CN1781999A - Nano carbon black with in-situ grafted organic compound and its producing method - Google Patents

Abstract

This patent relates to a nano-carbon black grafted with organic compounds in situ and a preparation method thereof. Said nano-carbon black is prepared by directly grafting carbon black with an organic compound having or capable of generating active free radicals at a temperature above its melting point under the action of a mechanical shear force field, and the resulting grafted carbon Black not only has better dispersibility and compatibility, but also shows nano-effects that general modified carbon blacks do not have. In addition, the carbon black modification method in the present invention not only needs no solvent, no pollution, simple process and low cost, but also is a modification method that can continuously produce carbon black in large quantities.

Description

Nano-carbon black with in-situ grafted organic compound and its manufacturing method

technical field

The present invention relates to a kind of surface-modified carbon black used in fields such as rubber industry, plastics industry, printing ink, paint, dry battery and its preparation method, specifically, to a kind of nano-carbon black and a kind of in-situ grafted organic compound its preparation method.

technical background

Carbon black is widely used in many industries such as rubber, plastics, etc. due to its reinforcement, function-giving, improved processability and additive effect. There are few occasions where powdery or granular carbon black is used alone, and most of them are used by uniformly dispersing carbon black in solid substances (such as raw rubber, polymers such as plastics and fibers) or liquid substances (water or solvents, etc.) . However, due to the large specific surface area of carbon black particles, it is very easy to agglomerate, and it is difficult to achieve its uniform dispersion in polymer matrix or organic solvents. Moreover, carbon black as an inorganic filler is also difficult to be compatible with organic substances such as polymers and solvents. limit its potential performance. On the other hand, with the rapid development of nanotechnology and information technology, the requirements for the dispersion of carbon black in polymer matrix or organic solvent and the compatibility between carbon black and polymer or organic solvent are also getting higher and higher.

In order to give full play to the characteristics of carbon black and improve the performance of carbon black/polymer composite materials or carbon black dispersions such as coatings, it is often necessary to modify carbon black. Currently known carbon black surface modification methods include oxidation method, surfactant treatment method, polymer dispersant treatment method and surface graft modification method. Among them, surface graft modification is the most effective.

The carbon black surface grafting technology developed rapidly in the past forty years is an important chemical modification method to improve the dispersion and compatibility of carbon black. According to previous research results, we can find that the dispersibility of carbon black in the polymer matrix or organic solvent and the compatibility with the dispersion medium can be improved by polymer graft modification on the surface of carbon black, and endow Various functions of carbon black, such as photosensitivity, heat sensitivity, gas sensitivity, biological activity, cross-linking ability and hydrophilic and lipophilic properties, improve the mechanical properties, electrical properties, optical properties and Anti-electromagnetic radiation, etc. Therefore, the surface graft modification of carbon black has always been a hot spot in the research of rubber and other industries.

The research on carbon black grafting can be traced back to the discussion on the carbon black reinforcement mechanism of rubber in the early 1950s. After 40 years of research accumulation, many methods for grafting and modifying the surface of carbon black have been invented. These researches can be summarized into the following three directions:

(1) Grafting on carbon black: the growing polymer chain is captured by free radicals, anion or cationic groups on the surface of carbon black and is connected on the surface of carbon black (such as Japanese Patent No. 42-22047, No. 44- 3826, JP 45-17248, JP 46-26970, JP 6-263830, U.S. Patents 3557040, 4530961, etc.);

(2) Polymerization and grafting from carbon black: Utilize active groups introduced on the surface of carbon black, or use discharge, ultraviolet rays, and ozone treatment to make the surface of carbon black generate peroxide groups to initiate polymerization of polymer monomers (such as Japan Patent No. 6-25573, No. 2003-64279, No. 2003-41149, etc.), the polymerization reaction can be subdivided into three types: radical polymerization, anionic polymerization, and cationic polymerization;

(3) Reaction of carbon black and macromolecules: the functional group on the surface of carbon black reacts with functional macromolecules (such as Japanese Patent 2-24868, Japanese Patent 6-27269, Japanese Patent 2000-154327, U.S. Patent 5952429, etc. ). It can be further divided into two types: the reaction of activated carbon black with polymers with hydroxyl or amino groups and the reaction of carboxyl or phenolic hydroxyl groups on the surface of carbon black with functional polymers with active end groups.

