CN104710565A - Preparation method of ternary polyacrylonitrile copolymer - Google Patents
Preparation method of ternary polyacrylonitrile copolymer Download PDFInfo
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- CN104710565A CN104710565A CN201510117463.0A CN201510117463A CN104710565A CN 104710565 A CN104710565 A CN 104710565A CN 201510117463 A CN201510117463 A CN 201510117463A CN 104710565 A CN104710565 A CN 104710565A
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- polyacrylonitrile copolymer
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Abstract
The invention relates to a preparation method of a ternary polyacrylonitrile copolymer, which comprises the steps of heating an aqueous solution of maleic anhydride, acrylamide and a dispersing agent to 55-75 DEG C under a nitrogen shielding condition, adding acrylonitrile to keep constant temperature for 20-30min, adding an initiator solution for reaction for 3-12h, and carrying out washing, demonomerisation, filtration and drying. The method employs a mixed solvent precipitation polymerization method for polymerization and has the advantages of high reaction yield, high viscosity average molecular weight, narrow distribution, easiness in temperature control, stable product quality and the like. The thermal property of the polyacrylonitrile copolymer prepared by the method can be effectively improved, and the copolymer has certain practical application prospects.
Description
Technical field
The invention belongs to the preparation field of carbon fibre precursor polyacrylonitrile, particularly a kind of preparation method of ternary polyacrylonitrile copolymer.
Background technology
Carbon fiber has a series of excellent properties such as high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, antifatigue, conduction, damping, heat transfer, radioprotective and proportion is little, is widely used in the industries such as aerospace, military and national defense, environmental protection, medicine equipment and sports goods.From homogeneity and the carbon yield of structure, homo-polypropylene nitrile is seemingly optimal.But exothermic peak is narrow during the preoxidation of homo-polypropylene nitrile, heat release is concentrated, and peak temperature is about 282 DEG C and easily blows fiber.Therefore, certain copolymerization component to be added with in the polymer, make in preoxidation, cause cyano group cyclisation and exothermic peak moves to low temperature side, make homo-polypropylene nitrile free radical type cyclization change ionic cyclization into, thus reduce cyclization exotherm rate, make reaction be easy to control.In addition, homo-polypropylene nitrile internal cohesive energy is large, and poorly soluble, fiber is stiff, and introducing comonomer can improving SNR.The production of polyacrylonitrile copolymer mainly utilizes the principle of radical polymerization, adopts the method for solution polymerization or precipitation polymerization to obtain.Mixed solvent precipitation polymerization adopts organic solvent and water mixed solution as reaction medium, in polymerization process, can form white flock precipitate after acrylonitrile polymer reaches certain polymerization degree, separate out from blending agent, this method has the two-fold advantage of aqueous suspension polymerization and homogeneous solution polymerization.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of ternary polyacrylonitrile copolymer, it is the 3rd comonomer that the inventive method adopts maleic anhydride to be the second comonomer acrylamide, mixed solvent precipitation polymerization process is adopted to prepare carbon fibre precursor polyacrylonitrile polymer, improve the high molecular structural regularity of polyacrylonitrile, improve its thermostability at hot stage.
The preparation method of a kind of ternary polyacrylonitrile copolymer of the present invention, comprising:
Under nitrogen protection condition, the aqueous solution of second comonomer maleic anhydride, Third monomer acrylamide, dispersion agent is warming up to 55-75 DEG C, add monomers acrylonitrile constant temperature 20-30min, then add initiator solution initiated polymerization, reaction 3-12h, obtains acrylonitrile polymer slurry, washing, take off list, filter to obtain white solid, dry, obtain ternary polyacrylonitrile copolymer; Wherein the mass ratio of vinyl cyanide, maleic anhydride, acrylamide is 96:2.5:1.5-98:1:1.
Described vinyl cyanide, maleic anhydride, acrylamide consumption account for the 16-30wt% of total mass (reaction system).
Described dispersion agent is polyvinyl alcohol, and consumption is the 0.5-2.0% of vinyl cyanide, maleic anhydride, acrylamide total mass.
Described polyvinyl alcohol be polyvinyl alcohol 1755, polyvinyl alcohol 1788, polyvinyl alcohol 1799 one or more.
The solvent of described initiator solution is organic solvent.
Described organic solvent is the one in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE.
The mass ratio of described organic solvent and water is 90:10-10:90.
Initiator in described initiator solution is Diisopropyl azodicarboxylate, and initiator amount is the 0.1-2.0% of vinyl cyanide, maleic anhydride, acrylamide total mass.
Described washing is that dehydrated alcohol and warm water wash 3-5 time.
Described drying temperature is 50-60 DEG C, and the time is 24-48h.
