CN101139412B - Low-molecular weight distributed polyacrylonitile and method for making same - Google Patents
Low-molecular weight distributed polyacrylonitile and method for making same Download PDFInfo
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Abstract
The present invention relates to a low-molecular distributed polypropylene nitrile and the preparation method of the polypropylene nitrile. The polypropylene is polymerized from acrylonitrile with theviscosity-average molecular weight of 1 is multiplied by 10 <SUP> 3 </ SUP> 5 is multiplied by 10-<SUP> 4 </ SUP>, and the molecular weight distribution of 1.04 to 1.56. The preparation method includes: (1) acrylonitrile, catalyst and coordination agent are added into the ionic liquid solvents in sequence and are dissolved at room temperature. Then initiator is added and inert gas is accessed tothe solvent for atom transfer radical polymerization; (2) after reaction, the solvent is stopped from polymerization reaction by use of ice bath; the polymerization nitrile product is coagulated by water and is cleaned, filtered and dried for a plurality of times for purifying; after that, PAN product is obtained. The method takes use of ionic liquid as the solvent, therefore reaction temperaturecan be effectively controlled and the reaction rate is accelerated; in addition, the ionic liquid is of no volatility which is conductive to the recover and reuse of the ionic liquid as well as the catalyst and coordination agent dissolved in the liquid. In addition, water is used as the coagulant which is conducive to the environmental protection. The molecular weight distribution of the polypropylene nitrile is very narrow. The polypropylene nitrile can be used as mono-dispersed sample or the big monomer used in the embedded-block copolymerization or graft copolymerization. The polypropylenenitrile is of great industry prospects.
Description
Technical field
The invention belongs to the preparation field of polyacrylonitrile, particularly relate to the preparation method of the acrylonitrile homopolymer of distribution of low molecular weight.
Background technology
Acrylonitrile homopolymer and multipolymer thereof are the macromolecular materials of using always, in plastics, rubber, fiber three big synthesized polymer materials application are arranged all.
The synthetic method of polyacrylonitrile, can be divided into radical polymerization, anionoid polymerization, polycoordination and group transfer polymerization (Masson J C.Aclylic fiber technology and application.New York:Macrel Pekker Inc by reaction mechanism, 1995,37～67).At present, using maximum is radical polymerization, and its implementation method has solution polymerization, suspension polymerization, aqueous phase precipitation polymerization.The method of solution polymerization wherein, the solvent that is adopted comprises the strong solution of dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), dimethyl sulfoxide (DMSO) (DMSO), Sodium Thiocyanate 99 (NaSCN), liquor zinci chloridi and nitric acid etc.The solution polymerization of vinyl cyanide in these solvents has that polymerization system viscosity is low, mixing and advantages such as heat transfer is easier to, easy temperature control system, but also there are a lot of shortcomings, low as monomer concentration, rate of polymerization slowly causes throughput and plant factor low, and makes molecular weight reduction etc. by the chain transfer that solvent causes.Particularly separated from solvent reclaims the cost increased, and to HUMAN HEALTH, harm that environmental pollution brought, is unfavorable for further developing of polyacrylonitrile.
Ionic liquid is as the green solvent of generally acknowledging in the world, be used for vinyl cyanide in 2004 first and evenly reached copolyreaction (patent ZL 200410016369.8), though the transformation efficiency of its polymerization rate and polymerisate has all improved greatly, but because they adopt all is conventional radical polymerization, in polymerization process, there is a large amount of termination reactions, therefore the polymolecularity and the molecular weight of strict technically controlled polymerization product are impossible, the very wide (M of the molecular weight distribution of resulting polymers
w/ M
n＞2).And the polyacrylonitrile of preparation distribution of low molecular weight is vital (Chen Hou, Liang Ying, Chengguo Wang.Journal of Applied Polymer Science, 2006,99,1050～1054) for the synthesized high-performance acrylic fiber.