Carbon black can be used in inks, coatings, nanocomposites, and gas sensors after being modified by grafting its surface polymers. However, the grafting reaction on the surface of these carbon blacks has some fatal defects. First of all, the above-mentioned three known carbon black surface graft modification reactions are all carried out in a solution system, which is not conducive to large-scale production, high cost, and easy to pollute the environment. Secondly, whether it is the direct grafting of polymer chains on the carbon black surface or the polymerization from the carbon black surface after monomer grafting, the structure of the modified layer on the carbon black surface is not easy to control. When using polymer grafting modification, because the polymer has low reactivity and great steric hindrance, the grafting rate is low; and the grafting monomer is re-initiated, although the grafting rate is high, but the synthesis process More loaded down with trivial details, and the molecular weight of grafted polymer is also difficult to control. The reaction between carbon black and macromolecules in method (3) can connect macromolecules with a specified structure, and it is easy to control the molecular weight and chain number of macromolecules grafted on the surface of carbon black. However, the types of macromolecules that can react with carbon black Limited (polymers with hydroxyl groups, amino epoxy groups and polymers), and only suitable for channel blacks with more oxygen-containing functional groups on the surface, for furnace blacks with fewer oxygen-containing functional groups on the surface (the leading species of carbon black, accounting for about %) is difficult to obtain satisfactory results. Third, polymer graft modification is carried out in a solution system. Although ultrasonic dispersion treatment is also performed, the agglomeration structure cannot be destroyed (as shown in Figures 1 and 2), and monodisperse primary particles cannot be obtained. .

In summary, it is extremely difficult to prepare monodisperse nano-carbon black that can be uniformly dispersed in a polymer matrix or in water or an organic solvent by applying the existing technology.

Contents of the invention

One of the purposes of the present invention is to provide a kind of in-situ grafting of organic compounds, high dispersibility in the polymer matrix or in organic solvents and good compatibility with the dispersion medium, and the size can be precisely controlled , nano carbon black that can form a stable dispersion system in organic solvents and polymer matrices.

The second object of the present invention is to provide a method for preparing the above-mentioned nano carbon black.

Design of the present invention is such:

In order to solve the problems in the prior art and realize the purpose of the present invention, the inventor found through in-depth research that there are oxygen-containing functional groups such as carboxyl groups, quinone groups, phenol groups and lactone groups on the surface of carbon black and active active groups on the edge of the layer. Hydrogen atoms, these groups or atoms are very active free radicals, if there are other active free radicals around the carbon black particles, they can undergo free radical termination reactions with them; hindered phenolic compounds, amine compounds, phosphate esters Antioxidants such as antioxidants, sulfur-containing compounds, and light stabilizers such as hindered amine compounds and phenolic compounds have the function of capturing active free radicals; therefore, under the action of strong shear force (carbon black aggregates can be destroyed and become Primary particles), carbon black and the above-mentioned organic compounds are directly grafted to obtain high dispersion in the polymer matrix or in organic solvents and good compatibility with the dispersion medium, and the size can be precisely controlled. The nano carbon black capable of forming a stable dispersion system in an organic solvent and a high polymer matrix, thereby achieving the purpose of the present invention.

The nano-carbon black of in-situ grafted organic compound in the present invention is characterized in that, with the organic compound having or being able to generate free radicals and carbon black as the main reactants, the organic compound having or being able to generate free radicals is passed through the original grafting reaction grafted to the surface of carbon black;

Wherein: said organic compound having or being able to generate free radicals is phenolic compounds, amine compounds and/or polymers that are broken into free radicals under the action of a mechanical shear force field; with 100 parts by weight of carbon black As a basis, the amount of the organic compound having or capable of generating free radicals is 5-300 parts (parts by weight).

