CN101824126A - Hydrophilic carbon black - Google Patents
Hydrophilic carbon black Download PDFInfo
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- CN101824126A CN101824126A CN 201010169589 CN201010169589A CN101824126A CN 101824126 A CN101824126 A CN 101824126A CN 201010169589 CN201010169589 CN 201010169589 CN 201010169589 A CN201010169589 A CN 201010169589A CN 101824126 A CN101824126 A CN 101824126A
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- carbon black
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- hydrophilic carbon
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Abstract
The invention relates to a hydrophilic carbon black which is mainly characterized in that a monomer containing an unsaturated group and a hydrophilic group serves as a modifier; in the presence of mechanical shear force field, the mechanical shear is obtained by polymerizing the carbon black and the modifier by in situ free radical. The dispersion degree of the provided hydrophilic carbon black is 5g/100 g H2O or above, the hydrophilic carbon black is directly dispersed in (natural) rubber latex after liquid phase blending to save blending time and blending energy consumption, and the hydrophilic carbon black fundamentally solves the problems of severe environment pollution and the like caused by carbon black dust and sizing material odour in the rubber blending process.
Description
Technical field
The present invention relates to a kind of modified carbon black, specifically, relate to the hydrophilic carbon black of compound (monomer) gained behind the radical polymerization modified carbon black that a kind of employing contains unsaturated group and hydrophilic radical.
Background technology
Carbon black is widely used in many industries such as rubber, plastics, coating, printing ink.But because the primary particle diameter of carbon black particle is little, very easily reunite, be difficult in dispersion uniform and stable in the medium, and, also be difficult to as the carbon black of mineral filler compatible with solvent or polymeric media, thereby limited the maximum performance of its potential performance.
Use the tensio-active agent treated carbon black, can obtain stable sooty water dispersion liquid.But because carbon blacksurface intensive hydrophobicity, very easily blend, solidify and drying process in sedimentation; And carbon black when being applied in the polymkeric substance tensio-active agent easily move to polymer surfaces, thereby reduced the use properties of product.
Along with the continuous development of tensio-active agent technology, the researchist has developed the polymerisable surfactant monomer, and it is by two keys being incorporated in the surfactant molecule structure, surfactant molecule for good and all being keyed on the polymeric matrix.Tsubokawa etc. have reported that carbon blacksurface peroxyester group causes graft polymerization reaction ([J] .PolymerJournal.1988 of vinyl monomer, 20 (3): 213-220, [J] .Polymer Journal.1990,22 (8): 661-670, [J] .Carbon.1977,15:194-195, [J] .Polymer Journal.1981,13:1093-1097, [J] .Journal ofPolymer Science PolymerChemistry.1988,26:2715-2724, [J] .Polymer Bulletin.1989,22:55-62, [J] .Polymer Journal.1996,28 (4): 317-322, [J] .Journal of Polymer Science Part A:Polymer Chemistry.1995,33:581-586, [J] .Polymer Journal.1988,20:721-728 and [J] .Journal of Macromolecular Science Part A:Pure andApplied Chemistry.1992, A29 (4/5): 311-321).They adopt carbon blacksurface acyl chlorides and tertbutyl peroxide reaction that the tert-butyl hydroperoxide ester group is introduced carbon blacksurface; And the introducing of carbon blacksurface acid chloride groups has three kinds of methods: the carboxyl and the sulfur oxychloride of (1) carbon blacksurface; (2) phenolic hydroxyl group of carbon blacksurface and adipyl chloride; (3) adopt ACV[4,4 '-azobis (4-cyanovalericacid)] treated carbon black aromatic ring introducing carboxyl, react with sulfur oxychloride again.The free yl graft polymerization of vinyl monomer also can be caused by the azo group of carbon blacksurface.
Hayashi has also disclosed a kind of free radical post-polymerization that is caused by the azo side group, thereby racemosus chain polymerization thing in the carbon blacksurface grafting ([J] .Journal of Macromolecular Science Part A:Pure and Applied Chemistry.1997, A34 (8): 1381-1394).The method of introducing azo group at carbon blacksurface has three kinds: (1) adopts sulfur oxychloride to make the carboxyl of carbon blacksurface be converted into acid chloride group, makes acid chloride group and ACP[2 again, 2 '-azobis (2-cyano-n-propanol)] reaction; (2) adopt Ben Yajiaji diisocyanate (or ester) treated carbon black, introduce isocyanate groups, and then react with ACV at carbon blacksurface; (3) hydroxyl of carbon blacksurface and ACV-COCl[4,4 '-azobis (4-cyanovaleryl chloride)] reaction.
