BRUNNER A N D TUCKER-REFLUXING STYRENE AND DRYING OILS.

IZ 563

THE NATURE OF THE PRODUCTS OBTAINED BY REFLUXING

STYRENE AND DRYING OILS IN XYLOL SOLUTION. II.*
ADDITIONAL DATA ON THE STYRENE-TUNG OIL REACTION
By H. BRUNNER and D. R. TUCKER
An examination has been made of the reaction products obtained by refluxing a mixture of equal
weights of styrene and tung oil in xylol solution in the absence of polymenzltion cstdpts.
Copolymerization occurs between styrene and tung oil. Saponificatiotrof the copolymer yields two
main types of styrenated elaeostearic acid. One, which gives an insoluble potassium salt, con- styrene
combined with elacostearic acid in the approximate average molecular ratio of 8 : I. T h e other styren-
ated acid, which is soluble in light petroleum and yields a soluble potassium salt, approxhatcs in
composition to a product derived from I molecule of styrene and I molecule of elaeostearic acid.
In the conditions described, about 6006 of the styrene remains unpolymerized and none forms a
self-polymer. Only about of the available elaeostearic groups take part in copolymer formation,
the remaining 40°& being recoverable in a styrene-free form.
It is believed that the I : I styrenated acid is formed by a Diels-Alder mechanism.

Introduction
In the original communication on this subject (Brunner & Tucker, 1949)it was shown that
when equal weights of styrene and tung oil are refluxed in xylol solution, considerable copolymeriza-
tion occurs, whereas when dehydrated castor oil is used in place of tung oil in similar conditions,
the product consists mainly of a mixture of polystyrene and dehydrated castor oil.
Since that publication, a number of papers by other workers in t h i s field have appeared. Some
of the results have shown agreement with our findings, others apparently conflict with them. There
is apparent unanimity that interaction takes place between styrene and tung oil. What is not so
clear is the structure of the reaction products and their exact mode of formation. Petit & Fournier
(1950)described experiments on the styrenation of linseed oil in the absence of solvent but using
benzoyl peroxide catalyst. They saponified the reaction product and eventually isolated a fraction
distilling at 270-280' c., which by analysis (acid value, carbon and hydrogen determinations)
corresponded with a compound derived from one molecule each of styrene and linoleic acid.
In view of their interesting results, we feel prompted to present data that we acquired in the
course of our work on the styrene-tung oil reaction. Although we did not succeed in isolating a
chemical entity which could be described as having been formed from elaeostearic acid and styrene,
we did show that from the products obtained by the reaction between equal weights of styrene and
tung oil we recovered by saponification 1618% of insoluble material and 6345"/, of materials
soluble in light petroleum, both of which fraaions contained styrenated fatty acid.
Our published data for styrenated tung oil were limited to acid- and iodinevaluc determinations
and to Sra-red spectroscopic examinations. Additional data acquired at the same time ace now
given. These allow deductions to be made regarding the compositions of the styrenated acids
resulting from saponification of the products.
Experimental
Method of rejluxing
Raw tung oil, purified styrene and purified commercial xylol were used. The styrene was
freed from inhibitor by washing with alkali and water, and was subsequently freshly distilled. The
xylol was washed with small amounts of sulphuric acid, then with water, and distilled before use.
A mixture of tung oil (25 parts by weight), styrene (25 parts by weight) and xylol (50 parts
by weight) was heated under reflux at 140' c. in a 1-1. flask using an electric oven. The heating
was maintained for 75 hours. Small samples were taken for viscosity determinations at regular
intervals and large samples were taken for analysis after 57 hours and 75 hours. After 57 hours
the viscosity of the mixture rose steeply and on the basis of its solids content of 35%, determined
by waporation of a sample at 110' c. to constant weight, it was estimated that 40% of the styrene
taken had polymerized.
A control run was made in which styrene was omitted from the charge.
Analysis of reaction products
The large samples obtained from the mixtures prepared as described above were saponified
by the method already described (Brunner & Tucker, 1949)to yield the following fractions :
A Insoluble in alcoholic potassium hydroxide C Acids insoluble in light petroleum
B Unsaponifiable D Acids soluble in light petroleum
For the sake of comparison a saponification was also carried out on the original untreated tung
oil as well as on the product obtained by refluxing equal weights of styrene and xylene for 25 hours (3).
* Part I : Research, 1949,2(Jan.) 42.