In the present invention, in order to graft more organic compounds to the carbon black surface, it is required that the carbon black surface has sufficient oxygen-containing functional groups such as carboxyl, quinone, phenol and lactone groups and active hydrogen atoms at the edge of the layer. Therefore, the oxygen content of the carbon black used is preferably above 0.1 wt%, and the hydrogen content is preferably above 0.2 wt%. If the oxygen content and hydrogen content of the carbon black used are lower than the above values, it can be oxidized by gas phase oxidation such as hot air oxidation and ozone oxidation, or by liquid phase oxidation such as nitric acid, hydrogen peroxide, potassium permanganate, sodium hypochlorite, bromine water, etc. Oxidation treatment to increase the oxygen and hydrogen content of carbon black.

The organic compounds with or capable of generating free radicals used in the present invention are phenolic compounds, amine compounds or/and polymers that are broken into free radicals under the action of a mechanical shear force field. The recommended organic compounds are hindered phenols or/and hindered amines.

Wherein said phenolic compounds include following compounds:

(organic compound 1)

(organic compound 2)

(organic compound 3)

(organic compound 4)

(organic compound 5)

(organic compound 6)

(organic compound 7)

(organic compound 8)

(organic compound 9)

(organic compound 10)

(organic compound 11)

(organic compound 12, n=1-100)

(organic compound 13)

(organic compound 14)

(organic compound 15)

(organic compound 16)

(organic compound 17)

(organic compound 18)

(organic compound 19)

(organic compound 20)

(organic compound 21)

(organic compound 22)

(organic compound 23)

(organic compound 24)

(organic compound 25)

(organic compound 26)

(organic compound 27)

(organic compound 28)

(organic compound 29)

(organic compound 30)

(organic compound 31)

(organic compound 32)

(organic compound 33)

(organic compound 34)

(organic compound 35)

(organic compound 36)

(organic compound 37)

(organic compound 38)

(organic compound 39)

(organic compound 40)

(organic compound 41)

(organic compound 42)

(organic compound 43)

(organic compound 44)

(organic compound 45)

(organic compound 46)

(organic compound 47)

R = alkyl

(organic compound 48, n=1-100)

(organic compound 49)

(organic compound 50)

(organic compound 51)

(organic compound 52)

(organic compound 53)

(organic compound 54)

(organic compound 55)

(organic compound 56)

(organic compound 57)

(organic compound 58)

(organic compound 59)

(organic compound 60)

(organic compound 61)

(organic compound 62)

R＝C ₇ H ₁₅ -C ₉ H ₁₉

(organic compound 63)

(organic compound 64)

(organic compound 65)

(organic compound 66)

(organic compound 67)

(organic compound 68)

(organic compound 69)

(organic compound 70)

(organic compound 71)

(organic compound 72)

(organic compound 73)

(organic compound 74)

(organic compound 75)

(organic compound 76)

(organic compound 77)

(organic compound 78)

(organic compound 79)

(organic compound 80)

(organic compound 81)

(organic compound 82)

(organic compound 83)

(organic compound 84)

(organic compound 85)

(organic compound 86)

(organic compound 87)

Said aromatic secondary amine compounds include following compounds:

(organic compound 88)

(organic compound 89)

(organic compound 90)

(organic compound 91)

R＝C ₇ H ₁₅ ~C ₉ H ₁₉

(organic compound 92)

(organic compound 93)

(organic compound 94)

(organic compound 95)

(organic compound 96)

(organic compound 97)

(organic compound 98)

(organic compound 99)

(organic compound 100)

(Organic Compounds 101)

