CN115368502B - Method for starting up aqueous suspension polymerization device by using seed slurry and prepared polymer - Google Patents
Method for starting up aqueous suspension polymerization device by using seed slurry and prepared polymer Download PDFInfo
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- CN115368502B CN115368502B CN202110547546.9A CN202110547546A CN115368502B CN 115368502 B CN115368502 B CN 115368502B CN 202110547546 A CN202110547546 A CN 202110547546A CN 115368502 B CN115368502 B CN 115368502B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 120
- 239000002002 slurry Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 10
- 239000007900 aqueous suspension Substances 0.000 title description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 209
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000000178 monomer Substances 0.000 claims description 53
- 239000008367 deionised water Substances 0.000 claims description 50
- 229910021641 deionized water Inorganic materials 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 12
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 5
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 5
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 5
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 8
- 230000000087 stabilizing effect Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 18
- 229920002239 polyacrylonitrile Polymers 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000012797 qualification Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 230000009172 bursting Effects 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 3
- 239000001284 azanium sulfanide Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037390 scarring Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a method for starting a water-phase suspension polymerization device by using seed slurry, and a prepared polymer, comprising a first polymerization kettle and a second polymerization kettle, wherein when the second polymerization kettle is required to start in the working state of normal polymerization of the first polymerization kettle, the method for starting the water-phase suspension polymerization device comprises the following steps: and (3) inputting the slurry overflowed from the first polymerization kettle into a second polymerization kettle, and after the second polymerization kettle overflows, adding various raw materials of the polymer into the second polymerization kettle to perform polymerization reaction. According to the multi-kettle start-up feeding method, the discharging slurry of the working polymerization kettle is input into the polymerization kettle to be started up and used as seed slurry, so that the polymerization start-up stabilizing time of the polymerization kettle to be started up can be shortened, the generation of unqualified polymers is reduced, and the uniform and stable product quality is facilitated.
Description
Technical Field
The invention belongs to the field of carbon fiber production, and particularly relates to a method for starting a water phase suspension polymerization device by using seed slurry and a prepared polymer.
Background
The process for producing the carbon fiber precursor comprises three working sections of polymerization, dope and spinning. In the current aqueous suspension polymerization process, the polymerization kettle is started in an empty kettle way, and mixed monomers, catalysts, activators, sulfuric acid, itaconic acid and desalted water are fed and polymerized according to the formula. The stability of polymerization feeding and starting in the production process of polyacrylonitrile-based carbon fiber precursor directly relates to the uniformity and stability of polymer quality and the generation of unqualified polymer, and influences the quality of glue preparation of subsequent stock solution, spinning spinnability and precursor product quality.
However, the temperature of the empty kettle of the existing polymerization kettle can be increased after about 40 minutes after the material is fed, the temperature is not easy to control, once the temperature is increased quickly, the inside of the polymerization kettle is extremely easy to explode and gather, and slurry is thick after overflowing, and the slurry is not easy to flow and blocks an overflow port of the polymerization kettle. After overflow, the materials can be diluted after the material formula is replaced, and the phenomenon of sticking of the materials is gradually relieved. Because the polymerization idle kettle starting method has long polymerization residence time and immature formula, the phenomena of bursting and aggregation can be generated sometimes after feeding and starting, the kettle temperature is not easy to control, the materials are sticky and easy to block pipelines and filters, the labor capacity of workers is greatly increased, a large amount of unqualified polymers are generated, the production is unstable, and the quality of polymer products is seriously affected.
The Chinese patent with the application number of CN201110170206.5 discloses a continuous polymerization kettle starting method for polyacrylonitrile precursor polymerization liquid, and the influence of air on polymerization reaction is reduced by isolating air through protective gas before a polymerization reaction kettle feeds materials. When the accumulated materials in the polymerization reaction kettle reach the upper surface of the temperature measuring port of the polymerization reaction kettle, the temperature of the polymerization reaction kettle is controlled, and the polymerization temperature is controlled and the continuous feeding of the materials is performed simultaneously. In the technical scheme, materials required by the polymerization reaction are introduced into a polymerization kettle, and the temperature is controlled after the kettle is full, but the mode still has the problems that the temperature is quickly raised and is not easy to control, slurry is sticky after overflow, the slurry is not easy to flow and an overflow port of the polymerization kettle is blocked.
In addition, according to the demand of the order of the precursor, the yields of the three working sections should be kept balanced, so that the polymerization working section can perform double-kettle starting or multi-kettle starting according to the demand of the spinning yield and the capacity of the stock bin at different periods. When a single kettle is operated, double-kettle driving or multi-kettle driving is carried out, so that qualified polymers are easily mixed with unqualified polymers generated by driving, and a large amount of unqualified polymers are generated. The traditional driving mode (namely, feeding and driving of an empty kettle) is long in qualified time of polymer indexes, and meanwhile, a large amount of unqualified polymers can be generated when double kettles are operated, so that cost is wasted.
The present invention has been made in view of this.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a method for feeding and starting a water-phase suspension polymerization device and a prepared polymer. According to the multi-kettle start-up feeding method, the discharging slurry of the working polymerization kettle is input into the polymerization kettle to be started up and used as seed slurry, so that the polymerization start-up stabilizing time of the polymerization kettle to be started up can be shortened, the generation of unqualified polymers is reduced, and the uniform and stable product quality is facilitated.
