WO2015184843A1 - 从有机材料制备磺化石墨烯的方法以及磺化石墨烯 - Google Patents

从有机材料制备磺化石墨烯的方法以及磺化石墨烯 Download PDF

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WO2015184843A1
WO2015184843A1 PCT/CN2015/072176 CN2015072176W WO2015184843A1 WO 2015184843 A1 WO2015184843 A1 WO 2015184843A1 CN 2015072176 W CN2015072176 W CN 2015072176W WO 2015184843 A1 WO2015184843 A1 WO 2015184843A1
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sulfonated graphene
temperature
graphene
reaction medium
organic material
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French (fr)
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蒋永华
栗建民
郝建东
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Suzhou Graphene-Tech Co Ltd
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Suzhou Graphene-Tech Co Ltd
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Priority to US15/315,422 priority Critical patent/US10233086B2/en
Priority to CN201580002367.XA priority patent/CN105764839B/zh
Priority to KR1020167033779A priority patent/KR101972436B1/ko
Priority to JP2017514764A priority patent/JP6377843B2/ja
Priority to EP15802712.8A priority patent/EP3138809B1/en
Publication of WO2015184843A1 publication Critical patent/WO2015184843A1/zh
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Definitions

  • the present invention relates to a method for producing graphene, and in particular to a method for producing a sulfonated graphene from an organic material, particularly an organic polymer material or an organic small molecule material such as a hydrocarbon, and a sulfonated graphene.
  • the present invention provides a novel process for the preparation of sulfonated graphene, and sulfonated graphene prepared by the process.
  • the present invention includes the following:
  • Embodiment 1 A method of preparing a sulfonated graphene from an organic material, the method comprising the steps of:
  • Second contacting step after the end of the first contacting step, the reaction temperature is raised to a second temperature in the same reaction medium to continue the reaction, thereby obtaining the sulfonated graphene.
  • Embodiment 2 The method of Embodiment 1, wherein the oxidizing sulfonating agent is selected from the group consisting of: a compound of the formula R-SO 3 H, wherein R is selected from the group consisting of F, Cl, Br; a combination of H 2 SO 4 and HCl; a combination of H 2 SO 4 and HF; concentrated sulfuric acid; fuming sulfuric acid; and combinations thereof,
  • the oxidizing sulfonating agent is selected from the group consisting of: a compound of the formula R-SO 3 H, wherein R is selected from the group consisting of F, Cl, Br; a combination of H 2 SO 4 and HCl; a combination of H 2 SO 4 and HF; concentrated sulfuric acid; fuming sulfuric acid; and combinations thereof,
  • the concentration of the oxidizing sulfonating agent in the reaction medium is greater than 98%.
  • Embodiment 3 The method of Embodiment 1, wherein the first temperature is a melting temperature of the organic material to be lower than a boiling point of the reaction medium, and the second temperature is above a boiling point of the reaction medium; preferably Wherein the first temperature is 40-130 ° C; and the second temperature is 150-220 ° C.
  • Embodiment 4 The method of Embodiment 1, wherein the first contacting step is performed for a period of from 1 hour to 40 hours; and the second contacting step is performed for a period of from 1 hour to 40 hours.
  • Embodiment 5 The method of Embodiment 1, wherein the organic material is selected from the group consisting of an organic polymer material and an organic small molecule material, wherein preferably, the organic polymer material is selected from the group consisting of polyethylene wax, chlorinated polyethylene, and acetylene.
  • the material is selected from a C 4 - C 30 linear hydrocarbon or an aromatic hydrocarbon having a benzene ring structure.
  • Embodiment 6 The method of Embodiment 1, wherein the organic material has a crystallinity of: 0-30%, or 20-40%, or 50-80%, or 60%-90%; molecular weight of the organic material It is: 50 to 50,000, preferably 50 to 10,000.
  • Embodiment 7 The method of Embodiment 1, wherein the weight ratio of the organic material to the reaction medium is from 5:1 to 1:500, preferably from 1:3 to 1:70.
  • Embodiment 8 A sulfonated graphene, wherein the sulfonated graphene has a sulfonic acid group, wherein the sulfonated graphene has a carbon/sulfur ratio of from 12:1 to 1:1. It is preferably 10:1 to 2:1; more preferably 8:1 to 3:1, most preferably 6:1 to 3:1.
  • Embodiment 9 The sulfonated graphene of embodiment 8, wherein the sulfonated graphene has a chip diameter (planar diameter of the material) of greater than 10 micrometers, preferably greater than 50 micrometers, more preferably greater than or equal to 100 micrometers to less than 1000 micrometers
  • the thickness is from 0.5 to 100 nm, preferably from 1 to 50 nm, preferably from 1 to 10 nm; preferably, the thickness of the sulfonated graphene (distance in the normal direction of the material plane) is more than 90%; preferably,
  • the sulfonated graphene has a film diameter of more than 90%.
  • Embodiment 10 The sulfonated graphene of Embodiment 8 or 9 in a transparent conductive electrode, a heat conductive material, a super capacitor, a transistor, a fuel cell, an integrated circuit, a solar cell, a bioburden, a complexing agent, a composite material, a chelating agent, and a water-based Use in coatings, waterborne lubrication, mobile equipment, aerospace materials, inks or photosensitive elements.
  • 1 and 2 are respectively scanning electron microscope images of sulfonated graphene prepared by the present invention, which shows The advantages of the sulfonated graphene powders produced by the process of the invention.
  • Organic material Also known as organic material, it has the meaning generally understood by those skilled in the art. They have few constituent elements, mainly carbon and hydrogen, and optionally other elements such as oxygen or nitrogen, and the relative molecular mass may be several tens, and the large one may be several million. Organic materials include organic polymeric materials and organic small molecular materials. An organic polymer material is a compound that is repeatedly linked by one or several organic structural units.
  • Common organic materials include: polyolefins (such as polyethylene, polypropylene, polyvinyl chloride, polydichloroethylene, polybutene, polyethylene-octene copolymer, polytetrafluoroethylene), polyacetylene (such as polyacetylene) ), polyester (such as polyethylene terephthalate, polybutylene terephthalate), polyether (such as polyphenylene ether), polyetheretherketone, polyamide (such as nylon), polyurea Butane, butene, hexane, octane, octene, benzene, and the like.
  • polyolefins such as polyethylene, polypropylene, polyvinyl chloride, polydichloroethylene, polybutene, polyethylene-octene copolymer, polytetrafluoroethylene
  • polyacetylene such as polyacetylene
  • polyester such as polyethylene terephthalate, polybutylene ter
  • Sulfonated graphene A two-dimensional material similar to graphene oxide and graphene, chemically bonded to a carbon material having a sulfonic acid or sulfonate functional group.
  • the terms "sulfonated graphene”, “sulfonated carbon material” or “sulfonate-functional carbon material” have similar meanings and may be used interchangeably. Applicants of the present invention have found that the sulfonated graphene of the present invention retains the layered structure of graphite, but introduces a plurality of sulfonate functional groups on the graphene monolith of each layer.
  • the layered structure of the sulfonated graphene of the present invention may have a thickness of from 1 to 300 nm, preferably from 1 to 200 nm, for example from 1 to 100 nm, for example from 1 to 50 nm, for example from 1 to 40. Nano, for example 1-30 nm, such as 3-20 nm, such as 3-15 nm, such as 5-10 nm.
  • Oxidizing sulfonating agent an oxidizing sulfonating agent.
  • the oxidizing and sulfonating properties in the oxidizing sulfonating agent may be provided by different substances, for example, one substance provides oxidative properties, and one substance provides sulfonation.
  • a typical oxidizing sulfonating agent is selected from the group consisting of compounds of the formula R-SO 3 H wherein R is selected from the group consisting of F, Cl, Br; a combination of H 2 SO 4 and HCl; a combination of H 2 SO 4 and HF; concentrated sulfuric acid ; fuming sulfuric acid; SO 3 ; and combinations thereof.
  • the reaction medium mainly refers to a combination of an oxidizing sulfonating agent and an optional solvent.
  • the solvent may be an organic solvent such as methyl chloride or ethanol, or an inorganic solvent such as hydrogen chloride.
  • the melting temperature as used herein refers to the melting point, Tg (glass transition temperature), or melting range of the organic material used in the present application when it is contacted with a reaction medium as described herein.
  • Tg glass transition temperature
  • melting range of the organic material used in the present application when it is contacted with a reaction medium as described herein.
  • the chip diameter of the sulfonated graphene refers to the plane diameter of the sulfonated graphene material.
  • Thickness of sulfonated graphene refers to the distance in the normal direction of the plane of the sulfonated graphene material.
  • Uniformity defines the density distribution within the range and thickness range. Therefore, there are two kinds of indices, one is the uniformity of the diameter and the uniformity of the thickness. Of course, for a product, the uniformity and thickness of the film are often It is the same, or the same.
  • the calculation method of uniformity is as follows: the chip diameter and the thickness are divided into 10 sections according to the size. Taking the chip diameter as an example, the prepared products are distributed at 1-100 micrometers, and the interval is distributed every 10 micrometers. That is, the degree of uniformity, if the prepared sample accounts for 80% of the density distribution of the prepared product at 70-80 micrometers, it can be said that the batch has a diameter of 70-80 micrometers and a uniformity of 80%.
