CN103421141A - Polyacrylonitrile copolymer spinning solution and preparation method thereof - Google Patents
Polyacrylonitrile copolymer spinning solution and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyacrylonitrile copolymer spinning solution and a preparation method thereof. In the invention, copolymerization reaction is performed on acrylonitrile in a tubular reactor containing a static mixer component; the tubular reactor, which contains the static mixer component and has the characteristics of mass transfer, efficient heat transfer, continuous and stable reaction and no mechanical stirring, is adopted to prepare the polyacrylonitrile copolymer spinning solution with high molecular weight and narrow molecular weight distribution. The polyacrylonitrile copolymer spinning solution is obtained after copolymerization reaction is performed on reaction liquid composed of monomers, a radical initiator and a solvent, wherein the percent concentration by weight of the monomers in the reaction liquid is 15% to 20%; the weight of the radical initiator is 0.4% to 1% of that of the monomers; the solvent is in balancing amount; the monomers are an acrylonitrile monomer and a comonomer. The dynamic viscosity of the polyacrylonitrile copolymer spinning solution provided by the invention is 200 to 800 Pa.S, and the molecular weight distribution is 1.5 to 2.6.
Description
Technical field
The invention belongs to the polyacrylonitrile preparation field, particularly a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions and the preparation method of fast and stable thereof.
Background technology
Carbon fiber has the characteristics such as high specific strength, high ratio modulus, heat-resisting, corrosion-resistant, antifatigue, creep resistance, is a kind of high performance fibre material, has been widely used in the industries such as aerospace, national defense construction, Leisure Sport articles for use, medicine equipment and building.PAN-based carbon fiber has outstanding mechanical property, is carbon fiber research in recent years and industrialized focus.The key of restriction PAN-based carbon fiber development is the quality of polyacrylonitrile fibril, and will obtain the high-quality polyacrylonitrile fibril, must set about from synthetic high-quality polyacrylonitrile copolymer spinning fluid and optimization spinning technique two aspects, only have the polyacrylonitrile copolymer spinning fluid of excellent performance just can spin out the polyacrylonitrile fibril of high-quality, thereby prepare high performance PAN-based carbon fiber.Theoretical and experimental study shows, desirable polyacrylonitrile multipolymer should have suitable high molecular and narrow molecular weight distributions, moderate and stable apparent viscosity, without bad structures such as Branching and cross-linkings; Wherein in microcosmic aspect polyacrylonitrile multipolymer macromolecular chain, stable preparation, the viscosity of the composition of copolymerization structural unit, distribution and macroscopical aspect polyacrylonitrile multipolymer are evenly important factor in order.
Mostly current domestic carbon fiber is to adopt solution polymerization process to prepare with azo-initiator with polyacrylonitrile, adopt batchwise polymerization, because the acrylonitrile polymerization heat release is more violent, and the system viscosity in the polymerization later stage is larger, cause mass transfer, heat transfer difficulty, reaction is difficult to control, thereby the polyacrylonitrile molecular weight distribution is broadened, gel content increases, the raising of the follow-up fibre property of remarkably influenced; At first from the angle of polymer production technique, intermittently its main reaction of autoclave polymerization is transient, heat release is concentrated, viscosity changes greatly, be difficult to provide a kind of rational whipped form to take into account the fast heat release of the initial low viscosity of polymerization and the slow heat release of the high viscosity in polymerization later stage, chain transfer reaction to solvent easily occurs when result causes polymerization, is unfavorable for preparing high-molecular weight polymer; Secondly in high conversion, high viscosity stage, gel effect easily occurs, cause polymerization stoste the change of molecular weight large, distribution broadens; Moreover high in polymerization later stage viscosity, cause material stirring in still to mix difficulty, in still, material is removed the heat difficulty, is prone to the implode phenomenon, thereby the production of polymerization stoste is difficult to stable carrying out.Poor in microphysics structure and chemical reactivity upward stability with the precursor of this multipolymer spinning, carbon fiber stably manufactured and performance are all had a negative impact.
Summary of the invention
A purpose of the present invention is to overcome the deficiency that above-mentioned prior art exists, provide a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
A further object of the present invention is to provide the copolymerization that completes vinyl cyanide in a kind of tubular reactor containing the static mixer assembly, steadily control polymerization process, the synthetic viscosity of fast and stable is even, the method for the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
An also purpose of the present invention is to provide a kind of tubular reactor that contains the static mixer assembly.
The present invention adopts propylene copolymerization nitrile in the tubular reactor that contains the static mixer assembly, (on principle, it belongs to piston flow reactor to the tubular reactor that utilization contains the static mixer assembly, relatively be applicable to the sticky system of height as polyacrylonitrile spinning solution, can accomplish to force preferably, reinforcing mass transfer and heat transfer, control the steady of polymerization process thereby be beneficial to, contribute to the viscosity of stable product and narrow form to distribute) there is mass transfer, conduct heat efficient, the reaction continuous and stable, without characteristics such as mechanical stirring, the preparation high molecular, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The tubular reactor that contains the static mixer assembly utilized in the present invention comprises by the static mixer assembly is installed in pipe, and mobile internal circulation pump and the necessary formations such as coupling of pipe, pressure reaction solution of endless tube chuck is installed outside pipe.
