CN102660036B - Method for reducing cracking of millimeter polyacrylonitrile small balls during oxidation - Google Patents
Method for reducing cracking of millimeter polyacrylonitrile small balls during oxidation Download PDFInfo
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- CN102660036B CN102660036B CN 201210123598 CN201210123598A CN102660036B CN 102660036 B CN102660036 B CN 102660036B CN 201210123598 CN201210123598 CN 201210123598 CN 201210123598 A CN201210123598 A CN 201210123598A CN 102660036 B CN102660036 B CN 102660036B
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Abstract
The invention relates to a method for reducing the cracking of millimeter polyacrylonitrile small balls during oxidation. The method comprises the following steps of: mixing polyacrylonitrile and itaconic acid, adding the mixture into dimethyl sulfoxide to prepare a solution, adding azodiisobutyronitrile serving as an initiator, keeping the constant temperature of between 55 and 70 DEG C for 5 to10 hours with stirring, and cooling naturally; adding carbon fibers of which the length-diameter ratio is (5-1):1 and the length does not exceed 2 millimeters, and cooling with stirring to room temperature to obtain a mother solution for balling; transferring the mother solution for balling into a liquid extruder, dripping the mother solution into an aqueous solution of the dimethyl sulfoxide dropwise, and curing for 1 to 5 hours for balling to obtain primary millimeter polyacrylonitrile small balls; and heating the primary millimeter polyacrylonitrile small balls to the temperature of between 220 and 300 DEG C by using excess air, and keeping constant temperature for 1 to 10 hours to obtain the millimeter polyacrylonitrile small balls. The method is easy and convenient to operate and easy to control; and the method has the advantage that the cracking of the millimeter polyacrylonitrile small balls in the process of oxidizing without melting can be reduced so as to keep the integrity of the small balls.
Description
Technical field
The invention provides a kind of technology of preparing of polyacrylonitrile bead, relate to a kind of millimeter method that grade polypropylene nitrile bead breaks of slowing down specifically in oxidising process.
Background technology
Polyacrylonitrile is because its nitrogen content is higher, has clear superiority at some particular application such as CO2 aspect catching, but the spherical polyacrylonitrile of reporting in the document mostly is micron order and nano level at present, can't be applied to CO2 catches: disclose a kind of preparation method of polyacrylonitrile base carbon nanospheres as Chinese invention patent 200810032942 " preparation method of polyacrylonitrile base carbon nanospheres ", comprised the following steps: the emulsifier-free emulsion polymerization of a. polyacrylonitrile ball; B. the cryostatic stabilizationization of polyacrylonitrile ball; C. the high temperature carbonization of polyacrylonitrile ball.This invention can obtain the different carbon nanospheres of particle diameter by the proportioning of monomer, initiator and the deionized water of adjusting polyacrylonitrile emulsifier-free emulsion polymerization.And for example Chinese invention patent 200810053597 " a kind of method for preparing monodisperse polyacrylonitrile nano-microsphere " discloses a kind of method for preparing monodisperse polyacrylonitrile nano-microsphere, acrylonitrile monemer with the 2-8 mass parts, the polyethylene of dispersing agent base pyrrolidone of 3-7 mass parts and the initiator of 0.02-0.06 mass parts are dissolved in the reaction medium of being made up of dehydrated alcohol and water successively, solution is moved into reaction vessel, speed revolving reaction container with 70-130 rev/min, temperature of reaction is 73-75 ℃, reaction times is 5-8h, leaves standstill product is centrifugal again.The technical scheme of inventing can prepare the polyacrylonitrile nano particulate that pattern is good and the monodispersity energy is good.The patent 201010564568.8 " preparation method of a kind of millimeter level activated charcoal pellets " that the preparation of millimeter level bead only has us to apply for, but this bead is in the experience oxidation not during thaw process, a large amount of crackles usually appear in spherome surface, when serious even break, its breakage rate causes to obtain high-quality gac ball up to more than 30%.
