CN102093497A - Method for preparing high-stereoregularity acrylonitrile resin - Google Patents
Method for preparing high-stereoregularity acrylonitrile resin Download PDFInfo
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- CN102093497A CN102093497A CN2010106033481A CN201010603348A CN102093497A CN 102093497 A CN102093497 A CN 102093497A CN 2010106033481 A CN2010106033481 A CN 2010106033481A CN 201010603348 A CN201010603348 A CN 201010603348A CN 102093497 A CN102093497 A CN 102093497A
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- methylimidazole
- vinyl cyanide
- lactic acid
- acid salt
- resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing high-stereoregularity acrylonitrile resin, which is characterized in that: dissolving ferric trichloride serving as a catalyst, an initiator, an acrylonitrile monomer, and ascorbic acid serving as a reducer in chiral ionic liquid, performing the atom transfer radical active polymerization of an activator regenerated by electron transfer, washing the product by concentrated hydrochloric acid, precipitating, performing suction filtration and drying to obtain polyacrylonitrile resin. When the preparation method disclosed by the invention is used, polyacrylonitrile resin with triad isotacticity ranging from 0.35 to 0.42 can be obtained.
Description
Technical field
The present invention relates to a kind of method for preparing high stereoregular polypropylenes nitrile resin, especially a kind of atom transferred free radical living polymerization that adopts the transfer transport regenerated catalyst prepares the method for high stereoregular polypropylenes nitrile resin.
Background technology
The taxis of the size of polymericular weight and molecular weight distribution thereof, molecular chain has great influence to its performance, moulding process and end product quality.Radical living polymerization is the polymerization technique that new development is got up, and allows monomer to carry out living control polymerization under the radical polymerization mechanism pattern, can be regulated and control polymericular weight size and distribution thereof and molecular chain taxis.
Atom transfer radical polymerization is one of effective implementation method in the radical living polymerization.This reaction is formed catalyst system with transistion metal compound and coordination agent, realizes the control to polyreaction.The atom transferred free radical living polymerization of the transfer transport regenerated catalyst that grows up on this basis, rely on excessive reductive agent that the high valence state transition metal that accumulates in the polymerization process constantly is converted into the lower valency catalyzer, the consumption of the initial transistion metal compound that adds can significantly reduce, and is a kind of living control polymerization technology that is very suitable for suitability for industrialized production.
Polyacrylonitrile is the important presoma of macromolecular material, is subjected to the extensive concern in many fields.
Chiral ionic liquid is a kind of green solvent, can influence polymer molecular chain sequential structure in the polymerization process.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing high stereoregular polypropylenes nitrile resin.
The invention provides the method for preparing high stereoregular polypropylenes nitrile resin, comprise the steps:
With the catalyzer iron trichloride, initiator, the monomer vinyl cyanide, the reductive agent dissolution of ascorbic acid is in the chirality ionic liquid, wherein, the mol ratio of vinyl cyanide and initiator is 400: 0.5～400: 2, the mol ratio of vinyl cyanide and iron trichloride is 400: 0.5～400: 2, the mol ratio of iron trichloride and xitix is 1: 4～1: 10, the volume ratio of vinyl cyanide and chiral ionic liquid is 1: 0.5～1: 3, polymeric reaction temperature is 60～75 degrees centigrade, reacted at least 6 hours, carry out the atom transferred free radical living polymerization of transfer transport regenerated catalyst, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
Used initiator is 2-isobutyl ethyl bromide, 2-bromopropionitrile etc. when preparing this resin, and chiral ionic liquid is with 1-ethyl-3-Methylimidazole L-lactic acid salt, 1-butyl-3-Methylimidazole L-lactic acid salt, 1-amyl group-3-Methylimidazole L-lactic acid salt, 1-hexyl-3-Methylimidazole L-lactic acid salt etc.