With the lower valency transition metal complex is that the atom transfer radical polymerization of catalyzer can effectively suppress the double-basis termination reaction, be that implementation structure is accurate, molecular weight is controlled and effective new technology of the polymkeric substance of narrow molecular weight distribution, (Luo Ning between the molecular weight distribution of resulting polymers can be controlled at 1.04～1.5, Ying Shengkang. the principle of atom transfer radical polymerization and characteristics. China Synthetic Rubber Industry, 1996,19 (5): 299～302).1999, Krzysztof Matyjasewski etc. has proposed atom transfer radical polymerization (the Krzysztof Matyjasewski of vinyl cyanide first, Seong Mu Jo, Hyun-jong Paik, andDevon A.Shipp.Macromolecules, 1999,32,6431～6438), and obtained the polymkeric substance of expection narrow molecular weight distributions, molecular weight distribution is controlled at 1.05～1.30, but because used solvent vinyl carbonate (EC) is to have strong volatile organic solvent, so polymerization rate very slow (react transformation efficiency has only 38.3% after 5 hours), and have only with the silicagel column separation method polymkeric substance and catalyst separating are come out, and there is the expense height in this separation method, easily causes the polymkeric substance loss, amplifies shortcomings such as separation scale difficulty.Chen Hou etc. has reported that then the atom transfer radical polymerization of vinyl cyanide in dimethyl formamide (DMF), result have obtained the very narrow polymkeric substance (1.10≤M of molecular weight distribution equally
w/ M
n≤ 1.30), but polymerization rate is still very slow, reacts that transformation efficiency has only 29.5% (ChenHou, Liang Ying, Chengguo Wang.Journal of Applied Polymer Science, 2006,99,1050～1054) after 3.5 hours.Therefore, adopt conventional solvent to prepare polyacrylonitrile with atom transfer radical polymerization method, though the molecular weight distribution of resulting polymers is low, exists polymerization rate catalyst separating difficulty and used solvent slow, that remain in the polymkeric substance and easily cause problems such as environmental pollution.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who prepares the polyacrylonitrile of distribution of low molecular weight, with remedy gained polymer molecular weight that existing conventional polymerization technique exists distribute wide, speed of reaction slowly and solvent for use have intensive corrodibility and volatility, cause defectives such as serious environmental pollution, satisfy the needs of producing with some field development.
The preparation method of the polyacrylonitrile of distribution of low molecular weight of the present invention comprises the following steps:
(1) vinyl cyanide, catalyzer, coordination agent are added in the ion liquid solvent successively, the room temperature dissolving adds initiator, and feeds rare gas element, carries out atom transition free radical polymerization reaction;
(2) reaction back stops polyreaction with ice bath, carries out purifying with the solid polymerisate of water-setting and repetitive scrubbing, filtration, drying, polyacrylonitrile.
Described lyate ion liquid is the compound that is made of positively charged ion and negatively charged ion;
Described positively charged ion comprises a kind of in the following positively charged ion:
Quaternary ammonium alkyl ion alkyl quaternary phosphonium ion alkyl imidazole ion alkyl pyridine ion
Wherein: R1, R2, R3, R4, R5 and R6 are that H or carbonatoms are the alkyl of 1-8, can be identical, also can be different;
Described negatively charged ion comprises Cl
-, Br
-, BF
4 -, PF
6 -, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-Or (CF
3SO
2)
3C
-In a kind of;
It is 10～35% that described vinyl cyanide accounts for ion liquid mass percent;
Described catalyzer is a transistion metal compound, is selected from a kind of in the halogenide of Cu (I), Fe (II), Ni (II), Ru (II), Rh (II), Mo (V) or Re (V), and consumption is 0.25～5.20% of a vinyl cyanide quality;
Described coordination agent is selected from 2,2 '-bipyridine and derivative thereof, N, N '-Tetramethyl Ethylene Diamine and other many methyl polyamines, two methylamino ethyl ether, N, a kind of in the amino Soxylat A 25-7 of N '-tetramethyl-, triethylene diamine, pentamethyl-diethylenetriamine, triethylene tetramine, triphenylphosphine, HMPA or the phenanthroline, consumption is 0.45～8.80% of a vinyl cyanide quality;
Described initiator is selected from a kind of in tetracol phenixin, 2-chloromethyl cyanide, 2-bromoacetonitrile, 2 bromopropionic acid methyl esters, 2-methyl chloropropionate, 2 bromopropionic acid ethyl ester, 2-chloropropionate, 1-phenyl-bromide ethane, 1-phenyl-chloride ethane, 1-bromotoluene or the 2-isobutyl ethyl bromide, and consumption is 0.85～6.50% of a vinyl cyanide quality;
Described rare gas element is nitrogen or argon gas;
Described reaction is meant 40～70 ℃ of reactions 0.5～7 hour, and reaction conversion ratio is 30～93%;
It is that the normal-temperature water of 3～15 times of reaction solution volumes is carried out polymkeric substance and solidified that described water-setting is meant admittedly with volume;
It is that normal temperature to 95 ℃, quality are 2～7 times the water washing 3～5 times of solids that described washing is meant with temperature;
Described drying is meant that 65 ℃ of following vacuum-dryings are to constant weight.
