CN103421141B - Polyacrylonitrile copolymer spinning fluid and preparation method thereof - Google Patents
Polyacrylonitrile copolymer spinning fluid and preparation method thereof Download PDFInfo
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- CN103421141B CN103421141B CN201310320102.7A CN201310320102A CN103421141B CN 103421141 B CN103421141 B CN 103421141B CN 201310320102 A CN201310320102 A CN 201310320102A CN 103421141 B CN103421141 B CN 103421141B
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Abstract
The present invention relates to polyacrylonitrile copolymer spinning fluid and preparation method thereof. The present invention adopts propylene copolymerization nitrile in the tubular reactor that contains static mixer assembly, the tubular reactor that utilization contains static mixer assembly has mass transfer, conducts heat efficiently, reaction continuous and stable, without features such as mechanical agitation, prepare the polyacrylonitrile copolymer spinning fluid of HMW, Narrow Molecular Weight Distribution. Described polyacrylonitrile copolymer spinning fluid is that the reactant liquor being made up of monomer, radical initiator and solvent obtains after copolymerization, wherein: the weight percent concentration of the monomer in described reactant liquor is 15～30%, described radical initiator is 0.4～1% of described monomer weight; Surplus is solvent; Described monomer is acrylonitrile monemer and comonomer. The dynamic viscosity of polyacrylonitrile copolymer spinning fluid of the present invention is 200～800Pa.S; Molecular weight distribution is 1.5～2.6.
Description
Technical field
The invention belongs to polyacrylonitrile preparation field, particularly a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionThe preparation method of lonitrile copolymer spinning solution and fast and stable thereof.
Background technology
Carbon fiber has the characteristics such as high specific strength, high ratio modulus, heat-resisting, corrosion-resistant, endurance, creep resistant, is a kind of highPerformance fibers material, has been widely used in the industries such as Aero-Space, national defense construction, Leisure Sport articles for use, medicine equipment and building.Polyacrylonitrile-based carbon fibre has outstanding mechanical property, is carbon fiber research in recent years and industrialized focus. Restriction poly-thirdThe key of alkene itrile group carbon fiber development is the quality of polyacrylonitrile fibril, must be from synthetic and will obtain high-quality polyacrylonitrile fibrilSet about high-quality polyacrylonitrile copolymer spinning fluid and optimization spinning technique two aspects, only has the polyacrylonitrile copolymerization of excellent performanceThing spinning solution just can spin out the polyacrylonitrile fibril of high-quality, thereby prepares high performance polyacrylonitrile-based carbon fibre. TheoreticalAnalyze and experimental study show, desirable polyacrylonitrile copolymer should have suitable HMW and Narrow Molecular Weight Distribution, moderateAnd stable apparent viscosity, without bad structures such as Branching and cross-linkings; Wherein in microcosmic aspect polyacrylonitrile copolymer macromolecular chainStable preparation, the viscosity of composition, distribution and macroscopical aspect polyacrylonitrile copolymer of copolymerization construction unit are evenly material impactsFactor.
Mostly current domestic carbon fiber is to adopt solution polymerization process to prepare with azo-initiator with polyacrylonitrile, adoptsBatchwise polymerization, because acrylonitrile polymerization heat release is more violent, and larger at the system viscosity in polymerization later stage, cause mass transfer, biographyHeat difficulty, reaction is difficult to control, thereby polyacrylonitrile molecular weight distribution is broadened, and gel content increases, and significantly affects follow-up fibreThe raising of dimension performance; First from the angle of polymer production technique, intermittently its main reaction of autoclave polymerization is transient,Heat release is concentrated, and viscosity changes greatly, is 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 poly-Close the slow heat release of high viscosity in later stage, the chain transfer reaction to solvent easily occurs when result causes polymerization, be unfavorable for preparing macromoleculeWeight polymers; Secondly easily there is gel effect in high conversion, high viscosity stage, cause polymerization stoste the change of molecular weight large, pointCloth broadens; Moreover high in polymerization later stage viscosity, cause material stirring in still to mix difficulty, in still, material is removed heat difficulty, easily goes outExisting implode phenomenon, thereby the production of polymerization stoste is difficult to stable carrying out. The precursor spinning with this copolymer is in microphysics structurePoor with chemical reactivity upward stability, carbon fiber steady production and performance are all had a negative impact.
Summary of the invention
An object of the present invention is to overcome the deficiency that above-mentioned prior art exists, provide a kind of viscosity evenly, narrow molecular-weightThe polyacrylonitrile copolymer spinning fluid distributing.