Compared with the prior art the present invention has following advantage: the atom transferred free radical living polymerization that the transfer transport regenerated catalyst causes is compared with traditional polymerization, the condition of polyreaction is more gentle, chiral ionic liquid is a green solvent, has obtained the triad degree of isotacticity and be 0.35～0.42 polyacrylonitrile resin.
Embodiment
Describe the present invention below in detail and provide several embodiment:
Embodiment 1: 0.092 gram iron trichloride, 0.084 milliliter of 2-isobutyl ethyl bromide, 0.803 gram xitix, 15.0 milliliters of vinyl cyanide are dissolved in 15.0 milliliters of 1-hexyls-3-Methylimidazole L-lactic acid salt, reaction flask is put into 70 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 20 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 20560, and molecular weight distribution is 1.18, and the triad degree of isotacticity is 0.39.
Embodiment 2: 0.092 gram iron trichloride, 0.084 milliliter of 2-isobutyl ethyl bromide, 0.803 gram xitix, 15.0 milliliters of vinyl cyanide are dissolved in 45.0 milliliters of 1-hexyls-3-Methylimidazole L-lactic acid salt, reaction flask is put into 70 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 20 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 14350, and molecular weight distribution is 1.21, and the triad degree of isotacticity is 0.42.
Embodiment 3: 0.184 gram iron trichloride, 0.097 milliliter of 2-bromopropionitrile, 1.505 gram xitix, 15.0 milliliters of vinyl cyanide are dissolved in 30.0 milliliters of 1-butyl-3-Methylimidazole L-lactic acid salt, reaction flask is put into 65 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 15 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 9970, and molecular weight distribution is 1.27, and the triad degree of isotacticity is 0.37.
Embodiment 4: 0.092 gram iron trichloride, 0.084 milliliter of 2-isobutyl ethyl bromide, 0.803 gram xitix, 15.0 milliliters of vinyl cyanide are dissolved in 15.0 milliliters of 1-ethyls-3-Methylimidazole L-lactic acid salt, reaction flask is put into 70 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 10 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 11980, and molecular weight distribution is 1.20, and the triad degree of isotacticity is 0.35.
Embodiment 5: 0.092 gram iron trichloride, 0.084 milliliter of 2-isobutyl ethyl bromide, 0.803 gram xitix, 15.0 milliliters of vinyl cyanide are dissolved in 20.0 milliliters of 1-butyl-3-Methylimidazole L-lactic acid salt, reaction flask is put into 75 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 15 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 15210, and molecular weight distribution is 1.25, and the triad degree of isotacticity is 0.36.
Claims (2)
1. method for preparing high stereoregular polypropylenes nitrile resin, it is characterized in that: with the catalyzer iron trichloride, initiator, the monomer vinyl cyanide, the reductive agent dissolution of ascorbic acid is in the chirality ionic liquid, wherein, the mol ratio of vinyl cyanide and initiator is 400: 0.5～400: 2, the mol ratio of vinyl cyanide and iron trichloride is 400: 0.5～400: 2, the mol ratio of iron trichloride and xitix is 1: 4～1: 10, the volume ratio of vinyl cyanide and chiral ionic liquid is 1: 0.5～1: 3, polymeric reaction temperature is 60～75 degrees centigrade, reacted at least 6 hours, carry out the atom transferred free radical living polymerization of transfer transport regenerated catalyst, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
2. used initiator is 2-isobutyl ethyl bromide, 2-bromopropionitrile etc. when it is characterized in that preparing this resin according to the described high stereoregular polypropylenes nitrile of claim 1. resin, and chiral ionic liquid is with 1-ethyl-3-Methylimidazole L-lactic acid salt, 1-butyl-3-Methylimidazole L-lactic acid salt, 1-amyl group-3-Methylimidazole L-lactic acid salt, 1-hexyl-3-Methylimidazole L-lactic acid salt etc.
