Dehydrogenated poly(spiro[2,4]hepta-4,6-diene) which is insoluble in organic solvents, has an electrical conductivity of at least 10.sup.-10 S.times.cm.sup.-1, and contains, relative to the total number of recurring structural units in the polymer, 0-90 mol % of the recurring structural units of the formulae I and II ##STR1## in which R.sup.1 is in each case a hydrogen atom or an alkyl group having 1 to 4 C atoms, and 10-100 mol % of at least one of the recurring structural units of the formulae III to VI ##STR2## in which R.sup.1 is as defined in formula I or II and X.sup.- is a bromide or iodide ion or an anion of a Lewis or protonic acid, is obtained by treating poly(spiro[2,4]-hepta-4,6-diene) with bromine, iodine or a Lewis or proton-donating acid, and can be used in an electrically conducting material for the production of, for example, conductors, electrodes, batteries or semiconductor components.

The present invention relates to degydrogenated 
poly-(spiro[2,4]hepta-4,6-diene) which is insoluble in organic solvents, 
to a process for its preparation and to its use, in particular as a 
semiconductor. 
It is known from the Journal of Polymer Science, part c, no. 4, pages 1,335 
to 1,346, that dehydrogenated polycyclopentadiene which is electrically 
conducting is obtained by brominating polycyclopentadiene with the 
elimination of hydrogen bromide. Both the stability to air and the 
electrical conductivity of the dehydrogenated polycyclopentadiene are 
unsatisfactory. It is also known from the Journal of Polymer Science, 
Polymer Physics Edition, volume 17 (1979), pages 1,995-2,006, that 
1,4-units and 1,2-units 
##STR3## 
are present in poly-(spiro[2,4]hepta-4,6-diene). 
It has now been found that dehydrogenated poly(spiro[2,4]hepta-4,6-diene) 
which has an improved conductivity and stability in air is obtained by 
treating poly-(spiro[2,4]hepta-4,6-diene) with oxidizing agents, such as 
halogens or Lewis or proton-donating acids, although the formation of a 
planar, conjugated .pi.-system is sterically hindered by the cyclopropane 
group and the content of 1,2-units in the 
poly-(spiro[2,4]hepta-4,6-diene). 
The present invention therefore relates to dehydrogenated 
poly(spiro[2,4]hepta-4,6-diene) which is insoluble in organic solvents, 
has an electrical conductivity of at least 10.sup.-10 Sxcm.sup.-1 and 
contains, relative to the total number of recurring structural units in 
the polymer, 0-90 mol% of the recurring structural units of the formulae I 
and II 
##STR4## 
in which R.sup.1 is in each case a hydrogen atom or an alkyl group having 
1 to 4 C atoms, and 10-100 mol % of at least one of the recurring 
structural units of the formulae III to VI 
##STR5## 
in which R.sup.1 is as defined in formula I or II and X.sup.- is a bromide 
or iodide ion or an anion of a Lewis or protonicacid 
The dehydrogenated poly(spiro[2,4]hepta-4,6-diene) preferably contains 0-80 
mol %, in particular 0-70 mol %, of the recurring structural units of the 
formulae I and II and 20-100 mol %, in particular 30-100 mol %, of at 
least one of the recurring structural units of the formulae III to VI. 
In a particular embodiment, the dehydrogenated 
poly(spiro[2,4]hepta-4,6-diene) contains 0-50 mol of the recurring 
structural units of the formulae I and II and 50-100 mol % of at least 
one of the recurring structural units of the formulae III to VI. 
In the formulae I to VI R.sup.1 is preferably a hydrogen atom in each case. 
X.sup.- in the formulae V and VI is in each case preferably an iodide ion 
or an anion of a Lewis acid, particularly an iodide ion. 
Dehydrogenated poly(spiro[2,4]hepta-4,6-diene) which is insoluble in 
organic solvents and has the recurring structural units of the formulae I 
to VI can be prepared, for example, by treating a 
poly(spiro[2,4]hepta-4,6-diene) which has an average molecular weight of 
5.times.10.sup.2 to 10.sup.6 and contains the recurring structural units 
of the formulae I and II with bromine, iodine or a Lewis or protonic acid 
as an oxidizing agent, in such a way that at least 10 mol % of the total 
recurring structural units of the formulae I and II are converted into 
conjugated structural units of the formulae III to VI. 