But above-mentioned existing initiation vinyl monomer all carries out in solution system at the graft polymerization method of modifying of carbon blacksurface, is unfavorable for scale production, and cost is high again, and easy contaminate environment.
In addition, can be limited with the high molecular kind of carbon black reaction (polymer of hydroxyl, carboxyl, amino and epoxy group(ing)), and only be applicable to the more carbon black of surface oxygen functional group (as channel black), 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.
Summary of the invention
The objective of the invention is to, a kind of hydrophilic carbon black is provided, and (its dispersity in water medium is 5g/100g H
2O or more than), overcome the defective that exists in the prior art.
The present invention is by under hot mechanical shearing force field, broken carbon black coacervate or bigger aggregate, and initiation vinyl surface active agent monomer coats in the carbon blacksurface polymerization, stablized the surface of new formation, the instantaneous living radical of the broken generation of carbon black particle simultaneously, can catch the polymer active chain free radical generation graft reaction that is increasing, make hydrophilic carbon black, its dispersity in water medium reaches 5g/100g H
2O or more than.Its technology is simple, and is with low cost, and can accomplish scale production.
Among the present invention hydrophilic carbon black is planted altogether without the simple liquid phase blend of any processing and utilizing, join in any commercially available rubber latex.Because grafting by the stable composition effect of steric hindrance repulsion and electrostatic repulsion, can stop the approaching mutually of carbon black particle, thereby realize its stable dispersion in water medium or/and the surfactant polymer layer that coats has extraordinary water-solublely.Therefore can obtain well behaved cross-linked rubber goods.
The said hydrophilic carbon black of the present invention, it mainly is: with the monomer that contains unsaturated group and hydrophilic radical is properties-correcting agent, under the existence condition of the mechanical shearing field of force, obtain after original position radical polymerization by carbon black and said properties-correcting agent, its dispersity in water medium is 5g/100g H
2O or more than;
Wherein: the weight ratio of carbon black and said properties-correcting agent is 1: (0.01～1.00), the temperature of said original position radical polymerization is higher than the fusing point of used properties-correcting agent but is less than or equal to 350 ℃, and the time of said original position radical polymerization is 15 minutes～30 minutes.
Description of drawings
Fig. 1. be the infrared spectrum of carbon black (Mogul-L) and hydrophilic carbon black (PSS-Mogul-L);
Fig. 2. for NASS, PSS and hydrophilic carbon black (PSS-Mogul-L)
1H NMR spectrogram;
Wherein: (a)-NASS
1H NMR spectrogram, (b) PSS-PSS
1H NMR spectrogram, (c)-hydrophilic carbon black (PSS-Mogul-L)
1H NMR spectrogram;
Fig. 3. be the TME figure of hydrophilic carbon black (PSS-N220);
Fig. 4 is the TME figure of carbon black (N220);
Fig. 5. be the stably dispersing linearity curve (pH=7.0) of hydrophilic carbon black (PSS-N234, PSS-N220, PSS-N330 and PSS-N660) in water medium of carbon black (N234, N220, N330 and N660) and its corresponding modification.
Embodiment
The mechanism for preparing hydrophilic carbon black of the present invention may be: in the mechanical shearing field of force (under the existence condition of 60Nm～300Nm), the agglomerate of carbon black particle and bigger aggregate at first are broken to less aggregate, thereby expose more new carbon blacksurface, absorption contains the monomer of unsaturated group (as groups such as carbon-carbon double bond or carbon-carbon triple bonds) and hydrophilic radical (as groups such as carboxylic acid or sulfonate), has stoped the reunion again of carbon black particle.Simultaneously, the π key (as the π key of carbon-carbon double bond) that contains unsaturated link(age) in the monomer of unsaturated group and hydrophilic radical breaks to form living radical, thereby cause the π bond rupture of more unsaturated link(age), form more polyradical, the high mars free radical that the π bond rupture forms, the polymer active chain free radical in increasing, can both with the broken moment living radical effect that forms of carbon black, graft reaction takes place, acquisition is grafted with the hydrophilic carbon black of molecular weight greater than 2,000 polymkeric substance at carbon blacksurface.
In the present invention, used carbon black can be channel black, furnace black or other any commercially available carbon black.
