CN101735361A - Method for preparing polyacrylonitrile resin - Google Patents
Method for preparing polyacrylonitrile resin Download PDFInfo
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- CN101735361A CN101735361A CN200910258798A CN200910258798A CN101735361A CN 101735361 A CN101735361 A CN 101735361A CN 200910258798 A CN200910258798 A CN 200910258798A CN 200910258798 A CN200910258798 A CN 200910258798A CN 101735361 A CN101735361 A CN 101735361A
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- iron trichloride
- polyacrylonitrile resin
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- vinyl cyanide
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Abstract
The invention discloses a method for preparing polyacrylonitrile resin. The method is characterized in that: dissolving ferric chloride serving as a catalyst, m-phthalic acid serving as a ligand, carbon tetrachloride serving as an initiator, ascorbic acid serving as a reducer and an acrylonitrile monomer in N,N-dimethylformamide serving as a solvent, repeatedly filling nitrogen gas to remove oxygen at least once, keeping the reaction for at least 8 hours, performing electron transfer to make active polymerization of atom transfer free radicals of the catalyst, and performing washing by concentrated hydrochloric acid, precipitation, pumping filtration and drying of the products. By the preparation method provided by the invention, the polyacrylonitrile resin with a molecular weight distribution of 1.15 to 1.36.
Description
(1) technical field: the present invention relates to a kind of method for preparing polyacrylonitrile resin, especially a kind of atom transferred free radical living polymerization that adopts transfer transport to produce catalyzer prepares the method for distribution of low molecular weight polyacrylonitrile resin.
(2) background technology: polyacrylonitrile is a kind of important macromolecular material, anti-common solvent, and facile hydrolysis is not anti-oxidant, and chemical stability is good, and excellent resistance to bacteria energy is arranged.Traditional free radical polymerisation process is the common method of preparation polyacrylonitrile, but because traditional radical polymerization exists chain transfer and chain termination reaction, therefore can not control molecular weight and molecular weight distribution preferably.The molecular weight distribution of the polyacrylonitrile of this method preparation is wide, has a strong impact on the performance of macromolecular material.
The atom transferred free radical living polymerization has the characteristics of radical polymerization and living polymerization concurrently, the running balance of spike and dormancy kind has caused the growth number of free radical very low in the reaction system, significantly reduced the termination reaction between the free radical, controllability is good, and the suitable monomers scope is wide, the reaction conditions gentleness.But the used catalyzer of atom transferred free radical active polymerization system is a transition metal halide of going back ortho states, to air and moisture-sensitive; Polymerization reaction system needs strict deoxygenation.
(3) summary of the invention: the deficiency that the objective of the invention is to overcome above-mentioned prior art, and provide a kind of permission trace oxygen to exist, with the alkyl halide is initiator, with the high oxidation state transition metal is catalyzer, organic acid is a part, prepares the novel method of distribution of low molecular weight polyacrylonitrile resin under the effect of non-harmful reductive agent by the atom transferred free radical living polymerization of transfer transport generation catalyzer.
Purpose of the present invention can reach by following measure: catalyzer iron trichloride, part m-phthalic acid, initiator tetracol phenixin, reductive agent xitix and monomer vinyl cyanide are dissolved into solvent N, in the dinethylformamide; Logical repeatedly nitrogen deoxygenation at least 1 time, reaction was carried out 8 hours at least, carried out the atom transferred free radical living polymerization that transfer transport produces catalyzer.Product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.Mol ratio between vinyl cyanide and the tetracol phenixin is (100～600): 1, mol ratio between iron trichloride and the tetracol phenixin is (1～3): 1, mol ratio between iron trichloride and the m-phthalic acid is 1: (1～3), mol ratio between iron trichloride and the xitix is 1: (0.5～1.25), the volumetric molar concentration of vinyl cyanide is 6～8 mol, and polymeric reaction temperature is 60～70 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 atom transferred free radical living polymerization, can obtain molecular weight distribution and be 1.15～1.36 polyacrylonitrile resin.
(4) embodiment: following detailed description the present invention also provides several embodiment:
Embodiment 1: 0.1217 gram iron trichloride, 0.2497 gram m-phthalic acid, 0.07 milliliter of tetracol phenixin, 0.0996 gram xitix, 10.0 milliliters of vinyl cyanide are dissolved into 15.0 milliliters of N, in the dinethylformamide, the inflated with nitrogen deoxygenation is 4 times repeatedly, reaction flask is put into 65 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 40 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 16548, and molecular weight distribution is 1.15.