  • a first aspect of the invention relates to a method of preparing a sulfonated graphene from an organic material, the method comprising the steps of:
  • Second contacting step after the end of the first contacting step, raising the temperature of the entire system to a second temperature to continue the reaction, thereby obtaining the sulfonated graphene.
  • the process of the invention is carried out in the same reaction medium.
  • the first temperature is preferably higher than the melting point of the organic material, in which case the organic material is in an amorphous molten state (if the organic material is present in solution in the reaction medium, it will also It is considered to be in an amorphous state.
  • the organic material is oxidized to a carbon material such as a bulk carbon having a certain size or a prototype of graphene, and a small amount of carbon is sulfonated. Since the carbon material formed in this first step is formed from an organic material in an amorphous state, the carbon material itself is very loose, such as when the state is a bulk carbon material, the number of layers of the graphene layer is small. .
  • the second temperature is preferably the boiling point of the reaction medium or High, at this time, the carbon material formed in the first step is sulfonated, and since the reaction temperature is relatively high, the reaction speed is fast, and sulfonation also occurs between the formed carbon materials such as graphite or graphene sheets. In this case, a sulfonated graphene product is formed.
  • the organic material used in the present invention is selected from the group consisting of an organic polymer material and an organic small molecule material, wherein preferably, the organic polymer material is selected from the group consisting of polyethylene wax, chlorinated polyethylene, acetylene oligomer, polyacetylene, a polyhalogenated alkyne (a halogen-containing polyalkyne), a polyethylene, a polyvinyl chloride, a polyhalogenene (a halogen-containing polyolefin); wherein preferably, the organic small molecule material is selected from the group consisting of C 4 To C 50 linear or aromatic hydrocarbons, such as C 8 -C 30 linear hydrocarbons, C 4 to C 50 olefins or alkynes, benzene or hydrazine or phenanthrene.
  • the organic polymer material is selected from the group consisting of polyethylene wax, chlorinated polyethylene, acetylene oligomer, polyacetylene, a polyhalogenated
  • the organic polymer material may have a molecular weight of from 200 to 50,000, such as from 500 to 40,000, such as from 1,000 to 30,000, such as from 2,000 to 20,000, such as from 3,000 to 15,000, such as from 4,000 to 12,000, such as from 5,000 to 11,000, such as from 6,000 to 10,000, for example 7000 to 9000, such as 8000 to 8500.
  • Polyethylene waxes having a molecular weight of between 3,000 and 10,000 are particularly suitable because such polyethylene waxes have a melting point between 90 and 110 ° C, are particularly suitable for operation, and have a wide range of raw materials.
  • the organic small molecule material is preferably a hydrocarbon compound such as an olefin or an alkyne or an aromatic hydrocarbon, preferably a C 4 to C 50 linear hydrocarbon such as a C 4 to C 50 alkane, an alkene or an alkyne, wherein the range C 4 to C 50 contain endpoints and cover all subranges therein, such as C 5 to C 40 , C 6 to C 45 , C 8 to C 30 , C 10 to C 25 , C 12 to C 20 , or C 14 to C 18 .
  • the molecular weight of the organic small molecule material may range from 50 to 800, such as from 80 to 700, such as from 100 to 500, such as from 150 to 300, such as from 200 to 250.
  • the organic small molecule material may still contain atoms other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, etc., but preferably the small molecule material contains only a nitrogen atom as a hetero atom, more preferably Contains no heteroatoms.
  • the first temperature used in the first contacting step is a melting temperature of the organic material to below a boiling point of the reaction medium, and the second temperature is above a boiling point of the reaction medium.
  • the choice of the first temperature depends on factors such as the melting temperature of the organic material, the boiling point of the reaction medium, and the desired reaction rate.
  • the first reaction temperature is between the melting temperature of the organic material and the boiling point of the reaction medium. The first temperature is selected such that the organic material is in an amorphous state, making it easy to form a loose carbon material for further sulfonation and delamination in the second contacting step, and obtaining a suitable reaction rate without causing a reaction Too intense and create security problems.
  • the first temperature can be selected to be relatively low, such as less than 100 ° C, such as less than 90 ° C, such as less than 80 ° C, such as less than 70 ° C, such as less than 60 ° C, such as less than 50 °C, often at less than 40 ° C, or lower temperatures such as less than 35 ° C, less than 30 ° C, less than 20 ° C, less than 15 ° C, less than 10 ° C, less than 5 ° C, or even less than 0 ° C.
  • the first temperature can be chosen to be higher because the melting temperature is often higher.
  • the first temperature is 40-140 ° C, such as 45 ° C to 130 ° C, such as 50 ° C to 125 ° C, such as 55 ° C to 120 ° C, such as 60 ° C to 115 ° C, such as 65 ° C to 110 ° C, for example 70 ° C to 105 ° C, such as 65 ° C to 100 ° C, such as 75 ° C to 95 ° C, such as 80 ° C to 90 ° C.
  • the second temperature is above the boiling point of the reaction medium.
  • the second reaction temperature is preferably the boiling point of the reaction medium or a higher temperature.
  • the second temperature is selected such that a layered sulfonated graphene sheet of uniform nature is formed in the second contacting step.
  • the concentration of the oxidizing sulfonating agent in the reaction medium is higher than 98%, more preferably higher than or equal to 99%, and most preferably 100% (i.e., the reaction medium is It is an oxidizing sulfonating agent).
  • the boiling point of chlorosulfonic acid is 151 ° C
  • the boiling point of fluorosulfonic acid is 163.5 ° C
  • the boiling point of sulfuric acid is 338 ° C.
  • the boiling point of the reaction medium is close to the boiling point of the oxidizing sulfonating agent under conditions of a high content of oxidizing sulfonating agent.
  • the boiling point of the medium may vary due to the dissolution of the solute in the reaction medium or the use of a mixed oxidizing sulfonating agent.
  • the second temperature is 150-220 ° C, such as 155-215 ° C, such as 160-210 ° C, such as 165-205 ° C, such as 170-200 ° C, such as 175-195 ° C, such as 180 -190 ° C.
  • the boiling point of the reaction medium is preferably higher than the melting temperature of the organic material, or the melting temperature of the organic material is lower than the boiling point of the reaction medium.
  • the boiling point of the reaction medium is higher than the melting temperature of the organic material by 10 ° C or higher, preferably 20 ° C or higher, preferably 30 ° C or higher, preferably 40 ° C or higher.
  • the process of the present invention is carried out under normal pressure, and therefore, unless otherwise stated to the contrary, the melting temperature and boiling point, etc. described in the present invention are all values measured under normal pressure. .
  • the present invention also contemplates that the process of the present invention can be carried out under high pressure or under vacuum (e.g., at a pressure of 1 kPa, 5 kPa, 10 kPa, 20 kPa, 50 kPa, etc.).
  • the second temperature of the second contacting step can be appropriately increased depending on the conditions and needs of the reaction.
  • the second temperature of the second contacting step can be appropriately lowered depending on the conditions and needs of the reaction.
  • the first contacting step is performed at a non-atmospheric pressure, the first temperature may also vary depending on the situation.
  • the time of the first contacting step and the second contacting step is not particularly limited as long as the object of the present invention can be achieved.
  • the first contacting step is carried out for a period of from 1 hour to 40 hours; and the second contacting step is carried out for a period of from 1 hour to 40 hours.
  • the range of 1 to 40 hours covers any value and subrange between 1 and 40 hours, such as 2 to 35 hours, 3 to 30 hours, 4 to 28 hours, 5 to 25 hours, 6 to 20 hours, 7 to 18 hours , 8 to 16 hours, 9 to 12 hours, 10 to 11 hours, and so on.
  • the organic material used in the present invention may have a certain degree of crystallinity at normal temperature and pressure.
  • the organic material has a crystallinity of 0-90%, such as 0-30%, or 20-40%, or 50-80%, or 60%-90%.
  • the organic material of the present invention has a crystallinity of 0-30%, or 0 to 15%, or 0-10%, or 0 to 5%.
  • the present inventors have found that an organic material is more favorable to rapidly reach an amorphous molten state above a melting temperature under conditions of low crystallinity, thereby facilitating formation of a loose carbon material. If the material having high crystallinity is not converted into a molten amorphous state in time, a protective layer to the internal material may be formed due to carbonization of the surface material, so that the organic material cannot be completely carbonized in the first contacting step.
  • the sulfonated graphene prepared by the method of the invention has a thickness of from 0.5 to 300 nm, such as from 1 to 200 nm, such as from 0.5 to 100 nm, preferably from 1 to 50 nm, such as from 1 to 20 nm, preferably from 1 to 10 nm.
  • the thickness of the produced sulfonated graphene can be controlled by adjusting the ratio of the reaction medium (or an oxidizing sulfonating agent such as chlorosulfonic acid or fluorosulfonic acid therein) to the organic material.
  • the weight ratio of the organic material to the reaction medium is from 1:1 to 1:500, preferably from 1:2 to 1:200, for example from 1:3 to 1:100, for example from 1:5 to 1:90.
  • 1:10 to 1:80, for example 1:20 to 1:70, for example 1:30 to 1:60, for example 1:40 to 1:50 is carried out in an excess amount in both the first contacting step and the second contacting step with an oxidizing sulfonating agent.
