CN106279521B - Preparation method of acrylonitrile spinning solution - Google Patents
Preparation method of acrylonitrile spinning solution Download PDFInfo
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- CN106279521B CN106279521B CN201610761802.3A CN201610761802A CN106279521B CN 106279521 B CN106279521 B CN 106279521B CN 201610761802 A CN201610761802 A CN 201610761802A CN 106279521 B CN106279521 B CN 106279521B
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- acrylonitrile
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- isopropanol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of preparation of acrylonitrile spinning solution, in particular to a preparation method of acrylonitrile spinning solution, which comprises the following steps: putting a solvent, an acrylonitrile monomer, an initiator and a comonomer into a reaction kettle, raising the temperature of materials in the reaction kettle to 60-70 ℃, adding tert-dodecyl mercaptan in the temperature raising process, adding isopropanol in 20-80 minutes after the temperature of the materials reaches 60-70 ℃, reacting for 20-30 hours after adding the isopropanol, and removing the monomer and the bubbles to obtain the acrylonitrile spinning solution. In the polymerization reaction process, the weight average molecular weight and the number average molecular weight of the copolymer are adjusted by adding the compound chain transfer agent step by step, the method is simple and feasible, the operation is easy, and the molecular weight distribution index of the finally prepared acrylonitrile copolymer can be controlled to be 2.0-2.2.
Description
Technical Field
The invention relates to the field of preparation of acrylonitrile spinning solution, in particular to a preparation method of acrylonitrile spinning solution.
Background
Carbon fibers have a series of excellent properties such as heat resistance, heat conduction, high specific strength, high specific modulus, light weight and the like, and are widely applied to various fields such as aerospace, sports and leisure goods, civil construction and the like.
The final structure and performance of the acrylonitrile copolymer can determine the structure and performance of the carbon fiber, the key is to prepare high-quality precursor fibers, and the spinning solution with excellent performance is the premise of obtaining the high-quality precursor fibers, so the spinning solution has the characteristics of moderate molecular weight, narrow molecular weight distribution, good spinnability and the like. Researches show that the high-performance spinning solution can be prepared from the acrylonitrile copolymer with the molecular weight distribution index of 2.0-2.2 after demonomerization and deaeration. The protofilament prepared by the spinning solution has excellent microscopic physical structure and chemical reaction uniformity, and the finally obtained carbon fiber has high strength and small variation coefficient. However, it is a technical difficulty to control the molecular weight distribution index of acrylonitrile copolymer to be 2.0-2.2.
Disclosure of Invention
In order to overcome the defects of the technical problems, the invention provides a preparation method of acrylonitrile spinning solution with narrow molecular weight distribution, which can completely solve the technical problems.
The technical scheme for solving the technical problems is as follows:
a preparation method of acrylonitrile spinning solution comprises the steps of adding a compound chain transfer agent in the polymerization reaction process, wherein the compound chain transfer agent is a mixture of tert-dodecyl mercaptan and isopropanol; the method comprises the following specific steps: putting a solvent, an acrylonitrile monomer, an initiator and a comonomer into a reaction kettle, raising the temperature of materials in the reaction kettle to 60-70 ℃, adding tert-dodecyl mercaptan in the temperature raising process, adding isopropanol in 20-80 minutes after the temperature of the materials reaches 60-70 ℃, reacting for 20-30 hours after adding the isopropanol, and removing the monomer and the bubbles to obtain the acrylonitrile spinning solution.
Further, the solvent is one of dimethyl sulfoxide or dimethylformamide.
Further, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide.
Further, the comonomer is any one or a mixture of two of itaconic acid, itaconic acid monomethyl ester, acrylic acid, methyl acrylate, ethyl methacrylate, vinyl acetate, methacrylamide or dimethylacrylamide.
Furthermore, the mass of the comonomer accounts for 0.1-8% of that of the acrylonitrile monomer.
