CN100532410C - Method for preparing polyacrylonitrile resin with narrow molecular weight distribution - Google Patents
Method for preparing polyacrylonitrile resin with narrow molecular weight distribution Download PDFInfo
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- CN100532410C CN100532410C CNB2007101036903A CN200710103690A CN100532410C CN 100532410 C CN100532410 C CN 100532410C CN B2007101036903 A CNB2007101036903 A CN B2007101036903A CN 200710103690 A CN200710103690 A CN 200710103690A CN 100532410 C CN100532410 C CN 100532410C
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- molecular weight
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- polyacrylonitrile resin
- narrow molecular
- vinyl cyanide
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Abstract
The present invention discloses process of preparing polyacrylonitrile resin with narrow molecular weight distribution. The process includes the following steps: dissolving metal halide FeCl3 and ligand itacoic acid in solvent N, N-dimethyl formamide; dissolving initiator azo diisobutyronitrile in monomer acrylonitrile and introducing N2 to eliminate O2; reverse atom transferring active free radical polymerization for at least 6 hr; precipitating the product, suction filtering, washing with concentrated hydrochloric acid solution and drying. By means of the said process, polyacrylonitrile resin with narrow molecular weight distribution of 1.14-1.21 may be prepared.
Description
(1) technical field:
The present invention relates to a kind of preparation method of polyacrylonitrile resin with narrow molecular weight distribution, especially a kind of method that adopts normal starter and high valence state metal halide to prepare polyacrylonitrile resin as the reverse atom transferred free radical living polymerization of catalyst system.
(2) background technology:
Polyacrylonitrile resin is the important presoma of polymeric material field, has excellent photostabilization, weathering resistance, anti-damaging by worms property, radiation resistance.The distribution of polymericular weight has very big influence to the production process and the quality product of macromolecular material, inquire into molecular weight distribution to the performance of improving macromolecular material, optimize molding technological condition, improving the quality of products has very important practical significance.At present, the preparation of the polyacrylonitrile resin of narrow molecular weight distribution has become the important subject that macromolecular material synthesizes the field.
The preparation method of polyacrylonitrile resin is more, generally is according to traditional radical polymerization mechanism, adopts solution polymerization, letex polymerization, suspension polymerization and bulk technique synthetic; But traditional radical polymerization only can obtain the wide polymkeric substance of molecular weight distribution, has a strong impact on the performance of polyacrylonitrile resin the finished product.
Activity polymerizating technology is the optimal technology of controlling polymers molecular weight distribution, mainly contains three kinds of cation activity polymerization, living anion polymerization and radical living polymerizations.The performance of acrylonitrile monemer itself causes it can't realize the cation activity polymerization, but living anion polymerization requires very harshness to reaction conditions, and the reaction process complexity, and the industrialization cost is high.
Radical living polymerization is the polymerization technique that eighties of last century grew up since the nineties, allow monomer under the pattern of radical polymerization mechanism, to carry out living control polymerization, can be regulated and control molecular weight distribution, be integrated the advantage of radical polymerization and living polymerization.Atom transfer radical polymerization is to have one of form of industrial prospect most in the radical living polymerization technology.Atom transition free radical polymerization reaction is a catalyzer with transition metal lower valency halogenide, and under suitable part effect, but synthetic molecular weight is distributed as 1.03～1.50 polymkeric substance.But there are two big defectives in conventional atom transfer radical polymerization: on the one hand used initiator halogenide poisonous, be difficult for making, be difficult for preservation; What catalyst metal halogenide was utilized on the other hand is that it goes back ortho states, and the as-reduced metal is very sensitive to oxygen or moisture.
(3) summary of the invention:
The objective of the invention is to overcome the deficiency of above-mentioned prior art, and a kind of method for preparing polyacrylonitrile resin with narrow molecular weight distribution with the conventional free radical initiator as initiator, with organic acid cheap and easy to get and high valence state metal halide as the reverse atom transferred free radical living polymerization of catalyst system is provided.
