GB2227247A - Substituted butadiene polymer - Google Patents

Substituted butadiene polymer Download PDF

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Publication number
GB2227247A
GB2227247A GB8928515A GB8928515A GB2227247A GB 2227247 A GB2227247 A GB 2227247A GB 8928515 A GB8928515 A GB 8928515A GB 8928515 A GB8928515 A GB 8928515A GB 2227247 A GB2227247 A GB 2227247A
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United Kingdom
Prior art keywords
material according
polymer
electron withdrawing
substituted butadiene
substituted
Prior art date
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GB8928515A
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GB8928515D0 (en
Inventor
Donald Alfred Bennett
Edward William Duck
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Individual
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Individual
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Publication of GB8928515D0 publication Critical patent/GB8928515D0/en
Publication of GB2227247A publication Critical patent/GB2227247A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/14—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

New electro-conducting organic polymeric systems based on mono or disubstituted butadiene polymers and optionally with organic dienophiles, are characterised in that at least one substituent should be electron withdrawing. The substituents are especially cyano or phenyl groups, and the preferred polymer is 2, 3-cyanobutadiene (preferably stereoregular) mixed with tetracyanoethylene.

Description

Electrically Conductive Materials This invention relates to electrically conductive materials. In particular it relates to electrically conductive polymeric materials.
Organic materials of a polymeric nature, which will conduct electricity, are known. One example is a polymer containing a continuous series of double bonds arranged consecutively, such as a polyacetylene, which has been doped with a promoter of an inorganic nature, such as iodine or a metal salt. The presence of the promoter means that the final material is not truly organic and it can have disadvantages e.g. encouragement of corrosion.
It is an object of our invention to produce an organic system for conducting electricity which is free from inorganic additive such as iodine.
According to the present invention an electrically conducting polymeric material comprises a polymer of a mono- or a di-substituted butadiene wherein the substituent(s) is/are one or more strongly electron withdrawing groups, such as cyano or phenyl.
The invention also includes the use of a polymer as just defined as an electrical conductor or as a component of an electrically conductive material.
It is surprising that such a polymer is electrically conductive and can form a polymeric material which is wholly organic and eSectrically conductive, without requiring an inorganic promoter since it has previously been supposed that for a polymeric material to be conductive it is necessary to have a continuous unbroken system of conjugated double bonds situated along the main chain. In contrast, in the polymer of our invention the polymer contains systems of double bonds which are not conjugated within the main polymer chain but instead has a plurality of pendant electron withdrawing side groups along the polymer chain.Without wishing to be bound by any particular theory we believe that electrical conductance is obtained in the polymers of the invention by concentrating electrons in the pendant side groups, as a result of the electron withdrawing nature of the side groups and that passage of electrons is achieved from one polymer chain to an adjacent polymer chain using overlapping electron-rich side groups as the path, as indicated schematically in Figure 1 of the accompanying drawings.
Examples of suitable mono- or di-substituted butadienes which may be used to form the polymer of the invention are 2,3 dicyanobutadiene 1,3; 1,3 dicyanobutadiene 1,3; 1,2 dicyanobutadiene 1,3, 2 cyanobutadiene 1,3, 2 phenyl butadiene 1,3, 2,3, diphenyl butadiene 1,3 and chloroprene.
Such monomers may polymerise in the is1,4, trans-1,4 or 1,2 configuration. Preferably the polymer contains a high proportion of only one of these configurations i.e. is a stereo regular polymer.
Stereo regular polymers of such monomers may be obtained using, for example, a Ziegler-Natta catalyst. However stereo regularity is not necessary to obtain electrically conductive polymers of our invention but is preferred since it enables closer packing of the polymer chains and crystallization in the polymer leads to more regular distribution of the pathways for electron flow.
Electrical conductivity may be enhanced by the incorporation in the polymer of a compatible organic compound having one or more electron withdrawing groups. Physical incorporation is adequate but some degree of chemical bonding may be advantageous. Dienophiles are one general class of organic compound which may be used to enhance electrical conductivity in this way. Examples of such materials are tetracyanoethylene, phenyl acetylene, diphenyl acetylene, para quinone, acetylene dicarboxylic ester, substituted thiophenes and thiophene sulphones. We believe that such dienophiles act as a powerful charge transfer reagent thus facilitating rapid movement of electrons along polymer chains and may have wider application than use in the polymers of the present invention.The present invention thus includes, in one embodiment, the use of a compatible organic compound having one or more electron withdrawing groups as a dopant for prior art type electrically conductive polymers having continuous unbroken systems of conjugated double bonds along the polymer chains (e.g. polyacetylene) instead of an inorganic dopant (e.g. iodine) as well as their use as a dopant for the polymers of the present invention.
Stretch orientation of the polymers of our invention may improve electrical conductivity still further.
An example of an electrically conducting polymeric material of our invention comprises a polymer of 2,3 cyanobutadiene, preferably stereoregular (e.g. having a very high content of cis, trans or 1,2 groups) containing a tetracyano ethylene as an electron transfer enhancing agent.
Figure 2 of the accompanying drawings shows the known hybridisation of acrylonitrile. It may be surmised that tetracyanoethylene hybridises in the same way as indicated schematically in Figure 3.