In order to solve the technical problems, the invention adopts the basic conception of the technical scheme that:
the first object of the invention is to provide a method for feeding and starting a water-phase suspension polymerization device, which comprises a first polymerization kettle and a second polymerization kettle, wherein when the second polymerization kettle is required to start under the working state of normal polymerization of the first polymerization kettle, the method for starting and feeding the second polymerization kettle comprises the following steps:
and (3) inputting the discharged slurry overflowed from the first polymerization kettle into a second polymerization kettle, and after the second polymerization kettle overflows, adding various raw materials of the polymer into the second polymerization kettle to perform polymerization reaction.
In the existing production method, in order to meet the yield requirement, when the second polymerization kettle is required to start production under the condition that the first polymerization kettle is in polymerization operation, a mode of independently starting the second polymerization kettle is adopted. That is, when the second polymerizer needs to be started under the single-kettle operation condition, deionized water is introduced into the polymerizer to be operated to establish a low liquid level (10% -45%), and various monomers, catalysts, activators, acid agents and desalted water are fed into the polymerizer according to the formula proportion for polymerization. The second polymeric kettle in this way needs to be heated for about 40 minutes to rise, and the temperature is not easy to control, once the temperature rises faster, the inside of the polymeric kettle is extremely easy to explode and gather, and the slurry is sticky after overflow, and is not easy to flow, so that overflow ports of the polymeric kettle are blocked, and a large number of unqualified products are caused. The double-kettle starting or multi-kettle starting is carried out in this way, so that the qualified polymer produced by the running polymerization kettle is very easy to be confused with the unqualified polymer produced by the polymerization kettle which is just started, a large amount of unqualified polymer is produced, and waste is caused.
In the invention, when the second polymerizer is required to be started in the working state of normal polymerization of the first polymerizer, discharging slurry overflowed from the first polymerizer is input into the second polymerizer, and after the second polymerizer overflows, all raw materials of the polymer are put into the second polymerizer for polymerization reaction. Therefore, the discharging slurry of the running polymerization kettle is used as the seed slurry of the second polymerization kettle, so that the second polymerization kettle can quickly reach a stable starting state, the generation of unqualified polymers is reduced, the time for reaching qualified indexes after the polymerization starting is shortened, the cost consumption is reduced, and the production benefit is improved. The driving mode is simple, feasible and easy to control, and the existing polymerization device of the existing polymer can be used for organizing production without adding any equipment.
The number of the first polymerization kettles is not limited, and the first polymerization kettles can be one polymerization kettle or a plurality of polymerization kettles; the number of the second polymerizers is not limited, and may be one or more. The overflow slurry from one first polymerizer may be fed to one or more second polymerizers, or the overflow slurry from a plurality of first polymerizers may be fed to one or more second polymerizers.
Further, under the normal production state of the first polymerization kettle, the feeding and starting method of the second polymerization kettle comprises the following steps:
(1) Filling deionized water into the second polymerization kettle to establish a liquid level, wherein the liquid level is 10% -30%;
(2) Introducing an acid agent to adjust the pH value;
(3) Feeding the discharge slurry from the first polymerizer to the second polymerizer,
(4) Stopping inputting after the second polymerizer overflows and the solid content of the slurry of the first polymerizer is consistent with that of the slurry of the second polymerizer, and adding an oxidant, a reducing agent, a first polymerized monomer, a second polymerized monomer, a third polymerized monomer and acidified deionized water into the second polymerizer to carry out polymerization reaction.
When the second polymerization kettle is charged and driven, only a very low liquid level of 10% -30% is needed to be established, a certain temperature is maintained, the discharged slurry in the first polymerization kettle is input into the second polymerization kettle to be used as seed slurry, deionized water is gradually replaced until the second polymerization kettle overflows, the solid contents of the slurry in the first polymerization kettle and the slurry in the second polymerization kettle are consistent, then materials are fed into the second polymerization kettle, and then the discharged slurry in the second polymerization kettle is a qualified product. Therefore, on one hand, the second polymerization kettle only needs to establish a very low liquid level, and the dosage of deionized water is small, and on the other hand, the unstable time of the earlier stage of the second polymerization kettle can be greatly shortened, so that the second polymerization kettle can quickly reach a stable starting state, and the generation of unqualified polymers can be greatly reduced.
In a further scheme, in the step (1), the temperature of deionized water in the second polymerization kettle is controlled to be 50-60 ℃; preferably 50-55 ℃.
When the polymerization kettle independently operates to establish liquid level, the temperature needs to be ensured to be 60-70 ℃ for subsequent reaction; in the normal operation state of the first polymerization kettle, the temperature of the discharged slurry is 50-70 ℃, so that the temperature of the deionized water with the built liquid level in the second polymerization kettle is not required to be controlled to be too high, the temperature of the deionized water with the built liquid level is 50-60 ℃, the requirement can be met, and the energy consumption of heating can be saved.
In a further scheme, in the step (4), the temperature of the second polymerization kettle is controlled to be 50-60 ℃; preferably 52-58 ℃.
In a further scheme, in the step (2), the pH value is controlled to be 2-3.5.
Further, the solids content of the effluent slurry in the first polymerizer is 22 to 26%, the intrinsic viscosity is 0.220 to 224L/g, and the conversion is 86 to 90%.
The solid content and the intrinsic viscosity of the discharged slurry in the first polymerization kettle are continuously detected and stable for 3 times, and when the discharged slurry reaches the qualified range, the discharged slurry is input into the second polymerization kettle and can be used as seed slurry, and the generation of unqualified polymer is reduced.