1. a d . Chem., I, December, 1951

564 BRUNNER AND TUCKER-REFLUXING STYRENE AND DRYING OILS. 11

Table I gives the quantifies of the several fractions obtained, calculated as a percentage of the
non-volatile matter in the sample.
The refluxing of tung oil in xylene for 57 and 75 hours resulted in a little polymerization
(or oxidation) since the original tung oil, on saponification, gave a soluble fraction (D) amounting
t0 92.5%.
Acid values.-Pure styrene and polystyrene have, of course, no measurable acid value. The
calculated acid value for tung acids is 201 '7 mg. KOH/g. This has been derived from information
published by the Armour Co. on the composition of the component acids of tung oil (see Table 11).

Table I Table II
Analysis of reaction mixtures by saponification Data on component acids of tung oil
(1) Styrene- (2) Tung (3) Styrene Component acids Amount, % Acid Val. (calc.)
tung oil oil alone alone Elaeostearic . .
.. 79'5 201.5
Time at Oleic . . . . 15.0 198.6
140°C.Y hr. 57 75 57 75 '5 Palmitic .. .. .. .. 4.0
1.5
218.8
FractionA,% 16.3 17.4 Nil Nil 87.6 Stearic 197.2
BYYO 4.3 3.8 0.6 0.6 2.2 -
CY% 4'4 5'2 1.6 1'4 Negligible Total (for tung acids) IOO 201 -7 *
D,% 64.6 63.7 80.9 82.6 Negligible -
Total, yo 89.6 90.1 83-1 84'6 89-8

Acid-value determinations were made on saponification fractions A and D of both reaction

mixtures (I) and (3) (Table I) as well as on tung acids obtained by the saponification of the
untreated oil. The value obtained for the last-named (201 * 5 ) agrees well with the calculated figure
given in Table 11. The acid values of fractions A and D are given in Table 111.
The acid values of the two insoluble fractions (A) show that styrene must be combined with
fatty acid since the only other possibility would be polystyrene with an acid value of nil. The
absence of polystyrene itself was confirmed since the entire fraction A formed a potassium salt
which was insoluble in water, ether, or benzene.
The drop in acid values of the fatty acids (fraction D) from mixtures (2)to mixture (I) also
provides evidence of combination between styrene and fatty acid.
For comparison with the acid values obtained experimentally (Table 111), a selection of
calculated acid values for styrenated acids is given in TabIe IV.

Table III Table IV

Experimental acid values (mean) of saponi5ed Calculated acid values for styrenated acids
reaction mixtures Acid value,
Fraction (I) Styrene-tung oil (2) Tung oil alone mg. KOH/g.
57 hr. 75 hr. 57 hr. 75 hr. Elaeostearic . . .. .. .. 201*51
A 56-7 [I1 53'7[11 - - Styrenated elaeostearic (I : I mol.) . . 146.3
D 170'9 141 167.05 121 199.85 [21 193'15 [21
>>
JJ ,, (7: I mol.) ..
.
,, ( 2 : I mol.) . 115-I
55.6
Note.-Figures in brackets [ I indicate number of ,J ,, (8 : I mol.) . . 50.4
determinations. Styrenated elaeostearic (I : I mol.)/
tung acids (57 hours reflux), I : I by
wt. .. .. .. . . .. 173'1
Styrenated elaeostearic (I : I mol.)/
tung acids (75 hours reflux), I : I by
wt. .. .. .. .. .. 169.7
Comparison between Tables I11 and IV shows that the insoluble styrenated acids (A) approximate
to a styrenated elaeostearic acid based on 7 mol. of styrene to I mol. of fatty acid, while the soluble
styrenated acids (D) correspond in acid value to an equal mixture (by weight) of unreacted tung
acids and styrenated elaeostearic acid (I : I mol.).
Iodine values.-' Total ' iodine values on the insoluble styrenated acids (A) and the soluble
styrenated acids (D) were carried out using the Woburn method. For these determinations
o . p ~ - i o d i n ebromide was used during a-period of I hour at 20' c. In the estimation of tung oil,
however, von Mikusch & Frazier (1941) found th-at these conditions resulted in an iodine value
of 220, whereas when they used 0*4o~-iodinebromide solution over a period of 3 hours at oo c.
a constant and more reliable value for tung oil of 225 was obtained. Thus the experimental values
given in Table V below are probably about 29% too low.
Iodine values of styrenated fatty acids should be treated with some reserve, partly because the
uptake of IBr by the aromatic ring in the copolymer is not known and partly because the
halogenation of a mixture of fatty acid and styrenated acid is unlikely to be quantitative in any one
given set of conditions. Nevertheless, a comparison with calculated values is of some interest.

