CN102199247A - Method for preparing polyacrylonitrile spinning solution - Google Patents
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- CN102199247A CN102199247A CN2010101337758A CN201010133775A CN102199247A CN 102199247 A CN102199247 A CN 102199247A CN 2010101337758 A CN2010101337758 A CN 2010101337758A CN 201010133775 A CN201010133775 A CN 201010133775A CN 102199247 A CN102199247 A CN 102199247A
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Abstract
The invention relates to a method for preparing polyacrylonitrile spinning solution, which mainly solves the problem that a reactor easily has phenomena of adhesion, gelation and shake in the late period of polymerization in the reaction process of preparing the polyacrylonitrile spinning solution in the prior art. The problem is better solved by a technical scheme that a reactor with a double helical ribbon stirring blade is adopted in the process of preparing the polyacrylonitrile spinning solution, the lower part of the reactor has a truncated cone shape, and the double helical ribbon stirring blade corresponding to the lower part is a conical double helical ribbon stirring blade. The method can be applied to industrial production of the polyacrylonitrile spinning solution.
Description
Technical field
The present invention relates to a kind of method for preparing polyacrylonitrile spinning solution.
Background technology
The polymerization process of alkene nitrile is more.Radical polymerization mainly contains solution polymerization (SL), letex polymerization, suspension polymerization (SP) and mass polymerization; Proportioning by polymerization single polymerization monomer can be divided into homopolymerization or copolymerization; Can be divided into organic solvent and inorganic solvent by the polymerization solvent for use; Can be divided into single stage method and two step method again by polymerization and spinning technique.The solvent that so-called single stage method is to use can dissolved monomer again can the solvent polymerization resin, the solution after the polymerization can directly be used for spinning, polymerization and spinning are complete production lines.The chain transfer constant difference of vinyl cyanide free radical in different solvents should take into full account during selective solvent.
Common solvent has dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO) (DMSO) and inorganic solvent Sodium Thiocyanate 99 (NaSCN), zinc chloride (ZnCl
2), nitric acid (HNO
3).Contain water in the solvent that two step method adopts, AN has certain solubleness in water, but PAN is insoluble in water; Along with the carrying out of polyreaction, polymkeric substance is flocks separates out, and makes the PAN powder through separation, drying; During spinning, be dissolved in again and make spinning solution in the solvent and carry out spinning.So polymerization and spinning are separately carried out, be two-step approach worthy of the name.Obviously, one-step technology advanced person and production cost are low.
In civilian acrylic fiber production process process, available Virahol is as chain regulator, and when producing carbon fibre precursor, do not use Virahol.Because it can influence the regularity of chain.Initiator amount needs strict control, generally is no more than 0.5%.
The constant of polymeric kettle temperature is very important in polymerization process, should strict controlled polymerization processing parameter.In order to improve the warm tandem control in can adopting of controlled polymerization temperature in the kettle precision, accuracy of temperature control can reach ± and 0.25 ℃, if batchwise polymerization then is provided with serpentine condenser in polymeric kettle, but the direct regulation and control temperature in the kettle.Residual monomer should not surpass 0.3% in spinning solution, preferably is no more than 0.1%.The characteristics of sulfoxide single stage method transfer eliminating dampness method spinning technique flow process are that molecular weight is easy to control, narrow molecular weight distribution, and the degree of branching is low, the good spinnability of polymer fluid, and unconverted monomer is recyclable re-uses.Usually the continuous stirred tank reaction unit easily causes the inhomogeneous of polymerization system viscosity, and high molecular weight reactive mixed solution residence time in reactor distributes very wide, and the back-mixing degree increases, and causes product molecular weight distribution wide, and polymerization is inhomogeneous.This polymerization is inhomogeneous, makes spinning produce hole in drawing process, causes textural defect.The transmission homogeneity that this shows inside reactor has a significant impact product performance.The exploitation of commercial run is faced with many engineering problems, as: 1) polymerization is prone to gel, and this requires reactor not have the dead band substantially; 2) the easy sticking still that polymkeric substance takes place in the polymerization process, this requires reactor highly polished simultaneously; 3) in case the polymerization system power of agitator greater than 40%, viscosity pole is acute to rise, and therefore requires reactor that rational stirring power configuration is arranged and removes by the use of thermal means; Patent CN101343337A, CN101215357A disclose the continuous polymerization preparation method of vinyl cyanide protofilament spinning fluid, relate generally to the connection between polymeric kettle, do not relate to the polymeric kettle structure.