Further, the feeding and starting method of the first polymerization kettle comprises the following steps:
(1) Filling deionized water into the empty polymerization kettle, and establishing a liquid level, wherein the volume of the added deionized water is 75-98% of the volume of the polymerization kettle; preferably, the liquid level is established to 80-95%;
(2) Introducing an acid agent, and adjusting the pH value to be less than or equal to 2.5;
(3) Adding a cocatalyst and stirring;
(4) Adding an oxidant and a reducing agent, and stirring;
(5) And (3) adding the first polymerization monomer, the second polymerization monomer, the third polymerization monomer and the acidified deionized water for polymerization reaction to obtain polymer slurry.
The invention also improves the feeding and starting mode of the single kettle. In the prior art, the polymerization kettle adopts a mode of empty kettle feeding or half kettle feeding (10-45% liquid level is established), the polymerization kettle can rise after about 40 minutes, the temperature is not easy to control, once the temperature rises faster, the inside of the polymerization kettle is extremely easy to burst, and a large amount of unqualified polymers are generated.
When the single kettle is charged and started, deionized water is firstly introduced into the polymerization kettle, 75-98% of liquid level is established, the temperature of the deionized water is controlled, the starting stability time of the polymerization kettle can be shortened, meanwhile, the temperature of the polymerization kettle is easy to control, the phenomenon of bursting and gathering in the polymerization kettle can be avoided, the generation of unqualified polymers can be reduced, the production stability is ensured, and the quality of polymer products is ensured.
As a preferable scheme, deionized water is firstly introduced into the polymerization kettle, the liquid level is established to 80-95%, the time for starting the polymerization kettle to stabilize is shorter, and the amount of unqualified polymer is smaller.
In a further scheme, in the step (1), the temperature of deionized water is controlled to be 60-70 ℃; preferably 62-65 ℃.
In the invention, deionized water with a liquid level of 75-98% is firstly introduced into a polymerization kettle, and the temperature of the deionized water is controlled at 60-70 ℃. Because the specific heat of water is good, the heating is easy, the temperature of the polymerization kettle is easy to control, the temperature rise is quick, and a stable environment can be provided for subsequent feeding quickly. The subsequent continuous feeding of materials can still maintain a stable environment, can avoid the phenomenon of bursting and gathering inside the polymerization kettle, and can reduce the generation of unqualified polymers.
Further still, in step (3), the promoter is selected from the group consisting of ferrous sulfate; the feeding amount of the ferrous sulfate is 0.0001-0.0009wt% based on the feeding total amount of all materials.
In the present invention, an oxidizing agent and a reducing agent are used as an initiator system. The initiator efficiency can be further improved by adding the cocatalyst prior to the addition of the oxidizing agent and the reducing agent. Specifically, when ferrous sulfate is used as an initiator, the following reaction occurs: s is S 2 O 8 2- +Fe 2+ —Fe 3+ +SO 4 2- +SO 4 - ；HSO 3 - +Fe 3+ —Fe 2+ +HSO 3 The method comprises the steps of carrying out a first treatment on the surface of the Thus, the initiation efficiency can be improved.
In a further scheme, after the cocatalyst is added, oxidant and reducing agent are added at intervals; the interval time is proper, the interval time is too long, and the cocatalyst is easy to react with oxygen in a contact way, so that the auxiliary catalytic performance is reduced; the interval time is too short, the cocatalyst is unevenly dispersed, and the cocatalyst cannot be uniformly contacted with the oxidant and the reducing agent.
Preferably, the oxidant and reductant are added after 5-10 minutes of adding the promoter. Thus, the cocatalyst can be fully and uniformly dispersed in the polymerization kettle, and can be fully contacted with the input oxidant and reducing agent, so that the initiation efficiency is improved.
Further, after the oxidant and the reducing agent are added, stirring is performed for 30-50 minutes.
After the oxidant and the reducing agent are added, stirring and running are carried out for 30-50 minutes, so that a uniform redox initiation environment is formed, and a primary free radical is generated to initiate a monomer to react to generate a monomer free radical, thereby facilitating the rapid and uniform polymerization after the monomer is put into the polymer, and facilitating the acquisition of a polymer with uniform and stable quality.
In a further scheme, in the step (5), the temperature of the polymerization kettle is controlled to be 50-70 ℃, and the reaction time is controlled to be 50-300 minutes.
In the invention, the raw materials adopted by the first polymerization kettle and/or the second polymerization kettle are as follows:
the first polymeric monomer comprises acrylonitrile and,
the second polymer monomer is selected from one of methyl acrylate, vinyl acetate and acrylamide;
the third polymerization monomer is selected from one of itaconic acid, acrylic acid, acrylamide and methacrylic acid;
the feeding amount of the first polymeric monomer is 90-98wt%, the feeding amount of the second polymeric monomer is 1-7wt% and the feeding amount of the third polymeric monomer is 1-3wt% based on the total feeding amount of all polymeric monomers;
the oxidant is one or more selected from ammonium persulfate, potassium persulfate and hydrogen peroxide; the reducing agent is one or more selected from ammonium bisulfate, ammonium sulfite, sodium bisulfate, sodium sulfite and sodium metabisulfite;
the feeding amount of the oxidant is 0.3-1.5wt% and the feeding amount of the reducing agent is 0.05-0.35wt% based on the feeding total amount of all materials;
the acid agent is selected from one or more of sulfuric acid, sulfurous acid and nitric acid, and is preferably sulfuric acid;
the feeding amount of the acidified deionized water is 60-85wt% based on the total feeding amount of all materials.
