CN106397666B - Preparation method of acrylonitrile spinning solution with narrow molecular weight distribution - Google Patents
Preparation method of acrylonitrile spinning solution with narrow molecular weight distribution Download PDFInfo
- Publication number
- CN106397666B CN106397666B CN201610763258.6A CN201610763258A CN106397666B CN 106397666 B CN106397666 B CN 106397666B CN 201610763258 A CN201610763258 A CN 201610763258A CN 106397666 B CN106397666 B CN 106397666B
- Authority
- CN
- China
- Prior art keywords
- acrylonitrile
- molecular weight
- spinning solution
- weight distribution
- narrow molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to the field of acrylonitrile spinning solution preparation, in particular to a preparation method of acrylonitrile spinning solution with narrow molecular weight distribution, which comprises the following specific steps: the method comprises the steps of putting a solvent, an acrylonitrile monomer, an initiator, a comonomer and a compound chain transfer agent into a reaction kettle at one time, controlling the temperature of materials in the reaction kettle at 60-75 ℃, carrying out polymerization reaction for 20-30 hours, removing the monomer and bubbles, and carrying out wet spinning to obtain the acrylonitrile spinning solution with narrow molecular weight distribution. The method is simple and feasible, is easy to operate, the molecular weight distribution index of the finally prepared acrylonitrile copolymer can be controlled to be 2.1-2.5, and the high-performance carbon fiber precursor can be prepared by adopting a wet spinning method after monomers and bubbles are removed from the spinning solution.
Description
Technical Field
The invention relates to the field of acrylonitrile spinning solution preparation, in particular to a preparation method of acrylonitrile spinning solution with narrow molecular weight distribution.
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 find that high-performance carbon fiber precursor can be prepared from the acrylonitrile copolymer with the molecular weight distribution index of 2.1-2.5 after demonomerization and deaeration, however, the control of the molecular weight distribution index of the acrylonitrile copolymer is a technical difficulty.
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 with narrow molecular weight distribution comprises the steps of adding a compound chain transfer agent in the polymerization reaction process; the method comprises the following specific steps: the method comprises the steps of putting a solvent, an acrylonitrile monomer, an initiator, a comonomer and a compound chain transfer agent into a reaction kettle at one time, controlling the temperature of materials in the reaction kettle at 60-75 ℃, carrying out polymerization reaction for 20-30 hours, and then removing the monomer and bubbles to obtain the acrylonitrile spinning solution with narrow molecular weight distribution.
The solvent is one of dimethyl sulfoxide or dimethylformamide.
The initiator is one of azodiisobutyronitrile, azodiisoheptonitrile or dibenzoyl peroxide.
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.
The mass of the comonomer accounts for 0.1-8% of that of the acrylonitrile monomer.
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.
The invention has the following advantages: in the polymerization reaction process, the compound chain transfer agent is added to adjust the weight average molecular weight and the number average molecular weight of the copolymer, 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 2.1-2.5, and after monomers and bubbles are removed from the spinning solution, a wet spinning method is adopted to prepare the high-performance carbon fiber precursor.
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, 0.05kg of azodiisobutyronitrile, 10kg of acrylonitrile, 0.01kg of itaconic acid, 0.009kg of tert-dodecyl mercaptan and 0.001kg of isopropanol are sequentially put into the reaction kettle, the temperature of the system is raised to 68 ℃, and after the system is kept reacting for 25 hours, monomers and bubbles in the polymer are removed in high vacuum under the condition of keeping stirring, so that high-quality spinning solution is obtained.
The acrylonitrile dope had a weight average molecular weight of Mw34 ten thousand and a number average molecular weight of Mn15 ten thousand as measured by gel chromatography, and the molecular weight distribution index was Mw/Mn of 2.27.
Example 2:
60kg of dimethylformamide is put into a reaction kettle, 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, 0.1kg of dimethylacrylamide, 0.004kg of tert-dodecyl mercaptan and 0.002kg of isopropanol are sequentially put into the reaction kettle, the system is heated to 60 ℃, and after reaction is kept for 20 hours, monomers and bubbles in the polymer are removed under high vacuum under the condition of keeping stirring, so that high-quality spinning solution is obtained.
When the weight average molecular weight of the acrylonitrile spinning solution measured by gel chromatography was mw32.8 ten thousand and the number average molecular weight was Mn14 ten thousand, the molecular weight distribution index was Mw/Mn of 2.34.
Example 3:
60kg of dimethylformamide is put into a reaction kettle, 0.1kg of dibenzoyl peroxide, 10kg of acrylonitrile, 0.2kg of ethyl methacrylate, 0.2kg of vinyl acetate, 0.004kg of tert-dodecyl mercaptan and 0.004kg of isopropanol are sequentially put into the reaction kettle, the temperature of the system is raised to 75 ℃, the reaction is kept for 30 hours, and then monomers and bubbles in the polymer are removed in high vacuum under the condition of keeping stirring, so that high-quality spinning solution is obtained.
When the weight average molecular weight of the acrylonitrile spinning solution measured by gel chromatography was mw31.5 ten thousand and the number average molecular weight was Mn13 ten thousand, the molecular weight distribution index was Mw/Mn of 2.42.
In the polymerization reaction process, the compound chain transfer agent is added to adjust the weight average molecular weight and the number average molecular weight of the copolymer, 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 2.1-2.5, and after monomers and bubbles are removed from the spinning solution, a wet spinning method is adopted to prepare the high-performance carbon fiber precursor.
