CN1781999A - Nano carbon black with in-situ grafted organic compound and its producing method - Google Patents
Nano carbon black with in-situ grafted organic compound and its producing method Download PDFInfo
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- CN1781999A CN1781999A CN 200410066739 CN200410066739A CN1781999A CN 1781999 A CN1781999 A CN 1781999A CN 200410066739 CN200410066739 CN 200410066739 CN 200410066739 A CN200410066739 A CN 200410066739A CN 1781999 A CN1781999 A CN 1781999A
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Abstract
The present invention relates to a kind of nano carbon black with in-situ grafted organic compound and its preparation process. Under the action of mechanical shearing force field, carbon black and organic compound possessing or capable of producing active free radical are made to produce direct grafting reaction at the temperature over the smelting point forming the grafted carbon black. The obtained grafted carbon black has high dispersivity and compatibility, as well as nano effect common modified carbon black does not have. In addition, the said carbon black modifying process needs no solvent, has no pollution, simple procedure and low cost, and is suitable for continuous production.
Description
Technical field
The present invention relates to a kind of fields such as rubber industry, plastics industry and printing ink, coating, drying battery that are applied to, surface modified carbon black and preparation method thereof specifically, relates to nano carbon black of a kind of in-situ grafted organic compound and preparation method thereof.
Technical background
Carbon black because of its enhancing, function endowing, improve processibility and the increment effect is widely used in many industries such as rubber, plastics.The occasion of using separately powdery or dustless carbon black seldom, great majority are evenly dispersed in carbon black in solid matter (as polymkeric substance such as rubber, plastics and fibers) or the aqueous material (water or solvent etc.) and use.But because the carbon black particle specific surface area is big, very easily aggegation is difficult to realize its homodisperse in macromolecule matrix or organic solvent, and, also be difficult to as the carbon black of mineral filler compatible with organism such as polymkeric substance, solvents, thereby limited the maximum performance of its potential performance.On the other hand, along with developing rapidly of nanotechnology, information technology, require also more and more higher to the dispersiveness requirement and the consistency of carbon black and polymkeric substance or organic solvent of carbon black in macromolecule matrix or organic solvent.
In order to give full play to the sooty characteristic, improve carbon black/polymer composites or, often need carbon black is carried out modification as the performance of carbon black dispersion liquids such as coating.Present known carbon blacksurface method of modifying has oxidation style, tensio-active agent facture, macromolecule dispersing agent facture and surface graft modification method.Wherein, the most effective with surface graft modification.
The carbon blacksurface crosslinking technology that developed rapidly in nearly 40 years is important chemical modification means improving carbon black dispersion, consistency.According to achievement in research in the past, we can find: by the polymer graft modification of carbon blacksurface, can improve carbon black dispersed in polymeric matrix or in the organic solvent and and dispersion medium between consistency, and give carbon black various functions, such as photosensitivity, thermo-sensitivity, gas sensing property, biological activity, crosslinked ability and amphipathic property, improve mechanical property, electric property, optical property and the anti-electromagnetic radiation etc. that contain the various matrix materials of sooty.So the sooty surface graft modification is a focus in the industrial research such as rubber always.
Research can be traced back to the discussion of the early fifties of eighties of last century about the black-reinforced mechanism of rubber to the carbon black grafted.Through the research accumulation in 40 years, invented many methods about the carbon blacksurface graft modification, these researchs can be generalized into following 3 directions:
(1) in grafting on the carbon black: the polymer chain of growth is caught by the free radical of carbon blacksurface, negatively charged ion or cation group and is connected on the carbon blacksurface (opening flat 6-263830, United States Patent (USP) 3557040,4530961 etc. as the special public clear 42-22047 of Japanese Patent, special public clear 44-3826, special public clear 45-17248, special public clear 46-26970, spy);
(2) graft polymerization from the carbon black: the active group that utilizes carbon blacksurface to introduce, perhaps utilize discharge, ultraviolet ray, ozonize make carbon blacksurface generate the monomeric polyreaction of peroxidation group initiated polymerization thing (as Japanese patent laid-open 6-25573, spy open 2003-64279, the spy opens 2003-41149 etc.), polyreaction can be segmented three kinds of radical polymerizations, anionoid polymerization, cationoid polymerisation;
(3) carbon black and high molecular reaction: the functional group of carbon blacksurface and functionality polymer react (opening 2000-154327, United States Patent (USP) 5952429 etc. as Japanese Patent special fair 2-24868, special fair 6-27269, spy).Can be further divided into two kinds of the sense high molecular weight reactives of the carboxyl of active black and hydroxyl or amino high molecular weight reactive and carbon blacksurface or phenolic hydroxyl and band active end group.