The described tubular reactor that contains the static mixer assembly can be connected in series a plurality of described pipes by the ring flange of installing on the pipe in forming described tubular reactor, is combined into the tubular reactor that contains the static mixer assembly of multistage.
One end of described pipe is connected with described internal circulation pump by pipeline, and the other end of described internal circulation pump is connected with the other end of described pipe by pipeline.
Be provided with material inlet on the pipeline of described internal circulation pump one end, on the pipeline of the other end, be provided with discharge port.
Further be provided with thief hole on pipeline before described discharge port.
Be separately installed with tensimeter on the pipeline at described internal circulation pump two ends.
On described pipeline, temperature control sensor is installed.
Be respectively arranged with water-in and water outlet on described endless tube chuck.
Described static mixer assembly is one or more the combination in the static mixer assemblies such as SK type, SX type, SH type.
Described internal circulation pump is toothed gear pump or the satisfactory pump of other form.
Described water-in is connected with the outer circulation pump by pipeline; Described outer circulation pump can be water pump, toothed gear pump or the satisfactory pump of other form.
Be connected with the water-cycling-media of temperature controllable in described endless tube chuck, required heat of polymerization initial stage is provided, the polymerization later stage is taken away the polymerization heat, remains on the temperature-stable of the polyacrylonitrile copolymerization in the tubular reactor that contains the static mixer assembly.
Introduce hydrophilic cosegment in polyacrylonitrile, build the polyacrylonitrile multipolymer, improved spinning solution thermostability, improved spinning property.
Polyacrylonitrile copolymer spinning fluid of the present invention, not only have high viscosity homogeneity, narrow molecular weight distribution, and possess high molecular weight, fast rate of polymerization and possess excellent spinning property.
Viscosity of the present invention is even, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions is that the reaction solution consisted of monomer, radical initiator and solvent obtains after copolymerization, wherein:
The weight percent concentration of the monomer in described reaction solution is 15～30%, and described radical initiator is 0.4～1% of described monomer weight; Surplus is solvent.
The kinetic viscosity of described polyacrylonitrile copolymer spinning fluid is that 200～800Pa.S(is to record under 45 ℃ in temperature).
The weight-average molecular weight of described polyacrylonitrile copolymer spinning fluid is 80000～200000.
The molecular weight distribution of described polyacrylonitrile copolymer spinning fluid is 1.5～2.6.
Described monomer is acrylonitrile monemer and comonomer, and described acrylonitrile monemer accounts for 90～99.5% of described total monomer weight, and described comonomer accounts for 0.5～10% of described total monomer weight.
Described comonomer is selected from one or both in methylene-succinic acid, vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, Methacrylamide, the two methyl esters of methylene-succinic acid, the two butyl esters of methylene-succinic acid.
Described radical initiator can be Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or their mixture.
Described solvent is dimethyl sulfoxide (DMSO), dimethyl formamide or N,N-DIMETHYLACETAMIDE.
Viscosity of the present invention is even, the preparation method of the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions comprises the following steps:
(1) solvent and the monomer that will account for solvent total amount 90～98wt% join in the batching kettle (as the stainless steel batching kettle with mechanical stirring device) with mechanical stirring device, be uniformly mixed (time generally be uniformly mixed is about 30 minutes) under room temperature, and carried out emptying deoxygenation with rare gas element (as nitrogen) in the process be uniformly mixed;
(2) radical initiator is joined in the container that is mounted with the solvent that accounts for solvent total amount 2～10wt%, carry out the rapid stirring dissolving under room temperature;
(3) under rare gas element (as nitrogen) protection and stirring, the disposable radical initiator solution that step (2) is obtained is put in the batching kettle of step (1), carry out rapid stirring (time of general rapid stirring is 1～2 minute) and obtain reaction solution under room temperature, wherein, the weight percent concentration of the described monomer in reaction solution is 15～30%, and described radical initiator is 0.4～1% of described monomer weight; Surplus is solvent;
(4) utilize the outer circulation pump, injected water in endless tube chuck outside pipe in the tubular reactor that contains from the static mixer assembly to formation, by the disposable pipe that is injected into fast the tubular reactor that contains the static mixer assembly of the reaction solution obtained in step (3) batching kettle; Regulate the water temperature in chuck by temperature control sensor, the temperature that makes reaction solution in pipe is 30～70 ℃, and the mixing (flow velocity of preferred reaction liquid is 50～200 ml/min) that utilizes that internal circulation pump is forced, the strengthening reaction solution circulates in the pipe that static mixer assembly (the static mixer assembly plays mixing) is installed, make reaction solution carry out copolymerization 3～12 hours, discharging after copolymerization completes, remove residual monomer and bubble, the acquisition viscosity of fast and stable is even, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
Described monomer is acrylonitrile monemer and comonomer, and described acrylonitrile monemer accounts for 90～99.5% of described total monomer weight, and described comonomer accounts for 0.5～10% of described total monomer weight.
