CA1043945A - Polymers of hydrocarbon-substituted diacetylene compounds - Google Patents
Polymers of hydrocarbon-substituted diacetylene compoundsInfo
- Publication number
- CA1043945A CA1043945A CA287,320A CA287320A CA1043945A CA 1043945 A CA1043945 A CA 1043945A CA 287320 A CA287320 A CA 287320A CA 1043945 A CA1043945 A CA 1043945A
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- diacetylenes
- hydrogen
- polymers
- same
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
Abstract
ABSTRACT OF THE DISCLOSURE
Diacetylenes of the formula R1-(CH2)8-C?C-C?C-(CH2)8-R2 where R1 and R2 ar? hydrogen or hydrocarbon ra?icals, R1 and R2 being the same or different, are disclosed. A
process for the manufacture of the diacetylenes is also disclosed.
The diacetylenes may be polymerized to give in particular conjugated polymers. A process for polymerizing the polymers and the polymers so obtained are disclosed.
Diacetylenes of the formula R1-(CH2)8-C?C-C?C-(CH2)8-R2 where R1 and R2 ar? hydrogen or hydrocarbon ra?icals, R1 and R2 being the same or different, are disclosed. A
process for the manufacture of the diacetylenes is also disclosed.
The diacetylenes may be polymerized to give in particular conjugated polymers. A process for polymerizing the polymers and the polymers so obtained are disclosed.
Description
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:
., ,.
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.
:
~.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 "`
~ 5 ~
.
4~
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 ~ .
,. . .
4~
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 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.
: _ g _ ,~
.
. ~ . ~ . .
. - -:-.
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:
., ,.
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.
:
~.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 "`
~ 5 ~
.
4~
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 ~ .
,. . .
4~
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 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.
: _ g _ ,~
.
. ~ . ~ . .
. - -:-.
Claims (13)
1. A polymer consisting essentially of the polymeriza-tion product of one or more diacetylenes of the formula:
R1 (CH2)8-C?C-C?C-(CH2)8-R2 where R1 and R2 are hydrogen or hydrocarbon radicals, R1 and R2 being the same or different.
R1 (CH2)8-C?C-C?C-(CH2)8-R2 where R1 and R2 are hydrogen or hydrocarbon radicals, R1 and R2 being the same or different.
2. The polymer of Claim 1 in which the polymer is a conjugated polymer.
3. The polymer of Claim 2 in which R1 and R2 are hydrogen or alkyl radicals.
4. The polymer of Claim 3 in which all the diacety-lenes are the same.
5. The polymer of Claim 3 in which R1 and R2 are hydrogen or linear alkyl groups of 1 to 8 carbon atoms.
6. The polymer of any one of Claim 2, Claim 3 and Claim 4 in which R1 and R2 are the same.
7. A process for the polymerization of one or more diacetylenes of the formula:
R1(CH2)8-C?C-C?C-(CH2)8-R2 where R1 and R2 are hydrogen or hydrocarbon radicals, R1 and R2 being the same or different, comprising the steps of crys-tallizing said diacetylenes, polymerizing the diacetylenes and separating the polymer so formed.
R1(CH2)8-C?C-C?C-(CH2)8-R2 where R1 and R2 are hydrogen or hydrocarbon radicals, R1 and R2 being the same or different, comprising the steps of crys-tallizing said diacetylenes, polymerizing the diacetylenes and separating the polymer so formed.
8. The process of Claim 7 in which the diacetylenes are polymerized using photoinitiation techniques.
9. The process of Claim 8 in which the photoinitiation uses electromagnetic radiations of wavelengths in, or less than, the visible range of the electromagnetic spectrum.
