Fluorinated triazinic compounds

Details Fluorinated triazinic compounds Fluorinated triazinic compounds

2000-03-02

2001-11-06

Raymond, Richard L. (Department: 1624)

Organic compounds -- part of the class 532-570 series

Organic compounds

Four or more ring nitrogens in the bicyclo ring system

C427S258000

Reexamination Certificate

active

06313291

ABSTRACT:

The present invention relates to products and their formulations for the treatment of natural or synthetic fiber textiles.
More specifically, it relates to products derived from fluorinated compounds able to confer hydro- and oil-repellence characteristics without modifying the textile surface appearance and contemporaneously to give a very good softness, said characteristics being substantially unchanged even after repeated washings with water and solvents.
Textile treatments, specifically cotton, nylon, polyester and mixed textiles comprising the above fibers, to confer hydra- and oil-repellence properties, are known in the prior art. Such treatments are usually carried out by using fluorinated polyacrylates, such as for example Scotchgaurd™ Asahigard™ etc. The drawback of these treatments is that they substantially modify the textile softness and besides the conferred hydra- and oil-repellence are removed through repeated washings, especially with the solvents used in the dry washing.
Tests carried out by the Applicant using fluorinated functional derivatives wherein the fluorinated part derives from a monofunctional perfluoropolyether residue with alcoholic end group show that said treatment does not confer any hydro- and oil-repellence to the textiles.
The need was felt to have available compounds able to confer to textiles high oil- and hydro-repellence without substantially modifying the textile surface appearance and contemporaneously to confer a very good softness, said characteristics remaining substantially unchanged even after repeated washings with water or with solvents.
It has been surprisingly and unexpectedly found by the Applicant that it is possible to solve the above technical problem, i.e., to confer to a substratum constituted by natural or artificial textiles such as cotton, wool, silk, polyester, polyamide or the like, or a combination thereof, hydro- and oil-repellence characteristics which are maintained during the time even after repeated washings also in the presence of solvents, without substantially changing the substratum softness properties, treating the textile with the compounds specified hereinunder.
An object of the present invention are fluorinated triazinic compounds having general formula selected from the following:
wherein Z=T—Y, wherein:
T=—(CH
2
)
q
—, —SO
2
—, —CO—, preferably —(CH
2
)
q
—, —SO
2
—;
q=is an integer from 1 to 20, preferably 1-5;
Y=—O—, —O(C
2
H
4
O)
p
—, —O(CH
2
)
n
—NR—, —O(CH
2
)
n
—O—, —O(C
3
H
6
O)
p
—, —NR—, —S—, —S(C
2
H
4
O)
p
—, —S(C
3
H
6
O)
p
—;
wherein R=H, linear or branched alkyl having from 1 to 10 C atoms, preferably 1-4 C atoms;
n=is an integer from 1 to 20, preferably 1-10;
p=is an integer from 1 to 5, preferably 1-3;
R
f
represents:
a linear or branched fluoroalkyl chain, optionally containing heteroatoms, preferably selected from N, O, containing from 1 to 30 C atoms, preferably from 1 to 12 C atoms;
a (per)fluoropolyether chain comprising repeating units selected from the following:
a) —(CF (CF
3
)—CF
2
O)—;
b) —(CF
2
CF
2
O)—;
c) —(CFLO)—, wherein L=—F, —CF
3
—,
d) —CF
2
CF
2
CF
2
O—,
e) —CH
2
CF
2
CF
2
O—,
f) —(CF
2
CF(CF
3
)O)—
X is selected from: Cl; R
f
—CF
2
—Z; CF
3
—Z, wherein Z and R
f
have the above defined meaning.
When R
f
is a perfluoropolyether chain and is monofunctional, then the terminal end is CF
3
O—, C
2
F
5
O—, C
3
F
7
O—, Cl(C
3
F
6
O)—, H(C
3
F
6
O)—. When R
f
is a linear or branched fluoroalkyl chain the end group is CF
3
—.
Specifically, R
f
is of the perfluoropolyether type and has preferably one of the following structures:
1) —(CF
2
O)
a
—(CF
2
CF
2
O)
b
— with b/a comprised between 0.3 and 10, extremes included;
2) —(CF
2
—CF
2
O)
b
—
3) —(C
3
F
6
O)
r
—(C
2
F
4
O)
b
—(CFLO)
t
—, with r/b=0.5-2.0 (r+b)/t=10-30
4) —(OC
3
F
6
)
r
—OCF
2
(R′
f
)
y
