CN1970644A - Method for preparing water-dispersive carbon black adopting surface graft modification method - Google Patents
Method for preparing water-dispersive carbon black adopting surface graft modification method Download PDFInfo
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- CN1970644A CN1970644A CN 200610155008 CN200610155008A CN1970644A CN 1970644 A CN1970644 A CN 1970644A CN 200610155008 CN200610155008 CN 200610155008 CN 200610155008 A CN200610155008 A CN 200610155008A CN 1970644 A CN1970644 A CN 1970644A
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Abstract
The invention discloses a making method of dispersing carbon black through surface grafting modifying method, which is characterized by the following: polymerizing with controllable free radical under HTEMPO or TEMPO; obtaining poly (N, N-dimethyl acrylamide) with TEMPO terminal group or polyphenylacetylene sodium sulfonate with HTEMPO terminal group; decomposing polymer with HTEMPO terminal group or TEMPO terminal group into polymer free radical under high temperature; making non-paired electron on the surface of carbon black catch polymer free radical; obtaining the modified carbon black grafted by polymer; dispersing in the water effectively; fitting for applying in the PTC material, air-sensitive material and ink domain.
Description
Technical field
The present invention relates to a kind of employing surface graft modification legal system and be equipped with water dispersible sooty method.
Background technology
Carbon black normally diameter mainly is made up of carbon at the aggregate of little carbon granule of 10～400nm, and carbon content is usually 90～99%, and its surface arrangement functional groups such as a spot of carboxyl, phenolic hydroxyl group, quinonyl and lactone group.Carbon black has been widely used in the preparation of conducing composite material, gas sensitive, coating and printing ink etc., is a kind of extremely important industrial chemicals.The basic condition that carbon black can enter these systems is that carbon black can disperse in these solvent systems or polymeric system well.Usually, carbon black is to be difficult to dispersive, especially carbon black almost can not disperse in water in these systems, and it is to improve one of effective ways of carbon black dispersed in solvent and the consistency in polymkeric substance that carbon blacksurface is carried out graft modification.
The method that the graft modification carbon black adopts usually has three kinds, be the surface graft modification method that the carbon blacksurface unpaired electron is caught free polymer readical, carbon blacksurface initiating group trigger monomer polymeric surface graft modification method and carbon blacksurface group and contain between the reactive end based polyalcohol surface graft modification method that condensation reaction takes place.After carbon blacksurface was introduced various initiating groups, surperficial initiating group can carry out radical polymerization, ring-opening polymerization, anionoid polymerization and cationoid polymerisation by trigger monomer, and the common step of the method for this carbon blacksurface graft modification is more loaded down with trivial details, condition is harsh.The functional group that utilizes carbon blacksurface carries out condensation reaction with the polymkeric substance that contains reactive terminal group and prepares the graft modification carbon black, and the common step of this surface graft modification sooty method is also more, narrow application range.Carbon blacksurface has condensed ring aromatic structure and quinonoid structure and unpaired electron is arranged on it, so carbon black catches effect to free radical, can make the free polymer readical of " work " terminate in carbon blacksurface, thereby reach the purpose at the carbon blacksurface graftomer.
Summary of the invention
The object of the present invention is to provide a kind of employing surface graft modification legal system to be equipped with water dispersible sooty method.
The technical solution adopted for the present invention to solve the technical problems is:
1) with Diisopropyl azodicarboxylate, toluene, N,N-DMAA and 2,2,6, the 6-tetramethyl piperidine nitrogen oxygen free radical joins in the container, and reaction system is after deoxygenation, under argon shield and stirring, employing oil bath heating is warmed up to 60 ℃ of reactions, after reaction finishes, use the normal hexane precipitated product, last vacuum-drying promptly makes poly-(N,N-DMAA) that have the TEMPO end group;
2) with the poly-(N that has the TEMPO end group of 1 part of carbon black and 4～15 parts of carbon black weight; the N-DMAA) joins in the container; with N; dinethylformamide is a solvent; reaction system is after deoxygenation; under argon shield and stirring; employing oil bath heating is warmed up to 130 ℃ of reactions 12 or 24 hours, after reaction finishes; products therefrom washs at ultrasonic water down; centrifugation then, such supersound washing-centrifugal separation processes are carried out 6～10 times repeatedly, at last with the drying precipitate that obtains; promptly make poly-(N,N-DMAA) modified carbon black.
