CN105088422B - Polyacryl-nitrile spinning fluid fills ammonia method in preparing - Google Patents
Polyacryl-nitrile spinning fluid fills ammonia method in preparing Download PDFInfo
- Publication number
- CN105088422B CN105088422B CN201510516718.0A CN201510516718A CN105088422B CN 105088422 B CN105088422 B CN 105088422B CN 201510516718 A CN201510516718 A CN 201510516718A CN 105088422 B CN105088422 B CN 105088422B
- Authority
- CN
- China
- Prior art keywords
- ammonia
- spinning solution
- spinning
- amount
- polyacryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 92
- 238000009987 spinning Methods 0.000 title claims abstract description 84
- 239000012530 fluid Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000003860 storage Methods 0.000 claims abstract description 14
- 238000005259 measurement Methods 0.000 claims abstract description 13
- 230000003068 static effect Effects 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005189 flocculation Methods 0.000 abstract description 3
- 230000016615 flocculation Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000004176 ammonification Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 150000003863 ammonium salts Chemical group 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
The method of ammonia is filled in being prepared the present invention relates to a kind of polyacryl-nitrile spinning fluid, belongs to the preparation field of high polymer material, it is characterised in that comprise the following steps：Lead to increase spinning solution flow meter on deaeration kettle pipeline in spinning liquid storage tank, the amount of ammonia is calculated for the amount of accurate measurement material, and the amount of the frequency accurate measurement spinning solution of spinning solution delivery pump is controlled by spinning solution flow meter, make the flow constant of material；Ammonia entrance is installed after spinning solution flow meter, and sets up the amount that ammonia is filled in the control of ammonia flow gauge；Static mixer is installed after ammonia entrance, ammonia is set to enter deaeration kettle after being sufficiently mixed with material, ammonia is sufficiently mixed with material in static mixer, prevent from causing the generation of small flocculation because ammonia is uneven, and extracted under the throwing disc and condition of negative pressure of unnecessary ammonia in deaeration kettle from material.
Description
Technical field
The present invention relates to a kind of preparation field of high polymer material, in prepared by specifically a kind of polyacryl-nitrile spinning fluid
Fill the method for ammonia.
Background technology
At present, carbon fiber is a kind of material of excellent performance, is with intensity height, modulus height, high temperature resistant, resistance to ablation etc. one
Arrange significant advantage.The every field such as Aeronautics and Astronautics, communications and transportation and Leisure Sport have been widely used at present, have been boats
Important substance guarantee and promoting technology power that empty Space Equipment, vehicles etc. develop to lighting, high-performance and high reliability.
The carbon fiber of high-quality is obtained, the precursor of high-quality is crucial.Therefore, the production of the China of raising comprehensively carbon fiber is wanted
Level it may first have to improve the level of production of precursor.In the production process of precursor, the production of spinning solution is a critically important step,
And it is an important step for producing spinning solution to fill ammonia, filling ammonia process makes spinning solution ammonification, and the spinning solution after ammonification has more
Hydrophily well, the diffusion velocity that can preferably suppress solidification phase separation reclaimed water simultaneously help to terminate polymerisation.Fill
The amount of ammonia also has certain scope, typically there is two quality index to the amount for filling ammonia, and one is to make carboxyl ammonification amount be 20% or so,
Two be that the pH value for making polymer fluid is controlled 8~10, is preferably controlled between 8.5~9.5., can be to spinning solution if it is too high to fill ammonia amount
There is thickening effect, and excess of ammonia gas can be escaped at any time, made spinning solution unstable, directly affected spinning effect, so strictly
It is to stablize the premise of ammonification effect that ammonia amount is filled in control.
It is general to reach ammonification effect using disposably ammonia is filled in polymerisation latter stage in production carbon fiber spinning solution, it is main
Flow such as Fig. 3 is wanted, fills inventory of the amount of ammonia in reactor to determine.
From the figure 3, it may be seen that it is that in polymeric kettle, it is in polymerisation latter stage to fill the ammonia time to fill ammonia position.According to polymer material
The amount of ammonia, ammonia is disposably filled using the mode weighed needed for amount is calculated.