Patent CN1144810A, CN1142509A disclose the method and apparatus of the multipolymer of vinylbenzene and vinyl cyanide, and described method comprises makes reacted constituent by having the recirculation reactor of at least one tubular reactor.Although horizontal reactor has self-cleaning advantage, i.e. no dead band in the whole reactor, the mechanical shearing that the everywhere can both be stirred helps avoiding the generation of gel, and owing to its complex structure, the Assembly And Disassembly difficulty is big, the manufacturing cost height.Therefore, from the angle that industry is amplified, when carrying out acrylonitrile solution polymerization scale operation, be good to select vertical stirred tank reactor for use.
Summary of the invention
Technical problem to be solved by this invention is in the conventional art in the acrylonitrile solution polymerization process, and reactor easily rocks, the problem of discharging difficulty and gel, and a kind of new method of rocking solution polymerization is provided.This method has and does not produce in preparation process that gel, stir shaft do not rock and discharging is easy to advantage.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing polyacrylonitrile spinning solution, is raw material with vinyl cyanide with one or more comonomers that are selected from unsaturated acid or the ester, to be selected from least a in dimethyl sulfoxide (DMSO), dimethyl formamide or the N,N-DIMETHYLACETAMIDE is solvent, with the azo compound is initiator, and wherein vinyl cyanide and comonomer weight ratio are 90～99.5: 0.5～10, account for 15～30% of whole system weight; Solvent load accounts for 70～85% of whole system weight; Initiator amount accounts for 0.3～1% of monomer weight.In reactor, it is 30～70 ℃ in temperature, pressure is to carry out solution polymerization under the condition of normal pressure, wherein used reactor comprises motor, reactor shell, reactor jacket, two ribbon stirring rakes and bottom, reactor jacket is positioned at the reactor outside and is close to reactor shell, two ribbon stirring rakes are fixed in and are positioned at reactor on the stir shaft vertically vertically by putting, the stir shaft two ends link to each other with bottom with motor respectively, it is characterized in that the reactor shell bottom is truncated cone-shaped, frustum cone height is 10～70% of a reactor shell height, the round platform partial volume accounts for 10～70% of reactor cubic capacity, the angle theta of the round platform conical surface and bottom horizontal plane is 30 °～80 °, and two ribbon stirring rakes partly are conical double ribbon band stirring rake at round platform.
In the technique scheme, unsaturated acid or ester are methylene-succinic acid, methacrylic acid, vinylformic acid, β-methylene-succinic acid methyl esters, β-methylene-succinic acid ethyl ester, β-methylene-succinic acid acid amides, β-methylene-succinic acid propyl ester, β-itaconic acid n-butyl, methyl acrylate.Azo compound is the mixing of a kind of of Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) or two kinds.
Wherein vinyl cyanide and comonomer weight ratio are 90～99.5: 0.5～10, and preferred version is 95～99: 5～1; Account for 15～30% of whole system weight, preferred version is 18～25%; Solvent load accounts for 70～85% of whole system weight, and preferred version is 75～82%; Initiator amount accounts for 0.3～1% of monomer weight, and preferred version is 0.4～0.6%.The frustum cone height preferred version is for being 20～40% of reactor shell height; The preferable range that the round platform partial volume accounts for the reactor cubic capacity is 15～45%.The preferable range of the angle theta of the round platform conical surface and bottom horizontal plane is 40 °～60 °; Between two ribbon stirring rake outer rims and reactor wall is greater than 0～10 millimeter apart from preferable range, and more preferably scope is greater than 0～8 millimeter.
Though satisfying, conventional two ribbon stirring rake mixes and strong requirement of shearing, but during low sticking, high rotating speed, the ribbon stirring rake easily forms bigger solid rotating part, promptly form very big whirlpool, can cause the caking or the skinning that cause owing to the polymerization system volumetric shrinkage at the liquid-gas interface place like this.To be designed to truncated cone-shaped at the bottom of the still, help reducing the solid rotating part, make that finally the bur at the liquid-gas interface place reduces.And be equipped with conical double ribbon band stirring rake, make the liquid that drips remain sufficient shearing, overcome the difficulty that common elipse head is operated when hanging down liquid level.When transformation efficiency greater than 50% the time because friction resistance increases, stir power consumption and increase severely, the stir shaft bottom tends to because stressed excessive and occur rocking.The bottom of stirring rake is designed to conical double ribbon band stirring rake among the present invention, and it is not enough effectively to overcome this point that adopts common double ribbon still.
