Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2000-06-15
2003-11-18
Berman, Susan W. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S025000, C522S168000, C522S169000, C522S170000, C522S181000, C522S148000, C522S099000, C528S013000, C528S033000, C528S417000, C528S418000, C528S421000
Reexamination Certificate
active
06649668
ABSTRACT:
FIELD OF THE INVENTION
The field of the invention is that of the catalysis of reactions for the cationic polymerization and/or crosslinking of monomers, oligomers and/or polymers, comprising reactive functional radicals capable of forming intra-chain and inter-chain bridges, so as to obtain a polymerized and/or crosslinked composite material or coating which has a certain level of hardness and a certain level of mechanical strength.
More specifically, the subject of the present invention is novel initiator systems for cationic polymerization and/or crosslinking. These initiators comprise at least one onium borate and at least one cyclic compound allowing the initiation and progress of reactions for forming polymers and/or resins, starting with substrates formed from monomers, oligomers and/or polymers containing reactive organofunctional groups.
The reactions more particularly concerned are those in which cationic agents act as direct promoters of inter-chain and/or intra-chain bonding.
In general, these reactions take place by photochemical and/or thermal activation and/or by activation with a beam of electrons. As a practical example, the light energy of a UV radiation allows the formation of active protagonists, for example by cleaving bonds, and thus triggering of the polymerization and/or crosslinking reactions is effected.
In the present description, the polymers and/or resins obtained are prepared from monomers, oligomers and/or polymers which are either (1) of organic nature, in particular exclusively hydrocarbon-based, or (2) of polyorganosiloxane nature, and comprise organofunctional groups in their structure, for example groups such as epoxides, oxetanes and/or alkenyl ethers, which react cationically and with the aid of the novel initiator systems according to the invention which are described below. It is also possible to use (3) monomers, oligomers and/or polymers with acrylic groups, for example pure acrylic or methacrylic groups, which can be added to the cationic polymerization medium.
A subject of the present invention is thus also compositions comprising base materials (monomers, oligomers and/or polymers) which can be polymerized and/or crosslinked cationically, the initiator systems described below, and optionally one or more additives chosen from those generally known in the applications for which these compositions are intended.
For example, these compositions can be used to make coatings on objects such as solid articles or supports, in particular a paper support, a polymer film of polyester or polyolefin type, an aluminium support and/or a tinplate support.
BACKGROUND OF THE INVENTION
Initiators for the polymerization and/or crosslinking, for example the photochemical polymerization and/or crosslinking, of monomers, oligomers and/or polymers comprising reactive organofunctional groups in their structure are described in EP-0 562 897 in the name of the Applicant. The initiator salts in that patent represent an appreciable technical advance over the initiators previously known, of onium salt type or of organometallic complex type, and in particular over those in which the anion of the initiator salt is SbF
6
−
which is one of the only types which is satisfactory in terms of catalytic performance, but which poses serious problems of use on account of the presence of heavy metals.
The initiator salts according to EP-A-0 562 897 are used, for example, for the preparation of coatings on paper starting with epoxidized monomers which are polymerized and crosslinked by UV irradiation. In order to assess the performance as initiator, the reactivity of the substrate/initiator couple and the speed of polymerization/crosslinking are evaluated, by means of the rate of throughput required to cure the layer coated onto the paper, as well as by means of the number of passages. The measured results are acceptable, but it nevertheless remains that, in order to satisfy the production efficiency requirements of the people using them, the initiator systems need to achieve higher and higher performance levels. They must thus make it possible to achieve polymerization/cross-linking reactivities and rates that are as high as possible, so as to be able to increase the coating rates.
Accordingly, one of the essential objects of the present invention is to satisfy the production efficiency requirements stated above.
Another essential object of the invention is to provide novel initiator systems which give high performance as initiators with respect to the majority of organofunctional monomers, oligomers and/or polymers which can be polymerized and/or crosslinked cationically; the monomers, oligomers and/or polymers being in particular (1) of organic nature, preferably exclusively hydrocarbon-based, or (2) of polyorganosiloxane nature, optionally as a mixture (3) with other monomers, oligomers and/or polymers containing acrylic groups.
Another essential object of the invention is to provide cationic initiator systems which are effective in small amount, but which are also easy to handle and relatively non-toxic, and which consequently make it possible to obtain composite coatings and/or materials which do not yellow over time and/or after curing.
Another object of the invention is to provide compositions of organofunctional monomers, oligomers and/or polymers which can be crosslinked cationically and under photonic and/or thermal activation and/or under activation with a beam of electrons.
Another object of the invention is to provide compositions of this type which can be used either as a thin layer, the thickness of which is, for example, in the range from 0.1 to 1 &mgr;m, or as a thicker layer, the thickness of which is, for example, in the range from a value of greater than one micrometer to several centimeters.
Another object of the invention is to provide compositions of this type for the preparation of a composite material.
DESCRIPTION OF THE INVENTION
These various objects are achieved by the invention which firstly relates, in its first subject, to novel initiator systems comprising at least one carefully selected onium borate and at least one carefully selected cyclic compound. Thus, the initiator system for polymerization and/or crosslinking comprises:
(1) at least one onium borate in which:
(i) the cationic species is chosen from the onium salts of formula (I)
[(R
1
)
n
−I−(R
2
)
m
]
+
(I)
in which formula:
the radicals R
1
, which may be identical or different, represent a carbocyclic or heterocyclic C
6
-C
20
aryl radical, it being possible for the said heterocyclic radical to contain nitrogen and/or sulphur as hetero elements,
the radicals R
2
, which may be identical or different, represent R
1
, a linear or branched C
1
-C
30
alkyl radical or a linear or branched C
1
-C
30
alkenyl radical,
the said radicals R
1
and R
2
optionally being substituted with:
a linear or branched C
1
-C
25
alkyl group,
an alkoxy group OR
13
a ketone group —(C═O)—R
13
,
an ester or carboxylic group —(C═O)—O—R
113
,
a mercapto group SR
13
,
a mercapto group SOR
13
,
R
13
being a radical chosen from the group consisting of a hydrogen atom, a linear or branched C
1
-C
25
alkyl radical, a C
6
-C
30
aryl radical and an alkylaryl radical in which the alkyl portion is linear or branched and C
1
-C
25
and the aryl portion is C
6
-C
30
,
a nitro group,
a chlorine atom,
a bromine atom, and/or
a cyano group,
n is an integer ranging from 1 to v+1, v being the valency of iodine,
m is an integer with n+m=v+1;
(ii) and in that the anionic borate species has the formula (II):
[BX
a
R
3
b
]
−
(II)
in which:
a and b are integers such that 0≦a≦4, 0≦b≦4, and a+b=4,
the symbols X, which may be identical or different, represent:
a halogen atom chosen from chlorine and/or fluorine with 0≦a≦3,
an OH function with 0≦a≦2, and
the radicals R
3
, which may be identical or different, represent:
a phenyl radical substituted with at least one electron-with
David Marie-Anne
Frances Jean-Marc
Berman Susan W.
Burns Doane Swecker & Mathis L.L.P.
Chimie Rhodia
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