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 (4)
1. A preparation method of acrylonitrile spinning solution with narrow molecular weight distribution is characterized in that a compound chain transfer agent is added in the polymerization reaction process; the method comprises the following specific steps: putting a solvent, an acrylonitrile monomer, an initiator, a comonomer and a compound chain transfer agent into a reaction kettle at one time, controlling the temperature of materials in the reaction kettle at 60-75 ℃, carrying out polymerization reaction for 20-30 h, and removing the monomer and bubbles to obtain an acrylonitrile spinning solution with narrow molecular weight distribution, wherein the compound chain transfer agent is a mixture of tert-dodecyl mercaptan and isopropanol in a mass ratio of 1: 0.1-1;
the mass of the comonomer accounts for 0.1-8% of that of the acrylonitrile monomer;
the mass of the initiator accounts for 0.1-1% of that of the acrylonitrile monomer;
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610763258.6A CN106397666B (en) | 2016-08-29 | 2016-08-29 | Preparation method of acrylonitrile spinning solution with narrow molecular weight distribution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610763258.6A CN106397666B (en) | 2016-08-29 | 2016-08-29 | Preparation method of acrylonitrile spinning solution with narrow molecular weight distribution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106397666A CN106397666A (en) | 2017-02-15 |
| CN106397666B true CN106397666B (en) | 2020-11-17 |
Family
ID=58003800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610763258.6A Active CN106397666B (en) | 2016-08-29 | 2016-08-29 | Preparation method of acrylonitrile spinning solution with narrow molecular weight distribution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397666B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628935A (en) * | 2013-11-06 | 2015-05-20 | 中国石油化工股份有限公司 | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257319C (en) * | 2004-08-16 | 2006-05-24 | 中国科学院长春应用化学研究所 | Process for preparing spin silk liquid of carbon fibre |
| CN101260172B (en) * | 2007-03-07 | 2010-05-19 | 中国科学院化学研究所 | Method for preparing super-high molecular weight polyacrylonitrile-base carbon fiber spinning primary fluid |
| 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 |
| CN102336857B (en) * | 2011-06-29 | 2014-09-24 | 中国石油天然气股份有限公司 | SAN resin with high nitrile content and narrow distribution and preparation method thereof |
| MY182047A (en) * | 2013-12-23 | 2021-01-18 | Cytec Ind Inc | Method for producing carbon fibers from polyacrylonitrile (pan) polymers with low pol ydispersity index (pdi) |
-
2016
- 2016-08-29 CN CN201610763258.6A patent/CN106397666B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628935A (en) * | 2013-11-06 | 2015-05-20 | 中国石油化工股份有限公司 | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106397666A (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103014894B (en) | Preparation method of acrylonitrile copolymer spinning solution with low molecular weight distribution | |
| AU2014370386B2 (en) | Polyacrylonitrile (PAN) polymers with low polydispersity index (PDI) and carbon fibers made therefrom | |
| CN100545181C (en) | A kind of hydrophilicity spinning fluid of PAN-based carbon fiber and preparation method | |
| CN106279521B (en) | Preparation method of acrylonitrile spinning solution | |
| CN100545326C (en) | A kind of method for preparing the acrylonitrile copolymer of high molecular, Narrow Molecular Weight Distribution | |
| CN103422187B (en) | The preparation method of low viscosity, high-performance carbon fibre spinning solution | |
| CN102746453B (en) | Method for preparing high-performance polyacrylonitrile solution for carbon fibers | |
| CN102199249B (en) | High molecular weight acrylonitrile terpolymer and preparation method thereof | |
| CN104231159B (en) | A kind of preparation method of carbon fiber PAN polymer | |
| CN104558397B (en) | The preparation method of the controllable high-hydrophilic acrylonitrile copolymer spinning solution of ammonification degree | |
| JP2022527859A (en) | Hydrophobic high temperature optical acrylic copolymer | |
| CN106397666B (en) | Preparation method of acrylonitrile spinning solution with narrow molecular weight distribution | |
| CN103030736B (en) | Preparation method of acrylonitrile copolymer spinning solution with low molecular weight distribution | |
| CN102102234B (en) | Ternary copolymerization highly hydrophilic polyacrylonitrile-based carbon fiber spinning solution and preparation method thereof | |
| US2776270A (en) | Mixtures comprising acrylonitrile polymers with polyacrylonitrile | |
| CN102887977B (en) | Production method of styrene modified carboxylic butadiene-acrylonitrite latex | |
| CN101413153A (en) | Acrylonitrile biopolymer spinning fluid having homogeneous chain structure and preparation thereof | |
| CN105622836B (en) | Polymolecular amount composition polyacrylonitrile spinning solution and its preparation method and application | |
| CN109810222B (en) | Carbon fiber precursor composition and preparation method of carbon fiber precursor | |
| Tong et al. | Copolymerization of acrylonitrile/1-vinyl-3-ethylimidazolium bromide and rheological, thermal properties of the copolymer | |
| CN105646797A (en) | Method for synthesizing acrylic ester modified epoxy toughening agents | |
| CN105273125A (en) | Polyacrylonitrile dry powder suitable for dry acrylic fiber spinning, and preparation method thereof | |
| CN111662407B (en) | Efficient polymerization preparation method of polyacrylonitrile polymer for carbon fiber | |
| KR20210029045A (en) | Method for preparing acrylonitrile based polymer | |
| CN104628935A (en) | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |