CN102120786B - Method for preparing highly syndiotactic polyacrylonitrile resin - Google Patents
Method for preparing highly syndiotactic polyacrylonitrile resin Download PDFInfo
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- CN102120786B CN102120786B CN2011100089948A CN201110008994A CN102120786B CN 102120786 B CN102120786 B CN 102120786B CN 2011100089948 A CN2011100089948 A CN 2011100089948A CN 201110008994 A CN201110008994 A CN 201110008994A CN 102120786 B CN102120786 B CN 102120786B
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- bromopropionitrile
- polyacrylonitrile resin
- ytterbiums
- iodate
- vinyl cyanide
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Abstract
The invention discloses a method for preparing highly syndiotactic polyacrylonitrile resin. The method is characterized by comprising the following steps: dissolving ytterbium diiodide used as catalyst, 2-Bromopropionitrile used as initiator, acrylonitrile used as monomer and 2,2'-dipyridine used as coordination agent in N, N-dimethylformamide, performing atom transfer radical polymerization, washing the product with hydrochloric acid, precipitating performing suction filtering, and drying to obtain polyacrylonitrile resin. By adopting the preparation method disclosed by the invention, the polyacrylonitrile resin of which degree of triad syndiotacticity reaches 0.35 can be obtained.
Description
Technical field
The present invention relates to a kind of method for preparing high syndiotactic polypropylene nitrile resin, especially a section adopts the atom transferred free radical living polymerization to prepare the method for high syndiotactic polypropylene nitrile resin.
Background technology
In recent years, synthesizing of the polyacrylonitrile resin that the syndiotaxy regularity is high received the extensive concern in polymer synthetic chemistry field.The polyacrylonitrile resin molecular chain taxis that the tradition free radical polymerisation process obtains is lower.The atom transferred free radical living polymerization is the polymerization technique that new development is got up; Adopt metallic compound and coordination agent to form catalystsystem; Allow monomer under the radical polymerization mechanism pattern, to carry out living control polymerization, can control the polymer molecular chain taxis.Lanthanide metal compound successfully causes monomeric active anionic polymerizations such as lactone, methacrylic ester.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing high syndiotactic polypropylene nitrile resin.
The invention provides the method for the high syndiotactic polypropylene nitrile resin of preparation, comprise the steps:
With catalyzer two iodate ytterbiums, initiator 2-bromopropionitrile, monomer vinyl cyanide, coordination agent 2,2 '-dipyridyl is dissolved into N, in the dinethylformamide, wherein; The mol ratio of vinyl cyanide and 2-bromopropionitrile is 400: 0.5～400: 2, and the mol ratio of 2-bromopropionitrile and two iodate ytterbiums is 1: 0.5～1: 4, two iodate ytterbiums and 2, and the mol ratio of 2 '-dipyridyl is 1: 1～1: 6; The volumetric molar concentration of vinyl cyanide is 5～9 mol, and polymeric reaction temperature is 55～75 degrees centigrade, logical repeatedly nitrogen deoxygenation at least 2 times; Carry out the atom transferred free radical living polymerization, reacted at least 6 hours, product washs through concentrated hydrochloric acid; Deposition, suction filtration, drying.
Compared with present technology the present invention has following advantage: provided by the invention method is simple, overcome the defective of traditional free radical polymerisation process, obtained the triad degree of syndiotacticity and reached 0.35 polyacrylonitrile resin.
Embodiment
Specify the present invention below and provide several embodiment:
Embodiment 1: with 0.244 gram, two iodate ytterbiums, 0.049 milliliter of 2-bromopropionitrile, 0.178 gram 2,2 '-dipyridyl, 15.0 milliliters of vinyl cyanide are dissolved into 23.0 milliliters of N, in the dinethylformamide; Reaction flask is put into 65 degrees centigrade of constant temperature oil baths, and the atom transferred free radical living polymerization is carried out in logical repeatedly nitrogen deoxygenation 3 times; React after 20 hours, product washs through concentrated hydrochloric acid, deposition; Suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 21870, and MWD is 1.19, and the triad degree of syndiotacticity is 0.29.
Embodiment 2: with 0.488 gram, two iodate ytterbiums, 0.025 milliliter of 2-bromopropionitrile, 0.534 gram 2,2 '-dipyridyl, 15.0 milliliters of vinyl cyanide are dissolved into 10.0 milliliters of N, in the dinethylformamide; Reaction flask is put into 70 degrees centigrade of constant temperature oil baths, and the atom transferred free radical living polymerization is carried out in logical repeatedly nitrogen deoxygenation 2 times; React after 15 hours, product washs through concentrated hydrochloric acid, deposition; Suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 40520, and MWD is 1.23, and the triad degree of syndiotacticity is 0.31.