Used properties-correcting agent is the compound that contains unsaturated group and hydrophilic radical, and wherein said unsaturated group can be: unsaturated groups such as carbon-carbon double bond or carbon-carbon triple bond, and said hydrophilic radical can be: hydrophilic radicals such as carboxylate salt or sulfonate; Preferred modifiers of the present invention is: contain the compound (monomer) of vinyl and sulfonate groups, more preferred modifiers is: by the vinylbenzene that sulfonate groups replaces, best properties-correcting agent is: sodium p styrene sulfonate.
The original position radical polymerization temperature of carbon black and said properties-correcting agent should be controlled at the fusing point that is higher than used properties-correcting agent but be less than or equal to 350 ℃, and the time of original position radical polymerization was good (what harm the long reaction times itself does not have, but uneconomical) with 15 minutes～30 minutes.
The equipment that can produce the said mechanical shearing of the present invention field of force can be: Haake torque rheometer, mill machine, twin screw extruder, continuous muller, Banbury mixer, Z-shaped kneader or other any commercially available mixing equipment that can produce the mechanical shear stress effect.
Hydrophilic carbon black of the present invention can directly be scattered in the water medium, sooty water dispersion liquid that must be stable; And utilize simple liquid phase blend method, and hydrophilic carbon black aqueous dispersions and rubber latex are mixed, to solidify, the low shearing of two roller low temperature extruded dehydration, drying.
In rubber, add Synergist S-421 95s such as promotor, activator, anti-aging agent, mixing at normal temperatures 5 minutes according to prescription.With the rubber unvulcanizate age overnight, can get carbon black enhanced rubber in 1 minute～60 minutes in 100 ℃～200 ℃ sulfurations according to common sulfuration process.
The invention provides a kind of hydrophilic carbon black, its dispersity in water medium is 5g/100g H
2O or more than.This hydrophilic carbon black directly is scattered in (natural) rubber latex through the liquid phase blend, can save mixing time and mixing energy consumption, and has fundamentally solved the problems such as serious environmental pollution that carbon powder dust in the rubber mixing process and sizing material stink cause.
The present invention is further elaborated below by embodiment, and its purpose only is better to understand content of the present invention.Therefore, the cited case does not limit protection scope of the present invention.
Embodiment one
With carbon black (Mogul-L, N220, N234, N330 or N660 etc., Cabot company) with sodium p styrene sulfonate (NASS, the farsighted company limited of company of rising in Shanghai) in the HAAKE torque rheometer in 200 ℃ of following preheatings, carbon black and sodium p styrene sulfonate weight ratio are 1: 0.2, are warmed up to 280 ℃ of reactions, and rotor speed is 60rpm, the blend time is 15min, (brief note is PSS-Mogul-L, PSS-N220, PSS-N234 respectively to make the hydrophilic nano carbon black with this understanding, PSS-N330 or PSS-N660), wherein PSS represents the polymkeric substance of sodium p styrene sulfonate.
Gained hydrophilic nano carbon black (PSS-Mogul-L with 3.0 grams is an example) is placed Soxhlet extractor, add the 200mL deionized water, refluxed 72 hours down at 100 ℃, with remove free or physical adsorption to the PSS macromole of carbon blacksurface (behind the extracting certain hour, with extract evaporate to dryness on Rotary Evaporators, and vacuum-drying is to constant weight, till no longer changing with meticulous balance weighing to extract extractives weight, the PSS that hydrophilic carbon black surface free or physical adsorption be described fully extracting fall, what residue can't extracting be fallen is the chemical graft part) extractive resistates to constant weight, is used for infrared and the nuclear-magnetism test 100 ℃ of following vacuum-dryings.The results are shown in Figure 1 and Fig. 2.
As shown in Figure 1: carbon black (Mogul-L) can't detect the obvious characteristics peak in whole infrared spectrum scope, and this is owing to the strong absorption characteristic of carbon black to infrared light, so be difficult to detect a small amount of functional group that carbon blacksurface exists.And new, tangible infrared signature absorption peak appearred on the FT-IR spectrogram of hydrophilic carbon black (PSS-Mogul-L).1030～1200cm wherein
-1The charateristic avsorption band that PSS aromatic sulphonic acid root occurred; 2850-2912cm
-1The stretching vibration absorption peak of zone C-H is coated to carbon blacksurface because of the PSS long-chain, and it absorbs obviously and strengthens.Equally, 1590cm
-1The absorption peak of place's aromatic ring also obviously strengthens.
