Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2000-01-21
2002-05-28
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S360000, C528S373000, C528S377000
Reexamination Certificate
active
06395867
ABSTRACT:
The invention relates to novel hyperbranched dendrimers and polymers containing thiol functional groups, to a process for their preparation and to the use of these hyperbranched dendrimers and/or polymers as ancioxidants.
Many hyperbranched polymers and dendrimers have already been described. Reference may be made, for example to: D. A. Tomalia et al., Angew. Chem. Int. Engl. 29 (1990) 138-175; N. Ardoin and D. Astruc, Bull. Soc. Chim. Fr. (1995) 132, 875-909; B. I. Voit, Acta Polymer, 46, 87-99 (1995).
The possibility of preparing dendrimers containing thiol end groups has been envisaged by certain authors, such as, for example, D. A. Tomalia in U.S. Pat. No. 4,587,329 and EP-A-234,408, although this preparation has never been effectively carried out, nor have the surprising properties, demonstrated by the Applicant, of these molecules been mentioned or suggested in the prior art.
In addition, the process for preparing hyperbranched polymers and dendrimers containing thiol functional groups is novel and it has many advantages, among which are the good synthetic yield, the use of commercially available starting materials and the ease of implementation.
Hyperbranched polymers are molecular constructions having a branched structure, generally about a core. Their structure generally lacks symmetry: the monomer or base units involved in the construction of the hyperbranched polymer can be of varied nature and they are distributed non-uniformly. The branches in the polymer can be of varied nature and length. The number of base units, or monomers, can be different according to the different branching. While remaining asymmetrical, hyperbranched polymers can have: an extremely branched structure, around a core; successive generations or layers of branching; a layer of end chains.
Hyperbranched polymers are generally obtained from the polycondensation of one or more monomers ABx, A and B being reactive groups capable of reacting together, x being an integer greater than or equal to 2, but other preparation processes can be envisaged. Hyperbranched polymers are characterized by their degree of polymerization DP=1−b, b being the percentage of non-terminal functional groups in B which have not reacted with a group A. Since the condensation is non-systematic, in contrast with the synthesis of dendrimers, the degree of polymerization is less than 100%. Usually, by the known synthetic methods, DP is between 15 and 90%. An end group T can be reacted with the hyperbranched polymer to obtain a specific functionality at the end of the chains.
Such polymers are described in particular in B. I. Voit, Acta Polymer, 46, 87-99 (1995); EP-682,059, WO-96/14346; WO-96/14345; WO-96/12754.
Several hyperbranched polymers can be combined together, by means of a covalent bond or another type of bonding, via their end groups. Such so-called “bridged” polymers come within the definition of the hyperbranched polymers according to the present invention.
Dendrimers are highly branched polymers and oligomers that are also known; they have a well-defined chemical structure and are said to be “perfect” hyperbranched polymers. As a general rule, dendrimers comprise a core, a determined number of generations of branches, or spindles, and terminal groups. The generations of spindles consist of structural units which are identical for the same generation of spindles and which can be identical or different for different generations of spindles. The generations of spindles extend radially in a geometrical progression from the core. The terminal groups of a dendrimer of the N
th
generation are the terminal functional groups of the spindles of the N
th
generation or terminal generation. Such polymers are described in particular in D. A. Tomalia, A. M. Naylor and W. A. Goddard III,
Angewandte Chemie
, Int. Ed. Engl. 29, 138-175 (1990); C. J. Hawker and J. M. J. Frechet,
J. Am. Chem. Soc
., 112, 7638 (1990); B. I. Voit, Acta Polymer, 46, 87-99 (1995); N. Ardoin and D. Astruc. Bull. Soc. Chim. Fr. 132, 875-909 (1995).
Dendrimers can also, more particularly, be defined by the formula (DI) below:
C[A
1
B
1
(
A
2
B
2
( . . . (
A
n−1
B
n−1
(
A
n
B
n
(
T
)
r
n
)
r
−1
)
r
n−2
. . . )
r
2
)
r
1
]s
(DI)
in which:
C represents the core, linked by a number s of functional groups to s spindles A
1
B
1
via the groups A
1
;
s is an integer greater than or equal to 1 and less than or equal to the number of functional groups in C;
for each spindle (A
i
B
i
) (i=1, 2 . . . n), the group B
i
is linked to r
i
groups A
i+1
of a spindle (A
i+1
B
i+1
);
each group A
i
(i>2) is linked to a single group B
i+1
of the spindle (A
i+1
B
i+1
);
r
i
(i=1, 2 . . . n−1) represents the number of functional groups in the group B
i
belonging to the spindle (A
i
B
i
), ri being an integer greater than or equal to 2;
the index i (i=1, 2 . . . n) is an integer which denotes the generation of each spindle;
the spindle of n
th
generation A
n
B
n
is linked chemically to a number r
n
of terminal groups T, r
n
being an integer greater than or equal to zero.
The dendrimer definition given above includes molecules containing symmetrical branching; it also includes molecules containing non-symmetrical branching such as, for example, dendrimers whose spindles are lysine groups, in which the branching of one generation of spindles onto the preceding generation takes place on the amines a and e of lysine, which leads to a difference in the length of the spindles for the different branching.
Dense star polymers, starburst polymers and rod-shaped dendrimers are included in the present definition of dendrimers. The molecules known as arborols and cascade molecules also fall within the definition of dendrimers according to the present invention.
Several dendrimers can be combined together, via a covalent bond or another type of bond, via their terminal groups in order to give species known as “bridged dendrimers” or “dendrimer aggregates”. Such species are included in the definition of dendrimers according to the present invention.
Dendrimers can be in the form of a set of molecules of the same generation, these being so-called monodispersed sets; they can also be in the form of sets of different generations, which are known as polydispersed sets. The definition of dendrimers according to the present invention includes monodispersed sets as well as polydispersed sets of dendrimers.
The subject of the invention is novel polymers chosen from hyperbranched polymers and dendrimers, characterized in that they contain functional groups corresponding to formula (I):
in which:
Y represents an oxygen atom or an NH group, preferably Y=O,
A represents a linear, branched or cyclic, saturated or unsaturated C
1
-C
12
alkanediyl group;
this alkanediyl group can optionally be interrupted by one or more hetero atoms, such as O or N;
this alkanediyl group can optionally be substituted with one of the following functions
amino: —NH
2
, optionally in the form of a salt of an inorganic or organic acid,
acylamino: —NH—COR, in which R represents a linear, branched or cyclic, saturated or unsaturated C
1
-C
10
alkyl group,
carboxylic acid,
C
1
-C
10
ester;
X represents a nucleophilic group, preferably:
an oxygen atom
or
a group —NR′— in which R′ is chosen from a hydrogen atom; a linear or branched, saturated or unsaturated C
1
-C
6
alkyl group; a linear or branched, saturated or unsaturated C
1
-C
6
mono- or polyhydroxyalkyl group; a C
1
-C
6
aminoalkyl group or a polyalkyleneimine group.
For example, A can be a methylene, ethylene, propylene, methylpropylene, ethylpropylene, tetramethylene, pentamethylene, hexamethylene, phenylene, phenyldiyl, etc. group.
Advantageously, A represents a radical corresponding to one of the formulae (a) to (d) below:
—CHR
1
—CHR
2
—CHR
3
— (a)
—CHR′
1
—CHR′
2
—CHR′
3
—CHR′
4
— (b)
—(CHR′″
1
)
k
—(CHR′″
2
) —CH(CO
2
H) —NH— &emsp
Boykin Terressa M.
Finnegan Henderson Farabow Garrett & Dunner L.L.P.
L'Oreal
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