CN115368503B - Method for feeding and starting water-phase suspension polymerization device and prepared polymer - Google Patents
Method for feeding and starting water-phase suspension polymerization device and prepared polymer Download PDFInfo
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- CN115368503B CN115368503B CN202110547555.8A CN202110547555A CN115368503B CN 115368503 B CN115368503 B CN 115368503B CN 202110547555 A CN202110547555 A CN 202110547555A CN 115368503 B CN115368503 B CN 115368503B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 91
- 239000000178 monomer Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 37
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 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 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical group [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- OQTRPSFMBXCQIY-UHFFFAOYSA-N azane;2-methylidenebutanedioic acid Chemical compound N.OC(=O)CC(=C)C(O)=O OQTRPSFMBXCQIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- BLRZZXLJCJKJII-UHFFFAOYSA-N 3-carbamoylbut-3-enoic acid Chemical compound NC(=O)C(=C)CC(O)=O BLRZZXLJCJKJII-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 claims 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 description 12
- 229920002239 polyacrylonitrile Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000012797 qualification Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 230000009172 bursting Effects 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
- 239000012190 activator Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 206010039509 Scab Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical group [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001284 azanium sulfanide Substances 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
- 238000001514 detection method Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002156 mixing Methods 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
- 239000012966 redox initiator Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037390 scarring Effects 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000002699 waste material 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
-
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for feeding and starting a water-phase suspension polymerization device and a prepared polymer, which 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; (2) introducing an acid agent, and adjusting the pH value; (3) adding a cocatalyst and stirring; (4) adding an oxidant and a reducing agent, and stirring; (5) Adding at least one monomer, an acid agent and deionized water for polymerization reaction 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 method of the invention can shorten the polymerization start-up stabilization time, reduce the generation of unqualified polymers, be beneficial to the uniform stabilization of the product quality, reduce the cost and improve the economic benefit.
Description
Technical Field
The invention belongs to the field of carbon fiber production, and particularly relates to a method for feeding and starting a water phase suspension polymerization device and a prepared polymer.
Background
The process for producing the carbon fiber precursor comprises three working sections of polymerization, dope and spinning. In the production process of polyacrylonitrile-based carbon fiber precursor, the starting stability of polymerization feeding in the polymerization stage is directly related 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.
In the current aqueous suspension polymerization process, the starting mode of the polymerization kettle is empty kettle starting, namely, mixing monomers, catalysts, activators, sulfuric acid, itaconic acid and desalted water are fed into the polymerization kettle according to the formula, and polymerization is carried out. 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. The material can be diluted after the material formula is replaced after overflow, and the phenomenon of material sticking 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, the temperature is controlled after the kettle is full, and 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 the overflow port of the polymerization kettle is blocked still exist in the mode.
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. The invention improves the method for feeding the material when the polymerization kettle is started, shortens the polymerization start-up stabilizing time, reduces the generation of unqualified polymers and is beneficial to the uniform and stable product quality.
In order to solve the technical problems, the invention adopts the basic conception of the technical scheme that:
the invention provides a method for feeding and starting a water phase suspension polymerization device, which 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 to adjust the pH value;
(3) Adding a cocatalyst and stirring;
(4) Adding an oxidant and a reducing agent, and stirring;
(5) Adding at least one monomer, an acid agent and deionized water for polymerization reaction 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.
In the aqueous suspension polymerization process, deionized water is introduced into a polymerization kettle to establish a low liquid level (10% -45%), and various monomers, catalysts, activators, acid agents and desalted water are fed into the polymerization kettle according to the formula proportion for polymerization. This kind of mode polymeric kettle needs to rise through about 40 minutes temperature just, and temperature is difficult to control, in case the temperature rise is very fast, extremely easily causes the inside explosion of polymeric kettle to gather to the slurry is more viscous after the overflow, and difficult flow blocks up the polymeric kettle overflow mouth, causes a large amount of unqualified products, influences the quality of polymer, if have unqualified polymer to mix, also influences follow-up spinning process.
In order to change the unstable situation of the empty kettle feeding or the semi-kettle feeding initial stage of the polymerization kettle, the invention discovers that deionized water is firstly introduced into the polymerization kettle, 75-98% 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 polymerization 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, the temperature of the deionized water is controlled to be 62-68 ℃.
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 cocatalyst is added in an amount of 0.0001 to 0.0008wt% based on the total amount of all monomers added.
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 A third party; 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.
In a further scheme, in the step (4), the oxidant is one or more selected from ammonium persulfate, potassium persulfate and hydrogen peroxide; preferably, the oxidant is ammonium persulfate;
the reducing agent is one or more selected from ammonium bisulfate, ammonium sulfite, sodium bisulfate, sodium sulfite and sodium metabisulfite; preferably, the reducing agent is ammonium bisulfide or ammonium sulfite;
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 total feeding amount of all monomers.