This design of the reactor that uses in the inventive method makes the polyacrylonitrile spinning solution discharging become very convenient.The bottom is truncated cone-shaped, and certain pitch angle is arranged, and material is easy to be transported under action of gravity or under certain stirring action the bottom, and the valve of opening the bottom gets final product discharging, need not special drawing mechanism, has obtained better technical effect.
Description of drawings
Accompanying drawing 1 is for being used to prepare the reactor of polyacrylonitrile spinning solution in the inventive method.
1 is agitator motor in the accompanying drawing 1, and 2 is reactor, and 3 is two ribbon stirring rakes, 4 is reactor jacket, and 5 are taper ribbon stirring rake, and 6 is bottom, θ is the angle of the round platform conical surface and bottom horizontal plane, and a1 is the reactor upper height, and a2 is a reactor lower part truncated cone-shaped height.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
(height of round platform part accounts for 33% of total still height to 10 liters of mechanical stirring kettles that adopt Fig. 1 to describe, volume accounts for 30% of still cumulative volume, tiltangle is 50 °, the distance of wherein two ribbon stirring rake outer rims and reactor wall is 10 millimeters), dimethyl sulfoxide (DMSO) (DMSO), vinyl cyanide (AN), methylene-succinic acid (IA), initiator Diisopropyl azodicarboxylate totally 5 kilograms add in the reactor successively, wherein ratio is a dimethyl sulfoxide (DMSO): vinyl cyanide: methylene-succinic acid=80: 19.6: 0.4, initiator amount are monomeric 0.55%.Stirring is up to the solution that becomes homogeneous; with vacuum pump system is vacuumized earlier; logical then nitrogen is protected; slowly be warmed up to target temperature, beginning solution is water white transparency, at 150 rev/mins of following stirring reactions; prolongation along with the reaction times; system viscosity rises gradually, and moment of torsion and power of agitator rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 3.3 amperes by initial 2 amperes, and discharging is convenient, reacts to the object time sampling, gel-free.Film is used hot water, cold water washing respectively, transformation efficiency 90%, weight-average molecular weight Mw=9 * 10
4, molecular weight distribution 2.8.
[embodiment 2]
(height of round platform part accounts for 40% of total still height to 10 liters of mechanical stirring kettles that adopt Fig. 1 to describe, volume accounts for 35% of still cumulative volume, tiltangle is 60 °, the distance of wherein two ribbon stirring rake outer rims and reactor wall is 8 millimeters) on, dimethyl sulfoxide (DMSO) (DMSO), vinyl cyanide (AN), methylene-succinic acid (IA), methyl acrylate (MA), the initiator Diisopropyl azodicarboxylate successively totally 5 kilograms add in the reactor successively, wherein ratio is a dimethyl sulfoxide (DMSO): vinyl cyanide: methylene-succinic acid: methyl acrylate=80: 19.6: 0.2: 0.2, and initiator amount is monomeric 0.6%.Stirring is up to the solution that becomes homogeneous; with vacuum pump system is vacuumized earlier; logical then nitrogen is protected; slowly be warmed up to target temperature, beginning solution is water white transparency, at 150 rev/mins of following stirring reactions; prolongation along with the reaction times; system viscosity rises gradually, and moment of torsion and power of agitator rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 3.0 amperes by initial 2 amperes, and discharging is convenient, reacts to the object time sampling, gel-free.Film is used hot water, cold water washing respectively, transformation efficiency 92%, weight-average molecular weight Mw=9.3 * 10
4, molecular weight distribution 2.9.
