GB2358867A

GB2358867A - Three dimensional benzenoid polymer compositions

Info

Publication number: GB2358867A
Application number: GB0002348A
Authority: GB
Inventors: Clive Stephen Delmonte
Original assignee: Individual
Current assignee: Individual
Priority date: 2000-02-03
Filing date: 2000-02-03
Publication date: 2001-08-08
Anticipated expiration: 2020-02-03
Also published as: GB2358867B; GB0002348D0

Abstract

Three dimensional benzenoid polymer compositions, represented by formula C<SB>6</SB>X<SB>3</SB> where X = CO, N, P, S or As, are made preferably from 1,3,5 isomers of benzene, such as 1,3,5-benzenetriol (phloroglucinol). The polymer compositions can be chelated with transition metals and the resulting materials used in various processes, such as catalysis of reduction and oxidation of nitrogen, formation of ethylene oxide, formation of propionaldehyde, and as catalysts for use in fuel cells. Also disclosed is a crystalline semi-conductor based on polymerised benzenehexanitrile (1,2,3,4,5,6-hexacyanobenzene) (C<SB>6</SB>(CN)<SB>6</SB>).

Description

DESCRIPTION A new class of electrically conducting compositions of matter is described which allows of a wide variety of applications, including, but not limited to: . Catalytic reactions, mostly of the oxidation, reduction and dehydrogenation of small molecules and mostly using transition metal complexes while chelated to the new compositions at ambient and near-ambient temperatures . Crystals of a new polymer showing anisotropic electrical conductivity . A new type of polymer for use in secondary cells for storage of electricity . A new class of organic and metallo-organic semi-conducting polymers . A new class of catalysts for use in fuel cells . A new class of catalysts to split water into its elements . A new class of catalysts for use as redox electrodes . The synthesis of a new class of polymers which are effective in chelating transition and other heavy metal ions in solutions.

Examples of the synthesis of this new class of compositions of matter are set out, but this description and claims are not limited to those examples. Within the current knowledge of skilled practitioners, very many other, derived formulations can be assembled which elaborate the methods and examples set out here.

Within the expertise of skilled practitioners there will be many ways of assembling compositions of matters having the same basic structure as that set out here, and one such approach is set out as follows, based upon the benzene ring, as an example.

The structures described herein can mostly be considered to be represented in terms of a basic monomeric unit, C6X3 (Diagram One, page 3), where, in a polymer, X = =CO, -CO-, #N, #N+R, =O, #O+, #P, #P=O, =S, #S+, #As, or a selection of any or all of these, and variously 2 or 3 bonds of X lying within rings of the polymer.

It is understood throughout that, though the preferred and most highly symmetrical polymers result from monomers which can be represented by the 1,3,5 isomers of benzene, similar polymers can be produced by similar means which include or are composed of other tri-substituted (tri-hydric) benzenoid rings, or di-substituted (dihydric) benzenoid rings, or mono-substituted (monohydric) benzenoid rings, or a mixture of any or all of these. Within the processes described here such polymers offer a graduation of properties which fall within the claims made.

Also within the description and claims, the novel electrodes can be based upon X = CO and X=O, and the novel crystalline organic semiconductor can also be based upon C6(NC)6 (1,2,3,4,5,6 - benzene hexa-isonitrile). Example 1 The Synthesis of A Composition of Matter Where X = N A known number of moles of phloroglucinol is dissolved in the minimum volume of 50% aqueous ethanol, previously saturated with potassium hydroxide, all at room temperature. To this mixture is added a freshly prepared solution of hydroxylamine hydrochloride itself dissolved in the minimum volume of 50% aqueous ethanol at room temperature and in the mole ratio of at least 3:1 hydroxylamine: phloroglucinol.

The mixture is warmed rapidly to 80 on a steam bath and clean air is bubbled through. An insoluble black powder settles out. By CHN analysis, after cooling, recovery and freeze drying, this powder has an empirical formula which approximates to CA. The powder has a 3-dimensional structure, set out in Figure 1 as a 2-dimensional representation.