Purpose of the present invention can reach by following measure: FERRIC CHLORIDE ANHYDROUS, methylene-succinic acid are dissolved into N, in the dinethylformamide; Diisopropyl azodicarboxylate is dissolved in the monomer vinyl cyanide (AN), and 4 letting nitrogen in and deoxidizing carry out reverse atom transferred free radical living polymerization repeatedly.Reacted at least 6 hours, product is through precipitating suction filtration, concentrated hydrochloric acid washing, drying.Mol ratio between vinyl cyanide and the initiator is (100～800): 1; Mol ratio between Diisopropyl azodicarboxylate and the FERRIC CHLORIDE ANHYDROUS is 1:(1～3); Mol ratio between FERRIC CHLORIDE ANHYDROUS and the methylene-succinic acid is 1:(1～4); The volumetric molar concentration of vinyl cyanide is 6～8 mol; Polymeric reaction temperature is 55～70 degrees centigrade.
Compared with the prior art the present invention has the following advantages: preparation method provided by the invention is simple and easy to do, has overcome the defective of traditional atom transfer radical polymerization, can obtain molecular weight distribution and be 1.14～1.21 polyacrylonitrile resin.
(4) embodiment:
Describe the present invention below in detail and provide several embodiment:
Embodiment 1: with the anhydrous FeCl of 0.071 gram
3, 0.114 the gram methylene-succinic acid be dissolved into 50.0 milliliters of N, in the dinethylformamide, with 0.072 the gram Diisopropyl azodicarboxylate be dissolved in 23.0 milliliters of vinyl cyanide, join in the reaction flask successively, fill the nitrogen deoxygenation 4 times repeatedly, reaction flask is put into 65 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 16 hours, product is through precipitating suction filtration, concentrated hydrochloric acid washing, drying.
The transformation efficiency of polyreaction is 74.6%, and the number-average molecular weight of gained polyacrylonitrile resin is 16180, and molecular weight distribution is 1.18.
Embodiment 2: with the anhydrous FeCl of 1.458 grams
3, 1.17 the gram methylene-succinic acids be dissolved into 50.0 milliliters of N, in the dinethylformamide, with 0.492 the gram Diisopropyl azodicarboxylate be dissolved in 19.7 milliliters of vinyl cyanide, join in the reaction flask successively, fill the nitrogen deoxygenation 4 times repeatedly, reaction flask is put into 55 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 10 hours, product is through precipitating suction filtration, concentrated hydrochloric acid washing, drying.
The transformation efficiency of polyreaction is 40.2%, and the number-average molecular weight of gained polyacrylonitrile resin is 1250, and molecular weight distribution is 1.21.
Embodiment 3: with the anhydrous FeCl of 0.142 gram
3, 0.341 the gram methylene-succinic acid be dissolved into 50.0 milliliters of N, in the dinethylformamide, with 0.144 the gram Diisopropyl azodicarboxylate be dissolved in 23.0 milliliters of vinyl cyanide, join in the reaction flask successively, fill the nitrogen deoxygenation 4 times repeatedly, reaction flask is put into 60 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 6 hours, product is through precipitating suction filtration, concentrated hydrochloric acid washing, drying.
The transformation efficiency of polyreaction is 30.6%, and the number-average molecular weight of gained polyacrylonitrile resin is 3520, and molecular weight distribution is 1.16.
Embodiment 4: with the anhydrous FeCl of 0.216 gram
3, 0.693 the gram methylene-succinic acid be dissolved into 50.0 milliliters of N, in the dinethylformamide, with 0.109 the gram Diisopropyl azodicarboxylate be dissolved in 26.3 milliliters of vinyl cyanide, join in the reaction flask successively, fill the nitrogen deoxygenation 4 times repeatedly, reaction flask is put into 70 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 20 hours, product is through precipitating suction filtration, concentrated hydrochloric acid washing, drying.