R＝C ₇ H ₁₅ ~C ₉ H ₁₉

(Organic Compound 102)

(Organic Compound 103)

(organic compound 104)

(organic compound 105)

(organic compound 106)

(organic compound 107)

(organic compound 108)

(organic compound 109)

(organic compound 110)

(Organic Compound 111)

(organic compound 112)

(organic compound 113)

(organic compound 114)

(organic compound 115)

(organic compound 116)

(organic compound 117)

(organic compound 118)

(organic compound 119, x=1-100)

(organic compound 120, x=1-100)

n=2～4

(organic compound 121)

(organic compound 122, n=1-100)

(organic compound 123, n=1-100)

(organic compound 124)

(organic compound 125)

(organic compound 126)

(organic compound 127)

(organic compound 128)

(organic compound 129)

(organic compound 130)

(organic compound 131)

(organic compound 132)

(organic compound 133)

(organic compound 134)

(organic compound 135)

(I) R ₁ -NHC ₆ H ₄ NHC ₆ H ₅

(II)R ₂ -OC ₆ H ₄ NHC ₆ H ₅

(organic compound 136)

(organic compound 137)

(organic compound 138)

(organic compound 139, m=1-100, n=1-100,)

Said polymer that breaks into free radicals under the action of the mechanical shear force field is preferably selected from natural rubber and olefinic rubber that contain less stable double bonds in the molecular chain, and the interaction between the molecular chains is relatively small.

In order to stabilize the nano-carbon black grafted with organic compounds in situ, phosphate compounds or/and sulfur-containing compounds can also be added as secondary antioxidants. The sulfur-containing compounds refer to mercaptans, thiophenols or thioether compounds, the amount of auxiliary antioxidant is 5-300 parts (parts by weight). Said auxiliary antioxidant comprises following compound:

(organic compound 140)

(organic compound 141)

(organic compound 142)

(organic compound 143)

(organic compound 144)

(organic compound 145)

(organic compound 146)

(organic compound 147)

(organic compound 148)

(organic compound 149)

(organic compound 150)

(organic compound 151)

(organic compound 152)

(organic compound 153)

(organic compound 154)

(organic compound 155)

The method for preparing said nano-carbon black of the present invention, its main steps are: disperse carbon black from agglomerate state into primary particles in a mechanical shear force field of 20-2000Nm, and then add an organic compound with or capable of generating free radicals , at a temperature above the melting point of the organic compound that has or can generate free radicals, the grafting reaction is directly carried out.

Wherein said mechanical shear force field can be obtained by using Haake rheometer, grinding machine, single-screw extruder, twin-screw extruder, planetary screw extruder, conical screw extruder, continuous kneading machine , internal mixer, Z-shaped kneader or any other commercially available mixing equipment that can produce mechanical shear force. It not only has simple process and low cost, but also can be produced continuously in large quantities.

Description of drawings

Figure 1 is a transmission electron microscope photo of carbon black

Fig. 2 is the schematic diagram of carbon black structural model

Fig. 3 is the centrifugal sedimentation experiment result of grafted carbon black and ungrafted carbon black

Figure 4 is an atomic force microscope photo of grafted carbon black

The present invention blends organic compounds such as phenolic compounds, amine compounds, and organic compounds that are broken into active free radicals under the action of mechanical shearing force with carbon black in a mixing device that can generate relatively large shearing force. The grafting reaction is directly carried out at a temperature above the melting point of the organic compound with active free radicals, so as to obtain the nano carbon black coated with the organic compound. The prepared carbon black not only has good dispersibility and compatibility, but also shows nano-effects that ordinary carbon black does not have. get used. The preparation method of the carbon black not only has simple process, no need of solvent, low cost and no pollution, but also can be mass-produced continuously.