As a two-dimensional representation, Figure One, overleaf, shows a repeating motif which assembles to form the high polymer. The high polymer has a central space which is accessible to small molecules, especially gases, and the central space contains on average nine ligand atoms which are available to coordinate to suitable atoms and ions, especially those of the transition metals, singly or in combination. In addition, ail the ligand atoms are bound within electrically conducting unsaturated rings upon which electric potentials, and magnetic fields can be imposed.

In the central space, transition metal complexes can be coordinated, such as those of single elements or those of multiple combinations of elements, such as can found in transition metal clusters, transition metal carbonyls, nitrosyls, hydrides, nitrides, etc. These are already known to skilled practitioners, and by thereafter imposing an applied potential, which may be chosen to be time- variable, with or without a magnetic field, a novel range of catalytic behaviours is seen.

Example 2 The Synthesis of A Composition of Matter Where X = 50 %N and 50% O+ The procedure of Example 1 is followed except that the mole ratio of hydroxylamine: phloroglucinol is reduced from at least 3:1 to 1.5:1.

The mixture is warned rapidly to 80 on a steam bath and clean air is bubbled through. An insoluble black powder settles out. By CHN analysis this powder has an empirical formula which approximates to C4N0. The powder has a 3- dimensional structure, set outin Figure 1 as a 2-dimensional representation. Example 3 The Synthesis of A Composition of Matter Where X = 50 IoNN and 50% P Under an inert atmosphere throughout (nitrogen in this example),a known number of moles of phloroglucinol is dissolved in theminimum volume of 50%

Figure One Two-dimensional representation of a fragment showing the central chelating ring of the nitrogen isomer (X=N)

of the polymer N (Distortions from planarity are due to the absence of some of the bonds of the 1 " tercovalent nitrogen) N N N N aqueous ethanol, previously saturated with potassium hydroxide, all at room temperature. To this mixture is added a freshly prepared solution of hydroxylamine hydrochloride itself dissolved in the minimum volume of 50% aqueous ethanol at room temperature and in the mole ratio of 9.5:9 hydroxylamine: phloroglucinol.

The mixture is warmed rapidly to 80 on a steam bath and clean air is bubbled through.

An insoluble black powder settles out. After freeze drying, the powder is refluxed with pyridine and tris-hydroxymethylphosphine in a quantity such that equimolar amounts of the phosphine and hydroxylamine have been used.

By CHN analysis, after cooling, recovery and freeze drying, the product has an empirical formula which approximates to C4NP. The powder has a 3- dimensional structure, set out in Figure 9 as a 2-dimensional representation. Example 4 The Synthesis of A Composition of Matter Where X = O Phloroglucinol was reacted with bromine water under conditions known to skilled practitioners in a mole ratio of bromine: phloroglucinol of 3:1 and the product recovered.

HBr was removed from the supematent liquor by refluxing with excess solid potassium carbonate in the presence of the aqueous salt.

By CHN analysis, after cooling, recovery and freeze drying, the product had an empirical formula which approximated to C20. The powder has a 3- dimensional structure, set out in Figure 1 as a 2-dimensional representation. Example 5 The Synthesis of A Composition of Matter Where X = P A known number of moles of the product of Example 4 was shaken with excess boron trifluoride in ether, through which dry chlorine had been passed. The product was recovered, and refluxed under an inert atmosphere, nitrogen in this example, with tris-hydroxymethyl phosphine in pyridine, for ten hours in a mole ratio of phosphine : product of Example 4 of 4:1.