Concrete condition is:
1) consumption of Diisopropyl azodicarboxylate is 2.0 * 10
-2Mol/L, 2,2,6, the mol ratio of 6-tetramethyl piperidine nitrogen oxygen free radical and Diisopropyl azodicarboxylate is 1.0;
2) consumption of N,N-DMAA is 1.66mol/L;
3) adopt the method vacuumize to remove oxygen in the reaction system;
4) centrifugation is 30 minutes, 3000 rev/mins of rotating speeds;
5) content of polymkeric substance is 6.1～11.1% in the above-mentioned modified carbon black that makes;
6) the above-mentioned modified carbon black particle diameter that makes is at 342～378nm;
7) the above-mentioned modified carbon black that makes can be dispersed in the water.
Scheme 2, that the sodium polystyrene sulfonate that has a HTEMPO end group prepares water dispersible sooty step is as follows:
1) with Potassium Persulphate, sodium bisulfite, 4-hydroxyl-2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, Sodium styrene sulfonate, deionized water and ethylene glycol join in the container, reaction system under argon shield and stirring, adopts the oil bath heating after deoxygenation, be warmed up to 130 ℃, reflux and react down, reaction is used the acetone precipitation product after finishing, last vacuum-drying promptly makes the sodium polystyrene sulfonate that has the HTEMPO end group;
2) with 1 part of carbon black; the sodium polystyrene sulfonate that has the HTEMPO end group that makes of 4～15 parts of carbon black weight joins in the container; mixture with deionized water and ethylene glycol is a solvent; reaction system is after deoxygenation; under argon shield and stirring; employing oil bath heating; be warmed up to 130 ℃; reaction down 3～24 hours refluxes; after reaction finishes; products therefrom washs at ultrasonic water down, centrifugation then, and such supersound washing-centrifugal separation processes is carried out 6～10 times repeatedly; with the drying precipitate that obtains, promptly make the sodium polystyrene sulfonate modified carbon black at last.The mechanism that carbon black is caught the sodium polystyrene sulfonate free radical as shown in Figure 1, the sodium polystyrene sulfonate modified carbon black in the stability in the water shown in Fig. 4 B.
Concrete condition is:
1) consumption of sodium bisulfite is 2.3 * 10
-2Mol/L, the mol ratio of Potassium Persulphate and sodium bisulfite is 1.36,4-hydroxyl-2,2,6, the mol ratio of 6-tetramethyl piperidine nitrogen oxygen free radical and sodium bisulfite is 2.42;
2) volume ratio of deionized water and ethylene glycol is 3: 1;
3) consumption of Sodium styrene sulfonate is 0.25g/L;
4) adopt the method vacuumize to remove oxygen in the reaction system;
5) centrifugation is 30 minutes, 3000 rev/mins of rotating speeds;
6) content of polymkeric substance is 4.1～7.6% in the above-mentioned modified carbon black that makes;
7) the above-mentioned modified carbon black particle diameter that makes is at 120～171nm;
8) the above-mentioned modified carbon black that makes can be dispersed in the water.
The beneficial effect that the present invention has is: preparation process of the present invention is simple, only needs two steps usually.Can be used for catching of carbon black p-poly-phenyl vinyl sulfonic acid sodium free radical and poly-(N,N-DMAA) free radical; Thereby make the carbon black with water dispersible of polymer modification.
Description of drawings
Fig. 1 carbon black is caught the mechanism of sodium polystyrene sulfonate free radical;
The AFM figure of poly-(N,N-DMAA) modified carbon black of Fig. 2;
The TEM figure of poly-(N,N-DMAA) modified carbon black of Fig. 3;
Observation figure is left standstill in the dispersion of Fig. 4 modified carbon black in water;
A: the deployment conditions (leave standstill 12 hour after) of carbon black in water; B: the deployment conditions (leave standstill three month after) of sodium polystyrene sulfonate modified carbon black in water; C: the deployment conditions (leave standstill 1 week after) of poly-(N,N-DMAA) modified carbon black in water.