The transformation efficiency of polyreaction is 86.3%, and the number-average molecular weight of gained polyacrylonitrile resin is 14250, and molecular weight distribution is 1.14.
Claims (1)
1. the preparation method of a polyacrylonitrile resin with narrow molecular weight distribution, it is characterized in that: with the metal halide FERRIC CHLORIDE ANHYDROUS, the part methylene-succinic acid is dissolved into solvent N, in the dinethylformamide, the initiator Diisopropyl azodicarboxylate is dissolved in the monomer vinyl cyanide, wherein, mol ratio between vinyl cyanide and the Diisopropyl azodicarboxylate is 100:1～800:1, mol ratio between Diisopropyl azodicarboxylate and the FERRIC CHLORIDE ANHYDROUS is 1:1～1:3, mol ratio between FERRIC CHLORIDE ANHYDROUS and the methylene-succinic acid is 1:1～1:4, the volumetric molar concentration of vinyl cyanide is 6～8 mol, and polymeric reaction temperature is 55～70 degrees centigrade, repeatedly 4 logical nitrogen deoxygenations, carry out reverse atom transferred free radical living polymerization, reacted at least 6 hours, product is through precipitation, suction filtration, the concentrated hydrochloric acid washing, drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2007101036903A CN100532410C (en) | 2007-04-28 | 2007-04-28 | Method for preparing polyacrylonitrile resin with narrow molecular weight distribution |
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| CNB2007101036903A CN100532410C (en) | 2007-04-28 | 2007-04-28 | Method for preparing polyacrylonitrile resin with narrow molecular weight distribution |
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| CN101077898A CN101077898A (en) | 2007-11-28 |
| CN100532410C true CN100532410C (en) | 2009-08-26 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735362B (en) * | 2009-12-22 | 2011-08-31 | 苏州大学 | Method for preparing polyacrylonitrile at room temperature in living polymerization way |
| CN102167764B (en) * | 2010-12-25 | 2012-07-25 | 鲁东大学 | Method for preparing polyacrylonitrile by single electron transfer active free radical polymerization |
| CN102120786B (en) * | 2011-01-04 | 2012-08-15 | 鲁东大学 | Method for preparing highly syndiotactic polyacrylonitrile resin |
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2007
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Non-Patent Citations (9)
| Title |
|---|
| An Investigation into the CuX/2,2'-Bipyridine (X ＝Br or Cl)Mediated Atom Transfer Radical Polymerization of Acrylonitrile. Krzysztof Matyjaszewski,et, ak.Macromulecules,No.32. 1999 |
| An Investigation into the CuX/2,2'-Bipyridine (X＝Br or Cl)Mediated Atom Transfer Radical Polymerization of Acrylonitrile. Krzysztof Matyjaszewski,et, ak.Macromulecules,No.32. 1999 * |
| Atom Transfer Radical Polymerization of Acrylonitrile. Chen Hou,et. al.Journal of Applied Polymer Science,No.99. 2006 |
| Atom Transfer Radical Polymerization of Acrylonitrile. Chen Hou,et. al.Journal of Applied Polymer Science,No.99. 2006 * |
| New Initiation System For Atom Trasnfer RadicalPolymerization. Kun-yuan Qiu et. al.Chinese Journal of Polymer Science,Vol.22 No.2. 2004 |
| New Initiation System For Atom Trasnfer RadicalPolymerization. Kun-yuan Qiu et. al.Chinese Journal of Polymer Science,Vol.22 No.2. 2004 * |
| 原子转移自由基聚合的原理和特点. 罗宁等.合成橡胶工业，第19卷第5期. 1996 |
| 用双官能团引发剂进行的原子转移自由基嵌段和无规共聚. 邹友思等.应用化学，第16卷第2期. 1999 |
| 铁系催化剂用于原子转移自由基聚合的研究. 张艳哲，24-34，河北大学硕士论文. 2004 |
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Granted publication date: 20090826 Termination date: 20110428 |