Carbon black can be used for printing ink, coating and nano composite material and gas sensor etc. by after its surface aggregate thing graft modification, has been subjected to the extensive concern of industrial community, and various applied researcies launch rapidly.But the graft reaction of these carbon blacksurfaces all exists some fatal defectives.At first above-mentioned three kinds of known carbon blacksurface graft modification reactions are all carried out in solution system, are unfavorable for scale production, and cost is high again, and easy contaminate environment.Secondly, no matter be that the direct grafting or the monomer-grafted back of polymer chain on carbon blacksurface begins polymerization from carbon blacksurface, the modified layer structure of carbon blacksurface is easy-regulating not.When adopting polymer graft modification, because the reactive behavior of polymkeric substance is lower and steric hindrance is very big, so percentage of grafting is lower; And by the polymerization of grafted monomer re-initiation, though percentage of grafting is higher, building-up process is more loaded down with trivial details, and the molecular weight of graftomer also is difficult to control.The carbon black of method (3) can be connected the polymer with specified structure with high molecular reaction, control carbon blacksurface high molecular molecular weight of institute's grafted and chain number easily, but, can be limited with the high molecular kind of carbon black reaction (hydroxyl, amino epoxy group(ing) and polymer), and only be applicable to the channel black that surface oxygen functional group is more, then be difficult to obtain satisfied result for the less furnace black of surface oxygen functional group (, accounting for 90%) for the leading kind of sooty.The 3rd, polymer graft modification all is to carry out at solution system, though also done the ultrasonic dispersing processing, all fails to destroy its aggregate structure (as shown in Figure 1, 2), can not get monodispersed primary partical.
In sum, using prior art for preparing goes out to be evenly dispersed in the polymeric matrix or the dispersed nano carbon black of water, organic solvent is extremely difficult.
Summary of the invention
One of purpose of the present invention is, provide in the polymeric matrix a kind of organic compound situ-formed graft, high or organic solvent in dispersiveness become reconciled and dispersion medium between consistency, size can accurately control, and can form the nano carbon black of stable dispersion system in organic solvent and superpolymer matrix.
Two of purpose of the present invention is, a kind of method for preparing above-mentioned nano carbon black is provided.
Design of the present invention is such:
The present inventor has problems for solving in the prior art, realize purpose of the present invention, by deep discovering: exist carboxyl, quinonyl, phenolic group and lactone group etc. to contain the reactive hydrogen atom at oxygen functional group and aspect edge on the carbon blacksurface, these groups or atom are very active free radicals, exist if any other living radical around carbon black particle, the free radical stopped reaction can take place with it in them; And photostabilizer such as oxidation inhibitor such as hindered phenol compound, aminated compounds, phosphate compounds, sulfocompound and hindered amine compound, phenolic compound has the function of catching living radical; So under powerful shear action (the carbon black coacervate can destroyedly become primary partical), carbon black and above-mentioned organic compound are directly carried out graft reaction, obtain in the high polymeric matrix or organic solvent in dispersiveness become reconciled and dispersion medium between consistency, size can accurately control, can in organic solvent and superpolymer matrix, form the nano carbon black of stable dispersion system, thereby reach purpose of the present invention.
The nano carbon black of the said in-situ grafted organic compound of the present invention, 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 to have the organic compound that maybe can produce free radical be phenolic compound, aminated compounds and/or 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 (parts by weight).