A further object of the present invention is to provide in a kind of tubular reactor containing static mixer assembly and completes propyleneThe copolymerization of nitrile, steadily controls polymerization process, and the synthetic viscosity of fast and stable is even, the polyacrylonitrile of Narrow Molecular Weight Distribution is total toThe method of polymers spinning solution.
An also object of the present invention is to provide a kind of tubular reactor that contains static mixer assembly.
The present invention adopts propylene copolymerization nitrile in the tubular reactor that contains static mixer assembly, utilizes and contains static stateThe tubular reactor of mixer assembly (in principle, it belongs to piston flow reactor, be relatively applicable to picture polyacrylonitrile spinning solution thisThe sticky system of height of sample, can accomplish good pressure, strengthening mass transfer and heat transfer, controls the steady of polymerization process thereby be beneficial to, and hasHelp the viscosity of stable product and narrow composition distribution) there is mass transfer, conduct heat efficiently, reaction continuous and stable, without mechanical agitationEtc. feature, prepare the polyacrylonitrile copolymer spinning fluid of HMW, Narrow Molecular Weight Distribution.
The tubular reactor that contains static mixer assembly utilizing in the present invention comprises by being provided with in pipe quietState mixer assembly, and pipe be provided with outward endless tube chuck pipe, force the mobile internal circulation pump of reactant liquor and necessaryThe formations such as coupling.
The described tubular reactor that contains static mixer assembly can pass through in the tubular reactor described in formingThe ring flange of installing on pipe is connected in series multiple described pipes, and what be combined into multistage contains static mixer assemblyTubular reactor.
One end of described pipe is connected with described internal circulation pump by pipeline, the other end of described internal circulation pumpBe connected with the other end of described pipe by pipeline.
On the pipeline of described internal circulation pump one end, be provided with material inlet, on the pipeline of the other end, be provided with discharging opening.
On pipeline before described discharging opening, be further provided with sample tap.
On the pipeline at described internal circulation pump two ends, be separately installed with Pressure gauge.
On described pipeline, temperature control sensor is installed.
On described endless tube chuck, be respectively arranged with water inlet and delivery port.
Described static mixer assembly is one or more in the static mixer assemblies such as SK type, SX type, SH typeCombination.
Described internal circulation pump is gear pump or the satisfactory pump of other form.
Described water inlet is connected with outer circulation pump by pipeline; Described outer circulation pump can be water pump, gear pumpOr the satisfactory pump of other form.
In described endless tube chuck, be connected with the water-cycling-media of controllable temperature, provide required heat of polymerization initial stage, after polymerizationPhase is taken away polymerization heat, remains on the temperature of the polyacrylonitrile copolymerization in the tubular reactor that contains static mixer assemblyDegree is stable.
In polyacrylonitrile, introduce hydrophilic cosegment, build polyacrylonitrile copolymer, improved the thermally-stabilised of spinning solutionProperty, improve spinning property.
Polyacrylonitrile copolymer spinning fluid of the present invention, not only has high viscosity uniformity, narrow molecular weight distribution, andAnd 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 Distribution is to be drawn by monomer, free radicalSend out that reactant liquor that agent and solvent form obtains after copolymerization, wherein:
The weight percent concentration of the monomer in described reactant liquor is 15～30%, and described radical initiator is institute0.4～1% of the monomer weight of stating; Surplus is solvent.
The dynamic viscosity of described polyacrylonitrile copolymer spinning fluid is that 200～800Pa.S(is to survey at 45 DEG C 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, the total monomer weight described in described acrylonitrile monemer accounts for90～99.5%, described comonomer accounts for 0.5～10% of described total monomer weight.
Described comonomer be selected from itaconic acid, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate,One or both in acrylamide, Methacrylamide, the two methyl esters of itaconic acid, the two butyl esters of itaconic acid.
Described radical initiator can be azodiisobutyronitrile, ABVN or their mixture.
Described solvent is dimethyl sulfoxide (DMSO), dimethyl formamide or dimethylacetylamide.