The second object of the invention is to provide a polyacrylonitrile polymer, wherein the solid content of the polyacrylonitrile polymer is 15-35%, the intrinsic viscosity is 0.220-0.225L/g, the viscosity average molecular weight is 45000-120000, the molecular weight distribution index is 2.10-2.80, the qualification rate is 95-97%, the conversion rate is 85-92%, the polymer has good solubility in a solvent, and the polymer particle diameter is less than 100um and reaches more than 95%;
preferably, the polyacrylonitrile polymer is prepared by adopting the feeding and starting method of the aqueous phase suspension polymerization device according to any one of the scheme or the combination scheme.
The polymer prepared by the invention has high qualification rate, good uniformity and stability and small batch-to-batch difference, and is beneficial to subsequent spinning.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects:
1. when the second polymerizer is required to be started in the normal polymerization working state of the first polymerizer, the discharged slurry overflowed from the first polymerizer is input into the second polymerizer, and after the second polymerizer overflows, all raw materials of the polymer are put into the second polymerizer to carry out polymerization reaction. Therefore, the discharging slurry of the running polymerization kettle is used as the seed slurry of the second polymerization kettle, so that the second polymerization kettle can quickly reach a stable starting state, the generation of unqualified polymers is reduced, the time for reaching qualified indexes after the polymerization starting is shortened, the cost consumption is reduced, and the production benefit is improved. The driving mode is simple, feasible and easy to control, and the existing polymerization device of the existing polymer can be used for organizing production without adding any equipment.
2. The method for feeding and starting the first polymerization kettle uses a full kettle starting mode, so that not only can the starting stable time be shortened, but also the generation of unqualified polymers can be reduced, meanwhile, the temperature of the polymerization kettle is easy to control, the solid content of the polymerization kettle is monitored after feeding, the intrinsic viscosity of slurry is detected, and the slurry is adjusted according to indexes.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments will be clearly and completely described in conjunction with the embodiments of the present invention, and the following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
The methods for detecting the performance parameters used in the following examples, test examples and comparative examples may be conventional methods unless otherwise specified.
Example 1
The first polymerization kettle is started to operate, and the polyacrylonitrile-based polymer is prepared, which comprises the following steps:
(1) Deionized water is filled into the empty polymerization kettle, and a liquid level of 80% is established; controlling the temperature to 63+/-1 ℃, immersing the liquid level into a layer of stirring, and immediately starting the stirring;
(2) Introducing concentrated sulfuric acid, and adjusting the pH value to be less than or equal to 2.5;
(3) Adding 0.0005 (wt) ferrous sulfate solution, stirring and running for 8 minutes;
(4) Adding 0.3 (wt%) of ammonium persulfate and 0.05 (wt%) of ammonium bisulfate, stirring and running for 40 min;
(5) Adding 27.8 (wt%) of acrylonitrile, 0.86 (wt%) of methyl acrylate, 0.29 (wt%) of itaconic acid, 0.02 (wt%) of sulfuric acid and 71.5 (wt%) of deionized water, controlling polymerization kettle temperature to 58+/-1 deg.C, and making polymerization reaction so as to obtain polymer slurry;
(6) The polymer slurry is subjected to the processes of removing monomers, washing and drying in sequence to obtain the polymer.
The index parameters of the prepared polymer are as follows: the intrinsic viscosity is 0.225, the solid content is 25%, the conversion rate is 90%, the viscosity average molecular weight is 71000, the molecular weight distribution index is 2.20, the qualification rate is 97%, the polymer has good solubility in a solvent, and the polymer particle diameter is 96% or less below 100 um.
Example 2
The first polymerization kettle is started to operate, and the polyacrylonitrile-based polymer is prepared, which comprises the following steps:
(1) Deionized water is filled into the empty polymerization kettle, and a 90% liquid level is established; controlling the temperature to be 61+/-1 ℃, immersing the liquid level into a layer of stirring, and immediately starting the stirring;
(2) Introducing concentrated sulfuric acid, and adjusting the pH value to be less than or equal to 2.5;
(3) Adding 0.0008 (wt) of ferrous sulfate solution, and stirring and running for 9 minutes;
(4) Adding 1.5 (wt%) of ammonium persulfate and 0.3 (wt%) of ammonium bisulfate, stirring and running for 30 min;
(5) Adding 25.6 (wt%) of acrylonitrile, 0.54 (wt%) of methyl acrylate, 0.53 (wt%) of itaconic acid, 0.02 (wt%) of sulfuric acid and 71.5 (wt%) of deionized water, controlling polymerization kettle temperature to 58+/-1 deg.C, and making polymerization reaction so as to obtain polymer slurry;
(6) The polymer slurry is subjected to the processes of removing monomers, washing and drying in sequence to obtain the polymer.
The index parameters of the prepared polymer are as follows: intrinsic viscosity 0.224, solid content 22%, conversion rate 88%, viscosity average molecular weight 76200, molecular weight distribution index 2.30, qualification rate 96%, good solubility of polymer in solvent, polymer particle diameter below 100um reaching 96%.
Example 3
The first polymerization kettle is started to operate, and the polyacrylonitrile-based polymer is prepared, which comprises the following steps:
(1) Deionized water is filled into the empty polymerization kettle, and a 98% liquid level is established; controlling the temperature to be 69+/-1 ℃, immersing the liquid level into a layer of stirring, and immediately starting the stirring;
(2) Introducing concentrated sulfuric acid, and adjusting the pH value to be less than or equal to 2.5;
(3) Adding 0.0002 (wt) of ferrous sulfate solution, and stirring and running for 9 minutes;
(4) Adding 0.5 (wt%) of ammonium persulfate and 0.1 (wt%) of ammonium bisulfate, stirring and running for 40 min;
(5) 31.68 (wt%) of acrylonitrile, 2.1 (wt%) of methyl acrylate, 1.0 (wt%) of itaconic acid, 0.02 (wt%) of sulfuric acid and 65 (wt%) of deionized water are added, and the polymerization reaction is conducted by controlling the temperature of a polymerization kettle to be 51+/-1 ℃ so as to obtain polymer slurry;
(6) The polymer slurry is subjected to the processes of removing monomers, washing and drying in sequence to obtain the polymer.