Claims (9)

Claims
1. An electrically conducting polymeric organic material comprising a polymer of a mono- or a di-substituted butadiene wherein the substituent(s) is/are one or more strongly electron withdrawing groups.
2. A material according to claim 1 in which at least one of the electron withdrawing groups of the substituted butadiene is cyano.
3. A material according to claim 1 or 2 in which at least one of the electron withdrawing groups of the substituted butadiene is phenyl.
4. A material according to any preceding claim in which the substituted butadiene is di-substituted and a second substituent is an electron donating group.
5. A material according to any preceding claim in which the material contains an additional component which is a dienophile, admixed or compounded therewith.
6. A material according to claim 5 in which the dienophile is tetracyanoethylene.
7. A material according to claim 5 in which the dienophile is diphenyl acetylene.
8. A material according to any preceding claim which has been subjected to stress orientation.
9. A material substantially as described with reference to the Examples.
GB8928515A 1988-12-20 1989-12-18 Substituted butadiene polymer Withdrawn GB2227247A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB888829649A GB8829649D0 (en) 1988-12-20 1988-12-20 Electrically conductive materials

Publications (2)

Publication Number Publication Date
GB8928515D0 GB8928515D0 (en) 1990-02-21
GB2227247A true GB2227247A (en) 1990-07-25

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GB888829649A Pending GB8829649D0 (en) 1988-12-20 1988-12-20 Electrically conductive materials
GB8928515A Withdrawn GB2227247A (en) 1988-12-20 1989-12-18 Substituted butadiene polymer

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GB888829649A Pending GB8829649D0 (en) 1988-12-20 1988-12-20 Electrically conductive materials

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GB (2) GB8829649D0 (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB569036A (en) * 1940-03-18 1945-05-02 Du Pont Manufacture of 2-cyanobutadiene-1:3
GB573530A (en) * 1941-07-04 1945-11-26 Herbert Gudgeon Improvements in or relating to the manufacture and application of synthetic rubber-like materials
DE2156451A1 (en) * 1971-11-13 1973-05-17 Bayer Ag (co) polymn of 2-cyanobutadiene - in soln, using organo-alkali cpd as initiator, for thermoplastics to elastomers
GB1329347A (en) * 1970-08-04 1973-09-05 Ciba Geigy Ag Process for the manufacture of 2,3-disubstituted 1,3-butadienes
SU438260A1 (en) * 1972-06-06 1977-09-05 Предприятие П/Я М-5927 Metnod of praparing 2-cyanbutadienecarbon acid
DE2745873A1 (en) * 1977-10-12 1979-04-19 Basf Ag 1-Cyano-1,3-butadiene prepn. useful as polymer starting material - by gas phase pyrolysis of 1-cyano-4-acyloxy-2-butene esp. the 4-acetoxy cpd.
US4313865A (en) * 1979-09-28 1982-02-02 Japan Synthetic Rubber Co., Ltd. Instant-setting adhesive composition
US4367329A (en) * 1981-05-20 1983-01-04 The United States Of America As Represented By The Secretary Of The Air Force Polyaromatic amides having acetylene groupings curable by Diels-Alder cycloaddition
JPS6031507A (en) * 1983-07-28 1985-02-18 Toyo Soda Mfg Co Ltd Production of chloroprene polymer
US4665257A (en) * 1986-10-20 1987-05-12 The United States Of America As Represented By The Secretary Of The Army Facile, high yield synthesis of 2,3-diphenyl-1,3-butadiene

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB569036A (en) * 1940-03-18 1945-05-02 Du Pont Manufacture of 2-cyanobutadiene-1:3
GB573530A (en) * 1941-07-04 1945-11-26 Herbert Gudgeon Improvements in or relating to the manufacture and application of synthetic rubber-like materials
GB1329347A (en) * 1970-08-04 1973-09-05 Ciba Geigy Ag Process for the manufacture of 2,3-disubstituted 1,3-butadienes
DE2156451A1 (en) * 1971-11-13 1973-05-17 Bayer Ag (co) polymn of 2-cyanobutadiene - in soln, using organo-alkali cpd as initiator, for thermoplastics to elastomers
SU438260A1 (en) * 1972-06-06 1977-09-05 Предприятие П/Я М-5927 Metnod of praparing 2-cyanbutadienecarbon acid
DE2745873A1 (en) * 1977-10-12 1979-04-19 Basf Ag 1-Cyano-1,3-butadiene prepn. useful as polymer starting material - by gas phase pyrolysis of 1-cyano-4-acyloxy-2-butene esp. the 4-acetoxy cpd.
US4313865A (en) * 1979-09-28 1982-02-02 Japan Synthetic Rubber Co., Ltd. Instant-setting adhesive composition
US4367329A (en) * 1981-05-20 1983-01-04 The United States Of America As Represented By The Secretary Of The Air Force Polyaromatic amides having acetylene groupings curable by Diels-Alder cycloaddition
JPS6031507A (en) * 1983-07-28 1985-02-18 Toyo Soda Mfg Co Ltd Production of chloroprene polymer
US4665257A (en) * 1986-10-20 1987-05-12 The United States Of America As Represented By The Secretary Of The Army Facile, high yield synthesis of 2,3-diphenyl-1,3-butadiene

Also Published As

Publication number Publication date
GB8829649D0 (en) 1989-02-15
GB8928515D0 (en) 1990-02-21

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