Embodiment 3: with 0.976 gram, two iodate ytterbiums, 0.098 milliliter of 2-bromopropionitrile, 0.356 gram 2,2 '-dipyridyl, 15.0 milliliters of vinyl cyanide are dissolved into 17.5 milliliters of N, in the dinethylformamide; Reaction flask is put into 60 degrees centigrade of constant temperature oil baths, and the atom transferred free radical living polymerization is carried out in logical repeatedly nitrogen deoxygenation 4 times; React after 25 hours, product washs through concentrated hydrochloric acid, deposition; Suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 10910, and MWD is 1.21, and the triad degree of syndiotacticity is 0.35.
Embodiment 4: with 0.732 gram, two iodate ytterbiums, 0.049 milliliter of 2-bromopropionitrile, 0.801 gram 2,2 '-dipyridyl, 15.0 milliliters of vinyl cyanide are dissolved into 30.5 milliliters of N, in the dinethylformamide; Reaction flask is put into 75 degrees centigrade of constant temperature oil baths, and the atom transferred free radical living polymerization is carried out in logical repeatedly nitrogen deoxygenation 3 times; React after 30 hours, product washs through concentrated hydrochloric acid, deposition; Suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 20710, and MWD is 1.26, and the triad degree of syndiotacticity is 0.33.
Claims (1)
1. method for preparing high syndiotactic polypropylene nitrile resin, it is characterized in that: with catalyzer two iodate ytterbiums, initiator 2-bromopropionitrile, monomer vinyl cyanide, coordination agent 2,2 '-dipyridyl is dissolved into N, in the dinethylformamide; Wherein, the mol ratio of vinyl cyanide and 2-bromopropionitrile is 400: 0.5～400: 2, and the mol ratio of 2-bromopropionitrile and two iodate ytterbiums is 1: 0.5～1: 4, two iodate ytterbiums and 2; The mol ratio of 2 '-dipyridyl is 1: 1～1: 6, and the volumetric molar concentration of vinyl cyanide is 5～9 mol, and polymeric reaction temperature is 55～75 degrees centigrade, logical repeatedly nitrogen deoxygenation at least 2 times; Carry out the atom transferred free radical living polymerization, reacted at least 6 hours, product washs through concentrated hydrochloric acid, deposition; Suction filtration, drying, the polyacrylonitrile resin triad degree of syndiotacticity that obtains is 0.29; 0.31,0.33,0.35.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100089948A CN102120786B (en) | 2011-01-04 | 2011-01-04 | Method for preparing highly syndiotactic polyacrylonitrile resin |
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| CN2011100089948A CN102120786B (en) | 2011-01-04 | 2011-01-04 | Method for preparing highly syndiotactic polyacrylonitrile resin |
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| CN102120786A CN102120786A (en) | 2011-07-13 |
| CN102120786B true CN102120786B (en) | 2012-08-15 |
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| CN2011100089948A Expired - Fee Related CN102120786B (en) | 2011-01-04 | 2011-01-04 | Method for preparing highly syndiotactic polyacrylonitrile resin |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6254239B2 (en) * | 2016-02-29 | 2017-12-27 | 大日精化工業株式会社 | Polymer production method |
| CN115417939B (en) * | 2022-09-23 | 2023-05-19 | 新创碳谷集团有限公司 | Acrylonitrile high-regularity high-molecular-weight anionic polymerization process initiated by propionitrile anions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077898A (en) * | 2007-04-28 | 2007-11-28 | 鲁东大学 | Method for preparing polyacrylonitrile resin with narrow molecular weight distribution |
| CN101139412A (en) * | 2007-09-06 | 2008-03-12 | 东华大学 | Low-molecular weight distributed polyacrylonitile and method for making same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077898A (en) * | 2007-04-28 | 2007-11-28 | 鲁东大学 | Method for preparing polyacrylonitrile resin with narrow molecular weight distribution |
| CN101139412A (en) * | 2007-09-06 | 2008-03-12 | 东华大学 | Low-molecular weight distributed polyacrylonitile and method for making same |
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| CN102120786A (en) | 2011-07-13 |
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Granted publication date: 20120815 Termination date: 20140104 |