[embodiment 3]
(height of round platform part accounts for 25% of total still height to 10 liters of mechanical stirring kettles that adopt Fig. 1 to describe, volume accounts for 28% of still cumulative volume, tiltangle is 40 °, the distance of wherein two ribbon stirring rake outer rims and reactor wall is 6 millimeters) on, dimethyl sulfoxide (DMSO) (DMSO), vinyl cyanide (AN), methylene-succinic acid (IA), initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) totally 5 kilograms add in the reactor successively, wherein ratio is a dimethyl sulfoxide (DMSO): vinyl cyanide: methylene-succinic acid=82: 17.6: 0.4, initiator amount are monomeric 0.5%.Stirring is up to the solution that becomes homogeneous; with vacuum pump system is vacuumized earlier; logical then nitrogen is protected; slowly be warmed up to target temperature, beginning solution is water white transparency, at 150 rev/mins of following stirring reactions; prolongation along with the reaction times; system viscosity rises gradually, and moment of torsion and stir current rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 3.8 amperes by initial 2 amperes, and discharging is convenient, reacts to the object time sampling, gel-free.Film is used hot water, cold water washing respectively, transformation efficiency 92%, weight-average molecular weight Mw=16.3 * 10
4, molecular weight distribution 2.0.
[embodiment 4]
(volume of bottom round platform part is 2.5 liters to 10 liters of mechanical stirring kettles that adopt Fig. 1 to describe, upper volume is 7.5 liters, tiltangle is 65 °, the distance of wherein two ribbon stirring rake outer rims and reactor wall is 3 millimeters) on, dimethyl sulfoxide (DMSO) (DMSO), vinyl cyanide (AN), methylene-succinic acid (IA), methyl acrylate (MA), initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) totally 5 kilograms add in the reactor successively, wherein ratio is a dimethyl sulfoxide (DMSO): vinyl cyanide: methylene-succinic acid: methyl acrylate=78: 17.6: 0.2: 0.2, and initiator amount is monomeric 0.4%.Stirring is up to the solution that becomes homogeneous; with vacuum pump system is vacuumized earlier; logical then nitrogen is protected; slowly be warmed up to target temperature, beginning solution is water white transparency, at 150 rev/mins of following stirring reactions; prolongation along with the reaction times; system viscosity rises gradually, and moment of torsion and power of agitator rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 4 amperes by initial 2 amperes, and discharging is convenient, reacts to the object time sampling, gel-free.Film is used hot water, cold water washing respectively, transformation efficiency 92%, weight-average molecular weight Mw=16.9 * 10
4, molecular weight distribution 2.1.
[embodiment 5]
(height of round platform part accounts for 33% of total still height to 10 liters of mechanical stirring kettles that adopt Fig. 1 to describe, volume accounts for 15% of still cumulative volume, tiltangle is 55 °, the distance of wherein two ribbon stirring rake outer rims and reactor wall is 4 millimeters) on, dimethyl sulfoxide (DMSO) (DMSO), vinyl cyanide (AN), methylene-succinic acid (IA), initiator Diisopropyl azodicarboxylate totally 5 kilograms add in the reactor successively, wherein ratio is a dimethyl sulfoxide (DMSO): vinyl cyanide: methylene-succinic acid=75: 24: 1, initiator amount are monomeric 0.65%.Stirring is up to the solution that becomes homogeneous; with vacuum pump system is vacuumized earlier; logical then nitrogen is protected; slowly be warmed up to target temperature, beginning solution is water white transparency, at 150 rev/mins of following stirring reactions; prolongation along with the reaction times; system viscosity rises gradually, and moment of torsion and power of agitator rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 5.3 amperes by initial 2 amperes, and discharging is convenient, reacts to the object time sampling, gel-free.Film is used hot water, cold water washing respectively, transformation efficiency 96%, weight-average molecular weight Mw=12 * 10
4, molecular weight distribution 2.88.