10. The process of Claim 9 in which R1 and R2 are hydrogen or alkyl radicals.
11. The process of Claim 10 in which all the diacetyl-enes are the same.
12. The process of Claim 11 in which R1 and R2 are hydrogen or linear alkyl radicals of 1 to 8 carbon atoms.
13. The process of any one of Claim 9, Claim 11 and Claim 12 in which R1 and R2 are the same.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA287,320A CA1043945A (en) | 1974-09-04 | 1977-09-23 | Polymers of hydrocarbon-substituted diacetylene compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA208,485A CA1034966A (en) | 1974-09-04 | 1974-09-04 | Hydrocarbon-substituted diacetylene compounds |
| CA287,320A CA1043945A (en) | 1974-09-04 | 1977-09-23 | Polymers of hydrocarbon-substituted diacetylene compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1043945A true CA1043945A (en) | 1978-12-05 |
Family
ID=25667684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA287,320A Expired CA1043945A (en) | 1974-09-04 | 1977-09-23 | Polymers of hydrocarbon-substituted diacetylene compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1043945A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258079A (en) * | 1979-12-13 | 1981-03-24 | International Business Machines Corporation | Preparation of continuous films of diacetylenic polymers |
| WO1987006692A1 (en) * | 1986-04-30 | 1987-11-05 | Centre National De La Recherche Scientifique (Cnrs | Temperature indicators based on polydiacetylenic compounds |
| US4789622A (en) * | 1983-11-26 | 1988-12-06 | Basf Aktiengesellschaft | Production of resist images, and a suitable dry film resist |
-
1977
- 1977-09-23 CA CA287,320A patent/CA1043945A/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258079A (en) * | 1979-12-13 | 1981-03-24 | International Business Machines Corporation | Preparation of continuous films of diacetylenic polymers |
| US4789622A (en) * | 1983-11-26 | 1988-12-06 | Basf Aktiengesellschaft | Production of resist images, and a suitable dry film resist |
| WO1987006692A1 (en) * | 1986-04-30 | 1987-11-05 | Centre National De La Recherche Scientifique (Cnrs | Temperature indicators based on polydiacetylenic compounds |
| FR2598225A1 (en) * | 1986-04-30 | 1987-11-06 | Centre Nat Rech Scient | TEMPERATURE INDICATORS BASED ON POLYDIACETYLENE COMPOUNDS |
| EP0248688A1 (en) * | 1986-04-30 | 1987-12-09 | Centre National De La Recherche Scientifique (Cnrs) | Temperature indicators based on polydiacetylenic compositions |
| US5085801A (en) * | 1986-04-30 | 1992-02-04 | Centre National De La Recherche Scientifique | Temperature indicators based on polydiacetylene compounds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5185391A (en) | Oxidation inhibited arylcyclobutene polymers | |
| Kiji et al. | Solid-state polymerization of derivatives of 2, 4, 6-octatriyne: 9. Topochemical reactions of monomers with conjugated triple bonds | |
| US20110306743A1 (en) | Novel crosslinked hexaaryl bisimidazole compound and derivative thereof, method for producing the compound and precursor compound to be used in the production method | |
| EP0629620B1 (en) | New photochromic Naphto(2,1-b)pyrans and method for their preparation | |
| SU1553014A3 (en) | Method of producing light stabilizer for polypropylene | |
| US4131748A (en) | P-Terphenylene-dicarboxylic acids and their synthesis | |
| EP0647874A1 (en) | Highly efficient nonlinear optical polyimides | |
| CA1043945A (en) | Polymers of hydrocarbon-substituted diacetylene compounds | |
| EP1025107A1 (en) | Photochromic compounds | |
| EP0625518B1 (en) | Spiro-pyranic compounds endowed with photochromic characteristics | |
| JP2002507980A (en) | Photochromic compounds, their preparation and their use in polymeric materials | |
| Colombi et al. | Synthesis and optical properties of a novel soluble polycarbazolyldiacetylene | |
| Wang et al. | Topochemical polymerization of unsymmetrical aryldiacetylene supramolecules with nitrophenyl substituents utilizing C–H⋯ π interactions | |
| Suh et al. | Synthesis and photochromism of polyacetylene derivatives containing a spiroxazine moiety | |
| US4118297A (en) | Fused poly-nuclear aromatic cyclic sulfonium zwitterions and polymers thereof | |
| Okada et al. | Preparation and nonlinear optical property of polydiacetylenes from dialkyltetraacetylene compounds | |
| Dworczak et al. | Azomethines with nonlinear optical properties and polyesters covalently functionalized with them. Syntheses with nitriles IC | |
| Zhang et al. | Main-chain polymers with nonlinear optical chromophores as a slipped shoulder-to-shoulder arrangement | |
| EP0012798A1 (en) | Polymerisable acetylenic oligomers and process for their preparation | |
| US4078142A (en) | Amino substituted-4-t-butylphthalic acid esters | |
| Fomine et al. | Diacetylene-containing polymers III. Poly (m, m′-butadiynylenesuccindianilide) and poly (m, m′-butadiynylene sebacodianilide): novel materials for preparation of transparent polydiacetylene containing films | |
| Jadhav et al. | Preparation of silicon containing polymers—III: Synthesis and characterization of organosilicon azopolyamides | |
| US4163014A (en) | 3,4,5,6-Tetrahydropyromellitdiimides | |
| JPS62255475A (en) | Novel diacetylene compound polymerizable in solid phase | |
| US4125536A (en) | Pyrolysis product of N-substituted-1-cyclohexene-1,2-dicarboximides |