Described comonomer is selected from one or both in methylene-succinic acid, vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, Methacrylamide, the two methyl esters of methylene-succinic acid, the two butyl esters of methylene-succinic acid.
Described radical initiator can be Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or their mixture.
Described solvent is dimethyl sulfoxide (DMSO), dimethyl formamide or N,N-DIMETHYLACETAMIDE.
Beneficial effect of the present invention:
1. by inside and outside two recycle pumps, take certain speed of circulation (flow velocity of preferred reaction liquid is 50～200 ml/min), pressure is carried out efficient mass transfer, heat transfer to polyacrylonitrile copolyreaction liquid, mass transfer, the heat transmission function of strengthening static mixer assembly, make material concentration, temperature in copolymerization process steady, be beneficial to the control copolymerization, the molecular weight high (> 80000 of gained polyacrylonitrile copolymer spinning fluid), molecular weight distribution significantly reduces, monomer composition is evenly distributed, stable viscosity.
2. adopt the radical initiator of low temperature, improved the molecular weight of polyacrylonitrile multipolymer, reduced the generation of the crosslinked and microgel in side reaction, the copolymerization process such as the oxidation of polyacrylonitrile multipolymer, the polyacrylonitrile copolymer spinning fluid look obtained is shallow transparent simultaneously.
3. the radical initiator of reinforcing mass transfer, heat transfer and employing low temperature, can also significantly improve copolymerization efficiency, improves throughput, improves plant factor.
4. synthesis technique of the present invention is simple, and stable reaction conditions is easily controlled, and the polyacrylonitrile copolymerization product viscosity of gained evenly, narrow molecular weight distribution, spinning solution good spinnability, can to lead multiple high, and the precursor prepared has the intensity advantages of higher.
The accompanying drawing explanation
The schematic diagram that Fig. 1 is the tubular reactor that contains the static mixer assembly.
The spectrogram of the gel permeation chromatography (GPC) that Fig. 2 is the polyacrylonitrile multipolymer that obtains of the embodiment of the present invention 4.
Reference numeral
1. endless tube chuck 2. static mixer assembly 3. internal circulation pump a. material inlet b. discharge ports
Embodiment
Embodiment 1
As shown in Figure 1, the tubular reactor that contains the static mixer assembly comprises by static mixer assembly 2 is installed in the pipe of making at stainless material, and the formations such as the pipe of endless tube chuck 1 and internal circulation pump 3 are installed outside pipe; And be connected in series four described pipes by the ring flange of installing on the pipe in forming described tubular reactor, be combined into the tubular reactor that contains the static mixer assembly of four sections.
An end that is combined into first the described pipe in the tubular reactor that contains the static mixer assembly of four sections is connected with an end of described internal circulation pump 3 by pipeline, and on this pipeline, tensimeter is installed; On second the described pipe be connected in series with first described pipe, temperature control sensor is installed, and is provided with material inlet a; The other end of described internal circulation pump 3 is connected with an end of the 4th the described pipe be connected in series by pipeline, and on this pipeline, be provided with on the pipeline before discharge port b(discharge port further be provided with thief hole), and tensimeter is installed.
Be respectively arranged with water-in and water outlet on described endless tube chuck, the intake-outlet on four endless tube chucks is connected mutually, and is connected with the outer circulation pump by pipeline.
Described internal circulation pump is toothed gear pump; Described outer circulation pump is water pump or toothed gear pump.
Described static mixer assembly is one or more the combination in the static mixer assemblies such as SK type, SX type, SH type.