As shown in Figure 2: three kinds of hydrogen atoms ,=CH are arranged on the vinyl of sodium p styrene sulfonate (NASS)
2-on two hydrogen atoms split significantly bimodal in chemical shift 5.7ppm and 5.1ppm punishment; Its=the chemical shift 6.8ppm punishment of hydrogen atom on the CH-splits quartet.On the spectrogram of PSS-Mogul-L, the resonance peak completely dissolve of three kinds of hydrogen atoms on the vinyl simultaneously, has occurred methylene radical (CH respectively at chemical shift 1.1-2.1ppm and 2.5-3.3ppm place
2-) and methyne (CH-) go up the vibration peak of hydrogen atom, this and pure PSS polymkeric substance
1H NMR spectrogram unanimity, this explanation reaction back carbon blacksurface has coated polymer P SS.
In addition, coat at PSS on the spectrogram of N220, (Fig. 2 c) chemical shift 7.5 and 7.8ppm place also occurred to the PSS spectrogram on similar phenyl ring proton peak.Above result shows carbon black and NASS monomer after heat machinery causes Raolical polymerizable, and carbon blacksurface has coated the molecular chain of polymer P SS.
Get carbon black (unmodified) and hydrophilic carbon black respectively and put into beaker for 1 part, add 100 parts of deionized waters, place ultrasonic cleaner (the letter instrument company in Shanghai), ultra-sonic dispersion 20 minutes, controlled temperature is 25 ℃, makes the sooty water dispersion liquid.(Nicomp 380ZLS type America) goes up its particle diameter of mensuration and distribution, sees Table 1 at the dynamic laser light scattering experimental analyser.
Table 1
Get dispersion liquid 100mL, natural subsidence 72min checks its dispersion stabilization.Take out the 5mL dispersion liquid every 15min, place ultraviolet-visible spectrophotometer, observe the ultraviolet absorption situation in wavelength 420nm place, as can be seen, four kinds of carbon black basic sedimentations in 15～30min are complete, and be prepared into the hydrophilic nano carbon black through present method, stable dispersion (see figure 4) still behind 72min.The centrifugal settling experiment has also proved this conclusion.It is stable for a long time that this explanation, the suspension of graft carbon black then keep, and realized purpose of the present invention.Hydrophilic carbon black sees Table 2 with the maximum dispersion degree of carbon black in water medium that be untreated.
Table 2
-expression can't disperse in water medium
Embodiment two
The application of hydrophilic carbon black (enhancing styrene-butadiene rubber(SBR)).
Carbon black (N220, Cabot company) and sodium p styrene sulfonate (NASS, the farsighted company limited of company of rising in Shanghai) weight ratio 1: 0.2.
Method by example 1 prepares hydrophilic carbon black, and carries out characterization test.
With the hydrophilic carbon black water mixture of 10wt%, 150rpm stirs 20min down, and ultrasonic (90W, 60Hz) 20min fully are distributed in the water medium, with 0.2mol/L NaOH solution its pH value are adjusted to 10.0.Styrene butadiene rubber latex is diluted to about 20wt%, and stirring at low speed 10min under the 150rpm is adjusted to 10.0 with 0.2mol/L NaOH solution with its pH value.At room temperature, under the stirring velocity of 150rpm, the hydrophilic carbon black aqueous dispersions is continued to stir in the latex that the adding dilution is good down.
Mixed solution solidifies under stirring at low speed through calcium chloride solution is arranged.With coagulum through two roller mill (XK-160 type, Wuxi morning twilight rubber and plastics machine factory) 1min that under low shear rate, dewater, in 30 ℃ dry down, be lower than 0.01wt%, preparation hydrophilic carbon black/styrene-butadiene rubber(SBR) master batch to moisture content.
By in the table 3 as seen, hydrophilic carbon black has good reinforced effects to styrene-butadiene rubber(SBR), the tensile strength of its master batch, elongation at breaks etc. all significantly improve.
Table 3
Table 4
Embodiment three
Hydrophilic carbon black strengthens natural rubber.
The hydrophilic carbon black of the condition of use-case two and method preparation.
The liquid phase blend method of use-case two prepares hydrophilic carbon black/natural rubber masterbatch.
According to the prescription of table 5, in natural rubber, add other Synergist S-421 95, on opening rubber mixing machine mixing 5 minutes, the sizing material standing over night press sulfurizing times down at 140 ℃ and is vulcanized.The mechanical property of gained cross-linked rubber is listed in table 6.