In the present invention, for can grafting more organic compound to carbon blacksurface, require carbon blacksurface to have enough carboxyls, quinonyl, phenolic group and lactone group etc. to contain the reactive hydrogen atom at oxygen functional group and aspect edge.Therefore, the sooty oxygen level of using is preferably in more than the 0.1wt%, and hydrogen richness is preferably in more than the 0.2wt%.Be lower than above-mentioned value as used sooty oxygen level and hydrogen richness, then can pass through to adopt gaseous oxidations such as warm air oxidation and ozone oxidation, or increase sooty oxygen level and hydrogen richness with handling as liquid-phase oxidations such as nitric acid, hydrogen peroxide, potassium permanganate, clorox, bromine waters.
It is employed among the present invention that to have the organic compound that maybe can produce free radical be 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.Recommend the organic compound use as hindered phenol or/and hindered amine compound.
Wherein said phenolic compound comprises 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)
The 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
7H
15-C
9H
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 amine compounds comprises following compounds:
(organic compound 88)
(organic compound 89)
(organic compound 90)
(organic compound 91)
R＝C
7H
15～C
9H
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 compound 101)
R＝C
7H
15～C
9H
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
6H
4NHC
6H
5
(II)R
2-OC
6H
4NHC
6H
5
(organic compound 136)
(organic compound 137)
(organic compound 138)
(organic compound 139, m=1-100, n=1-100)
The said polymkeric substance that fragments into free radical under being subjected to the mechanical shearing force field is preferably selected two keys and smaller natural rubber, the olefines rubber of molecular chain interphase interaction that contains less stable in the molecular chain for use.
For the nano carbon black of organifying compound situ-formed graft tends towards stability, can also add phosphate compounds or/and the sulfur-bearing compounds as aid anti-oxidants, said sulfur-bearing compounds is meant mercaptan, thiophenol or thio-ether type compounds, and the consumption of aid anti-oxidants is 5～300 parts (parts by weight).Said aid anti-oxidants comprises following compounds:
(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 the said nano carbon black of the present invention, its 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, directly carry out graft reaction.
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.Not only technology is simple for it, and cost is low, and can produce in enormous quantities continuously.
Description of drawings
Fig. 1 is a sooty transmission electron microscope photo
Fig. 2 is the synoptic diagram of carbon structure model
Fig. 3 is the graft carbon black and the centrifugal settling experimental result of graft carbon black not
Fig. 4 is the atomic force microscope photo of graft carbon black
The present invention can produce in the mixing apparatus of larger shearing force, the organic compounds such as phenolic compound, aminated compounds and the organic compound and the carbon black that are subjected to fragment into living radical under the mechanical shear stress effect are carried out blend, under the temperature more than the fusing point of the organic compound with living radical, directly carry out graft reaction, thereby obtain the nano carbon black that organic compound coats. The carbon black that makes not only has preferably dispersiveness and compatibility, but also has shown the unexistent nano effect of general carbon black, is expected to obtain using in many fields such as transparent conductive material, radiation proof material, printing ink, ink powder, coating. The preparation method of this carbon black not only technique simple, need not solvent, cost is low, pollution-free, but also can produce continuously in enormous quantities.
Embodiment
The present invention is further elaborated below by embodiment, its objective is better understanding content of the present invention.Therefore, the cited case does not limit protection scope of the present invention:
Embodiment 1
Use the nano carbon black of oxidation inhibitor AO-80: 100 parts of carbon blacks (N220, Mitsubishi Chemical Industrial Co., Ltd), AO-80 (Asahi Denka Kogyo K. K) is 80 parts.
AO-80 is a hindered phenolic oxidation inhibitor, AO-80 is its trade(brand)name, and chemical name is 3, and 9-two { 1,12 methyl-2[β-3-tertiary butyl-4-hydroxy-5-cresylol] propionyloxy } ethyl group)-2,4,8,10-Si Evil spiral shell [5,5] undecane, fusing point is 125 ℃, can produce living radical, and molecular formula is as follows:
With carbon black and AO-80 in Haake torque rheometer at 140 ℃ of following melt blendings that are higher than AO-80 fusing point (125 ℃), the rheometer rotating speed is 60rpm, the blend time is 30min.When about blend time to 3.5 minute, when temperature rose to 175 ℃, the moment of torsion of AO-80 and sooty mixture sharply increased, and after reacting completely, moment of torsion is tending towards a stationary value.
