CN113683715B - Radiation solution polymerization method for polyacrylonitrile - Google Patents
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- CN113683715B CN113683715B CN202111104302.XA CN202111104302A CN113683715B CN 113683715 B CN113683715 B CN 113683715B CN 202111104302 A CN202111104302 A CN 202111104302A CN 113683715 B CN113683715 B CN 113683715B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The invention relates to the technical field of polyacrylonitrile preparation, in particular to a polyacrylonitrile radiation solution polymerization method, which comprises the following specific steps: s1, dissolving the weighed acrylonitrile into an organic solvent to obtain a mixed solution A; s2, placing the mixed solution A in a radiation bottle, and covering a bottle stopper; s3, placing the radiation bottle in 60 In a Co source chamber, taking out an irradiation bottle when the absorption dose is 15-30 kGy under room temperature radiation at the dose rate of 11Gy/min to obtain a mixed solution B; s4, pouring the mixed solution B into a coagulating bath, and precipitating to obtain a polymer C; and S5, drying the polymer C to obtain a polymerization product D, namely polyacrylonitrile. The invention uses gamma-ray to radiate at room temperature to initiate the homogeneous solution copolymerization reaction of acrylonitrile and comonomer in organic solvent, to prepare polyacrylonitrile copolymer; the polyacrylonitrile copolymer has the advantages of high purity, high molecular weight, narrow molecular weight distribution and the like.
Description
Technical Field
The invention relates to the technical field of polyacrylonitrile preparation, in particular to a polyacrylonitrile radiation solution polymerization method.
Background
The most applied polymerization mode in the industrial production of polyacrylonitrile is homogeneous solution polymerization, the molecular weight of the prepared polyacrylonitrile is about 5-10 ten thousand, and the polyacrylonitrile can only be applied to the field of common acrylic products; however, for some high-tech fields, such as carbon fibers, high molecular weight polyacrylonitrile is required as a raw material, wherein volojinana V studies that the weight average molecular weight of polyacrylonitrile is at least more than 10 ten thousand if high-performance carbon fibers are to be obtained; however, the existing polyacrylonitrile adopts a chemical method, but the chemical method requires high temperature conditions for reaction, so that the chain transfer constant of free radicals to a solvent is increased, and the molecular weight of a polymerization product is not high. Meanwhile, when the chemical method initiates the polymerization of the acrylonitrile solution, azobisisobutyronitrile needs to be added as an initiator, the thermal property of polyacrylonitrile can be affected by the decomposition product of the residual azobisisobutyronitrile, and the existing polyacrylonitrile preparation method can not meet the production requirement of polyacrylonitrile.
Disclosure of Invention
The invention aims to provide an efficient, convenient, economic and environment-friendly polyacrylonitrile radiation solution polymerization method aiming at the problems in the background art.
The technical scheme provided by the invention is a polyacrylonitrile radiation solution polymerization method, which comprises the following specific steps:
s1, dissolving weighed acrylonitrile into an organic solvent to obtain a mixed solution A; wherein the mass ratio of the acrylonitrile to the organic solvent is 1;
s2, placing the mixed solution A in a radiation bottle, and covering a bottle stopper;
s3, placing a radiation bottle in 60 In a Co source chamber, taking out an irradiation bottle when the absorption dose is 15-30 kGy under room temperature radiation at the dose rate of 11Gy/min to obtain a mixed solution B; the viscosity of the mixed solution is 80-250 Pa.s;
s4, pouring the mixed solution B into a coagulating bath, and precipitating to obtain a polymer C;
s5, drying the polymer C to obtain a polymerization product D, namely polyacrylonitrile;
the number average molecular weight of the polymerization product D is 8-12 ten thousand measured by a gel permeation chromatograph, the weight average molecular weight is 14-21 ten thousand, and the molecular weight distribution index is 1.6-1.8;
the weight average molecular weight of the polymer D measured by a viscosity method is 13 to 19 ten thousand.
Preferably, the sealing film is used for covering the bottle stopper and the bottle mouth in S2.
Preferably, the polymer C is dried in S5 by storing the polymer C in a forced air oven at 60 ℃ for 10 to 14 hours.
Preferably, the mixed solution A in S1 also contains 4-vinylpyridine; the mass ratio of the total weight of the acrylonitrile and the 4-vinylpyridine to the organic solvent is 1; the mass ratio of the 4-vinylpyridine to the acrylonitrile is 1.
Preferably, the mixed solution A in S1 also contains methyl acrylate and itaconic acid; the mass ratio of the total weight of the acrylonitrile, the methyl acrylate and the itaconic acid to the organic solvent is 1; the mass ratio of itaconic acid, methyl acrylate and acrylonitrile is 3: 4.