Describedly solidify, wash, filter the washings that obtains, ionic liquid that obtains after the processed and dissolved catalyzer thereof and coordination agent can repeatedly be recycled and reused for above-mentioned reaction.
Described polyacrylonitrile is to be formed by the vinyl cyanide homopolymerization, and viscosity-average molecular weight is 1 * 10
3～5 * 10
4, molecular weight distribution is 1.04～1.56, residual catalyst≤10ppm can be used as monodispersed standard model or as the big monomer of block copolymerization or graft copolymerization.
Beneficial effect of the present invention:
(1) the very narrow 1.04≤M of polyacrylonitrile molecular weight distribution of the present invention
w/ M
n≤ 1.56;
(2) atom transfer radical polymerization of Cai Yonging can effectively be controlled the molecular weight and the molecular weight distribution of polyacrylonitrile, has the favorable industrial prospect;
(3) solvent of Cai Yonging is an ionic liquid, and melting range is wide, in the temperature range of polyreaction, helps the control of temperature of reaction, and can accelerate the speed of polyreaction greatly, and the transformation efficiency after 3 hours can reach more than 60%;
(4) ionic liquid non-volatility helps reacting the recovery and reuse that finish the back ionic liquid and be dissolved in catalyzer coordination agent wherein, is peptizer with water simultaneously, helps environment protection.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Under the room temperature with ionic liquid 1-butyl-3-Methylimidazole muriate (45.67g, 0.26mol), vinyl cyanide (8.06g, 0.15mol), CuBr (0.22g, 1.5mmol), pentamethyl-diethylenetriamine (0.39g, 3mmol) stirring makes it the thorough mixing dissolving, and feeds nitrogen, is heated to 65 ℃ and lasting feeding nitrogen, add 2 bromopropionic acid ethyl ester (0.27g behind the constant temperature 15min, 1.5mmol), polyreaction stopped polyreaction after 7 hours in ice bath, be that the water-setting of 183ml is solid with the normal temperature lower volume then, via hole diameter is to be 65 ℃ with temperature again behind the filter membrane suction filtration of 0.45 μ m, quality is the water repetitive scrubbing 4 times of 36.63g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and reaction conversion ratio is 90.90%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 2.7ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.13, and it is 8.74 * 10 that viscosimetry records viscosity-average molecular weight
3The ionic liquid that obtains after the washings processed and dissolved catalyzer thereof and coordination agent are repeated 5 times be used for above-mentioned reaction, under the same conditions, the viscosity-average molecular weight of its transformation efficiency, resulting polymers and molecular weight distribution all do not have obviously to descend, and be as shown in the table:
Embodiment 2
Under the room temperature with ionic liquid 1-butyl-3-Methylimidazole bromide (45.67g, 0.21mol), vinyl cyanide (8.06g, 0.15mol), CuBr (0.22g, 1.5mmol), pentamethyl-diethylenetriamine (0.39g, 3mmol) stirring makes it the thorough mixing dissolving, and feeds nitrogen, is heated to 65 ℃ and lasting feeding nitrogen, add 2-isobutyl ethyl bromide (0.29g behind the constant temperature 15min, 1.5mmol), polyreaction stopped polyreaction after 5 hours in ice bath, be that the water-setting of 183ml is solid with the normal temperature lower volume then, via hole diameter is to be 65 ℃ with temperature again behind the filter membrane suction filtration of 0.45 μ m, quality is the water 4 times repeatedly of 35.27g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 87.53%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 4.3ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.21, and it is 5.32 * 10 that viscosimetry records viscosity-average molecular weight
3
Embodiment 3
Under the room temperature with ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate (72.54g, 0.32mol), vinyl cyanide (8.06g, 0.15mol), CuBr (0.43g, 3mmol), 2, and 2 '-bipyridine (0.94g, 6mmol) stirring makes it the thorough mixing dissolving, and feeding nitrogen, be heated to 55 ℃ and the lasting nitrogen that feeds, and adding 2-bromoacetonitrile behind the constant temperature 15min (0.36g, 3mmol), after the polyreaction 7 hours, stopping polyreaction in ice bath, is that the water-setting of 218ml is solid with the normal temperature lower volume then, and via hole diameter is to be 95 ℃ with temperature again behind the filter membrane suction filtration of 1.5 μ m, quality is the water repetitive scrubbing 3 times of 46.35g, obtain acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, wherein transformation efficiency is 82.15%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 6.4ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.43, and it is 4.71 * 10 that viscosimetry records viscosity-average molecular weight