The size distribution figure of Fig. 5 modified carbon black in water;
A: sodium polystyrene sulfonate modified carbon black, B: poly-(N,N-DMAA) modified carbon black.
Embodiment
1) with 4.1mL N; N-DMAA (40mmol), 20ml toluene, 98.5mg Diisopropyl azodicarboxylate (0.48mmol) and 81.2mg TEMPO (0.48mmol) join in the there-necked flask of 50ml; reaction system is after deoxygenation; under argon shield and stirring; employing oil bath heating is warmed up to 90 ℃ of reaction 16h.Reaction is used cooled with liquid nitrogen after finishing, and product precipitates with normal hexane, and last vacuum-drying promptly makes poly-(N,N-DMAA) that have the TEMPO end group.
2) with 50mg carbon black, 5mlN, poly-(N,N-DMAA) of the band TEMPO end group that dinethylformamide and 0.2019g make joins in the 25ml two neck bottles; after the reaction system deoxygenation; under argon shield and stirring, adopt the oil bath heating, be warmed up to 130 ℃ of reactions 12 hours.After reaction finished, products therefrom washed centrifugation then at ultrasonic water down; Such supersound washing-centrifugal separation processes is carried out 6 times repeatedly, and the throw out that obtains at last promptly makes poly-(N,N-DMAA) modified carbon black through super-dry.The AFM figure and the TEM figure of poly-(N,N-DMAA) modified carbon black see Fig. 2, Fig. 3 respectively, gather (N,N-DMAA) modified carbon black in the stability in the water shown in Fig. 4 C.
Embodiment 2
1) with embodiment 1
2) with 50mg carbon black, 5mlN, poly-(N,N-DMAA) of the band TEMPO end group that dinethylformamide and 0.2020g make joins in the 25ml two neck bottles; after the reaction system deoxygenation; under argon shield and stirring, adopt the oil bath heating, be warmed up to 130 ℃ of reactions 24 hours.After reaction finished, products therefrom washed centrifugation then at ultrasonic water down; Such supersound washing-centrifugal separation processes is carried out 6 times repeatedly, and the throw out that obtains at last promptly makes poly-(N,N-DMAA) modified carbon black through super-dry.
Embodiment 3
1) with embodiment 1
2) with 50mg carbon black, 5mlN, poly-(N,N-DMAA) of the band TEMPO end group that dinethylformamide and 0.7509g make joins in the 25ml two neck bottles; after the reaction system deoxygenation; under argon shield and stirring, adopt the oil bath heating, be warmed up to 130 ℃ of reactions 24 hours.After reaction finished, products therefrom washed centrifugation then at ultrasonic water down; Such supersound washing-centrifugal separation processes is carried out 6 times repeatedly, and the throw out that obtains at last promptly makes poly-(N,N-DMAA) modified carbon black through super-dry.
Embodiment 4
1) with 10.0024g Sodium styrene sulfonate (48.6mmol), 0.1702g sodium bisulfite (0.90mmol), 0.3304g Potassium Persulphate (1.22mmol), 51.2mg HTEMPO (2.18mmol) and 30ml deionized water; 10ml ethylene glycol joins in the there-necked flask of 100ml; reaction system is after deoxygenation; under argon shield and stirring; employing oil bath heating; at 60 ℃ of reaction 1h, be warmed up to 125 ℃ then earlier, reflux and continue reaction 7h down.After reaction finishes, the product acetone precipitation, last vacuum-drying promptly makes the sodium polystyrene sulfonate that has the HTEMPO end group.
2) sodium polystyrene sulfonate of the band HTEMPO end group that 30mg carbon black, 3.75ml deionized water, 1.25ml ethylene glycol and 0.3021g are made joins in the 25ml two neck bottles; after the reaction system deoxygenation; under argon shield and stirring; employing oil bath heating; be warmed up to 130 ℃, reaction down 3 hours refluxes.After reaction finished, products therefrom washed centrifugation then at ultrasonic water down; Such supersound washing-centrifugal separation processes is carried out 6 times repeatedly, and the throw out that obtains at last promptly makes the sodium polystyrene sulfonate modified carbon black through super-dry.