Table 5
The performance of table 6 carbon black/natural rubber vulcanized rubber (content of carbon black 20phr)
By in the table 6 as seen, hydrophilic carbon black has good reinforced effects to natural rubber, the tensile strength of its cross-linked rubber, elongation at break, tear strengths etc. all significantly improve.
Claims (8)
1. hydrophilic carbon black, it mainly is: with the monomer that contains unsaturated group and hydrophilic radical is properties-correcting agent, under the existence condition of the mechanical shearing field of force, obtain after original position radical polymerization by carbon black and said properties-correcting agent, its dispersity in water medium is 5g/100g H
2O or more than;
Wherein: the weight ratio of carbon black and said properties-correcting agent is 1: (0.01～1.00), the temperature of said original position radical polymerization is higher than the fusing point of used properties-correcting agent but is less than or equal to 350 ℃, and the time of said original position radical polymerization is 15 minutes～30 minutes.
2. hydrophilic carbon black as claimed in claim 1 is characterized in that, wherein said unsaturated group is the group of carbon-carbon double bonds.
3. hydrophilic carbon black as claimed in claim 2 is characterized in that, wherein said unsaturated group is a vinyl.
4. hydrophilic carbon black as claimed in claim 1 is characterized in that, wherein said hydrophilic radical is carboxylate salt or sulfonate groups.
5. as claim 3 or 4 described hydrophilic carbon blacks, it is characterized in that wherein used properties-correcting agent is the vinylbenzene that is replaced by sulfonate groups.
6. hydrophilic carbon black as claimed in claim 5 is characterized in that, wherein used properties-correcting agent is sodium p styrene sulfonate.
7. hydrophilic carbon black as claimed in claim 1 is characterized in that, the wherein said mechanical shearing field of force is 60Nm～300Nm.
8. as claim 1 or 7 described hydrophilic carbon blacks, it is characterized in that the equipment that wherein can produce the said mechanical shearing field of force is: Haake torque rheometer, mill machine, twin screw extruder, continuous muller, Banbury mixer, Z-shaped kneader or other any commercially available mixing equipment that can produce the mechanical shear stress effect.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453356A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Manufacturing method of nano carbon black through in-situ polyethylene grafting |
| CN110105793A (en) * | 2019-06-19 | 2019-08-09 | 焦作市和兴化学工业有限公司 | A kind of method of acetylene carbon black modification |
| CN111171607A (en) * | 2020-04-09 | 2020-05-19 | 北京化工大学 | Method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof |
| CN117070028A (en) * | 2023-10-16 | 2023-11-17 | 广州顶顺机电设备有限公司 | High-temperature-resistant wear-resistant covering adhesive for conveyor belt and preparation method thereof |
Citations (1)
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| CN1781999A (en) * | 2004-09-28 | 2006-06-07 | 华东理工大学 | Nano carbon black with in-situ grafted organic compound and its producing method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781999A (en) * | 2004-09-28 | 2006-06-07 | 华东理工大学 | Nano carbon black with in-situ grafted organic compound and its producing method |
Non-Patent Citations (2)
| Title |
|---|
| 《Composites Science and Technology》 20080622 Xuelian He et al "Poly(sodium 4-styrenesulfonate) modified carbon nanoparticles by a thermo-mechanical technique and its reinforcement in natural rubber latex" 3027-3032 1-8 第68卷, 2 * |
| 《高分子学报》 20091130 何雪莲等 "对苯乙烯磺酸钠改性炭黑对天然橡胶胶乳力学性能的影响" 1101-1106 1-8 , 第11期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453356A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Manufacturing method of nano carbon black through in-situ polyethylene grafting |
| CN110105793A (en) * | 2019-06-19 | 2019-08-09 | 焦作市和兴化学工业有限公司 | A kind of method of acetylene carbon black modification |
| CN111171607A (en) * | 2020-04-09 | 2020-05-19 | 北京化工大学 | Method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof |
| CN111171607B (en) * | 2020-04-09 | 2021-05-04 | 北京化工大学 | Method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof |
| CN117070028A (en) * | 2023-10-16 | 2023-11-17 | 广州顶顺机电设备有限公司 | High-temperature-resistant wear-resistant covering adhesive for conveyor belt and preparation method thereof |
| CN117070028B (en) * | 2023-10-16 | 2024-01-26 | 广州顶顺机电设备有限公司 | High-temperature-resistant wear-resistant covering adhesive for conveyor belt and preparation method thereof |
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