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 first monomer and the second monomer, or the first monomer, the second monomer and the third monomer are added;
preferably, the first monomer comprises acrylonitrile,
the second monomer is selected from one of acrylic acid, methacrylic acid, methyl acrylate, vinyl acetate, acrylamide and methyl methacrylate; preferably one of methyl acrylate, vinyl acetate and acrylamide;
the third monomer is selected from one of itaconic acid, itaconic acid ammonia and itaconic acid amide; preferably, the third monomer is itaconic acid;
preferably, the first polymeric monomer is fed in an amount of 90 to 98wt%, the second polymeric monomer is fed in an amount of 1 to 7wt%, and the third polymeric monomer is fed in an amount of 1 to 3wt%, based on the total amount of all the polymeric monomers fed.
In a further scheme, in the step (5), the feeding amount of deionized water is 60-85wt% based on the total feeding amount of all materials.
In a further scheme, in the step (5), the temperature of the polymerization kettle is controlled to be 50-70 ℃.
Further, in the steps (2) and (5), the acid agent is selected from one or more of sulfuric acid, sulfurous acid and nitric acid, preferably, the acid agent is sulfuric acid;
preferably, in the step (5), the feeding amount of the acid agent is 0.02-0.12wt% based on the total feeding amount of all materials.
Preferably, in the step (2), an acid agent is introduced, and the pH value is regulated to be less than or equal to 2.5.
Further, in the steps (1) to (5), the stirring speed is 30 to 100rpm.
The second object of the invention is to provide a polyacrylonitrile-based polymer, wherein the solid content of the polyacrylonitrile-based 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 96-97%, the conversion rate is 86-92%, the polymer has good solubility in a solvent, and the polymer particle diameter is less than 100um and reaches more than 96%;
preferably, the polyacrylonitrile polymer is prepared by adopting the feeding and starting method of the aqueous phase suspension polymerization device according to any one scheme or 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. in order to change the unstable situation of the initial feeding stage of the empty polymeric kettle, the invention improves the feeding and starting mode of the polymeric kettle, firstly, deionized water is introduced into the polymeric kettle, the liquid level of 75-98% is established, the temperature of the deionized water is controlled, and then the materials are sequentially fed, so that the starting and stabilizing time of the polymeric kettle can be shortened, the temperature of the polymeric kettle is also easy to control, the explosion aggregation phenomenon in the polymeric kettle can be avoided, the scab in the polymeric kettle can be avoided, the generation of unqualified polymers can be reduced, the production stability is ensured, the quality of polymer products is ensured, and the labor intensity of workers is also reduced.
2. The invention further adjusts each technological parameter in polymerization, provides stable initiation environment, improves initiation efficiency, and the obtained polymer has high qualification rate, good uniformity and stability and small batch-to-batch difference, and is beneficial to subsequent spinning.
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 preparation of the polyacrylonitrile-based polymer 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 preparation of the polyacrylonitrile-based polymer 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 preparation of the polyacrylonitrile-based polymer 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
The preparation of the polyacrylonitrile-based polymer comprises the following steps:
(1) Deionized water is filled into the empty polymerization kettle, and a 75% liquid level is established; controlling the temperature to 65+/-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 0.0004 (wt) of ferrous sulfate solution, and stirring and running for 9 minutes;
(4) Adding 1.0 (wt%) of ammonium persulfate and 0.15 (wt%) of ammonium bisulfate, stirring and running for 45 min;
(5) Adding 17.2 (wt%) of acrylonitrile, 0.73 (wt%) of vinyl acetate, 0.18 (wt%) of itaconic acid, 0.12 (wt%) of sulfuric acid and 80.6 (wt%) of deionized water, controlling polymerization kettle temperature to 65+/-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 polymer are: intrinsic viscosity 0.220, solids content 21%, conversion 86%.
Example 5
The preparation of the polyacrylonitrile-based polymer comprises the following steps:
(1) Deionized water is filled into the empty polymerization kettle, and a 95% liquid level is established; controlling the temperature to be 68+/-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 0.0006 (wt) of ferrous sulfate solution, and stirring and running for 9 minutes;
(4) Adding 0.8 (wt%) of ammonium persulfate and 0.2 (wt%) of ammonium bisulfate, stirring and running for 50 min;
(5) 26.5 (wt%) of acrylonitrile, 1.25 (wt%) of acrylamide, 0.34 (wt%) of itaconic acid ammonia, 0.12 (wt%) of sulfuric acid and 70.8 (wt%) of deionized water are added, and the polymerization reaction is conducted by controlling the temperature of a polymerization kettle to 68+/-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 polymer are: intrinsic viscosity 0.223, solids content 25%, conversion 87%.
Comparative example 1
The method for preparing the polyacrylonitrile-based polymer in this comparative example comprises the steps of:
(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%.
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
By adopting the method of the example 1, 10 batches are repeated, the rejection rate of the polymer in each batch is reduced to 50-70 tons from 90-110 tons before modification, and the slag discharge rate is reduced by about 85 percent. The rate of difference between batches is within 10%. The method has good repeatability and high stability.