The index parameters of the prepared polymer are as follows: intrinsic viscosity 0.223, solid content 20%, conversion rate 86%, viscosity average molecular weight 78000, molecular weight distribution index 2.37, qualification rate 96%, good solubility of polymer in solvent, polymer particle diameter below 100um reaching 96%.
Example 4
When the first polymerization kettle is operated, the second polymerization kettle is started to prepare the polyacrylonitrile-based polymer, and the method comprises the following steps of:
the first polymerization kettle is in a normal production state, the solid content of the discharged slurry in the first polymerization kettle is 26%, the intrinsic viscosity is 0.223, and the conversion rate is 90%;
the second polymeric kettle feeding and driving method comprises the following steps:
(1) The second polymerization kettle is filled with deionized water to establish a liquid level which is 10%; the temperature is controlled to be 55 ℃;
(2) Adding sulfuric acid, and controlling the pH value to be 2.5;
(3) Feeding the discharged slurry from the first polymerizer into the second polymerizer as seed slurry,
(4) Controlling the temperature of the second polymerizer to 50 ℃, after the second polymerizer overflows and the solid content of the slurry of the first polymerizer is consistent with that of the slurry of the second polymerizer, adding 0.3 (wt%) ammonium persulfate, 0.05 (wt%) ammonium bisulfide, 27.8 (wt%) acrylonitrile, 0.86 (wt%) methyl acrylate, 0.29 (wt%) itaconic acid, 0.02 (wt%) sulfuric acid and 71.5 (wt%) deionized water into the second polymerizer for polymerization reaction, and then discharging the slurry which is all qualified products;
(5) The polymer slurry is subjected to the processes of removing monomers, washing and drying in sequence to obtain the polymer.
The obtained polyacrylonitrile polymer has the solid content of 23%, the intrinsic viscosity of 0.225, the viscosity average molecular weight of 72400, the molecular weight distribution index of 2.35, the qualification rate of 95%, the conversion rate of 89.5%, and the polymer has good solubility in a solvent, and the particle diameter of the polymer is below 100um and reaches 95%.
Example 5
When the first polymerization kettle is operated, the second polymerization kettle is started to prepare the polyacrylonitrile-based polymer, and the method comprises the following steps of:
the first polymerization kettle is in a normal production state, the solid content of the discharged slurry in the first polymerization kettle is 25%, the intrinsic viscosity is 0.223, and the conversion rate is 89%;
the second polymeric kettle feeding and driving method comprises the following steps:
(1) The second polymerization kettle is filled with deionized water to establish a liquid level which is 30%; the temperature is controlled to be 60 ℃;
(2) Adding sulfuric acid, and controlling the pH value to be 3.5;
(3) Feeding the discharged slurry from the first polymerizer into the second polymerizer as seed slurry,
(4) Controlling the temperature of the second polymerizer to 58 ℃, after the second polymerizer overflows and the solid content of the slurry of the first polymerizer is consistent with that of the slurry of the second polymerizer, adding 0.3 (wt%) ammonium persulfate, 0.05 (wt%) ammonium bisulfide, 27.8 (wt%) acrylonitrile, 0.86 (wt%) methyl acrylate, 0.29 (wt%) itaconic acid, 0.02 (wt%) sulfuric acid and 71.5 (wt%) deionized water into the second polymerizer for polymerization reaction, and then discharging the slurry which is all qualified products;
(5) The polymer slurry is subjected to the processes of removing monomers, washing and drying in sequence to obtain the polymer.
The obtained polyacrylonitrile polymer has the solid content of 25%, the intrinsic viscosity of 0.224, the viscosity average molecular weight of 72000, the molecular weight distribution index of 2.35, the qualification rate of 95%, the conversion rate of 88%, and the polymer has good solubility in a solvent, and the particle diameter of the polymer is below 100um and reaches 95%.
Example 6
The first polymerizer and the second polymerizer are started to operate to prepare the polyacrylonitrile-based polymer, and the method comprises the following steps:
(1) Deionized water is filled into the empty polymerization kettle, and a liquid level of 80% is established; controlling the temperature to 63+/-1 ℃, immersing the liquid level into a layer of stirring, and immediately starting the stirring;
(2) Introducing concentrated sulfuric acid, and adjusting the pH value to be less than or equal to 2.5;
(3) Adding 0.0005 (wt) ferrous sulfate solution, stirring and running for 8 minutes;
(4) Adding 0.3 (wt%) of ammonium persulfate and 0.05 (wt%) of ammonium bisulfate, stirring and running for 40 min;
(5) Adding 27.8 (wt%) of acrylonitrile, 0.86 (wt%) of methyl acrylate, 0.29 (wt%) of itaconic acid, 0.02 (wt%) of sulfuric acid and 71.5 (wt%) of deionized water, controlling polymerization kettle temperature to 58+/-1 deg.C, and making polymerization reaction so as to obtain polymer slurry;
the solids content of the effluent slurry in the first polymerizer was 25%, the intrinsic viscosity was 0.225, and the conversion was 90%;
(6) The second polymerization kettle is filled with deionized water to establish a liquid level which is 20%; the temperature is controlled to be 50 ℃;
(7) Adding sulfuric acid, and controlling the pH value to be 2.5;
(8) Feeding the discharged slurry from the first polymerizer into the second polymerizer as seed slurry,
(9) Controlling the temperature of the second polymerizer to be 52 ℃, after the second polymerizer overflows and the solid content of the slurry of the first polymerizer is consistent with that of the slurry of the second polymerizer, adding 0.3 (wt%) ammonium persulfate, 0.05 (wt%) ammonium bisulfide, 27.8 (wt%) acrylonitrile, 0.86 (wt%) methyl acrylate, 0.29 (wt%) itaconic acid, 0.02 (wt%) sulfuric acid and 71.5 (wt%) deionized water into the second polymerizer for polymerization reaction, and then discharging the slurry which is all qualified products.
