Polymers

Details Polymers Polymers

2001-11-26

2004-12-28

Truong, Duc (Department: 1711)

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

Synthetic resins

Treating polymer containing material or treating a solid...

C528S422000, C528S486000, C525S540000, C428S423100

Reexamination Certificate

active

06835805

ABSTRACT:

The present invention relates to self polymerisation products of diamino anthracenes (DAA) and polymerisation of DAA with diiminoanthracenes (DIA). In particular, the invention relates to homopolymers or co-polymers of 9,10 diaminoanthracene or substituted DAA or DIA or substituted DIA. The polymerisation products may be polymers or oligomers (e.g. of 2 to 12 or 15 repeat units) and the processes of the present invention enables homopolymers and co-polymers to be made with many variations in structure and in the substituents which are attached to the anthracene backbone, but with little variation in the backbone itself. The polymers and co-polymers can be expected on reduction to produce materials which are electroconductive.
They may also be sufficiently transparent to be used in thin film applications where they may be used as transparent coatings, used extensively in displays, e.g. electroluminescent and liquid crystal displays and to some extent in electromagnetic shielding windows. The polymers and copolymers disclosed herein can be used in antistatic applications.
Polymers of aniline and applications thereof have been known for many years. Poly (1-aminoanthracene) (P1-AA hereafter) has also been described (Takakazu Yamamoto et al.,
Macromolecules
, 1993, 26, pages 6992-6997). These polymers have similar structures to poly(aniline) and are dark coloured, varying from bluish-black, brown to brown-black powders. Yamamoto states P1-AA has conductivity of the order of 1×10
−4
S cm
−1
. P1-AA is stated by Yamamoto to be soluble in organic solvents such as HCOOH, DMF, DMSO and NMP, slightly soluble in CHCl
3
and THF, and insoluble in CH
3
OH, C
2
H
5
OH, CH
3
CN, benzene and toluene. Yamamoto gives no indication of the transparency of P1-AA.
The applicants are also aware of two articles namely A. Everaerts et al.,
Polym. Prepr
. (
J. of Polymer Science; Part A
: Polym. Chem.) 24 (7)pp 1703-16 (1986) (hereafter Everaerts) and P. A. Williams et al,
Macromolecules
26 (21) pp5820-1 (1993) (hereafter Williams).
The present inventors have been seeking to develop a conductive polymer or oligomer of sufficient transparency to enable it to be used where light transmission as well as conductivity is required, and in addition solubility which would facilitate fabrication into useful structures, such as films, by solvent methods. In contrast to P1-AA we have discovered surprisingly that certain polymerisation products of 9,10 diaminoanthracene are sufficiently transparent and soluble to be useful electroconductive polymers.
These products may exhibit a particular advantage over the transparent Indium Tin Oxide (ITO) films currently employed in transparent coatings. The ITO coatings lose most or all of their electroconductivity if the surface is bent. However, the products according to the present invention can be expected to maintain their electroconductivity even when bent.
In addition the present inventors wished to devise a procedure by which polymers could be provided in which the polymer backbone was constant or subject to little variation and significant flexibility was provided for varying the substitution on the backbone.
According to one aspect of the invention a method of production of a homopolymer or copolymer or homo-oligomer or co-oligomer product is characterised in that the product is obtained by condensation by fusion in a sealed vessel or space of a diaminoanthracene, substituted or not, optionally with a diiminoanthracene substituted or not, in the absence of any solvent and in the absence of anthraquinone substituted or not.