  • the amount of the reaction medium (or oxidizing sulfonating agent) is 60 times or more that of the organic material, sulfonated graphene having a thickness of 1-2 nm can be obtained, which corresponds to 1 to 2 layers of sulfonate.
  • the thickness of the graphene layer is preferred embodiment, when the amount of the reaction medium (or oxidizing sulfonating agent) is 60 times or more that of the organic material, sulfonated graphene having a thickness of 1-2 nm can be obtained, which corresponds to 1 to 2 layers of sulfonate. The thickness of the graphene layer.
  • the amount of the agent used is generally 100 times or less of that of the organic material. In a preferred embodiment, when the amount of the reaction medium (or oxidizing sulfonating agent) is 30 times to less than 60 times that of the organic material, sulfonated graphene having a thickness of 3-5 nm can be obtained. In a preferred embodiment, when the amount of the reaction medium (or oxidizing sulfonating agent) is from 20 times to less than 30 times that of the organic material, sulfonated graphene having a thickness of 5 to 10 nm can be obtained.
  • the amount of the reaction medium (or oxidizing sulfonating agent) is from 10 times to less than 20 times that of the organic material, sulfonated graphene having a thickness of 10 to 20 nm can be obtained.
  • the process of the present invention is carried out in a homogeneous state of solution or melting, the entire reaction process is uniform with the aid of the reaction medium, and therefore, the uniformity of the obtained sulfonated graphene product is high.
  • the sulfonated graphene of the present invention has a degree of homogeneity of more than 50%, preferably more than 60%, even more than 70%, even more than 80%, even more than 90%, and most preferably more than 91%.
  • the uniform description refers to both the uniformity of thickness and the uniformity of the film diameter, unless otherwise specified.
  • the higher uniformity of sulfonated graphene is particularly useful in applications.
  • the sulfonated graphene of the present invention is applied to a reinforcing of a polymer material such as an epoxy resin, the bending strength and the impact strength can be remarkably improved without substantially lowering the tensile strength of the polymer material.
  • the sulfonated graphene prepared by the method of the present invention has a sheet diameter of generally greater than or equal to 10 microns to less than or equal to 1000 microns, such as greater than or equal to 50 microns, greater than or equal to 100 microns, and greater than or equal to 300 microns.
  • the chip size of sulfonated graphene can be controlled by selecting the molecular weight of the organic material. Specifically, the higher the molecular weight of the organic material, the larger the chip diameter of the obtained sulfonated graphene, and vice versa.
  • the obtained sulfonated graphene has a sheet diameter of 90 to 120 ⁇ m.
  • the obtained sulfonated graphene has a sheet diameter of from 80 to 100 ⁇ m.
  • the obtained sulfonated graphene has a sheet diameter of 60 to 90 ⁇ m.
  • the obtained sulfonated graphene has a sheet diameter of 50 to 80 ⁇ m.
  • the carbon/sulfur ratio (carbon to sulfur ratio) of the sulfonated graphene prepared by the method of the present invention is from 12:1 to 1:1. It is preferably 10:1 to 2:1; more preferably 8:1 to 3:1, most preferably 6:1 to 3:1.
  • the term carbon-sulfur ratio (or carbon/sulfur ratio) as used in the present invention means the ratio of the number of carbon atoms in the obtained sulfonated graphene to the number of sulfur atoms, and is also a molar ratio.
  • the carbon to sulfur ratio of the sulfonated graphene can be controlled by controlling the temperature of the first and second contacting steps and the reaction time.
  • the longer the contact step the higher the sulfur content of the sulfonated graphene and vice versa.
  • the higher the reaction temperature the lower the carbon to sulfur ratio of the obtained sulfonated graphene, that is, the higher the sulfur content, and vice versa.
  • the sulfonated graphene of the present invention has a carbon to sulfur ratio of greater than 3:1 and less than 120:1, that is, the number of sulfur atoms is less than or equal to one third of the number of carbon atoms but greater than or equal to carbon atoms.
  • the carbon to sulfur ratio reflects the amount of sulfonic acid groups attached to the sulfonated graphene.
  • the sulfonated graphene obtained by the process of the present invention may have a water solubility of from about 2.0% by weight to about 30% by weight and a copper ion complexing amount of from about 0.30 to about 5 g/g.
  • the obtained graphene may have a water solubility of up to about 27% by weight, a copper ion complexation amount of about 4.85 g/g, and a carbon-sulfur ratio of 12/1.
  • the water solubility of the graphene may be up to about 15% by weight, the copper ion complexation amount may be about 2.15 g/g; when the carbon-sulfur ratio is 30/1, the water solubility of the obtained graphene is about 8 wt%, copper ion.
  • the complexation amount is about 1.02 g/g; when the carbon-sulfur ratio is 60/1, the obtained graphene has a water solubility of about 3.2 wt%, and the copper ion complexation amount can reach 0.60 g/g; when the carbon-sulfur ratio is At 120/1, the obtained graphene had a water solubility of about 2.0% by weight and a copper ion complexation amount of about 0.35 g/g.
  • the obtained sulfonated graphene product may be subjected to a high temperature treatment, for example, a nitrogen atmosphere protection furnace at 300 ° C or 350 ° C for a period of time, for example, 15 minutes to 8 hours, for example, 30 minutes.
  • the carbon-sulfur ratio was adjusted by 1 hour, 4 and a half hours, 8 hours, and the like.
  • this treatment the higher the water temperature, the longer the treatment time, the more the proportion of sulfur atoms decreases, and vice versa.
  • a second aspect of the invention relates to a sulfonated graphene product, wherein the sulfonated graphene has a sulfonic acid group, characterized in that the sulfonated graphene has a carbon/sulfur ratio of from 12:1 to 1:1, preferably 10:1 to 2:1; more preferably 8:1 to 3:1, most preferably 6:1 to 3:1.
  • carbon to sulfur ratio as used in the present invention is The ratio of the number of carbon atoms in the obtained sulfonated graphene to the number of sulfur atoms is also a molar ratio.
  • the carbon to sulfur ratio reflects the amount of sulfonic acid groups attached to the sulfonated graphene.
  • the sulfonated graphene obtained by the process of the present invention may have a water solubility of from about 2.0% by weight to about 25% by weight, and a copper ion complexing amount of from about 0.30 to 5 g/g.
  • the obtained graphene when the ratio of the sulfur atom to the carbon atom is 1/6, the obtained graphene may have a water solubility of up to about 21% by weight, and the copper ion complexation amount may reach about 4.85 g/g; when the sulfur atom and the carbon atom are When the ratio is 1/12, the obtained graphene may have a water solubility of up to about 15% by weight, a copper ion complexation amount of about 2.15 g/g, and a ratio of a sulfur atom to a carbon atom of 1/30.
  • the graphene has a water solubility of about 8 wt%, a copper ion complexation amount of about 1.02 g/g, and when the ratio of the sulfur atom to the carbon atom is 1/60, the obtained graphene has a water solubility of about 3.2 wt%, copper.
  • the ion complexation amount can reach 0.60 g/g; when the ratio of the sulfur atom to the carbon atom is 1/120, the obtained graphene has a water solubility of about 2.0% by weight and a copper ion complexation amount of about 0.35 g/g.
  • the sulfonated graphene of the present invention has a sheet diameter (planar diameter of the material) of greater than 10 microns, preferably greater than 50 microns, more preferably greater than or equal to 100 microns to less than 1000 microns.
  • the sulfonated graphene of the present invention has a thickness of from 0.5 to 100 nm, preferably from 1 to 50 nm, preferably from 1 to 10 nm.
  • the thickness of the sulfonated graphene (distance in the normal direction of the material plane) is more than 90%.
  • the sulfonated graphene has a sheet diameter uniformity of more than 90%.
  • FIG. 1 and 2 are scanning electron microscope images of sulfonated graphene prepared in Example 2 of the present invention, which demonstrate the above-described advantages of the sulfonated graphene powder prepared by the method of the present invention. Specifically, it can be seen from the figure that the sulfonated graphene has a sheet diameter of 50-100 ⁇ m, a thickness of 1-2 nm, a thickness uniformity of 95%, and a sheet diameter of 80-90 ⁇ m and a uniformity of 92%.
  • a third aspect of the invention relates to the use of the sulfonated graphene product of the invention or the sulfonated graphene obtained by the process of the invention.
  • the sulfonated graphene products prepared by the present invention can be used in various known graphene applications, and are not limited thereto.
  • Sulfonated graphene is widely used in materials.
  • Sulfonation Graphene is a new type of carbon material with excellent performance, high specific surface area and rich sulfonic acid functional groups. Sulfonated graphene can be used to prepare composite materials, including polymer composites and inorganic composites.
  • the sulfonated graphene of the present invention can be applied to transparent conductive electrodes, heat conductive materials, super capacitors, transistors, fuel cells, integrated circuits, solar cells, bio-loads, complexing agents, composite materials, chelating agents, water-based coatings. , water-based lubrication, mobile equipment, aerospace materials, inks or photosensitive elements.
  • Example 14 of the present invention illustrates one use of the sulfonated graphene of the present invention for forming a polymer composite.
  • the sulfonated graphene of the present invention is mixed with an epoxy resin to obtain a toughened epoxy resin, and the toughened resin has a marked improvement in bending strength and impact strength under the condition that the tensile strength remains substantially unchanged. This effect is significantly better than the effects of graphene or modified graphene in the prior art.