Embodiment 5
1) with embodiment 4
2) sodium polystyrene sulfonate of the band HTEMPO end group that 30mg carbon black, 3.75ml deionized water, 1.25ml ethylene glycol and 0.3011g are made joins in the 25ml two neck bottles; after the reaction system deoxygenation; under argon shield and stirring; employing oil bath heating; be warmed up to 130 ℃, reaction down 6 hours refluxes.After reaction finished, products therefrom washed centrifugation then at ultrasonic water down; Such supersound washing-centrifugal separation processes is carried out 6 times repeatedly, and the throw out that obtains at last promptly makes the sodium polystyrene sulfonate modified carbon black through super-dry.
Embodiment 6
1) with embodiment 4
2) sodium polystyrene sulfonate of the band HTEMPO end group that 30mg carbon black, 3.75ml deionized water, 1.25ml ethylene glycol and 0.4501g are made joins in the 25ml two neck bottles; after the reaction system deoxygenation; under argon shield and stirring; employing oil bath heating; be warmed up to 130 ℃, reaction down 24 hours refluxes.After reaction finished, products therefrom washed centrifugation then at ultrasonic water down; Such supersound washing-centrifugal separation processes is carried out 6 times repeatedly, and the throw out that obtains at last promptly makes the sodium polystyrene sulfonate modified carbon black through super-dry.
The test-results of poly-(N,N-DMAA) modified carbon black of table one
| Run | Reaction times (h) | Poly-(N,N-DMAA)/carbon black (wt/wt) | Polymer content (%) | Particle diameter (nm) |
| 1 2 3 | 12 24 24 | 4 4 15 | 6.1 7.5 11.1 | 378 356 342 |
Polymer content (%) is measured with TGA; Particle diameter (nm) is measured with dynamic light scattering.
The test-results of table two sodium polystyrene sulfonate modified carbon black
| Run | Reaction times (h) | Sodium polystyrene sulfonate/carbon black (wt/wt) | Polymer content (%) | Particle diameter (nm) |
| 1 2 3 4 | 3 6 12 24 | 4 4 10 15 | 4.1 6.0 7.2 7.6 | 128 171 120 128 |
Polymer content (%) is measured with TGA; Particle diameter (nm) looses with dynamic light
Claims (4)
1. one kind is adopted the surface graft modification legal system to be equipped with water dispersible sooty method, it is characterized in that adopting poly-(N,N-DMAA) preparation water dispersible sooty step that has the TEMPO end group as follows:
1) with Diisopropyl azodicarboxylate, toluene, N,N-DMAA and 2,2,6, the 6-tetramethyl piperidine nitrogen oxygen free radical joins in the container, and reaction system is after deoxygenation, under argon shield and stirring, employing oil bath heating is warmed up to 60 ℃ of reactions, after reaction finishes, use the normal hexane precipitated product, last vacuum-drying promptly makes poly-(N,N-DMAA) that have the TEMPO end group;
2) with the poly-(N that has the TEMPO end group of 1 part of carbon black and 4～15 parts of carbon black weight; the N-DMAA) joins in the container; with N; dinethylformamide is a solvent; reaction system is after deoxygenation; under argon shield and stirring; employing oil bath heating is warmed up to 130 ℃ of reactions 12 or 24 hours, after reaction finishes; products therefrom washs at ultrasonic water down; centrifugation then, such supersound washing-centrifugal separation processes are carried out 6～10 times repeatedly, at last with the drying precipitate that obtains; promptly make poly-(N,N-DMAA) modified carbon black.
2. a kind of employing surface graft modification legal system according to claim 1 is equipped with water dispersible sooty method, it is characterized in that:
1) consumption of Diisopropyl azodicarboxylate is 2.0 * 10
-2Mol/L, 2,2,6, the mol ratio of 6-tetramethyl piperidine nitrogen oxygen free radical and Diisopropyl azodicarboxylate is 1.0;
2) consumption of N,N-DMAA is 1.66mol/L;
3) adopt the method vacuumize to remove oxygen in the reaction system;
4) centrifugation is 30 minutes, 3000 rev/mins of rotating speeds;
5) content of polymkeric substance is 6.1～11.1% in the above-mentioned modified carbon black that makes;
6) the above-mentioned modified carbon black particle diameter that makes is at 342～378nm;
7) the above-mentioned modified carbon black that makes can be dispersed in the water.
