CN105525362B - The method for homogenization preparation of high molecular weight, high concentration polyacrylonitrile-base carbon fiber spinning primary fluid - Google Patents
The method for homogenization preparation of high molecular weight, high concentration polyacrylonitrile-base carbon fiber spinning primary fluid Download PDFInfo
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Abstract
The invention discloses a kind of high molecular weight, the method for homogenization preparation of high concentration polyacrylonitrile-base carbon fiber spinning primary fluid.This method carries out polymerisation in solution using inorganic solvent, its concentration for first passing through control polymerization stage polymer solution (total solid) and the suitable molecular weight regulator of addition, obtain the polymer solution of low concentration, low viscosity, high molecular weight, then using the process of multi-step pressure reduction dehydration, deaeration, the polymer solution of high concentration is obtained.Preparation method of the present invention is simple, is suitble to industrialization；" micelle " generated because polymerizeing temperature in the kettle hot-spot is not present in the spinning solution obtained by the method for the invention, will not generate secondary " micelle " in subsequent dehydration, and uniformity significantly improves, and meets high compactness solidification and requires；It is used for that post-processing process is steadily smooth, obtained precursor quality is higher more stable.
Description
Technical field
The invention belongs to textile processing technical fields, and in particular to a kind of high molecular weight, high concentration polyacrylonitrile-based carbon
The method for homogenization preparation of fiber spinning dope.
Background technique
For polymer chain architecture, high molecular weight and high stereoregularity are to improve the main path of carbon fiber performance,
The intensity of polyacrylonitrile fibril can be improved in the structure of high molecular weight, densification, so that fibrous mechanical property is more excellent.And carbon fiber
It is closely related to tie up homogenizing for the high molecular weight of precursor, high stereoregularity and polyacrylonitrile-base carbon fiber spinning primary fluid.Because
Cyano in PAN chain has big dipole, so that PAN strand is arranged in the form of screw cylindrical, when these coiled strands are put together
When, neighbouring cyano will take antiparallel manner arrangement to form strong interaction, thus, impart PAN chain height
Orderly structure.It also is exactly the complexity for the solution behavior that interaction strong between this cyano results in them.Polypropylene
Nitrile (PAN) is soluble in DMF, DMAc, DMSO, concentrated nitric acid, ZnCl2In aqueous solution and NaSCN aqueous solution, it is various molten
Gel behavior can be all shown in liquid, and spinning solution molecular weight is higher, stereoregularity is better, the active force of molecule interchain
It is stronger, PAN- dicyandiamide solution gel more easy to form.The usual molecular weight of spinning solution for preparing carbon fiber is all higher, up to 100000
~300000, this is prepared the polymerization of PAN carbon fibre precursor spinning solution, spinning is all brought compared with burden, is mainly manifested in poly-
It closes kettle heat transfer and unevenly, in kettle reacts uneven；Spinning solution filtration difficulty, the sprinkler operational period is short, and plug-hole easily occurs for spray head, raw
It is poor to produce stability；Spinneret state is easily deteriorated, and the discrete performance of precursor is big, Yi Fasheng lousiness, fracture of wire etc..Therefore, Yao Shixian polypropylene
The high performance of nitrile precursor, the condensed state structure for controlling PAN solution are particularly significant.Under the prior art, regular parking is generallyd use,
The method for cleaning polymeric kettle with solvent remains gel to remove in kettle, keep conducting heat in kettle uniform, guarantee stock solution quality in kettle
Uniformity.In addition, can also be by using the microgel in the relatively high fine filter removal spinning solution of filtering accuracy, but exist
Filter cycle is shorter, and frequent switching, production stability is poor, and filter expense is also higher, a higher problem of input cost.
For precursor structure, high compactness, high orientation are the main paths for improving carbon fiber performance.It is former to increase spinning
The concentration of polymer in liquid can then be such that as-spun fibre density increases, and fiber Hole number is reduced, and fibre structure is fine and close, structure
Homogeneity improves, and the performance of precursor is improved.But polymer concentration is higher (solution solid content is higher) in spinning solution, molten
In liquid polymerization process, heat transfer is more uneven in kettle, the phenomenon that being more easy to appear hot-spot and form microgel.Patent No.