  • Graphene (characterization) In general, graphene can be processed by X-ray diffraction, infrared spectroscopy, Raman spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), etc. To characterize.
  • sulfonated graphene is mainly characterized by infrared spectroscopy, X-ray diffraction, Raman spectroscopy and atomic force microscopy, wherein when the infrared spectrum has absorption peaks at 1130 cm -1 and 1400 cm -1 , X-ray diffraction
  • the product characterized by atomic force microscopy has a two-dimensional shape and the thickness is 1-20. In the case of nanometers, the product is sulfonated graphene.
  • C/S ratio carbon to sulfur ratio
  • the carbon to sulfur ratio of sulfonated graphene can be determined by elemental analysis, XPS, spherical aberration-corrected electron mirror scanning, etc. The results of these methods are similar.
  • the C/S ratio is measured by an elemental analysis method.
  • Chip diameter The chip diameter of sulfonated graphene can be measured by optical microscopy such as transmission electron microscopy, SEM, AFM, and the like. The results of these methods are similar. In the present invention, it is mainly measured by scanning electron microscopy and atomic force microscopy.
  • Thickness The thickness of sulfonated graphene can be measured by AFM, optical microscopy, transmission electron microscopy, and the like. The results of these methods are similar. In the present invention, it is mainly measured by atomic force microscopy.
  • Melting temperature (melting point, Tg, melting range): The melting point (melting temperature), Tg or melting range of the material in the present invention is measured by a melting point apparatus, DSC or the like, or by using a thermometer. These measurement methods are well known to those skilled in the art.
  • Boiling Point The boiling point of the material in the present invention can be measured by a method generally used by those skilled in the art using a thermometer.
  • the uniformity of thickness and chip diameter of sulfonated graphene can be obtained based on the thickness and the chip diameter measured above, by the following steps: dividing the chip diameter and thickness by size, taking the chip diameter as an example, the product is prepared. 1-100 micron has a distribution, divided into 10 zones for every 10 micron interval The average value of the distribution is uniform. If the sample is prepared at 70-80 microns, it accounts for 80% of the prepared product. It can be said that the product has a diameter of 70-80 microns and a uniformity of 80%. In addition, the thickness is taken as an example.
  • the prepared product is distributed at 0-10 nm, a total of 10 intervals are divided into one interval per 1 nanometer, and the extreme value of the distribution is uniformity, such as the thickness of the prepared sample at 1-2 nm.
  • 80% of the product can be said to have a thickness of 1-2 nm and a uniformity of 80%.
  • the carbon to sulfur ratio is 3:1.
  • Applicants also use a polyethylene wax with a molecular weight of 3000, which is directly added to chlorosulfonic acid heated to 160 ° C for reaction, but the reaction is too fast and may explode, so it is not recommended to directly put the organic matter into a strong acid above the boiling point.
  • the reaction is carried out in a reaction medium.
  • Example 4 The test of Example 4 was repeated except that the ratio of chlorosulfonic acid to the organic material was adjusted to find the relationship between the ratio of the raw materials and the thickness of the sulfonated graphene.
  • the test results obtained are shown in the following table:
  • Example 4 The test of Example 4 was repeated except that polyethylene wax having a different molecular weight was used in order to find the relationship between the molecular weight of the organic material and the sheet diameter of the obtained sulfonated graphene. owned The test results are shown in the following table:
  • Example 2 The product in Example 2 was treated with 300 ° C and 350 ° C for 0.5 h with a carbon-to-sulfur ratio of 12:1 and 60:1, respectively, and the product was subjected to a high temperature of 300 ° C for 2 hours under a nitrogen gas protection. A product having a carbon to sulfur ratio of 30:1 and treated at 350 ° C for 6 hours gave a product having a carbon to sulfur ratio of 120:1. The water solubility and copper ion complexation efficiency tests were then carried out.
  • the complexing ability of commercially available complexing agent EDTA to copper ions is now 0.1-0.15 g/g.