J. appl. Chem., I, December, 1951

 BRUNNER AND TUCKER-REFLUXING STYRENE AND DRYING OILS. II 565
Table V Table VI
Experimental iodine values of saponi$ed Calculated iodine values for styrenated acih
reaction nrixtures
3 double 2 double I double
(I) Styrene-tung oil (2)Tung oil alone bonds bonds bond
Fraction 57 hr. 75 hr. 57hr.
- -
75 hr. Elaeostearic a a d .. 273'5
A 4 7 ' 3 [I] 4 3 ' 3 [I] Tung acjds .. 231.5
D 171'2[ z ] 165.7 [z] 213.2 [2] 211.5 [I] Styrenated el&xtearic
Note.-Figures in brackets [ ] indicate number of acid (I : I rnol.) 132'7 66'3
determinations. Styrenated elaeosteaic
acid (2 : I mol.) . . 102.3 52-2
Styrenated elaeostearic
acid (7 : I mol.) .. 50.4 25.2
Styrenated elaeostearic
.
acid (8 : I mol.) . 45.7 22-8
Styrenated elaeostearic
( I : I mol.)/tung acids
(57hours) I : I bywt. 172'9
Styrenated elaeostearic
(I : I rnol.)/tung acids
(75 hours) I : I by wt. 172.1

Table VI includes the calculated iodine

values for styrenatedacids, assuming the presence
of compounds containing I, 2 and 3 double
bonds. The iodine value for tung acids has been
computed from the assumed composition of
these acids and the calculated iodine values for
elaeostearic acid (273.5)and oltic acid (89.9).
With mixed styrenated and free acids the
calculated iodine values are based on the assump-
tion that the qrenated acids possessed only two
determinable double bonds.
Good agreement is shown between the
iodine value of fraction A (Table V) derived
from the styrene-tung oil reaction mixture, and
the calculated value (assuming two double bonds
per molecule) for a styremitexi elaeostearic acid
containing 7-8 molecules of styrene per m o l d e
of fatty acid. Similarly, there is good agreement
between the iodine value of fraction D (Table V)
A P F A m'lmg
and the calculated value for a mixture of equal
parts of styrenated (I : I mol.) elaeostearic acid
FIG. I. Force-area diagram for rung oil-styrene fatty and tung acids. Thus there is good correlation
acid monofilms on 0 ' IN-hydrochloric acid
between the results of acid- and iodine-value
determinations.
Unintokcular-j2m examination.-Use was made of the surface-tilm technique (Iangmuk
trough) for a comparison of the fatty acids of tung oil with the fatty acids derived from styrenated
tung oil. This technique is valuable in providing information concerning the shape and size of
molecules and their orientation and packing at fluid interfaces. Unimolecular films (monolayers)
of the fatty acids are repared by spreading a known weight of the material on a cleaned water surface.
P
By measuring the orce exerted by the films on a floating barrier, force-area relationships are
obtained.
The fatty acids did not give stable monolayers on the water and therefore a repeat set of
determinations was made on 0.IN-HCl when more reliable results were obtained.
It is seen from Fig. I that heat treatment of tung oil appears to lower the collapse point
slightly. The curves for the styrenated acids indicate definite signs of copolymerization, increasing
with increasing reaction-time. Compared with the original tung acids, they give less expanded
films below 10 dynesjcm., are practically identical in the incompressible region \10-20dynes/cm.)
and collapse at lower pressures. This would be expected for a copolymer of tung oil with styrene.
No force-area curves were obtained for styrene or polystyrene, a? they do not spread to monolayers.
Znfra-red absorption analysis.-The results obtained here have already been published in detail
(Brunner & Tucker, 1949). Conclusive evidence was afforded that both the 'insoluble' and
' soluble ' acids obtained from the saponified styrene-tung oil reaction mixture were styrenated.
The soluble acid fractions (D) of mixture I (57 and 75 hours) exhibited strong bands at 10.1p.
characteristic of tung oil (triene conjugation), indicating the presence of unreacted material. After