This is a kind of production widely used shortcoming filled ammonia mode, be primarily present of carbon fiber：It polymerize temperature in the kettle too high,
Fill ammonia after ammonia to react rapidly with material, be likely to result in the generation of small range gel particle；Disposably ammonia, ammonia are filled in polymeric kettle
Stirring is uneven；Material is too many in polymeric kettle, and the amount of ammonia can not accomplish accurate measurement.
The content of the invention
In order to overcome the deficiencies in the prior art, the present invention provides a kind of method that ammonia is filled in prepared by polyacryl-nitrile spinning fluid,
Polyacryl-nitrile spinning fluid pH stable, fills ammonia, temperature is relatively low after material is cooled down through spinning liquid storage tank, favorably on spinning solution pipeline
It is ammonium salt in the dissolving of ammonia and converting carboxylate groups, and because pipeline space is smaller and installs static mixer additional, is conducive to ammonia
Uniform with material is mixed so that the polyacryl-nitrile spinning fluid better performances of preparation, and lot stability is improved.
The technical solution adopted for the present invention to solve the technical problems is：A kind of polyacryl-nitrile spinning fluid fills ammonia in preparing
Method, it is characterised in that comprise the following steps：Lead to increase spinning solution flow meter on deaeration kettle pipeline in spinning liquid storage tank, be used for
The amount of accurate measurement material controls the frequency of spinning solution delivery pump accurate to calculate the amount of ammonia by spinning solution flow meter
The amount of spinning solution is measured, makes the flow constant of material；Ammonia entrance is installed after spinning solution flow meter, and sets up ammonia flow
Gauge controls to fill the amount of ammonia；Static mixer is installed after ammonia entrance, ammonia is entered deaeration after being sufficiently mixed with material
Kettle, ammonia is sufficiently mixed with material in static mixer, prevents from causing the generation of small flocculation because ammonia is uneven, and
Unnecessary ammonia is extracted under the throwing disc and condition of negative pressure in deaeration kettle from material.
The present invention can be also achieved by the following measures：Ammonia inlet diameter is designed in below 1mm.
The beneficial effects of the invention are as follows polyacryl-nitrile spinning fluid pH stable fills ammonia, material is through spinning on spinning solution pipeline
Temperature is relatively low after silk liquid storage tank cooling, and the dissolving and converting carboxylate groups for being conducive to ammonia are ammonium salt, and because pipeline space is smaller
And install static mixer additional, be conducive to ammonia to be mixed with the uniform of material so that the polyacryl-nitrile spinning fluid better performances of preparation,
Lot stability is improved.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is process chart of the invention.
Fig. 2 is the structural representation of polyacryl-nitrile spinning fluid preparation facilities of the present invention.
Fig. 3 is the process chart of background of invention.
Fig. 4 is the spinning solution pH value in comparative example spinning liquid storage tank.
Fig. 5 is the spinning solution pH value in embodiment spinning liquid storage tank.
1. spinning solution delivery pump in figure, 2. spinning solution flow meters, 3. ammonia regulating valves, 4. ammonia flow gauge, 5. is static mixed
Clutch, 6. deaeration kettles, 7. polymeric kettles, 8. spinning liquid storage tanks.
Embodiment
As shown in Figure 1 and Figure 2, a kind of polyacryl-nitrile spinning fluid fills the method for ammonia in preparing, and its step includes：
（1）Spinning solution accurate measurement：Lead in spinning liquid storage tank 8 and spinning solution flow meter 2 is installed on the pipeline of deaeration kettle 6, use
In the amount of accurate measurement spinning solution, according to the flow of the flow control ammonia of spinning solution.There is spinning solution before spinning solution flow meter 2
Delivery pump 1, sets spinning solution flow meter 2 to control the frequency of spinning solution delivery pump 1, the flow of spinning solution is kept in a long time
It is constant.