By CHN analysis, after cooling, recovery and freeze drying, the product had an empirical formula which approximated to C2P. The powder had a 3- dimensional structure, set out in Figure 9 as a 2-dimensional representation. Example 6 The Synthesis of A Composition of Matter Where X = CO A known number of moles of trimesic acid, 1, 3, 5 - benzene tricarboxylic acid, was refluxed with excess thionyl chloride in the presence of a small quantity of anhydrous zinc chloridefor six hours. After removal of thionyl choride and zinc chloride, followed by recovery of product, the acyl chloride was treated with excess diazabicyclononene (DBN) in an inert organic solvent, warmed, and left to stand for two hours.

By CHN analysis, after recovery and drying, the product had an empirical formula which approximated to C3O. The powder has a 3-dimensional structure, set out in Figure 1 as a 2-dimensional representation, where X=-CO. Example 7 Application of an Electric Potential to the Product of Example 4 The product of Example 4 was made positive at an electrode by applying a potential of 4 volts.

It was deduced that this resulted in the conversion of the heterocyclic oxygen atoms to #O+.

The composition of matter in Example 7 can be used as the positive electrode in a secondary cell and as an electrochemical probe.

Example 8 Application of an Electric Potential to the Product of Example 6 The product of Example 6 was made negative at an electrode by applying a potential of -4 volts.

It was deduced that this resulted in the conversion of the exocyclic oxygen atoms to -O-.

The composition of matter in Example 7 can be used as the negative electrode in a secondary cell and as an electrochemical probe.

Example 9 A Secondary Cell Arising from the Application of an Electric Potential to the Products of Examples 1 and 8 The products of Example 9 (choosing to form X from a 50:50 mixture of hydroxylamine and N-methyl-hydroxylamine hydrochlorides) and Example 8 were made respectively positive and negative at electrodes by applying a potential of +4 and -4 volts.

Skilled practitioners, using a solid electrolyte such as a zwitterionic polymer betweenthe electrodes, can use the electrodes as a secondary cell.

In this novel secondary cell, there are nomoving chemicalspecies. There is a high charge to massratio and charging is rapid. This cell suits especially certain specific applications, such ascar batteries, and particularly those batteries used in vehicles based upon electric motors, as well as in space vehicles. Large amounts of charge must be transported ideally in a small mass and allow rapid recharging for continuous usage.

In addition, when such a road vehicle brakes, the kinetic energy loss can be rapidly reconverted back into stored electrical energy in the novel secondary cell described here.

Example 10 A Composition of Matter which is a Crystalline Organic Semiconductor 9, 2, 3, 4, 5, 6 - benzene hexa-isonitrile, C6(NC)6, is made by means known to a skilled practitioner and is deposited as crystals in vacuo. The crystal is irradiated with subatomic particles to initiate polymerisation to form the planar structure represented in Figure 9, of empirical formula C2N.

By diffusion of atoms, ions or by other means, a semi-conducting 'chip' can be created. Bandwidths and positive and negative 'holes' are created by the incorporation of suitable chemical species in each layer.

The polymer conducts electricity within the layer, but, can, if required, conduct electricity at right-angles to the layer plane by making use of the anisotropic electrical conductivity of the stacked aromatic rings.

The central space in the polymer can accommodate a molecular "on-off' switch.

Example 11 A Composition of Matter which is an Organic Semi conductor 1 2, 3, 4, 5, 6 - benzene hexa-isonitrile, C6(NC)s, is made by means known to a skilled practitioner and is deposited in vacuo over a mask. Each monolayer is irradiated with subatomic particles to initiate polymerisation to form the planar structure represented in Figure 1, of empirical formula C2N.

By diffusion of atoms, ions or by other means, a semi-conducting 'chip' can be created. Bandwidths and positive and negative 'holes' arecreated by the incorporation of suitable chemical species in each layer.

The polymer conducts electricity within the layer, but, can, if required, conduct electricity at right angles tothe layer plane by making use of the conductivity of thestacked aromatic rings.