The technical scheme of the invention has the following beneficial technical effects:
the polyacrylonitrile radiation solution polymerization method provided by the invention initiates polymerization reaction by adopting a radiation mode, does not need to add a chemical initiator, does not introduce impurities, has higher purity of the prepared product, does not need to be heated, can be carried out at room temperature or lower temperature, greatly reduces the chain transfer constant of free radicals to a solvent, has radiation effect among polymers at the later stage of the reaction, and can effectively improve the molecular weight of the product; meanwhile, the radiation-initiated polymerization can continuously generate free radicals and uniformly distribute the free radicals in a reaction system;
the invention adopts solution radiation polymerization to directly dissolve polyacrylonitrile in the solvent, and can obtain the spinning solution product which can be directly used for solution spinning without secondary dissolution of polyacrylonitrile, thereby greatly simplifying the operation flow of the spinning process and being worth popularizing;
the invention adopts gamma rays or high-energy electron beams to carry out polymerization reaction for polymerizing polyacrylonitrile, overcomes the defects of low molecular weight, temperature control on a reaction system and the like of chemically polymerized polyacrylonitrile, and the obtained polyacrylonitrile copolymer has the characteristics of high purity, high molecular weight, narrow molecular weight distribution and the like.
Drawings
FIG. 1 is a comparative graph of the polymerization product D in examples 1-3 after infrared spectrum detection.
FIG. 2 is a comparison of the results of the hydrogen nuclear magnetic resonance spectroscopy analyses of the polymerization products D obtained in examples 1 to 3.
FIG. 3 is a comparative graph showing that the polymerization product D in examples 1 to 3 was detected by gel permeation chromatography.
FIG. 4 is a comparative graph showing that the polymerization product D in examples 1 to 3 was measured by a viscometric method.
Detailed Description
Example 1
The invention provides a polyacrylonitrile radiation solution polymerization method, which comprises the following steps:
s1, weighing 50g of acrylonitrile, and dissolving into 200g of an organic solvent to obtain a mixed solution A;
s2, placing the mixed solution A in a radiation bottle, covering the bottle stopper, and coating the bottle stopper and the bottle mouth with a sealing film; selecting a Parafilm M sealing film as a sealing film; wherein, the radiation bottle is made of quartz material;
s3, placing a radiation bottle in 60 In a Co source chamber, taking out an irradiation bottle when the absorbed dose is 15.8kGy under room temperature radiation at the dose rate of 11Gy/min to obtain a mixed solution B; the viscosity of the mixed solution is 86 pas; or the radiation bottle can be placed in an environment capable of generating high-energy electron beams, and the high-energy electron beams are used as energy sources to initiate polymerization reaction;
s4, pouring the mixed solution B into a coagulating bath, and precipitating to obtain a polymer C;
s5, storing the polymer C in a forced air oven at 60 ℃ for 12h to obtain a polymerization product D, namely polyacrylonitrile;
weighing the mass of the polymer solution and the mass of the polymerization product D and calculating the yield, wherein the yield is 87%;
in FIGS. 1 and 2, 2244cm -1 Has an absorption peak ofA characteristic absorption peak of a cyano group (-C is identical to N), wherein delta 3.00-3.25 ppm in a hydrogen spectrum belongs to chemical shift of an H atom in a-CH group connected with-CN, and the obtained product is polyacrylonitrile;
the number average molecular weight of the polymerization product D was 8.4 ten thousand, the weight average molecular weight was 14.9 ten thousand, and the molecular weight distribution index was 1.77 as measured by gel permeation chromatography, as shown in fig. 3;
according to the relation between the viscosity of polyacrylonitrile solution and weight average molecular weight in the literature: [ eta ] of]＝3.35×10 -4 M w 0.72 (Journarof Polymer science PartA-1, polymer chemistry,1968,6 (1): 147-159), and the weight average molecular weight of the polymer D was measured by the viscosity method to be 18.5 ten thousand, as shown in FIG. 4.