Utilize the above-mentioned tubular reactor that contains the static mixer assembly to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 30Kg solvent dimethyl sulfoxide (DMSO) joins in the stainless steel batching kettle with mechanical stirring device together with 8.536Kg vinyl cyanide, 176g methyl acrylate, 88g methylene-succinic acid, stirring at room is mixed about 30 minutes, and uses the emptying deoxygenation of nitrogen bubble in the process be uniformly mixed;
(2) accurately take 1.2Kg solvent dimethyl sulfoxide (DMSO) and join in container together with 61.6g radical initiator Diisopropyl azodicarboxylate, the room temperature rapid stirring dissolves;
(3) under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put in the batching kettle of step (1), and the mixing of room temperature rapid stirring obtains reaction solution in 2 minutes;
(4) utilize the outer circulation water pump, the water that in endless tube chuck outside four pipes in being combined into the tubular reactor that contains the static mixer assembly of four sections, implantation temperature is 61 ℃, valve under opening steps (3) batching kettle, rely on that gravity is disposable to be injected in the pipe of the tubular reactor that contains the static mixer assembly by the reaction solution in batching kettle fast by material inlet; Regulate the water temperature in chuck by temperature control sensor, make the temperature-stable of reaction solution in pipe at 61 ± 1 ℃, and utilize that the internal recycle toothed gear pump is forced, the strengthening reaction solution circulates mixing in four pipes that the static mixer assembly is installed with the speed of 100 ml/min, carry out copolymerization 7 hours, then under 2kg pressure, pass through discharge hole for discharge; Vacuumize and remove residual monomer and bubble in de-single, deaeration still, fast and stable obtain a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The transformation efficiency of acrylonitrile monemer is 72%, and the weight-average molecular weight that records the polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC) is 9.5 ten thousand, and molecular weight distribution is 2.4, and kinetic viscosity is 368Pa.S(45 ℃).Carry out wet spinning under standard conditions, obtain the rounded section precursor, its fiber number is that 1.2dtex, intensity are that 5.4cN/dtex, elongation at break are 13%.
Embodiment 2
Utilize the tubular reactor that contains the static mixer assembly of embodiment 1 to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 28.4Kg solvent dimethyl formamide joins in the stainless steel batching kettle with mechanical stirring device together with 9.408Kg vinyl cyanide, 192g methacrylic acid, stirring at room is mixed about 30 minutes, and uses the emptying deoxygenation of nitrogen bubble in the process be uniformly mixed;
(2) accurately take 2Kg solvent dimethyl formamide and join in container together with 57.6g radical initiator Diisopropyl azodicarboxylate, the room temperature rapid stirring dissolves;
(3) under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put in the batching kettle of step (1), and the mixing of room temperature rapid stirring obtains reaction solution in 2 minutes;
(4) utilize the outer circulation water pump, the water that in endless tube chuck outside four pipes in being combined into the tubular reactor that contains the static mixer assembly of four sections, implantation temperature is 65 ℃, valve under opening steps (3) batching kettle, rely on that gravity is disposable to be injected in the pipe of the tubular reactor that contains the static mixer assembly by the reaction solution in batching kettle fast by material inlet; Regulate the water temperature in chuck by temperature control sensor, make the temperature-stable of reaction solution in pipe at 65 ± 1 ℃, and utilize that the internal recycle toothed gear pump is forced, the strengthening reaction solution circulates mixing in four pipes that the static mixer assembly is installed with the speed of 100 ml/min, carry out copolymerization 5 hours, then under 2kg pressure, pass through discharge hole for discharge; Vacuumize and remove residual monomer and bubble in de-single, deaeration still, fast and stable obtain a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The transformation efficiency of acrylonitrile monemer is 83%, and the weight-average molecular weight that records the polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC) is 100,000, and molecular weight distribution is 2.4, and kinetic viscosity is 585Pa.S(45 ℃).Carry out wet spinning under standard conditions, obtain the rounded section precursor, its fiber number is that 1.17dtex, intensity are that 5.6cN/dtex, elongation at break are 12%.
Embodiment 3
Utilize the tubular reactor that contains the static mixer assembly of embodiment 1 to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 26.8Kg solvent dimethyl sulfoxide (DMSO) joins in the stainless steel batching kettle with mechanical stirring device together with 10.864Kg vinyl cyanide, 224g acrylamide, 112g methylene-succinic acid, stirring at room is mixed about 30 minutes, and uses the emptying deoxygenation of nitrogen bubble in the process be uniformly mixed;
(2) accurately take 2Kg solvent dimethyl formamide and join in container together with 67.2g radical initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), the room temperature rapid stirring dissolves;
(3) under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put in the batching kettle of step (1), and the mixing of room temperature rapid stirring obtains reaction solution in 2 minutes;
(4) utilize the outer circulation water pump, the water that in endless tube chuck outside four pipes in being combined into the tubular reactor that contains the static mixer assembly of four sections, implantation temperature is 52 ℃, valve under opening steps (3) batching kettle, rely on that gravity is disposable to be injected in the pipe of the tubular reactor that contains the static mixer assembly by the reaction solution in batching kettle fast by material inlet; Regulate the water temperature in chuck by temperature control sensor, make the temperature-stable of reaction solution in pipe at 52 ± 1 ℃, and utilize that the internal recycle toothed gear pump is forced, the strengthening reaction solution circulates mixing in four pipes that the static mixer assembly is installed with the speed of 75 ml/min, carry out copolymerization 3 hours, then under 2kg pressure, pass through discharge hole for discharge; Vacuumize and remove residual monomer and bubble in de-single, deaeration still, fast and stable obtain a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The transformation efficiency of acrylonitrile monemer is 68%, and the weight-average molecular weight that records the polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC) is 120,000, and molecular weight distribution is 2.2, and kinetic viscosity is 673Pa.S(45 ℃).Carry out wet spinning under standard conditions, obtain the rounded section precursor, its fiber number is that 1.01dtex, intensity are that 6.1cN/dtex, elongation at break are 11%.