(10) The polymer slurry is subjected to the processes of removing monomers, washing and drying in sequence to obtain the polymer.
The obtained polyacrylonitrile polymer has the solid content of 25%, the intrinsic viscosity of 0.224, the viscosity average molecular weight of 71000, the molecular weight distribution index of 2.25, the qualification rate of 97%, the conversion rate of 90%, good solubility of the polymer in a solvent and the particle diameter of the polymer below 100um reaching 96%.
Comparative example 1
The method for preparing the polyacrylonitrile-based polymer in the comparative example for single-kettle operation and starting comprises the following steps:
(1) Deionized water is filled into the empty polymerization kettle, and a 45% liquid level is established; controlling the temperature to 55 ℃, immersing a layer of stirring in the liquid level, and immediately starting stirring;
(2) Introducing concentrated sulfuric acid, and adjusting the pH value to be less than or equal to 2.5;
(3) Adding 0.0005 (wt) ferrous sulfate solution, stirring and running for 8 minutes;
(4) Adding 0.3 (wt%) ammonium persulfate, 0.05 (wt%) ammonium bisulfate, 27.8 (wt%) acrylonitrile, 0.86 (wt%) methyl acrylate, 0.29 (wt%) itaconic acid, 0.02 (wt%) sulfuric acid and 71.5 (wt%) deionized water, controlling polymerization kettle temperature to 56+/-0.5 ℃ and making polymerization reaction so as to obtain polymer slurry;
(6) The polymer slurry is subjected to the processes of removing monomers, washing and drying in sequence to obtain the polymer.
The index parameters of the polymer are: intrinsic viscosity 0.224, solids content 24%, conversion 85%.
Comparative example 2
In the comparative example, the first polymerizer was charged and started by the method of comparative example 1, and was in a normal operation state. When the second polymerization kettle needs to be started, the method of the comparative example 1 is adopted for feeding and independently starting.
Test example 1
The intrinsic viscosities of the samples sampled during the polymer preparation process of the two methods of example 1 and comparative example 1 were compared.
In the present invention, the judgment that the polymer quality is acceptable is that the intrinsic viscosity is in the range of 0.220 to 0.225L/g, and a polymer having an intrinsic viscosity outside this range is regarded as an unacceptable polymer.
After the polymerization kettle runs, judging whether the polymerization state in the polymerization kettle is stable or not according to the intrinsic viscosity index. The judging method comprises the following steps: sampling and detecting the intrinsic viscosity every 4 hours from 0h, and if the intrinsic viscosity of the polymer is in the range of 0.220-0.225L/g after 3 times of continuous detection, the polymerization kettle is considered to be stable, and the produced polymer is a qualified product.
The results are shown in table 1 below:
TABLE 1
Analysis of results:
by adopting the method of the comparative example 1, the temperature can be increased after about 40 minutes after feeding, the temperature is not easy to control, the time required for stabilizing the intrinsic viscosity of the polymer in the polymerization process is 64 hours, and 95 tons of unqualified polymer are produced.
With the method of example 1, the temperature is maintained after the deionized water establishes the liquid level, only 20 minutes is required; the time required for the intrinsic viscosity of the polymer to stabilize during the polymerization was 32 hours, resulting in 50 tons of off-grade polymer.
Compared with comparative example 1, the polymerization time for stabilizing the polymerization in the polymerization kettle in example 1 is greatly shortened, the amount of produced unqualified polymer is also greatly reduced, waste is reduced, cost is reduced, and production benefit is improved.
Test example 2
(1) In examples 1-3 and comparative examples 1-2, the performance index and process parameters of the polymers prepared with a single pot before and after the improvement of the driving mode are compared with those shown in Table 2 below:
TABLE 2
In examples 1-3 and comparative example 1, the objective was to produce acceptable products, and in the case of sufficiently long polymerization times, the polymers produced could all meet acceptable standards, i.e. intrinsic viscosities in the range of 0.220-0.225L/g.
However, by adopting the method of the invention in examples 1-4, the time required for the polymerization kettle to reach the stability (namely, stably preparing the qualified polymer) is 32-44 hours, the generated unqualified polymer is 50-65 tons, and the slag discharge amount is 3-8 kg/ton. In comparative example 1, the time required for the polymerization is 64 hours, the generated unqualified polymer is 95 tons, the slag discharge amount is 15 kg/ton, meanwhile, the inside of the polymerization kettle is scarred, the explosion polymerization phenomenon occurs, and the temperature is not easy to control.
