CN113683715A - Radiation solution polymerization method for polyacrylonitrile - Google Patents
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- CN113683715A CN113683715A CN202111104302.XA CN202111104302A CN113683715A CN 113683715 A CN113683715 A CN 113683715A CN 202111104302 A CN202111104302 A CN 202111104302A CN 113683715 A CN113683715 A CN 113683715A
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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
- C08F120/42—Nitriles
- C08F120/44—Acrylonitrile
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
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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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- C08F220/44—Acrylonitrile
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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- C08F220/48—Acrylonitrile with nitrogen-containing monomers
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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 in 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 in60In 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; 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 polymerization of acrylonitrile and comonomer in organic solventCarrying out copolymerization reaction on the phase solution to obtain a 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 performance of polyacrylonitrile can be affected by the residual azobisisobutyronitrile decomposition product, 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 technology.
The technical scheme provided by the invention is a polyacrylonitrile radiation solution polymerization method, which comprises the following specific steps:
s1, dissolving the weighed acrylonitrile in an organic solvent to obtain a mixed solution A; wherein the mass ratio of the acrylonitrile to the organic solvent is 1: 4;
s2, placing the mixed solution A in a radiation bottle, and covering a bottle stopper;
s3, placing the radiation bottle in60In 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 polymerization product D is 13-19 ten thousand measured by a viscosity method.
Preferably, in S2, a sealing film is used to cover the bottle stopper and the bottle mouth.
Preferably, 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.
Preferably, the mixed solution A in S1 further contains 4-vinylpyridine; the mass ratio of the total weight of the acrylonitrile and the 4-vinylpyridine to the organic solvent is 1: 4; the mass ratio of the 4-vinylpyridine to the acrylonitrile is 1: 23-25.
Preferably, the mixed solution a in S1 further 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: 4; the mass ratio of itaconic acid, methyl acrylate and acrylonitrile is 3: 4: 118-122.
The technical scheme of the invention has the following beneficial technical effects:
according to the radiation solution polymerization method for polyacrylonitrile, provided by the invention, the polymerization reaction is initiated by adopting a radiation mode, a chemical initiator is not required to be added, impurities are not introduced, the purity of the prepared product is higher, heating is not required, the polymerization can be carried out at room temperature or lower temperature, the chain transfer constant from free radicals to a solvent is greatly reduced, the radiation-initiated polymerization has the radiation effect among polymers at the later stage of the reaction, and the molecular weight of the product can be effectively improved; 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 comparison of the products of polymerization D of examples 1-3, as detected by IR spectroscopy.
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 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 the radiation bottle in60Irradiating at room temperature in Co source chamber at dose rate of 11Gy/min until absorbed dose is 15.8kGy, taking out the irradiation bottle, and mixingMixing the 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-1The absorption peak is a characteristic absorption peak of a cyano group (-C ≡ N), and 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, which indicates that 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 ]]＝3.35×10-4Mw 0.72(Journarof Polymer science PartA-1: Polymer chemistry,1968,6(1): 147-.
Example 2
The invention provides a polyacrylonitrile radiation solution polymerization method, which comprises the following steps:
s1, weighing 48.055g of acrylonitrile and 1.945g of 4-vinylpyridine, and jointly dissolving the acrylonitrile and the 1.945g of 4-vinylpyridine 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 with 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 in60In 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; also can be combined withThe radiation bottle is arranged in an environment capable of generating high-energy electron beams, and the high-energy electron beams are used as an energy source 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-1The absorption peak is a characteristic absorption peak of a cyano group (-C ≡ N), and 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, 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-1And 1414cm-1A 1000cm stretching vibration absorption peak of pyridine ring skeleton-1Is located at 825cm and is a C-H in-plane bending vibration peak-1The 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 the literature: [ eta ]]＝3.35×10-4Mw 0.72(Journarof Polymer science PartA-1: Polymer chemistry,1968,6(1): 147-.
