WO2022174360A1

WO2022174360A1 - Anisotropic polycyclic carbonates

Info

Publication number: WO2022174360A1
Application number: PCT/CH2022/050005
Authority: WO
Inventors: Thierry Schwitzguebel
Original assignee: Thierry Schwitzguebel
Priority date: 2021-02-22
Filing date: 2022-02-21
Publication date: 2022-08-25
Also published as: KR20230159447A

Abstract

The field of the invention relates to a novel family of polycyclic carbonates made of mixed cyclic and linear carbonates functions showing a surprising anisotropic behaviour in their electrically conductive properties. Films of those polycyclic carbonates show an electric conductive behaviour perpendicular to the conductor or semiconductor treated surface and an electrical resistance typical to polymers in the direction of the film formed on the surface. This surprising behaviour is useful for the performance improvement and modification of electron transfer devices and elements, such as batteries, all electronic devices and components, visual displays, memories, quantum dots, electrodes and solar energy converting elements to name some.

Description

Title

Anisotropic electrical and ionic conductivity properties of polycyclic carbonates

Description

Electrodes and semiconductor surfaces are subject to loss of performance and degradation due to their interfaces with foreign materials, migration of doping components to the neighbourhood and the contact with materials to be transformed. This problem is particularly important for elements containing alkali metals, alkaline earth, metals, metalloids, lanthanides alone or in combination or alloys, with or without C, N, 0, P, S and Se or polymer surfaces Those electrodes and semiconductor surfaces when used for the production of batteries, such as but not limited to Lithium-Ion batteries, electrolysing devices for the production of carburants such as but not limited to Hydrogen, Oxygen, or Carbon monoxide, lightening and display equipment or solar energy conversion elements have loss of performances due to material degradation, such as corrosion or dissolution, migration of doping components to the neighbourhood, or efficiency reduction due to the loss of electric charges.

In some applications, such as batteries or perovskite solar cells to name some the surface degradation can lead to the destruction of the object in which the electrode or semiconductor surface is included.

In the case of batteries such as for example hybrid battery cells combining liquid electrolytes (LEs) with inorganic solid electrolyte (SE) separators or different SEs and polymer electrolytes (PEs), respectively, are developed to solve the issues of single-electrolyte cells. Among the issues that can be solved are detrimental shuttle effects, decomposition reactions between the electrolyte and the electrodes, and dendrite propagation. However, the introduction of new interfaces by contacting different ionic conductors leads to other problems, which cannot be neglected before commercialization is possible. The interfaces between the different types of ionic conductors (LE/SE and PE/SE) often result in significant charge-transfer resistances, which increase the internal resistance considerably.

Display device, tactile or not have electric consumption strongly related to the loss of currents on their interphases. For example, in Indium Tin oxide glass coated surfaces, the electrical consumption can be related to the interphase loss.

Description of the invention:

To solve those unmet performance, efficiency and yield problems on electrodes and semiconductor surfaces, the inventors surprisingly discovered that the class of chemical substances described in this invention allow to produce novel polycyclic carbonates with anisotropic conductive electric properties, allowing to solve the problem described above. The anisotropic conductive behaviour of those polycyclic carbonates is surprising and new.

It is detailed below how the application of the chemical substances discovered in this invention can surprisingly generate a film on the element to be treated and how this film does allow the electron transfer only in the perpendicular direction of the treated surface and show an insulating behaviour in all other directions. This anisotropic conductive behaviour combined with the barrier properties of

Feuilles de remplacements Regie 26 polycyclic carbonates toward ions, dopants, or more generally atom migration allow to solve the problems described above.

Organic carbonates molecules of the invention with more than one carbonate function and in which those organic carbonates are combinations of cyclic carbonates, with cycles of 5 or 6 atoms or linear carbonates with aryls, substituted aryls, alkyls, or substituted alkyls such as but not limited to phenyl, p-nitrophenyl, picryl, methyl, ethyl, t-butyl, trichloromethyl, trifluoromethyl, trichloroethane, trifluoroethane, allyl, vinyl, or imidazole, it's substitutes and salts. Those chemical substances when applied to the surfaces to be treated as per the description of this invention, with either any known solution technologies or dry powder and physical transfer technologies, such as but not limited to electro-deposition, chemical and physical transfer technologies, will provide the treated element with a polycyclic carbonates protection while allowing the electron transmission in the perpendicular direction of the surface.