Example 2
The invention provides a polyacrylonitrile radiation solution polymerization method, which comprises the following specific steps:
s1, weighing 48.055g of acrylonitrile and 1.945g of 4-vinylpyridine, and jointly dissolving into 200g of organic solvent to obtain a mixed solution A;
s2, placing the mixed solution A in a radiation bottle, covering the bottle stopper, and coating the bottle stopper and the bottle mouth by using a sealing film; the sealing film is a ParafilmM sealing film; wherein, the radiation bottle is made of quartz material;
s3, placing the radiation bottle in 60 In a Co source chamber, taking out an irradiation bottle when the absorption dose is 30kGy under room temperature radiation at the dose rate of 11Gy/min to obtain a mixed solution B; the viscosity of the mixed solution is 250 Pa.s; or the radiation bottle can be placed in an environment capable of generating high-energy electron beams, and the high-energy electron beams are used as energy sources to initiate polymerization reaction;
s4, pouring the mixed solution B into a coagulating bath, and precipitating to obtain a polymer C;
s5, placing the polymer C in a forced air oven at 60 ℃ for preservation for 10h to obtain a polymerization product D, namely polyacrylonitrile;
weighing the mass of the polymer solution and the mass of the polymerization product D and calculating the yield, wherein the yield is 90%;
in FIGS. 1 and 2, the infrared spectrum was 2244cm -1 The absorption peak is the characteristic absorption peak of cyano (-C ≡ N), and the absorption peak in hydrogen spectrumDelta 3.00-3.25 ppm belongs to chemical shift of H atom in-CH group connected with-CN, which indicates that the obtained product is polyacrylonitrile;
in addition, the infrared spectrum also shows obvious characteristic absorption peaks of pyridine rings: 1597cm -1 、1555cm -1 And 1414cm -1 1000cm at the absorption peak of the stretching vibration of the pyridine ring skeleton -1 Is located at 825cm and is a C-H in-plane bending vibration peak -1 The peak is the out-of-plane bending vibration peak of C-H. Two peaks in the hydrogen spectrum at delta 8.57ppm and delta 7.35ppm are the chemical shifts of the H atom attached to C adjacent to and alternating with N on the pyridine ring, respectively. The analysis of an infrared absorption spectrogram and a nuclear magnetic resonance hydrogen spectrum shows that the 4-vinylpyridine successfully participates in the copolymerization reaction of the acrylonitrile;
the number average molecular weight of the polymerization product D was 9.8 ten thousand, the weight average molecular weight was 16.6 ten thousand, and the molecular weight distribution index was 1.39 as measured by gel permeation chromatography, as shown in fig. 3;
according to the relation between the viscosity of polyacrylonitrile solution and weight average molecular weight in literature: [ eta ]]＝3.35×10 -4 M w 0.72 (Journarof Polymer science PartA-1, polymer chemistry,1968,6 (1): 147-159), and the weight average molecular weight of the polymer product D was measured by the viscosity method to be 13.6 ten thousand, as shown in FIG. 4.
Example 3
The invention provides a polyacrylonitrile radiation solution polymerization method, which comprises the following steps:
s1, weighing 47.225g of acrylonitrile, 1.58g of methyl acrylate and 1.195g of itaconic acid, and dissolving into 200g of organic solvent to obtain a mixed solution A;
s2, placing the mixed solution A in a radiation bottle, covering the bottle stopper, and coating the bottle stopper and the bottle mouth by using a sealing film; the sealing film is a ParafilmM sealing film; wherein, the radiation bottle is made of quartz material;
s3, placing the radiation bottle in 60 In a Co source chamber, taking out an irradiation bottle when the room temperature irradiation is carried out at the dose rate of 11Gy/min until the absorbed dose is 16kGy, and obtaining a mixed solution B; the viscosity of the mixed solution was 167Pa · s; the radiation bottle can also be placed in an environment capable of generating high-energy electron beams, and the high-energy electron beams are used as the electron beamsInitiating a polymerization reaction by an energy source;
s4, pouring the mixed solution B into a coagulating bath, and precipitating to obtain a polymer C;
s5, placing the polymer C in a forced air oven at 60 ℃ for storage for 14h to obtain a polymerization product D, namely polyacrylonitrile;
weighing the mass of the polymer solution and the mass of the polymerization product D and calculating the yield, wherein the yield is 90%;
in FIGS. 1 and 2, 2244cm -1 The absorption peak at (A) is a characteristic absorption peak of a cyano group (-C ≡ N); 1737cm -1 Corresponding to the stretching vibration of CO in C = O, the delta 1.75-2.30 ppm on the hydrogen spectrum is assigned to the H atom absorption peak in-CH 2 group; delta 3.00-3.25 ppm belongs to the absorption peak of H atom in-CH group; the proton (-OCH 3) chemical shift of the methoxy group on methyl acrylate is approximately delta 3.60-3.75 ppm. In the infrared spectrum of 950cm -1 The absorption peak at (a) is due to bending vibration of hydroxyl (-OH) groups on carboxylic acid; according to the infrared absorption spectrogram and the nuclear magnetic resonance hydrogen spectrum analysis, the methyl acrylate and the itaconic acid successfully participate in the copolymerization reaction of the acrylonitrile;
the number average molecular weight of the polymerization product D was 11.7 ten thousand, the weight average molecular weight was 20.6 ten thousand, and the molecular weight distribution index was 1.76 as measured by gel permeation chromatography, as shown in fig. 3;
according to the relation between the viscosity of polyacrylonitrile solution and weight average molecular weight in the literature: [ eta ]]＝3.35×10 -4 M w 0.72 (Journarof Polymer science PartA-1, polymer chemistry,1968,6 (1): 147-159), and the weight average molecular weight of the polymerization product D was measured by the viscosity method to be 18.7 ten thousand, as shown in FIG. 4.