Embodiment 4
Utilize the tubular reactor that contains the static mixer assembly of embodiment 1 to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 30.2Kg solvent dimethyl sulfoxide (DMSO) joins in the stainless steel batching kettle with mechanical stirring device together with 8.624Kg vinyl cyanide, the two methyl esters of 88g methylene-succinic acid, 88g methylene-succinic acid, stirring at room is mixed about 30 minutes, and uses the emptying deoxygenation of nitrogen bubble in the process be uniformly mixed;
(2) accurately take 1Kg solvent dimethyl sulfoxide (DMSO) and join in container together with 44g radical initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), the room temperature rapid stirring dissolves;
(3) under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put in the batching kettle of step (1), and the mixing of room temperature rapid stirring obtains reaction solution in 2 minutes;
(4) utilize the outer circulation water pump, the water that in endless tube chuck outside four pipes in being combined into the tubular reactor that contains the static mixer assembly of four sections, implantation temperature is 50 ℃, valve under opening steps (3) batching kettle, rely on that gravity is disposable to be injected in the pipe of the tubular reactor that contains the static mixer assembly by the reaction solution in batching kettle fast by material inlet; Regulate the water temperature in chuck by temperature control sensor, make the temperature-stable of reaction solution in pipe at 50 ± 1 ℃, and utilize that the internal recycle toothed gear pump is forced, the strengthening reaction solution circulates mixing in four pipes that the static mixer assembly is installed with the speed of 100 ml/min, carry out copolymerization 6 hours, then under 2kg pressure, pass through discharge hole for discharge; Vacuumize and remove residual monomer and bubble in de-single, deaeration still, fast and stable obtain a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The transformation efficiency of acrylonitrile monemer is 75%, and the weight-average molecular weight that records the polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC) is 12.1 ten thousand, and molecular weight distribution is 1.61, and kinetic viscosity is 560Pa.S(45 ℃).Gpc chromatogram is shown in Fig. 1.The weight-average molecular weight/number-average molecular weight of molecular weight distribution (Mw/Mn=121336/75537) equals 1.6 as seen from Figure 1, illustrate obtained high molecular, viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distribution.Carry out wet spinning under standard conditions, obtain the rounded section precursor, its fiber number is that 1.00dtex, intensity are that 6.6cN/dtex, elongation at break are 11%.
Embodiment 5
Utilize the tubular reactor that contains the static mixer assembly of embodiment 1 to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 30Kg solvent dimethyl sulfoxide (DMSO) joins in the stainless steel batching kettle with mechanical stirring device together with 7.76Kg vinyl cyanide, 160g methyl methacrylate, 80g methylene-succinic acid, stirring at room is mixed about 30 minutes, and uses the emptying deoxygenation of nitrogen bubble in the process be uniformly mixed;
(2) accurately take 2Kg solvent dimethyl sulfoxide (DMSO) and join in container together with 40g radical initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), the room temperature rapid stirring dissolves;
(3) under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put in the batching kettle of step (1), and the mixing of room temperature rapid stirring obtains reaction solution in 2 minutes;
(4) utilize the outer circulation water pump, the water that in endless tube chuck outside four pipes in being combined into the tubular reactor that contains the static mixer assembly of four sections, implantation temperature is 45 ℃, valve under opening steps (3) batching kettle, rely on that gravity is disposable to be injected in the pipe of the tubular reactor that contains the static mixer assembly by the reaction solution in batching kettle fast by material inlet; Regulate the water temperature in chuck by temperature control sensor, make the temperature-stable of reaction solution in pipe at 45 ± 1 ℃, and utilize that the internal recycle toothed gear pump is forced, the strengthening reaction solution circulates mixing in four pipes that the static mixer assembly is installed with the speed of 150 ml/min, carry out copolymerization 8 hours, then under 2kg pressure, pass through discharge hole for discharge; Vacuumize and remove residual monomer and bubble in de-single, deaeration still, fast and stable obtain a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The transformation efficiency of acrylonitrile monemer is 69%, and the weight-average molecular weight that records the polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC) is 11.8 ten thousand, and molecular weight distribution is 1.9, and kinetic viscosity is 286Pa.S(45 ℃).Carry out wet spinning under standard conditions, obtain the rounded section precursor, its fiber number is that 1.10dtex, intensity are that 5.8cN/dtex, elongation at break are 12%.