In 200810227312 China's application, precursor compact structure is improved by improving spinning solution concentration, in polypropylene
When nitrile dissolves, a kind of low-boiling dilution solubilizer is added in traditional dissolution system, the polyacrylonitrile of uniform low viscosity is made
Solution, so that the solid content of solution is improved, it is (highly concentrated finally to obtain uniform high solids content using devolatilization is depressurized after filter
Degree) polyacrylonitrile spinning solution inevitably will form a kind of impurity in precursor, no due to joined solubilizer in the method
Harsh carbon fiber is required conducive to application and preparation.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of high molecular weight, high concentration polypropylene
The method for homogenization preparation of itrile group carbon fiber spinning primary fluid is by PAN and inorganic solvent (such as NaSCN, ZnCl2Deng) aqueous solution
The PAN spinning solution of composition, or the preparation method of PAN spinning solution being made of PAN and low boiling point solvent.Pass through the method
Polyacrylonitrile-base carbon fiber spinning primary fluid composition obtained is stablized, solid content is high, does not have microgel, and filter operation is excellent, raw
Production stability is good, and precursor end breakage rate is low, compact structure, function admirable, can effectively improve the intensity of carbon fiber.
The present invention first passes through the concentration (total solid) of control polymerization stage polymer solution, and suitable molecular weight is added
Regulator, to obtain the polymer solution of low concentration, low viscosity, high molecular weight；Then using multi-step pressure reduction dehydration, deaeration
Process removes moisture or solvent in polyacrylonitrile solution, final to obtain polyacrylonitrile spinning have good uniformity, high concentration
Stoste.It is the specific technical solution of the present invention below:
The method for homogenization preparation of a kind of high molecular weight, high concentration polyacrylonitrile-base carbon fiber spinning primary fluid, specific steps
It is as follows:
(1) it using acrylonitrile, methyl acrylate and itaconic acid as polymerized monomer, using isopropanol as molecular weight regulator, uses
Inorganic solvent carries out polymerization reaction, obtains polymerization stoste；Wherein: in the reaction system, polymerized monomer total amount is 10~25wt%,
Methyl acrylate inventory accounts for 0~6wt% of all polymerized monomer total amounts, and itaconic acid inventory accounts for all polymerized monomer total amounts
0.50wt%~2wt%, polymeric reaction temperature are 52 DEG C~80 DEG C, the reaction time 1~5 hour；
(2) the polymerization stoste that step (1) obtains is heated to 70~80 DEG C, it is high then to stitch film-lowering type by the grid vacuumized
Deaeration tower is imitated, bubble and moisture are removed；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 15~35 DEG C；
(3) stoste that step (2) obtain is heated to 75~85 DEG C, it is high then to stitch film-lowering type by the second level grid vacuumized
Deaeration tower is imitated, bubble and moisture are removed；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 35~55 DEG C；
(4) stoste that step (3) obtain is heated to 80~95 DEG C, it is high then to stitch film-lowering type by the three-level grid vacuumized
Deaeration tower is imitated, bubble and moisture are removed；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 40~58 DEG C；
(5) stoste that step (4) obtain is filtered, temperature adjustment, pressure regulation, obtains the spinning solution for meeting spinning requirement.
NaSCN aqueous solution, ZnCl are selected from for the inorganic solvent of polymerisation in solution in above-mentioned steps (1)2Aqueous solution or HNO3Water
It is any in solution.
In above-mentioned steps (1), polymeric reaction temperature is preferably 60 DEG C~70 DEG C.
In above-mentioned steps (1), in the reaction system, polymerized monomer total amount is preferably 12~18wt%.
In above-mentioned steps (1), on the basis of polymerized monomer total amount, the dosage of isopropanol is preferably 0.15~
0.25wt%.
In above-mentioned steps (2), it is preferred that polymerization stoste is heated to 72~76 DEG C, the temperature difference control of deaeration tower 19~
30℃。
In above-mentioned steps (3), it is preferred that stoste is heated to 76~80 DEG C, the temperature difference of deaeration tower is controlled at 38~50 DEG C.
In above-mentioned steps (4), it is preferred that stoste is heated to 85~90 DEG C, the temperature difference of deaeration tower is controlled at 45~55 DEG C.
The vacuum dehydration step of above-mentioned steps (2), step (3) and step (4) can recycle multiple progress, pre- until obtaining
The stoste of phase forms.
Above-mentioned steps (2), step (3) and step (4) are also suitble to spinning solution group to become PAN+ solvent+water, and (or other are low
Volatile component) system.
The present invention passes through the concentration of control polyacrylonitrile solution in polymerization stage, so that solution system viscosity in kettle
Low, heat of polymerization is easy to remove, and system temperature is uniform in kettle, be less prone to because cooling not in time caused by local temperature overheat due to
Caused reaction locally aggravates, in reaction kettle the phenomenon that runaway reaction.Therefore obtained low concentration (total solid), low viscosity it is poly-
Acrylonitrile solution structure is uniform, no microgel, best in quality；The polymerization stoste of above-mentioned acquisition is passed through into Multi-stage heating, deaeration again
The process of companion's dehydration, obtains the spinning solution of high concentration (high solids content), meets uniform, fine and close when spinning solution goes out spinneret orifice coagulate
Solid requirement.
