Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
The present invention relates to polymers of hydro-
carbon-substituted diacetylene compounds and in particular
to conjugated polymers of such compounds. The present inven-
tion also relates to hydrocarbon-substituted diacetylene com-
pounds and their manufacture.
Diacetylene compounds arle capable of being polymer-
ized to form conjugated polymers. Such polymers may be use-
ful in a variety of applications, for example, in end uses
utilizing the toughness, colour and/or the electrical proper-
ties of such polymers. The polymers may have adva~tages overother known con~ugated compounds, for example anthracene der-
ivatives as a result of the physical properties of the poly-
mers.
Polymers of acetylenic compounds are known. F.
Bohlmann et al disclose the reaction products of polyynes
of the formula Rl-(C-C)n- ~, where n is equal to or greater
than 2, in Canadian Patent 679,842 which issued on February
11, 1964. The polyynes disclosed by Bohlmann et al are
generally characterized by values of n equal to or in partic-
ular greater than 2 and by substituents Rl and R2 which arepolar and/or which are con~ugated with the acetylenic bonds
of the compound.
The polymerization of acetylenes having polar sub-
stituents is also disclosed in German Offenlegungsschrift
; 1,940,691 of Badische Anilin and Soda-Fabrik, published Feb-
ruary 25, 1971.
It has now been found that hydrocarbon-substituted
diacetylenes having substituents that are neither polar nor
conjugated with the acetylenic bond and the polymers derived
therefrom may be manufactured.
Accordingly, the present invention provides diacetyl-
enes of the formula: ~.
" - 1
. . .
. -
`` ' ' . '' ` 1 ' ". "',.1 '`` '` :
~ 4
Rl-(CH2)8-C-c-c-c-~cH2)8-
where Rl and R2 are hydrogen or hydrocarbon radicals, Rl and
being the same or different.
The present invention also provides a process for
the manufacture of diacetylenes of the formula:
Rl (CH2)8-C-C-C-C-(CH2)8-~2
where Rl and R2 are hydrogen or hydrocarbon radicals, Rl and R2
being tne same or different, c~mprising contacting monoacetyl-
enes of the formula:
R-(CH2)8-C-C-H, where R is Rl or R2 with a cupric
salt in an inert solvent in the presence of an amine, said
cupric salt and said amine being soluble in said solvent and
the ratio of monoacetylene : cupric ion being maintained at
less than 1:3 on a molar basis, and separating the diacetylene
so formed.
In a preferred embodiment of the process for the
manufacture of the diacetylenes of the present invention, the
.~ cupric salt is cupric acetate.
Furthermore, the present invention provides a polymer
consisting essentially of the polymerization product of diacetyl-
enes of the formula:
l (cH2)8-c--c-c--c-(cH2)g-R2
where Rl and R2 are hydrogen or hydrocarbon radicals, Rl and R2
being the same or different.
In a preferred embodiment of the polymer o~ the present
invention Rl and R2 are alkyl groups and especially linear alkyl
groups having 1-8 carbon atoms.
In another embodiment the polymer is a conjugated polymer.
In yet another embodiment all the diacetylenes are
identical and in particular Rl and R2 are the same.
In additio~, the present invention provides a process
for the polymerization of one or more diacetylenes of the formula:
-- 2 --
., ,.
Rl- ( CH2 )8-C--C-C--C- ( CH2 )8-R2
where R and R2 are hydrogen or hydrocarbon radicals, ~1 and
R2 being the same or different, comprising the steps of crystal-
lizing said diacetylenes, polymerizing the diacetylenes and
separating the polymer so formed.
In a preferred embodiment of the process of the
present invention the diacetylenes are polymerized using photo-
initiation techniques especially with electromagnetic radiation
of wavelength in, or less than, the visible range of the electro-
magnetic spectrum
The polymers of the present invention are obtainedby polymerization of diacetylenes of the formula:
R -(cH2)8-c-c-c-c-(cH2)8-R2
Rl and R2 having been defined hereinabove. These diacetylenes
are capable of being polymerized at ambient temperatures. At
such temperatures the diacetylenes of the above formula are
capable of being crystallized and polymerization of the diacetyl-
enes is preferably carried out with the diacetylenes in a
crystallized form, i.e., in the solid state. In order for
polymerization of crystallized diacetylenes to take place the
acetylenic bonds of the diacetylene compounds must be aligned
in a manner that facilitates polymerization. m e shape of
- the diacetylene molecule will be an important factor in deter-
mining the structure of the crystal formed therefrom and in
particular whether the crystal structure is such that polymer-
ization may readily occur. Polymerization to linear con~ug-
` ated polymers is preferred. m e diacetylenes of the present
invention, which are capable of being polymerized in the solid
state, are characterized by substituted linear C8 alkyl radicals
attached to each acetylenic group.
