EP1879965A2

EP1879965A2 - Method for further processing the residue obtained during the production of fullerene and carbon nanostructures

Info

Publication number: EP1879965A2
Application number: EP06754848A
Authority: EP
Inventors: Nicolas Probst; Frédéric Fabry; Thomas GRÜNBERGER; Eusebiu Grivei; Laurent Fulcheri; José GONZALEZ-AGUILAR
Original assignee: Imerys Graphite and Carbon Switzerland SA
Current assignee: Imerys Graphite and Carbon Switzerland SA
Priority date: 2005-04-26
Filing date: 2006-04-25
Publication date: 2008-01-23
Also published as: CA2606031A1; WO2006114419A3; EA200702333A1; DE102005019301A1; WO2006114419A2; JP2008539152A; MX2007013303A; US20080279749A1; BRPI0610766A2; AU2006239347A1; KR20080005577A; TW200708476A; CN101248143A

Abstract

The invention relates to a method for further processing the carbon-containing residue obtained during the production of fullerene and carbon nanostructures. The inventive method is characterized in that the residue is functionalized by introducing chemical substituents while said functionalization is done during or following the production. Also disclosed are the functionalized carbon-containing residue obtained according to said method and the use thereof as a hydroxylating agent, a wetting agent, an additive in rubber compounds, and for tether-directed remote functionalization.

Description

Timcal S.A.

Process for the further processing of the residue resulting from fullerene and carbon nanostructure production

Field of the invention

The present invention relates to a process for the further processing of the carbonaceous residue from the fullerene and carbon nanostructure production, the processed residue and its use.

Brief description of the prior art

The fullerenes C ₆₀ and C ₇₀ , carbon compounds with both 6- and 5-membered closed-cage rings and an even number of carbon atoms, were first reported by Kroto et al. in carbon vapor obtained by laser irradiation of graphite, a carbon evaporation technique has been described (Nature 318 (1985), 162-164). Since then, the number of known fullerenes has increased rapidly, encompassing C ₇₆ , C ₇₈ , C ₈₄ and larger structures including "giant fullerenes" characterized by C _n with n> 100, nanotubes and nanoparticles, and carbon nanotubes show promise Applications including nano-scale electronic devices, high-strength materials, electronic field emission, scanning probe microscopy tips, and gas storage. The preparation of fullerenes is described inter alia in the following patents: US Pat. No. 6,358,375; 5, US 177,248; US 5,227,038; 5, 275, 705; US 5,985,232. At present, five major possibilities for the synthesis of carbon nanotubes are known. These include laser ablation (laser ablation) of carbon (Thess, A. et al., Science 273 (1996), 483, the arc discharge of a graphite rod (Journet C. et al., Nature 388 (1997), 756, Chemical Vapor Deposition of Hydrocarbons (Ivanov, V. et al., Chem. Phys. Lett 223, 329 (1994), Li, A. et al., Science 274, 1701 (1996)), the Solar Method (Fields, Clark L. , et al, US Pat. No. 6,077,401), and plasma technology (European Patent Application EP0991590).

The production of multiwall carbon nanotubes by catalytic cracking of hydrocarbons is described in U.S. Patent No. 5,578,543. The preparation of single-wall carbon nanotubes by laser techniques (Rinzler, AG et al., Appl. Phys. A. 67, 29 (1998)) and, arch techniques (Haffner, JH et al., Chem. Phys. Lett. 296, 195 (1998)) is described.

U.S. Patent No. 5,985,232 relates to a process for producing fullerene nanostructures which comprises combusting an unsaturated hydrocarbon and oxygen in a non-arc discharge combustion chamber at reduced pressure to produce a flame, collecting the condensable portions of the flame, wherein the condensable parts include fullerene nanostructures and carbon black, and comprising separating the fullerene nanostructures from the carbon black. The obligatory separation of the fullerene structures from the carbon black can be carried out by known extraction and purification methods. These include simple and Soxhlet extraction in solvents of different polarity. The condensable parts may also be carried out by electrostatic separation techniques or by inert separation using aerodynamic forces. Furthermore, HPLC is described as suitable for the separation and purification of the fullerene structures. The US '232 is no further processing of the resulting in fullerene production carbonaceous residue to remove.

Similar structures were found by Donnet and coworkers at Furnacerußen. However, at Furnacerußen, these fullerene-like structures rarely occur and in most cases only to a very limited extent.