Embodiment 6
Utilize the tubular reactor that contains the static mixer assembly of embodiment 1 to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 30.8Kg solvent dimethyl sulfoxide (DMSO) joins in the stainless steel batching kettle with mechanical stirring device together with 7.056Kg vinyl cyanide, 72g Methacrylamide, 72g methylene-succinic acid, stirring at room is mixed about 30 minutes, and uses the emptying deoxygenation of nitrogen bubble in the process be uniformly mixed;
(2) accurately take 2Kg solvent dimethyl sulfoxide (DMSO) and join in container together with 32.4g radical initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), the room temperature rapid stirring dissolves;
(3) under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put in the batching kettle of step (1), and the mixing of room temperature rapid stirring obtains reaction solution in 2 minutes;
(4) utilize the outer circulation water pump, the water that in endless tube chuck outside four pipes in being combined into the tubular reactor that contains the static mixer assembly of four sections, implantation temperature is 45 ℃, valve under opening steps (3) batching kettle, rely on that gravity is disposable to be injected in the pipe of the tubular reactor that contains the static mixer assembly by the reaction solution in batching kettle fast by material inlet; Regulate the water temperature in chuck by temperature control sensor, make the temperature-stable of reaction solution in pipe at 45 ± 1 ℃, and utilize that the internal recycle toothed gear pump is forced, the strengthening reaction solution circulates mixing in four pipes that the static mixer assembly is installed with the speed of 200 ml/min, carry out copolymerization 12 hours, then under 2kg pressure, pass through discharge hole for discharge; Vacuumize and remove residual monomer and bubble in de-single, deaeration still, fast and stable obtain a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The transformation efficiency of acrylonitrile monemer is 66%, and the weight-average molecular weight that records the polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC) is 14.3 ten thousand, and molecular weight distribution is 2.0, and kinetic viscosity is 267Pa.S(45 ℃).Carry out wet spinning under standard conditions, obtain the rounded section precursor, its fiber number is that 1.0dtex, intensity are that 6.3cN/dtex, elongation at break are 12%.
Embodiment 7
Utilize the tubular reactor that contains the static mixer assembly of embodiment 1 to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 31.6Kg solvent dimethyl sulfoxide (DMSO) joins in the stainless steel batching kettle with mechanical stirring device together with 6.24Kg vinyl cyanide, 160g acrylamide, stirring at room is mixed about 30 minutes, and uses the emptying deoxygenation of nitrogen bubble in the process be uniformly mixed;
(2) accurately take 2Kg solvent dimethyl sulfoxide (DMSO) and join in container together with 32g radical initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), the room temperature rapid stirring dissolves;
(3) under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put in the batching kettle of step (1), and the mixing of room temperature rapid stirring obtains reaction solution in 2 minutes;
(4) utilize the outer circulation water pump, the water that in endless tube chuck outside four pipes in being combined into the tubular reactor that contains the static mixer assembly of four sections, implantation temperature is 35 ℃, valve under opening steps (3) batching kettle, rely on that gravity is disposable to be injected in the pipe of the tubular reactor that contains the static mixer assembly by the reaction solution in batching kettle fast by material inlet; Regulate the water temperature in chuck by temperature control sensor, make the temperature-stable of reaction solution in pipe at 35 ± 1 ℃, and utilize that the internal recycle toothed gear pump is forced, the strengthening reaction solution circulates mixing in four pipes that the static mixer assembly is installed with the speed of 50 ml/min, carry out copolymerization 12 hours, then under 2kg pressure, pass through discharge hole for discharge; Vacuumize and remove residual monomer and bubble in de-single, deaeration still, fast and stable obtain a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The transformation efficiency of acrylonitrile monemer is 66%, and the weight-average molecular weight that records the polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC) is 15.1 ten thousand, and molecular weight distribution is 1.7, and kinetic viscosity is 250Pa.S(45 ℃).Carry out wet spinning under standard conditions, obtain the rounded section precursor, its fiber number is that 0.98dtex, intensity are that 6.7cN/dtex, elongation at break are 11%.
Embodiment 8
Utilize the tubular reactor that contains the static mixer assembly of embodiment 1 to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 29.2Kg solvent dimethyl sulfoxide (DMSO) joins in the stainless steel batching kettle with mechanical stirring device together with 8.624Kg vinyl cyanide, 176g methylene-succinic acid, stirring at room is mixed about 30 minutes, and uses the emptying deoxygenation of nitrogen bubble in the process be uniformly mixed;
(2) accurately take 2Kg solvent dimethyl sulfoxide (DMSO) and join in container together with 88g radical initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), the room temperature rapid stirring dissolves;
(3) under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put in the batching kettle of step (1), and the mixing of room temperature rapid stirring obtains reaction solution in 2 minutes;
(4) utilize the outer circulation water pump, the water that in endless tube chuck outside four pipes in being combined into the tubular reactor that contains the static mixer assembly of four sections, implantation temperature is 60 ℃, valve under opening steps (3) batching kettle, rely on that gravity is disposable to be injected in the pipe of the tubular reactor that contains the static mixer assembly by the reaction solution in batching kettle fast by material inlet; Regulate the water temperature in chuck by temperature control sensor, make the temperature-stable of reaction solution in pipe at 60 ± 1 ℃, and utilize that the internal recycle toothed gear pump is forced, the strengthening reaction solution circulates mixing in four pipes that the static mixer assembly is installed with the speed of 100 ml/min, carry out copolymerization 3 hours, then under 2kg pressure, pass through discharge hole for discharge; Vacuumize and remove residual monomer and bubble in de-single, deaeration still, fast and stable obtain a kind of viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distributions.