It is preferable to employ, in the process according to the invention, a 
poly(spiro[2,4]hepta-4,6-diene) containing the recurring structural units 
of the formulae I and II in which R.sup.1 is in each case a hydrogen atom. 
Examples of suitable Lewis acids which can be employed in the process 
according to the invention are SbCl.sub.5, SbF.sub.5, AsF.sub.5, 
AsCl.sub.5, BiCl.sub.5, BiF.sub.3 , BCL.sub.3 and the bromides of 
phosphorus and aluminium and the chlorides of phosphorus, aluminium, iron 
and tin. It is preferable to employ SbCl.sub.5, SbF.sub.5 and AsF.sub.5 as 
the Lewis acids. 
Suitable protonic acids which can be employed in the process according to 
the invention are organic acids, for example methane sulphonic acid, 
trifluoromethanesulfonic acid, benzene sulfonic acid or p-toluene sulfonic 
acid, or inorganic acids, for example hydrogen fluoride, chloride or 
bromide, oxygenated acids of nitrogen, chlorine, sulfur or phosphorus and 
complex acids containing the anion of the formula MX.sub.n.sup.-, in which 
M is a metal or metalloid atom and X is a halogen atom, preferably 
fluorine or chlorine, and n is 4,5 or 6 and is higher by one than the 
valency of M, or containing the anion of the formula SbF.sub.5 (OH).sup.-. 
M is preferably a boron or bismuth atomand very particularly an antimony, 
arsenic or phosphorus atom. Examples of anions MX.sub.n.sup.- which can be 
present in these complex acids are BiCl.sub.6 --or BF.sub.4 --, but 
particularly preferably PF.sub.6 --, SbF.sub.6 --or AsF.sub.6 --. 
It is preferable to use iodine or a Lewis acid, particularly iodine, as the 
oxidizing agent in the process according to the invention. 
The oxidizing agents used in the process according to the invention are 
preferably employed in amounts such that at least one mol of the 
appropriate oxidizing agent is present per mol of monomer unit in the 
poly(spiro[2,4]hepta-4,6-diene). 
The dehydrogenation of the poly(spiro[2,4]hepta-4,6-diene) can be carried 
out either in solution, in which case the solvents employed are organic 
solvents which do not react with the oxidizing agents, for example carbon 
tetrachloride, chloroform, cyclohexane, 1,2-dichloroethane, benzene or 
toluene, or in a solid form, for example in the form of a film or coating. 
The dehydrogenated poly(spiro[2,4]hepta-4,6-diene) obtained in the process 
according to the invention is a solid substance of a dark to black colour 
which is insoluble in organic solvents and has an electrical conductivity 
of at least 10.sup.-10 Sxcm.sup.-1. The dehydrogenated 
poly-(spiro[2,4]hepta-4,6-diene) according to the invention preferably has 
an electrical conductivity of at least 10.sup.-9 in particular 10.sup.-8, 
Sxcm.sup.-1. The dehydrogenated poly-(spiro[2,4]hepta-4,6-diene) according 
to the invention can be employed as an electrically conducting material 
for the production of conductors, electrodes, batteries, switch gear and 
semiconductor components and in imparting an antistatic finish or an 
electromagnetic screening to electronic components. 
As an electrically conducting material, the dehydrogenated 
poly(spiro[2,4]hepta-4,6-diene) is processed in an advantageous manner 
together with polymers which are soluble in organic solvents, preferably 
in the form of electrically conducting films or coatings. 
The present invention therefore also relates to compositions containing 
dehydrogenated poly(spiro[2,4]hepta4,6-diene) and polymer which is soluble 
in an organic solvent. 