[embodiment 6]
(height of round platform part accounts for 33% of total still height to 10 liters of mechanical stirring kettles that adopt Fig. 1 to describe, volume accounts for 25% of still cumulative volume, tiltangle is 63 °, the distance of wherein two ribbon stirring rake outer rims and reactor wall is 9 millimeters) on, dimethyl sulfoxide (DMSO) (DMSO), vinyl cyanide (AN), methylene-succinic acid (IA), initiator Diisopropyl azodicarboxylate totally 5 kilograms add in the reactor successively, wherein ratio is a dimethyl sulfoxide (DMSO): vinyl cyanide: methylene-succinic acid: methyl acrylate=70: 29.4: 0.3: 0.3., initiator amount are monomeric 0.5%.Stirring is up to the solution that becomes homogeneous; with vacuum pump system is vacuumized earlier; logical then nitrogen is protected; slowly be warmed up to target temperature, beginning solution is water white transparency, at 150 rev/mins of following stirring reactions; prolongation along with the reaction times; system viscosity rises gradually, and moment of torsion and power of agitator rise slowly steadily in the polymerization process, and stirring rake does not shake yet when high conversion.Stir current rises to the highest 6.3 amperes by initial 2 amperes, and discharging is convenient, reacts to the object time sampling, gel-free.Film is used hot water, cold water washing respectively, transformation efficiency 98%, weight-average molecular weight Mw=14 * 10
4, molecular weight distribution 2.98.
[comparative example 1]
Polymerizing condition is identical with embodiment 1, and different is to adopt conventional drum shaped reaction device, and polymerization process post torque and power of agitator rise very fast, and stirring rake shakes when high conversion.Stir current rises to the highest 6 amperes by initial 2 amperes, is not easy discharging.Transformation efficiency 82%, weight-average molecular weight Mw=8.2 * 10
4, molecular weight distribution 3.2.
[comparative example 2]
Polymerizing condition is identical with embodiment 2, and different is to adopt general baffle plate stirring rake, and polymerization process post torque and power of agitator rise very fast, and stirring rake shakes when high conversion.Owing to there are a large amount of gels to occur, polyreaction has to finish ahead of time.Transformation efficiency 70%, weight-average molecular weight Mw=8.3 * 10
4, molecular weight distribution 3.9.
[comparative example 3]
Polymerizing condition is identical with embodiment 3, and different is to adopt conventional drum shaped reaction device, and polymerization process post torque and stir current rise very fast, and stirring rake shakes when high conversion.Stir current rises to the highest 7 amperes by initial 2 amperes.Transformation efficiency 87%, weight-average molecular weight Mw=14.7 * 10
4, molecular weight distribution 2.5.
[comparative example 5]
Polymerizing condition is identical with embodiment 5, and different is to adopt general baffle plate stirring rake, and polymerization process post torque and power of agitator rise very fast, and stirring rake shakes when high conversion.Owing to there are a large amount of gels to occur, polyreaction has to finish ahead of time.Transformation efficiency 60%, weight-average molecular weight Mw=11.3 * 10
4, molecular weight distribution 3.9.
[comparative example 6]
Polymerizing condition is identical with embodiment 6, and different is to adopt conventional drum shaped reaction device, and polymerization process post torque and stir current rise very fast, and stirring rake shakes when high conversion.Stir current rises to the highest 10 amperes by initial 2 amperes.The stopped reaction of having to, transformation efficiency 67%, weight-average molecular weight Mw=13.9 * 10
4, molecular weight distribution 4.1.
Claims (7)
1. method for preparing polyacrylonitrile spinning solution, is raw material with vinyl cyanide with at least a comonomer that is selected from unsaturated acid or the ester, to be selected from least a in dimethyl sulfoxide (DMSO), dimethyl formamide or the N,N-DIMETHYLACETAMIDE is solvent, with the azo compound is initiator, wherein vinyl cyanide and comonomer weight ratio are 95～99: 1～5, account for 15～30% of whole system weight; Solvent load accounts for 70～85% of whole system weight; Initiator amount accounts for 0.3～1% of monomer weight.In reactor, it is 30～70 ℃ in temperature, pressure is to carry out solution polymerization under the condition of normal pressure, wherein used reactor comprises motor, reactor shell, reactor jacket, two ribbon stirring rakes and bottom, reactor jacket is positioned at the reactor outside and is close to reactor shell, two ribbon stirring rakes are fixed in and are positioned at reactor on the stir shaft vertically vertically by putting, the stir shaft two ends link to each other with bottom with motor respectively, the reactor shell bottom is truncated cone-shaped, frustum cone height is 10～70% of a reactor shell height, the round platform partial volume accounts for 10～70% of reactor cubic capacity, the angle theta of the round platform conical surface and bottom horizontal plane is 30 °～80 °, and two ribbon stirring rakes partly are conical double ribbon band stirring rake at round platform.