Viscosity of the present invention is even, the preparation method of the polyacrylonitrile copolymer spinning fluid of Narrow Molecular Weight Distribution comprises followingStep:
(1) by account for the solvent of solvent total amount 90～98wt% and monomer join batching kettle with mechanical stirring device (asWith the stainless steel batching kettle of mechanical stirring device) in, under room temperature, be uniformly mixed that (time being generally uniformly mixed is 30About minute), and carry out emptying deoxygenation with inert gas (as nitrogen) in the process being uniformly mixed;
(2) radical initiator is joined in the container that is mounted with the solvent that accounts for solvent total amount 2～10wt%, in room temperatureUnder carry out rapid stirring dissolving;
(3) under inert gas (as nitrogen) protection and stirring, the disposable radical initiator that step (2) is obtained is moltenLiquid is put in the batching kettle of step (1), carries out rapid stirring (time of general rapid stirring is 1～2 minute) under room temperatureObtain reactant liquor, wherein, the weight percent concentration of the described monomer in reactant liquor is 15～30%, and described free radical drawsSending out agent is 0.4～1% of described monomer weight; Surplus is solvent;
(4) utilize outer circulation pump, the endless tube outside the pipe in the tubular reactor that contains static mixer assembly to formationInjected water in chuck, contains static mixer group by disposable the reactant liquor obtaining in step (3) batching kettle being injected into fastIn the pipe of the tubular reactor of part; Regulate the water temperature in chuck by temperature control sensor, make the temperature of reactant liquor in pipe be30～70 DEG C, and (static mixer assembly rises static mixer assembly is installed to utilize internal circulation pump to force, strengthen reactant liquorThe effect mixing) pipe in the mixing (flow velocity of preferred reaction liquid is 50～200 ml/min) that circulates, make reactant liquorCarry out copolymerization 3～12 hours, discharging after copolymerization completes, removes residual monomer and bubble, the obtaining of fast and stableViscosity evenly, the polyacrylonitrile copolymer spinning fluid of Narrow Molecular Weight Distribution.
Described monomer is acrylonitrile monemer and comonomer, the total monomer weight described in described acrylonitrile monemer accounts for90～99.5%, described comonomer accounts for 0.5～10% of described total monomer weight.
Described comonomer be selected from itaconic acid, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate,One or both in acrylamide, Methacrylamide, the two methyl esters of itaconic acid, the two butyl esters of itaconic acid.
Described radical initiator can be azodiisobutyronitrile, ABVN or their mixture.
Described solvent is dimethyl sulfoxide (DMSO), dimethyl formamide or dimethylacetylamide.
Beneficial effect of the present invention:
1. by inside and outside two circulating pumps, taking certain circulation rate (flow velocity of preferred reaction liquid as 50～200 milliliters/Minute), force polyacrylonitrile copolyreaction liquid to carry out efficient mass transfer, heat transfer mass transfer, the heat transfer of strengthening static mixer assemblyFunction, makes material concentration, temperature in copolymerization process steady, is beneficial to control copolymerization, the copolymerization of gained polyacrylonitrileThe molecular weight high (> 80000 of thing spinning solution), molecular weight distribution significantly reduces, monomer composition is evenly distributed, viscosity stabilization.
2. adopt the radical initiator of low temperature, improved the molecular weight of polyacrylonitrile copolymer, reduced poly-third simultaneouslyThe generation of the crosslinked and microgel in side reaction, the copolymerization process such as the oxidation of alkene lonitrile copolymer, the polyacrylonitrile copolymer obtainingSpinning solution look shallow is transparent.
3. the radical initiator of strengthening mass transfer, heat transfer and employing low temperature, can also significantly improve combined polymerization efficiency, improvesProduction capacity, the utilization rate of equipment and installations that improves.
4. synthesis technique of the present invention is simple, and stable reaction conditions is easily controlled the polyacrylonitrile copolymerization product viscosity of gainedEvenly, narrow molecular weight distribution, spinning solution good spinnability, can to lead multiple high, the precursor preparing has intensity advantages of higher.
Brief description of the drawings
Fig. 1 is the schematic diagram of the tubular reactor that contains static mixer assembly.
Fig. 2 is the spectrogram of the gel permeation chromatography (GPC) of the polyacrylonitrile copolymer 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. discharging openings
Detailed description of the invention
Embodiment 1
As shown in Figure 1, the tubular reactor that contains static mixer assembly comprises by the pipe of making at stainless steel materialStatic mixer assembly 2 is inside installed, and the formation such as pipe and internal circulation pump 3 of endless tube chuck 1 is installed outward at pipe; AndBe connected in series the pipe described in four, group by the ring flange of installing on the pipe forming in described tubular reactorThe tubular reactor that contains static mixer assembly of synthetic four sections.