  • the sulfonated graphene obtained by the method of the present invention has high water solubility and high copper ion complexing ability. From the sulfonate content, the higher the ratio of sulfur content to carbon content in the sulfonate, the better the water solubility of the product, and the higher the sulfonate content, the better the complexing ability for metal ion complexation.
  • Example 16 Example of application performance with respect to uniformity
  • Example 2 The sample of the above Example 2, 3.75 g (homogeneity: 92%), was homogenized with 500 g of epoxy resin (commercially available, Baling Petrochemical) in a stainless steel mold to obtain a toughened epoxy resin.
  • epoxy resin commercially available, Baling Petrochemical

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Abstract

本发明涉及一种从有机材料制备磺化石墨烯的方法以及由其制备的磺化石墨烯，所述方法包括以下步骤：第一接触步骤：在第一温度使含有氧化性磺化剂的反应介质与所述有机高分子材料接触；和第二接触步骤：在第一接触步骤结束后，在同一反应介质中，将反应温度升高至第二温度使其继续反应，从而获得所述磺化石墨烯。

Description

从有机材料制备磺化石墨烯的方法以及磺化石墨烯 技术领域
本发明涉及石墨烯的制备方法，具体地涉及从有机材料尤其是有机高分子材料或者有机小分子材料如烃类制备磺化石墨烯的方法，以及磺化石墨烯。
背景技术
现有生产石墨烯及氧化石墨烯的技术主要有：化学气相沉积法(CVD)，氧化还原法及其他方法。现有技术中生产氧化石墨烯时，往往以石墨或者石墨烯产品作为起始原料进行生产，产量小，成本高，污染重，产品质量低，产物的性状不易控制。例如现有方法生产石墨烯的不足与缺陷是：CVD法生产过程要求严格，成本高；氧化还原法：工艺复杂，需要用到重金属离子。磺化石墨烯作为功能化石墨烯中的重要的一种，越来越多地用于各种石墨烯应用中。本领域中仍然需要规模化制备磺化石墨烯的新方法，同时对于性质均一的磺化石墨烯也存在大量的需求。
发明内容
本发明提供一种新的制备磺化石墨烯的方法，以及由该方法制备的磺化石墨烯。
具体地，本发明包含以下内容：
实施方式1.一种从有机材料制备磺化石墨烯的方法，所述方法包括以下步骤：
第一接触步骤：在第一温度使含有氧化性磺化剂的反应介质与所述有机材料接触；和
第二接触步骤：在第一接触步骤结束后，在同一反应介质中，将反应温度升高至第二温度使其继续反应，从而获得所述磺化石墨烯。
实施方式2.实施方式1的方法，其中所述氧化性磺化剂选自：通式R-SO3H的化合物，其中R选自F、Cl、Br；H2SO4与HCl的组合；H2SO4与HF的组合；浓硫酸；发烟硫酸；及其组合，
优选地，其中所述氧化性磺化剂在所述反应介质中的浓度为高于98％。
实施方式3.实施方式1的方法，其中所述第一温度为所述有机材料的熔融温度至低于所述反应介质的沸点，所述第二温度为所述反应介质的沸点以上；优选地，其中所述第一温度为40-130℃；所述第二温度为150-220℃。
实施方式4.实施方式1的方法，其中所述第一接触步骤进行的时间为1小时至40小时；所述第二接触步骤进行的时间为1小时至40小时。
实施方式5.实施方式1的方法，其中所述有机材料选自有机高分子材料和有机小分子材料，其中优选地，所述有机高分子材料选自：聚乙烯蜡、氯化聚乙烯、乙炔低聚物、聚乙炔、含卤族元素的聚炔烃如聚卤族炔、聚乙烯、聚氯乙烯、含卤族元素的聚烯烃如聚卤族烯；其中优选地，所述有机小分子材料选自C4-C30直链烃或带苯环结构的芳香烃。
实施方式6.实施方式1的方法，其中所述有机材料的结晶度为：0-30％，或者20～40％，或者50～80％，或者60％～90％；所述有机材料的分子量为：50-50000，优选50至10000。
实施方式7.实施方式1的方法，其中所述有机材料与反应介质的重量比为：5:1至1:500，优选1:3至1:70。
实施方式8.一种磺化石墨烯，其中所述磺化石墨烯带有磺酸基团，其特征在于，所述磺化石墨烯的碳/硫比为：12:1至1:1，优选10:1至2:1；更优选8:1至3:1，最优选6:1至3:1。
实施方式9.实施方式8的磺化石墨烯，其中所述磺化石墨烯的片径(材料的平面直径)为大于10微米，优选大于50微米，更优选大于或等于100微米至小于1000微米；厚度为0.5至100纳米，优选1至50纳米，优选1至10纳米；优选地，所述磺化石墨烯的厚度(材料平面法向方向的距离)均一度超过90％；优选地，所述磺化石墨烯的片径均一度超过90％。
实施方式10.实施方式8或9的磺化石墨烯在透明导电电极、导热材料、超级电容、晶体管、燃料电池、集成电路、太阳能电池、生物负载、络合剂、复合材料、螯合剂、水性涂料、水性润滑、移动设备、航空航天材料、油墨或感光元件中的用途。
附图说明
图1和图2分别是本发明制备的磺化石墨烯的扫描电镜图像，其表明了 本发明的方法制备的磺化石墨烯粉末的优点。
具体实施方式
定义
有机材料：又称为有机物质，其具有本领域技术人员一般理解的含义。它们的组成元素不多，主要是碳和氢，还任选地包括其它元素比如氧或氮等，相对分子质量小的可为几十，大的可高达几百万。有机材料包括有机高分子材料和有机小分子材料。有机高分子材料是由一种或几种有机结构单元多次重复连接起来的化合物。通常的有机材料包括：聚烯烃(如聚乙烯、聚丙烯、聚氯乙烯、聚二氯乙烯、聚丁烯、聚乙烯-辛烯共聚物、聚四氟乙烯)、聚炔烃(如聚乙炔)、聚酯(如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯)、聚醚(如聚苯醚)、聚醚醚酮、聚酰胺(如尼龙)、聚脲、丁烷、丁烯、己烷、辛烷、辛烯、苯等。
磺化石墨烯：一种类二维材料，与氧化石墨烯和石墨烯相似，以化学键连有磺酸或磺酸根官能团的碳材料。在本发明中，术语“磺化石墨烯”、“磺化的碳材料”或“含有磺酸根官能团的碳材料”之间具有类似的含义，可以互换使用。本发明的申请人发现，本发明的磺化石墨烯仍保持石墨的层状结构，但在每一层的石墨烯单片上引入了许多磺酸根官能团。这些磺酸根官能团的引入使得单一的石墨烯结构变得复杂，引入了亲水性，使得这样的磺化石墨烯在各种应用中带来石墨烯的优良性质的同时还提高了易用性。在本发明的磺化石墨烯的层状结构中，其层状结构的厚度可以为1-300纳米，优选为1-200纳米，例如1-100纳米，例如1-50纳米，例如1-40纳米，例如1-30纳米，例如3-20纳米，例如3-15纳米，例如5-10纳米。
氧化性磺化剂：具有氧化性的磺化剂。所述氧化性磺化剂中的氧化性和磺化性可以分别由不同的物质提供，例如，一种物质提供氧化性，一种物质提供磺化性。通常的氧化性磺化剂选自：通式R-SO3H的化合物，其中R选自F、Cl、Br；H2SO4与HCl的组合；H2SO4与HF的组合；浓硫酸；发烟硫酸；SO3；及其组合。
反应介质：在本申请中，反应介质主要指的是氧化性磺化剂和任选的溶剂的组合。其中所述溶剂可以为有机溶剂如氯甲烷、乙醇，也可以为无机溶剂如氯化氢。
熔融温度：本申请所述的熔融温度是指本申请使用的有机材料在与本申请所述的反应介质接触时的熔点、Tg(玻璃化转变温度)、或者熔程。换句话说，当在本申请中提及熔融温度、熔点、Tg(玻璃化转变温度)、或者熔程时，是指在该有机材料与所述反应介质接触时，该有机材料处于无定形状态的最低温度或温度范围。
磺化石墨烯的片径：是指该磺化石墨烯材料的平面直径。
磺化石墨烯的厚度：是指该磺化石墨烯材料平面法向方向的距离。
均一度：定义片径及厚度范围内的密度分布，因此均一度存在两种指数，一个是片径均一度和厚度均一度，当然对于一个产品来说，这个片径均一度和厚度均一度常常是一致的，或者说是相同的。均一度的计算方法如下：将片径和厚度按尺寸划分为10个区间，以片径为例，制备的产物在1-100微米都有分布，按每10微米为一个区间，分布的极值即为均一度，如制备的样品在70-80微米占制备产品密度分布的80％，可以说该批产品直径为70-80微米，均一度为80％。
第一方面
本发明的第一方面涉及一种从有机材料制备磺化石墨烯的方法，所述方法包括以下步骤：
第一接触步骤：在第一温度使含有氧化性磺化剂的反应介质与所述有机材料接触；和
第二接触步骤：在第一接触步骤结束后，将整个体系的温度升高至第二温度使其继续反应，从而获得所述磺化石墨烯。在优选的实施方式中，本发明的方法是在同一反应介质中进行的。
在本发明方法的第一接触步骤中，第一温度优选为高于有机材料的熔点，此时，有机材料处于无定形的熔融状态(如果有机材料以溶液形式存在于反应介质中时，也将其认为是无定形状态)，有机材料在该状态下被氧化成碳材料如具有一定尺寸的块状碳或者石墨烯的雏形，有少量的碳被磺化。由于这种第一步骤中形成的碳材料是从无定形状态的有机材料形成的，所以该碳材料本身非常疏松，比如当是块状碳材料状态时，它的石墨烯层的层数较少。
在本发明方法的第二接触步骤中，第二温度优选为反应介质的沸点或更 高，此时，在第一步骤中形成的碳材料被磺化，并且由于反应温度比较高，反应速度快，磺化也会发生于形成的碳材料如石墨或石墨烯的片层之间，在这种情况下，就形成了磺化石墨烯产品。
如果仅使用一步接触，那么往往不能达到本发明的目的，不能获得均一度高的磺化石墨烯产品。