The organic carbonates molecules useful for the polycyclic carbonates surprisingly discovered in this invention are made from linear or cyclic polyols with X hydroxyl functions, X being an integer between 4 and 6, such as but not limited to erythritol, pentaerythritol, xylitol, sorbitol, mannitol, inositol, or anhydro-glucitol. The carbonation or partial carbonation greater than 1 up to a limit equivalent to the number of the hydroxyl functions of the polyols is achieved by known technologies such as chemical synthesis with the use of alkyl chloroformates, halogenated substituted alkyl chloroformate, more particularly tricholrethyl chloroformate, phenyl chloroformate, p-Nitrophenyl chloroformate or alternatively with phosgene, di and triphosgene or carbonyl diimidazole. Some formations of bis-cyclic carbonates are more specifically described for instance in European patent application 0057360 A2 and international patent application WO 2007/055929. Their properties as monomers for polymer or copolymer formation are also disclosed in those documents as well as in international patent application WO 93/13154 A1 describing polycarbonates and mixed polycarbonates - polyesters. More recently, the synthesis and usage of spiro and ortho bis-cyclic carbonates have been described in international patent application WO the WO 2018/109714 A2. Another production method is described in the US patent 3,663,569 dated May 16th, 1972. Some specific use of fully substituted polyols with 4 hydroxyl groups, known as aprotic substituted cyclic carbonate molecules for the treatment of surface and interface of metallic or metalloid objects has been described in the previously filed documents PCT/IB2020/061143 and PCT/IB2020/058007.

The organic carbonates molecules described above are for example put into a solution of dialkyl diethyl ether deposited on the surface of a conductive or semiconductive surface and heated until the solvent evaporates, and a film is formed on the surface of the conductive or semiconductive surface of alkali metals, alkaline earth, metals, metalloids, lanthanides alone or in combination or alloys, with or without C, N, O, P, S and Se or polymer surfaces.

The measurement of the ohmic resistance on the various elements of the treated parts show the following results.

1 - The untreated contact points of the conducting or semiconducting surfaces show unmodified electric resistance between the measurement points.

2 - The conducting or semiconducting treated surfaces with the polycyclic carbonates s show on the surface contact points an ohmic resistance close to a perfect electrical isolator.

3 - The ohmic resistance between the internal part of the conducting or semiconducting element and the external portion of the polycyclic carbonates' treatment show a resistance value similar to the point 1 for all conducting o polycyclic carbonates semiconducting composition.

Feuilles de remplacements Regie 26 Example 1

3,75 g of pentaerythritol is introduced in a reactor containing 100 ml of diethylene glycol dimethyl ether and 50 ml of diethylene glycol diethyl ether. The reactor is heated at 160°C with agitation under a small current of nitrogen. When the reaction mixture is transparent, a solution of 2,1 equivalent of phenyl chloroformate dissolved in 120 ml of diethylene glycol diethyl ether is added drop wise over a period of time between 30 minutes and 4 hours, preferably around 2 hours. At the end of the adjunction, heating bath temperature is set to 190°C and a gentle distillation of the solvent is allowed. The distillation is carried until the vapour show the absence of acidity. The operation is carried over a period of about 12 hours. The reaction mixture is not allowed to go below 100 ml thanks to the adjunction of fresh diethylene glycol diethyl ether. The adjunction ranges from 20 to 200 ml, more particularly 110 ml, but this quantity depends on the flux of nitrogen applied into the system during the reaction.

At the end of the reaction time, the neutral reaction mixture is allowed to cool down. The clear solution of pentaerythritol phenyl carbonate is used as such for the treatment of the cupper electrode surface.

0,5 mg of pentaerythritol phenyl carbonate in diethylene glycol diethyl ether solution is applied on a 7,5 x 7,5 mm cupper surface. The cupper piece is dried and heated with an infrared source of 1100 W for 5 minutes. The pentaerythritol phenyl carbonate form a polycyclic-carbonate transparent film on the treated surface.

Conductivity measurements show that the film on the surface has a resistivity greater than 1012 Ohms/sqm. The measurement of the resistivity between the cupper mass of the treated piece and the surface of the formed film is zero with equipment used, similarly to the pure copper.

Example 2

A glass slide square of 2,5 x 2,5 cm coated with semiconductor Indium Tin Oxide and showing a resistance of 100 Ohms per sqm. Drops of the solution of the example 1 are used for spin coating of the semiconductor material. After heat drying and polymerisation with a 1100 W thermal source, a film is formed on the semiconductor. Surface resistivity is greater than 1012 Ohms/sqm. Resistivity between the internal ITO semiconductor and the external surface of the polycyclic carbonate is measured at 120 Ohms per sqm.