In addition, inventor has found through a large number of experiments, polyacrylonitrile solution in reaction kettle is reduced in polymerization stage
Concentration, have no effect on the molecular weight of polyacrylonitrile solution, by control molecular weight regulator dosage, still can obtain high score
The polyacrylonitrile solution of son amount, without influencing requirement of the carbon fibre precursor to polymeric amount.Meanwhile inventor also sends out
Now, while deaeration tower efficient using grid seam film-lowering type, by controlling suitable heating temperature and the deaeration temperature difference, by macromolecule
The spinning of high concentration (high solids content) finally can be obtained by subsequent multiple vacuum deaerator, dehydration in amount, the polymerization stoste of low viscosity
Silk stock solution.Grid stitch the utilization of the efficient deaeration tower of film-lowering type, so that stoste uniform falling liquid film in deaeration tower, film surface repeats to update, water
Point removing more evenly, avoid deaeration, in dehydration secondary " micelle " generation.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention controls the viscosity of polymer fluid in kettle in polymerization stage, and required time is shorter and is easy to industrialize and connect
It is continuous, and the polymer fluid uniformity of low concentration, low viscosity significantly improves, and there is no because polymerizeing temperature in the kettle hot-spot in stoste
And " micelle " generated, secondary " micelle " will not be generated in subsequent dehydration, obtain the spinning that high compactness solidification requires
Stoste, spinning and post-processing process are steadily smooth, and obtained precursor quality is higher more stable.
2, present invention process is simple, is easy to industrialize.
Specific embodiment
Below will by specific embodiment, the invention will be further described, the solvent that the present invention uses is existing
It is common in technology, and be it is known in the art, in order to better describe Key detail of the invention, embodiment only enumerates sulphur cyanogen
Acid sodium aqueous solution is solvent.Those skilled in the art is not difficult to deduce, when the other chemical combination enumerated using technical solution of the present invention
Effect of the invention will not be had an impact when object.
[Examples 1 to 9]
The sodium thiocyanate water solution for being 48~53wt% using concentration prepares third as solvent, using the technique of continuous solution polymerization
Alkene lonitrile copolymer.The polymerized monomer of acrylonitrile copolymer includes acrylonitrile (AN), methyl acrylate (MA) and itaconic acid (ITA),
For 97:2:1 initiator azodiisobutyronitrile is added in required ratio in system, with isopropanol in the mass ratio that feeds intake of each monomer
For molecular weight regulator.The total solid content for controlling one acrylonitrile copolymer solution of polymerizate is 9~10.5wt%, and viscosity is
5500CP, molecular weight 90000.Thick stoste derived above is efficient subsequently into the grid seam film-lowering type of vacuum state by preheating
Deaeration tower, thick stoste pass through the distributor of top of tower, enter next layer in film flaky along grid seam.Through multistage de- single, deaeration and
After dehydration, stoste solid content reaches 15.5wt%, and viscosity 123600CP, obtained stoste is transparent, is spun then after filtering
Silk stock solution.
Monomer total amount, initiator amount, reaction temperature and reaction time are shown in each specific reaction system of embodiment
Table 1, the deaeration of each embodiment, dehydration conditions are shown in Table 2.
Table l
Table 2
[comparative example]
Experiment is using solvent identical with Examples 1 to 9, comonomer and initiator system, one polypropylene of polymerizate
The total solid content of nitrile solution is 15wt%, and viscosity 119000CP, after de- single, deaeration, solid content reaches copolymer solution
15.5wt% obtains spinning solution then after filtering.
Monomer total amount, initiator amount, reaction temperature and reaction time are shown in each specific reaction system of comparative example
Table 3.
Table 3.
In order to investigate embodiment and the uniformity of spinning solution that comparative example obtains, surveyed referring to the blockage factor of filtering flow
Method for testing measures the filterability of spinning solution, specific test method are as follows:
It is 25 DEG C of spinning solution in the case where imposing 150KPa pressure by temperature, respectively by being equipped with 400 mesh or 800
The filter of mesh filter material, filter nozzle outlet diameter are 3mm.500mL spinning solution is first discharged in the case where not installing nozzle, so
After nozzle is installed, then pick up the spinning solution material filtered out in 20 minutes, weigh, investigate obstruction feelings when material passes through filter
Condition.It will be appreciated that the uniformity of material better, " micelle " content it is fewer, then the material filtered out is the more.Test result is shown in Table 4.