Summary of the invention

The present invention provides a process for further processing the carbonaceous residue from fullerene and carbon nanostructure production, characterized in that the residue is functionalized by incorporation of chemical substituents.

The inventors of the present invention have found that the carbonaceous residue obtained upon fullerene or carbon nanostructure fabrication has valuable properties after functionalization. Specifically, it is shown in the examples that gum / carbon black / silane compounds made with the functionalized residue of this invention have typical behavior for low roll loss blends versus rubber compounds made with known carbon blacks.

Figure 1 shows a TEM image of a fullerene residue obtained from a plasma process. We clearly see the total coverage of the soot surface by fullerene-like carbon layers. These fullerene structures are most likely obtained by condensing fullerenes, fullerene precursors or fullerene condensates during or after the quenching phase. Figure 2 shows a graph describing the evolution of the cross-linking isotherm of the mixtures over time. The functionalized fullerene black clearly shows the strong interaction between carbon black and polymer compared to normal carbon black.

Figure 3 shows the dependency of tan delta on temperature for different rubber compounds. The mixture containing the fullerene black shows an identical behavior as the mixtures based on silicic acid. The reference carbon black shows the typical soot behavior, high tan delta values at high temperatures and low tan delta at low temperatures.

Figure 4 shows the module as a function of the temperature. Again, we see a complete overlay of results achieved with the silica mixtures.

Below are some terms to be defined as they should be understood in connection with the following invention.

"Carbonaceous residue from fullerene and carbon nanostructure production" means a residue that contains a substantial proportion of fullerene-like nanostructures, and the proportion of fullerene-type carbon compounds is determined by the presence of 5- or 6-membered carbon rings that form curved layers The proportion of fullerene-like carbon nanostructures is usually close to 100%, but may be less, but the need to allow functionalization that produces a significant change in the properties of the carbon black is preferred the proportion of 80% to 100%, however, this preferred proportion may change with the application.

Detailed description of the invention In principle, all known processes for fullerene and / or carbon nanostructure production are suitable for obtaining the carbonaceous residue. Furnace carbon black, or carbon blacks according to other methods are also suitable, provided that the fullerene-like residues on the surface are sufficient.

According to a preferred embodiment, the carbonaceous residue is obtained by ablation of a carbon electrode by means of an arc, laser or solar energy. A method described for arc ablation is available from Journet, C. et al., Nature 388 (1997), 756. A method suitable for laser ablation of carbon and to obtain a carbonaceous residue is described in Thess, A. et al., Science 273 (1996), 483. A process suitable for the preparation of a carbonaceous residue by chemical vapor deposition of hydrocarbons is described in Ivanov et al., Chem Phys. Lett. 223, 329 (1994). A manufacturing process using plasma technology is described in Taiwanese Patent Application No. 93107706. A solar energy process suitable for the preparation of a carbonaceous residue is described in Fields et al., US Pat. 6,077,401.

The carbonaceous residue can be obtained by incomplete combustion of hydrocarbons. For example, fullerene production was observed in flames of premixed benzene / acetylene (Baum et al., Ber. Bunsenges Phys., Chem., 96 (1992), 841-847.) Other examples of the preparation of a carbonaceous residue are suitable hydrocarbons for combustion ethylene, toluene, propylene, butylene, naphthalene, or other polycyclic aromatic hydrocarbons, especially petroleum, heavy oil, and tar, may also be used, and materials derived from coal, kerogen, and biomass, which mainly contain hydrocarbons, may be used, as well as other elements Nitrogen, May contain sulfur and oxygen. A particularly preferred process for the combustion of hydrocarbons is described in US 5,985,232.

According to a further preferred embodiment, the carbonaceous residue can be obtained by treating carbon powder in a thermal plasma in addition to fullerenes. Alternatively, the carbonaceous residue can be obtained by recondensation of carbon in an inert or partially inert atmosphere.

For example, PCT / EP94 / 03211 describes a process for converting carbon in a plasma gas. Fullerenes and carbon nanotubes can also be made by this method.

Preferably, the carbonaceous residue is prepared by the following steps, preferably in this order:

^■ A plasma is generated with electrical energy.

^■ A carbon precursor and / or one or more contact substances or catalysts and a carrier plasma gas are introduced into a reaction zone. This reaction zone is optionally in an airtight high temperature resistant vessel.