Comparative example
The invention provides a polyacrylonitrile radiation solution polymerization method, which comprises the following steps:
s1, weighing 50 acrylonitrile, and dissolving into 200g of an organic solvent to obtain a mixed solution A;
s2, placing the mixed solution A in a radiation bottle, covering the bottle stopper, and coating the bottle stopper and the bottle mouth by using a sealing film; the sealing film is a ParafilmM sealing film; wherein, the radiation bottle is made of quartz material;
s3, placing the radiation bottle in 60 In a Co source chamber, taking out an irradiation bottle when the room temperature irradiation is carried out at the dose rate of 11Gy/min until the absorbed dose is 7kGy, and obtaining a mixed solution B; the viscosity of the mixed solution is 8Pa · s;
s4, pouring the mixed solution B into a coagulating bath, and precipitating to obtain a polymer C;
s5, placing the polymer C in a forced air oven at 60 ℃ for storage for 12 hours to obtain a polymerization product D, namely polyacrylonitrile;
the mass of the polymer solution and the mass of the polymerization product D were weighed and the yield was calculated, which was 60.9%.
While the embodiments of the invention have been described in detail, the invention is not limited thereto, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the invention.
Claims (3)
1. A polyacrylonitrile radiation solution polymerization method is characterized by comprising the following specific steps:
s1, dissolving weighed acrylonitrile into an organic solvent to obtain a mixed solution A;
the mixed solution A also contains methyl acrylate and itaconic acid; the mass ratio of the total weight of the acrylonitrile, the methyl acrylate and the itaconic acid to the organic solvent is 1; the mass ratio of itaconic acid to methyl acrylate to acrylonitrile is 3: 4;
s2, placing the mixed solution A in a radiation bottle, and covering a bottle stopper;
s3, placing the radiation bottle in 60 In a Co source chamber, taking out an irradiation bottle when the room temperature irradiation is carried out at the dose rate of 11Gy/min until the absorbed dose is 15-30 kGy, thus obtaining a mixed solution B; the viscosity of the mixed solution is 80-250 Pa.s;
s4, pouring the mixed solution B into a coagulating bath, and precipitating to obtain a polymer C;
s5, drying the polymer C to obtain a polymerization product D, namely polyacrylonitrile;
the number average molecular weight of the polymerization product D is 8-12 ten thousand, the weight average molecular weight is 14-21 ten thousand and the molecular weight distribution index is 1.6-1.8 measured by a gel permeation chromatograph;
the weight average molecular weight of the polymerization product D as measured by a viscosity method is 13 to 19 ten thousand.
2. The polyacrylonitrile radiation solution polymerization method according to claim 1, wherein in S2, the sealing film is used to cover the bottle stopper and the bottle mouth.
3. The radiation solution polymerization method for polyacrylonitrile according to claim 1, characterized in that, the method for drying the polymer C in S5 is to store the polymer C in a blast oven at 60 ℃ for 10-14 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1126127A (en) * | 1966-07-26 | 1968-09-05 | Rumanian Minister For Chemical | Process for polymerization and copolymerization of acrylonitrile |
| CN106749807A (en) * | 2016-12-01 | 2017-05-31 | 苏州大学 | A kind of green synthesis method of acrylonitrile polymer |
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| RU2422467C2 (en) * | 2009-06-03 | 2011-06-27 | Федеральное государственное унитарное предприятие "Научно-исследовательский физико-химический институт им. Л.Я. Карпова" (ФГУП "НИФХИ им. Л.Я. Карпова") | Fibre-forming acrylonitrile copolymer and synthesis method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1126127A (en) * | 1966-07-26 | 1968-09-05 | Rumanian Minister For Chemical | Process for polymerization and copolymerization of acrylonitrile |
| CN106749807A (en) * | 2016-12-01 | 2017-05-31 | 苏州大学 | A kind of green synthesis method of acrylonitrile polymer |
Non-Patent Citations (3)
| Title |
|---|
| 丙烯腈γ辐射聚合的NMR研究;邹琴等;《波谱学杂志》;20060630(第02期);第187-192页 * |
| 丙烯腈辐射聚合机理的NMR研究;赵新等;《核技术》;20000710(第07期);第499-502页 * |
| 辐射引发丙烯腈－丙烯酸甲酯－衣康酸三元沉淀共聚合;张志成，葛学武，葛敏，张健;《高等学校化学学报》;19941015(第10期);第1575-1577页 * |
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