-- 3 --
:
~.i , . .. ~ -
~ 4 ~
The polymerization of the diacetylenes of the present
invention is preferably carried out using photoinitiation tech-
niques J such techniques being known in the art. The wavelength
of the radiation used for photoinitiation may be varied over
a wide range of the electromagnetic spectrum, especially radi-
ation of wavelengths in, or less than, the visible range of
the electromagnetic spectrum. For example, so-called soft X-rays,
ultra-violet light and visible light may be used, as is exempli-
fied hereinafter.
The substituents Rl and R2 are hydrocarbon radicals.
Such radicals may include alkyl radicals, especially linear
alkyl radicals, or radicals containing aryl, cyclohexyl and
olefinic groups. Alkyl radicals, especially linear alkyl
radicals and in particular linear Cl-C8 alkyl radicals are
preferred. The substituents Rl and R2 may be the same or
different although it is preferred that Rl and R2 be the same.
The polymers of the present invention are con~ugated
polymers. The properties of colour, toughness and high melting
temperature, as illustrated hereinafter, make the polymer capable
of use in a variety of end uses. The polymers may be useful in
semiconductor electrical applications. The polymers are also
capable of being blended with other polymers especially polymers
of ethylene and the like.
The monomers from which the polymers of the invention
may be manufactured may be obtained by the oxidative coupling
of terminal monoacetylenes, i.e., R-(CH2)8-C-C-H, where R is
the Rl or R2 of the polymer defined hereinabove. The oxidatlve
coupling reaction is carried out in an inert solvent in the
- presence of cupric salts soluble in the solvent. An example
of a suitable cupric salt is cupric acetate. The solvent should
` - 4 -
4 ~ 4 ~
contain an amine soluble in the solvent, e.g., pyridine, to
maintain the solution in a mildly alkaline condition. A suit-
able solvent mixture is diethyl ether/pyridine. The solvent
mixture containing the cupric salt is refluxed and the mono-
acetylene compound is slowly added pre~erably so that the
ratio of cupric ion to monoacetylene is maintained greater
than about 3. The product of the reaction may be separated
from the reaction mixture by e~traction or by addition of
the reaction mixture to an ice-dilute hydrochloric acid mix-
ture and separation of the then solidified reaction product.
The oxidative coupling reaction may be used for
the manufacture of diacetylenes in which Rl and R2, in the
formula hereinabove, are hydrogen or a hydrocarbon radical.
One or more different hydrocarbon radicals may be used al-
though in a preferred embodiment Rl and R2 are hydrogen or
one type of hydrocarbon radical. In further embodiments R
and R2 are alkyl groups especially linear alkyl groups hav-
ing 1-8 carbon atoms.
The inve~tion may be ilIustrated by the following
examples:
EXAMPLE I
Dotriaconta-15,17-diyne, i.e., the diacetylene of
the formula R -(CH2)8-C-C-C-C-(CH2)8 R2 1 2 3
(CH2)5-, was crystallized in a microcrystalline form on a
filter support and then exposed to low power ultra-violet
radiation (MINERALIGHT* W Shortwave lamp, principal wave-
length 2540 ~) at a distance of about one inch. Over the s
period of one hour the crystals of the diyne turned yellow
and then brick red indicating the formation of a con~ugated
compaund.
*denotes trade mark
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.
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EXAMPLE II
Dotriaconta-15,17-diyne was dissolved in benzene and
placed in a vessel capable of having an ultra-violet lamp
inserted therein. The vessel was ~umbled from side to side
and the benzene was removed under vacuum. ~he diyne crystal-
lized over a large proportion of the inne~ surface of the vessel.
A low pressure mercury lamp (2.5 watts total power, principal
wavelength 2540 A, obtained from Ace Glass Inc.) was inserted
in the vessel and, after purging the vessel with nitrogen,
the diyne was irradiated for about 7 hours. The diyne was
re-dissolved in benzene which was then removed again under
vacuum so as to renew the layer of diyne. The irradiation
was repeated. The re-dissolutuon of diyne, removal of ben-
zene and irradiation was repeated 10 times. The unreacted
diyne was separated and the yield o~ polymer was shown to
be 14~.
In related experiments the yield of polymer was
shown to be dependent on irradiation time and power of the
source of ultra-violet light.