^■ The carbon precursor is preferably vaporized at a temperature of 4000 ° C or higher in part at very high temperatures in this vessel.

^■ The carrier plasma gas, the vaporized carbon precursor and the contact material are passed through a nozzle whose diameter is in the direction of the

Plasma gas flow narrows, expands or remains constant

^■ The carrier plasma gas, vaporized carbon precursor and contact material are passed through the nozzle into a quench zone for nucleation, growth and quenching. This quench zone is operated under flow conditions operated by aerodynamic and electromagnetic forces such that there is no appreciable return of feedstock or products from the quench zone to the reaction zone.

■ The gas temperature in the quench zone is controlled between about 4000 ° C in the upper part of this zone and about 800 ° C in the lower part of this zone.

^■ The carbon precursor used may be a solid carbon material comprising one or more of the following materials: carbon black, acetylene black, thermal black, graphite, coke, plasma carbon nanostructures, pyrolitic carbon, carbon airgel, activated carbon, or any other solid carbon material.

^■ Alternatively, the carbon precursor used may be a hydrocarbon, which preferably consists of one or more of the following: methane, ethane, ethylene, acetylene, propane, propylene, heavy oil, waste oil, pyrolysis fuel oil or any other liquid carbon material. The carbon precursor may also be any organic molecule, for example

Vegetable fats such as rapeseed oil.

^■ The gas that produces a carbon precursor and / or plasma includes and consists of one or more of the following gases: hydrogen, nitrogen, argon, helium, or any other pure carbon-free gas that is preferably oxygen-free.

With regard to further process variants, reference is made to WO04 / 083119, the disclosure of which is hereby incorporated by reference.

Particularly preferred is the carbon, carbon black, graphite, another carbon allotrope or a mixture thereof.

According to the invention, the carbonaceous residue obtained in the fullerene and / or carbon nanostructure production by introducing chemical Functionalized substituents. The functionalization reactions can be carried out during or after the preparation.

The functionalization reactions comprise one or more of the following reactions:

^■ hydroxylation of the residue, preferably by an oxidizing agent, more preferably the oxidizing agent is potassium permanganate.

■ Reacting the residue with ammonia to give amino groups.

■ Reaction of the residue with alkyl or arylamines. ■ Reaction of the residue with ozone to form ozonides and subsequently carbyl compounds.

^■ Treatment of the residue with a halogenating agent, preferably the halogenating agent is chlorine or bromine.

■ Subjecting the residue of a cycloaddition reaction. ■ subjecting the residue to a Grignard reaction.

^■ Hydrogenation of the residue.

■ Subjecting the residue of an electrochemical reaction.

■ subject the residue to a Diels-Alder reaction.

■ Formation of donor-acceptor molecular complexes. ■ In addition to the above reactions, all are still in the

Technique known functionalization reactions in connection with fullerenes suitable.

According to another aspect of the present invention there is provided the functionalized carbonaceous residue obtainable by the process of the invention.

The functionalized carbonaceous residue is useful as a hydroxylating agent. The functionalized carbonaceous residue is also useful as a wetting agent in aqueous systems.

Another application of the functionalized carbonaceous residue is in the reaction with silanes. The inventively iunktionalisierte residue know a similar behavior as silica in rubber compounds. As can be seen from the example, the residue when used in rubber compounds inversion of the loss tangent in the temperature range of -30 ° C to 100 ° C. This feature allows use in tire treads where better low temperature adhesion and reduced rolling resistance at higher temperatures is desired.

Another application of the functionalized carbonaceous residue is as a modifier by the tethered remote functionalization. In this way, rotaxanes, catenanes, ion sensors and porphyrin conjugates can be made that are otherwise difficult to access.

Furthermore, the functionalized carbonaceous residue can be used for condensing amines with organic acids.

Another use of the functionalized carbonaceous residue is with regard to cycloaddded products. The functionalized carbonaceous residue can be used here for the polymerization of, for example, cyclopentadiene.

The following examples illustrate the subject matter of the invention but are not intended to limit its scope. Rather, other embodiments of the present invention will become apparent to those skilled in the art directly from the present disclosure. Examples

example

Four formulations, two of which are based on silicic acid with 50 and 80 parts each, a mixture with the reference carbon black, which is used in fullerene production as a carbon precursor and the mixture with the hydroxylated fullerene residue.

Mixture preparation The mixtures were produced in four stages on a measuring mixer system "Haake Polylab Rheomix 600" and on a laboratory rolling mill.