Be combined into one end of the pipe described in first in the tubular reactor that contains static mixer assembly of four sectionsBe connected with one end of described internal circulation pump 3 by pipeline, and on this pipeline, Pressure gauge be installed; With described in firstPipe be connected in series second described in pipe on temperature control sensor is installed, and be provided with material inlet a; DescribedThe other end of internal circulation pump 3 be connected with one end of the pipe described in the 4th that is connected in series by pipeline, and at thisOn pipeline, be provided with on discharging opening b(discharging opening pipeline before and be further provided with sample tap), and Pressure gauge is installed.
On described endless tube chuck, be respectively arranged with water inlet and delivery port, the intake-outlet on four endless tube chucks is mutualSeries connection, and be connected with outer circulation pump by pipeline.
Described internal circulation pump is gear pump; Described outer circulation pump is water pump or gear pump.
Described static mixer assembly is one or more in the static mixer assemblies such as SK type, SX type, SH typeCombination.
Utilize the above-mentioned tubular reactor that contains static mixer assembly to carry out the preparation of polyacrylonitrile copolymer spinning fluid.
(1) accurately take 30Kg solvent dimethyl sulfoxide (DMSO) and 8.536Kg acrylonitrile, 176g methyl acrylate, 88g itaconic acidJoin together in the stainless steel batching kettle with mechanical stirring device, stirring at room temperature is mixed about 30 minutes, and mixed in stirringIn the process of closing, use the emptying deoxygenation of nitrogen bubble;
(2) accurately take 1.2Kg solvent dimethyl sulfoxide (DMSO) adds together with 61.6g radical initiator azodiisobutyronitrileIn container, room temperature rapid stirring dissolves;
(3), under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put into step(1), in batching kettle, the mixing of room temperature rapid stirring obtains reactant liquor for 2 minutes;
(4) utilize outer circulation water pump, to being combined into four in the tubular reactor that contains static mixer assembly of four sectionsIn endless tube chuck outside individual pipe, implantation temperature is the water of 61 DEG C, and the valve under opening steps (3) batching kettle relies on gravity onceProperty is injected into the reactant liquor in batching kettle by material inlet the circle of the tubular reactor that contains static mixer assembly fastGuan Zhong; Regulate the water temperature in chuck by temperature control sensor, make the temperature stabilization of reactant liquor in pipe at 61 ± 1 DEG C, and utilizeInterior cycle gear pump is forced, strengthening reactant liquor with the speed of 100 ml/min at four circles that static mixer assembly is installedThe mixing that circulates in pipe, carries out copolymerization 7 hours, then under 2kg pressure, passes through discharge hole for discharge; De-single, de-Bubble vacuumizes in still and removes residual monomer and bubble, fast and stable obtain a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionLonitrile copolymer spinning solution.
The conversion ratio of acrylonitrile monemer is 72%, records polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC)Weight average molecular weight be 9.5 ten thousand, molecular weight distribution is 2.4, dynamic viscosity is 368Pa.S(45 DEG C). Under standard conditions, carry outWet spinning, obtains circular cross-section precursor, and 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 static mixer assembly of embodiment 1 to carry out polyacrylonitrile copolymer spinning fluidPreparation.
(1) accurately take 28.4Kg solvent dimethyl formamide adds together with 9.408Kg acrylonitrile, 192g methacrylic acidEnter in the stainless steel batching kettle with mechanical stirring device, stirring at room temperature is mixed about 30 minutes, and the mistake being uniformly mixedIn journey, use the emptying deoxygenation of nitrogen bubble;
(2) accurately take 2Kg solvent dimethyl formamide adds together with 57.6g radical initiator azodiisobutyronitrileIn container, room temperature rapid stirring dissolves;
(3), under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put into step(1), in batching kettle, the mixing of room temperature rapid stirring obtains reactant liquor for 2 minutes;
(4) utilize outer circulation water pump, to being combined into four in the tubular reactor that contains static mixer assembly of four sectionsIn endless tube chuck outside individual pipe, implantation temperature is the water of 65 DEG C, and the valve under opening steps (3) batching kettle relies on gravity onceProperty is injected into the reactant liquor in batching kettle by material inlet the circle of the tubular reactor that contains static mixer assembly fastGuan Zhong; Regulate the water temperature in chuck by temperature control sensor, make the temperature stabilization of reactant liquor in pipe at 65 ± 1 DEG C, and utilizeInterior cycle gear pump is forced, strengthening reactant liquor with the speed of 100 ml/min at four circles that static mixer assembly is installedThe mixing that circulates in pipe, carries out copolymerization 5 hours, then under 2kg pressure, passes through discharge hole for discharge; De-single, de-Bubble vacuumizes in still and removes residual monomer and bubble, fast and stable obtain a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionLonitrile copolymer spinning solution.
