Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-10-30
2002-10-22
Kumar, Shailendra (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C524S458000, C524S460000, C525S327600, C526S318440, C526S932000, C564S282000
Reexamination Certificate
active
06469204
ABSTRACT:
The present invention relates to novel acrylate monomers comprising several quaternary amino groups in the alcohol part, to their process of manufacture and to the novel (co)polymers obtained from these novel monomers.
Compounds of the type of those of formula:
in which:
R
(0)
represents H or CH
3
;
A represents —O—or —NH—;
D represents a linear or branched C
1
-C
6
alkylene chain;
R
(1)
and R
(2)
which are identical or different, each independently represent H or C
1-5
alkyl;
are well known in the literature.
Important compounds of this family are N,N-dimethylaminoethyl acrylate (ADAME) and N,N-dimethylaminoethyl methacrylate (MADAME):
with R
(0)
=H or CH
3
.
A very extensive patent literature discloses the manufacture of aqueous solutions of quaternary ammonium salts from ADAME and MADAME, it being possible for these salts, for the most representative among them, to be represented by the formula:
with R
(0)
═H or CH
3
and R
(3)
═CH
3
or benzyl, it being possible for these salts to be denoted by the abbreviation (M)ADAMQUAT MC or (M)ADAMQUAT BZ, according to whether R
(3)
represents CH
3
or benzyl.
This reaction is a quaternization, in the presence of water, of the starting compound with a quaternizing agent R
(3)
—Cl.
The aqueous solutions of quaternary salts thus obtained are used in particular to prepare polymers intended to act as cationic flocculents in water treatment.
Patent CZ-A-250 962 has disclosed compounds of formula:
in which:
R
(0)
represents H or —CH
3
;
R
(2)
represents —CH
3
, —C
2
H
5
, —C
3
H
7
or —C
4
H
9
;
R
(3)
represents —CH
3
, —C
2
H
5
, —C
3
H
7
, —C
4
H
9
, —C
6
H
5
or
—CH
2
C
6
H
5
; and
X
−
represents Cl
−
or Br
−
.
French Patent Application No. 00/00834 of Jan. 24, 2000 has also disclosed compounds of formula:
in which:
R
(0)
represents H or —CH
3
;
R
(2)
represents —CH
3
, —C
2
H
5
, —C
3
H
7
or —C
4
H
9
; and
the compound optionally being quaternized on one of the nitrogens; when the compound is quaternized on only one nitrogen, R
(3)
and X
−
have the following meanings: R
(3)
represents —CH
3
or —CH
2
C
6
H
5
and X
−
represents Cl
−
or CH
3
OSO
3
−
or R
(3)
represents a C
1
-Cl
12
alkyl group and X
−
represents Br
−
or I
−
; when the compound is quaternized on both nitrogens, the two X
−
groups can be identical or different and the two R
(3)
groups can be identical, in which case R(3) represents a C
5
-C
12
alkyl group and X
−
represents CH
3
OSO
3
−
, Br
−
or I
−
, or different, in which case one of the R
(3)
groups represents —CH
3
or —CH
2
C
6
H
5
and X
−
represents Cl
−
or CH
3
OSO
3
−
and the other represents a C
5
-C
12
alkyl group and X
−
represents Br
−
or I
−
.
These known monomers all make possible access to useful flocculents but with a cationicity which is regarded as still inadequate for some applications.
The Applicant Company has now discovered novel monomers which meet this expectation. These monomers thus form the subject-matter of the present invention, as do their process of manufacture and the homo- or copolymers comprising units derived from these novel monomers.
A subject-matter of the present invention is thus first a compound of formula (Ia) or (Ib):
in which:
R
1
represents hydrogen or methyl; and
R2 represents ethyl or isopropyl.
The compounds of the invention can advantageously be provided in aqueous solution, having a concentration of compound (Ia) or (Ib) which is in particular from 60 to 80% by weight.
Another subject-matter of the present invention is a process for the manufacture of the compound of formula (Ia) or (Ib) as defined above, characterized in that:
in a first stage, p-xylylene dichloride:
is reacted with a compound of formula (II):
in which R
2
is as defined above,
to produce a compound of formula (III):
in a second stage, the compound of formula (III) thus obtained is reacted with a compound of formula (IVa) or (IVb):
in which R
1
is as defined above,
resulting in an aqueous solution of the compound (Ia) or (Ib) respectively, the water of which is removed, if appropriate.
In the first stage, the reaction is generally carried out in a solvent medium, such as tetrahydrofuran, with a molar ratio of the p-xylylene dichloride to the compound (II) of 0.8 to 1.2, preferably 0.9 to 1.1, at a temperature of 5 to 60° C., preferably of 15 to 40° C., for a period of time ranging from 8 to 144 hours, preferably from 10 to 96 hours.
The product is obtained in the form of colourless crystals.
The reaction of the second stage is carried out with a molar ratio of the compound (III) to the compound (IVa) or (IVb) of between 0.95 and 2.1, according to the situation, at a temperature of 30 to 70° C., preferably of 40 to 55° C., for a period of time of 0.5 to 8 hours, preferably of 1 to 6 hours.
Furthermore, the second stage is generally carried out in the presence of at least one stabilizer chosen in particular from hydroquinone methyl ether, 3,5-di(tert-butyl)-4-hydroxytoluene and hydroquinone, and mixtures of these stabilizers, in a proportion of 100 to 2 000 ppm with respect to the charge.
Another subject-matter of the present invention is homopolymers or copolymers comprising units of at least one monomer of formula (Ia) or (Ib) as defined above.
The copolymers based on the monomers (Ia) and (Ib) can be water-soluble or hydrophobic polymers presented in the form of an aqueous dispersion, latex, aqueous solution, inverse emulsion or powder. They are prepared by radical copolymerization by various synthetic processes, such as dispersion, solution, direct emulsion, inverse emulsion, inverse suspension and water-in-water polymerization processes.
The present invention also relates to the compounds of formula (III) as defined above as intermediate compounds in the preparation of the compounds (I).
REFERENCES:
patent: 3904660 (1975-09-01), Doss
patent: 4009201 (1977-02-01), Steckler et al.
patent: 6171505 (2001-01-01), Maury et al.
patent: 6174950 (2001-01-01), Nzudie et al.
patent: 0 839 767 (1998-05-01), None
patent: 1.529.000 (1968-10-01), None
Chaplinski Vladimir
Riondel Alain
Atofina
Kumar Shailendra
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