Embodiment 2: 0.1215 gram iron trichloride, 0.2509 gram m-phthalic acid, 0.04 milliliter of tetracol phenixin, 0.1319 gram xitix, 9.9 milliliters of vinyl cyanide are dissolved into 15.0 milliliters of N, in the dinethylformamide, the inflated with nitrogen deoxygenation is 4 times repeatedly, reaction flask is put into 60 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 24 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 16812, and molecular weight distribution is 1.17.
Embodiment 3: 0.7291 gram iron trichloride, 0.7472 gram m-phthalic acid, 0.14 milliliter of tetracol phenixin, 0.3962 gram xitix, 9.8 milliliters of vinyl cyanide are dissolved into 15.0 milliliters of N, in the dinethylformamide, the inflated with nitrogen deoxygenation is 4 times repeatedly, reaction flask is put into 65 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 32 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 16099, and molecular weight distribution is 1.15.
Embodiment 4: 0.0405 gram iron trichloride, 0.1241 gram m-phthalic acid, 0.03 milliliter of tetracol phenixin, 0.0546 gram xitix, 9.9 milliliters of vinyl cyanide are dissolved into 15.0 milliliters of N, in the dinethylformamide, the inflated with nitrogen deoxygenation is 1 time repeatedly, reaction flask is put into 70 degrees centigrade of constant temperature oil baths, carry out polymerization.React after 48 hours, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
The number-average molecular weight of polyreaction gained polyacrylonitrile resin is 29059, and molecular weight distribution is 1.36.
Claims (1)
1. method for preparing polyacrylonitrile resin, it is characterized in that: with the catalyzer iron trichloride, the part m-phthalic acid, the initiator tetracol phenixin, monomer vinyl cyanide and reductive agent dissolution of ascorbic acid are to solvent N, in the dinethylformamide, wherein, the mol ratio of vinyl cyanide and tetracol phenixin is 100: 1～600: 1, the mol ratio of iron trichloride and tetracol phenixin is 1: 1～3: 1, the mol ratio of iron trichloride and m-phthalic acid is 1: 1～1: 3, the mol ratio of iron trichloride and xitix is 1: 0.5～1: 1.25, the volumetric molar concentration of vinyl cyanide is 6～8 mol, and polymeric reaction temperature is 60～70 degrees centigrade, polymerization reaction time at least 8 hours, logical repeatedly nitrogen deoxygenation at least 1 time, carry out the atom transferred free radical living polymerization of transfer transport generation catalyzer, product washs through concentrated hydrochloric acid, precipitation, suction filtration, drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910258798A CN101735361A (en) | 2009-12-14 | 2009-12-14 | Method for preparing polyacrylonitrile resin |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910258798A CN101735361A (en) | 2009-12-14 | 2009-12-14 | Method for preparing polyacrylonitrile resin |
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| CN101735361A true CN101735361A (en) | 2010-06-16 |
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| CN200910258798A Pending CN101735361A (en) | 2009-12-14 | 2009-12-14 | Method for preparing polyacrylonitrile resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093497A (en) * | 2010-12-18 | 2011-06-15 | 鲁东大学 | Method for preparing high-stereoregularity acrylonitrile resin |
| CN102167764A (en) * | 2010-12-25 | 2011-08-31 | 鲁东大学 | Method for preparing polyacrylonitrile by single electron transfer active free radical polymerization |
| CN107723825A (en) * | 2017-10-28 | 2018-02-23 | 长沙秋点兵信息科技有限公司 | Preparation method of enhanced acrylic fibers for wearing |
-
2009
- 2009-12-14 CN CN200910258798A patent/CN101735361A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093497A (en) * | 2010-12-18 | 2011-06-15 | 鲁东大学 | Method for preparing high-stereoregularity acrylonitrile resin |
| CN102093497B (en) * | 2010-12-18 | 2012-06-27 | 鲁东大学 | Method for preparing high-stereoregularity acrylonitrile resin |
| CN102167764A (en) * | 2010-12-25 | 2011-08-31 | 鲁东大学 | Method for preparing polyacrylonitrile by single electron transfer active free radical polymerization |
| CN102167764B (en) * | 2010-12-25 | 2012-07-25 | 鲁东大学 | Method for preparing polyacrylonitrile by single electron transfer active free radical polymerization |
| CN107723825A (en) * | 2017-10-28 | 2018-02-23 | 长沙秋点兵信息科技有限公司 | Preparation method of enhanced acrylic fibers for wearing |
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Open date: 20100616 |