The conversion ratio of acrylonitrile monemer is 83%, records polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC)Weight average molecular weight be 100,000, molecular weight distribution is 2.4, dynamic viscosity is 585Pa.S(45 DEG C). Under standard conditions, wetSpin, obtain circular cross-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 static mixer assembly of embodiment 1 to carry out polyacrylonitrile copolymer spinning fluidPreparation.
(1) accurately take 26.8Kg solvent dimethyl sulfoxide (DMSO) and 10.864Kg acrylonitrile, 224g acrylamide, 112g clothing healthAcid joins in the stainless steel batching kettle with mechanical stirring device together, and stirring at room temperature is mixed about 30 minutes, and is stirringIn the process of mixing, use the emptying deoxygenation of nitrogen bubble;
(2) accurately take 2Kg solvent dimethyl formamide adds together with 67.2g radical initiator ABVNIn container, room temperature rapid stirring dissolves;
(3), under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put into step(1), in batching kettle, the mixing of room temperature rapid stirring obtains reactant liquor for 2 minutes;
(4) utilize outer circulation water pump, to being combined into four in the tubular reactor that contains static mixer assembly of four sectionsIn endless tube chuck outside individual pipe, implantation temperature is the water of 52 DEG C, and the valve under opening steps (3) batching kettle relies on gravity onceProperty is injected into the reactant liquor in batching kettle by material inlet the circle of the tubular reactor that contains static mixer assembly fastGuan Zhong; Regulate the water temperature in chuck by temperature control sensor, make the temperature stabilization of reactant liquor in pipe at 52 ± 1 DEG C, and utilizeInterior cycle gear pump is forced, strengthening reactant liquor with the speed of 75 ml/min at four circles that static mixer assembly is installedThe mixing that circulates in pipe, carries out copolymerization 3 hours, then under 2kg pressure, passes through discharge hole for discharge; De-single, de-Bubble vacuumizes in still and removes residual monomer and bubble, fast and stable obtain a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionLonitrile copolymer spinning solution.
The conversion ratio of acrylonitrile monemer is 68%, records polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC)Weight average molecular weight be 120,000, molecular weight distribution is 2.2, dynamic viscosity is 673Pa.S(45 DEG C). Under standard conditions, wetSpin, obtain circular cross-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 static mixer assembly of embodiment 1 to carry out polyacrylonitrile copolymer spinning fluidPreparation.
(1) accurately take 30.2Kg solvent dimethyl sulfoxide (DMSO) and 8.624Kg acrylonitrile, the two methyl esters of 88g itaconic acid, 88g clothingHealth acid joins in the stainless steel batching kettle with mechanical stirring device together, and stirring at room temperature is mixed about 30 minutes, and is stirringMix in the process of mixing with the emptying deoxygenation of nitrogen bubble;
(2) accurately take 1Kg solvent dimethyl sulfoxide (DMSO) and join appearance together with 44g radical initiator ABVNIn device, room temperature rapid stirring dissolves;
(3), under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put into step(1), in batching kettle, the mixing of room temperature rapid stirring obtains reactant liquor for 2 minutes;
(4) utilize outer circulation water pump, to being combined into four in the tubular reactor that contains static mixer assembly of four sectionsIn endless tube chuck outside individual pipe, implantation temperature is the water of 50 DEG C, and the valve under opening steps (3) batching kettle relies on gravity onceProperty is injected into the reactant liquor in batching kettle by material inlet the circle of the tubular reactor that contains static mixer assembly fastGuan Zhong; Regulate the water temperature in chuck by temperature control sensor, make the temperature stabilization of reactant liquor in pipe at 50 ± 1 DEG C, and utilizeInterior cycle gear pump is forced, strengthening reactant liquor with the speed of 100 ml/min at four circles that static mixer assembly is installedThe mixing that circulates in pipe, carries out copolymerization 6 hours, then under 2kg pressure, passes through discharge hole for discharge; De-single, de-Bubble vacuumizes in still and removes residual monomer and bubble, fast and stable obtain a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionLonitrile copolymer spinning solution.
The conversion ratio of acrylonitrile monemer is 75%, records polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC)Weight average molecular weight be 12.1 ten thousand, molecular weight distribution is 1.61, dynamic viscosity is 560Pa.S(45 DEG C). Gpc chromatogram is shown in Fig. 1. ByFig. 1 can find out that the weight-average molecular weight/number-average molecular weight (Mw/Mn=121336/75537) of molecular weight distribution equals 1.6, explanationObtained HMW, viscosity evenly, the polyacrylonitrile copolymer spinning fluid of narrow molecular weight distribution. Under standard conditions, wetSpin, obtain circular cross-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 static mixer assembly of embodiment 1 to carry out polyacrylonitrile copolymer spinning fluidPreparation.