Compositions of this type can be prepared, for example, by subjecting 
mixtures of poly(spiro[2,4]hepta4,6-diene) and a polymer soluble in an 
organic solvent, preferably together in the form of films or coatings, to 
treatment with an oxidizing agent indicated above. The composition can 
also be obtained, however, by adding dehydrogenated 
poly(spiro[2,4]hepta-4,6-diene), for example present in the form of 
powder, to the appropriate polymer in the melt or in the form of 
solutions. 
The compositions preferably contain at least 10% by weight, in particular 
at least 25% by weight, of dehydrogenated poly(spiro[2,4]hepta-4,6-diene), 
relative to the total weight of dehydrogenated 
poly(spiro[2,4]hepta-4,6-diene) and polymer soluble in the organic 
solvents, for example a polycyclopentadiene or a polyimide containing 
phenylindane radical. 
In the context of the present invention, polymers soluble in organic 
solvents are to be understood as meaning polymers having a solubility of 
at least 10 g of polymer per litre of organic solvent, preferably 20 g of 
polymer per litre of organic solvent. 
As polymers soluble in organic solvents, the compositions according to the 
invention preferably contain a polycyclopentadiene or a polyimide 
containing phenylindane radicals. 
The polycyclopentadiene present in the composition according to the 
invention is known and can be prepared, for example, in accordance with 
the process described in the Journal of Polymer Science, Polym. Chem. Ed., 
11 (1973), 1917, by polymerizing cyclopentadiene, using TiCl.sub.4 as a 
cationic catalyst. In general, a polycyclopentadiene having an average 
molecular weight of 500 to 1,000,000 is used for the compositions. 
Examples of solvents which can be used for polycyclopentadiene are dioxane, 
tetrahydrofuran, chlorobenzene, 1,2-dichlorethane, methylene chloride, 
chloroform, toluene or benzene. 
Suitable polyimides soluble in organic solvents and containing a 
phenylindane radical are those in which at least 10 mol % of the recurring 
structural units contain a phenylindane radical. Polyimides of this type 
are disclosed in German Pat. No. 2,446, 383 and consist essentially of the 
recurring unit of the formula 
##STR6## 
in which the four carbonyl groups are attached to different carbon atoms 
and each pair of carbonyl groups is in the orthoposition or peri-position 
relative to the other, 
Z is a tetravalent radical containing at least one aromatic ring and 
Z' is a divalent organic radical selected from aromatic, aliphatic, 
alkyl-aromatic, cycloaliphatic and heterocyclic radicals, combinations 
thereof and radicals having bridge groups containing oxygen, sulfur, 
nitrogen, silicon or phosphorus, subject to the proviso that 
1) 
(A) in 0 to 100 mol % of the total number of recurring polyimide units, Z 
is a phenylindane radical or the structural formula 
##STR7## 
in which R.sub.1 ' is hydrogen or an alkyl radical having 1 to 5 carbon 
atoms, and 
(B) in 0 to 100 mol % of such units, Z' is a phenylindane radical of the 
structural formula 
##STR8## 
in which 
R.sub.1 ' l is hydrogen or an alkyl group having 1 to 5 carbon atoms and 
R.sub.2, R.sub.3 and R.sub.5 independently of one another are hydrogen, 
halogen or alkyl groups having 1 to 4 carbon atoms, and 
(2) at least 10 mol % of the total number of the radicals Z and Z' are 
phenylindane radicals. 
As regards the preparation and the preferred fields of these polyimides, 
reference should be made to the description in this patent specification. 
The following should be mentioned as examples of organic solvents for the 
soluble polyimides: N,N-dimethylformamide, N,N-dimethylacetamide, 
N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylacetamide, 
N-methylcaprolactam, dioxane, dimethyl sulphoxide, tetramethylurea, 
pyridine, dimethyl sulfone, hexamethylphosphoric amide, tetramethylene 
sulfone, formamide, N-methylformamide, .gamma.-butyrolactone, 
tetrahydrofuran, m-cresol, phenol, 2-methoxyethyl acetate, 
1,2-dimethoxyethane, bis-(2-methoxyethyl) ether, chloroform and 
nitrobenzene. 