Detailed ways

The present invention is described further below by embodiment, and its purpose is to better understand content of the present invention. Therefore, the examples given do not limit the protection scope of the present invention:

Example 1

Nano-carbon black using antioxidant AO-80: 100 parts of carbon black (N220, Mitsubishi Chemical Industry Co., Ltd.), and 80 parts of AO-80 (Asahi Denka Kogyo Co., Ltd.).

AO-80 is a hindered phenolic antioxidant, AO-80 is its trade name, and its chemical name is 3,9-bis{1,12methyl-2[β-3-tert-butyl-4-hydroxy-5 -cresol]propionyloxy}ethyl)}-2,4,8,10-tetraoxaspiro[5,5]undecane, with a melting point of 125°C, capable of producing active free radicals, the molecular formula is as follows:

The carbon black and AO-80 were melt-blended in a Haake rheometer at 140° C. higher than the melting point of AO-80 (125° C.), the rheometer rotation speed was 60 rpm, and the blending time was 30 minutes. When the blending time reaches about 3.5 minutes and the temperature rises to 175°C, the torque of the mixture of AO-80 and carbon black increases sharply, and the torque tends to a stable value after the reaction is complete.

The reaction product of carbon black and AO-80 obtained above was put into a Soxhlet extractor and extracted with toluene for 72 hours to ensure that there was no free AO-80 in the carbon black. The extracted filtrate and carbon black samples were taken for FTIR-ATR test, the results showed that there was no AO-80 in the filtrate, and the extraction was complete. The FTIR-ATR spectrum of the carbon black sample modified with AO-80 shows that the surface of the carbon black is grafted with AO-80.

Take 1 part of ungrafted carbon black and grafted carbon black respectively and put them into a beaker, add 100 parts of acetone, place them in an ultrasonic cleaner (DL-360D) produced by Shanghai Zhixin Instrument Co., and disperse them ultrasonically for 10 min. At 25°C, a carbon black dispersion was prepared. Then, the centrifugal sedimentation experiment was carried out on the LDZ4-0.8 centrifuge produced by Beijing Medical Centrifuge Factory to test its dispersion effect. Take 5ml of the dispersion, place it in a centrifuge (4000rpm), and take it out every 10 minutes to measure the dispersibility index. As shown in Figure 3, in the case of no grafting, the carbon black will settle immediately, otherwise, the suspension of grafted carbon black remains stable for a long time, and the purpose of the present invention is achieved.

The particle size distribution in the suspension was measured with a BECKMAN COUTLER laser scattering particle size analyzer, and the obtained particle size distribution is shown in Table 1. In the ultrasonic dispersion suspension of ungrafted carbon black (N220), the precipitation of larger carbon black aggregates can be clearly observed, and the particle size distribution in the suspension is shown in Table 2. Comparing Table 1 and Table 2, it can be found that the grafting effect of AO-80 on the surface of carbon black is very significant.

The particle size distribution of the grafted carbon black (N220/AO-80) of table 1 embodiment 1 in acetone solvent Size(nm) 48 52 57 413 Number(%) 49 35 15 1

Table 2 Particle size distribution of ungrafted carbon black (N220) Size(nm) 94 122 139 158 180 205 234 1749 Number% twenty one 7 10 twenty three 19 3 4 3

The stable suspension was taken for AFM observation, and a nearly monodisperse photo of carbon black was obtained, with a particle size of about 40nm (as shown in Figure 4). It is completely consistent with the particle size test result of the above-mentioned laser scattering particle size analyzer.

Some conventional characterizations have been carried out to this grafted carbon black, and the obtained results are as follows:

Table 3 The conventional characterization of the grafted carbon black (N220/AO-80) of Example 1

The iodine absorption value and CTAB value of grafted carbon black are lower than those of untreated carbon black, indicating that the specific surface area of grafted carbon black is smaller, indicating that the surface of carbon black is coated with organic molecules, which reduces its specific surface area. The decrease of DBP absorption value shows that the structure of grafted carbon black is low, there are no large aggregates, and the distribution is relatively uniform.

