weight, temp: 75–1008C, time: 3–6 h.

Tributylsilyl Methacrylate
3877
(70 eV) coupling with a gas chromatograph equipped with a capillary column
(WCOT fused silica, 25 m  0.25 mm) whose stationary phase is CPSil5CB
(0.12 mm). Helium is used as gas carrier, detector temperature is 3008C,
and injector temperature is 2808C.
Typical Procedure for 1
Method A
A mixture of 10 mmol of methoxytributylsilane, 11 mmol of methyl metha-
crylate, 2000 ppm of EMHQ, and 1%wt of catalyst is stirred at 1008C for
6 h without any solvent. Catalysts are eventually removed by filtration, and
analyses showed that the reaction did not take place.
Method B
A mixture of 10 mmol of methoxytributylsilane, 2000 ppm of EMHQ, and
1%wt of catalysts is stirred at 1008C. Then, 11 mmol of methacrylic acid
are added, and the media is stirred for 6 h. Catalysts are eventually removed
by filtration, and the tributylsilyl methacrylate is purified by distillation
under low pressure.
Method C
A mixture of 10 mmol of methoxytributylsilane, 10 mmol of acetic anhydride,
2000 ppm of BHT and Topanol A, and 1%wt of catalyst is stirred at 1108C.
During the distillation of methyl acetate, 12 mmol of methacrylic acid is
slowly added. When methyl acetate and acetic acid are totally removed, tribu-
tylsilyl methacrymate is distilled under low pressure.
Method D
A mixture of 10 mmol of methoxytributylsilane, 11 mmol of methacrylic
anhydride, 2000 ppm of Topanol A, and 1%wt of catalyst is stirred at 75 to
1008C for 3 to 6 h. Methyl methacrylate, formed during the reaction, is pro-
gressively removed to increase the reaction speed. Then, tributylsilyl metha-
crylate is purified by distillation under low pressure. Bp: 1358C (7 mmHg);
1H NMR (CDCl3): d 6.10 (1H, s), 5.59 (1H, s), 1.92 (3H, s), 1.34 (12H, m),
0.89 (9H, t, J ¼ 6.6 Hz), 0.79 (6H, m); 13C NMR (CDCl3): d 166.5, 137.5,
125.2, 26.1, 24.8, 18.0, 13.5, 12.8; GC-MS (70 eV) [m/z (%)]: 41(39),
69(52), 85(10), 199(1), 227(100), 284(1).

3878
D. Mancardi et al.
CONCLUSION
A convenient synthesis of the tributylsilyl methacrylate 1 has been developed
from methoxytributylsilane, either with acetic acid and methacrylic acid or
with methacrylic anhydride, in very good yields (95%) and very high purity
(99.5%).
ACKNOWLEDGMENTS
We thank our industrial partner, ARKEMA, for financial and scientific
support.
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