The compositions according to the invention are suitable for the production 
of self-supporting, electrically conducting films having a high glass 
transition temperature and ultimate tensile strength. Films of this type 
can be used in the field of electronics or microelectronics, for example 
as conductive composite materials in the production of electrical 
conductors, electrodes, batteries, switch gear or semiconductor 
components, and in imparting an antistatic finish or electromagnetic 
screening to electronic components. 
The polyspiroheptadienes (PSHD) A, B and C used in the following examples 
were prepared in accordance with the instructions in the literature. 
PSHD-A and PSHD-B were synthesized by the method of O. Ohara et al, J. 
Polym. Sci., Polym. Chem. Ed 11 (1973) 1917, and PSHD-C was synthesized by 
the method of S. Hayashi et al, J. Polym. Sci., Polym. Phys. Ed. 17 (1979) 
1995. 
TABLE 1 
__________________________________________________________________________ 
Polyspiroheptadiene - initiators used and character- 
ization of the samples. 
1,4-Content*.sup.1 
PSHD 
Initiator 
Yield 
(%) C,H found*.sup.2 
##STR9## 
__________________________________________________________________________ 
A TiCl.sub.4 
98% 52.0 C = 90.20% 
62,000 
H = 8.60% 
B TiCl.sub.4 /CCl.sub.3 COOH 
98% 35.1 C = 91.04% 
14,000 
H = 8.92% 
C 0.sub.3 C.sup.+ BF.sub.4 .sup.- 
65% 69.6 C = 89.26% 
4,300 
H = 8.91% 
__________________________________________________________________________ 
*1 Determined by .sup.1 HNMR spectroscopy 
*2 Found: C = 91.25%; H = 8.75% 
*3 Number average value of the molecular weight, determined by viscometry 
on the basis of [.eta.] = 4.5 .times. 10.sup.-9 --M.sub.n 1.71 (T = 
30.degree. C.; toluene), [S. Hayashi et al., J. Polymer Sci. Polm. Phys. 
Ed. 17 (1979) 1995]-

EXAMPLE 1 
4. 61 g of PSHD-A [50 mmol per monomer unit] are dissolved, under N.sub.2, 
in 100 ml of anhydrous CCl.sub.4 in a 3-necked flask equipped with a 
stirrer, a reflux condenser and a dropping funnel. A solution of 7.99 g 
[50 mmol]of Br.sub.2 in ml of CCl.sub.4 is put into the dropping funnel. 
The bromine solution is then added dropwise, with stirring, at a 
temperature kept constant at 20.degree. C. A yellowish precipitate is 
formed. When the dropwise addition is complete, the mixture is boiled 
under reflux for 18 hours, with stirring. The precipitate gradually turns 
dark. The mixture is then cooled and the precipitate is filtered off with 
suction in an atmosphere of nitrogen. It is rinsed with three times 50 ml 
of CCl.sub.4. The product is dried in a high vacuum at 30.degree. C. 
Yield: 8.1 g of a black, insoluble powder. Specific conductivity .sigma.: 
see Table 2. 
Elementary Analysis: found C:45.78%, H: 3.92%, Br: 43.49%. 
EXAMPLE 2 
1.84 g of PSHD-A [20 mmol per monomer unit] are dissolved, under N.sub.2, 
in 100 ml of anhydrous CCl.sub.4 in a 3-necked flask equipped with a 
stirrer, a reflux condenser and a dropping funnel. A solution of 5.07 g 
[20 mmol]of I.sub.2 in 200 ml of CCl.sub.4 is put into the dropping 
funnel. The iodine solution is then added dropwise, with stirring, while 
the temperature is kept constant at 20.degree. C. A violet-black 
precipitate is formed after a short time. When the dropwise addition is 
complete, the mixture is boiled under reflux for 18 hours, with stirring, 
and the product is worked up as described in Example 1. 
Yield: 4.6 g of a black, insoluble powder. 
Specific conductivity: see Table 2. 
Elementary analysis: found C: 34.17%, H: 3.19%, I: 59.68%. 