3
Embodiment 4
Under the room temperature with ionic liquid 1-butyl-3-Methylimidazole hexafluorophosphate (32.24g, 0.12mol), vinyl cyanide (8.06g, 0.15mol), FeCl
2(0.10g, 0.75mmol), Tetramethyl Ethylene Diamine (0.17g, 1.5mmol) stir and to make it the thorough mixing dissolving, and feeding nitrogen, be heated to 70 ℃ and the lasting nitrogen that feeds, add 2-chloromethyl cyanide (0.06g behind the constant temperature 15min, 0.75mmol), polyreaction stopped polyreaction after 7 hours in ice bath, be that the water-setting of 183ml is solid with the normal temperature lower volume then, via hole diameter is to be 75 ℃ with temperature again behind the filter membrane suction filtration of 0.45 μ m, quality is the water repetitive scrubbing 3 times of 44.82g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 92.68%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 3.4ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.04, and it is 4.49 * 10 that viscosimetry records viscosity-average molecular weight
4
Embodiment 5
Under the room temperature with ionic liquid 1-ethyl-3-methyl imidazolium tetrafluoroborate (72.54g, 0.32mol), vinyl cyanide (8.06g, 0.15mol), MoBr
2(0.77g, 3mmol), triethylene diamine (0.34g, 6mmol) stirring makes it the thorough mixing dissolving, and feeding argon gas, be heated to 55 ℃ and the lasting argon gas that feeds, add 2 bromopropionic acid methyl esters (0.50g behind the constant temperature 15min, 3mmol), polyreaction stopped polyreaction after 0.5 hour in ice bath, be that the water-setting of 218ml is solid with the normal temperature lower volume then, via hole diameter is to be 95 ℃ with temperature again behind the filter membrane suction filtration of 1.5 μ m, quality is the water repetitive scrubbing 3 times of 26.59g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 47.12%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 7.6ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.47, and it is 1.21 * 10 that viscosimetry records viscosity-average molecular weight
3
Embodiment 6
Under the room temperature with ionic liquid monobutyl San Jia Ji Phosphonium two (trifluoromethyl sulphonyl) imonium salt (14.97g, 0.036mol), vinyl cyanide (8.06g, 0.15mol), RuCl
2(0.065g, 0.375mmol), two methylamino ethyl ether (0.12g, 0.75mmol) stir and to make it the thorough mixing dissolving, and feeding argon gas, be heated to 40 ℃ and the lasting argon gas that feeds, add tetracol phenixin (0.058g behind the constant temperature 15min, 0.375mmol), polyreaction stopped polyreaction after 0.5 hour in ice bath, be that the water-setting of 285ml is solid with the normal temperature lower volume then, via hole diameter is again with under the normal temperature behind the filter membrane suction filtration of 2.0 μ m, quality is the water repetitive scrubbing 5 times of 4.84g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 30%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 10.0pm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.56, and it is 3.07 * 10 that viscosimetry records viscosity-average molecular weight
3
Embodiment 7
Under the room temperature with ionic liquid monobutyl QAE three (trifluoromethyl sulphonyl) methyl salt (45.67g, 0.087mol), vinyl cyanide (8.06g, 0.15mol), RhBr
2(0.39g, 1.5mmol), triethylene tetramine (0.44g, 3mmol) stirring makes it the thorough mixing dissolving, and feeding nitrogen, be heated to 65 ℃ and the lasting nitrogen that feeds, add 1-bromotoluene (0.26g behind the constant temperature 15min, 1.5mmol), polyreaction stopped polyreaction after 2 hours in ice bath, be that the water-setting of 183ml is solid with the normal temperature lower volume then, via hole diameter is to be 40 ℃ with temperature again behind the filter membrane suction filtration of 0.45 μ m, quality is the water repetitive scrubbing 4 times of 26.76g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 66.41%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 6.2ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.38, and it is 2.16 * 10 that viscosimetry records viscosity-average molecular weight
3
Embodiment 8
Under the room temperature with ionic liquid 1-ethyl-3,5-lutidine trifluoromethyl carboxylate salt (32.24g, 0.13mol), vinyl cyanide (8.06g, 0.15mol), FeBr
2(0.16g, 0.75mmol), triphenylphosphine (0.39g, 1.5mmol) stir and to make it the thorough mixing dissolving, and feeding nitrogen, be heated to 50 ℃ and the lasting nitrogen that feeds, add 1-phenyl-bromide ethane (0.139g behind the constant temperature 15min, 0.75mmol), polyreaction stopped polyreaction after 3 hours in ice bath, be that the water-setting of 183ml is solid with the normal temperature lower volume then, via hole diameter is to be 75 ℃ with temperature again behind the filter membrane suction filtration of 0.45 μ m, quality is the water repetitive scrubbing 3 times of 15.75g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 65.12%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 4.5ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.27, and it is 2.92 * 10 that viscosimetry records viscosity-average molecular weight