The carbon black of above-mentioned gained and the reactant of AO-80 are put into apparatus,Soxhlet's, with toluene extracting 72 hours, to guarantee that no free AO-80 exists in the carbon black.The filtrate and the carbon black sample of getting respectively after the extracting are carried out the FTIR-ATR test, and the result shows does not have AO-80 in the filtrate, and extracting is complete.And this FTIR-ATR spectrogram with the carbon black sample of AO-80 modification has shown on the sooty surface grafting AO-80.
Get not graft carbon black and graft carbon black respectively and put into beaker for 1 part, add 100 parts of acetone, the ultrasonic cleaner (DL-360D) that places the letter instrument company in Shanghai to produce, ultra-sonic dispersion 10min, controlled temperature is 25 ℃, makes carbon black dispersion liquid.On the LDZ4-0.8 type whizzer that Beijing Medical Centrifugal Machine Factory produces, carry out the centrifugal settling experiment then, check its dispersion effect.Get dispersion liquid 5ml, place whizzer (4000rpm), took out every 10 minutes and measure dispersed index.As shown in Figure 3, grafted occasion not, sedimentation can take place in carbon black at once, on the contrary it is stable for a long time that the suspension of graft carbon black then keeps, and realized purpose of the present invention.
With the size-grade distribution in this suspension of BECKMAN COUTLER laser light scattering particle size analyzer determination, the size distribution such as the table 1 that obtain.And not in the ultra-sonic dispersion suspension of graft carbon black (N220), can observe the precipitation of bigger carbon black coacervate significantly, and size-grade distribution such as table 2 in the suspension.Comparison sheet 1 and table 2, the AO-80 graft effect that can find carbon blacksurface is very significant.
The size-grade distribution of the graft carbon black of table 1 embodiment 1 (N220/AO-80) in acetone solvent
| Size(nm) | 48 | 52 | 57 | 413 |
| Number(％) | 49 | 35 | 15 | 1 |
Table 2 is the size distribution of graft carbon black (N220) not
| Size(nm) | 94 | 122 | 139 | 158 | 180 | 205 | 234 | 1749 |
| Number％ | 21 | 7 | 10 | 23 | 19 | 3 | 4 | 3 |
Get this steady suspension and carry out the observation of atomic force microscope, obtained carbon black and be close to monodispersed photo, size is (as shown in Figure 4) about 40nm.In full accord with the particle diameter test result of above-mentioned laser light scattering particle size analyzer.
This graft carbon black has been carried out the sign of some routines, and the gained result is as follows:
The routine of the graft carbon black of table 3 embodiment 1 (N220/AO-80) characterizes
The iodine absorption value of graft carbon black and CTAB value all are lower than untreated carbon black, show that the specific surface area of graft carbon black is less, illustrate that the sooty surface has coated organic molecule, has reduced its specific surface area.The reduction of DBP absorption value shows the structural lower of graft carbon black, no big aggregate, and it is more even to distribute.
Embodiment 2
Use the nano carbon black of oxidation inhibitor AO-60: 100 parts of carbon blacks (N220, Mitsubishi Chemical Industrial Co., Ltd), AO-60 (Asahi Denka Kogyo K. K) is 80 parts.
AO-60 also is a Hinered phenols antioxidant, and AO-60 is its trade(brand)name, and chemical name is 4[β-(3,5-di-t-butyl-4-phenol) propionyloxy] methane, structural formula is as follows, and fusing point is 115 ℃, can produce living radical equally.
The design temperature of Haake torque rheometer is 130 ℃ in experiment, and all the other conditions are identical with embodiment 1.The size-grade distribution such as the table 4 of laser light scattering particle size analyzer determination.