Stage 1: Basic mixing stage (measuring mixer)

Stage 2: Remill stage 1 (measuring mixer)

Stage 3: Remill stage 2 (measuring mixer)

Stage 4: Mixing up sulfur and accelerators (rolling mill) Between the individual stages, the mixture skins were stored at room temperature for 24 h. The reached batch temperatures in the first 3 stages were between 150 and 160 ° C. The parameters of the mixture preparation are as follows:

step 1

Kneading degree: 70%

Preheating: 140 ° C Rotor speed: 50 rpm Mixing time: 10 minutes

Level 2

Kneading degree: 70%

Preheating: 140 ° C

Rotor speed: 50 rpm

Mixing time: 8 - 10 minutes

level 3

Kneading degree: 70%

Preheating: 140 ° C Rotor speed: 100 rpm Mixing time: 8 - 10 minutes

Level 4

Roll temperature: cooled

Roller speed: 16:20 rpm

Mixing time: 7 minutes

vulcanization 2 mm thick test panels were vulcanized at 160 ° C. The vulcanization time was tgo + 2 minutes.

results

Rheometer data at 160 ° C

The mixture based on the hydroxylated fullerene residue shows the same image in Figure 3 as the silica mixture. Compared to the reference soot, we observe a spectacular increase in the loss tangent at low temperatures and a noticeably lower tangent at higher temperatures.

Claims

claims

1. A process for the further processing of the carbonaceous residue from the fullerene and carbon nanostructure production, characterized in that the residue is functionalized by introducing chemical substituents and the functionalization during or after the

Manufacturing is performed.

2. The method of claim 1, wherein the carbonaceous residue by

Ablation of a carbon electrode by means of arc, laser or solar energy is obtained

3. The process of claim 1, wherein the carbonaceous residue is obtained by incomplete combustion of hydrocarbons.

4. The method of claim 1, wherein the carbonaceous residue is obtained by treating carbon powder in a thermal plasma.

5. The method of claim 1, wherein the residue is obtained by recondensation of gaseous carbon in an inert or partially inert atmosphere.

6. The method of claim 4, wherein the carbon is carbon black, graphite, another carbon allotrope, or a mixture thereof.

7. The method according to any one of claims 1 to 6, wherein the residue is hydroxylated.

8. The method of claim 7, wherein the hydroxylation is carried out by means of an oxidizing agent.

The method of claim 8, wherein the oxidizing agent is potassium permanganate.

10. The method according to any one of claims 1 to 6, wherein the residue is reacted with ammonia to obtain amino groups.

11. The method according to any one of claims 1 to 6, wherein the residue is reacted with alkyl or arylamines.

12. The method according to any one of claims 1 to 6, wherein the residue is reacted with ozone to obtain ozonides and further carbyl compounds therefrom.

13. The method according to any one of claims 1 to 6, wherein the residue with a

Halogenating agent is treated.

14. The method of claim 13, wherein the halogenating agent is chlorine or bromine.

15. The method according to any one of claims 1 to 6, wherein the residue is subjected to a cycloaddition reaction.

16. The method according to any one of claims 1 to 6, wherein the residue is subjected to a Grignard reaction.

17. The method according to any one of claims 1 to 6, wherein the residue is hydrogenated.

18. The method according to any one of claims 1 to 6, wherein the residue is subjected to an electrochemical reaction.

19. A process according to any one of claims 1 to 6, wherein the residue is subjected to a Diels-Alder reaction.

20. The method according to any one of claims 1 to 6, wherein donor-acceptor molecular complexes are formed.

21. The method according to any one of claims 1 to 6, wherein the residue is in principle exposed to all fullerene reactions.

22. A functionalized carbonaceous residue obtainable by one of the processes of claims 1 to 20.

23. Use of the functionalized carbonaceous residue according to claim 22 as a hydroxylating agent.

24. Use of the functionalized carbonaceous residue according to claim 22 as a wetting agent in aqueous systems.

25. Use of the functionalized carbonaceous residue according to claim 22 as an additive in rubber compounds.

26. Use of the functionalized carbonaceous residue according to

Claim 22 for tether-directed remote functionalization.

27. Use of the functionalized carbonaceous residue according to claim 22 for the condensation of amines with organic acids.

28. Use of the functionalized carbonaceous residue according to claim 22 in a cycloaddition reaction.