Summary of the invention
The purpose of this invention is to provide a kind of millimeter grade polypropylene nitrile bead that slows down and crackle do not occur to keep the method for its spheroid integrity in the thaw process in oxidation.
Concrete preparation method of the present invention is as follows:
(1) polyacrylonitrile and methylene-succinic acid are by weight (80-95): after (20-5) mixing, join in the dimethyl sulfoxide (DMSO) (DMSO), be mixed with the solution of 20-25wt% concentration, the Diisopropyl azodicarboxylate of adding polyacrylonitrile weight 0.5-1%, is lowered the temperature under agitation in 55-70 ℃ of constant temperature 5-10h afterwards naturally as initiator.The length-to-diameter ratio that polyacrylonitrile weight 0.5-5% is added in cooling simultaneously is (5-1): 1 length is no more than the charcoal fiber of 2mm, under agitation cools to room temperature afterwards always, obtains to be used for the mother liquor of balling-up;
(2) the balling-up mother liquor changes in the fluid extruding device, dropwise drips in the aqueous solution of 10-70wt% methyl-sulphoxide and is cured balling-up, behind the set time 1-5h, obtains elementary millimeter grade polypropylene nitrile bead;
(3) elementary millimeter grade polypropylene nitrile bead is raised to 220-300 ℃ of also constant temperature 1-10h with excess air with the temperature rise rate of 1-20 ℃/h, namely makes a millimeter grade polypropylene nitrile bead.
Aforesaid charcoal fiber is PAN-based carbon fiber, pitch-based carbon fiber, rayon-based carbon fiber or resol based carbon fiber.
Detection method of the present invention: randomly draw 20 beads have crackle on microscopically reading bead surface bead, calculating has the crackle bead to account for the ratio of whole beads, is breakage rate, repeats 3 times, averages.
Advantage of the present invention is:
Easy and simple to handle, be easy to control; Preparation process is slowed down millimeter grade polypropylene nitrile bead and is not occurred crackle in the thaw process to keep its spheroid integrity in oxidation.
Embodiment
Embodiment 1
Polyacrylonitrile and methylene-succinic acid join among the DMSO after mixing by weight 80:20, are mixed with the solution of 25wt% concentration, and the Diisopropyl azodicarboxylate that adds polyacrylonitrile weight 1%, is lowered the temperature under agitation in 55 ℃ of constant temperature 10h afterwards naturally as initiator.The length-to-diameter ratio that polyacrylonitrile weight 0.5% is added in cooling simultaneously under agitation cools to room temperature afterwards for 5:1 length is the polyacrylonitrile charcoal fiber of 2mm always, obtains to be used for the mother liquor of balling-up.This balling-up mother liquor is changed in the fluid extruding device, dropwise drip to and obtain a millimeter grade polypropylene nitrile bead after being cured 1h in the aqueous solution of 10wt% methyl-sulphoxide.The bead that obtains is raised to 300 ℃ of also constant temperature 1h with excess air with the temperature rise rate of 1 ℃/h, makes a millimeter grade polypropylene nitrile bead.The bead breakage rate is 1.8%.
Embodiment 2
Polyacrylonitrile and methylene-succinic acid join among the DMSO after mixing by weight 95:5, are mixed with the solution of 20wt% concentration, and the Diisopropyl azodicarboxylate that adds polyacrylonitrile weight 0.5%, is lowered the temperature under agitation in 65 ℃ of constant temperature 3h afterwards naturally as initiator.The length-to-diameter ratio that polyacrylonitrile weight 1% is added in cooling simultaneously is the asphalt carbon fiber of 1mm for 2:1 length, under agitation cools to room temperature afterwards always, obtains to be used for the mother liquor of balling-up.This balling-up mother liquor is changed in the fluid extruding device, dropwise drip to and obtain a millimeter grade polypropylene nitrile bead after being cured 5h in the aqueous solution of 70wt% methyl-sulphoxide.The bead that obtains is raised to 220 ℃ of also constant temperature 10h with excess air with the temperature rise rate of 10 ℃/h, makes a millimeter grade polypropylene nitrile bead.The bead breakage rate is 2.3%.