The central space in the polymer can accommodate a molecular "on-off" switch. Example 12 A Composition of Matter where X=P and which catalyses the reduction of dinitrogen (N2) The product of Example 5 was treated first with sufficient ruthenium carbonyl to occupy one quarter of the sites and then with Pd +2 and Co+3 ions. At a sinusoidal potential of 6v at 9 KHz, dry and oxygen-free dinitrogen and then hydrogen were left to equilibrate with the catalyst under ambient conditions. Traces of hydrazine and ammonia were later detected spectroscopically.

In the absence of the polymer, and under otherwise identical conditions, no reaction products were detected.

Example 13 A Composition of Matter where X=P and which catalyses the oxidation of dinitrogen (N2) The product of Example 5 was treated with the carbonyls of iron and ruthenium in the presence of iridium ions, and, at a sinusoidal potential of 6v at 1 KHz, the mixture was left to equilibrate with dry air under ambient conditions.

Traces of nitrogen oxide and dioxide were later detected spectroscopically. In the absence of the polymer, and under otherwise identical conditions, no reaction products were detected.

Example 14 A Composition of Matter where X=P and which catalyses the reduction of dinitrogen to ammonia using water The product of Example 5 was treated first with insufficient nickel carbonyl to occupy all the sites and then with Pd +2 Co+3 and 1r+2 ions. At a sinusoidal potential of 6v at 1 KHz, dry and moist dinitrogen and was left to equilibrate with the catalyst under ambient conditions.

Traces of ammonia and hydroxylamine were later detected spectroscopically. In the absence of the polymer, and under otherwise identical conditions, no reaction products were detected.

Example 15 A Composition of Matter where X=P and which catalyses the formation of organic oxides The product of Example 5 was treated first with nickel carbonyl to occupy one quarter of the sites and then with Rh+3, Pt+2 and Ir+2 ions. At a sinusoidal potentialof 6v at 1 KHz, dry ethene and oxygenwas left to equilibrate with the catalystunder ambient conditions.

Traces of ethylene oxide were later detected spectroscopically. In the absence of the polymer, and under otherwise identical conditions, no reaction products were detected.

Example 16 A Composition of Matter where X=P and which catalyses the hydroformylation of alkenes The product of Example 5 wastreated with nickel carbonyl to occupy one quarter of the sites and then with Rh+3 ions. At a sinusoidal potential of 6v at 1 KHz, dry ethene, carbon monoxide and hydrogen was left to equilibrate with the catalyst under ambient conditions.

Traces of propionaldehyde were detected spectroscopically.

Example 17 A Novel Composition of Matter forming an electrode and a redox probe A composition of matter where X= CO is formed on an electrode by treating 1,3,5 - benzenetricarbonyl chloride with methanolic potassium cyanide solution and gently hydrolysing the product by known means. The resulting 1, 3, 5 - tri-keto-carboxylic acid potassium salt was deposited from methanolic solution onto a smooth platinum anode using the conditions of the Kolbe electrolysis.

The novel composition of matter, where X = CO, was bonded firmly to the platinum.

The novel composition of matter, where X = CO, would allow the coordination of a wide range of transition metal compounds, and others, to be coordinated within the conducting composition of matter, where X = CO.

The novel composition of matter deposited upon the electrode also functions as an electrochemical probe Skilled practitioners will be able to vary the transition metals and their compounds over the wide range of all the known such elements, in addition to the lanthanides and actinides, which can all form complexes with the basic structure of the novel compositions of matter characterised by being able to be represented as polymers of the monomer unit of Diagram One. This is to be taken to include the various other tri-, di- and mono-substituted benzenoid rings known to skilled practitioners which would undergo similar changes under similar conditions as are described herein and which offer modified or graduated properties to the compositions of matter described here and fall within the claims made. Skilled practitioners can also use such compositions as claimed herein in stationary bed and, or, fluidised bed mode in laboratory, pilot plant and full-scale manufacture.