Example 3

100 mM of finely grounded Pentaerythritol is added to 350 ml anhydrous diethylene glycol diethyl ether. A solution of 202 mM of 2,2,2-Trichloethyl Chloroformate in anhydrous diethylene glycol dimethyl ether is added drop wise under agitation over a period of around 8 hours with a constant flow of Argon through the reactor. The mixture is heated between 160 and 170° C and stirred for 10 to 60 hours until the distillate does not contain HCI. Anhydrous diethylene glycol diethyl ether is added to keep the reaction volume around 300 - 350 ml.

The reaction mixture is cooled at around zero degree and the product 2,4,8, 10-tetraoxaspiro [5,5] undecane-3, 9-dione precipitates. It is filtered and washed diethyl ether.

We obtain around 75 mM of solid 2,4,8, 10-tetraoxaspiro [5,5] undecane-3, 9-dione. The product has a single 1H-NMR signal at 4.4 ppm in DMSO and C13-NMR signals at 147(s) (Carbonyl), 68.8(s) and 39.5(m) (Quaternary).

Feuilles de remplacements Regie 26 2,4,8, 10-tetraoxaspiro [5,5] undecane-3, 9-dione is made in a 2% solution with Propylene Glycol Carbonate. The solution is used as such for the spin coating of titanium oxide surface. The surface is allowed to dry for 5 minutes at 120°C allowing the monomer 2,4,8, 10-tetraoxaspiro [5,5] undecane- 3, 9-dione to form a polycyclic carbonate on the surface of the Titanium oxide. Measurements of the recombination rate at the interface are showing an 80 folds improvement in time resolution.

Example 4

The solution of the example 3 is applied with the same procedure to a LED visible light activated mesoporous Ti02.

The quantum yield of the device is improved by two.

Example 5

2, 4, 8, 10-tetraoxaspiro [5,5] undecane-3, 9-dione is made in a 2% solution with pyridine. The pyridine Bis-cyclic carbonate is applied to the perovskite surface with spin coating.

The device is allowed to dry and polymerize making a transparent film of polycyclic carbonate with very good protecting properties of the perovskite. The life of the device is increased by at least a factor two.

Example 6

A three necks reactor of 1.5 litre is fitted with a mechanical agitation, a short Vigreux column and a condenser. The reactor is blanketed with Argon, preheated at 80°C and loaded with 250 g of diglycerol, 8 g of sodium carbonate and 550 ml of diethyl carbonate. The agitation with anker is set at 3'500 rpm and the temperature under Argon increased to 125°C with the oil bath. After 3 hours, the theoretical ethanol has distilled and is collected. The reaction mixture is allowed to cool down for crystallisation for 18h. The product is filtrated and recrystallize in Ethyl acetate - Methanol.

A 0.5% solution of the product in diethoxy diethyl ether is made. The solution is applied on the surface of an ITO treated transparent conductive glass with a blade technique. The surface is allowed to polymerize and dry at 175°C in a ventilated oven. The treated surface has a ohmic resistance reduced by 30% from its original value.

Example 7

A three necks reactor of 1.5 litre is fitted with a mechanical agitation, a short Vigreux column and a condenser. The reactor is blanketed with Argon, preheated at 90°C and loaded with 180 g of triglycerol, 5 g of sodium carbonate and 500 ml of diethyl carbonate. The agitation with anker is set at 3750 rpm and the temperature under Argon increased to 130°C with the oil bath. After 3 hours, the theoretical ethanol has distilled and is collected. The reaction mixture is allowed to cool down to 105°C and vacuum is applied to further distillate 200 ml of the remaining diethyl carbonate.

The cold reaction media is diluted with two times its volume of Chloroform. The solution is extracted two time with its volume of water. The organic phase is dried at 45°C under vacuum (25 mbar). The product is an oil with two identical carbonyl FTIR peaks at 1780 and 1739 nm typical of respectively C5 cyclic and linear carbonates. The hydroxyl peak has fully disappeared.

A 2% DMSO solution of the product is prepared with the adjunction of finely grounded 0.15% and 0.05% of Lithium carbonate, Lithium iodide. The solution is applied on the surface of a NMC cathode and dried under vacuum at 160°C for 10 minutes. The cathode can work in cycling experiments with 5 volts potential without degradation of the LiPF6 electrolyte mixture.