Example 2

Nano carbon black using antioxidant AO-60: 100 parts of carbon black (N220, Mitsubishi Chemical Industry Co., Ltd.), 80 parts of AO-60 (Asahi Denka Co., Ltd.).

AO-60 is also a hindered phenolic antioxidant. AO-60 is its trade name and its chemical name is 4[β-(3,5-di-tert-butyl-4-phenol)propionyloxy]methane. The structural formula is as follows, The melting point is 115°C, and it can also generate active free radicals.

Except that the set temperature of the Haake rheometer was 130°C in the experiment, other conditions were the same as in Example 1. The particle size distribution determined by the laser scattering particle size analyzer is shown in Table 4.

The particle size distribution of the grafted carbon black (N220/AO-60) of table 4 embodiment 2 in acetone solvent Size(nm) 46 54 64 253 300 Number(%) 36 40 11 5 8

The particle size of the obtained carbon black is also about 50nm, it can form a stable suspension in acetone, and its dispersion performance is very good. The general physical properties of carbon black are also similar to Example 1.

Example 3

Nano carbon black using light stabilizer LA-57: 100 parts of carbon black (N220, Mitsubishi Chemical Industry Co., Ltd.), 80 parts of LA-57 (Asahi Denka Kogyo Co., Ltd.).

LA-57 is a light stabilizer, LA-57 is its trade name, and its standard name is 2,2,6,6-tetramethyl-4-piperidinyl-1,2,3,4-butyrate , the structural formula is as follows, the melting point is 132°C, and it can generate active free radicals.

In the experiment, the set temperature of the Haake rheometer was 150°C, and the blending time was extended to 40 minutes. All the other conditions are the same as in Example 1. The particle size distribution measured by the laser scattering particle size analyzer is shown in Table 5.

The particle size distribution of the grafted carbon black (N220/LA-57) of table 5 embodiment 3 in acetone solvent Size(nm) 68 71 78 81 180 197 Number(%) 10 28 51 5 4 2

The particle size of the obtained carbon black is less than 100nm, the monodispersity is very good, and a stable suspension can be formed in acetone. The general physical properties of carbon black are also similar to Example 1.

Example 4

Nano-carbon black using antioxidant N300: 100 parts of carbon black (N220, Mitsubishi Chemical Industry Co., Ltd.), and 80 parts of N300 (Ouchi Shinko Chemical Industry Co., Ltd.).

Antiaging agent N300 is its trade name, its structural formula is as follows, and its standard name is: 4-4'thiobis(3-methyl-6-tert-butylphenol), its structural formula is as follows, its melting point is 155°C, and it can generate active free radicals.

In the experiment, the set temperature of the Haake rheometer was 170°C, and the blending time was extended to 40 minutes. All the other conditions are the same as in Example 1. The particle size distribution measured by the laser scattering particle size analyzer is shown in Table 6.

The particle size distribution of the grafted carbon black (N220/N300) of table 6 embodiment 4 in acetone solvent Size(nm) 60 63 66 70 182 191 Number(%) twenty one 36 29 12 1 1

The particle size of the obtained carbon black is less than 100nm, the monodispersity is very good, and a stable suspension can be formed in acetone. The general physical properties of carbon black are also similar to Example 1.

Example 5

Grafted carbon black using natural rubber: 100 parts of carbon black (N220, Mitsubishi Chemical Industry Co., Ltd.), 100 parts of natural rubber (Shanghai Ruiyang Rubber Chemical Co., Ltd.).

The main component of natural rubber commonly used at present is polyisoprene, with a glass transition temperature Tg of -73°C and a melting point of 30°C.

In the experiment, the set temperature of the Haake rheometer was 100° C., the blending time was 120 minutes, and the rest of the conditions were the same as in Example 1. The particle size distribution measured by laser scattering particle size analyzer is shown in Table 7

The particle size distribution of the grafted carbon black (N220/NR) of table 7 embodiment 5 in acetone solvent Size(nm) 162 278 400 500 600 Number(%) 58 twenty two 11 6 3

The resulting carbon black has good dispersibility in acetone and can form a stable suspension. The general physical properties of carbon black are also similar to Example 1.