在本发明中使用的有机材料选自有机高分子材料和有机小分子材料，其中优选地，所述有机高分子材料选自：聚乙烯蜡、氯化聚乙烯、乙炔低聚物、聚乙炔、聚卤族炔(含卤族元素的聚炔烃)、聚乙烯、聚氯乙烯、聚卤族烯(含卤族元素的聚烯烃)；其中优选地，所述有机小分子材料选自C4至C50直链烃或芳香烃，例如C8-C30直链烃，C4至C50烯烃或炔烃，苯或芘或菲。所述有机高分子材料的分子量可以为200至50000，例如500至40000，例如1000至30000，例如2000至20000，例如3000至15000，例如4000至12000，例如5000至11000，例如6000至10000，例如7000至9000，例如8000至8500。分子量在3000至10000之间的聚乙烯蜡是特别合适的，这是因为这样的聚乙烯蜡的熔点在90至110℃之间，在操作上特别适合，并且原料来源广泛。所述有机小分子材料优选为烃类化合物，例如烯烃或炔烃或芳香烃，优选C4至C50直链烃，例如C4至C50烷烃、烯烃或炔烃，其中所述的范围C4至C50包含端点，并且涵盖其中的所有子范围，例如C5至C40、C6至C45、C8至C30、C10至C25、C12至C20、或C14至C18。所述有机小分子材料的分子量范围可以为50至800，例如80至700，例如100至500，例如150至300，例如200至250。如所定义的，所述有机小分子材料中仍然可以包含除碳和氢之外的原子，例如氧、氮、硫等，但是优选所述小分子材料中仅含有氮原子作为杂原子，更优选不含有杂原子。
在一种实施方式中，第一接触步骤中使用的第一温度为所述有机材料的熔融温度至低于所述反应介质的沸点，所述第二温度为所述反应介质的沸点以上。第一温度的选择取决于有机材料的熔融温度、反应介质的沸点和所期望的反应速度等因素。在优选的实施方式中，第一反应温度处于有机材料的熔融温度和反应介质的沸点之间。选择这样的第一温度这是为了使有机材料处于无定形状态，使得容易形成疏松的碳材料用于第二接触步骤中的进一步磺化和分层，并且获得合适的反应速度，不会导致反应过于激烈而产生安全问题。在条件允许下，如果需要反应速度较快，那么优选使用较高的反应温 度。一般而言，对于有机小分子材料而言，第一温度可以选择得比较低，例如为小于100℃，例如小于90℃，例如小于80℃，例如小于70℃，例如小于60℃，例如小于50℃，常常为在小于40℃，或者更低的温度例如小于35℃，小于30℃，小于20℃，小于15℃，小于10℃，小于5℃，甚至是小于0℃。
对于有机高分子材料而言，由于其熔融温度常常会比较高，因此第一温度可以选择得比较高一些。在一种实施方式中，所述第一温度为40-140℃，例如45℃至130℃，例如50℃至125℃，例如55℃至120℃，例如60℃至115℃，例如65℃至110℃，例如70℃至105℃，例如65℃至100℃，例如75℃至95℃，例如80℃至90℃。
在本发明的方法的一种实施方式中，所述第二温度为所述反应介质的沸点以上。第二反应温度优选为反应介质的沸点或者更高的温度。这样选择第二温度使得在第二接触步骤中形成性质均一的分层的磺化石墨烯片。对于温度的上限而言没有限制，但是应该使反应满足安全生产的要求。在本发明所用的反应介质中，所述氧化性磺化剂在反应介质中的浓度为高于98％，更优选为高于或等于99％，最优选为100％(即所述反应介质即为氧化性磺化剂)。本发明中使用的氧化性磺化剂中，氯磺酸的沸点为151℃，氟磺酸的沸点为163.5℃，硫酸的沸点为338℃。在具有高含量的氧化性磺化剂的条件下，反应介质的沸点接近于该氧化性磺化剂的沸点。但是介质的沸点可能由于反应介质中溶解了溶质或者使用混合的氧化性磺化剂而发生一定的变化。在具体的实施方式中，所述第二温度为150-220℃，例如155-215℃，例如160-210℃，例如165-205℃，例如170-200℃，例如175-195℃，例如180-190℃。
在本发明的实施方式中，反应介质的沸点优选高于有机材料的熔融温度，或者说，有机材料的熔融温度低于反应介质的沸点。在优选的实施方式中，反应介质的沸点高于有机材料的熔融温度10℃以上，优选20℃以上，优选30℃以上，优选40℃以上。反应介质的沸点和有机材料的熔融温度之间的差较大时，可以将第一接触步骤和第二接触步骤容易地通过反应温度区分开，有利于反应的控制。
一般而言，本发明的方法在常压下进行，因此，除非有相反的明确指出，否则，本发明中所述的熔融温度和沸点等都是对于在常压下测得的值而言的。当然本发明也预期，本发明的方法能够在高压下进行，或者在真空(例如压力为1kPa，5kPa，10kPa，20kPa，50kPa等)的条件下进行。在高压下 进行时，第二接触步骤的第二温度可以根据反应的情况和需要适当提高。在真空下进行时，第二接触步骤的第二温度可以根据反应的情况和需要适当降低。类似地，在非大气压下进行第一接触步骤时，第一温度也可以根据情况进行变动。
在本发明中，对于第一接触步骤和第二接触步骤的时间没有特别的限制，只要能够实现本发明的目的即可。一般情况下，第一接触步骤进行的时间为1小时至40小时；第二接触步骤进行的时间为1小时至40小时。其中该范围1至40小时涵盖1至40小时之间的任何值和子范围，例如2至35小时，3至30小时，4至28小时，5至25小时，6至20小时，7至18小时，8至16小时，9至12小时，10至11小时等等。
本发明使用的有机材料在常温常压下可以具有一定的结晶度。在具体的实施方式中，所述有机材料的结晶度为：0-90％，例如0-30％，或者20～40％，或者50～80％，或者60％～90％。在优选的实施方式中，本发明的有机材料的结晶度为0-30％，或0至15％，或者0-10％，或者0至5％。本发明人发现，有机材料在低结晶度的条件下更加有利于在熔融温度以上迅速达到无定形熔融状态，从而有利于形成疏松的碳材料。高结晶度的材料如果没有及时转变成熔融的无定形状态，可能会由于表面材料的碳化而形成对内部材料的保护层，使得有机材料在第一接触步骤中不能够被完全碳化。
通过本发明的方法制备的磺化石墨烯的厚度为0.5至300纳米，例如1至200纳米，例如0.5至100纳米，优选1至50纳米，例如1至20纳米，优选1至10纳米。可以通过调节反应介质(或者说其中的氧化性磺化剂例如氯磺酸或氟磺酸)和有机材料的配比控制生产的磺化石墨烯的厚度。一般情况下，所述有机材料与反应介质的重量比为：1:1至1:500，优选1:2至1:200，例如1:3至1:100，例如1:5至1:90，例如1:10至1:80，例如1:20至1:70，例如1:30至1:60，例如1:40至1:50。一般情况下，本发明的方法以氧化性磺化剂在第一接触步骤和第二接触步骤中都过量的量进行。本申请的申请人出乎意料地发现，原料的配比中，反应介质(或者氧化性磺化剂)的比例越高，也即反应介质(或者氧化性磺化剂)的量越高，得到的磺化石墨烯的厚度越低。在优选的实施方式中，当反应介质(或者氧化性磺化剂)的量为有机材料的60倍以上时，可以得到厚度为1-2nm的磺化石墨烯，这对应于1至2层磺化石墨烯层的厚度。考虑到成本问题，反应介质(或者氧化性磺化 剂)的使用量一般为有机材料的100倍以下。在优选的实施方式中，当反应介质(或者氧化性磺化剂)的量为有机材料的30倍至低于60倍时，可以得到厚度为3-5nm的磺化石墨烯。在优选的实施方式中，当反应介质(或者氧化性磺化剂)的量为有机材料的20倍至低于30倍时，可以得到厚度为5-10nm的磺化石墨烯。在优选的实施方式中，当反应介质(或者氧化性磺化剂)的量为有机材料的10倍至低于20倍时，可以得到厚度为10-20nm的磺化石墨烯。
由于本发明的方法在溶液或者熔融的均匀状态下进行，整个反应过程在反应介质的帮助下是均一的，因此，获得的磺化石墨烯产品的均一度很高。通常本发明的磺化石墨烯的均一度超过50％，优选超过60％，甚至是超过70％，甚至是超过80％，甚至是超过90％，最优选超过91％。在本申请中，没有特别指明的情况下，均一度的描述既指代厚度均一度，也指代片径均一度。
有机材料的结晶度越低，反应介质与有机材料比例越高，反应过程控制越精细，最终产品的均一度越高。
均一度较高的磺化石墨烯在应用中尤其是表现出很强的实用性。例如，当将本发明的磺化石墨烯应用于对高分子材料如环氧树脂进行增强时，能够在基本上不降低高分子材料的拉伸强度的情况下，明显改善弯曲强度和冲击强度。
通过本发明的方法制备的磺化石墨烯的片径一般为大于或等于10微米至小于或等于1000微米，例如大于或等于50微米，大于或等于100微米，大于或等于300微米。申请人出乎意料地发现，通过选择有机材料的分子量的大小可以控制磺化石墨烯的片径。具体地，有机材料的分子量越高，得到的磺化石墨烯的片径就越大，反之亦然。更具体地，当有机材料的分子量为8000以上时，得到的磺化石墨烯的片径为90-120μm。当有机材料的分子量为5000至低于8000时，得到的磺化石墨烯的片径为80-100μm。当有机材料的分子量为3000至低于5000时，得到的磺化石墨烯的片径为60-90μm。当有机材料的分子量为2000至低于3000时，得到的磺化石墨烯的片径为50-80μm。当使用更小的分子量的有机材料，甚至是使用有机小分子材料时，得到的磺化石墨烯的片径为20-50μm。
通过本发明的方法制备的磺化石墨烯的碳/硫比(碳硫比)为：12:1至1:1， 优选10:1至2:1；更优选8:1至3:1，最优选6:1至3:1。本发明中所用的术语碳硫比(或碳/硫比)是指得到的磺化石墨烯中碳原子的个数与硫原子的个数的比例，也是摩尔比。一般来说，通过控制第一、第二接触步骤的温度和反应时间可以控制磺化石墨烯的碳硫比。具体地，接触步骤的时间越长，磺化石墨烯的硫含量越高，反之亦然。还具体地，反应温度越高，得到的磺化石墨烯的碳硫比也越低，也即硫含量越高，反之亦然。但是优选本发明的磺化石墨烯的碳硫比为高于3:1和低于120:1，也即硫原子的数量少于或等于碳原子数量的三分之一但是大于或等于碳原子数量的120分之一。碳硫比反映的是磺化石墨烯中连接的磺酸基团的量。当硫原子的含量较高时，石墨烯的水溶性较高，铜离子络合效率也较高，反之亦然。本发明的方法获得的磺化石墨烯的水溶性可以为约2.0wt％至约30wt％，铜离子络合量可以为约0.30至5g/g。例如，当碳硫比为6/1时，得到的石墨烯的水溶性可以为高达约27wt％，铜离子络合量可以达到约4.85g/g；当碳硫比为12/1时，得到的石墨烯的水溶性可以为高达约15wt％，铜离子络合量可以达到约2.15g/g；当碳硫比为30/1时，得到的石墨烯的水溶性为约8wt％，铜离子络合量为约1.02g/g；当碳硫比为60/1时，得到的石墨烯的水溶性为约3.2wt％，铜离子络合量可以达到0.60g/g；当碳硫比为120/1时，得到的石墨烯的水溶性为约2.0wt％，铜离子络合量为约0.35g/g。然而，当硫含量过高，硫原子的比例超过碳原子数目的1/3时，得到的磺化石墨烯产品中石墨烯的结构被破坏比较严重，这可能会导致磺化石墨烯在应用中的功效劣化。当硫含量过低，石墨烯的水溶性会降低，此时可能会降低石墨烯在应用中的使用量，同样导致不能达到理想的应用性能。另外，对于磺化石墨烯中的碳硫比，可以通过将得到的磺化石墨烯产品经过高温处理，例如300℃或350℃的氮气氛保护炉处理一段时间例如15分钟至8小时例如30分钟、1小时、4个半小时、8小时等来调整该碳硫比。一般情况下，在该处理中，水温越高，处理时间越长，硫原子的比例下降得越多，反之亦然。
第二方面