According to another aspect of the present invention, there is provided a polymeric or oligomeric product obtainable from the reaction of an aromatic diamine with itself or a substituted form thereof or with a diimino version or a substituted version thereof, characterised in that the diamine is a diamino anthracene which is substituted or is not substituted, and the diimine is diiminoanthracene which is substituted or not, and in that the reaction is by melting under vacuum, in the absence of solvent and in the absence of anthraquinone whether substituted or not.
The substitution may be such that the product is a homopolymer or homo-oligomer, or the substitution may be such that the product is a co-polymer or a co-oligomer.
The diaminoanthracene is preferably a 9,10-diaminoanthracene, which may be substituted or not.
The sole reactant may be DAA or the only reactants may be DAA and DIA,
or the only reactants may be one or more substituted DAAs and DAA.
or the only reactants may be substituted DAAs which may be the same or different.
or the only reactants may be one or more substituted DAAs and DIA.
or the only reactants may be DAA and one or more substituted DIAs.
or the only reactants may be one or more substituted DAAs and one or more substituted DIAs.
The ratio of DAA to DIA may be in the range 5:1 to 1:5, preferably in the range 3:1 to 1:3, and more preferably in the range 2:1 to 1:2.
The product produced by the method of the present invention preferably has the general formula I (see
FIG. 10
of the accompanying drawings)
where, R
1
may be the same as or different to R
1
′, which may be the same as or different to R
2
, which may be the same as or different to R
2
′ and each of R
1
, R
1
′, R
2
, and R
2
′ is a hydrogen atom or —CH
3
, CH
3
CH
2
—, —OCH
3
, —OCH
2
CH
3
, —CH
2
OCH
3
, —CH
2
OCH
2
CH
2
OCH
3
, methoxyethoxyethoxymethyl, aryloxymethyl, phenyl, Cl, Br, CN or NO
2
, —CH
2
COOR′″ or —CH
2
NHCOR′″ (where R′″ is C
1
-C
6
alkyl or a phenyl or biphenyl group), or a C
1
-C
5
alkyl group, or an aryl group e.g. a benzyl group, or an —SO
3
H group or a hydroxyl group or a C
1
-C
5
alkoxy group or an H
2
PO
3
group, and R
1
and R
1
′ are different to R
2
and R
2
′ and n is an integer ranging from 2 to 100 preferably 5 to 100, more preferably 6-20.
Alternatively the product may have the general formula I
where, R
1
may be the same as or different to R
1
′, and each of R
1
and R
1
′ is a hydrogen atom or —CH
3
, CH
3
CH
2
—, —OCH
3
, —OCH
2
CH
3
, —CH
2
OCH
3
, —CH
2
OCH
2
CH
2
OCH
3
, methoxyethoxyethoxymethyl, aryloxymethyl, phenyl, Cl, Br, CN or NO
2
, —CH
2
COOR′″ or —CH
2
NHCOR′″ (where R′″ is C
1
-C
6
alkyl or a phenyl or biphenyl group), and R
2
may be the same or different to R
2
′ and each of R
2
and R
2
′ is a hydrogen atom or a C
1
-C
5
alkyl group, or an aryl group e.g. a benzyl group, or an —SO
3
H group or a hydroxyl group or a C
1
-C
5
alkoxy group or an H
2
PO
3
group, and R
1
and R
1
′ are different to R
2
and R
2
′ and n is an integer ranging from 2 to 100 preferably 5 to 100, more preferably 6-20.
R
1
may be the same as R
1
′ but may be different from R
2
and R
2
′ and R
2
and R
2
′ may be the same;
or R
1
may be the same as R
1
′ and as R
2
and R
2
′ but is not hydrogen;
or R
1
may be different from R
1
′ and R
2
may be different from and R
2
′ and R
1
and R
1
′ may both be different from R
2
and R
2
′;
or that R
1
and R
2
are not hydrogen and R
1
and R
2
′ are not the same.
The DAA may be substituted with a single substituent e.g. a C
1
-C
5
alkyl, an aryl e.g. a benzyl group, an —SO
3
H or —OH, or C
1
-C
5
alkoxy, or aryloxy, e.g. phenoxy or substituted phenoxy or biphenyloxy group or an H
2
PO
3
group or with more than one substituent.
In a preferred embodiment of the invention the fusion reaction is carried out in a sealed space e.g. a sealed ampoule containing equimolar proportions of 9,10-diaminoanthracene and 9,10-diiminoanthracene e.g. at 200° C. for 4 hours under vacuum as shown in reaction Scheme 1 given in the drawings as
FIG. 7.
9,10-diiminoanthracene may be synthesised by aerial oxidation of 9,10-diaminoanthracene e.g. in benzene e.g. at 65° C. for 30 minutes. This compound is more stable than its precursor, 9,10-diaminoanthracene.
In reaction Schem

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