TABLE 2 
______________________________________ 
Specific conductivity .sigma. of the dehydrogenated PSHD 
after various periods of storage 
Sample .sigma.[S .times. cm.sup.-1 ]* 
from Immediately after 
example synthesis After 10 days 
After 4 weeks 
______________________________________ 
1 1.4 .times. 10.sup.-6 
** ** 
2 1.9 .times. 10.sup.-6 
1.9 .times. 10.sup.-6 
2.0 .times. 10.sup.-6 
3 1.1 .times. 10.sup.-6 
1.2 .times. 10.sup.-6 
1.3 .times. 10.sup.-6 
4 7.8 .times. 10.sup.-7 
2.6 .times. 10.sup.-6 
4.6 .times. 10.sup.-6 
5 1.8 .times. 10.sup.-5 
3.5 .times. 10.sup.-5 
3.3 .times. 10.sup.-5 
6 1.6 .times. 10.sup.-6 
** ** 
7 2.1 .times. 10.sup.-8 
8.0 .times. 10.sup.-7 
1.6 .times. 10.sup.-6 
8 1.1 .times. 10.sup.-5 
7.6 .times. 10.sup.-7 
1.6 .times. 10.sup.-6 
______________________________________ 
*.sigma. was determined on powder mouldings at room temperature 
**Not determined 
EXAMPLE 3 
The procedure is as in Example 2, but 
PSHD-B is used instead of PSHD-A. 
Yield: 4.6 g of a black, insoluble powder. 
Specific conductivity .sigma.: see Table 2. 
Elementary analysis: found: C: 35.18%, H: 2.94%, I: 58.90%. 
EXAMPLE 4 
The procedure is as in Example 2, but PSHD-C is used instead of PSHD-A. 
Yield: 4.3 g of a black, insoluble powder. 
Specific conductivity .sigma.: see Table 2. 
Elementary analysis: found: C: 32.01%, H:3,02%, I:63.03%. 
EXAMPLE 5 
The procedure in as in Example 2, but modified in that 12.70 g [50 mmol]of 
I.sub.2 in 500 ml of CCl.sub.4 are added dropwise. 
Yield 6.3 g of a black, insoluble powder. 
specific conductivity .sigma.: see table 2. 
Elementary analysis: found: C: 26.22%, H: 2.48%, I: 67.99%. 
EXAMPLE 6 
1.84 g of PSHD-A [20 mmol of monomer unit]are dissolved, under N.sub.2, in 
a three-necked flask equipped with a stirrer, a reflux condenser and a 
dropping funnel, in 150 ml of cyclohexane dried over P.sub.2 O.sub.5. A 
mixture of 1.45 ml [20 mmol]of SbF.sub.5 and 20 ml of cyclohexane dried 
over P.sub.2 O.sub.5 is put into the dropping funnel. The SbF.sub.5 
mixture is then added dropwise, with stirring, at a temperature kept 
constant at 20.degree. C. A black precipitate is formed immediately. When 
the dropwise addition is complete, the mixture is stirred for a further 
hour. The product is then filtered off with suction in an atmosphere of 
nitrogen. It is rinsed three times with anhydrous cyclohexane. The product 
is then dried in a high vacuum at 30.degree. C. 
Yield: 4 g of a black, insoluble powder. 
Specific conductivity .sigma.: see Table 2. 
Elementary analysis: found: C: 16.19%, H: 2.86%, Sb: 47.90% 
F:17.01% 
EXAMPLE 7 
1.84 g PSHD-A [20 mmol of monomer unit]are dissolved, under N.sub.2, in 150 
ml of anhydrous CCl.sub.4 in a 3-necked flask equipped with a stirrer, a 
reflux condenser and a dropping funnel. A solution of 5.98 g [20 mmol] of 
The SbCl.sub.5 in 20 ml of CCl.sub.4 is put into the dropping funnel. 
SbCl.sub.5 solution is then added dropwise, with stirring, at a 
temperature kept constant at 20.degree. C. A deep brown precipitate is 
formed immediately. When the dropwise addition is complete, the mixture is 
boiled under reflux for a further 18 hours, and the product is worked up 
as described in 
Example 1.l 
Yield: 4.7 g of a black, insoluble powder. 