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| CN2010106033481A CN102093497B (en) | 2010-12-18 | 2010-12-18 | Method for preparing high-stereoregularity acrylonitrile resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911304A (en) * | 2012-11-12 | 2013-02-06 | 鲁东大学 | Preparation method for high isotactic polyacrylonitrile resin |
| CN102936760A (en) * | 2012-11-05 | 2013-02-20 | 歌山建设集团有限公司 | Flame retardant polyacrylonitrile fiber and preparation method thereof |
| CN103484966A (en) * | 2013-08-15 | 2014-01-01 | 苏州龙杰特种纤维股份有限公司 | Polyacrylonitrile fiber with flame resistance and preparation method thereof |
| CN106589193A (en) * | 2016-12-22 | 2017-04-26 | 沈阳化工研究院有限公司 | Preparation method of high-regularity acrylonitrile polymer |
| CN113809315A (en) * | 2021-09-15 | 2021-12-17 | 上海交通大学 | High-conductivity sulfur-based positive electrode material for secondary battery and secondary battery |
Citations (3)
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| US5886118A (en) * | 1997-04-14 | 1999-03-23 | Case Western Reserve University | Process for polymerizing acrylonitrile |
| CN101735361A (en) * | 2009-12-14 | 2010-06-16 | 鲁东大学 | Method for preparing polyacrylonitrile resin |
| CN101864016A (en) * | 2010-06-22 | 2010-10-20 | 鲁东大学 | Preparation method of polyacrylonitrile resin |
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2010
- 2010-12-18 CN CN2010106033481A patent/CN102093497B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886118A (en) * | 1997-04-14 | 1999-03-23 | Case Western Reserve University | Process for polymerizing acrylonitrile |
| US5886118C1 (en) * | 1997-04-14 | 2001-02-20 | Univ Case Western Reserve | Process for polymerizing acrylonitrile |
| CN101735361A (en) * | 2009-12-14 | 2010-06-16 | 鲁东大学 | Method for preparing polyacrylonitrile resin |
| CN101864016A (en) * | 2010-06-22 | 2010-10-20 | 鲁东大学 | Preparation method of polyacrylonitrile resin |
Non-Patent Citations (1)
| Title |
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| 《 Journal of Macromolecular Science Part A 》 20100921 Jing Ma et al. FeCl3/Acetic Acid-mediated Reverse Atom Transfer Radical Polymerization of Acrylonitrile 第1075页右栏第2段到第1076页右栏第1段 权利要求第1-2项 第47卷, 第11期 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936760A (en) * | 2012-11-05 | 2013-02-20 | 歌山建设集团有限公司 | Flame retardant polyacrylonitrile fiber and preparation method thereof |
| CN102936760B (en) * | 2012-11-05 | 2015-04-22 | 歌山建设集团有限公司 | Flame retardant polyacrylonitrile fiber and preparation method thereof |
| CN102911304A (en) * | 2012-11-12 | 2013-02-06 | 鲁东大学 | Preparation method for high isotactic polyacrylonitrile resin |
| CN102911304B (en) * | 2012-11-12 | 2014-05-07 | 鲁东大学 | Preparation method for high isotactic polyacrylonitrile resin |
| CN103484966A (en) * | 2013-08-15 | 2014-01-01 | 苏州龙杰特种纤维股份有限公司 | Polyacrylonitrile fiber with flame resistance and preparation method thereof |
| CN106589193A (en) * | 2016-12-22 | 2017-04-26 | 沈阳化工研究院有限公司 | Preparation method of high-regularity acrylonitrile polymer |
| CN106589193B (en) * | 2016-12-22 | 2019-05-21 | 沈阳化工研究院有限公司 | A kind of preparation method of the acrylonitrile polymer of high regularity |
| CN113809315A (en) * | 2021-09-15 | 2021-12-17 | 上海交通大学 | High-conductivity sulfur-based positive electrode material for secondary battery and secondary battery |
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| CN102093497B (en) | 2012-06-27 |
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