Fluorine-containing macroazo compound

Details Fluorine-containing macroazo compound Fluorine-containing macroazo compound

1999-10-01

2001-03-13

Dawson, Robert (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S215000, C526S219100

Reexamination Certificate

active

06201082

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to a fluorine-containing macroazo compound having a fluorine segment in the molecule thereof, which is useful, for example, as a polymerization initiator or the like.
In recent years, polymeric materials have become used in more and more diversified fields, and with this trend, the properties required of polymers are also being diversified. Particularly, polymers having a perfluoroalkylene group (Rf group) in the molecule thereof are noticed with interest because the Rf group part having a low surface free energy is concentrated into the surface region of the polymer to exhibit excellent water-repellency, oil-repellency, heat resistance, weather resistance, slipping characteristics, and the like.
Hitherto, it has been attempted to introduce an Rf group-containing polymer into base material by the method of blending or the like. Such attempts, however, have not given a sufficient effect.
Thus, introduction of Rf group into polymer molecule is being attempted by various methods.
For example, a method of introducing Rf group by the reaction of a polymer formed by living anionic polymerization with an Rf group-containing alkyl halide has been reported in Polymer Preprints Japan., 44, 948 (1995), etc.
Further, methods for producing a polymer having a fluorine segment by polymerization reaction of a fluorine-containing monomer have also been disclosed. Particularly, a synthesis of block polymer using a monomer having a perfluoroalkylene group is being studied energetically because this method makes it possible to introduce perfluoroalkylene group into molecule in a high efficiency and a high concentration.
However, the method of reacting a polymer with Rf group-containing alkyl halide is limited in the kind of polymer usable, and therefore is low in reactivity. On the other hand, the method of polymerizing a fluorine-containing monomer is disadvantageous in that fluorine segment cannot be introduced into an intended site of polymer molecule and a block polymer cannot be obtained.
As a means for solving the above-mentioned problems, it has been attempted to introduce a fluorine segment through a condensation reaction between a prepolymer having fluorine-containing alkylene group and a polymer.
This method, however, cannot introduce fluorine segment in a high yield because the prepolymer having a fluorine-containing alkylene group is low in solubility.
SUMMARY OF THE INVENTION
In view of above, an object of the present invention is to provide a fluorine-containing macroazo compound useful for introducing a fluorine segment into a polymer, and a block polymer having, in the molecule thereof, a fluorine segment derived from said fluorine-containing macroazo compound.
The present invention provides a fluorine-containing macroazo compound comprising repeating units represented by the following formula:
wherein
R
1
and R
3
independently represent a lower alkyl group;
R
2
and R
4
independently represent a lower alkyl group or a cyano group;
A
1
and A
2
independently represent a lower alkylene group which may contain one or more oxygen atoms and/or an aromatic ring;
Z
1
and Z
2
independently represent an ester linkage or an amido linkage;
T
1
and T
2
independently represents —CONH— or a direct link; and
Q represents a fluorine-containing segment.
The present invention also provides a process for producing the fluorine-containing macroazo compound mentioned above by reacting an azo compound with a fluorine-containing compound.
The present invention further provides a macroazo initiator containing the above-mentioned fluorine-containing macroazo compound.
Further, the present invention provides a process for producing a fluorine-containing block polymer by polymerizing a monomer by the use of the above-mentioned fluorine-containing macroazo compound.
Further, the present invention provides a fluorine-containing block polymer containing units (or a segment) derived from the above-mentioned fluorine-containing macroazo compound and monomer units as constituents thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The fluorine-containing macroazo compound of the present invention is characterized by having repeating units represented by the following formula [1]:
wherein
R
1
and R
3
independently represent a lower alkyl group;
R
2
and R
4
independently represent a lower alkyl group or a cyano group;
A
1
and A
2
independently represent a lower alkylene group which may contain one or more oxygen atoms and/or an aromatic ring at an end or both ends of the alkylene group or interposed in the alkylene group;
Z
1
and Z
2
independently represent an ester linkage or an amido linkage;
T
1
and T
2
independently represent —CONH— or a direct link; and
Q represents a fluorine-containing segment.
In the formula [1], the lower alkyl group represented by R
1
to R
4
may be linear or branched chain lower alkyl groups, and examples thereof include alkyl groups having 1-6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 3,3-dimethylbutyl group, a 1,1-dimethylbutyl group, a 1-methylpentyl group, a n-hexyl group, an isohexyl group and the like. The lower alkylene group represented by A
1
and A
2
which may contain one or more oxygen atoms and/or an aromatic ring may be linear or branched chain lower alkylene groups, of which examples include alkylene groups having 1-6 carbon atoms. When said lower alkylene group has one or more oxygen atoms, lower alkylene groups having —O— group in a number of one or more, preferably 1-5 more preferably 1-3 at one end or both ends of the alkylene group (or chain) or at any position in the alkylene chain can be referred to. When said lower alkylene group has an aromatic ring, lower alkylene groups having an aromatic ring such as a phenylene group, a diphenylene group or the like at one end or both ends or in the alkylene chain can be referred to. Specific examples of such lower alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a 2-methylpropylene group, a pentylene group, a 2,2-dimethylpropylene group, a 2-ethylpropylene group, a hexylene group, a —CH
2
—C
6
H
4
— group, an o-xylen-&agr;,&agr;′-diyl group, a —O—CH
2
— group, a —O—CH
2
CH
2
— group, a —CH
2
—O—CH
2
— group, a —CH
2
CH
2
—O—CH
2
— group, a —CH
2
CH
2
—O—CH
2
CH
2
— group, a —CH
2
CH
2
—O—CH
2
CH
2
—O—CH
2
CH
2
— group, a —CH
2
—O—C
6
H
4
— group and the like, although the invention is not limited by these examples. As the ester linkage represented by Z
1
and Z
2
, —COO— and —OCO— can be referred to. As the amido linkage, —CONH— and —NHCO— can be referred to.
As the fluorine-containing segment represented by Q, for example, fluorine-containing oxyalkylene groups represented by the following formula [2] can be referred to:
—(Q
1
—O)
p
—(Q
2
—O)
q
—(Q
3
—O)
r
—(Q
4
—O)
s
—Q
5
—  [2]
wherein
Q
1
and Q
4
independently represent an alkylene group;
Q
2
and Q
3
independently represent a fluorine-containing alkylene group;
Q
5
represents an alkylene group or a fluorine-containing alkylene group;
p and s independently represent 0 or a natural number e.g., 1 to 1000; and
q and r independently represent a natural number, e.g., 1 to 1000.
In the formula [2], the alkylene group represented by Q
1
, Q
4
and Q
5
may be linear, branched chain or cyclic alkylene groups, and examples thereof are alkylene groups having 1-10 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a 2-methylpropylene group, a pentylene group, a 2,2-dimethylpropylene group, a 2-ethylpropylene group, a hexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylane group, a cyclopropylene group, a cyclopentylene group, a cyclohexyl

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