- The polymer was shown to be insoluble in methanol,
diethyl ether, benzene, chloroform, hexamethylenephosphor-
trisamide, dimethylformamide, dimethylsulfoxide, o-dichloro-
benzene, dichloromethane, polyethylene glycols, e.g., CARBOWAX*
1500 and CARBOWAX 4000, and slightly soluble (0.1~ by weight)
in hot decahydronaphthalene. On heating to 350C. the polymer
did not melt and showed only a slight darkening in colour. The
polymer was shown by Raman and visible spectroscopy to be a
con~ugated polymer.
~denote~ trade ~ark
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EXAMPLE III
Hexatriaconta-17,19-diyne was polymerized us~ng the
procedure of Example II. The solvent used was petroleum ether.
The diyne layer was renewed three times. Total irradiation
time was 65 hours. The yield of red polymer was 776 and the
properties of this polymer were similar to those of the polymer
from dotriaconta-15,17-diyne.
EXAMPLE IV
Molten dotriaconta-15,17-diyne was placed in a
10 0.55 mm diameter X-ray capillary tube and cooled so that the
diyne solidified. The diyne was irradiated with so-called
soft X-rays whereupon the diyne turned a deep red colour.
The polymer formed was shown by R~man spectroscopy to be
identical to the polymer formed in Example II.
EXAMPLE V
Molten dotria~onta_l5,17_diyne was placed in a 0.55
mm diameter X-ray capillary tube and cooled to -160C. The
diyne was then irradiated with visible light of a wavelength
of 5682 A from a krypton gas laser of 250 milliwatts power.
20 Subsequent analysis using Raman spectroscopy indicated that
polymer was formed.
EXAMPLE VI
5,7-Dodecadiyne, i.e., the diacetylene of the formula
R-C-C-C-C-R where R is CH3-(CH2)3-) which is a liquid at
ambient temperatures, was placed in a vessel capable of having
an ultra-violet lamp inserted therein. The vessel was tumbled
^ from side to side to spread the diyne over the walls o:E the
vessel. The diyne was cooled to -75C. to crystallize the
diyne and then irradiated with the ultra-violet lamp used
30 in Example II. Irradiation for in excess of 72 hours yielded
A
_ 7 _
: ~ - ~ , - . , ,
. . ,. , ~ .
less than 0.1~ of brown-reddish material. The diyne was re-
covered from the vessel.
A similar result was obtained when the abo~e experi-
ment was repeated using 2,4-hexadiyne, i.e. J the diacetylene
of the formula R-C-C-C-C-R where R is CH3-.
EXAMPLE VII
0.0057 Moles of hexadecyne-l~ i.e., the monoacetyl-
ene R-C-C-H where R is CH3-(CH2)13-, was dissolved in 180 ml.
of a 6:1 volume/volume mixture of pyridine and diethyl ether.
The resultant solution was added at a rate of 60 ml./hour to
a solution of 4.3 gms. of cupric acetate in 700 ml. of the
same mixture of pyridine and diethyl ether. The solution was
maintained under total reflux during the addition of the mono-
acetylene. After refluxing for a further 24 hours the re-
sultant solution was allowed to cool to ambient temperature
and poured onto a mixture of ice and 1. 5 N hydrochloric acid.
The solid waxy layer of product so formed was separated, dis-
- solved in diethyl ether and purified by the addition of char-
coal and alumina. The yield of purified product, dotriaconta-
15J 17-diyne was 95%. The product was a white crystalline
solid of waxy appearance which melted at 48C-
EXAMPLE VIII
.
The process of Example VII was repeated using a
solution of 0.0072 moles of decyne-l, i.e., the monoacetylene
of the formula R-C-C-H where R is CH3-(CH2)7-, in the pyridine/
diethyl ether solvent and a solution of 4 . 73 gms. of cupric
acetate in the pyridine/diethyl ether solvent. Eicosa-9,11-
diyne was formed as a pale yellow liquid which crystallized
between -15 C. and 0C- The yield was 85~.
EXAMPLE IX
The process of Example VII was repeated using a
solution of o . oo8 moles of octadecyne-l, i.e., the monoacetyl-
ene of the formula R-C-C-H where R is CH3-(CH2)15, in the
- 8 -
pyridine/diethyl ether solv ~4a~ solution of 8.34 gms. of
cupric acetate in the pyridine/diethyl ether solvent. Hexa-
triaconta-17,19-diyne was formed as a white crystalline solid
of waxy appearance with a melting point of 58C.
The structure of the diacetylenes of Examples VII to
IX was confirmed by elemental analysis, hydrogenation and by
in~rared, Raman, ultra-violet and nuclear magnetic resonance
spectroscopy.
The application iS a division of copending application
serial No. 208 48~ filed September 4, 1974.
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