Fluorinated triazine monomers

Details Fluorinated triazine monomers Fluorinated triazine monomers

2000-04-06

2003-02-04

Juska, Cheryl A. (Department: 1771)

Fabric (woven, knitted, or nonwoven textile or cloth, etc.)

Coated or impregnated woven, knit, or nonwoven fabric which...

Coating or impregnation specified as water repellent

C442S079000, C442S080000, C526S261000

Reexamination Certificate

active

06514887

ABSTRACT:

The present invention relates to novel monomeric compounds which can be used in the production of polymers which have a high degree of oil and water-repellency and which may be fixed to substrates such as clothing, to processes for their preparation and to polymers produced therefrom.
Oil- and water-repellent treatments are in widespread use, in particular for outdoor clothing applications, sportswear, leisurewear and in military applications. These treatments generally require the incorporation of a fluoropolymer into or more particularly, fixed onto the surface of the clothing fabric. The degree of oil and water repellency is a function of the number of fluorocarbon groups or moieties that can be fitted into the available space. The greater the concentration of such moieties, the greater the repellency of the finish.
In addition however, the polymeric compounds must be able to form durable bonds with the substrate. Oil- and water-repellent textile treatments are generally based on fluoropolymers that are applied to fabric in the form of an aqueous emulsion. The fabric remains breathable and permeable to air since the treatment simply coats the fibres with a very thin, liquid-repellent film. In order to make these finishes durable, they are sometimes co-applied with cross-linking resins that bind the fluoropolymer treatment to fibres. Whilst good levels of durability towards laundering and dry-cleaning can be achieved in this way, the cross-linking resins can seriously damage cellulosic fibres and reduce the mechanical strength of the material. WO 97/13024 discloses a group of fibre reactive polymers, which include a functional group such as a triazine group, which binds the polymer to the material substrate.
British patent No 1,102,903 describes certain fluoro alkyl containing compounds which are used in water- and oil-repellent compositions.
The applicants have produced certain novel monomers, which give rise to polymers which have a high number of fluorocarbon substituents per monomer unit.
The present invention provides a compound of formula (I)
wherein R
1
and R
2
are independently selected from saturated fluorocarbon substituted side chains;
R
3
is an unsaturated moiety which may be polymerised, and X is O, S or NR
4
where R
4
is hydrogen or alkyl.
As used herein, the term “alkyl” refers to straight or branched chain alkyl or cycloalkyl groups, in particular those having from 1 to 12 and preferably from 1 to 6 carbon atoms. The term “saturated” refers to groups which do not contain carbon-carbon double bonds. Conversely the term “unsaturated” refers to groups which include carbon-carbon double bonds.
Suitable fluorocarbon substituted side chains for R
1
and/or R
2
include groups which are hydrophobic groups which are able to confer water- and/or oil- repellency on the resultant polymer. In particular R
1
and R
2
are independently selected from NR
5
(CH
2
)
n
C
m
F
2m+1
, O(CH
2
)
n
C
m
F
2m+1
, S(CH
2
)
n
C
m
F
2m+1
, NR
5
S(O)
2
(CH
2
)
p
C
m
F
2m+1
or CR
5
[CO
2
(CH
2
)
n
C
m
F
2m+1
]
2
, where R
5
is hydrogen or alkyl, and n and m are independently an integer of 1-12, and p is 0 or an integer of from 1-12.
Conveniently R
1
and R
2
are the same. They are preferably selected from O(CH
2
)
n
C
m
F
2m+1
or NR
5
S(O)
2
(CH
2
)
p
C
m
F
2m+1
. Suitably R
5
is methyl, ethyl or n-propyl, in particular ethyl. Preferred integers for n and p are from 1-3, suitably 2, whilst preferred integers for m are from 6 to 10, most preferably 8.
Suitable polymerisable groups R
3
are alkenes or alkynes which may also include a functional group such as an acyloxy group. Particularly preferred groups for R
3
are groups of formula (CH
2
)
q
OC(O)C(R
6
)CR
7
R
8
where q is an integer of from 1 to 12, suitably from 1 to 4 and especially 2, and R