Specific conductivity .sigma.: see Table 2. 
Elementary analysis found: C: 34.86%, H: 2.98% Cl: 31.30% 
EXAMPLE 8 
The procedure is as in Example 7, but modified in that 11.96 g [40 mmol] of 
SbCl.sub.5 in 15 ml of CCl.sub.4 are added dropwise. 
Yield: 5.9 g of black, insoluble powder. 
Specific conductivity .sigma.: see Table 2. 
Elementary analysis: found: C: 31.59%, H: 2.03%, Cl: 33.54 %, 
Sb: 28.6 % 
EXAMPLE 9 
1.0 g of I.sub.2 crystals are initially placed in a thoroughly dried 700 ml 
vessel, flushed with argon and equipped with a stirrer. Glass 
supports.sup.1 coated with PSHD-A (film thickness approx. 1 .mu.m) are 
then put into the vessel. After about 1 hour the PSHD films assume a brown 
colour. After about 10 hours they are completely black and exhibit a 
metallic reflection. 
FNT Coating was effected by spin coating (concentration of the PSHD solution: 
0.1 g/ml of toluene; speeds of rotation: 30 seconds at 1200 r.p.m. and 
then 30 seconds at 3000 r.p.m.). Increase in weight after 21 hours: 3.89 
mg of Iodine/mg of polymer. .sigma..sub.(RT) (after 21 hours) 
2.4.times.10.sup.-6 Sxcm.sup.-1 (determined on powder mouldings). 
EXAMPLE 10 
The procedure is as in Example 9, but modified in that a glass support 
which has been coated with a polymer mixture consisting of PSHD-A and 
DAPI-polyimide containing the following recurring structural unit: 
##STR10## 
and having an intrinsic viscosity of 0.84 dl/g, measured at 25.degree. C. 
in N-methyl pyrrolidone, is used. The coating is effected by spin coating 
(concentration of the polymer solution: 0.1 g of mixture/ml or 
1,2-dichloroethane; speed of rotation: 30 seconds at 1,200 r.p.m. and then 
30 seconds at 3,000 r.p.m.). The composition of the polymer mixtures and 
the characteristic properties of the films treated with iodine can be seen 
from 
TABLE 3 
______________________________________ 
Composition of the mixed films composed of PSHD and DAPI- -polyimide and 
their characteristic properties after iodine 
treatment 
Proportion of PSHD 
Increase in weight after 
present in the 
47 hours (mg of iodine/mg 
.sigma.RT 
mixed film (% by wt.) 
of polymer mixture) 
[S .times. cm.sup.-1 ] 
______________________________________ 
10 0.37 2.2 .times. 10.sup.-9 
25 0.76 2.8 .times. 10.sup.-8 
75 1.83 1.1 .times. 10.sup.-6 
90 2.18 1.7 .times. 10.sup.-6 
______________________________________ 
EXAMPLE 11 
The procedure is as in Example 9, but modified in that glass supports are 
used which have been coated.sup.2 with a mixed film composed of 
polycyclopentadiene and PSHD-A in a 1:1 ratio by weight (thickness about 
15 .mu.m). 
FNT 2 The coating is effected by applying the polymer solution (4 g of 
mixture/30 ml of toluene) by means of a 100 .mu. doctor blade. 
After approx. 1 hour the mixed films assume a brown colour. After 24 hours 
they are completely black and exhibit a metallic reflection. 
Specific conductivity: .sigma..sub.RT (after 48 hours): 6.1.times.10.sup.-5 
Sxcm.sup.-1 (determined on powder mouldings). 
The polycyclopentadiene used above was synthesized using TiCl.sub.4 as a 
cationic initiator analogously to the working instructions for the 
preparation of polyspiroheptadiene in J. Polymer Sci., Poly. Chem. Ed., 11 
(1973) 1917. 
Yield: 74 % of theory; 1,4-content .gtoreq.99 % (detrmined by NMR 
spectroscopy). Molecular weight 28,300 (determined by viscometry). 
Elementary analysis: found: C 89.77%; calculated: C 90.85%, H 9.03 %; 
calculated: H 9.15 %.