CN106279521A - A kind of preparation method of acrylonitrile spinning solution - Google Patents

A kind of preparation method of acrylonitrile spinning solution Download PDF

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Publication number
CN106279521A
CN106279521A CN201610761802.3A CN201610761802A CN106279521A CN 106279521 A CN106279521 A CN 106279521A CN 201610761802 A CN201610761802 A CN 201610761802A CN 106279521 A CN106279521 A CN 106279521A
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acrylonitrile
spinning solution
preparation
isopropanol
temperature
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CN201610761802.3A
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CN106279521B (en
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杨永岗
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Sinofibers Technology Co Ltd
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Sinofibers Technology Co Ltd
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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
    • 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
    • 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
    • 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
    • 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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  • 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)

Abstract

The present invention relates to acrylonitrile spinning solution preparation field, a kind of preparation method of acrylonitrile spinning solution, concretely comprise the following steps: solvent, acrylonitrile monemer, initiator and comonomer are put in reactor, the temperature of material in reactor is increased to 60～70 DEG C, in temperature-rise period, add tert-dodecyl mercaptan, after temperature of charge reaches 60～70 DEG C, isopropanol is added in 20～80 minutes, after reacting 20～30h after adding isopropanol, can get acrylonitrile spinning solution through removing monomer and bubble.The present invention is in polymerization process, use substep to add compounding chain-transferring agent and regulate weight average molecular weight and the number-average molecular weight of copolymer, the method simple possible, easily operates, and the final acrylonitrile copolymer molecular weight distributing index prepared can be controlled between 2.0～2.2.

Description

A kind of preparation method of acrylonitrile spinning solution
Technical field
The present invention relates to acrylonitrile spinning solution preparation field, the preparation method of a kind of acrylonitrile spinning solution.
Background technology
A series of excellent properties such as carbon fiber has heat-resisting, heat conduction, high specific strength, high ratio modulus, lightweight, extensively should For multiple fields such as Aero-Space, Leisure Sport articles for use, civil construction.
Structure that acrylonitrile copolymer is final and performance can determine structure and the performance of carbon fiber, prepare high-quality former Silk is crucial, and the spinning solution of function admirable is the premise obtaining high-quality precursor, and therefore spinning solution should have moderate dividing The features such as son is measured, Narrow Molecular Weight Distribution, good spinnability.Research finds, molecular weight distributing index propylene between 2.0～2.2 Lonitrile copolymer can prepare high performance spinning solution after de-single deaeration.With the microcosmic thing of the precursor that this spinning solution prepares Reason structure and chemical reaction homogeneity are the most excellent, and the carbon fiber strength finally given is high, and the coefficient of variation is little.But, how The molecular weight distributing index controlling acrylonitrile copolymer is technological difficulties between 2.0～2.2.
Summary of the invention
The present invention is in order to overcome the deficiency of above-mentioned technical problem, it is provided that a kind of Narrow Molecular Weight Distribution acrylonitrile spinning solution Preparation method, above-mentioned technical problem can be fully solved.
The technical scheme solving above-mentioned technical problem is as follows:
The preparation method of a kind of acrylonitrile spinning solution, adds compounding chain-transferring agent in polymerization process, described Compounding chain-transferring agent is the mixture of tert-dodecyl mercaptan and isopropanol；Concretely comprise the following steps: by solvent, acrylonitrile monemer, initiation Agent and comonomer are put in reactor, and the temperature of material in reactor is increased to 60～70 DEG C, in temperature-rise period, add Tert-dodecyl mercaptan, after temperature of charge reaches 60～70 DEG C, added isopropanol in 20～80 minutes, anti-after adding isopropanol After answering 20～30h, can get acrylonitrile spinning solution through removing monomer and bubble.
Further, described solvent is the one in dimethyl sulfoxide or dimethylformamide.
Further, described initiator is in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or dibenzoyl peroxide A kind of.
Further, described comonomer is itaconic acid, monomethyl itaconate, acrylic acid, acrylic acid methyl ester., acrylic acid Any one or two kinds in ethyl ester, ethyl methacrylate, vinylacetate, Methacrylamide or DMAA Mixture.
Further, the quality of described comonomer accounts for the 0.1～8% of acrylonitrile monemer quality.
Further, the quality of described initiator accounts for the 0.1～1% of acrylonitrile monemer quality.
Further, described compounding chain-transferring agent is that tert-dodecyl mercaptan and isopropanol are in mass ratio for 1:0.1～1 Mixture.
Further, described compounding chain-transferring agent accounts for the 0.05～0.1% of acrylonitrile monemer quality.
The invention have the advantages that the present invention, in polymerization process, uses substep to add compounding chain-transferring agent The weight average molecular weight of regulation copolymer and number-average molecular weight, the method simple possible, easily operate, the final acrylonitrile compolymer prepared Thing molecular weight distributing index can be controlled between 2.0～2.2, with the microcosmic thing of the precursor that this spinning solution wet spinning prepares Reason structure and chemical reaction homogeneity are the most excellent, and the carbon fiber strength finally given is high, and the coefficient of variation is little.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further detailed explanation.
Embodiment 1:
In reactor, put into 60kg dimethyl sulfoxide, then put into azodiisobutyronitrile 0.05kg, acrylonitrile 10kg successively, Itaconic acid 0.01kg, is increased to 65 DEG C by the temperature of material in reactor, in temperature-rise period, adds tert-dodecyl mercaptan 0.009kg, after temperature of charge reaches 65 DEG C, added isopropanol 0.001kg in 20 minutes, reacts 25h after adding isopropanol After, can get acrylonitrile spinning solution through removing monomer and bubble.
Being Mw33 ten thousand by the weight average molecular weight of the acrylonitrile spinning solution of gel chromatography survey, number-average molecular weight is Mn15.7 Ten thousand, then molecular weight distributing index is Mw/Mn=2.109.
Embodiment 2:
In reactor, put into 60kg dimethylformamide, then put into 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.01kg, acrylonitrile successively 10kg, monomethyl itaconate 0.1kg, acrylic acid 0.1kg, acrylic acid methyl ester. 0.1kg, ethyl acrylate 0.1kg, methacrylic acid Ethyl ester 0.1kg, vinylacetate 0.1kg, Methacrylamide 0.1kg, DMAA 0.1kg, by thing in reactor The temperature of material is increased to 60 DEG C, in temperature-rise period, adds tert-dodecyl mercaptan 0.004kg, after temperature of charge reaches 60 DEG C, Adding isopropanol 0.002kg in 80 minutes, after reacting 20h after adding isopropanol, through removing monomer and bubble, wet spinning can obtain To acrylonitrile spinning solution.
Being Mw32.8 ten thousand by the weight average molecular weight of the acrylonitrile spinning solution of gel chromatography survey, number-average molecular weight is Mn15 Ten thousand, then molecular weight distributing index is Mw/Mn=2.186.
Embodiment 3:
In reactor, put into 60kg dimethylformamide, then put into dibenzoyl peroxide 0.1kg, acrylonitrile successively 10kg, ethyl methacrylate 0.2kg, vinylacetate 0.2kg, the temperature of material in reactor is increased to 70 DEG C, heats up During, add tert-dodecyl mercaptan 0.004kg, after temperature of charge reaches 70 DEG C, in 50 minutes, add isopropanol, add After reacting 30h after isopropanol, through removing monomer and bubble, wet spinning can get acrylonitrile spinning solution.
Being Mw31.3 ten thousand by the weight average molecular weight of the acrylonitrile spinning solution of gel chromatography survey, number-average molecular weight is Mn14.8 Ten thousand, then molecular weight distributing index is Mw/Mn=2.114.
The precursor performance parameter obtained through wet spinning with the spinning solution of above-described embodiment 1～3 is as shown in table 1:
Table 1
Embodiment Intensity (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
The present invention, in polymerization process, uses substep to add compounding chain-transferring agent and regulates the Weight-average molecular of copolymer Amount and number-average molecular weight, the method simple possible, easily operate, and the final acrylonitrile copolymer molecular weight distributing index prepared is controlled System is between 2.0～2.2, and the microphysics structure of precursor and the chemical reaction homogeneity that prepare with this spinning solution all compare Excellence, the carbon fiber strength finally given is high, and the coefficient of variation is little.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction, every depends on According to any simple modification in the technical spirit of the present invention, above example made, equivalent variations, each fall within the guarantor of the present invention Within the scope of protecting.