The viscosity-average molecular weight of described ternary polyacrylonitrile copolymer is 2.84 × 10
5-3.36 × 10
5, molecular weight is 1.20-1.91.
Transformation efficiency of the present invention is greater than 86%.
The preparation method of the ternary polyacrylonitrile copolymer of a kind of high conversion height molecular-weight average of the present invention, this invention is the second comonomer with maleic anhydride, acrylamide is the 3rd comonomer, mixed solvent precipitation polymerization process is adopted to prepare carbon fibre precursor polyacrylonitrile polymer, improve the high molecular structural regularity of polyacrylonitrile, improve its thermostability at hot stage.
beneficial effect
(1) in the present invention, Diisopropyl azodicarboxylate initiation reaction is comparatively stable, for first order reaction, do not have side reaction, activation energy lower (29.76kJ/mol) and the moderate better control of rate of decomposition, can reach the requirement of high conversion within the shorter reaction times;
(2) present invention process is simple, and the reaction times is shorter;
(3) polymerization process of the present invention is mild, decreases concentrated heat release, avoids the impact of acceleration effect;
(4) polyacrylonitrile copolymer of the present invention by regulating the different mass ratio of solvent and water can obtain narrow molecular weight distribution (1.20-1.91);
(5) polyacrylonitrile polymer that prepared by the present invention effectively can improve its High Temperature Pre oxidation stage thermal characteristics, has certain application prospect;
(6) the present invention utilizes mixed solvent precipitation polymerization process to be polymerized, there is reaction yield high, high and the narrowly distributing of average viscosity-average molecular weight, easy temperature control system, the advantages such as constant product quality, polyacrylonitrile copolymer prepared by the present invention can effectively improve its thermal characteristics, has certain actual application prospect.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
First the aqueous solution of maleic anhydride, acrylamide and polyvinyl alcohol is warmed up to 65 DEG C under nitrogen protection; then add acrylonitrile monemer constant temperature 30min, finally add the dimethyl sulphoxide solution being dissolved with Diisopropyl azodicarboxylate, reaction 6h; obtaining transformation efficiency is 91.7%, and viscosity-average molecular weight is 2.97 × 10
5, molecular weight distribution is the polyacrylonitrile copolymer of 1.56.Under nitrogen atmosphere, DSC test (uses U.S. TA company Q20 differential scanning calorimeter, 310 DEG C are risen to from 30 DEG C) with the speed of 5 DEG C/min, its cyclisation starting temperature comparatively homo-polypropylene nitrile (prepared by same polymeric condition, viscosity-average molecular weight 30.2 ten thousand) reduces by 27.6 DEG C; Cyclisation thermal discharge is 567.3J/g, and comparatively acrylonitrile homopolymer thermal discharge adds 54.4J/g, and the increase of cyclisation thermal discharge shows that cyclization degree improves.Each amount of substance is in table 1.
Table 1
| Formula | Vinyl cyanide | Maleic anhydride | Acrylamide | Polyvinyl alcohol | Diisopropyl azodicarboxylate | Dimethyl sulfoxide (DMSO) | Deionized water |
| Weight | 22.54g | 0.23g | 0.23g | 0.23g | 0.23g | 69.3g | 7.7g |
Embodiment 2
According to the formula of table 2; first the aqueous solution of maleic anhydride, acrylamide and polyvinyl alcohol is warmed up to 65 DEG C under nitrogen protection; then acrylonitrile monemer constant temperature 30min is added; finally add the dimethyl sulphoxide solution being dissolved with Diisopropyl azodicarboxylate; reaction 6h; obtaining transformation efficiency is 90.3%, and viscosity-average molecular weight is 2.89 × 10
5, molecular weight distribution is the polyacrylonitrile copolymer of 1.74.Under nitrogen atmosphere, DSC test (uses U.S. TA company Q20 differential scanning calorimeter, 310 DEG C are risen to from 30 DEG C) with the speed of 5 DEG C/min, its cyclisation starting temperature comparatively homo-polypropylene nitrile (prepared by same polymeric condition, viscosity-average molecular weight 30.8 ten thousand) reduces by 29.0 DEG C; Cyclisation thermal discharge is 598.9J/g, and comparatively acrylonitrile homopolymer thermal discharge adds 67.5J/g, and the increase of cyclisation thermal discharge shows that cyclization degree improves.
Table 2
| Formula | Vinyl cyanide | Maleic anhydride | Acrylamide | Polyvinyl alcohol | Diisopropyl azodicarboxylate | Dimethyl sulfoxide (DMSO) | Deionized water |
| Weight | 24.25g | 0.50g | 0.25g | 0.13g | 0.23g | 60.0g | 15g |
Embodiment 3
First the aqueous solution of maleic anhydride, acrylamide and polyvinyl alcohol is warmed up to 65 DEG C under nitrogen protection according to the formula of table 3; then acrylonitrile monemer constant temperature 30min is added; finally add the dimethyl sulphoxide solution being dissolved with Diisopropyl azodicarboxylate; reaction 6h; obtaining transformation efficiency is 94.6%, and viscosity-average molecular weight is 3.06 × 10
5, molecular weight distribution is the polyacrylonitrile copolymer of 1.91.Under nitrogen atmosphere, DSC test (uses U.S. TA company Q20 differential scanning calorimeter, 310 DEG C are risen to from 30 DEG C) with the speed of 5 DEG C/min, its cyclisation starting temperature comparatively homo-polypropylene nitrile (prepared by same polymeric condition, viscosity-average molecular weight 32.5 ten thousand) reduces by 31.4 DEG C; Cyclisation thermal discharge is 634.9J/g, and comparatively acrylonitrile homopolymer thermal discharge adds 54.2J/g, and the increase of cyclisation thermal discharge shows that cyclization degree improves.
Table 3
| Formula | Vinyl cyanide | Maleic anhydride | Acrylamide | Polyvinyl alcohol | Diisopropyl azodicarboxylate | Dimethyl sulfoxide (DMSO) | Deionized water |
| Weight | 24.25g | 0.38g | 0.37g | 0.37g | 0.38g | 52.5g | 22.5g |
Claims (10)
1. a preparation method for ternary polyacrylonitrile copolymer, comprising:
Under nitrogen protection condition, the aqueous solution of maleic anhydride, acrylamide, dispersion agent is warming up to 55-75 DEG C, adds vinyl cyanide constant temperature 20-30min, then initiator solution is added, reaction 3-12h, washing, de-single, filtration, dry, obtain ternary polyacrylonitrile copolymer; Wherein the mass ratio of vinyl cyanide, maleic anhydride, acrylamide is 96:2.5:1.5-98:1:1.
2. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 1, is characterized in that: described maleic anhydride, acrylamide, vinyl cyanide consumption are the 16-30wt% of total mass.
3. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 1, is characterized in that: described dispersion agent is polyvinyl alcohol, consumption is the 0.5-2.0% of vinyl cyanide, maleic anhydride, acrylamide total mass.
4. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 3, is characterized in that: described polyvinyl alcohol be polyvinyl alcohol 1755, polyvinyl alcohol 1788, polyvinyl alcohol 1799 one or more.
5. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 1, is characterized in that: the solvent of described initiator solution is organic solvent, and the mass ratio of organic solvent and water is 90:10-10:90.
6. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 5, is characterized in that: described organic solvent is the one in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE.
7. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 1, it is characterized in that: the initiator in initiator solution is Diisopropyl azodicarboxylate, initiator amount is the 0.1-2.0wt% of vinyl cyanide, maleic anhydride, acrylamide total mass.
8. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 1, it is characterized in that: described drying temperature is 50-60 DEG C, time of drying is 24-48h.
9. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 1, is characterized in that: the viscosity-average molecular weight of described ternary polyacrylonitrile copolymer is 2.84 × 10
5-3.36 × 10
5, molecular weight is 1.20-1.91.
10. the preparation method of a kind of ternary polyacrylonitrile copolymer according to claim 1, is characterized in that: transformation efficiency is greater than 86%.
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Cited By (4)
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| CN107245770A (en) * | 2017-02-16 | 2017-10-13 | 王和军 | A kind of tencel for neutralizing soda acid |
| CN108441979A (en) * | 2018-04-27 | 2018-08-24 | 芜湖天科生物科技有限公司 | A kind of antibacterial conductive fiber and preparation method thereof |
| CN111088529A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing high-performance thermal stabilization fiber by controlling chemical structure of polyacrylonitrile carbon |
| US11046792B2 (en) | 2017-09-29 | 2021-06-29 | Lg Chem, Ltd. | Method of preparing (meth)acrylonitrile-based polymer for preparing carbon fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107245770A (en) * | 2017-02-16 | 2017-10-13 | 王和军 | A kind of tencel for neutralizing soda acid |
| US11046792B2 (en) | 2017-09-29 | 2021-06-29 | Lg Chem, Ltd. | Method of preparing (meth)acrylonitrile-based polymer for preparing carbon fiber |
| CN108441979A (en) * | 2018-04-27 | 2018-08-24 | 芜湖天科生物科技有限公司 | A kind of antibacterial conductive fiber and preparation method thereof |
| CN111088529A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing high-performance thermal stabilization fiber by controlling chemical structure of polyacrylonitrile carbon |
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