Table 4.
Claims (9)
1. the method for homogenization preparation of a kind of high molecular weight, high concentration polyacrylonitrile-base carbon fiber spinning primary fluid, which is characterized in that
Specific step is as follows:
(1) using acrylonitrile, methyl acrylate and itaconic acid as polymerized monomer, using isopropanol as molecular weight regulator, use is inorganic
Solvent carries out polymerization reaction, obtains polymerization stoste；Wherein: in the reaction system, polymerized monomer total amount is 10~25wt%, propylene
Sour methyl esters inventory accounts for 0~6wt% of all polymerized monomer total amounts, and itaconic acid inventory accounts for all polymerized monomer total amounts
0.50wt%~2wt%, polymeric reaction temperature are 52 DEG C~80 DEG C, and the reaction time is 1~5 hour；
(2) the polymerization stoste that step (1) obtains is heated to 70~80 DEG C, then stitches film-lowering type by the grid vacuumized and efficiently takes off
Bubble column removes bubble and moisture；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 15~35 DEG C；
(3) stoste that step (2) obtain is heated to 75~85 DEG C, then stitches film-lowering type by the second level grid vacuumized and efficiently takes off
Bubble column removes bubble and moisture；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 35~55 DEG C；
(4) stoste that step (3) obtain is heated to 80~95 DEG C, then stitches film-lowering type by the three-level grid vacuumized and efficiently takes off
Bubble column removes bubble and moisture；Deaeration tower vacuum is controlled using the temperature difference, and temperature difference control is 40~58 DEG C；
(5) stoste that step (4) obtain is filtered, temperature adjustment, pressure regulation, obtains the spinning solution for meeting spinning requirement.
2. preparation method according to claim 1, which is characterized in that be used for the inorganic solvent of polymerisation in solution in step (1)
Selected from NaSCN aqueous solution, ZnCl2Aqueous solution or HNO3It is any in aqueous solution.
3. preparation method according to claim 1, which is characterized in that in step (1), polymeric reaction temperature is 60 DEG C~70
℃。
4. preparation method according to claim 1, which is characterized in that in step (1), in the reaction system, polymerized monomer
Total amount is 12~18wt%.
5. preparation method according to claim 1, which is characterized in that in step (1), on the basis of polymerized monomer total amount,
The dosage of isopropanol is 0.15~0.25wt%.
6. preparation method according to claim 1, which is characterized in that in step (2), polymerization stoste is heated to 72~76
DEG C, the temperature difference control of deaeration tower is 19~30 DEG C.
7. preparation method according to claim 1, which is characterized in that in step (3), stoste is heated to 76~80 DEG C,
The temperature difference control of deaeration tower is 38~50 DEG C.
8. preparation method according to claim 1, which is characterized in that in step (4), stoste is heated to 85~90 DEG C,
The temperature difference control of deaeration tower is 45~55 DEG C.
9. preparation method according to claim 1, which is characterized in that the vacuum of step (2), step (3) and step (4) is de-
The step of bubble removing and moisture, circuits sequentially multiple progress, until obtaining expected stoste composition.
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| CN1536107A (en) * | 2003-04-04 | 2004-10-13 | 中国石油天然气集团公司 | Preparation method of polyacrylonitrile carbon raw yarn |
| CN102400239A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for manufacturing polyacrylonitrile base carbon fiber precursor |
| CN102400234A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for preparing polyacrylonitrile-based carbon fiber protofilament spinning stock solution |
| CN102953141A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament |
| CN103469316A (en) * | 2013-09-11 | 2013-12-25 | 中石化上海工程有限公司 | Defoaming method for PAN (Polyacrylonitrile) carbon fiber stock solution preparation |
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| JPS60209005A (en) * | 1984-03-28 | 1985-10-21 | Toray Ind Inc | Wet or dry jet-wet spinning method and apparatus therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536107A (en) * | 2003-04-04 | 2004-10-13 | 中国石油天然气集团公司 | Preparation method of polyacrylonitrile carbon raw yarn |
| CN102400239A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for manufacturing polyacrylonitrile base carbon fiber precursor |
| CN102400234A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for preparing polyacrylonitrile-based carbon fiber protofilament spinning stock solution |
| CN102953141A (en) * | 2011-08-25 | 2013-03-06 | 中国石油化工股份有限公司 | Manufacturing method for polyacrylonitrile-based carbon fiber protofilament |
| CN103469316A (en) * | 2013-09-11 | 2013-12-25 | 中石化上海工程有限公司 | Defoaming method for PAN (Polyacrylonitrile) carbon fiber stock solution preparation |
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