Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1996-04-15
2001-06-05
Wilson, Donald R. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S213000, C526S217000, C526S228000, C525S404000, C524S493000, C524S425000, C524S426000, C524S442000, C524S444000
Reexamination Certificate
active
06242549
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to a composition based on a dicyclopentenyloxyalkyl ester of (meth)acrylic acid, the said composition being intended to be used in the building sector, as binder in the preparation of synthetic resin concretes or mortars, or as bonding primer, or alternatively as finishing coat, in which case the composition can contain one or more pigments in order to obtain the desired final colour.
The development of floorings based on methyl methacrylate resin concretes or mortars has made it possible to be able to carry out construction operations under temperature conditions close to 0° C., conditions under which epoxy- or polyurethane-based systems are inoperative. Moreover, the low viscosity of this monomer introduces the advantage of thoroughly filling the spaces and cracks, thus improving the mechanical behaviour. However, the major disadvantages of the use of methyl methacrylate are its odor, its low ignition point and its high shrinkage.
With the aim of reducing these disadvantages, the use of a particular methacrylic monomer, namely dicyclopentenyloxyethyl methacrylate (DCPOEMA), has been proposed in Patents U.S. Pat. No. 4,299,761, EP-A-47,120, U.S. Pat. No. 4,400,413 and U.S. Pat. No. 4,460,625. This monomer, which has a high boiling point and which carries two double bonds of different natures and reactivities, in fact possesses a very slight odor and results in shrinkage which is markedly less than that of methyl methacrylate.
The use having a monomers of high boiling point and a high molar mass poses, however, problems of limitation of the rate of surface polymerization due to inhibition by atmospheric oxygen which is reflected by the persistence of a stickiness for a period of time ranging up to more than 24 hours. These problems are particularly evident when DCPOEMA and analogous monomers are used.
In accordance with the abovementioned patents, this problem can be solved by covering the surface with an immiscible liquid which forms a barrier to oxygen and which can contain a polymerization initiator. This solution nevertheless brings with it the disadvantage of causing the appearance of the fillers at the surface and of reducing the chemical resistance of the material.
It is also known that the use of salts or complexes of transition metals, such as cobalt, manganese and zirconium, commonly called drying agents, makes it possible to reduce the curing time of the surface without, however, falling below 8 hours. In order to increase the drying rate and to decrease the water gain, it is also possible to incorporate unsaturated fatty acids as described in European Patent Application EP-A-157,596. However, this improvement in the drying time still does not make it possible to obtain a time during which stickiness is displayed which is less than 6-8 hours. In order to inhibit the effect of oxygen, reducing agents, such as aldehydes and imines, can be added at the time of polymerization, as described in European Patent Application EP-A-169,702, with, however, the disadvantages of a possible premature oxidation of the aldehyde and of the necessity of the presence of water in order to open the imine functional group (blocked aldehyde functional group).
The development of synthetic resin concretes based on dicyclopentenyloxyethyl methacrylate and analogous compounds thus requires new solutions in order to solve the technical problems related to the low rate of drying of the coating.
Moreover, this market also demands materials exhibiting improved thermal resistance and good resistance to chemical agents, such as acids, bases and solvents.
SUMMARY OF THE INVENTION
It has now been discovered that, surprisingly, the use of poly(allyl glycidyl ether)s for activating the polymerization of dicyclopentenyloxyethyl methacrylate and of analogous monomers made it possible to obtain binders for synthetic resin mortars or concretes which exhibit an improved drying time and floorings exhibiting, only 2 to 4 hours after application, a hard, dry, smooth and impermeable surface which is resistant to weathering and chemical attacks and which exhibits a very marked improvement with respect to the prior state of the art.
The use of poly(allyl glycidyl ether)s in binder compositions for concrete or mortars or bonding primer compositions or finishing coat compositions, mostly composed of dicyclopentenyloxyalkyl (meth)acrylate or analogous compounds, is not known to date:
PRIOR ART
J. W. Knapczyk, “Journal of Coating Technology”, Vol. 60, No. 756, January 1988, pages 63 to 72, has described the acceleration in the formation of films of pentaerythritol triacrylate, of dipentaerythritol hydroxypentaacrylate, of trimethylolpropane triacrylate, of acrylate urethane, of epoxy acrylate, of tetraethylene glycol diacrylate and of hexanediol diacrylate, under the effect of poly(allyl glycidyl ether)s. W. Demarteau and J. M. Loutz, “Double Liaison—Chimie des Peintures” [Double Bond—Chemistry of Paints], No. 411-412, January-February 1990, pages 11/29 to 34/16, have shown that it is possible to cure prepolymers carrying acrylate functional groups (acrylate polyesters, ethoxyacrylates, acrylate urethanes) by a chain mechanism using initiators which are generators of free radicals, provided that a poly(allyl glycidyl ether) is added to the formulations. E. S. Jensen et al., “Journal of Applied Polymer Science”, Vol. 42, 2681-2689 (1991), pages 2681-2689, have shown that poly(allyl glycidyl ether) resins, in combination with an initiator and a catalyst, promote the curing of multifunctional acrylates in the presence of air, without achieving thereby the same result as in the absence of air.
However, it could not be deduced from the above described prior art that the incorporation of poly(allyl glycidyl ether)s in formulations based on dicyclopentenyloxyalkyl (meth)acrylate and analogous compounds would make possible such a fast reaction, resulting in an extremely rapid disappearance of the stickiness (“tack”) at the surface. In fact, the rate of polymerization of DCPOEMA is markedly slower in the presence of air than that of multifunctional monomers. Moreover, it is well known that the rate of polymerization of multifunctional monomers is faster than that of monofunctional monomers (the allylic double bond of DCPOEMA does not participate in the polymerization but in the subsequent crosslinking by treatment with drying agent(s)). However, for multi-functional (meth)acrylates, this higher reactivity is accompanied by a high level of residual monomers due to the gelling of the mixture by establishment of a three-dimensional network, which results in a residual “tack”. In this context, the use of poly(allyl glycidyl ether)s as secondary initiators makes it possible to greatly decrease the content of residual monomers.
In the case of DCPOEMA and analogous monomers, the poly(allyl glycidyl ether)s intervene more in trapping atmospheric oxygen and preventing the formation of low molecular weight oxygen-containing oligomers, the rate of polymerization of DCPOEMA and analogous compounds not being limited.
Moreover, it has been observed that poly(allyl glycidyl ether)s result, in the case of the present invention, in resin concretes which are less rigid and in coats which are more flexible.
A subject of the present invention is therefore first a composition intended to be used as a binder in the preparation of synthetic resin concretes or mortars or as bonding primer or as finishing coat, characterized in that it comprises:
(A) a system of monomers comprising:
(a1) 50 to 90 parts by weight of a dicyclopentenyloxyalkyl ester of formula (I):
in which
R represents H or CH
3
;
n has the value 1 or 2; and
R
1
represents a C
2
-C
6
alkylene group;
(a2) 0 to 25 parts by weight of at least one heavy (meth)acrylate giving a homopolymer in which the glass transition temperature is higher than the glass transition temperature of a homopolymer of the ester (a1);
(a3) 0 to 25 parts by weight of at least one heavy (meth)acrylate giving a homopolymer in which the glass tra
Barbier Yves
Cerf Martine
Vanhoye Didier
Wnuk Mieczyslaw
Elf Atochem S.A.
Millen White Zelano & Branigan P.C.
Wilson Donald R.
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