Claims

CLAIMS 1 Compositions of matter which contain polymers which can represented as containing substances of empirical formula C2X where X = =CO, -CO-, #N, #N+R, =0, #0+, #P, #P=O, =S, #S+, #As, or a selection of any or all of these
2 Compositions of matter which contain polymers which can be represented as based upon a monomer which is a benzene ring of formula C6X3 with substituents at positions 1,3,5 where X = =CO, #CO-, #N, #N+R, =O, #0+, #P, #P=O, =S, #_S+, #As, or a selection of any or

all of these as set out in the diagram in this Claim
3 Compositions of matter which contain polymers which can be represented as based upon a monomer which is a benzene ring of formula C6N3 with nitrogen atoms at positions 1,3,5 as set out in the diagram in this Claim
4 Compositions of matter which can represented when pure as comprising polymers of the monomer 1,3,
5 - triaza - 2,4,
6 - tri-dehydro - benzene 5 Compositions of matter which can represented as containing polymers of the monomer benzene 1,2,3,4,5,6 - hexa - isonitrile 6 Compositions of matter which are polymers which can be represented as based upon a monomer which is a benzene ring of formula CsP3 with phosphorus atoms at positions 1,3,5 as set out I the diagram in this Claim
7 Compositions of matter as claimed in claims 1,2,3,4,5 and 6 which contain transition metals, either as a single transition metal, or in a mixture of any or all of the transition metals 8 Compositions of matter as claimed in claims 1,2,3,4,5,6 and 7 which contain transition metal ions, either as those of a single transition metal, or in a mixture of any or all of the transition metals 9 Compositions of matter as claimed in claims 1,2,3,4,5,6,7 and 8 which contain transition metal compounds, either as that of a single transition metal, or in a mixture of any or all of the transition metals 10 Compositions of matter as claimed in claims 1,2,3,4,5,6,7,8 and 9 which contain transition metal cluster compounds, either as that of a single transition metal, or in a mixture of any or all of the transition metals 11 Compositions of matter as claimed in claims 1 to 10 inclusive which contain transition metal carbonyl compounds, either as that of a single transition metal, or in a mixture of any or all of the transition metals 12 Compositions of matter as claimed in claims 1 to 11 inclusive which have been deposited as films by the Langmuir-Blodgett method 13 Compositions of matter as claimed in claims 1 to 11 inclusive which have been deposited as films by known methods in producing semi-conducting electronic components 14 Compositions of matter as claimed in claims 1 to 13 inclusive to which a voltage is applied 15 Compositions of matter as claimed in claims 1 to 14 inclusive to which a variable voltage is applied 16 Compositions of matter as claimed in claims 1 to 15 inclusive which are negatively charged 17 Compositions of matter as claimed in claims 1 to 15 inclusive which are positively charged 18 Compositions of matter as in Example 1 19 Compositions of matter as in Example 2 20 Compositions of matter as in Example 3 21 Compositions of matter as in Example 4 22 Compositions of matter as in Example 5 23 Compositions of matter as in Example 6 24 Compositions of matter as in Example 7 25 Compositions of matter as in Example 8 26 Compositions of matter as in Example 9 27 Compositions of matter as in Example 10 28 Compositions of matter as in Example 11 29 Compositions of matter as in Example 12 30 Compositions of matter as in Example 13 31 Compositions of matter as in Example 14 32 Compositions of matter as in Example 15 33 Compositions of matter as in Example 16 34 Compositions of matter as in Example 17 35 Compositions of matter made wholly or in part by the process of Example 1 36 Compositions of matter made wholly or in part by the process of Example 2 37 Compositions of matter made wholly or in part by the process of Example 3 38 Compositions of matter made wholly or in part by the process of Example 4 39 Compositions of matter made wholly or in part by the process of Example 5 40 Compositions of matter made wholly or in part by the process of Example 6 41 Compositions of matter made wholly or in part by the process of Example 7 42 Compositions of matter made wholly or in part by the process of Example 8 43 Compositions of matter made wholly or in part by the process of Example 9 44 Compositions of matter made wholly or in part by the process of Example 10 45 Compositions of matter made wholly or in part by the process of Example 11 46 Compositions