2. according to the described method for preparing polyacrylonitrile spinning solution of claim 1, it is characterized in that unsaturated acid or ester are at least a in methylene-succinic acid, methacrylic acid, vinylformic acid, β-methylene-succinic acid methyl esters, β-methylene-succinic acid ethyl ester, β-methylene-succinic acid acid amides, β-methylene-succinic acid propyl ester, β-itaconic acid n-butyl, the methyl acrylate.
3. according to the described method for preparing polyacrylonitrile spinning solution of claim 1, it is characterized in that azo compound is a kind of of Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
4. according to the described method for preparing polyacrylonitrile spinning solution of claim 1, it is characterized in that frustum cone height is 20～40% of a reactor shell height.
5. according to the described method for preparing polyacrylonitrile spinning solution of claim 1, it is characterized in that the round platform partial volume accounts for 15～45% of reactor cubic capacity.
6. according to the described method for preparing polyacrylonitrile spinning solution of claim 1, the angle theta that it is characterized in that the round platform conical surface and bottom horizontal plane is 40 °～60 °.
7. according to the described method for preparing polyacrylonitrile spinning solution of claim 1, it is characterized in that the distance between two ribbon stirring rake outer rims and reactor wall is less than 10 millimeters.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103668524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of low-viscosity high-performance binary acrylonitrile polymer spinning liquor |
| CN104204007A (en) * | 2012-02-03 | 2014-12-10 | 帝斯曼知识产权资产管理有限公司 | Polymer, process and composition |
| CN104562265A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber precursor |
| CN104628935A (en) * | 2013-11-06 | 2015-05-20 | 中国石油化工股份有限公司 | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
| CN105524213A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile spinning stock solution |
| CN105524278A (en) * | 2014-09-29 | 2016-04-27 | 中国科学院大连化学物理研究所 | Method for preparing linear macromolecules with controllable molecular weight by solution polycondensation reaction |
| CN109012408A (en) * | 2018-08-16 | 2018-12-18 | 章立香 | A kind of multi-angle stirred type liquid manure mixing machine |
| CN110684149A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Preparation method of narrow-distribution polyacrylonitrile-based carbon fiber spinning solution |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104204007A (en) * | 2012-02-03 | 2014-12-10 | 帝斯曼知识产权资产管理有限公司 | Polymer, process and composition |
| CN104204007B (en) * | 2012-02-03 | 2017-03-08 | 帝斯曼知识产权资产管理有限公司 | Polymer, method and composition |
| CN103668524B (en) * | 2012-09-05 | 2016-07-13 | 中国石油化工股份有限公司 | Low viscosity, high-performance binary acrylonitrile copolymer spinning solution preparation method |
| CN103668524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of low-viscosity high-performance binary acrylonitrile polymer spinning liquor |
| CN104562265A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber precursor |
| CN104628935A (en) * | 2013-11-06 | 2015-05-20 | 中国石油化工股份有限公司 | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
| CN104628935B (en) * | 2013-11-06 | 2017-02-15 | 中国石油化工股份有限公司 | Preparation method of carbon fiber spinning stock solution with low viscosity, high molecular weight and narrow molecular weight distribution |
| CN105524278A (en) * | 2014-09-29 | 2016-04-27 | 中国科学院大连化学物理研究所 | Method for preparing linear macromolecules with controllable molecular weight by solution polycondensation reaction |
| CN105524278B (en) * | 2014-09-29 | 2018-07-20 | 中国科学院大连化学物理研究所 | A kind of method that solution polycondensation reaction prepares the controllable linear polymeric of molecular weight |
| CN105524213A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile spinning stock solution |
| CN105524213B (en) * | 2014-10-27 | 2018-01-09 | 中国石油化工股份有限公司 | The preparation method of polyacrylonitrile spinning solution |
| CN110684149A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Preparation method of narrow-distribution polyacrylonitrile-based carbon fiber spinning solution |
| CN110684149B (en) * | 2018-07-06 | 2021-11-30 | 中国石油化工股份有限公司 | Preparation method of narrow-distribution polyacrylonitrile-based carbon fiber spinning solution |
| CN109012408A (en) * | 2018-08-16 | 2018-12-18 | 章立香 | A kind of multi-angle stirred type liquid manure mixing machine |
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