J. appl. Chem., I, December, 1951

566 BRUNNER A N D TUCKER-REFLUXING STYRENE A N D DRYINGS. OIL I I

75 hours reaction the 10.~ pband

. was less intense than after 57 hours, showing that copolymerization
had continued in the meantime. An approximate measurement of thc amount of unreacted tung
oil was obtained by comparing the logarithm of the percentage transmission (or absorption) a t
10.1~. for tung acids and for the acids of the styrene-tung oil reaction mixture. The calculation
showed that after 57 hours at 140' c. the conversion of tung acids to copolymer was slightly less
than 50%, but that after 75 hours it was somewhat greater than 50%.
With the insoluble copolymer acids there was no particularly noticeable absorption at IO'I~.,
providing evidence for the loss of the triene conjugation structure of tung acids during their
copolymerization.
Ultra-viclet absorption analysis.-Examination of the various acid fractions from tung oil
(original or refluxed with xylol) and styrene-tung oil showed that maximum absorption was obtained
at 265 (inflexion), 273 and 283p., with one or two slight deviations for all the soluble acids
(fraction D). These results are consistent with the presence of elaeostearic acid in each of these
fractions. The absorptions of the insoluble fractions (fraction A) were rather weak and indicated
absence of conjugated triene. No positive evidence for carboxyl groups or conjugated diene in
these (A) fractions could be obtained from the ultra-violet absorption data.
Since no ultra-violet spectrographic data were available for pure copolymer acid, it was not
possible to ascertain the relative amounts of combined and uncombined fatty acids in the soluble
acid fraction
From a knowledge of the acid values and extinction coefficients (E,'c?.) for tung acids
and the mixed tung-copolymer acids, some evidence was obtained from derived equivalent weights
that the pure copolymer acid was more likely to be based on equal molecules of styrene and
elaeostearic acid than on any other molecular ratio of hydrocarbon to fatty acid.

Discussion
Heating a reaction mixture based on equal weights of styrene and tung oil (styrene :tung
oil :xylene = I : I : 2) for 57-75 hours at 140' c. results in 40% of the styrene becoming ' fixed '
as copolymer, the remainder being unchanged monomer.
The non-volatile portion of the reaction product has the following approximate composition,
as shown by fractionation of the saponified product, followed by acid- and iodine-value deter-
minations of the resulting fractions :
Non-styrenated elaeostearic groups . . .. .. .. . . .. .. .. 400;
Styrenatcd elaeostearic groups (elaeosteariclstyrene, ca. I : I mol.) .. .. .. 40'6
Sryrcnated elaeostearic groups (elaeost~ariclstyrene,ca. I : 8 mol.) ..
.. . . 20:;,
It is of interest to record here that Powers (1950)styrenated linseed acids at 160-225' c. and
obtained a product comprising about equal weights of fatty acids containing 8-25 styrene segments
and acids containing about one styrene segment.
Structure of' soluble ' stymated acids
Since the I : I-copolymer acids were soluble in both ether and light petroleum, they were
obviously of low molecular weight. Hence the copolymer acids were most probably formed from
I molecule each of elaeostearic acid and styrene.
Iodine-value determinations show that the product contained 2 double bonds per molecule.
Such a product could have been formed by a I : 4- (Diels-Alder) addition :
-CH=CH- CH=CH-CH=CH..-. --_ -----, -CH -CH-CH-CH-=CH--CH--
I
' 1'4'-ring I I
CH,=:CHPh addition CH,----- CHPh
Much less likely would be a I : &addition to give an 8-membered ring or addition to the benzene
nucleus, leading to the formation of a hydrindene derivative :
- -CH-CH--CH=CH-CH=CH- - CII -CH --CH =CH-CH-CH-.
--.A I \
1 '
CH, =c . 0
.- CH,---CH--\ \/
a-Methylstyrene is known to dimerize to I : I : 3 .trimethyl-3-phenylhydrindene (Bergmann,
Taubadel & Weiss, 1931)~ but only in the presence of strong acid catalysts.
A possible argument against the I : 4-ring addition is that dienes do not usually condense with
mono-olefink hydrocarbons to give substituted cyclohexene derivatives, i.e. styrene is not a good
dienophile. However, Alder & Rickert (1938)have shown that the vinyl group of vinylcyclohexene
can add to butadiene to yield bicyclohexene :