of matter made wholly or in part by the process of Example 12 47 Compositions of matter made wholly or in part by the process of Example 13 48 Compositions of matter made wholly or in part by the process of Example 14 49 Compositions of matter made wholly or in part by the process of Example 15 50 Compositions of matter made wholly or in part by the process of Example 16 51 Compositions of matter made wholly or in part by the process of Example 17 52 Compositions of matter as in Claims 1 to 12 inclusive which bind nitrogen as in Example 12 53 Compositions of matter as in Claims 1 to 12 inclusive which bind nitrogen as in Example 12 and to which a voltage is applied 54 Compositions of matter as in Claims 1 to 12 inclusive which bind nitrogen as in Example 13 55 Compositions of matter as in Claims 1 to 12 inclusive which bind nitrogen as in Example 13 and to which a voltage is applied 56 Compositions of matter as in Claims 1 to 12 inclusive which bind nitrogen as in Example 14 57 Compositions of matter as in Claims 1 to 12 inclusive which bind nitrogen as in Example 14 and to which a voltage is applied 58 Compositions of matter as in Claims 1 to 12 inclusive which bind ethene as in Example 15 59 Compositions of matter as in Claims 1 to 12 inclusive which bind ethene as in Example 15 and to which a voltage is applied 60 Compositions of matter as in Claims 1 to 12 inclusive which bind alkenes as in Example 15 61 Compositions of matter as in Claims 1 to 12 inclusive which bind alkenes as in Example 15 and to which a voltage is applied 62 Compositions of matter as in Claims 1 to 12 inclusive which bind ethene as in Example 16 63 Compositions of matter as in Claims 1 to 12 inclusive which bind ethene as in Example 16 and to which a voltage is applied 64 Compositions of matter as in Claims 1 to 12 inclusive which bind alkenes as in Example 16 65 Compositions of matter as in Claims 1 to 12 inclusive which bind alkenes as in Example 16 and to which a voltage is applied 66 Compositions of matter as in Claims 1 to 12 inclusive which bind hydrogen as in Example 12 67 Compositions of matter as in Claims 1 to 12 inclusive which bind hydrogen as in Example 12 and to which a voltage is applied 68 Compositions of matter as in Claims 1 to 12 inclusive which bind oxygen as in Example 13 69 Compositions of matter as in Claims 1 to 12 inclusive which bind oxygen as in Example 13 and to which a voltage is applied 70 Compositions of matter as in Claims 1 to 12 inclusive which form complexes with oxides of nitrogen as in Example 13 71 Compositions of matter as in Claims 1 to 12 inclusive which bind nitrogen oxides as in Example 13 and to which a voltage is applied 72 Compositions of matter as in Claims 1 to 12 inclusive made wholly or in part by the process of Example 1 which form chelation complexes with transition metal ions 73 Compositions of matter as in Claims 1 to 12 inclusive made in part by the process of Example 1 which form chelation complexes with "heavy metal" ions 74 Ammonia when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 75 Hydrazine when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 76 Hydroxylamine when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 77 Ethylene oxide when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 78 Alkene oxides when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 79 Nitrogen oxides when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 80 Products of hydroformylation when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 81 Alcohols when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 82 Carboxylic acids when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 83 Alkenes when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 84 Alkynes when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive 85 Ammonia when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive and as in Example 12 86 Hydrazine when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive and as in Example 12 87 Hydroxylamine when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive and as in Example 14 88 Ethylene oxide when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive and as in Example 15 89 Alkene oxides when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive and as in Example 15 90 Products of hydroformylation when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive and as in Example 16 91 Propionaldehyde when synthesised in the presence of compositions of matter as in Claims 1 to 12 inclusive and as in Example 16