Embodiment 3
Polyacrylonitrile and methylene-succinic acid join among the DMSO after mixing by weight 90:10, are mixed with the solution of 22wt% concentration, and the Diisopropyl azodicarboxylate that adds polyacrylonitrile weight 0.6%, is lowered the temperature under agitation in 70 ℃ of constant temperature 3h afterwards naturally as initiator.The length-to-diameter ratio that polyacrylonitrile weight 3% is added in cooling simultaneously is the rayon-based carbon fiber of 0.5mm for 1:1 length, under agitation cools to room temperature afterwards always, obtains to be used for the mother liquor of balling-up.This balling-up mother liquor is changed in the fluid extruding device, dropwise drip to and obtain a millimeter grade polypropylene nitrile bead after being cured 2h in the aqueous solution of 40wt% methyl-sulphoxide.The bead that obtains is raised to 250 ℃ of also constant temperature 5h with excess air with the temperature rise rate of 20 ℃/h, makes a millimeter grade polypropylene nitrile bead.The bead breakage rate is 3.1%.
Embodiment 4
Polyacrylonitrile and methylene-succinic acid join among the DMSO after mixing by weight 85:15, are mixed with the solution of 20wt% concentration, and the Diisopropyl azodicarboxylate that adds polyacrylonitrile weight 0.8%, is lowered the temperature under agitation in 58 ℃ of constant temperature 8h afterwards naturally as initiator.The length-to-diameter ratio that polyacrylonitrile weight 5% is added in cooling simultaneously is the resol based carbon fiber of 0.1mm for 3:1 length, under agitation cools to room temperature afterwards always, obtains to be used for the mother liquor of balling-up.This balling-up mother liquor is changed in the fluid extruding device, dropwise drip to and obtain a millimeter grade polypropylene nitrile bead after being cured 4h in the aqueous solution of 60wt% methyl-sulphoxide.The bead that obtains is raised to 280 ℃ of also constant temperature 4h with excess air with the temperature rise rate of 15 ℃/h, makes a millimeter grade polypropylene nitrile bead.The bead breakage rate is 1.1%.
Embodiment 5
Polyacrylonitrile and methylene-succinic acid join among the DMSO after mixing by weight 88:12, are mixed with the solution of 23wt% concentration, and the Diisopropyl azodicarboxylate that adds polyacrylonitrile weight 0.7%, is lowered the temperature under agitation in 67 ℃ of constant temperature 3h afterwards naturally as initiator.The length-to-diameter ratio that polyacrylonitrile weight 2% is added in cooling simultaneously under agitation cools to room temperature afterwards for 4:1 length is the polyacrylonitrile charcoal fiber of 1mm always, obtains to be used for the mother liquor of balling-up.This balling-up mother liquor is changed in the fluid extruding device, dropwise drip to and obtain a millimeter grade polypropylene nitrile bead after being cured 3.5h in the aqueous solution of 50wt% methyl-sulphoxide.The bead that obtains is raised to 250 ℃ of also constant temperature 5h with excess air with the temperature rise rate of 10 ℃/h, makes a millimeter grade polypropylene nitrile bead.The bead breakage rate is 1.3%.
Comparative Examples 1
Pure polyacrylonitrile joins among the DMSO, is mixed with the solution of 20wt% concentration, and the Diisopropyl azodicarboxylate of adding polyacrylonitrile weight 1% under agitation in 55 ℃ of constant temperature 10h, cools to room temperature as initiator afterwards naturally, obtains to be used for the mother liquor of balling-up.This balling-up mother liquor is changed in the fluid extruding device, dropwise drip to and obtain a millimeter grade polypropylene nitrile bead after being cured 1h in the aqueous solution of 10wt% methyl-sulphoxide.The bead that obtains is raised to 300 ℃ of also constant temperature 1h with excess air with the temperature rise rate of 1 ℃/h, makes a millimeter grade polypropylene nitrile bead.The bead breakage rate is 26.8%.