3. one kind is adopted the surface graft modification legal system to be equipped with water dispersible sooty method, and it is as follows to it is characterized in that adopting the sodium polystyrene sulfonate that has the HTEMPO end group to prepare water dispersible sooty step:
1) with Potassium Persulphate, sodium bisulfite, 4-hydroxyl-2,2,6,6-tetramethyl piperidine nitrogen oxygen free radical, Sodium styrene sulfonate, deionized water and ethylene glycol join in the container, reaction system under argon shield and stirring, adopts the oil bath heating after deoxygenation, be warmed up to 130 ℃, reflux and react down, reaction is used the acetone precipitation product after finishing, last vacuum-drying promptly makes the sodium polystyrene sulfonate that has the HTEMPO end group;
2) with 1 part of carbon black; the sodium polystyrene sulfonate that has the HTEMPO end group that makes of 4～15 parts of carbon black weight joins in the container; mixture with deionized water and ethylene glycol is a solvent; reaction system is after deoxygenation; under argon shield and stirring; employing oil bath heating; be warmed up to 130 ℃; reaction down 3 hours～24 hours refluxes; after reaction finishes; products therefrom washs at ultrasonic water down, centrifugation then, and such supersound washing-centrifugal separation processes is carried out 6～10 times repeatedly; with the drying precipitate that obtains, promptly make the sodium polystyrene sulfonate modified carbon black at last.
4. a kind of employing surface graft modification legal system according to claim 3 is equipped with water dispersible sooty method, it is characterized in that:
1) consumption of sodium bisulfite is 2.3 * 10
-2Mol/L, the mol ratio of Potassium Persulphate and sodium bisulfite is 1.36,4-hydroxyl-2,2,6, the mol ratio of 6-tetramethyl piperidine nitrogen oxygen free radical and sodium bisulfite is 2.42;
2) volume ratio of deionized water and ethylene glycol is 3: 1;
3) consumption of Sodium styrene sulfonate is 0.25g/L;
4) adopt the method vacuumize to remove oxygen in the reaction system;
5) centrifugation is 30 minutes, 3000 rev/mins of rotating speeds;
6) content of polymkeric substance is 4.1～7.6% in the above-mentioned modified carbon black that makes;
7) the above-mentioned modified carbon black particle diameter that makes is at 120～171nm;
8) the above-mentioned modified carbon black that makes can be dispersed in the water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018184341A1 (en) * | 2017-04-07 | 2018-10-11 | 苏州海凌达电子科技有限公司 | Preparation method for high-performance material for use in supercapacitor |
| CN111788726A (en) * | 2018-03-23 | 2020-10-16 | 日本瑞翁株式会社 | Binder composition for secondary battery, conductive material paste for secondary battery electrode, slurry composition for secondary battery electrode, method for producing slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery |
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| DE69832720T2 (en) * | 1997-10-31 | 2006-09-07 | Cabot Corp., Boston | PARTICLES COMPRISING A STABILIZED FREE RADICAL, POLYMERIZED MODIFIED PARTICLES AND METHOD OF PRODUCTION THEREOF |
| US6368239B1 (en) * | 1998-06-03 | 2002-04-09 | Cabot Corporation | Methods of making a particle having an attached stable free radical |
| US6402825B1 (en) * | 2001-07-27 | 2002-06-11 | Lexmark International, Inc | Surface modified carbon black |
| CN1260411C (en) * | 2003-06-30 | 2006-06-21 | 南京大学 | Method for modifying planar mono-crystal silicon surface |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018184341A1 (en) * | 2017-04-07 | 2018-10-11 | 苏州海凌达电子科技有限公司 | Preparation method for high-performance material for use in supercapacitor |
| CN111788726A (en) * | 2018-03-23 | 2020-10-16 | 日本瑞翁株式会社 | Binder composition for secondary battery, conductive material paste for secondary battery electrode, slurry composition for secondary battery electrode, method for producing slurry composition for secondary battery electrode, electrode for secondary battery, and secondary battery |
| CN111788726B (en) * | 2018-03-23 | 2023-11-24 | 日本瑞翁株式会社 | Binder composition for secondary battery, conductive material paste for electrode, slurry composition, method for producing same, electrode, and secondary battery |
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