J. appl. Chem., I, December, 1951

 BRUNNER AND TUCKER-REFLUXING STYRENE AND DRYING OILS. I I 567
Indene has been shown (Deno, 1950) to give a Diels-Alder addition with sorbic and muconic
acids to yield tetrahydrofluorene derivatives :
COtH

R
where R is Me or CO,H.
a-Methylstyrene adds to sorbic acid to give 4 : 6-dimethyl-6-phenylcyclohexene-r-carboxylic
acid :

C0,H
Petit & Fournier (1950) hold that the styrenated linseed acid they isolated resulted from a
Diels-Alder reaction between styrene and conjugated linoleic acid, the latter having been formed
by isomerization of g : 12-linoleic acid.
Proof of the formation of a Diels-Alder adduct from I molecule of elaeostearic acid and I
molecule of styrene could be afforded by isolation of the compound from unchanged fatty acid,
using fractional-precipitation or molecular-distillation techniques, followed by an examination of the
product by ozonolysis or by Waterman's ring-analysis method (Vlugter, Waterman & van Westen,
1932J '935).
Structure of insoluble styrenated acids (fraction A )
The structures possible for the styrenated acids which were estimated to be based on a
fatty acids-styrene molecular ratio of I : 8 (approx.) are much more diverse than for the
I : I-product discussed above.
In the simplest case these styrenated acids would all be monobasic, i.e. derived from
I molecule of elaeostearic acid and a varying number of molecules of styrene. A knowledge of the
acid- and iodine-values, however, does not help to distinguish between such a mixture and a mixture
containing styrenated acids based on more than one molecule of elaeostearic acid, for which there
are possibilities of the following reactions in addition to the Diels-Alder ring-addition :
ti) Simple I : 4-addition to form a molecule containing repeating units of styrene and elaeosteaiic
acid.-The synthetic styrene-butadiene rubbers such as Hycar 0s and Buna S are largely made
up of styrene and butadiene copolymerized through the terminal carbon atoms of butadiew. This
is the same mechanism as proposed by Hewitt & Armitage (1946) for styrenetung oil
copolymerization.
(ii) I : 2-Addition analogous fo the I : 4-addition in @).-In butadiene-styrene copolymerization
the reaction is not entirely a I : +addition, and Alekseeva & Belitskaya (1941, 1942) have given
proof in ozonolysis experiments that butadiene also adds on at the I :2-position to form the
inter-polymer (Marchionaa, 1946).
Hence in styrene-tung oil copolymerization we have the possibility of I :2- or 5 :&addition.
The possibility of a mixed I :2- and 5 : &addition arises because of the dissymmetry of the fatty
acid molecule but the possibility of both I : 2- and 5 : 6-additions on the same f k t y acid molecule
is more remote.
(iii) I : &Addition.-This may be charact_eristic of copolymers based on conjugated trienes.
No examples can be cited from the literature but the possibility of such a reaction Occurring should
not be overlooked. The copolymer will contain a conjugated diene unit.
(iv) Hydrocarbon addition fo active methyZene groups via a hydrogen shift or proton transfm.-
This is unlikely to apply to the conjugated elaeostearic acid, but has been suggested by Rinse (1950)
and by Powers (1950) for non-conjugated oils. This su estion, which is in direct opposition to
that of Petit & Fournier (1950)~brings into being an a & n e n t of opposing schools of thought
markedly analogous to the schools of thought concerned with the thermal polymerization of linseed
oil t a stand oil.
The weight of evidence concerning the mechanism of formation of stand oil, particularly that
supplied by Bradley (I 947), inclines towards the Diels-Alder reaction being the preponderating
one. Whether this holds equally well for the wpolymers corresponding to the insoluble styrenated
(8: I) elaeostearic acid is difficult to say with the limited experimental evidence available,
J. appl. Chem., I, December, 1951
568 JONES-POL YMERS AND COPOLYMERS OF ACENAPHTHYLENE
Certainly no categorical opinion can be ventured at this stage, unless with the sole object of
inviting discussion.