(1) accurately take 30Kg solvent dimethyl sulfoxide (DMSO) and 7.76Kg acrylonitrile, 160g methyl methacrylate, 80g clothingHealth acid joins in the stainless steel batching kettle with mechanical stirring device together, and stirring at room temperature is mixed about 30 minutes, and is stirringMix in the process of mixing with the emptying deoxygenation of nitrogen bubble;
(2) accurately take 2Kg solvent dimethyl sulfoxide (DMSO) and join appearance together with 40g radical initiator ABVNIn device, room temperature rapid stirring dissolves;
(3), under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put into step(1), in batching kettle, the mixing of room temperature rapid stirring obtains reactant liquor for 2 minutes;
(4) utilize outer circulation water pump, to being combined into four in the tubular reactor that contains static mixer assembly of four sectionsIn endless tube chuck outside individual pipe, implantation temperature is the water of 45 DEG C, and the valve under opening steps (3) batching kettle relies on gravity onceProperty is injected into the reactant liquor in batching kettle by material inlet the circle of the tubular reactor that contains static mixer assembly fastGuan Zhong; Regulate the water temperature in chuck by temperature control sensor, make the temperature stabilization of reactant liquor in pipe at 45 ± 1 DEG C, and utilizeInterior cycle gear pump is forced, strengthening reactant liquor with the speed of 150 ml/min at four circles that static mixer assembly is installedThe mixing that circulates in pipe, carries out copolymerization 8 hours, then under 2kg pressure, passes through discharge hole for discharge; De-single, de-Bubble vacuumizes in still and removes residual monomer and bubble, fast and stable obtain a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionLonitrile copolymer spinning solution.
The conversion ratio of acrylonitrile monemer is 69%, records polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC)Weight average molecular weight be 11.8 ten thousand, molecular weight distribution is 1.9, dynamic viscosity is 286Pa.S(45 DEG C). Under standard conditions, carry outWet spinning, obtains circular cross-section precursor, and 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 static mixer assembly of embodiment 1 to carry out polyacrylonitrile copolymer spinning fluidPreparation.
(1) accurately take 30.8Kg solvent dimethyl sulfoxide (DMSO) and 7.056Kg acrylonitrile, 72g Methacrylamide, 72g clothingHealth acid joins in the stainless steel batching kettle with mechanical stirring device together, and stirring at room temperature is mixed about 30 minutes, and is stirringMix in the process of mixing with the emptying deoxygenation of nitrogen bubble;
(2) accurately take 2Kg solvent dimethyl sulfoxide (DMSO) joins together with 32.4g radical initiator ABVNIn container, room temperature rapid stirring dissolves;
(3), under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put into step(1), in batching kettle, the mixing of room temperature rapid stirring obtains reactant liquor for 2 minutes;
(4) utilize outer circulation water pump, to being combined into four in the tubular reactor that contains static mixer assembly of four sectionsIn endless tube chuck outside individual pipe, implantation temperature is the water of 45 DEG C, and the valve under opening steps (3) batching kettle relies on gravity onceProperty is injected into the reactant liquor in batching kettle by material inlet the circle of the tubular reactor that contains static mixer assembly fastGuan Zhong; Regulate the water temperature in chuck by temperature control sensor, make the temperature stabilization of reactant liquor in pipe at 45 ± 1 DEG C, and utilizeInterior cycle gear pump is forced, strengthening reactant liquor with the speed of 200 ml/min at four circles that static mixer assembly is installedThe mixing that circulates in pipe, carries out copolymerization 12 hours, then under 2kg pressure, passes through discharge hole for discharge; De-single, de-Bubble vacuumizes in still and removes residual monomer and bubble, fast and stable obtain a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionLonitrile copolymer spinning solution.
The conversion ratio of acrylonitrile monemer is 66%, records polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC)Weight average molecular weight be 14.3 ten thousand, molecular weight distribution is 2.0, dynamic viscosity is 267Pa.S(45 DEG C). Under standard conditions, carry outWet spinning, obtains circular cross-section precursor, and 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 static mixer assembly of embodiment 1 to carry out polyacrylonitrile copolymer spinning fluidPreparation.