In conclusion, the method of the invention has the advantages that the temperature of the polymerization kettle is easy to control, the fluctuation is small, the inside of the kettle is not easy to scar, the sight glass opening of the polymerization kettle is clean, the phenomenon of implosion is avoided, the intrinsic viscosity index is stable and fast, less unqualified polymer is produced, and the labor intensity of workers is greatly reduced. Through operation observation, the deslagging particles of the dryer are obviously reduced, and a foundation is laid for improving the yield of the polymerization kettle.
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 (23)
1. A method for feeding and starting an aqueous phase suspension polymerization device, which is characterized by comprising 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; and controlling the temperature of deionized water to be 60-70 ℃;
(2) Introducing an acid agent to adjust the pH value;
(3) Adding a cocatalyst and stirring;
(4) Adding an oxidant and a reducing agent, and stirring;
(5) Adding at least one monomer, an acid agent and deionized water for polymerization reaction to obtain polymer slurry;
(6) The polymer slurry is subjected to the processes of removing monomers, washing and drying in sequence to prepare a polymer;
in the step (5), the first monomer and the second monomer, or the first monomer, the second monomer and the third monomer are added;
wherein the first monomer comprises acrylonitrile,
the second monomer is selected from one of acrylic acid, methacrylic acid, methyl acrylate, vinyl acetate, acrylamide and methyl methacrylate;
the third monomer is selected from one of itaconic acid, itaconic acid ammonia and itaconic acid amide.
2. The method of claim 1, wherein the third monomer is itaconic acid.
3. The method of claim 1, wherein deionized water is added to establish the liquid level to 80-90% in step (1).
4. The method of claim 1, wherein in step (1), the temperature of deionized water is controlled to be 62-68 ℃.
5. The method of claim 1, wherein in step (3), the promoter is selected from the group consisting of ferrous sulfate; the cocatalyst is added in an amount of 0.0001 to 0.0008wt% based on the total amount of all monomers added.
6. The method according to claim 1, wherein in the step (4), the oxidizing agent is one or more selected from the group consisting of ammonium persulfate, potassium persulfate, and hydrogen peroxide;
the feeding amount of the oxidant is 0.3-1.5wt% based on the feeding total amount of all materials.
7. The method of claim 6, wherein in step (4), the oxidant is ammonium persulfate.
8. The method according to claim 1, 6 or 7, wherein in the step (4), the reducing agent is selected from one or more of ammonium bisulphite, ammonium sulfite, sodium bisulphite, sodium sulfite and sodium metabisulfite;
the feeding amount of the reducing agent is 0.05-0.35wt% based on the total feeding amount of all materials.
9. The method of claim 8, wherein in step (4), the reducing agent is ammonium bisulfate or ammonium sulfite.
10. The method according to claim 1, 6 or 7, wherein in step (4), after the addition of the oxidizing agent and the reducing agent, stirring is performed for 30 to 50 minutes.
11. The method of claim 8, wherein in step (4), after the oxidizing agent and the reducing agent are added, stirring is performed for 30 to 50 minutes.
12. The method of claim 9, wherein in step (4), after the oxidizing agent and the reducing agent are added, stirring is performed for 30 to 50 minutes.
13. The method according to claim 1, wherein in the step (5), the amount of the first monomer is 90 to 99wt%, the amount of the second monomer is 0.5 to 7wt%, and the amount of the third monomer is 0.5 to 3wt%, based on the total amount of all the monomers; the feeding amount of deionized water is 60-85wt% based on the total feeding amount of all materials.
14. The process according to claim 1 or 13, wherein in step (5), the polymerization vessel temperature is controlled to 50-70 ℃.
15. The method according to claim 1 or 13, wherein in steps (2) and (5), the acid agent is selected from one or more of sulfuric acid, nitric acid, sulfurous acid.
16. The method of claim 15, wherein in steps (2) and (5), the acid is sulfuric acid.
17. The method according to claim 15, wherein in the step (2), an acid agent is introduced to adjust the pH to 2.5 or less.
18. The method according to claim 15, wherein in step (5), the amount of the acid agent added is 0.02 to 0.12% by weight based on the total amount of all materials added.
19. The method of claim 14, wherein in steps (2) and (5), the introduced acid agent is selected from one or more of sulfuric acid, nitric acid, sulfurous acid.
20. The method of claim 19, wherein in steps (2) and (5), the acid is sulfuric acid.
21. The method according to claim 19, wherein in the step (2), an acid agent is introduced to adjust the pH to 2.5 or less.
22. The method according to claim 19, wherein in step (5), the amount of the acid agent added is 0.02 to 0.12% by weight based on the total amount of all materials added.
23. The method of claim 1, wherein the second monomer is selected from one of methyl acrylate, vinyl acetate, and acrylamide.
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