Feuilles de remplacements Regie 26

Claims

1- Use of organic carbonated molecules for the production of anisotropic conductive polycyclic carbonates.

2- Use according to claim 1 of organic carbonated molecules made from linear or cyclic polyols with X hydroxyl functions, X being an integer between 4 and 8, such as but not limited to carbonated erythritol, carbonated pentaerythritol, carbonated diglycerol, carbonated xylitol, carbonated triglycerol, carbonated sorbitol, carbonated mannitol, carbonated inositol, or carbonated anhydro-glucitol, to name some, forthe production of anisotropic conductive polycyclic carbonates.

3- Use of organic carbonated molecules made from linear, cyclic, or combination of linear and cyclic polycarbonates of claims 1 and 2 in which the number of cyclic carbonated functions is at least 2 molar equivalents.

4- Use of organic carbonated molecules of claim 3 in which the organic carbonated molecule is a combination of cyclic carbonates, with cycles of 5 or 6 atoms and linear mixed carbonates between the polyols and aryls, substituted aryls, alkyls, or substituted alkyls such as but not limited to phenyl, p-nitrophenyl, picryl, methyl, ethyl, t-butyl, trichloromethyl, trifluoromethyl, trichloroethane, trifluoroethane, allyl, vinyl, or imidazoline substituted or not.

5- Use of organic carbonated molecules of claim 3 with at least two cyclic carbonates functions, such as but not limited to 4- [(2-oxo-l,3-dioxolan-4-yl)methoxymethyl] - l,3-dioxolan-2-one ; 4,4a,8,8a-tetrahydro- [1,3] dioxino [5,4-d] [1,3] dioxin-2, 6-dione; bis (2-oxo-l,3-dioxolan-4-yl) methyl ethyl carbonate; ethyl [2-[ (2-oxo-l,3-dioxolan-4- yl) methoxy ]-l-[ (2-oxo-l,3-dioxolan-4-yl) methoxy methyl] ethyl] carbonate;

2,4,8, 10-tetraoxaspiro [5.5] undecane-3, 9-dione; 2,5,7, 10, 12-pentaoxatricyclo [7.4.0.0³'⁸] tridecane-6, 11-dione.

6- Use of organic carbonated molecules of claim 4 and 5 in a solution to be applied on alkali metals, alkaline earth, metals, metalloids, lanthanides alone or in combination or alloys, with or without C, N, O, P, S and Se or polymer surfaces. The organic carbonated molecule solution is heated at a temperature between 35°C and 350°C to form an anisotropic conductive polycyclic carbonate on the treated surface. 7- Use of organic carbonated molecules of claim 4 and 5 applied on alkali metals, alkaline earth, metals, metalloids, lanthanides alone or in combination or alloys, with or without C, N, O, P, S and Se or polymer surfaces by known dry powder coating techniques such as but not limited to electro deposition, chemical vapor deposition, plasma or other assisted chemical or physical deposition technologies and heated at a temperature between 35°C and 350°C to form an anisotropic conductive polycyclic carbonate on the treated surface.

8- Objects treated according to the claims 6 and 7 which are light and electroluminescent display elements, such as screen, solid or flexible, or integrated circuits, electronic circuits and their electromagnetic protection, or corrosion inhibitors, or batteries, such as but not limited to lithium ions and their anodes and cathodes, or electrodes, such as anodes and cathodes useful for the production of hydrogen, oxygen or the conversion of gases such as carbon dioxides, monoxide, or fuel cells, or light emitting diodes and Organic light emitting diodes, or solar energy conversion elements such as perovskite, silicon panel, or transistors, field effect transistor, or anti-static coating, and anti-radar detection surface treatment, or memories and quantum dots memories, or purely organic electronic components made in combination with PEDOT, polyaniline, poly(thiophene), poly(pyrrole), poly(phenylene vinylidene), polyethylene dioxy thiophene) to name some known intrinsic conducting polymers.

9- Object according to the claim 8 forming purely organic transistors, memories, quantum dots memories, display and tactile display elements, solar energy harvesting elements, batteries, electrodes, or any novel p-n organic electronic devices with the combination of electron transporting elements made of the polycyclic carbonates of the present invention and hole transporting elements based on PEDOT, polyaniline, poly(thiophene), poly(pyrrole), poly (phenylene vinylidene), poly (ethylene dioxy thiophene) to name some.