Therefore, compared with the method of starting the half kettle in comparative example 1, the starting and feeding modes of examples 1-4 in the invention have the advantages that the time for stabilizing the polymerization kettle is shorter, the polymerization kettle is free from scarring, the explosion polymerization phenomenon is avoided, the weight of produced unqualified polymer is greatly reduced, and the slag discharge amount is reduced. Among these, the process parameters of example 1 were especially used, and the time required for stabilization was the shortest, the yield of off-grade polymer was the smallest, and the amount of slag discharge was the smallest.
Test example 3
The intrinsic viscosities of the samples sampled during the second polymerizer run were compared during the polymer preparation process by both methods of example 6 and comparative example 2.
In the present invention, the judgment that the polymer quality is acceptable is that the intrinsic viscosity is in the range of 0.220 to 0.225L/g, and a polymer having an intrinsic viscosity outside this range is regarded as an unacceptable polymer.
After the polymerization kettle runs, judging whether the polymerization state in the polymerization kettle is stable or not according to the intrinsic viscosity index. The judging method comprises the following steps: sampling and detecting the intrinsic viscosity every 4 hours from 0h, and if the intrinsic viscosity of the polymer is in the range of 0.220-0.225L/g after 3 times of continuous detection, the polymerization kettle is considered to be stable, and the produced polymer is a qualified product.
The results are shown in Table 3 below:
TABLE 3 Table 3
Analysis of results:
by adopting the method of comparative example 2, the first polymerization kettle and the second polymerization kettle respectively and independently run, a half kettle starting mode is adopted, the temperature can be increased after about 40 minutes of single kettle feeding, the temperature is not easy to control, the time required for stabilizing the intrinsic viscosity of the polymer is 68 hours, and 230 tons of unqualified polymer are produced.
Using the method of example 6, the first polymerization kettle was driven by full kettle driving, and the second polymerization kettle was driven by using the discharge slurry from the first polymerization kettle as seed slurry; after the second polymerizer is started in this way, the time required for the intrinsic viscosity of the polymer to reach stability is 36 hours, and 120 tons of off-grade polymer are produced.
Test example 4
The results and process parameters of the polymers prepared before and after the start-up mode of the second polymerizer in examples 4 to 6 and comparative example 3 are compared with those shown in Table 4 below:
TABLE 4 Table 4
As shown in the table above, compared with the method of independently starting the second polymerization kettle in comparative example 2 by using a half kettle, the starting and feeding mode of the second polymerization kettle in examples 4 to 5 of the present invention requires shorter time for the second polymerization kettle to reach stability, does not scar in the polymerization kettle, does not cause the phenomena of bursting and aggregation, greatly reduces the weight of the produced unqualified polymer, and reduces the slag discharge amount.
Test example 5 batch test
Three batches were tested using the seed slurry start-up procedure of example 6, with the second polymerization vessel having a discharge slurry index that was acceptable after 36 hours, and with the first and second polymerization vessels producing less than 130 tons of unacceptable polymer. The rate of difference between batches is within 10%.
Therefore, the output slurry in the operation kettle is used as another kettle seed slurry driving mode, the yield of the unqualified polymer is greatly reduced, the seed slurry polymerization driving method greatly reduces the generation of the unqualified polymer, reduces the cost waste, and has good repeatability and high stability.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (22)
1. The method for starting the aqueous phase suspension polymerization device by using seed slurry is characterized by comprising a first polymerization kettle and a second polymerization kettle, wherein when the second polymerization kettle is required to be started under the working state of normal polymerization of the first polymerization kettle, the method for starting the second polymerization kettle comprises the following steps:
(1) Filling deionized water into the second polymerization kettle to establish a liquid level, wherein the liquid level is 10% -30%;
(2) Introducing an acid agent to adjust the pH value;
(3) Feeding the discharge slurry from the first polymerizer into the second polymerizer to replace deionized water in the second polymerizer;
(4) Stopping inputting after the second polymerizer overflows and the solid content of the slurry of the first polymerizer is consistent with that of the slurry of the second polymerizer, and adding an oxidant, a reducing agent, a first polymerization monomer, a second polymerization monomer, a third polymerization monomer and acidified deionized water into the second polymerizer to carry out polymerization reaction;
wherein the first polymerized monomer comprises acrylonitrile;
the second polymer monomer is selected from one of methyl acrylate, vinyl acetate and acrylamide;
the third polymeric monomer is selected from one of itaconic acid, acrylic acid, acrylamide and methacrylic acid.
2. The method of claim 1, wherein in step (1), the temperature of deionized water in the second polymerization vessel is controlled to be 50-60 ℃.
3. The method of claim 2, wherein the temperature of deionized water in the second polymerization vessel is controlled to be 50-55 ℃.
4. The process of claim 1, wherein in step (4), the temperature of the second polymerizer is controlled to be 50 to 60 ℃.
5. The process of claim 4, wherein in step (4), the temperature of the second polymerizer is controlled to be 52℃to 58 ℃.
6. The process according to claim 2, wherein in step (4), the temperature of the second polymerizer is controlled to be 50 to 60 ℃.
7. The process of claim 2, wherein in step (4), the temperature of the second polymerizer is controlled to be 52 to 58 ℃.
8. The method according to claim 2, wherein in step (2), the pH is controlled to 2 to 3.5.
9. The process according to any of claims 1 to 8, wherein the solids content of the effluent slurry in the first polymerizer is 22 to 26%, the intrinsic viscosity is 0.220 to 0.224L/g, and the conversion is 86 to 90%.