The transformation efficiency of acrylonitrile monemer is 89%, and the weight-average molecular weight that records the polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC) is 8.8 ten thousand, and molecular weight distribution is 2.5, and kinetic viscosity is 253Pa.S(45 ℃).Carry out wet spinning under standard conditions, obtain the rounded section precursor, its fiber number is that 1.2dtex, intensity are that 5.3cN/dtex, elongation at break are 13%.
Claims (11)
1. a polyacrylonitrile copolymer spinning fluid, it is characterized in that: described polyacrylonitrile copolymer spinning fluid is that the reaction solution consisted of monomer, radical initiator and solvent obtains after copolymerization, wherein:
The weight percent concentration of the monomer in described reaction solution is 15～30%, and described radical initiator is 0.4～1% of described monomer weight; Surplus is solvent;
Described monomer is acrylonitrile monemer and comonomer, and described acrylonitrile monemer accounts for 90～99.5% of described total monomer weight, and described comonomer accounts for 0.5～10% of described total monomer weight;
Described comonomer is selected from one or both in methylene-succinic acid, vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, Methacrylamide, the two methyl esters of methylene-succinic acid, the two butyl esters of methylene-succinic acid.
2. polyacrylonitrile copolymer spinning fluid according to claim 1, it is characterized in that: the kinetic viscosity of described polyacrylonitrile copolymer spinning fluid is 200～800Pa.S; The molecular weight distribution of described polyacrylonitrile copolymer spinning fluid is 1.5～2.6.
3. polyacrylonitrile copolymer spinning fluid according to claim 1 and 2, it is characterized in that: the weight-average molecular weight of described polyacrylonitrile copolymer spinning fluid is 80000～200000.
4. polyacrylonitrile copolymer spinning fluid according to claim 1, it is characterized in that: described radical initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or their mixture.
5. polyacrylonitrile copolymer spinning fluid according to claim 1, it is characterized in that: described solvent is dimethyl sulfoxide (DMSO), dimethyl formamide or N,N-DIMETHYLACETAMIDE.
6. the preparation method of the described polyacrylonitrile copolymer spinning fluid of claim 1～5 any one, is characterized in that, described preparation method comprises the following steps:
(1) solvent and the monomer that will account for solvent total amount 90～98wt% join in batching kettle, be uniformly mixed under room temperature, and carry out emptying deoxygenation with rare gas element in the process be uniformly mixed;
(2) radical initiator is joined in the container that is mounted with the solvent that accounts for solvent total amount 2～10wt%, carry out stirring and dissolving under room temperature;
(3) under protection of inert gas and stirring, the disposable radical initiator solution that step (2) is obtained is put in the batching kettle of step (1), stir and obtain reaction solution under room temperature, wherein, the weight percent concentration of the described monomer in reaction solution is 15～30%, and described radical initiator is 0.4～1% of described monomer weight; Surplus is solvent;
(4) injected water in the endless tube chuck outside the pipe in the tubular reactor that contains the static mixer assembly to formation, by the disposable pipe that is injected into the tubular reactor that contains the static mixer assembly of the reaction solution obtained in step (3) batching kettle; Regulate the water temperature in injection ring pipe clamp cover by temperature control sensor, the temperature that makes reaction solution in pipe is 30～70 ℃, and utilize internal circulation pump to make the reaction solution mixing that circulates in the pipe that the static mixer assembly is installed, make reaction solution carry out copolymerization 3～12 hours, discharging after copolymerization completes, remove residual monomer and bubble, obtain the polyacrylonitrile copolymer spinning fluid;
Described monomer is acrylonitrile monemer and comonomer, and described acrylonitrile monemer accounts for 90～99.5% of described total monomer weight, and described comonomer accounts for 0.5～10% of described total monomer weight;
Described comonomer is selected from one or both in methylene-succinic acid, vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, Methacrylamide, the two methyl esters of methylene-succinic acid, the two butyl esters of methylene-succinic acid.
7. preparation method according to claim 6 is characterized in that: the described reaction solution flow velocity mixed that circulates in the pipe that the static mixer assembly is installed is 50～200 ml/min.