4The ionic liquid that obtains after the washings processed and dissolved catalyzer thereof and coordination agent are repeated 5 times be used for above-mentioned reaction, under the same conditions, the viscosity-average molecular weight of its transformation efficiency, resulting polymers and molecular weight distribution all do not have obviously to descend, and be as shown in the table:
Embodiment 9
Under the room temperature with ionic liquid 1-ethyl-3-methyl imidazolium tetrafluoroborate (18.81g, 0.095mol), vinyl cyanide (8.06g, 0.15mol), ReCl
5(0.13g, 0.5mmol), hexamethylphosphoramide (0.18g, 1.0mmol) stir and to make it the thorough mixing dissolving, and feeding argon gas, be heated to 70 ℃ and the lasting argon gas that feeds, add 2-methyl chloropropionate (0.062g behind the constant temperature 15min, 0.5mmol), polyreaction stopped polyreaction after 3 hours in ice bath, be that the water-setting of 170ml is solid with the normal temperature lower volume then, via hole diameter is to be 95 ℃ with temperature again behind the filter membrane suction filtration of 0.22 μ m, quality is the water repetitive scrubbing 3 times of 15.39g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 76.36%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 5.2ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.17, and it is 3.34 * 10 that viscosimetry records viscosity-average molecular weight
4
Embodiment 10
Under the room temperature with ionic liquid 1-butyl-3-Methylimidazole trifluoromethyl sulfonic acid (45.67g, 0.16mol), vinyl cyanide (8.06g, 0.15mol), NiCl
2(0.019g, 0.15mmol), phenanthroline (0.054g, 0.3mmol) stir and to make it the thorough mixing dissolving, and feeding nitrogen, be heated to 60 ℃ and the lasting nitrogen that feeds, add 2-chloropropionate (0.20g behind the constant temperature 15min, 1.5mmol), polyreaction stopped polyreaction after 0.5 hour in ice bath, be that the water-setting of 183ml is solid with the normal temperature lower volume then, via hole diameter is to be 65 ℃ with temperature again behind the filter membrane suction filtration of 0.45 μ m, quality is the water repetitive scrubbing 4 times of 12.75g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 31.63%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 2.9ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.31, and it is 3.29 * 10 that viscosimetry records viscosity-average molecular weight
3
Embodiment 11
Under the room temperature with ionic liquid 1-butyl-3-Methylimidazole trifluoromethyl sulfonic acid (45.67g, 0.16mol), vinyl cyanide (8.06g, 0.15mol), NiCl
2(0.097g, 0.75mmol), phenanthroline (0.27g, 1.5mmol) stir and to make it the thorough mixing dissolving, and feeding nitrogen, be heated to 45 ℃ and the lasting nitrogen that feeds, add 1-phenyl-chloride ethane (0.21g behind the constant temperature 15min, 1.5mmol), polyreaction stopped polyreaction after 7 hours in ice bath, be that the water-setting of 183ml is solid with the normal temperature lower volume then, via hole diameter is to be 65 ℃ with temperature again behind the filter membrane suction filtration of 0.45 μ m, quality is the water repetitive scrubbing 4 times of 28.58g, obtains acrylonitrile polymer 65 ℃ of following vacuum-drying to constant weights at last, and wherein transformation efficiency is 70.93%.According to the atomic absorption spectrochemical analysis test, the catalyst content that remains in the polymkeric substance is 3.1ppm, and according to the GPC test, the molecular weight distribution of prepared polyacrylonitrile is 1.15, and it is 6.46 * 10 that viscosimetry records viscosity-average molecular weight
3
Claims (10)
1. the preparation method of the polyacrylonitrile of distribution of low molecular weight comprises the following steps:
(1) vinyl cyanide, catalyzer, coordination agent are added in the ionic liquid successively, the room temperature dissolving adds initiator, and feeds rare gas element, carries out atom transition free radical polymerization reaction;
(2) reaction back stops polyreaction with ice bath, carries out purifying with the solid polymerisate of water-setting and repetitive scrubbing, filtration, drying, polyacrylonitrile;
Described lyate ion liquid is the compound that is made of positively charged ion and negatively charged ion, and positively charged ion comprises a kind of in the following positively charged ion:
Quaternary ammonium alkyl ion alkyl quaternary phosphonium ion alkyl imidazole ion alkyl pyridine ion
Wherein: R1, R2, R3, R4, R5 and R6 are that H or carbonatoms are the alkyl of 1-8, and be identical or different;
Described negatively charged ion comprises Cl
-, Br
-, BF
4 -, PF
6 -, CF
3SO
3 -, CF
3COO
-, (CF
3SO
2)
2N
-Or (CF
3SO
2)
3C
-In a kind of.
2. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: it is 10～35% that described vinyl cyanide accounts for ion liquid mass percent.
3. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: described catalyzer is a transistion metal compound, be selected from a kind of in the halogenide of Cu (I), Fe (II), Ni (II), Ru (II), Rh (II), Mo (V) or Re (V), consumption is 0.25～5.20% of a vinyl cyanide quality.
4. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: described coordination agent is selected from 2,2 '-bipyridine and derivative thereof, N, N '-Tetramethyl Ethylene Diamine and other many methyl polyamines, two methylamino ethyl ether, N, a kind of in the amino Soxylat A 25-7 of N '-tetramethyl-, triethylene diamine, pentamethyl-diethylenetriamine, triethylene tetramine, triphenylphosphine, HMPA or the phenanthroline, consumption is 0.45～8.80% of a vinyl cyanide quality.
5. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: described initiator is selected from a kind of in tetracol phenixin, 2-chloromethyl cyanide, 2-bromoacetonitrile, 2 bromopropionic acid methyl esters, 2-methyl chloropropionate, 2 bromopropionic acid ethyl ester, 2-chloropropionate, 1-phenyl-bromide ethane, 1-phenyl-chloride ethane, 1-bromotoluene or the 2-isobutyl ethyl bromide, and consumption is 0.85～6.50% of a vinyl cyanide quality.
6. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: described rare gas element is nitrogen or argon gas.
7. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: described reaction is meant 40～70 ℃, reacts 0.5～7 hour, reaction conversion ratio is 30～93%.
8. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: it is that the normal-temperature water of 3～15 times of reaction solution volumes is carried out polymkeric substance and solidified that described purifying is meant with volume, with temperature is that normal temperature to 90 ℃, quality are 2～7 times the water washing 3～5 times of solids, and 65 ℃ of following vacuum-dryings are to constant weight.
9. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: step 2 is described solidifies, washs, filters the washings that obtains, and ionic liquid that obtains after the processed and dissolved catalyzer thereof and coordination agent can repeatedly be recycled and reused for above-mentioned reaction.
10. the preparation method of the polyacrylonitrile of distribution of low molecular weight according to claim 1, it is characterized in that: the described polyacrylonitrile of step 2 is to be formed by the vinyl cyanide homopolymerization, viscosity-average molecular weight is 1 * 10
3～5 * 10
4, molecular weight distribution is 1.04～1.56, residual catalyst content≤10ppm.
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| CN101139412B true CN101139412B (en) | 2010-05-19 |
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| CN101735362B (en) * | 2009-12-22 | 2011-08-31 | 苏州大学 | Method for preparing polyacrylonitrile at room temperature in living polymerization way |
| CN101864016B (en) * | 2010-06-22 | 2011-08-31 | 鲁东大学 | Preparation method of polyacrylonitrile resin |
| 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 |
| CN104403476A (en) * | 2014-11-28 | 2015-03-11 | 安徽省金盾涂料有限责任公司 | Self-cleaning antibacterial fluorocarbon coating |
| CN106167467A (en) * | 2016-09-27 | 2016-11-30 | 河北科技大学 | The preparation of a kind of polyaza ligand bit function ionic liquid for ATRP reaction and application |
| EP3548524B1 (en) | 2016-12-01 | 2020-07-15 | SABIC Global Technologies B.V. | Process for the production of polyacrylonitrile |
| CN109342134A (en) * | 2018-09-25 | 2019-02-15 | 金发科技股份有限公司 | The preparation method of PP plastics Reference Materials of PAHs |
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