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 with 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 in60In a Co source chamber, taking out an irradiation bottle when the absorption dose is 16kGy under room temperature radiation at the dose rate of 11Gy/min to obtain a mixed solution B; the viscosity of the mixed solution was 167 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 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-1The absorption peak at (A) is a characteristic absorption peak of a cyano group (-C ≡ N); 1737cm-1Corresponding to the stretching vibration of CO in C ═ O, the delta 1.75-2.30 ppm on a hydrogen spectrum is assigned to an H atom absorption peak in a-CH 2 group; delta 3.00-3.25 ppm belongs to an H atom absorption peak in a-CH group; the chemical shift of the proton (-OCH3) of the methoxy group on the methyl acrylate is approximately delta 3.60-3.75 ppm. In the infrared spectrum of 950cm-1The 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 ]]＝3.35×10-4Mw 0.72(JournalofPolymerSciencePartA-1:PolymerChemistry,1968,6(1):147-159) The weight average molecular weight of the polymerization product D measured by the viscosity method was 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 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; the sealing film is a ParafilmM sealing film; wherein, the radiation bottle is made of quartz material;
s3, placing the radiation bottle in60In a Co source chamber, taking out an irradiation bottle when the absorption dose is 7kGy under room temperature radiation at the dose rate of 11Gy/min to obtain a mixed solution B; the viscosity of the mixed solution is 8 Pa.s;
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;
the mass of the polymer solution and the mass of the polymerization product D were weighed and the yield was calculated to be 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 without departing from the spirit of the invention within the knowledge of those skilled in the art.
Claims (5)
1. A polyacrylonitrile radiation solution polymerization method is characterized by comprising the following specific steps:
s1, dissolving the weighed acrylonitrile in an organic solvent to obtain a mixed solution A; wherein the mass ratio of the acrylonitrile to the organic solvent is 1: 4;
s2, placing the mixed solution A in a radiation bottle, and covering a bottle stopper;
s3, placing the radiation bottle in60In a Co source chamber, taking out an irradiation bottle when the room temperature radiation is irradiated at the dose rate of 11Gy/min until the absorbed dose is 15-30 kGy, and obtaining a mixtureSolution 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 polymerization product D is 13-19 ten thousand measured by a viscosity method.
2. The method of claim 1, wherein a sealing film is used to cover the stopper and the mouth of the bottle in S2.
3. The polyacrylonitrile radiation solution polymerization method according to claim 1, wherein the method for drying the polymer C in the S5 is to store the polymer C in a blast oven at 60 ℃ for 10-14 h.
4. The radiation solution polymerization method of polyacrylonitrile according to claim 1, characterized in that, the mixed solution a in S1 further contains 4-vinylpyridine; the mass ratio of the total weight of the acrylonitrile and the 4-vinylpyridine to the organic solvent is 1: 4; the mass ratio of the 4-vinylpyridine to the acrylonitrile is 1: 23-25.
5. The radiation solution polymerization method of polyacrylonitrile according to claim 1, characterized in that the mixed solution a in S1 further 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: 4; the mass ratio of itaconic acid, methyl acrylate and acrylonitrile is 3: 4: 118-122.
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| CN114736329A (en) * | 2022-04-02 | 2022-07-12 | 安徽大学 | Cobalt 60 radiation polymerization method of polyacrylonitrile for carbon fiber precursor |
Citations (3)
| 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 |
| RU2009121094A (en) * | 2009-06-03 | 2010-12-10 | Федеральное государственное унитарное предприятие "Научно-исследовательский физико-химический институт им. Л.Я. Карпова" (ФГУП "НИФХИ и | FIBER-FORMING ACRYLONITRIL POLYMER AND METHOD FOR ITS PRODUCTION |
| 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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Patent Citations (3)
| 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 |
| RU2009121094A (en) * | 2009-06-03 | 2010-12-10 | Федеральное государственное унитарное предприятие "Научно-исследовательский физико-химический институт им. Л.Я. Карпова" (ФГУП "НИФХИ и | FIBER-FORMING ACRYLONITRIL POLYMER AND METHOD FOR ITS PRODUCTION |
| 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 |
|---|
| 张志成，葛学武，葛敏，张健: "辐射引发丙烯腈－丙烯酸甲酯－衣康酸三元沉淀共聚合", 《高等学校化学学报》 * |
| 赵新等: "丙烯腈辐射聚合机理的NMR研究", 《核技术》 * |
| 邹琴等: "丙烯腈γ辐射聚合的NMR研究", 《波谱学杂志》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736329A (en) * | 2022-04-02 | 2022-07-12 | 安徽大学 | Cobalt 60 radiation polymerization method of polyacrylonitrile for carbon fiber precursor |
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