(1) accurately take 31.6Kg solvent dimethyl sulfoxide (DMSO) joins together with 6.24Kg acrylonitrile, 160g acrylamideIn stainless steel batching kettle with mechanical stirring device, stirring at room temperature is mixed about 30 minutes, and in the process being uniformly mixedWith the emptying deoxygenation of nitrogen bubble;
(2) accurately take 2Kg solvent dimethyl sulfoxide (DMSO) and join appearance together with 32g radical initiator ABVNIn device, room temperature rapid stirring dissolves;
(3), under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put into step(1), in batching kettle, the mixing of room temperature rapid stirring obtains reactant liquor for 2 minutes;
(4) utilize outer circulation water pump, to being combined into four in the tubular reactor that contains static mixer assembly of four sectionsIn endless tube chuck outside individual pipe, implantation temperature is the water of 35 DEG C, and the valve under opening steps (3) batching kettle relies on gravity onceProperty is injected into the reactant liquor in batching kettle by material inlet the circle of the tubular reactor that contains static mixer assembly fastGuan Zhong; Regulate the water temperature in chuck by temperature control sensor, make the temperature stabilization of reactant liquor in pipe at 35 ± 1 DEG C, and utilizeInterior cycle gear pump is forced, strengthening reactant liquor with the speed of 50 ml/min at four circles that static mixer assembly is installedThe mixing that circulates in pipe, carries out copolymerization 12 hours, then under 2kg pressure, passes through discharge hole for discharge; De-single, de-Bubble vacuumizes in still and removes residual monomer and bubble, fast and stable obtain a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionLonitrile copolymer spinning solution.
The conversion ratio of acrylonitrile monemer is 66%, records polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC)Weight average molecular weight be 15.1 ten thousand, molecular weight distribution is 1.7, dynamic viscosity is 250Pa.S(45 DEG C). Under standard conditions, carry outWet spinning, obtains circular cross-section precursor, and 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 static mixer assembly of embodiment 1 to carry out polyacrylonitrile copolymer spinning fluidPreparation.
(1) accurately take 29.2Kg solvent dimethyl sulfoxide (DMSO) and join band together with 8.624Kg acrylonitrile, 176g itaconic acidHave in the stainless steel batching kettle of mechanical stirring device, stirring at room temperature is mixed about 30 minutes, and uses in the process being uniformly mixedThe emptying deoxygenation of nitrogen bubble;
(2) accurately take 2Kg solvent dimethyl sulfoxide (DMSO) and join appearance together with 88g radical initiator ABVNIn device, room temperature rapid stirring dissolves;
(3), under nitrogen protection and stirring, the disposable radical initiator solution by step (2) preparation is put into step(1), in batching kettle, the mixing of room temperature rapid stirring obtains reactant liquor for 2 minutes;
(4) utilize outer circulation water pump, to being combined into four in the tubular reactor that contains static mixer assembly of four sectionsIn endless tube chuck outside individual pipe, implantation temperature is the water of 60 DEG C, and the valve under opening steps (3) batching kettle relies on gravity onceProperty is injected into the reactant liquor in batching kettle by material inlet the circle of the tubular reactor that contains static mixer assembly fastGuan Zhong; Regulate the water temperature in chuck by temperature control sensor, make the temperature stabilization of reactant liquor in pipe at 60 ± 1 DEG C, and utilizeInterior cycle gear pump is forced, strengthening reactant liquor with the speed of 100 ml/min at four circles that static mixer assembly is installedThe mixing that circulates in pipe, carries out copolymerization 3 hours, then under 2kg pressure, passes through discharge hole for discharge; De-single, de-Bubble vacuumizes in still and removes residual monomer and bubble, fast and stable obtain a kind of viscosity evenly, the polypropylene of Narrow Molecular Weight DistributionLonitrile copolymer spinning solution.
The conversion ratio of acrylonitrile monemer is 89%, records polyacrylonitrile copolymer spinning fluid with gel permeation chromatography (GPC)Weight average molecular weight be 8.8 ten thousand, molecular weight distribution is 2.5, dynamic viscosity is 253Pa.S(45 DEG C). Under standard conditions, carry outWet spinning, obtains circular cross-section precursor, and its fiber number is that 1.2dtex, intensity are that 5.3cN/dtex, elongation at break are 13%.