本发明的第二方面涉及一种磺化石墨烯产品，其中所述磺化石墨烯带有磺酸基团，其特征在于，所述磺化石墨烯的碳/硫比为：12:1至1:1，优选10:1至2:1；更优选8:1至3:1，最优选6:1至3:1。本发明中所用的术语碳硫比是 指得到的磺化石墨烯中碳原子的个数与硫原子的个数的比例，也是摩尔比。
碳硫比反映的是磺化石墨烯中连接的磺酸基团的量。当硫原子的含量较高时，石墨烯的水溶性较高，铜离子络合效率也较高，反之亦然。本发明的方法获得的磺化石墨烯的水溶性可以为约2.0wt％至约25wt％，铜离子络合量可以为约0.30至5g/g。例如，当硫原子与碳原子的比例为1/6时，得到的石墨烯的水溶性可以为高达约21wt％，铜离子络合量可以达到约4.85g/g；当硫原子与碳原子的比例为1/12时，得到的石墨烯的水溶性可以为高达约15wt％，铜离子络合量可以达到约2.15g/g；当硫原子与碳原子的比例为1/30时，得到的石墨烯的水溶性为约8wt％，铜离子络合量为约1.02g/g；当硫原子与碳原子的比例为1/60时，得到的石墨烯的水溶性为约3.2wt％，铜离子络合量可以达到0.60g/g；当硫原子与碳原子的比例为1/120时，得到的石墨烯的水溶性为约2.0wt％，铜离子络合量为约0.35g/g。然而，当硫含量过高，硫原子的比例超过碳原子数目的1/3时，得到的磺化石墨烯产品中石墨烯的结构被破坏比较严重，这可能会导致磺化石墨烯在应用中的性质劣化。当硫含量过低，石墨烯的水溶性会降低，此时可能会降低石墨烯在应用中的使用量，同样导致不能达到理想的应用性能。
在一种具体的实施方式中，本发明的磺化石墨烯的片径(材料的平面直径)为大于10微米，优选大于50微米，更优选大于或等于100微米至小于1000微米。在一种具体的实施方式中，本发明的磺化石墨烯的厚度为0.5至100纳米，优选1至50纳米，优选1至10纳米。在优选的实施方式中，所述磺化石墨烯的厚度(材料平面法向方向的距离)均一度超过90％。在进一步优选的实施方式中，所述磺化石墨烯的片径均一度超过90％。
图1和图2是本发明的实施例2制备的磺化石墨烯的扫描电镜图像，其表明了本发明的方法制备的磺化石墨烯粉末的以上所述的优点。具体的，从图上可以看出，该磺化石墨烯的片径为50-100微米，厚度为1-2纳米，厚度均一度为95％，片径80-90微米均一度为92％。
第三方面
本发明的第三方面涉及本发明的磺化石墨烯产品或者通过本发明的方法获得的磺化石墨烯的用途。本发明制备的磺化石墨烯产品可以用于已知的各种石墨烯应用中，并且不限于此。磺化石墨烯在材料应用范围很广。磺化 石墨烯是一种性能优异的新型碳材料，具有较高的比表面积和丰富的磺酸官能团。磺化石墨烯可以用来制备复合材料，包括聚合物类复合材料以及无机物类复合材料。目前来说，本发明的磺化石墨烯可以应用于透明导电电极、导热材料、超级电容、晶体管、燃料电池、集成电路、太阳能电池、生物负载、络合剂、复合材料、螯合剂、水性涂料、水性润滑、移动设备、航空航天材料、油墨或感光元件中。
本发明的实施例14示例了本发明的磺化石墨烯用于形成聚合物复合材料的一种用途。其中将本发明的磺化石墨烯与环氧树脂混合获得了增韧的环氧树脂，该增韧的树脂在拉伸强度基本保持不变的情况下，弯曲强度和冲击强度有了明显的改善，这一效果明显优于目前现有技术中的石墨烯或改性石墨烯的效果。
实施例
本申请的实施例中使用以下原料，其它的原料都是常规的，或者可以从市场上购得：
表1
Figure PCTCN2015072176-appb-000001
Figure PCTCN2015072176-appb-000002
测试方法
石墨烯(的表征)：一般而言，石墨烯可以通过X射线衍射、红外光谱、拉曼(Raman)光谱、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、原子力显微镜(AFM)等方法来表征。在本申请中，磺化石墨烯主要是通过红外光谱、X射线衍射、拉曼光谱及原子力显微镜来表征，其中当红外光谱在1130㎝-1和1400㎝-1处存在吸收峰，X射线衍射谱在2θ＝26°处有非晶包络峰，拉曼光谱在1360㎝-1及1580㎝-1出现D峰及G峰，原子力显微镜表征的产品呈二维形态，且厚度在1-20纳米时，表示产品为磺化石墨烯。
C/S比(碳硫比)：磺化石墨烯的碳硫比可以通过元素分析、XPS、球差校正电镜面扫等方法来测定，这些方法测定的结果是类似的。在本发明中，C/S比采用元素分析方法测得。
片径：磺化石墨烯的片径可以通过光学显微镜法如透射电镜法、SEM、AFM等方法测得。这些方法测定的结果是类似的。在本发明中，主要采用扫描电镜和原子力显微镜法测得。
厚度：磺化石墨烯的厚度可以通过AFM、光学显微镜、透射电镜法等方法测得。这些方法测定的结果是类似的。在本发明中，主要采用原子力显微镜法测得。
熔融温度(熔点、Tg、熔程)：本发明中材料的熔点(熔融温度)、Tg或者熔程通过熔点仪、DSC等方法、或者使用温度计测得。这些测量方法是本领域技术人员所熟知的。
沸点：本发明中材料的沸点可以使用温度计通过本领域技术人员通常使用的方法测得。
均一度：磺化石墨烯在厚度和片径方面的均一度可以基于以上测量的厚度和片径，通过以下步骤获得：将片径和厚度按尺寸划分，以片径为例，制备的产物在1-100微米都有分布，按每10微米为一个区间总共划分10个区 间，分布的极值即为均一度，如制备的样品在70-80微米占制备产品的80％，可以说该批产品直径为70-80微米，均一度为80％；另外以厚度为例，如果制备的产物在0-10纳米都有分布，按每1纳米为一个区间总共划分10个区间，分布的极值即为均一度，如制备的样品的厚度在1-2纳米占制备产品的80％，可以说该批产品厚度为1-2纳米，均一度为80％。
实施例1
(十六烷，无色液体，熔点18℃，沸点287℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氯磺酸作为反应介质，使用油浴将该反应器加热至50℃，并保持该温度，加入10克十六烷，反应3小时，然后缓慢升温至160℃，恒温反应12小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到9g磺化石墨烯产物，为黄褐色粉末。磺化石墨烯的表征：用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和拉曼光谱碳材料明显的G和D特征峰；产物经测试发现：该磺化石墨烯片径为10-20μm，在该范围内的片径均一度为95％，厚度在1-2nm，在该范围内的厚度均一度为95％，碳硫比为3:1。
实施例2
(分子量为3000的聚乙烯蜡，蜡状固体，熔点为：98-102℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氯磺酸作为反应介质，使用油浴将该反应器加热至110℃，并保持该温度，加入10克分子量为3000的聚乙烯蜡，反应4小时，然后缓慢升温至180℃，恒温反应10小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到15g磺化石墨烯产物，为黄褐色粉末。磺化石墨烯的表征：用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和红外光谱碳材料在1360㎝-1及1580㎝-1明显的D和G特征峰；产物经测试发现：磺化石墨烯的片径为80-90微米，在该范围内的片径均一度为92％，厚度为1-2纳米，在该范围内的厚度均一度为95％，碳硫比为6:1。
实施例3
(分子量为30000低密度聚乙烯，白色颗粒，熔点为127-129℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氯磺酸作为反应介质，使用油浴将该反应器加热至130℃，并保持该温度，加入20克分子量为30000的低密度聚乙烯，反应4小时，然后缓慢升温至180℃，恒温反应12小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到15g磺化石墨烯产物，为黄褐色粉末。磺化石墨烯的表征：用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和红外光谱碳材料在1380㎝-1及1530㎝-1明显的D和G特征峰；产物经测试发现：该磺化石墨烯片径为90-100μm，在该范围内的片径均一度为70％，厚度为3-5nm，在该范围内的厚度均一度为83％，碳硫比12:1。
实施例4
(分子量为2000的聚乙烯蜡，蜡状固体，熔点为：96-99℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氯磺酸作为反应介质，使用油浴将该反应器加热至100℃，并保持该温度，加入20克分子量为2000的聚乙烯蜡，反应6小时，然后缓慢升温至180℃，恒温反应12小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到32g磺化石墨烯产物，为黄褐色粉末。磺化石墨烯的表征：用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和红外光谱碳材料在1380㎝-1及1560㎝-1明显的D和G特征峰；产物经测试发现：该磺化石墨烯片径为50-60μm，在该范围内的片径均一度为90％，厚度在3-5nm，在该范围内的厚度均一度为90％，碳硫比为6:1。
实施例5
(分子量为30000的聚氯乙烯，白色粉末，熔点为163-167℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氟磺酸作为反应介质，使用油浴将该反应器加热至120℃，并保持该温度，加入15克分子量为50000的聚氯乙烯，反应6小时，然后缓慢升温至180℃，恒温反应12小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到12g磺化石墨烯产物，为褐色粉末。磺化石墨烯的表征：用XRD及红 外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和红外光谱碳材料在1350㎝-1及1570㎝-1明显的D和G特征峰；产物经测试发现：该磺化石墨烯片径为100-110μm，在该范围内的片径均一度为65％，厚度为3-5nm，在该范围内的厚度均一度为75％，碳硫比12:1。
实施例6