6
, R
7
and R
8
are independently selected from hydrogen or alkyl such as C
1-4
alkyl. Preferably R
6
, R
7
and R
8
are all hydrogen.
Compounds of formula (I) are suitably prepared by reacting a compound of formula (II)
where R
1
and R
2
are as defined in relation to formula (I) and Y is a leaving group, with a group of formula (III)
 R
a
—X—R
3′
  (III)
where X is as defined in relation to formula (I) and R
3
is a group R
3
as defined in relation to formula (I) or a precursor group which may be reacted to form a group R
3
and R
8
is hydrogen or alkyl; and thereafter if necessary converting a precursor group R
3
to a group R
3
.
Preferably R
a
is hydrogen or a lower alkyl, for example a C
1-3
alkyl, in particular methyl.
Suitable leaving groups for Y include halogen such as fluorine and chlorine, in particular chlorine, or amine leaving groups such as substituted pyridines for instance nicotinic acid or colladine.
The reaction is suitably effected in an organic solvent such as tetrahydrofuran (THF), acetone, toluene or chloroform. It may be effected at temperatures of from 0 to 200° C., suitably from 25 to 150° C., depending upon the precise nature of the reactants and solvents involved. Conveniently the reaction may be effected at room temperature or under reflux conditions.
Preferably the reaction is effected under basic conditions. Weak bases may suffice, and in some instances, the compound of formula (III) may itself act as an acid scavenger and so the use of an excess, particularly a 2 molar excess of the compound of formula (III) will ensure that that the reaction proceeds effectively.
Suitable groups R
3
′ which are precursor groups to R
3
would be apparent to the skilled person. For example, where R
3
is a group (CH
2
)
q
OC(O)C(R
6
)CR
7
R
8
, a suitable precursor group R
3
would be (CH
2
)
q
OH, which can be readily converted to R
3
by reaction with a suitable acid halide for example an acid chloride of formula ClC(O)C(R
6
)CR
7
R
7
in the presence of a base, such as a weak base, for example pyridine or a pyridine derivative such as collidine. This reaction is suitably effected in an organic solvent such as toluene at elevated temperatures, conveniently at the reflux temperature of the solvent.
Certain compounds of formula (II) are known (see for example British Patent No. 1,102,903). These compounds can be prepared by reacting a compound of formula (IV)
where R
1
is as defined in relation to formula (I), Y is as defined in relation to formula (II) and Y′ is a leaving group,
with a compound of formula (V)
R
2
H  (V)
where R
2
is as defined in relation to formula (I), in the presence of a base.
Suitable bases are those which react with a compound of formula (V) so as to produce a nucleophilic moiety of formula (V′)
(R
2
)
−
  (V′)
Thus the selection of suitable bases will depend upon the precise nature of the group R
2
and will be readily understood or determinable by the skilled person. For example, where R
2
is a group O(CH
2
)
n
C
m
F
2m+1
, strong bases such as alkali metal hydroxides, in particular lithium hydroxide, may be used. Alternatively, where R
2
is a group NR
5
S(O)
2
(CH
2
)
p
C
m
F
2m+1
, stronger bases such as alkali metal alkoxides, in particular sodium or potassium methoxide or ethoxide may be used.
Compounds of formula (IV) are suitably prepared by reacting a compound of formula (VI)
wherein Y, Y′and Y″ are the same or different leaving groups, with a compound of formula (VII)
R
1
H  (VII)
where R
1
is as defined in relation to formula (I), in the presence of a base.
Reaction conditions will be generally similar to those described above in relation to the reaction between compounds of formula (IV) and formula (V).
Where compounds of formula (V) and formula (VII) are the same, compounds of formula (II) may be prepared directly in one pot. If necessary, the reaction can be controlled in a stepwise manner in order to maximise yield of the target compound by controlling the reaction temperature. For example, where R
1
and R
2
are groups of formula NR
5
S(O)
2
(CH
2
)
n
C
m
F
2m+1
, the compound of formula (IV) may be prepared at d

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