Furthermore, the mass of the initiator accounts for 0.1-1% of the mass of the acrylonitrile monomer.
Further, the compound chain transfer agent is a mixture of tert-dodecyl mercaptan and isopropanol according to a mass ratio of 1: 0.1-1.
Furthermore, the compound chain transfer agent accounts for 0.05-0.1% of the mass of the acrylonitrile monomer.
The invention has the following advantages: in the polymerization reaction process, the weight average molecular weight and the number average molecular weight of the copolymer are adjusted by adding the compound chain transfer agent step by step, the method is simple, feasible and easy to operate, the molecular weight distribution index of the finally prepared acrylonitrile copolymer can be controlled to be 2.0-2.2, the microcosmic physical structure and the chemical reaction uniformity of the precursor fiber prepared by wet spinning of the spinning solution are excellent, and the finally obtained carbon fiber has high strength and small variation coefficient.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1:
60kg of dimethyl sulfoxide is put into a reaction kettle, then 0.05kg of azodiisobutyronitrile, 10kg of acrylonitrile and 0.01kg of itaconic acid are sequentially put into the reaction kettle, the temperature of materials in the reaction kettle is raised to 65 ℃, 0.009kg of tert-dodecyl mercaptan is added in the process of raising the temperature, 0.001kg of isopropanol is added in 20 minutes after the temperature of the materials reaches 65 ℃, and after the isopropanol is added and the reaction is carried out for 25 hours, the acrylonitrile spinning solution can be obtained by removing monomers and bubbles.
The acrylonitrile spinning solution had a weight average molecular weight of Mw33 ten thousand and a number average molecular weight of mn15.7 ten thousand as measured by gel chromatography, and the molecular weight distribution index was Mw/Mn of 2.109.
Example 2:
60kg of dimethylformamide is put into a reaction kettle, then 0.01kg of azobisisoheptonitrile, 10kg of acrylonitrile, 0.1kg of itaconic acid monomethyl ester, 0.1kg of acrylic acid, 0.1kg of methyl acrylate, 0.1kg of ethyl methacrylate, 0.1kg of vinyl acetate, 0.1kg of methacrylamide and 0.1kg of dimethylacrylamide are sequentially put into the reaction kettle, the temperature of materials in the reaction kettle is raised to 60 ℃, 0.004kg of tert-dodecyl mercaptan is added in the process of temperature rise, 0.002kg of isopropanol is added in 80 minutes after the temperature of the materials reaches 60 ℃, the materials are reacted for 20 hours after the isopropanol is added, monomers and bubbles are removed, and the acrylonitrile spinning solution can be obtained through wet spinning.
When the weight-average molecular weight of the acrylonitrile dope measured by gel chromatography was mw32.8 ten thousand and the number-average molecular weight was Mn15 ten thousand, the molecular weight distribution index was Mw/Mn of 2.186.
Example 3:
adding 60kg of dimethylformamide into a reaction kettle, sequentially adding 0.1kg of dibenzoyl peroxide, 10kg of acrylonitrile, 0.2kg of ethyl methacrylate and 0.2kg of vinyl acetate, raising the temperature of materials in the reaction kettle to 70 ℃, adding 0.004kg of tert-dodecyl mercaptan in the temperature raising process, adding isopropanol in 50 minutes after the temperature of the materials reaches 70 ℃, reacting for 30 hours after adding the isopropanol, removing monomers and bubbles, and carrying out wet spinning to obtain the acrylonitrile spinning solution.
The acrylonitrile spinning solution had a weight average molecular weight of mw31.3 ten thousand and a number average molecular weight of mn14.8 ten thousand as measured by gel chromatography, and the molecular weight distribution index was Mw/Mn of 2.114.
