Stock material or miscellaneous articles – Coated or structually defined flake – particle – cell – strand,... – Particulate matter
Reexamination Certificate
1999-01-04
2001-07-24
Moore, Margaret G. (Department: 1712)
Stock material or miscellaneous articles
Coated or structually defined flake, particle, cell, strand,...
Particulate matter
C524S497000, C524S586000, C524S584000, C524S579000, C523S203000, C523S209000, C523S212000, C523S213000
Reexamination Certificate
active
06265069
ABSTRACT:
The present invention relates to new treated particles which can in particular be used in thermoplastics.
Inorganic particles used as pigments in plastics are generally introduced in pulverulent form into polymer mixtures for plastics. However, this introduction in pulverulent form requires specific equipment, with which plastic manufacturers are not always equipped.
To overcome this disadvantage, it is possible to use particles in the form of masterbatches, which are mixtures of thermoplastic polymer(s) and of a high proportion of particles. It suffices for the plastics manufacturer, to whom the masterbatch is sold, to dilute the said masterbatch in a larger amount of polymer(s) in order to obtain the desired content of particles and to prepare plastics.
The advantage of these masterbatches is that they are easier to handle than particles in pulverulent form.
However, the very manufacture of these masterbatches requires very powerful stirring devices, which consume a large amount of energy, in order to be able to incorporate the particles in the polymers. In order to improve the wetting of the particles by the polymers, provision has been made for treating the particles, for example with silicones of polydimethylsiloxane (PDMS) type.
Masterbatches of particles treated with such products which are currently marketed exhibit a particle concentration not exceeding 70% by weight. Higher particle concentrations can only be obtained, with the particles of the prior art, by using additives (polyethylene, carboxylates, and the like) which make it possible to improve the introduction of the fillers into the polymer mixture and with the aid of stirring devices which require the use of a large amount of energy, resulting in a preparation process which is not very profitable on an industrial scale.
One aim of the present invention is to provide new particles for the preparation of masterbatches which exhibit a higher particle concentration than the masterbatches of the prior art.
Another aim is to provide new particles which make possible the preparation of masterbatches using a small amount of energy.
For this purpose, the invention relates first of all to inorganic particles, with the exception of silica, comprising at least one functionalized polyorganosiloxane grafted over all or part of their surface, the said polyorganosiloxane being functionalized by:
at least one alkoxy group,
and at least one organic group W chosen from alkyls, alkenyls, mercaptoalkyls, sulphoxides, epoxys, (meth)acryloyloxy groups, amino groups, hydroxyl groups, siloxy groups, ethers, ketones, esters, phosphorus-containing groups or polymer portions comprising vinylaromatic, ether, amide or sulphur repeat units.
The invention also relates to processes for the preparation of these particles.
The invention also relates to a composition comprising particles according to the invention and at least one thermoplastic polymer.
The invention relates in addition to the use of the particles according to the invention in thermoplastic polymers.
Finally, the invention relates to the items obtained from thermoplastic polymers and comprising particles according to the invention.
The invention relates first of all to inorganic particles, with the exception of silica, comprising at least one polyorganosiloxane grafted over all or part of their surface, the said polyorganosiloxane being functionalized by:
at least one alkoxy group,
and at least one organic group chosen from alkyls, alkenyls, mercaptoalkyls, sulphoxides, epoxys, (meth)acryloyloxy groups, amino groups, hydroxyl groups, siloxy groups, ethers, ketones, esters, phosphorus-containing groups or polymer portions comprising vinylaromatic, ether, amide or sulphur repeat units.
The invention thus relates to particles treated at the surface with a polyorganosiloxane which must have at least two functionalities. The first is an alkoxy functional group and the second can be of fairly varied nature. The grafted polyorganosiloxane can have one or a number of functional groups of the second type.
According to the invention, the functionalized polyorganosiloxane which can be grafted to the surface of the particles comprises, per molecule:
&agr;—on the one hand, at least one functional siloxy unit of formula (I):
R
a
YSi(O)
(3−a)/2
(I)
in which:
a=0 or 1, and preferably 1,
R is a monovalent hydrocarbon radical chosen from linear or branched alkyls having from 1 to 6 atoms, in particular methyl, ethyl, propyl or butyl, and/or from aryls, and in particular phenyl, methyl being more particularly preferred, the R radicals being identical or different when a=2,
Y is a linear or branched alkoxy radical preferably chosen from C
1
-C
4
alkoxys, in particular methoxy, ethoxy and (iso)propoxy being more particularly used,
&bgr;—and, on the other hand, at least one functional siloxy unit of formula (II):
R
b
WSi(O)
3−b/2
(II)
in which:
b=0, 1 or 2,
R corresponds to the same definition as that given above for the R substituent of the unit (I) and can be identical to or different from the latter,
W is a monovalent hydrocarbon radical saving from 2 to 30 carbon atoms and optionally S and/or O atoms and constituting a functional residue connected to the silicon via an Si—C bond, this residue being chosen from the following groups:
(i) a linear or branched alkyl group comprising at least 7 carbon atoms,
(2i) a linear or branched C
2
-C
20
alkenyl group containing one or a number of double bonds in the chain(s) and/or at the chain end(s), the said double bonds preferably being conjugated and/or combined with at least one activating group situated in the &agr;-position and advantageously consisting of an ether or a thioether,
(3i) an unsaturated mono- or bicyclic aliphatic group containing 5 to 20 cyclic carbon atoms and one or two ethylenic double bond(s) in the ring, which double bond(s) is/are optionally substituted by one or two linear or branched C
1
-C
3
alkyl group(s), the said cyclic group optionally being connected to the silicon via a linear or branched C
2
-C
10
alkylene radical,
(4i) a mercaptoalkyl group of formula:
—R
1
—S—A (4i)
in which:
R
1
represents a linear or branched C
2
-C
10
alkylene radical optionally comprising at least one oxygen heteroatom or one alkylene-cycloalkylene radical, the alkylene part of which has the same definition as that given immediately above and the cyclic part of which contains 5 to 10 carbon atoms and is optionally substituted by one or two linear or branched C
1
-C
3
alkyl group(s),
A corresponds:
either to hydrogen,
or to a masking group M connected to S by a bond which is labile under given conditions and which makes possible the replacement of M by H or the creation of an active species —R
1
—S.;
(5i) a group comprising a polysulphide entity and corresponding to the following formula:
with:
x=1 to 6,
R
2
having the definition as R above,
R
3
is a linear or branched C
l
-C
10
alkyl,
(6i) a group containing at least one ring, at least one of the elements of which is a sulphur atom, and corresponding to the formulae below:
in which
i=0, 1 or 2 and j=1 to 6
the R
4
and R
5
substituents are divalent radicals as defined above for R,
(7i) a sulphoxide group of formula:
in which the R
1
and M symbols have the definitions given above for the formula (4i);
&ggr;—and, optionally, at least one residual siloxy unit of formula (III):
R
c
H
d
Si(O)
4−(c+d))/2
(III)
in which:
c=0, 1, 2 or 3, d=0 or 1 and c+d ≦3
the R substituents being as defined above in the units (I) and (II).
In this type of polyorganosiloxane, the first alkoxy functionality Y is carried by the units of formula (I), whereas the second hydrocarbon functionality W appears in the units of formula (II) defined above.
The first type of functionalized polyorganosiloxane can contain, in addition to the units (I) and (II), at least one residual unit (III).
According to a terminology usual in silicones, these units (I) and (II) can be D units but also T
Bomal Yves
Guez Anny
Velleret Gerard
Burns Doane Swecker & Mathis L.L.P.
Moore Margaret G.
Rhodia Chimie
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