Claims (8)

1. the preparation method of an acrylonitrile spinning solution, it is characterised in that add compounding chain tra nsfer in polymerization process Agent, the described mixture that compounding chain-transferring agent is tert-dodecyl mercaptan and isopropanol；Concretely comprise the following steps: by solvent, acrylonitrile Monomer, initiator and comonomer are put in reactor, the temperature of material in reactor is increased to 60～70 DEG C, heated up Cheng Zhong, adds tert-dodecyl mercaptan, after temperature of charge reaches 60～70 DEG C, adds isopropanol, add in 20～80 minutes After reacting 20～30h after isopropanol, can get acrylonitrile spinning solution through removing monomer and bubble.
The preparation method of acrylonitrile spinning solution the most according to claim 1, it is characterised in that described solvent is diformazan One in base sulfoxide or dimethylformamide.
The preparation method of acrylonitrile spinning solution the most according to claim 1, it is characterised in that described initiator is even One in nitrogen bis-isobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or dibenzoyl peroxide.
The preparation method of acrylonitrile spinning solution the most according to claim 1, it is characterised in that described comonomer is Itaconic acid, monomethyl itaconate, acrylic acid, acrylic acid methyl ester., ethyl acrylate, ethyl methacrylate, vinylacetate, first Any one or the mixture of two kinds in base acrylamide or DMAA.
The preparation method of acrylonitrile spinning solution the most according to claim 1, it is characterised in that described comonomer Quality accounts for the 0.1～8% of acrylonitrile monemer quality.
The preparation method of acrylonitrile spinning solution the most according to claim 1, it is characterised in that the matter of described initiator Amount accounts for the 0.1～1% of acrylonitrile monemer quality.
The preparation method of acrylonitrile spinning solution the most according to claim 1, it is characterised in that described compounding chain tra nsfer The mixture that agent is tert-dodecyl mercaptan and isopropanol is 1:0.1～1 in mass ratio.
The preparation method of acrylonitrile spinning solution the most according to claim 1, it is characterised in that described compounding chain tra nsfer Agent accounts for the 0.05～0.1% of acrylonitrile monemer quality.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
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
CN111004350A (en) * 2019-12-27 2020-04-14 山东非金属材料研究所 Preparation method of acrylonitrile-itaconic acid copolymer standard substance
CN114687010A (en) * 2022-04-18 2022-07-01 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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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111004350A (en) * 2019-12-27 2020-04-14 山东非金属材料研究所 Preparation method of acrylonitrile-itaconic acid copolymer standard substance
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
CN114687010A (en) * 2022-04-18 2022-07-01 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
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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