The performance parameters of the precursor obtained by wet spinning the spinning solution of examples 1 to 3 are shown in Table 1:
TABLE 1
| Examples | Strength (CN/D) | Boiling Water shrinkage (%) | Elongation at Break (%) | CV/％ |
| 1 | 4.93 | 5.36 | 11.22 | 1.70 |
| 2 | 5.02 | 5.41 | 10.95 | 1.95 |
| 3 | 5.05 | 5.22 | 10.98 | 1.86 |
In the polymerization reaction process, the weight average molecular weight and the number average molecular weight of the copolymer are adjusted by adding the compound chain transfer agent step by step, the method is simple, feasible and easy to operate, the molecular weight distribution index of the finally prepared acrylonitrile copolymer can be controlled to be 2.0-2.2, the microcosmic physical structure and the chemical reaction uniformity of the precursor prepared by using the spinning solution are excellent, and the finally obtained carbon fiber has high strength and small variation coefficient.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiment according to the present invention are within the scope of the present invention.
Claims (5)
1. The preparation method of the acrylonitrile spinning solution is characterized in that a compound chain transfer agent is added in the polymerization reaction process, and the compound chain transfer agent is a mixture of tert-dodecyl mercaptan and isopropanol; the method comprises the following specific steps: putting a solvent, an acrylonitrile monomer, an initiator and a comonomer into a reaction kettle, raising the temperature of materials in the reaction kettle to 60-70 ℃, adding tert-dodecyl mercaptan in the temperature raising process, adding isopropanol in 20-80 minutes after the temperature of the materials reaches 60-70 ℃, reacting for 20-30 hours after adding the isopropanol, and removing the monomer and bubbles to obtain an acrylonitrile spinning solution; the mass of the initiator accounts for 0.1-1% of that of the acrylonitrile monomer; the compound chain transfer agent is a mixture of tert-dodecyl mercaptan and isopropanol in a mass ratio of 1: 0.1-1; the compound chain transfer agent accounts for 0.05-0.1% of the mass of the acrylonitrile monomer.
2. The method of claim 1, wherein the solvent is one of dimethyl sulfoxide and dimethylformamide.
3. The method of claim 1, wherein the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, or dibenzoyl peroxide.
4. The method of claim 1, wherein the comonomer is one or a mixture of itaconic acid, monomethyl itaconate, acrylic acid, methyl acrylate, ethyl methacrylate, vinyl acetate, methacrylamide or dimethylacrylamide.
5. The method of claim 1, wherein the comonomer is present in an amount of 0.1 to 8% by weight based on the mass of the acrylonitrile monomer.
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| CN109430957A (en) * | 2018-11-30 | 2019-03-08 | 海南中美达纳米技术股份有限公司 | A kind of nanofiber ecological heat preservation underwear |
| CN111004350B (en) * | 2019-12-27 | 2021-06-04 | 山东非金属材料研究所 | Preparation method of acrylonitrile-itaconic acid copolymer standard substance |
| CN114687010B (en) * | 2022-04-18 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | High-strength high-modulus high-elongation carbon fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101413152A (en) * | 2008-12-04 | 2009-04-22 | 中国科学院长春应用化学研究所 | Acrylonitrile terpolymer spinning fluid containing hydrophilic group and preparation thereof |
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| CN100545326C (en) * | 2007-09-18 | 2009-09-30 | 中国科学院长春应用化学研究所 | A kind of method for preparing the acrylonitrile copolymer of high molecular, Narrow Molecular Weight Distribution |
| CN101805936A (en) * | 2010-03-09 | 2010-08-18 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with high molecular weight and narrow distribution and preparation method thereof |
| CN102336857B (en) * | 2011-06-29 | 2014-09-24 | 中国石油天然气股份有限公司 | SAN (Styrene Acrylonitrile) resin with high nitrile content and narrow distribution and preparation method thereof |
| RU2647861C2 (en) * | 2013-12-23 | 2018-03-21 | Сайтек Индастриз Инк. | Polyacrylonetrile (pan) polymers with low index of polydispersity (ipd) and carbon fibers received from them |
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