The size-grade distribution of the graft carbon black of table 4 embodiment 2 (N220/AO-60) in acetone solvent
| Size(nm) | 46 | 54 | 64 | 253 | 300 |
| Number(％) | 36 | 40 | 11 | 5 | 8 |
The particle size carbon black of gained about 50nm, can form steady suspension equally in acetone, dispersing property is very good.The conventional rerum natura of sooty is also similar to embodiment 1.
Embodiment 3
Use the nano carbon black of photostabilizer LA-57: 100 parts of carbon blacks (N220, Mitsubishi Chemical Industrial Co., Ltd), LA-57 (Asahi Denka Kogyo K. K) is 80 parts.
LA-57 is a kind of photostabilizer, and LA-57 is its trade(brand)name, standard called after 2,2,6, and 6-tetramethyl--4 piperidyl-1,2,3,4-fourth tetracid ester, structural formula is as follows, and fusing point is 132 ℃, can produce living radical.
The design temperature of Haake torque rheometer is 150 ℃ in the experiment, and blend time lengthening is 40 minutes.All the other conditions are identical with embodiment 1.The size-grade distribution such as the table 5 of laser light scattering particle size analyzer determination.
The size-grade distribution of the graft carbon black of table 5 embodiment 3 (N220/LA-57) in acetone solvent
| Size(nm) | 68 | 71 | 78 | 81 | 180 | 197 |
| Number(％) | 10 | 28 | 51 | 5 | 4 | 2 |
The particle size carbon black of gained is less than 100nm, and monodispersity is very good, can form steady suspension in acetone.The conventional rerum natura of sooty is also similar to embodiment 1.
Embodiment 4
Use the nano carbon black of anti-aging agent N300: 100 parts of carbon blacks (N220, Mitsubishi Chemical Industrial Co., Ltd), N300 (the emerging chemical industry of imperial palace Co., Ltd.) is 80 parts.
Anti-aging agent N300 is its trade(brand)name, and structural formula is as follows, the standard name: 4-4 ' thiobis (3 methy 6 tert butyl phenol), and structural formula is as follows, and fusing point is 155 ℃, can produce living radical.
The design temperature of Haake torque rheometer is 170 ℃ in the experiment, and blend time lengthening is 40 minutes.All the other conditions are identical with embodiment 1.The size-grade distribution such as the table 6 of laser light scattering particle size analyzer determination.
The size-grade distribution of the graft carbon black of table 6 embodiment 4 (N220/N300) in acetone solvent
| Size(nm) | 60 | 63 | 66 | 70 | 182 | 191 |
| Number(％) | 21 | 36 | 29 | 12 | 1 | 1 |
The particle size carbon black of gained is less than 100nm, and monodispersity is very good, can form steady suspension in acetone.The conventional rerum natura of sooty is also similar to embodiment 1.
Embodiment 5
Use the graft carbon black of natural rubber: 100 parts of carbon blacks (N220, Mitsubishi Chemical Industrial Co., Ltd), 100 parts of natural rubbers (Shanghai Rui Yang rubber chemicals company limited).
Natural rubber main component commonly used at present is a polyisoprene, and glass transition temperature Tg is-73 ℃, 30 ℃ of fusing points.
The design temperature of Haake torque rheometer is 100 ℃ in the experiment, and the blend time is 120 minutes, and all the other conditions are identical with embodiment 1.The size-grade distribution such as the table 7 of laser light scattering particle size analyzer determination
The size-grade distribution of the graft carbon black of table 7 embodiment 5 (N220/NR) in acetone solvent
| Size(nm) | 162 | 278 | 400 | 500 | 600 |
| Number(％) | 58 | 22 | 11 | 6 | 3 |
The carbon black of gained favorable dispersity in acetone can form steady suspension.The conventional rerum natura of sooty is also similar to embodiment 1.
Embodiment 6
Use the nano carbon black of oxidation inhibitor AO-80: glossy black with colour carbon black (Raven 1035, Columbian Chemicals Co.) 100 parts, AO-80 (Asahi Denka Kogyo K. K) is+80 parts.
In order to realize the application of nano carbon black of the present invention in printing ink, the contriver has adopted the printing ink colour carbon black.All experiment conditions are identical with embodiment 1, and gained result (table 8) proves that this kind method is applicable to carbon black for printing ink.