—CF
2
O—(C
3
F
6
O)
r
—
5) —(CF
2
CF
2
CH
2
O)
q
—OCF
2
(R′
f
)
y
—O—(CH
2
CF
2
CF
2
O)
s
—
wherein:
L is selected from F, CF
3
—;
—(C
3
F
6
O)— can represent units of formula:
—(CF(CF
3
)CF
2
O)—
and/or
—(CF
2
—CF(CF
3
)O)—
a, b, q, r, s, t, are numbers comprised between 0 and 25, such that the R
f
shows number average molecular weight {overscore (M)}
n
values in the range of about 300-5,000, and preferably 300-3,000;
R′
f
=perfluoroalkylenic group containing from 1 to 4 carbon atoms;
y is 0 or 1.
The most preferred perfluoropolyether chain R
f
is selected from the following structures:
—(CF
2
O)
a
—(CF
2
CF
2
O)
b
—;
—(C
3
F
6
O)
r
—(C
2
F
4
O)
b
—(CFLO)
t
—;
—(C
3
F
6
O)
r
—(CFLO)
t
—;
wherein L and the a, b, r, t indexes have the above mentioned value.
It has been found by the Applicant that Z is a linking group bound to the R
f
chain by a chemical stable bond under the application and use conditions of the product and ageing-resistant. The bond between the linking group and the triazine molecule is preferably of ether or amine type, deriving from the nucleophilic substitution of the chlorine in the chlorotriazine with a hydroxyl or amine group.
A process for preparing the compounds of formula (I) and (II) of the present invention requires the reaction of alcohols having the formula:
R
f
—CF
2
—T—YH  (III)
wherein:
T=—(CH
2
)
q
—, —SO
2
—, —CO—, preferably —(CH
2
)
q
—, —SO
2
—;
Y=—O—, —O(C
2
H
4
O)
p
—, —O(CH
2
)
n
—O—, —O(C
3
H
6
O)
p
—;
the n, p, q indexes have the above mentioned meaning;
with a 1,3,5-trichlorotriazine of formula:
The reaction is carried out in an inert solvent able to solubilize the reactants in the reaction conditions, such as for example tetrahydrofurane, dioxane, toluene, xylene, acetone, etc. in the presence of an hydrochloric acid acceptor such as for example sodium or potassium bicarbonate, sodium or potassium carbonate, sodium or potassium hydroxide. Preferably the reaction uses HCl acceptors such as pyridine, 2,6-di-methylpyridine, 2-methylquinoline and 2,4,6-trimethylpyridine (from now on called 2,4,6-collidine or more simply collidine)
For the monosubstituted product, i.e. the invention compounds of formula (I) and (II) wherein X=Cl, the reaction is carried out by gradual addition of the alcohol to a mixture formed by the solvent, the hydrochloric acid acceptor (base) and by the trichlorotriazine. The reaction temperature is in the range 0-10° C.
The bisubstituted products, i.e. the compounds of formula (I) and (II) wherein X is different from Cl, can be obtained in two steps, by using as reaction intermediates the compounds of formula (I) or (II) with X=Cl. The reaction is carried out at a temperature of 30°-40° C. by gradual addition of the alcohol to a mixture constituted by the solvent, by the hydrochloric acid acceptor (base) and by the compounds of formula (I) or (II) with X=Cl.
An equimolecular ratio between the alcohol and the triazinic derivative is required for the reaction, while for the base a light excess, about 10% molar, is required.
The reaction times are of about 3 hours. At the end of the reaction the mixture is filtered to eliminate the precipitated salts during the reaction, and then the product is isolated by stripping the solvent and the base in excess, when the latter is liquid.
Optionally the reaction can be carried out by letting react the trichloro-triazine with the sodium or potassium salt (alcoholate) of the alcohols of formula (III), separately prepared by reaction with bases as known in the prior art.
Generally the reaction is carried out at atmospheric pressure, although the pressure is not critical for the process.
A preparation process of the compounds of formula (I) and (II) wherein Y=—O(CH
2
)
n
—NR—, —NR—, —S—, —S(C
2
H
4
O)
p
—, —S(C
3
H
6
O)
p
—, is substantially similar to the above described process for the preparation of the compounds wherein Y=—O—, —O(C
2
H
4
O)
p
—, —O(CH
2
)
n
—O—, —O(C
3
H
6
O)
p
—, starting from the corresponding intermediates.
The textiles preferably treated according to the invention are natural fiber textiles, such as cotton, wool, silk, or the like, or syntheti

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