Acknowledgments
The authors wish to place on record their thanks to all those members of I.C.I. Ltd., Paints
Division, who rendered assistance in the prosecution of this work. In particular, thanks are due
to Dr. N. W. Hanson, with whom many analytical problems were discussed, and to Dr.
J. P. Wiltshire for the results obtained by unimolecular-film evaluation.
Imperial Chemical Industries Ltd.
Paints Division
Wexham Road
Slough
Received 19 March, IYSI

References
Alder, K. & Rickert, H. F. (1938). Ber. drsch. c h m .
Ges. [B] 71, 373.
Alekseeva, E. N. & Belitskaya, R. F. (1941). 3. gen.
Chem. USSR 11, 358 ; Chem. abstr. p. 5859.
Alekseeva, E. N. & Belitskaya, R. F. (1942). Rubb.
chem. Tech. 15,693.
Bergmann, E.,Taubadel, H. & Weiss, H. (1931).Ber.
dtsctt. chem. Ges. 64. IAO?.
Bradley, T. F. (1947).‘ J’.’bil Col. Chem: Ass. 30
(July), 225.
Brunner, H. & Tucker, D. R. (1949). Research 2,
(Jan.), 42.
Deno, N. C.(1950). 3.Amer. chem. SOC.72, 4057;
Hewitt, D. H. & Annitage, F. (1946). 3. Oil Col.
Chem. Ass. 29 (June), 109.
Marchionna, F. (1946). ‘ Butalastic Polymers,’ p. 147,
(New York : Reinhold Publishing Corpn.).
Petit, J. & Fournier, P. (1950). 08.Dig. 307 (Aug.),
609.
Powers, P. 0. (1950). Industr. Engag Chem. 42,2096.
Rinse, J. (1950). Chem. Weekbl. 22, 373; Chem.
Abstr. p. 8675 ; B.P. Appl. 14537i49.
Vlugter, J. C., Waterman, H. I,’& van Westen, H. A.
(1932). 3. Insr. Petrol. Tech. 18,735.
Vlugter, J. C., Waterman, H. I. &van Westen, H. A.
(1935). 3.Inst. Petrol. Tech. 21, 661.
Von Mikusch, J. D. & Frazier, C. (1941). Industr.
Engng Chem. (analyr. Ed.) 13, 782.

POLYMERS AND COPOLYMERS OF ACENAPHTHYLENE

By J. IDRIS JONES
An exploratory survey of the polymerization and copolymerization of acenaphthylene has been
carried out to see whether there are possibilities of its use as an industrial monomer. Polyacenaphthy-
lene been prepared by thermal polymerization with and without peroxide-type catalysts, by Friedel-
Crafts polymerization and by the emulsion technique. The molecular weight of a thermal polymcr
exceeded 100,000.
Some aspects of the copolymerization of acenaphthylene with styrene have been studied and it has
been shown that a substantial elevation in the softening point of polystyrene results from the incorpora-
tion of accnaphthylene units in the polymer chain. The electrical properties of the copolymers are
not significantly different from those of polystyrene.
Copolymers of acenaphthylene and isobutylene haw been obtained by low-temperature poly-
merization with Friedel-Crafts-type catalysts. The products were of a relatively low order of molecular
wcight. Examination of the ultra-violet absorption spectra of the copolymers has revealed a tendency
for the acenaphthylene units to enter the macromolecules in groups rather than randomly in single
units.
Butadiene and acenaphthylene which, in certain conditions, undergo a Diels-Alder condensation to
give tetrahydrofluoranthene, furnish linear copolymersby emulsion polymerization. Attempts to prepare
copolymers of acenaphthylene with ethylene proved unsuccessful, acenaphthylene showing a very
pronounced inhibiting effect on the polymerization.
High yields of acenaphthylene (I)* are obtained by vapour-phase dehydrogenation of acenaph-
thene (11), a hydrocarbon potentially available in considerable quantities from coal tar (Kynaston
& Jones, 1949). Acenaphthylene, a yellow crystalline material, m.p. 92*5Oc., has a marked tendency
t o polymerize, yielding dimers and polymers. Dziewonski & Rapalski (1912) showed that on
prolonged exposure to sunlight acenaphthylene gives the two stereoisomeric modifications of
heptacyclene (111). This photochemical dimerization has been the subject of a recent study by
Bowen & Marsh (1947). With acid catalysts another dimer, diacenaphthenylidene (IV) is formed
The British system of numbering the carbon atoms has been followed in this paper. In the American
system NO. I carbon atom is not part of the naphthalene ring.

J. appl. Chem., I, December, 1951