Comparative Examples 2
After polyacrylonitrile and methylene-succinic acid mix by weight 80:20, join among the DMSO, be mixed with the solution of 20wt% concentration, the Diisopropyl azodicarboxylate that adds polyacrylonitrile weight 1% as initiator under agitation in 55 ℃ of constant temperature 10h, naturally cool to room temperature afterwards, obtain to be used for the mother liquor of balling-up.This balling-up mother liquor is changed in the fluid extruding device, dropwise drip to and obtain a millimeter grade polypropylene nitrile bead after being cured 1h in the aqueous solution of 10wt% methyl-sulphoxide.The bead that obtains is raised to 300 ℃ of also constant temperature 1h with excess air with the temperature rise rate of 1 ℃/h, makes a millimeter grade polypropylene nitrile bead.The bead breakage rate is 18.9%.
Claims (2)
1. one kind is slowed down millimeter method of grade polypropylene nitrile bead oxide breaks, it is characterized in that comprising the steps:
(1) after polyacrylonitrile and methylene-succinic acid mix by weight 80-95:20-5, join in the dimethyl sulfoxide (DMSO), be mixed with the solution of 20-25wt% concentration, the Diisopropyl azodicarboxylate of adding polyacrylonitrile weight 0.5-1%, is lowered the temperature under agitation in 55-70 ℃ of constant temperature 5-10h afterwards naturally as initiator;
The length-to-diameter ratio that polyacrylonitrile weight 0.5-5% is added in cooling simultaneously is 5-1:1, and length is no more than the carbon fiber of 2mm, under agitation cools to room temperature afterwards always, obtains to be used for the mother liquor of balling-up;
(2) the balling-up mother liquor changes in the fluid extruding device, dropwise drips in the aqueous solution of 10-70wt% methyl-sulphoxide and is cured balling-up, behind the set time 1-5h, obtains elementary millimeter grade polypropylene nitrile bead;
(3) elementary millimeter grade polypropylene nitrile bead is raised to 220-300 ℃ of also constant temperature 1-10h with excess air with the temperature rise rate of 1-20 ℃/h, namely makes a millimeter grade polypropylene nitrile bead.
2. a kind of millimeter method of grade polypropylene nitrile bead oxide breaks of slowing down as claimed in claim 1 is characterized in that described carbon fiber is PAN-based carbon fiber, asphalt base carbon fiber, viscose-based carbon fiber or resol base carbon fibre.
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| CN104692375A (en) * | 2013-12-09 | 2015-06-10 | 中国科学院山西煤炭化学研究所 | Preparation method for millimeter-level polyacrylonitrile spherical activated carbon with high nitrogen content |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811697A (en) * | 2010-05-05 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | Method for preparing pressed active carbon |
| CN101983918A (en) * | 2010-11-25 | 2011-03-09 | 中国科学院山西煤炭化学研究所 | Preparation method of millimeter activated carbon beads |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811697A (en) * | 2010-05-05 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | Method for preparing pressed active carbon |
| CN101983918A (en) * | 2010-11-25 | 2011-03-09 | 中国科学院山西煤炭化学研究所 | Preparation method of millimeter activated carbon beads |
Non-Patent Citations (2)
| Title |
|---|
| "DSC STUDY OF STABILIZATION REACTIONS IN POLY(ACRYLONITRILE-co-ITACONIC ACID) WITH PEAK-RESOLVING METHOD";Q. Ouyang et al.;《Journal of Thermal Analysis and Calorimetry》;20080815;第94卷(第1期);第85-88页 * |
| Q. Ouyang et al.."DSC STUDY OF STABILIZATION REACTIONS IN POLY(ACRYLONITRILE-co-ITACONIC ACID) WITH PEAK-RESOLVING METHOD".《Journal of Thermal Analysis and Calorimetry》.2008,第94卷(第1期), |
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