The size-grade distribution of the graft carbon black of table 8 embodiment 6 (Raven 1035/AO-80) in acetone solvent
| Size(nm) | 63 | 66 | 69 | 72 | 169 | 177 |
| Number(％) | 27 | 35 | 27 | 8 | 2 | 1 |
Embodiment 7
Use the nano carbon black of oxidation inhibitor AO-80: 100 parts of high graphitized carbon blacks (ENSACO 350G, Te Migao graphite company limited), AO-80 (Asahi Denka Kogyo K. K) is 80 parts.
High graphitized carbon black structural very high, aggregate is highly stable.In order to realize the application of nano carbon black of the present invention in conductive coating paint and composite conducting material, the contriver has adopted high graphitized carbon black.All experiment conditions are identical with embodiment 1, and gained result (table 9) proves that this kind method is applicable to high graphitized carbon black.
The size-grade distribution of the graft carbon black of table 9 embodiment 7 (ENSACO 350G/AO-80) in acetone solvent
| Size(nm) | 60 | 75 | 95 | 119 | 189 | 300 |
| Number(％) | 50 | 33 | 11 | 3 | 2 | 1 |
Embodiment 8
Use the nanometer carbon black of oxidation inhibitor AO-80 and oxygenated black: (Seast 300 obtains through oxide treatment oxygenated black, be called for short OCB, its surface-area and oil number are as shown in table 10, East Sea carbon black chemical industry Co., Ltd.) 100 parts, 80 parts of AO-80 (Asahi Chemical Industry Co., Ltd).
Table 10 sooty oxide treatment effect
| Sample | Nitrogen adsorption specific surface area (m 2/g) | DBP absorption value (ml/100g) | The pH value |
| Seast 300 | 84 | 75 | 7.9 |
| OCB | 123 | 122 | 3.1 |
Its surface functional group number of carbon black after oxide treatment increases, and more helps the carrying out of graft reaction.And specific surface area is bigger, is high structure, so its coacervate ratio is easier to destroyed under same mixing condition.The contriver adopts oxidized black, and all the other experiment conditions are identical with embodiment 1, and gained result (table 11) shows the grafts of oxygenated black, and not only particle diameter is little, and is single dispersion.So use the graft modification effect of oxidized black more more effective than general carbon black.
The size-grade distribution of the graft carbon black of table 11 embodiment 8 (Seast 300/AO-80) in acetone solvent
| Size(nm) | 42 | 180 | 210 |
| Number(％) | 98 | 1 | 1 |
Embodiment 9
Use the nanometer carbon black of oxidation inhibitor AO-80 and the 3rd component: 100 parts of carbon blacks (N220, Mitsubishi Chemical Industrial Co., Ltd), 80 parts of AO-80 (Asahi Chemical Industry Co., Ltd), 40 parts of TNP (the emerging chemical industry of imperial palace Co., Ltd.).
The contriver adds the 3rd component TNP in system, its structural formula is as follows, and all the other experiment conditions are identical with embodiment 1.Compare with embodiment 1, (table 12) is more effective to the sooty graft modification after finding to add the 3rd component TNP.
The size-grade distribution of the graft carbon black of table 12 embodiment 9 (N220/AO-80/TNP) in acetone solvent
| Size(nm) | 44 | 52 | 61 | 190 | 210 |
| Number(％) | 40 | 38 | 20 | 1 | 1 |
One of innovation of the present invention is exactly that carbon black aggregate is broken to primary partical under the powerful shearing force field effect, and realizes the situ-formed graft of organic compound in this process.Mixing equipment is used the MD50-100 type continous way internal mixer of the mechanical company limited of times Long Keya of section (Nanjing) instead, and prescription and preparation method are identical with embodiment 2.The size-grade distribution such as the table 13 of laser light scattering particle size analyzer determination, this shows that to prepare the engrafted nanometer carbon black with the continous way internal mixer that can be suitable for scale operation effective equally.
The size-grade distribution of the graft carbon black of table 13 embodiment 10 (N220/AO-60) 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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