Example 6

Nano carbon black using antioxidant AO-80: 100 parts of pigment carbon black (Raven 1035, Columbia Chemical Company) for oil black, and +80 parts of AO-80 (Asahi Denka Industry Co., Ltd.).

In order to realize the application of the nano-carbon black of the present invention in ink, the inventors have adopted pigment carbon black for ink. All experimental conditions are the same as in Example 1, and the obtained results (Table 8) prove that this method is applicable to carbon black for ink.

The particle size distribution of the grafted carbon black (Raven 1035/AO-80) of table 8 embodiment 6 in acetone solvent Size(nm) 63 66 69 72 169 177 Number(%) 27 35 27 8 2 1

Example 7

Nano-carbon black using antioxidant AO-80: 100 parts of high-conductivity carbon black (ENSACO 350G, Temegao Graphite Co., Ltd.), and 80 parts of AO-80 (Asahi Denka Kogyo Co., Ltd.).

Highly conductive carbon black has a very high structure and very stable aggregates. In order to realize the application of nano-carbon black of the present invention in conductive coatings and composite conductive materials, the inventors adopted high-conductivity carbon black. All experimental conditions are the same as in Example 1, and the obtained results (Table 9) prove that this method is applicable to highly conductive carbon black.

The particle size distribution of the grafted carbon black (ENSACO 350G/AO-80) of table 9 embodiment 7 in acetone solvent Size(nm) 60 75 95 119 189 300 Number(%) 50 33 11 3 2 1

Example 8

Nano carbon black using antioxidant AO-80 and oxidized carbon black: oxidized carbon black (Seast 300 obtained through oxidation treatment, referred to as OCB, its surface area and oil absorption are shown in Table 10, Tokai Tanhei Chemical Industry Co., Ltd.) 100 parts, AO-80 (Asahi Kasei Industries Co., Ltd.) 80 parts.

Table 10 Oxidation treatment effect of carbon black sample Nitrogen adsorption specific surface area (m ² /g) DBP absorption value (ml/100g) pH value Seat 300 84 75 7.9 OCB 123 122 3.1

The number of functional groups on the surface of the oxidized carbon black increases, which is more conducive to the grafting reaction. Moreover, the specific surface area is large and the structure is high, so the aggregates are relatively easy to be destroyed under the same mixing conditions. The inventors used oxidized carbon black, and the rest of the experimental conditions were the same as in Example 1. The obtained results (Table 11) showed that the grafted oxidized carbon black not only had a small particle size, but also was monodisperse. Therefore, the effect of graft modification using carbon black is more effective than that of general carbon black.

The particle size distribution of the grafted carbon black (Seast 300/AO-80) of table 11 embodiment 8 in acetone solvent Size(nm) 42 180 210 Number(%) 98 1 1

Example 9

Nano carbon black using antioxidant AO-80 and the third component: 100 parts of carbon black (N220, Mitsubishi Chemical Industry Co., Ltd.), 80 parts of AO-80 (Asahi Chemical Industry Co., Ltd.), TNP (Ouchi Shining Chemical Industry Co., Ltd.) Co., Ltd.) 40 copies.

The inventor added the third component TNP into the system, its structural formula is as follows, and the rest of the experimental conditions are the same as in Example 1. Compared with Example 1, it was found that the graft modification of carbon black was more effective after adding the third component TNP (Table 12).