（2）Ammonia accurate measurement：Ammonia entrance is set up after spinning solution flow meter 2, and ammonia flow gauge 4 and ammonia are installed
Regulating valve 3 controls to fill the amount of ammonia.Being calculated according to spinning solution flow needs the amount of ammonia, and in normal production, the flow of ammonia is
Fixed value.To prevent on pipeline pressure is excessive to cause spinning solution to block ammonia entrance, ammonia pressure is influenceed, causes to fill the change of ammonia amount
Change, ammonia inlet diameter is designed in below 1mm；
（3）Ammonia is sufficiently mixed with material：Static mixer 5 is installed after ammonia entrance, ammonia is filled with spinning solution
Divide and enter deaeration kettle 6 after mixing, ammonia is sufficiently mixed in static mixer 5 with spinning solution, prevents from making because ammonia is uneven
Pulled out into the generation of small flocculation, and under the throwing disc and condition of negative pressure of unnecessary ammonia in deaeration kettle 6 from spinning solution
Come, reduce the influence to spinning threadling coagulating bath.
The present invention operation principle be：When preparing polyacryl-nitrile spinning fluid, ammonification is a very important step, ammonia
Change makes spinning solution be changed into middle strong basicity from faintly acid, and strand section is solidified after ammonification and is more easy to as circle, the precursor degree of orientation of ammonification,
Relative density and carbon fiber tensile strength are all higher than non-ammonification.But in process of production, fill ammonia position and mode to ammonia
The effect of change has a great impact, and ammonia is filled in accurate measurement on pipeline, is conducive to being sufficiently mixed for ammonia and spinning solution, improves poly-
The stability of acrylonitrile spinning solution pH value.
Comparative example：Polymerization reaction late stage fills ammonia in polymeric kettle 7, determines the spinning solution pH value in spinning liquid storage tank, sees figure
4。
Embodiment：Lead to accurate measurement on the pipeline of deaeration kettle 6 in spinning liquid storage tank 8 and fill ammonia, determine in spinning liquid storage tank and spin
Silk liquid pH value, is shown in Fig. 5.
It can be seen that according to specifically comparing for upper figure：
（1）From comparative example as can be seen that after polymerization the phase fill ammonia, spinning solution pH value is changed greatly, and pH is relative
Higher, CV values are 4.43%；
（2）From embodiment as can be seen that spinning liquid storage tank it is unconventional bubble kettle pipeline on accurate measurement fill ammonia, spinning solution pH value
Change is smaller, and CV values are 1.96%；
（3）Compare comparative example, embodiment can be seen that spinning liquid storage tank it is unconventional bubble kettle pipeline on filled by accurate measurement
Preferably, the stability bandwidth of spinning solution pH value is small compared with when polymeric kettle fills ammonia, and the pH value of spinning solution is maintained at preferable for ammonia effect
In the range of, this has using the appearance of spinning solution thickening behavior is prevented, can obtain the polyacryl-nitrile spinning fluid of excellent performance.
Claims (2)
1. a kind of polyacryl-nitrile spinning fluid fills ammonia method in preparing, it is characterised in that comprise the following steps：In spinning liquid storage tank
Lead to increase spinning solution flow meter on deaeration kettle pipeline, the amount of ammonia is calculated for the amount of accurate measurement material, and by spinning
Silk flow meters control the amount of the frequency accurate measurement spinning solution of spinning solution delivery pump, make the flow constant of material；
Ammonia entrance is installed after spinning solution flow meter, and sets up the amount that ammonia is filled in the control of ammonia flow gauge；Install quiet after ammonia entrance
State blender, makes ammonia enter deaeration kettle after being sufficiently mixed with material, ammonia is sufficiently mixed with material in static mixer, many
Remaining ammonia is extracted under the throwing disc and condition of negative pressure in deaeration kettle from material.