10. The method of any one of claims 1-8, wherein the method of feeding and driving the first polymerizer comprises:
(1) Filling deionized water into the empty polymerization kettle, and establishing a liquid level, wherein the volume of the added deionized water is 75-98% of the volume of the polymerization kettle;
(2) Introducing an acid agent, and adjusting the pH value to be less than or equal to 2.5;
(3) Adding a cocatalyst and stirring;
(4) Adding an oxidant and a reducing agent, and stirring;
(5) Adding a first polymerization monomer, a second polymerization monomer, a third polymerization monomer and acidified deionized water to carry out polymerization reaction to obtain polymer slurry;
wherein the first polymerized monomer comprises acrylonitrile;
the second polymer monomer is selected from one of methyl acrylate, vinyl acetate and acrylamide;
the third polymeric monomer is selected from one of itaconic acid, acrylic acid, acrylamide and methacrylic acid.
11. The method of claim 10, wherein deionized water is introduced into the empty polymerizer to establish a liquid level of 80-95%.
12. The method of claim 10, wherein in step (1), the temperature of the deionized water is controlled to be 60-70 ℃.
13. The method of claim 12, wherein in step (1), the temperature of the deionized water is controlled to be 62-65 ℃.
14. The method of claim 10, wherein in step (3), the promoter is selected from the group consisting of ferrous sulfate; the feeding amount of the ferrous sulfate is 0.0001-0.0008wt% based on the total feeding amount of all materials.
15. The method according to any one of claims 1 to 8, wherein,
the feeding amount of the first polymeric monomer is 90-98wt%, the feeding amount of the second polymeric monomer is 1-7wt% and the feeding amount of the third polymeric monomer is 1-3wt% based on the total feeding amount of all polymeric monomers;
the oxidant is one or more selected from ammonium persulfate, potassium persulfate and hydrogen peroxide; the reducing agent is one or more selected from ammonium bisulfate, ammonium sulfite, sodium bisulfate, sodium sulfite and sodium metabisulfite;
the feeding amount of the oxidant is 0.3-1.5wt% and the feeding amount of the reducing agent is 0.05-0.35wt% based on the feeding total amount of all materials;
the acid agent is selected from one or more of sulfuric acid, nitric acid and sulfurous acid;
the feeding amount of the acidified deionized water is 60-85wt% based on the total feeding amount of all materials.
16. The method of any one of claims 1-8, wherein the acid agent is sulfuric acid.
17. The method of claim 9, wherein the step of determining the position of the substrate comprises,
the feeding amount of the first polymeric monomer is 90-98wt%, the feeding amount of the second polymeric monomer is 1-7wt% and the feeding amount of the third polymeric monomer is 1-3wt% based on the total feeding amount of all polymeric monomers;
the oxidant is one or more selected from ammonium persulfate, potassium persulfate and hydrogen peroxide; the reducing agent is one or more selected from ammonium bisulfate, ammonium sulfite, sodium bisulfate, sodium sulfite and sodium metabisulfite;
the feeding amount of the oxidant is 0.3-1.5wt% and the feeding amount of the reducing agent is 0.05-0.35wt% based on the feeding total amount of all materials;
the acid agent is selected from one or more of sulfuric acid, nitric acid and sulfurous acid;
the feeding amount of the acidified deionized water is 60-85wt% based on the total feeding amount of all materials.
18. The method of claim 9, wherein the acid agent is sulfuric acid.
19. The method of claim 10, wherein the step of determining the position of the first electrode is performed,
the feeding amount of the first polymeric monomer is 90-98wt%, the feeding amount of the second polymeric monomer is 1-7wt% and the feeding amount of the third polymeric monomer is 1-3wt% based on the total feeding amount of all polymeric monomers;
the oxidant is one or more selected from ammonium persulfate, potassium persulfate and hydrogen peroxide; the reducing agent is one or more selected from ammonium bisulfate, ammonium sulfite, sodium bisulfate, sodium sulfite and sodium metabisulfite;
the feeding amount of the oxidant is 0.3-1.5wt% and the feeding amount of the reducing agent is 0.05-0.35wt% based on the feeding total amount of all materials;
the acid agent is selected from one or more of sulfuric acid, nitric acid and sulfurous acid;
the feeding amount of the acidified deionized water is 60-85wt% based on the total feeding amount of all materials.
20. The method of claim 10, wherein the acid agent is sulfuric acid.
21. The method according to any one of claims 11-14, wherein,
the feeding amount of the first polymeric monomer is 90-98wt%, the feeding amount of the second polymeric monomer is 1-7wt% and the feeding amount of the third polymeric monomer is 1-3wt% based on the total feeding amount of all polymeric monomers;
the oxidant is one or more selected from ammonium persulfate, potassium persulfate and hydrogen peroxide; the reducing agent is one or more selected from ammonium bisulfate, ammonium sulfite, sodium bisulfate, sodium sulfite and sodium metabisulfite;
the feeding amount of the oxidant is 0.3-1.5wt% and the feeding amount of the reducing agent is 0.05-0.35wt% based on the feeding total amount of all materials;
the acid agent is selected from one or more of sulfuric acid, nitric acid and sulfurous acid;
the feeding amount of the acidified deionized water is 60-85wt% based on the total feeding amount of all materials.
22. The method of any one of claims 11-14, wherein the acid agent is sulfuric acid.
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| KR20200084632A (en) * | 2019-01-03 | 2020-07-13 | 주식회사 엘지화학 | Method for preparing acrylonitrile based polymer |
| CN110305247A (en) * | 2019-07-24 | 2019-10-08 | 长春工业大学 | A kind of polyacrylonitrile base carbon fiber precursors polymer and preparation method thereof, a kind of polyacrylonitrile-based carbon fibre and preparation method thereof |
| CN112679654A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile resin with controllable particle size and uniform distribution |
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