The particle size distribution of the grafted carbon black (N220/AO-80/TNP) of table 12 embodiment 9 in acetone solvent Size(nm) 44 52 61 190 210 Number(%) 40 38 20 1 1

Example 10

One of the innovations of the present invention is that under the action of a strong shear force field, the carbon black aggregates are broken into primary particles, and in-situ grafting of organic compounds is realized in the process. The mixing equipment was changed to the MD50-100 continuous mixer of Coperon Keya (Nanjing) Machinery Co., Ltd., and the formula and preparation method were the same as in Example 2. The particle size distribution measured by the laser scattering particle size analyzer is shown in Table 13, which shows that it is also effective to prepare grafted nano-carbon black with a continuous mixer suitable for large-scale production.

The particle size distribution of the grafted carbon black (N220/AO-60) of table 13 embodiment 10 in acetone solvent Size(nm) 56 117 141 170 204 428 Number(%) 78 8 7 4 2 1

Claims (10)

1, a kind of nano carbon black of in-situ grafted organic compound, it is characterized in that, to have the organic compound and the carbon black that maybe can produce free radical is the principal reaction thing, will have the organic compound that maybe can produce free radical and arrive the sooty surface by the situ-formed graft reactive grafting;

Wherein: said have the organic compound that maybe can produce free radical and comprise that phenolic compound, aminated compounds are or/and at the polymkeric substance that is subjected to fragment under the mechanical shearing force field free radical; Carbon black with 100 parts by weight is a benchmark, and the consumption with the organic compound that maybe can produce free radical is 5～300 parts.

2, nano carbon black as claimed in claim 1 is characterized in that, wherein said sooty oxygen level is at least 0.1wt%, and hydrogen richness is at least 0.2wt%.

3, nano carbon black as claimed in claim 1 or 2 is characterized in that, wherein said to have the organic compound that maybe can produce free radical be that hindered phenol is or/and hindered amine compound.

4, nano carbon black as claimed in claim 3 is characterized in that, wherein said to have the organic compound that maybe can produce free radical be 3,9-pair 1, the 12 methyl-2[β-3-tertiary butyl-4 monohydroxies-5-cresylol] and propionyloxy } ethyl group)-2,4,8,10-Si Evil spiral shell [5,5] undecane or 4[β-(3,5-di-t-butyl-4-phenol) propionyloxy] methane, 2,2,6,6-tetramethyl--4 piperidyl-1,2,3,4-fourth tetracid ester or 4-4 ' thiobis (3 methy 6 tert butyl phenol).

5, nano carbon black as claimed in claim 1 or 2 is characterized in that, wherein reactant also comprises phosphate compounds or/and the sulfur-bearing compounds, and its consumption is 5～300 parts by weight.

6, nano carbon black as claimed in claim 5 is characterized in that, wherein said sulfur-bearing compounds is mercaptan, thiophenol or thio-ether type compounds.

7, the method for preparation nano carbon black as claimed in claim 1 or 2, it is characterized in that, said preparation method's key step is: in the mechanical shearing field of force is among 20～2000Nm carbon black to be dispersed into primary partical from the coacervate state, add then and have the organic compound that maybe can produce free radical, under the temperature more than the fusing point with the organic compound that maybe can produce free radical, after directly carrying out graft reaction, be target compound.

8, the described preparation method of claim 7, it is characterized in that the wherein said mechanical shearing field of force can be realized by using Haake torque rheometer, mill machine, single screw extrusion machine, twin screw extruder, Planetary Screw Extruder, conical screw extruder, continuous muller, internal mixer, Z-shaped kneader or other any commercially available mixing equipment that can produce the mechanical shear stress effect.

9, claim 1 is described has an organic compound that maybe can produce living radical, it is characterized in that oligopolymer, superpolymer are fragmented into by the mechanical shearing force field and have the organic compound that maybe can produce living radical.

10, claim 9 is described has an organic compound that maybe can produce living radical, when it is characterized in that oligopolymer, superpolymer are subjected to the mechanical shearing force field, at ultrasonic wave, microwave, ultraviolet ray, electromagnetic wave irradiation such as infrared, or under ozonization, or under other any oxygenant effect, fragment into organic compound with living radical.

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