8. a tubular reactor that contains the static mixer assembly, comprise by the static mixer assembly is installed in pipe, and pipe and the internal circulation pump formation of endless tube chuck are installed outside pipe; It is characterized in that:
One end of described pipe is connected with described internal circulation pump by pipeline, and the other end of described internal circulation pump is connected with the other end of described pipe by pipeline;
Be provided with material inlet on the pipeline of described internal circulation pump one end, on the pipeline of the other end, be provided with discharge port;
Be separately installed with tensimeter on the pipeline at described internal circulation pump two ends;
On described pipeline, temperature control sensor is installed;
Be respectively arranged with water-in and water outlet on described endless tube chuck.
9. the tubular reactor that contains the static mixer assembly according to claim 8, it is characterized in that: the described tubular reactor that contains the static mixer assembly is connected in series a plurality of described pipes by the ring flange of installing on the pipe in forming described tubular reactor, is combined into the tubular reactor that contains the static mixer assembly of multistage.
10. the tubular reactor that contains the static mixer assembly according to claim 8 or claim 9 is characterized in that: described static mixer assembly is one or more the combination in SK type, SX type, SH type static mixer assembly.
11. contain the tubular reactor of static mixer assembly according to claim 8, it is characterized in that: described internal circulation pump is toothed gear pump; Described water-in is connected with the outer circulation pump by pipeline; Described outer circulation pump is water pump or toothed gear pump.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199042A (en) * | 2015-10-22 | 2015-12-30 | 天津工业大学 | Preparation method and application of thermoplastic acrylonitrile-based terpolymer |
| CN107556431A (en) * | 2017-09-29 | 2018-01-09 | 中安信科技有限公司 | A kind of method that dimethyl sulfoxide method continuous polymerization prepares polyacrylonitrile solution |
| CN108780894A (en) * | 2016-03-28 | 2018-11-09 | 日本瑞翁株式会社 | Electro-chemical element electrode adhesive composition, electro-chemical element electrode paste compound, electrode for electrochemical device and electrochemical element |
| CN111234081A (en) * | 2020-03-06 | 2020-06-05 | 长春工业大学 | Low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and preparation method thereof |
| CN113417025A (en) * | 2021-07-16 | 2021-09-21 | 常州市宏发纵横新材料科技股份有限公司 | Preparation method of polyacrylonitrile for high-performance carbon fibers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781809A (en) * | 2010-03-09 | 2010-07-21 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with uniform chain structure and narrow molecular-weight distribution and preparation method thereof |
| CN101671417B (en) * | 2008-09-11 | 2012-07-25 | 北京英诺威逊聚合技术有限公司 | Acrylonitrile polymerized loop reactor for carbon fibers |
-
2013
- 2013-07-26 CN CN201310320102.7A patent/CN103421141B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671417B (en) * | 2008-09-11 | 2012-07-25 | 北京英诺威逊聚合技术有限公司 | Acrylonitrile polymerized loop reactor for carbon fibers |
| CN101781809A (en) * | 2010-03-09 | 2010-07-21 | 中国科学院化学研究所 | Acrylonitrile copolymer spinning solution with uniform chain structure and narrow molecular-weight distribution and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 章日让: "《石化工艺及系统设计实用技术问答》", 30 April 2007, 中国石化出版社 * |
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|---|---|---|---|---|
| CN105199042A (en) * | 2015-10-22 | 2015-12-30 | 天津工业大学 | Preparation method and application of thermoplastic acrylonitrile-based terpolymer |
| CN105199042B (en) * | 2015-10-22 | 2017-12-05 | 天津工业大学 | The preparation method and purposes of thermoplastic propene's itrile group terpolymer |
| CN108780894A (en) * | 2016-03-28 | 2018-11-09 | 日本瑞翁株式会社 | Electro-chemical element electrode adhesive composition, electro-chemical element electrode paste compound, electrode for electrochemical device and electrochemical element |
| US11046797B2 (en) * | 2016-03-28 | 2021-06-29 | Zeon Corporation | Binder composition for electrochemical device electrode, slurry composition for electrochemical device electrode, electrochemical device electrode, and electrochemical device |
| CN108780894B (en) * | 2016-03-28 | 2021-09-14 | 日本瑞翁株式会社 | Binder composition for electrochemical element electrode, slurry composition for electrochemical element electrode, electrode for electrochemical element, and electrochemical element |
| CN107556431A (en) * | 2017-09-29 | 2018-01-09 | 中安信科技有限公司 | A kind of method that dimethyl sulfoxide method continuous polymerization prepares polyacrylonitrile solution |
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| CN111234081B (en) * | 2020-03-06 | 2022-12-20 | 长春工业大学 | Low-molecular-weight narrow-distribution styrene-maleic anhydride copolymer and preparation method thereof |
| CN113417025A (en) * | 2021-07-16 | 2021-09-21 | 常州市宏发纵横新材料科技股份有限公司 | Preparation method of polyacrylonitrile for high-performance carbon fibers |
| CN113417025B (en) * | 2021-07-16 | 2023-03-07 | 常州市宏发纵横新材料科技股份有限公司 | Preparation method of polyacrylonitrile for high-performance carbon fibers |
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