2. polyacryl-nitrile spinning fluid fills the method for ammonia according to claim 1 in preparing, it is characterised in that described ammonia enters
Mouth diameter design is in below 1mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510516718.0A CN105088422B (en) | 2015-08-21 | 2015-08-21 | Polyacryl-nitrile spinning fluid fills ammonia method in preparing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510516718.0A CN105088422B (en) | 2015-08-21 | 2015-08-21 | Polyacryl-nitrile spinning fluid fills ammonia method in preparing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105088422A CN105088422A (en) | 2015-11-25 |
| CN105088422B true CN105088422B (en) | 2017-10-24 |
Family
ID=54569714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510516718.0A Active CN105088422B (en) | 2015-08-21 | 2015-08-21 | Polyacryl-nitrile spinning fluid fills ammonia method in preparing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105088422B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113718375B (en) * | 2021-10-14 | 2023-06-16 | 山东永成新材料有限公司 | Method and device for post-treatment of carbon fiber production stock solution |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171918C (en) * | 2002-08-13 | 2004-10-20 | 中国科学院山西煤炭化学研究所 | Method for preparing polyacrylonitrile based carbon fibre spinning solution |
| CN202152326U (en) * | 2011-06-29 | 2012-02-29 | 中国科学院宁波材料技术与工程研究所 | Ammoniation treatment device for polyacrylonitrile polymerization liquid |
| CN102336865B (en) * | 2011-06-29 | 2013-08-28 | 浙江泰先新材料股份有限公司 | Ammonification method of polyacrylonitrile polymerization liquid and device for realizing same |
| JP5906734B2 (en) * | 2011-12-28 | 2016-04-20 | 三菱レイヨン株式会社 | Method for producing nitrogen-containing compound |
-
2015
- 2015-08-21 CN CN201510516718.0A patent/CN105088422B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105088422A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106478940B (en) | Prepare continuous micro-reaction device, method and the product of meta-aramid resin | |
| CN103910974A (en) | Hollow-microsphere-filled epoxy resin composite foam material and preparation method thereof | |
| CN104611779B (en) | A kind of ammonating process of polyacrylonitrile spinning solution and its device | |
| CN104372445A (en) | Preparation method of polyacrylonitrile carbon fiber with evenly distributed copolymerization sequence | |
| CN105088422B (en) | Polyacryl-nitrile spinning fluid fills ammonia method in preparing | |
| CN102627448A (en) | Method for preparing ceramic fibers | |
| CN110054727B (en) | Preparation method and device of polyacrylamide nano-microspheres | |
| CN104250330B (en) | Dicyclopentadiene and carbon cloth combined manhole cover and manufacture method thereof | |
| CN104028173A (en) | Polymerizer feeding device and using method thereof | |
| CN205024370U (en) | Fill ammonia device in preparation of polyacrylonitrile dope | |
| CN1029578C (en) | Nuclear fuel micro ball prepared by full gelatinizing method | |
| CN104945548B (en) | Preparation method of ultrahigh-molecular-weight polyacrylamide | |
| CN105732867B (en) | Rare-earth isoprene rubber solution polymerization method | |
| CN105400470B (en) | A kind of LED white-light nixie tubes packaging plastic and preparation method thereof | |
| CN216856695U (en) | Device for controlling slurry fluidity and curing efficiency | |
| CN203971898U (en) | A kind of constant voltage feed system of copolymer emulsion | |
| CN212374903U (en) | Colloidal antimony pentoxide manufacturing device | |
| CN209237920U (en) | A kind of production equipment of gasoline and diesel hydrogenation antisludging agent | |
| CN203782211U (en) | Rare earth oxalate precipitation reaction device | |
| CN204914273U (en) | Resin diamond wire saw system line constant temperature feeding system | |
| CN107353368B (en) | Ammonia adding device for PAN (polyacrylonitrile) polymerization liquid | |
| CN207143163U (en) | The ammonifying device of PAN polymer fluids | |
| CN206351039U (en) | A kind of carbon fibre precursor polymerize continuous feed system | |
| CN203144315U (en) | Automatic natural latex parallel-flow acid adding device | |
| CN211561943U (en) | Mixed resin defoaming device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240412 Address after: 264200 No.6, Kaiyuan West Road, Lingang Economic and Technological Development Zone, Weihai City, Shandong Province Patentee after: WEIHAI TUOZHAN FIBER Co.,Ltd. Country or region after: China Patentee after: Inner Mongolia Guangwei Carbon Fiber Co.,Ltd. Address before: 264200 North Zhejiang Road and West Kaiyuan Road, Lingang District, Weihai City, Shandong Province Patentee before: WEIHAI TUOZHAN FIBER Co.,Ltd. Country or region before: China |