(分子量为30000的聚氯乙烯，性状白色粉末，熔点为：163-167℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g氯磺酸与发烟硫酸(氯磺酸与发烟硫酸体积比2:1)作为反应介质，使用油浴将该反应器加热至120℃，并保持该温度，加入15克分子量为30000的聚氯乙烯，反应6小时，然后缓慢升温至180℃，恒温反应12小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到11g磺化石墨烯产物，为褐色粉末。磺化石墨烯的表征：用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和红外光谱碳材料在1360㎝-1及1580㎝-1明显的D和G特征峰；产物经测试发现：该磺化石墨烯片径在100-110μm，在该范围内的片径均一度为52％，厚度为3-6nm，在该范围内的厚度均一度为60％，碳硫比为18:1。
实施例7
(分子量为3000的聚乙烯蜡，蜡状固体，熔点为：98-102℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氟磺酸作为反应介质，使用油浴将该反应器加热至110℃，并保持该温度，加入10克分子量为3000的聚乙烯蜡，反应4小时，然后缓慢升温至180℃，恒温反应10小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到15g磺化石墨烯产物，为黄褐色粉末。磺化石墨烯的表征：用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和红外光谱碳材料在1360㎝-1及1580㎝-1明显的D和G特征峰；产物经测试发现：磺化石墨烯的片径为80-90微米，在该范围内的片径均一度为90％，厚度为1-2纳米，在该范围内的厚度均一度为94％，碳硫比6:1。
对比例8
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氯磺酸作为反应介质，使用油浴将该反应器加热至100℃，并保持该温度，加入20克分子量为5000的聚乙烯蜡，反应6小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到25g黑色粉末。用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料及聚乙烯蜡的混合物；
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为96％的浓硫酸作为反应介质，使用油浴将该反应器加热至130℃，并保持该温度，加入20g以上得到的黑色粉末，反应12小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到黑色粉末。该黑色粉末具有XRD在2θ＝26°处的碳材料包络峰和2θ＝21°和2θ＝24°处聚乙烯的结晶峰。
对比例9(第一反应温度不够高的情况)
(分子量为3000的聚乙烯蜡，性状是蜡状固体，熔点为98-102℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氯磺酸作为反应介质，使用油浴将该反应器加热至70℃，并保持该温度，加入10克分子量为3000的聚乙烯蜡，反应4小时，然后缓慢升温至180℃，恒温反应10小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到12g黑色块状物质。黑色块状物质具有XRD在2θ＝26°处的碳材料包络峰和2θ＝21°和2θ＝24°处聚乙烯的结晶峰。
对比例10(第二反应温度不够高的情况)
(分子量为3000的聚乙烯蜡，性状为蜡状固体，熔点为98-102℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氯磺酸作为反应介质，使用油浴将该反应器加热至110℃，并保持该温度，加入10克分子量为3000的聚乙烯蜡，反应4小时，然后缓慢升温至140℃，恒温反应10小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗得到13g磺化石墨烯产物，为褐色粉末。用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和红外光谱碳材料在1360㎝-1及1580㎝-1明显的D和G特征峰；产物经测试发现：该磺化石墨烯片径在80-90μm，在该范围内的片径均一度为75％，厚度在1-15nm，在该范围内的厚度均一度为85％，碳硫比为8.3:1。
对比例11(仅使用第一接触步骤的情况)
(分子量为3000的聚乙烯蜡，性状为蜡状固体，熔点为98-102℃)
在通风橱中，向敞口的2升三颈玻璃反应器中，加入600g纯度为99％的氯磺酸作为反应介质，使用油浴将该反应器加热至110℃，并保持该温度，加入10克分子量为3000的聚乙烯蜡，反应14小时，将反应冷却，将反应器内容物过滤，并用去离子水清洗(100ml*3)得到12g黑色粉末。用XRD及红外光谱表征发现：产物为含有磺酸基团的碳材料，其具有XRD在2θ＝26°处的包络峰和红外光谱碳材料在1360㎝-1及1580㎝-1明显的D和G特征峰；产物经测试发现：该磺化石墨烯片径在80-90μm，在该范围内的片径均一度为60％，厚度在1-20nm，在该范围内的厚度均一度为70％，碳硫比为9.8:1。
对比例12(仅使用第二接触步骤的情况)
申请人也使用分子量为3000的聚乙烯蜡，将其直接添加到加热至160℃的氯磺酸中进行反应，但是反应太快，可能发生爆炸，因此不建议直接将有机物放入沸点以上的强酸反应介质中进行反应。
实施例13
重复实施例4的试验，所不同的是，调节氯磺酸和有机材料的配比，以期发现原料的配比与磺化石墨烯的厚度之间的关系。得到的试验结果如下表所示：
表2
配比 60:1 30:1 20:1 10:1
厚度 1-2nm 3-5nm 5-10nm 10-20nm
从以上结果可以看出，氯磺酸与有机材料的比例越高，得到的磺化石墨烯的厚度越薄，反之，氯磺酸与有机材料的比例越低，得到的磺化石墨烯的厚度越厚。
实施例14
重复实施例4的试验，所不同的是，使用具有不同分子量的聚乙烯蜡，以期发现有机材料的分子量与得到的磺化石墨烯的片径之间的关系。得到的 试验结果如下表所示：
表3
有机材料分子量 2000 3000 5000 8000
片径 50-80μm 60-90μm 80-100μm 90-120μm
从以上结果可以看出，有机材料的分子量越高，得到的磺化石墨烯的片径越大，反之，有机材料的分子量越低，得到的磺化石墨烯的片径越小。
实施例15(关于C/S比的应用性能实施例)
使用实施例2中的产物在通氮气保护情况下经300℃、350℃高温处理0.5h碳硫比分别为12:1和60:1，在通氮气保护下产物经300℃高温2小时，得到碳硫比为30:1的产物、经350℃处理6小时得碳硫比为120：1的产物。然后进行水溶性以及铜离子络合效率试验。
表4不同碳硫比磺化石墨烯的水溶性及铜离子络合效率
Figure PCTCN2015072176-appb-000003
现在市售常用络合剂EDTA对铜离子的络合能力为0.1-0.15g/g。从以上的数据可以看出，本发明的方法获得的磺化石墨烯的水溶性高，并且具有很高的铜离子络合能力。从磺酸根含量来说，当磺酸根中硫含量与碳含量比值越高，产物的水溶性达到越好，同时对于金属离子络合而言，磺酸根含量越高，络合能力越好。
实施例16(关于均一度的应用性能实施例)
取以上实施例2中的样品3.75g(均一度为92％)，将其与500g环氧树脂(市售，巴陵石化)在不锈钢模具中匀质浇铸，得到的增韧的环氧树脂。
根据国家标准GB/T1447-2005和GB1449-2005分别进行切割并铣到规定的形状和尺寸，在Instron3369万能试验机上测试未添加的环氧树脂以及得到的增韧的环氧树脂拉伸强度、弯曲强度、冲击强度，所得的性能数据比较 如下(所有的数据都是测试五组数据的平均值)，如表5所示：
表5不同样品的力学性能
Figure PCTCN2015072176-appb-000004
从表5的性能对比可知：由于本发明的方法获得的磺化石墨烯具有较高的均一度，在拉伸强度基本保持不变的情况下，弯曲强度和冲击强度有了明显的改善。

Claims (10)

  1. 一种从有机材料制备磺化石墨烯的方法，所述方法包括以下步骤：
    第一接触步骤：在第一温度使含有氧化性磺化剂的反应介质与所述有机材料接触；和
    第二接触步骤：在第一接触步骤结束后，在同一反应介质中，将反应温度升高至第二温度使其继续反应，从而获得所述磺化石墨烯。
  2. 权利要求1的方法，其中所述氧化性磺化剂选自：通式R-SO3H的化合物，其中R选自F、Cl、Br；H2SO4与HCl的组合；H2SO4与HF的组合；浓硫酸；发烟硫酸；及其组合，
    优选地，其中所述氧化性磺化剂在所述反应介质中的浓度为高于98％。
  3. 权利要求1的方法，其中所述第一温度为所述有机材料的熔融温度至低于所述反应介质的沸点，所述第二温度为所述反应介质的沸点以上；优选地，其中所述第一温度为40-130℃；所述第二温度为150-220℃。
  4. 权利要求1的方法，其中所述第一接触步骤进行的时间为1小时至40小时；所述第二接触步骤进行的时间为1小时至40小时。
  5. 权利要求1的方法，其中所述有机材料选自有机高分子材料和有机小分子材料，其中优选地，所述有机高分子材料选自：聚乙烯蜡、氯化聚乙烯、乙炔低聚物、聚乙炔、含卤族元素的聚炔烃、聚乙烯、聚氯乙烯、含卤族元素的聚烯烃；其中优选地，所述有机小分子材料选自C4-C50直链烃或带苯环结构的芳香烃。
  6. 权利要求1的方法，其中所述有机材料的结晶度为：0-30％，或者20～40％，或者50～80％，或者60％～90％；所述有机材料的分子量为：50-50000，优选50-10000。
  7. 权利要求1的方法，其中所述有机材料与反应介质的重量比为：5:1至1:500，优选1:3至1:70。
  8. 一种磺化石墨烯，其中所述磺化石墨烯带有磺酸基团，其特征在于，所述磺化石墨烯的碳/硫比为：12:1至1:1，优选10:1至2:1；更优选8:1至3:1，最优选6:1至3:1。
  9. 权利要求8的磺化石墨烯，其中所述磺化石墨烯的片径(材料的平面直径)为大于10微米，优选大于50微米，更优选大于或等于100微米至 小于1000微米；厚度为0.5至100纳米，优选1至50纳米，优选1至10纳米，优选1至5纳米；优选地，所述磺化石墨烯的厚度(材料平面法向方向的距离)均一度超过90％；优选地，所述磺化石墨烯的片径均一度超过90％。
  10. 权利要求8或9的磺化石墨烯在透明导电电极、导热材料、超级电容、晶体管、燃料电池、集成电路、太阳能电池、生物负载、络合剂、复合材料、螯合剂、水性涂料、水性润滑、移动设备、航空航天材料、油墨或感光元件中的用途。
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