Claims (5)
1. a polyacrylonitrile copolymer spinning fluid, is characterized in that: described polyacrylonitrile copolymer spinning fluid be by monomer, fromThe reactant liquor being made up of base initator and solvent, through completing acrylonitrile in the tubular reactor that contains static mixer assemblyCopolymerization after obtain, wherein:
The weight percent concentration of the monomer in described reactant liquor is 15～30%, and described radical initiator is described0.4～1% of monomer weight; Surplus is solvent;
Described monomer is acrylonitrile monemer and comonomer, 90 of the total monomer weight described in described acrylonitrile monemer accounts for～99.5%, described comonomer accounts for 0.5～10% of described total monomer weight;
Described comonomer is selected from itaconic acid, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, propyleneOne or both in acid amides, Methacrylamide, the two methyl esters of itaconic acid, the two butyl esters of itaconic acid;
The dynamic viscosity of described polyacrylonitrile copolymer spinning fluid is 200～800Pas; Described polyacrylonitrile copolymerThe molecular weight distribution of spinning solution is 1.5～2.6;
The weight average molecular weight of described polyacrylonitrile copolymer spinning fluid is 80000～200000;
Described radical initiator is azodiisobutyronitrile, ABVN or their mixture;
Described solvent is dimethyl sulfoxide (DMSO), dimethyl formamide or dimethylacetylamide;
Described static mixer assembly is one or more the combination in SK type, SX type, SH type static mixer assembly.
2. a preparation method for polyacrylonitrile copolymer spinning fluid claimed in claim 1, is characterized in that, described preparation sideMethod comprises the following steps:
(1) solvent and the monomer that account for solvent total amount 90～98wt% are joined in batching kettle, under room temperature, are uniformly mixed,And carry out emptying deoxygenation with inert gas in the process being uniformly mixed;
(2) radical initiator is joined in the container that is mounted with the solvent that accounts for solvent total amount 2～10wt%, under room temperature, enterRow stirring and dissolving;
(3) under inert gas shielding and stirring, the disposable radical initiator solution that step (2) is obtained is put into step(1), in batching kettle, under room temperature, stir and obtain reactant liquor, wherein, the weight percent of the described monomer in reactant liquorSpecific concentration 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 static mixer assembly to formation, will walkSuddenly the disposable pipe that is injected into the tubular reactor that contains static mixer assembly of reactant liquor obtaining in (3) batching kettleIn; Regulate the water temperature in injection ring pipe clamp cover by temperature control sensor, the temperature that makes reactant liquor in pipe is 30～70 DEG C, and profitMake the reactant liquor mixing that circulates with internal circulation pump in the pipe that static mixer assembly is installed, make reactant liquor carry out copolymerizationClose reaction 3～12 hours, discharging after copolymerization completes, removes residual monomer and bubble, obtains polyacrylonitrile copolymer and spinsSilk liquid;
Described static mixer assembly is one or more the combination in SK type, SX type, SH type static mixer assembly;
Described monomer is acrylonitrile monemer and comonomer, 90 of the total monomer weight described in described acrylonitrile monemer accounts for～99.5%, described comonomer accounts for 0.5～10% of described total monomer weight;
Described comonomer is selected from itaconic acid, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, propyleneOne or both in acid amides, Methacrylamide, the two methyl esters of itaconic acid, the two butyl esters of itaconic acid;
Described reactant liquor in the pipe that static mixer assembly is installed, circulate mix flow velocity be 50～200 milliLiter/min.
3. for the preparation of a tubular reactor that contains static mixer assembly for polyacrylonitrile copolymer spinning fluid, comprise byStatic mixer assembly is installed in pipe, and pipe and the internal circulation pump formation of endless tube chuck are installed outward at pipe; ItsFeature is:
One end of described pipe is connected with described internal circulation pump by pipeline, and the other end of described internal circulation pump passes throughPipeline is connected with the other end of described pipe;
On the pipeline of described internal circulation pump one end, be provided with material inlet, on the pipeline of the other end, be provided with discharging opening;
On the pipeline at described internal circulation pump two ends, be separately installed with Pressure gauge;
On described pipeline, temperature control sensor is installed;
On described endless tube chuck, be respectively arranged with water inlet and delivery port;
Described static mixer assembly is one or more the combination in SK type, SX type, SH type static mixer assembly.
4. the tubular reactor that contains static mixer assembly according to claim 3, is characterized in that: described containing is quietThe tubular reactor of state mixer assembly is undertaken by the ring flange of installing on the pipe forming in described tubular reactorBe connected in series multiple described pipes, be combined into the tubular reactor that contains static mixer assembly of multistage.
5. the tubular reactor that contains static mixer assembly according to claim 3, is characterized in that: described interior circulationPump is gear pump; Described water inlet is connected with outer circulation pump by pipeline; Described outer circulation pump is water pump or gear pump.
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